FORAERONAUTICS
TECHNICAL NOTE
No.1247
THE PREPARATION
PROPERTIES OF SEVERAL
ALIPHATICHYDROCARBONS .AND INTERMEDIATES
(.,
.,
By FrankL.How-d, ThomasW. Mears,A. Fookson,
Philip
Pomersntz,
and,Donald
B. Brooks
National
BureauofStmdards
Washington
May 1947
._—
.-,
..
!MBLEOF CONTENTS
Page
SUNMARY
.... .
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lTJTRODUCTION
APPARATUS
..
Reaotion
Vessels
Hydrogenation
Equipment. . . . .
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PREPARATION
OFMATERIALS, . .’. .
Preparation
ofGri@erdReagents
n-Pentane. . . . . . . . . . .
2-Methylbutene
(Isopentane)
..
2j2-Dimethylpropane
(I?eopentane) 9
3-Methylpentene
........
.
2j2-Dimethylbutane
(Neohexane)
.
2-Methylpentane
,.......
.
Investigation
ofButeneAlkylate
2,3-?Xmethylbutane
.....
2,4-?)imethylpentane
.....
2,3-Dimethylp&&ane
fromIsooctane .
2,2,3-Trimethylbutaue
(Triptane)
.
.
2-Methyl-3-Et&lpentane
.....
2,3,3-Tr&thyip&nta.ne
.....
2,2,3-Trimethylpentane
and2,3jk-Trlmethylpentaue
.
2,2,5-Trimeihylhexane . . . . . . . .
2,3,5-Trimethylhexane
.......
2,2,&Trimethylhexene
.......
b
.
2,2-Dimethyl-3-Ethylpentane
....
~2;&-Dimet&l-~-Et&lpentane
....
~2S2,3,3-Tetremethylpentane
(Tetrane)
2,2,3,@etramethylpentane
and2,3,3,&Tetramethylpentane
—
Dimethyl-Zinc
S@hesls ofThreeTetramethylpentanes
..
b
2,2,3,3-Tetramethylpentane
.............
2,2,3,4and.
2,3,3,&Tetramethylpentanes
......
~2,&-Dimethyl-3-Isopropylpentene
(Triisopropylmethane)
.
.
Pentemethylpentanes
........... ...... .
.
2,2,5,5-Tetremethylhexane
end2,2,4,5-Tetremethylhexsne
*2,2j3,3-Tetramethylhexene
. . ; “.j . . . . . . . . . .
3j3,4,4-Tetramethylhexene
..........,...
2,3-Dimethyl-l-Butene
and2,3-Dimethyl-2-Butene
...
.
3-Methyl-2
-Pentenes
(cisan~trens). .
,.. . . .
Investigation
ofDiisobutylene
.
Investigation
of Hot-Acid
OilCompany)
Polymer
(Shell
. . . .6 . . . * .*
xmFEBENas*..
TABLES,’..,. 9 a a n Q .*# e . .
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52
NATIONAL
ADVISORY
COMMITTEE
IK3R
AERONA~ICS
.>,
.
TTICENI@L”
NO”~NO.1247
.
THEPREPARATION
ANDPHYSICAL
PROEf!RTIES
OFSEVEML
ALII%ATIC
,EmRomRBoNs
Juvi
rmEmEDDms
~y FrenkL. Howerd,
Thomas
W.Mears, A.Fookson,
Philip
Pomersntz,
andDonald
B.Brooks
,.
.
‘Inthecouree
ofan.investigation
oftheknockratings
ofaliphatic
hydrocarbons,
pureTarafflns
endolefins
wereprepared
inquantities
sufficient
forengine
tests.Thisreport
describes
themethods
ofpreparation
andpurification
ofthreepentanes,
fourhexanes,
threeheptsnes,
fouroctanes,
eightnonsnes,
sevendecanes,
fourhexenes,
fiveoctenes,
sixnonenes,
sixdecenes,
anda number
ofalcohols,
ketones,
esters,
end
alkylhelldes.
Mostof thesecompounds
werehighly
purified.
Physical
oonstants
measured
included
freezing
point,
boiling
pointanditsvariationwithpressure,
refractive
indexanddensity,
endtheirvariations
withtemperatyme.
INTRODUCTION
,.
In1934theAutomotive
Section
of theNationalBureau
of.
Standards
undertook
an investigation
of the.
impurities
present
inthecertified
lscoctane
(2,2,.&trimethy3pentsne)
usedasa @2narystendard
inthe
knockrating
offuels.In thecourse
of this.work,
abouta scoreof
paraffin
hydrocarbons
wereisolated
and.thqir
physical
properties
and
hock ratings
weredetermined.
(Seereference
1.) Theinformation
obtained
inthisworkindicated
thatsomeof thehigher
paraffin
hydro- .
carbons
should
be decidedly
superior
toisooctene
inknockrating.
b
.
Theresults
ofthisworkledto a researchproject
thatwasinltlatedwiththeobjective
ofpreparing,
inquantities sufficient
forengins
tests;
theparaffin
hydrocarbons
likely
tobe of interest
ascomponents
ofCombat
aviation
fuel.Thispro~ect
wasbegunin1937underJoint
sponsorship
of theNational
Advisory
Comuittee
forAeronautics,
theAzmy
AirForces,
andthel?avy
Bureau.of
Aeronautics
andhasbeenactively
prosecuted
sincethattime.Therestits
ofportions
ofthisinvestigation
,,
.-
,
2
NACATNNO.12k7
completed
priorto1940havebeenpresented
Inreferences
2 to5, and
the~yntheses
andphysical
properties
ofa number
ofaddittonel
al.iphatic
hydrocarbons
aredescribed
inthepresent
paper.
.
SincetheolJective
ofthisworkwasthepreparation
of purehydrocarbons
forengine
testing
‘to
determine
hock rating,
itwasgenerally
necessary
to subordinate
otherconsiderations
tothispurpose.
Inmany
cases,
itwastherefore
notpossible
tomakedetailed
studies
ofthereactions
or todetermine
properties
of someofthenewor,little-known
intermediates.
Aclmowledgments
areduethefollowing
people
foraidandadvice
on
various
phases
ofthiswork:Dr.CecilE.Boord,
OhioStateUniversity,
Dr.George
Calingaert
andDr.Harold
A.Soroos,
EthylCorporaticm
Research
Laboratories,
Dr.Nathan
L, Drake,
University
ofMaryland,
Dr.
Merrill
R. Fenske
andDr.FrankC.Whitmore,
Pennsylvania
StateCollege,
andDr.Frederick
D.Rosslni,
National
Bureau
oft%andard~.
APPARATUS
Reaction
Vessels
Small-scale
exploratory
reactions
weregenerally
carried
outin5literglassflasks.In somecases,
whereanwnmal.ly
lowyleldof
finalproduct
wasexpected,
12-liter
flasks
wereused.Theuseofthese
larger
flasks
wasdiscontinued
in1944,andreactions
of thissizewere
thenconducted
inlk-liter
brassdouble-walled
vessels.
Forsynthesis
on a larger
scale,
twocopper
reactors
wereusedinittally.
Eachof
thesereactors
hada capacity
of60liters
andwasdouble
walled.Water
atanydesired
temperature
between
5°and75°C!couldbe circulated
in
thespacebetween
thewallstocontrol
thetemperature
ofthereaction.
Thereactors
wereequipped
withmultiple-paddle
stirrers
(60to200rpm),
reflux
condensers
(multtple
copper
tube),
separator
funnels
foraddi,‘tion
ofreactants,
anddraw-off
valves
forremoval
ofproducts.
These
reactors
wereuseduntilearlyin1944,whentwo50-gal.lon
kettles
(one
glasslinefij
onestainless
steel)
wereputintoservice.
Thecopper
reactors
werethenusedasdistillation
receivers
Inconjunction
with
thelargekettles.
Thelargekettles
werestandard
commercial
items
andwereinstalled
sothatanytemperature
between
5°and150°C could
bemaintained
intheJackets.- -
.
.
~drogenation
Equipment
Hydrogenation
reaotions
wereaccomplished
inhigh-pressure
hydrogenato~s,
designed
afterthosedescribed
byAdkins
iireference
6.
1
.
NACA~NO. 1247
3
Threesizeswereused,withcapacities
of1, 3,and.
20liters.Thecatalystusedwasa commercial
nickel-cm-kieselguhr
preparation,
which
proved
tobe econmical
andefficient.
l?odifflctity
wasencount&ed
in
hydrogenating
anyof thematerials,
provided
theywerehalogen-free.
Most.of
thehydrogenation
reactions took,place
attemperatures
below
1600C sadpressties
below2000~@is persq~e inch.
..
stills
.
Forconvenience,
the’
va@ousstills
usedXnthiswork&e desig-”
natedinthetextbynumbers.Thesalient
features
of thesestills’&e
givenintatle1. Someof thesecolumns
&e no longer
inuse,hatipg
beensupplanted
by others
oflaterdesigns.operations
formerly
performed
InColurms
1 and2 werelatercarried
outin19 snd20,andColumns8 and9 werereplaced
by 17 and18. Column
20wasabandoned
in
1942,whenC!oiumn
11wasputintooperation.
Columns
3 to7 werere-“
pla0e&by21to 27latein1945.
.
Still1.-Thisstfllisofthe.
tot~-reflux,
intermitt&nt
take-off
type,andhasbeenpreviously
descriled
inreference
5. Thereflux
rate
wasapproximately
1500ml perhourInmostcase,s,
thetake-off
ratebeinggeyorned
by thecomposition
of thecharge
andthepurity
desired
in
theproduct.Samples
of78mI eachwer~removed
automatically
atpredetermlned
intervals
varying
fromO.~to24hours.Theefficiency
is,
approximately
ninetytoninety-five
theoretical
plates,
@ndthe”
hold-up
is
.260ti..
Still2.-Thecolumn
of this-still
consists
of150actual
plates,
following
thedesign
byJ. H.Brunn.(Seereference
7.) Thevolume
of
eachfr~tionremoved
was65ml. Refluxratewasstout&10ml.perhour.
Thisstill4asalsobeendescr+bea
inreference
5. Themechanisms
of
operation
andsemple
removal
arethesameas forStill1..In-both
Stills
1 and2 theheadtemperatu&e
wasfollowed
during
the’day
bymeans
of a platfnmn
resistance
thermometer,
endthetiming
operations
were
scheduled
sothatsamples
wereYemoved
whenth$.s
temperature
(corrocted
to760mmHg)became
reasonably
constant
(generally
towithin
a change
oflessthan0.005°
C perhr).
v’”
.
.
.-&&l stille
p~ttimedafterthosedescribed
by,
Whitmore
,and.Lux
reference
8)were,usqd
toremove
otherfromreacttoh
mixtirres,
forpurification
of iritermedlatcm,
forprelimiriary
purificationoffinalproducts,
andfor fraotionaticn
of mall charges.
These
stills
aredesignated
as,3 to9 intable1*
,,
,.
still1o.-Priortotheconstruction
’ofotherlarge-capacity
stills,
Still10wasusedfor.preli~ fracttcna~ion
ofcommercial
synthetic
crudes.ThepotwaspartQfa domestic
hot-,water
tank,~h~column
a
,..
,..
,.
4
l?ACATN
No.1247
wasgwernedby a l/8-tnch
peedle
lenglih
of2-i.noh
pipe,Thetake-off
.Wve.
Still11.- Inordertohavea higher-oapaol~,
higher-efficiency
stillthen10,Still11wasconstructed.,
.Theentiro
stillismadeof
monelmetal.Thereflux
rateisabout4 ltters
perhour,asmeasured
by
gainM temperaimro
ofthecondenser
water~Thetake-off
rataisgo~- ,
ernedby a comDMrcWl
I/&inchsoIenoid
valve,
operated
byanautomatic
thingdevice.Theefficiency
of’
thesttllisaboutsixty-five
theoreb
icsl plates
underoperating
conditions
(3.5to4.5liters
perhr reflux).
Safety
devices
include
overflow
tanksforthesalvaging
ofmaterial
distflled
through
thecondenser
lfthewaterIsaccidentally
cutoff,a
product oVerflcw
tenkforretaining
material
whichmaybe delivered
becauseoffaulty
operation
ofthesolenoid
valve,
@ a“pot-teWeratWelimitcontrol.
AU openings
tothestillarevented
totheoutside
of
the.tmililing.
. StiZls
12toIL.-Thesecolumns
wereconstructed
forsnalysis
of
comnercle2
crudes,
puriftcatim
oflargequantities
ofmaterial,
and
isolation
ofhydrocarbons
fromcommercial
mixtures.
Thesewereputinto
operation
in1943,andlater(1945)
Column
11waslengthened
by 4 feet
andaddedtothegroup.Thetake-off
onallthesestills
isgoverned
by
a ttmerandsmallsolenoid
valves.Condensers
inthelarger
columns
are
ofthemultlple
cold-finger
type.Thecolmnns
areheated
byresistance
wirecontrolled
byvariable
trsnsformors.
Temperatures
aremeasured
by
copper-constentan
thermocouples.
Safety
devices
include
overflow
+emks,
automatic
pot-temperature-limtt
control,
forcod
ventilation,
automatic
carbon-dioxide
firecontrol
(controlled
by thermal-plugs),
andautomatic
warning if’ the atmosphere
approaches
a combustible
mizlmre.Thepotsof
Stills
12to16aremadeofmildsteel”.
we columns
of12and13are ‘
madeof galvanized
ptpe,andthecolumns
of1.4
end15aremadeof #kinlesssteel.Condensers-are
ofcopper,
brass,
ormonelmetal
●
IEH5EWNATION
OFPHYSIC!AL
PROEERTJES
Fromtheplotsofrefraotfve
indices,
boiling
points,
orfreezing
points
offractions
withrespect
tovolume
ofdisttl.late,
thosefracticns
:
containing
thebestmatqrial
were selected
andusedforthedetermination
.
.,
ofphysical
constants.
Themethods
usedforthedetermination
ofphysical
constants
have
beendescribed
inreferenoe
4. Thefreezing-point
apparatus
wasmodified
lnDecember
1944,sothatadditional
control
oftherateofcoollng
could
beobta!ned.
Thiswasdoneby installing
a pumping
system
ont,he
evacuatedchaniber
surrounding
thesam~le$
sothattherateofcooling
oouldbe
governed
by thepressure
intheevacuated
chamber.
Thismodification
of
.
NACATNNO.1247
.
5
theequipnnt
hasbeencbquatekw
described
byMair(reference
9).
Table2 liststhemeasured
phystcsl
properties
oftheocmpmnxls
described
hexein.
.
Thefreezing-point
dataon2,2,5,3-tetrsmethylhexane
areconsidered
representative,
snaareill.ustrated,
infigure
1. Boiling-point
dataon
fourcompounds
areshowninfigure
2. Th9sefigures
me ~:esented.
as
t.ypicsl
exemples
ofmeasured
physical
properties.
Refractive
indices
weremeasuzzed
on anAbbetype(Valentine)
refractometer
until1943when
a BauschendLorn?J
precision-oil
refractometer
(alsoAbbetype)wasput
intouse. An estimate
ofthepurity
of theindividual.
compounds
maybe
madefromthedataliste~
M table2 undertheheading
.AT:20
to @ percant,whichindicates
thenumber
ofdegrees
difference
between
thetemperature
atwhich20percent
ofthematerial
haddistilled
endthetemperature
atwhich80percent
hafl
distilled.
Thepresence
ofperoxides
intheolefin
semples
tended
tomakethisdifference
extraordinarily
large.
PREPARATION
03’MMWUALS
,
Gyignard.
Reagents
.
Thepreparation
ofGrignan.reagents
in
quantities
(upto
330moles)has%.een
foundtobe subject
tothe”saelimite.tions
aathe
preparation
of smallamounts,
except
thattheyields,
ingeneral,
are
slightly
Larger,Themethods
usesintypical
rum ofrepresentative
meukers
ofthealiphatic
series
am givenasfollows,
andarenotrepeatedinthediscussion
of thevarious
sptheses.Decomposition
of
reaction complexes
fo~e~Iy theaction
ofGrignard
reagents
onvarious
compounds
followed
theclassical methods
andne@ notberepeated.
Miage
.
.
Meth@magnesium
bromide.To thereactor
wasaddedlQOgramatomsz”
(2.43kg)of~~esi~ turnings
andenough
ethertocover themagnesium.
A smallamount
ofmet~lbromi~e
wasadded.If’reactiond.id
notetmt
im&ediately,
a little
methyliodide
(orpreviously,
prepsred
Gri~ard
reagent)
wasadded.kfte~reaction
hadbeeninitiated
thestirrer
was
started,
andmsthyl
~rotide
froma cylinder
supported
froma steelyard
wasallowed
toflowthrough
a coilofcopper
tubing
surrounded
by a dryIcebathwhereitcondensed
~d dropped
intz)
thereaction
mixture.F1OW
wasregulated
by a smallneedle
valve.Afterthereaction
waswell
started;
pooling
Wter wasadmitted
to thejacket,
andanexcess
of
methyl
bromide
wasaddedasfastas itwouldreact.During
theaddition
Of~tiyllro~d~,etherwasaddedin2-llter
portions
untilthetoti
etheraddedwas20 liters
(200IL&pergramatomofmagnesium).
The
=~t ofmethyl
bromide
addedwasdete~~ by the10SSofweight
of
thecylinder,
anditwasfoundthatpractically
nom&hylbromide
was
lostduri~theoperaticm.
Afteraddition
ofmethyl
bromide
was
I
.
6
NACATNNO,124’7
.
complete,
thereaction
mixture
waswarmed
for2 to3 hours.Ifthemixturecontained
slud~e
orpieces
of unreacted
_eeium, itwasallowed
to
standuntilthesludge
hadsettled,
andthentheclear-solution
wassiphoned
off. Thesludge
wasnextwashed
withdryetherandallowed
to
settle,
thenthesiphoning
procedure
wasrepeated.
Iftheamoung
of
sludge
w’as
small,
thislastoperation
wascarrted
outadvantageously
in
a separator
funnel,
inwhichthesludge
couldbedrawnoffeasily.
Theyields
varied
from88to95percent,
basedonmagnesium,
asdetcmmined
by titration.
Similar
yields
wererealized
whenethylmagnesium
chloride
wasprepsred,
butinthiscaseslower
addition
ofhalide
was
necessary
inordertoavoidtheformation
ofappreciable
amounts
of
sludge.
xsoropylm~esivm
Magnesium
turnings
(1.5kg,63 gram
——. chl.oride.——
atomsand5
liters
ofe-tuer
woreplaced
inthereactor,
endreaction
?+
wasstarted
by ‘&eaddition
ofa smallmountofisopropyl
chloride,
Afterthereaction
wasinitiated,
thestirrer
wasstarted
and1 liter
of isopropyl
chloride
III
2 liters
ofetherwasaddedslowly.Afterthis
firstcharge ofchloride
wascomplete,
~ liters
ofetherendtherestof
themagnesium
(1.5kg,63@am atoms)
wereadded,
audcooling
waterwas
circulated
through
thejaoket.Thentherestofthechloride
andether
wasaddedintheratioof1 llterofchloride
for2.0to !2.5
liters
of
other,
untila totalof125molesofchloride
and37.5liters
ofether
hadbeenused.Thisaddition
wascarried
outasfastaspossible,
still
keeping
thereflux
fromthecondenser
dropwise
endnotina steady
stream.
About35hourswererequired
fora 125-mlerun, Afterremoval
ofthe
olew solution
fromthesludge,
theyield,
calculated
fromtitration
data,
amounted
to90 to93percent
ofthetheoretical
quantity-.
t-Butylmagnesium
chloride.Thispreparation
wascsrried
outin essentially
thesamemanner
asdescribed
forthepreparation
ofisopropylmgnesiumchloride,
except
thattheaddition
ofchloride
wasnecessarily
slower
in order toretard
formation
ofhexamethylethaiie,
isotmtylene,
and
diisolmtylene.
A 70-mole
runrequired
approximately
35hours.Thelatterhalfofthechloride
addedwasmoredilute
thanthefirsthalf(reference
10)’
endtherateofaddition
wasslowed
upprogressively
asthereaction
neared
completion.
TheJacket
of thereactor
wasnotcooled
so “
muchinthispreparation
aswiththelesshighly
branched
halides.
The
tendency
oft-butyl
chloride
toformsludge
ismuchgreater
thanthatof
thesimpler
halides,
although
menyrumsweremadeinwhichpractically
no
sludge
wasobserved.
Theyields
varied
from80to92percent.
i
n-Pentane
Onegallon
ofcommercial
n-pentane
wasfractionated
inStill1.
Fzymthisdistillation
therewasobtained
1792ml.ofmaterial,
the ,
I
-
.
.
NACATNNO.124?
7
1.3574
to1.3575.
A
fraotions
ofwhichhada refractive
indexnD20 of’
Phyefcsl
eonstents:
“best’’,
samplewasselected
fordeterminatzlon
of
..
2-Methylbutane
(hopentane)
Onegallon
ofcommercial
isopentene
wasfraotlonited
inStill1.
Therewasobtained
2200ml ofmaterial,
nD20= 1.3535
to1.3536,
whtch
wascollectsd
whiletheheadtemperature
of thecolumn
was27.87°
to
27.88°
C. Latera totslof47liters
ofhigh-purit
ymaterfal
waspreparedfromtheseine
source
b~ fractionation
inStill11.
~
.
2,2-Dimethylpropane
(Neopentane)
.
h 1933,
Whitmore
endFh&ing(reference
11)described
tieprepara“’tion
ofneopentsne
by reaotion
between
methylmagnesium
chbrideand
t-butyl
chloride
intoluene at 4~0”to 500C.Yields
of42 to50percent
werereported.
‘.@ thepresent
work,a methodisdescribed
whereb~
somewhatlarger
$ields
ofpuzzer
produot
wereobtained.
,.
In thiswork,neopentane
wasprepared
by aotion
ofdiqwthyl
zincon
t-butyl
chloride
int@ueneat5° C. Theadvantage
ofcausing
reaction
atthistemperature,
r@herthtitheoftenusedhigher
temper+re(35°
to50°C),for,re~tfons
o?@s typehasbeenpreviously
demonstratefl.
(Seereference
2.) D@thyl’zincwas.prepsred
inthemayner
described
inreference
2;however,
certain
improvements
inthetechnique
ofhsndltngthi~me,terial
have
been
made.
.. .. ,.
..- A 5-liter,’
si&le-neck
flask,
which&s usedford~ethyl-zinc
prep,aratlon,
“was
placedin:ano’il
lathendfittedwith
a @O-millimeter
rqflux
condenser
.Tothetopofthecondenser
wasa$taohed
a lmidge
of
10-millimeter
glasstubing
whichled.to
thetipofa similar
reflux
condenser
attaohed
toa 5-liter,
three-neck
flask.Thislatter
flask,
into
whichdimekhyl
zincwasdistilled,
wassituated
ina cold-water
b@h and
~s provided
witha separator
funnel(500?d.)
anda stirrer.
A side
,m on thebridge
prdvided
‘for
the’introduction
ofinert gas (carbon
..
dioxide).
.
Thezinc-copper
couple
fromg60gramsofzincdustand120grsmsof
cuprio.oxide
wasplacedin”the
one-neck
flask,
and1100~~ (7.75
moles)ofmethyliddide
added.Thetemperature
offile
otlbathwas
raised.
to about45°C,anda slowstreem
ofcsrbon
dioxide
waspassed
in
tiesidearmofthebridge
ad out-through theseparator
funnel
intoa
venting-tube
madeof2@tUMme%& glasstubfng.Reaothnbetween
methyl iodide end.the
couple
wascomplete
after10hours,
provtded
that
thecouple
wassufficiently”
ziotive.
Whenreaction
hadc&seal,,
as shown
by thecessation
ofreflux,
thecarbon-dioxide
flowwasstqp6d,500ti
.
8
liACA
TNNo.1247
of tuluene
wasaddedtothethree-neck
flask,
andthetopoftheseparator funne~
wasfitted
witha teetube.Thereflux
condenser
ontheoneneckflaskwasheated
withsteam,
andthetemperature
of theoilbath
wasgradually
raised
overa period
of2 hourstoaboutl&1°C. This
caused
themethylztnc
iodide
intheflasktodecompose
intodimethyl
zinc
‘andzinciodide.Thedimethyl
zincdistilled
across
thebridge
intothe
toluene
inthethree-neck
flask.Carbon
dioxide
wasallowed
toflow
through
thetopof theteewhiledistillation
ofdhethylc
zincwasin
progress.
Afterdistillation
ofdimethyl
zincwascomplete,
thesingle-neck
flaskwasallowed
tocoolandthesidearmonthebridge
connected
toa
gas-purification
traincomprising,
intheordernamed,
a washbottle
ccmtaintng
water,
twobottles
containing
@-percent
sulfuric
acid,anempty
bottle,
a bottle
containing
40-percent
potassium
hydroxide,
a calciumchloride
drying
tower,
and a 100- by 1.5-centimeter
tubefjlled
with
sillca
gel. Afterpassing
through.this
train,
thegaswasledintoa
condensing
system
comprising
a copper
coilcondenser
at -10°C, a receiver
at -78°c,andfinally
a trap at -78°C.
Theflaskcontaining
toluene
anddimetlqrl
zfnc.
wascooled
@ 5°C,
and525ml (about
4.8moles)
oft-butyl
chloride
in75oml ofdrytoluene
wasaddedduring
5 hours.During
theaddition
ofchloride,
methene
was
evolved
by thereaction.
Aftertheaddition
ofchloride
wascomol’ete.
thereaction
mixture
wasallowed
‘tostan.fi
15hcum. T&m the%a~hternperature
wasraised
gradually
to50°C,during
whichthe moregaswas
givenoffwhichwasnotaffected
by thesulfuric
acidandwhichdfdnot
condense
Inthe-780’
C tra~.
.,
.
Waterwasthenadded.
tothereaction
mixture,through
theseparator
funnd. 1%wasnecessary
toexercise
considerable
careinthisoperation,since.a.violent
evolution
ofneopentane
tookplaceatthispoint,
This,
gaswascondensed
inthe-10°C condenser,
andsolidified
inthe
receiver.
Therewasnodiscoloration
ofthesulfuric
acid.After,
about
200ml ofwaterhadbeenaddedandtheevolution
ofgashadsubsided,
theapparatus
wassweptoutwithnitrogen.
The.
resulting
neopentane
wastransferred
toa glasstubeendsealed.
Theyieldamounted
to164.5grams,
whichis59percent
ofthattheoreticallypossible,
basedononehalftheamount
ofmethyliodide
used[2
molesofmethyliodide
gfve1 moleofdimethyl
zinc).Theresidue
from
thedimethyl
zinc,whichcontained
zinciodtdej
wasusedtoprepare
additional
methyl
Iodide
by themethod
described
Inreference
12.
In assembling
theapparatus,
corks,
rather
thanrubber
stoppers,
wereusedexclusively
andafterassembly
theywerecoated
withshellac.
In onepreliminary
experiment,
inwhichrubber
stoppers
wereused,the
product
wascontaminated
witha material
whichhadtheodorofmethyl
.
.
.
l?ACA
TNNo.1247 c “
9
mercaptan.
Wherery%ber
tubing
wasnecessary
inmakingconnections
to
thesidearmon the%ridge,’
ti~g-t
was?n@esothata minimum
of
rubber
surface
wasexposed.
.
.
$.
,:
,.
#
,.
,.
Theyieldreported
on thefirstrunwasverifted
laterwhennine “ ‘
addit.io&l
runsof,thfs
preparation
were”mejinwhichan average
yieM
~ twoof ~~se -s, tiecouple
wasless
of65.6,
pe~entwas,
obtained.
active
”timi
intheotherpreparations,
andtheproduct
wascontaminated
withmethyliodide.Thepresenceof
methyliodide
wascharacterized
by
a pinkcolorwhichdeveloped
intheproduct
aftera fewdays.we yield“
obtained
fn.one
runwaslowbecause
a stoppage
dev@ped inthepurfficatiohtr~n,andsomematerial
waslostthrough
a“looseneil
connection..
,,
,: Freezin&point”
heasurement8
madeon thematerial
fromthreeexperi-16.61°,
and-16.600
C, respectively.
m@ts gave“the
yalues-16.61°,
Thesedsj%maybe compare~.with
thevalue-16,63ti.10°
C,calcizlated
f@ thefreezing
pointof100-percent-pure
neopentsme
byAstonand
Messetil$:
‘(Speyeference
13.),
,
.
.
,...
..
..
3-M6thylpentane
- “
,,
,
From75.2 molesofethytiesiumchloride
and37molesofethyl
acetate
therewasprepared
3660ml af 3-methyl-3-pentanol,
whichwas
purified
by
distillation
inColurm7
(b.p.
120°
ta124°
C
at760m).
,.
Deh@ration
of thiscerbino~
by refluxing
with0.2-percent
~~fiaphthalene
[email protected]:yfelded
a mixti”e
of,alkenes
whichboiled
65°to71°C at
758mil~imeters.
Thisdehydration
wotidbe expected
toyieldchiefly
3methyl-2-pentsne,
witha sm@le”r
amou@ of2-ethyl-l-butene.
No attempt
,yas’niade
to separate
thetwo’
olefins.since
bothcompounds
yieldthesame
aZken~
when.
lqydrogenated..
l@rogenatiog
of thismixttigavecrude
alk@ewhichwas,
filtered”
through
silica’
gelenddistilled
&.Column
k
to.
yield19@ ml of’material
whichboll@”
64.5°to65.50C (uncorrected).
Redistillation
inColumnlgave.
l@O ml ofhydrocarbon
madeup offractionsremoved
whiletheheadtemperature
was63.319°
to63.3220’c
(761.1
~~$) sndforwhich.nD20=.1.3764
to1.3765.
,..
.
.“..
..
.
.
“2y2-Dim&hylbutane
(Neohexane)
“’
.
Thesynthesis
ofneohe%ane
hasbeenreportg~
previ~usly
h referenc~4. “Since
thencommercial
neohexene
has%ecome
available.
Several
charges
of thismaterial
werefractionated
inStills
1 end2;.Fromeach
run,onlythelatter
half-of
thedistillate
consisted
ofmaterial
having
thepropertiesof
neohex~e.Theforerun
contained
.an.
&upurity
of
highefi
refractive
Indexand”
slightly
lowerboiling-point.
No extensive
investigation
wasmadeofthisforerun,
butthemostllkely
,Impurlty
was
cyclopentene.
Thisfactwaa”
latersubstantiatedby
thenmnu$acturer.
‘
TNNO.12h7
I?ACA
10
A totalof.38liters
of’purified
neohexane
wasprepared
by fraotfonation
of75liters”
ofthecommercial
crudemixture
inStill11.
2-Methylpente.ne
About77lifers
ofcommercial
crudeneohexane
wasfractiaated.
to
prepare
38liters
of2,2-dimethyllnztane.
Fro?n
thedistillations
of this
material,
therewasobtained
3320ml ofresidue,
which.was
fractionated
inco1unr12
into46fractions:
I “.
II
Boiling
rsnge
Fraction(Headayrature) VolumeRefractive
‘
index,nD20
(~) .
2 to 22
23 tO44
45ix)
46
n
58.8b 60..2
60.2~ok60
.4
●
1500
lyoo
140
I
1.3748
to1.3717
1.3715
to1.3717
1.3717
to1.37kk
Fractions
35to37werecombined,
filtered
through
silica
gel.,
endused
intliedeterminations
ofphysical
properties
of2-methylpentane.
ofButene
Alkylate
Investigation
Seventy’five
liters
ofButene
Al@latewasfractionated
inStill10.
Theheadtemperature
wasmeasured
bymeansofa recording
thermometer
of
thegas-expsnsion
type.Thereflux
ratiowasmaintained’at
about100to
1. Fractions
ofnottirethan3.87”liters
eachwere collected,
thevolume‘ofthefraction
depending
on thetime-temperature
curvt.After
measurement
of refractive
indicee,.like
fractions
fromdifferent
runs
werecombined
andrefractionated
inSt12.1
2. Fractionation
of theloWest”boilirqj
portion.from
Still10wascarried
outfirst,
‘then
thesecond
lowest
toiling
wasaddedto,the
residue
andfractionated,
endsoon.
Therefractive
indexofeachfraotfon
wasmeasured,
anda plotofrefractiveindexversus
fraction
numiber
wasmade.Semples
represented
by sfngleplateaus
werecombined
and&edistilled
inC!dlumn
1 or2. Several
hydrocarbons
wereisolated
thereby,
andarelisted
intable3.
.
The2,3-dimethylbutane
fromButene
Alkylate
!3-Dimethylbutane.(2~132ml)
was’
addedto1255ml of2,3-dimethylbutane
ofapproximately
theseine
purity
fromanother
source.Thecombined
material
waswashed
tithsulfuric
acid,water,
sodium-carbonate
solution,
andagainwtth
water.
Afteritwasdr~edandfiltered
through
silioa
gel;itwasfractionated
inStIll2, andgave23oOml ofmaterial
forwhich
“
n&o = l~3T48to1.3749.
.
11
NACATNNO.1247
2,4-Dimetiy
Ipentsne.The2,k-dtmethylpentene
from33utene
Al@late
(2610ml)wasrefractionated
inStill2. Thefractions
forwhich
nI)20
= 1.3816
to1.3817
werereserved
asthebestportion,
andamounted
to985ml.
s-,
Q,3-Dimethylpentane
fmm Isooctane
-~
,,
Seventy-five
liters
of isooctane
(acommercial
mixture
ofbranched.
chainhydrocarbons)
wasfractionated
inStill10 inthemanner
described
inthepreceding
section.
Fractions
whichdistilled
between
85°and
to1.3914)
werecom~$ned.
(28,051
ml)andrefraction950c (q)20= 1.3886
atedinStill11. Fromthisdistillation
therewasobtained
7165ml of
hydrocarbon
whichboiled8$)
.7°to~ .OOC (nDao= 1~3918
to1.3921)
which
waarefractionated
in%111.2. Thepurified
2,3-dimethylpentsne
thereby
obtained
emounted
to47$0ml titerfiltration
through
silica
gel. The
refractive
indexrangenD20,o’f
various
fractions
was1.3919z
to1.39196.
.. .
. ..‘,.’
.
.
2,2,3-Trimethyllxr&ne
(Triptane)”.
Thesynthesis
of triptqne
involve’d
twore~tione::(a)%hepreparationof2-chloro2,3-dimethylbutane,
tid(b)thereaction
ofthischloride@thdimetll~l
zinc. .
.
,“,.
.
.
.,
,..,
.
,...
2-Chloro2,3-dimethylbutane.““
we .a&p&rat~”used
wassimilar
to
that.
descri~ed
fn.?eferencb
2 for.
the”
prqjaka$ion
ofk-ctioro2,2,htrimethylpentme.
Itwasmodified.so
that~bberstoppers
were%plaee&
withground-glass
connections.
Thealkene
wed wasatixtureof2,3and2,3-dinetl@-2-bute~e.
whichwasformed
by dehydra. . dimethyl-1-buteqe
t$onofpinac.@yl’
.elgoh61
(3,3~~imethyl-2~b&nol)*
[Seerefer-&nce
s.)
Theoriginal.slkepe
mixture
con@ined@small.
amotit.
of 3,3-dim6thyl-l.
.
,butene,
in,addition
to,*6pexenes.,
tkf~hydrocarbon
WS removed
for
,,
.. In+t
“uge:j
in.enbthSr,
Bjnthesfs..
.
...... ..,,
.,.
.
h 2 hours,
15CX3
ml ofthealkene
mixture,
alongwithexcess drogeg<chloyide,
waspaqsed
t
@ou@
*O
chambers
kept
@ abath.at-78 C.
..
.Oc,c.asion&llj
Ltwasri&essa&y’to
remote”.the,baths
in.order
toallowthe
solidified
chlor~de
to”melt.
d,pass onthoughtheapparatus.
‘T~Gproduct.
w
as:waqhed
with
water,
w
iti,~.-percent
sodium-bicarbonate
,solutton,
. .’
againw$M wa~erj
~d,d&ied’with
twosuccessive
portione
offreshanhy‘tious
“potadsiti
ce&bonate.
DistQlation.of
theresulting
material
in
Column3 gave,aftera forerim
ofunchanged
alkene675gr&nsof2-chloro2,S-dimethylbutane
(b.p.@o to70°C at 190mmHg~.
,
Synthesis
of triptene.Withapparatus
likethatusedinthepreparation
ofneopentane,
dimetbyl
zincwasprepared
fromlKKlgrams(7.75
,
12
NACATNNo.~2k’7
moles)
ofmetl@iodide
anddistilled
intoa ~-liter
flaskcontaining
XO ti oftoluene.
Theflaskwassurrounded
by Ice,andthechlorfde
600grams,
5 moles)
in1000ml oftoluene
wasaddedduring
4 hours.The
mixture
wasallowed
to standfor16hours,
endwasthentreated
wtth
waterendwithdilute
hydrochloric
acid.Thereactton
product,
2060@,
wasfractionated
inColumn
5 togivea smallmountofmethyl
todide,
someoleftiic
material,
presumably
dimethylbutenes
formed
by dehydrochlorinatlon
oftheallqrl’chloride,
and297ml ofcrudetriptsme
boiling
at78°to83°C,with nD20= 1.3g32.TWOpassages
through
silica
gel
gavea product
ofthefollowing
properties,
compared
withthoseofhigh—
purity
material:
.
Ei@-purfty
Property
Present
material
.preparwtion
(reference
5)
Refractive
index,nD20
1.3897
1.3947
Density,d~=o
0.6896
0.69000
Freezing
point,‘C
-26.1
-25.059
Boiling
point,%
81.0 (Cottrell) 80.879
Theyieldofcrudetrlptsme
smounted
to51 percent
of thetheoretical.
In subsequent
experiments
itwasfoundthata largeexcess
of alkyl
chloride
offered
no advantage,
a 2- to3-percent
excess
givhga comparableyield.Theexcess
chloride
wasfoundtobe easily
removedby
boillng
thecrudemixture
witha ~-percent
solutlon
ofpotasdum
hydroxide
f.n
alcohol
.
.
Ineachof several
experiments,
theyieldamounted
to~ to52percentofcrudetriptane.
Thetimeellowed
foraddition’of
chloride
was
varied
frmn3 to8 hours,
endthetemperateofreactton
from0° to30°C
tithout
~ appreciable
change
h yield.fioneexpe~nt, In~~~chi&ooctane
(2,2,4-trimethylpentane)
wasusedasa solvent,
theyieldwas48
percent.
Undertheconditions
ofhydrochlorlnation,
2,3-dimethyl-l-%utene
was
foundtoeddhydrogen
chloride
moreea~fly
then2,3-dimetl&l-2-butene.
Theunreacted
al.kene
whichwasrecovered
whena mixture
ofthetwowas
liyi&ochlorinated
wasfoundtobe practically
pure2,3-dimethyl-2-butene.
Veq cltght
decomposition
of2-chloro2,3-dimethylbutane
takesplace
whenitisboiled
atatmospheric
pressure.
.
13.
I!?ACA
~NO. 12k7-
.
.
p+iethyl-s-~hylpentane
Thfsoctane
wasprepared
byhydrogenation
oftheolefins’w~ich
re-’
suited
fromthedehyiiration
of2-methyl-~-ethyl-3-pentanol.
Thecarldnol
wasprepared
by tlze
action
ofethylmagnesium
chloride
on isobutyl
isolmtyrate.
To a solution
molesofethylma~esium
chloride
in20
liters
ofether was added6.335
grams(.44
moles)
of isobutyl
isobutyrate
in10.5liters
ofether.Theproduct
wasdriedwithsodium
carbonate
end
distilleti
inColumn
6, Therewasobtaiaea
56@ ml hf2-methyl-3-ethyl3-pentanol
(55°to57°C at48mmHg). Demdratlon
waseffected
by refluxing thecwrbinol
with0.2 percent
by weight
of&naphthalene
sulfonlc
acid,whichgave5235ml ofcrudea2kene
mixture,
bollin$
at114°to
llgoc. Sincedehydration
of2-methyl-3-ethyl-3-pentenol
should
yield
twoalkenes:
nmely,2-methyl-3-ethyl-2-pentene
(b.p.about1.170
C) end
k-methyl-3-ethyl-2-pentene
~b.p.about1160~),bothofwhichyieldthe
sameelksne
onhydrogenation,
no attempt
wasma?ie
to separate
thetwo=
Theelkene
mixture
wasarid withcalcium
chloriae
anddistillea
frcmsoaium.A portion
ofthedistillate
(4721
ml)washydrogenated
tothe
- alkane,
which,
aftertwodistillations
fromsodium
enafiltration
through
silica
gel,smounted”to
hQ50ml, Thecompound
%~sfinally
fractionated
InStill1,.yielding 3300.ml ofmateria.1,
,which
hada refractive
inaex
constant
within
0,0001.
containing
.
.
90
2j3,3-Trimethylpentane
,
.Thishyarocarbo
nresulted
fromthereaction
between
isopzmpylmagnesiumchloriao
ana.t-anyl
chloride.
,.
.
.
To 90.5molesof iso&opyln&jnesium
c~oridein30.9liters
of ether
solution
wassdriea
g600grams(~ moles)oft-sin@
chloride
during
a
period
ofabout12houre.Stirring
wascontinued
untilseparation
ofsolidmaterial
prewntea.adequate
mixing.Thenthermotionmixture
was
allowed
to etsnd2 to 3 weeksat15°to20°C untilnomoreGrignard
reagentwaspresent.
Theproduct
wastreated
withice&d diltite
hydrochloric
acidendthereeultfng
orgsnic
material
distilled
inColumn
3.
Aftera forerun
of ether,,
isoamylene,
andt-amyl
chloride,
therewasobtalneti
4400ml ofcruae2,3,3-trimethylpentane
(31-percent
yield~
which
,.boilea
112°to115°C. Whenrefractionated
inColumn
1, thecrudeparaff$ngave3600tioffractions
forwhich~20 = 1.4074
to1.4075.
:Retlistillation
ofsccumulatea
foreruns
fromseveral
batohes
gaveenadditional
quantity
ofpuromateriel.
Fromseveral
run+a.total
of 39liters
of
pure2,3,~-trimethylpentsne
waaprepared.
Earlyexperiments
onthispreparation
weremadeinwhicha largeexoessofGriguard
reagent
wasassymwl
b he desirable,.lut
itwasfound
1
??ACA
TNNo,124~
,
thattheyieldofproduct
wasactually
decreased
by emexce
SBofGrfgnard
reagent.
Forexample,
h oneruninwhich72molesofisopropylmagnesium
t-emyl.
chloride,
theyield
chloride
wasallowed
toreactwith57moles”of
of2,3,
3-trfmethylpentane
WaEI
only21percent,
2,2,3-Wimethylpentsne
qnd2,3,&Trimethylpentsne
By fractionation
of several
cutsofalkylate
mixtures,
38.6liters
of2,2,3-trimethylpentene
and37.9liters
of2,3,4-trimethylpentene
were
prepare~.
Thesource
materials
werealkylates,
‘hydro-codimers,
andtsooctanes
whiohhadacctmmlated
atthelaboratory.
Thesematerials
tot~ed
approximately
85gallons.
Someofthemwerepartially
fractionated,
some
were‘fas
received.”
Theunresolved
alkylates
andresidues
wereroughly
fractionated
in
Stills
30and11 intoconcentrates
richin2,2,3-trimethylpentene
and
2,3,4-trimethylpentane.
Theseconcentrates
wereredistilled
inColumn
11.
Mostofthematerial
wasobtained
by thesedlQtillations.
Foreruns,
intermediates,
endafterruns
wereagainfractionated
inStills
1 end2.
Froma totalof47distillations
therewereobtained
38,610
ml (at25°C)
of2,2j3-trimethylpentane
(nD20= 1.4026
to1.bo29)
@ 37,955
ml (at
25~(?)of2,3,k-trimethylpentane
(nD20= 1.4041
to1.4045).
Physical
“constants
of thetwocompounds
weremeasured,
endagreed
wellwiththose
measured
onthepurematerials,
asreported
inreferences
4 and5.
.
.
2,2,~-Trimethylhexane
Thepresence
of2,2,5-trimethylhexene
in’
isooctane
residue
wasreported
byBrooks,
Cleaton, andCarter
in1937.(Seereference
1.) By
dlstillatton
ofanadditional
76liters
of thismaterial
inStill10,a
concentrate
rfchinthisnonane
wasobtained.
TMs concentrate
(4525
ml.,
b.p.123°tO225°C,~20 = 1.399toIJKIO)
wasrefractlonated
inStill
1. Therewasobtained
2005ml.of2,2,5:trim@hy2hexane
with‘arefraotive$ndexrangeof1.3995
to1.3996.
2,3,5-Trimethylhexane
,
“’Thtsnonane
wasprepared
byhydrogenating
2,3,5-trimethyl-2-hexenaJ
whichresulted
frm thereaction
of isopropylma~esium
chloride
on1chloro-2,3-dimethyl-2-butene.
Therewasd’soformed
a ?mallsmount
of
2,3,3,&tetramethyl-1-pentene
inthisreaction. ,
2,3-Dimethyl-1,3
-Imtsdiene.Pinacol
hydrate,
prepared
bythemethod
ofreference
5,wasdehydrated
toanhydrouepihacol
bydidtfllation
in
columns
4 to7. Theseaistflldtions
werecarried
outatatmospheric
,
.
:,
,
●“”” tiAcAIWNo.
.
:.
,,
lz?h’7
15
.
,..“
Pr&@e’”’
ti~il’
theh?~’~perEdmre;reqohed’
122°,
~;,“’wli~~,
thepressure
was
.
.
~
redtied
to
@
tiIIititers”
ofmercury.
At:
this
pressure
the{
a
nlxydrous
. .
.:-. ” p,tiaiol’
at‘.ll1°
.: ..“.- .’ .:-:I‘-...:. ..d“stlllbd
..
:’. to114°fl;.
..
...... ..,.,:..:..
.,.,..
....
,.
‘.’Iliordert~.d6tdi-mine
thebptizm,im
conditions
forconversion
ofthe
made.
@yc”ol
t
o‘2,
3-dimethyl-1,
3-lnMadiene,
a
series
o
fr
test
rims
were
:.
rssults
are:
show inthefollowing
table:..: .“
;..::.“~hb
:,.
;,,
... ........... .‘.”.
..
,.!,
.,”.
,.,
.. .
.,
’...
.
.
.
. . .,;
,, ......
,.,
,,’.
., .‘DEHYDRATION
. .....
mADICNE-1,3
OFPII?ACC)L
TO 2,3-DIMETEU9
.
. . .
,. ...:
.’...”. ‘!.
,. .,.
. . .
:. -..
1’.
.
“.’,
~:AltD’.l?INACOLONE
(3,3-DIMIMIYL-27BUMI?ONE)
.
. .,
. ..
-1””
.1””..””Catslyet..
Plnacol
...
Yield(percent)
of . .
Dimethyl,.
... ‘“.
Riii.. taken “...’.”.”’.
butadienePi’ticolone
,.
:,...
~.
,.
?(m)
,
:’.
.’
,
. ,.
,,.,“:;
.
. .
“,”. ,,.. 1“’
45 .:,,“;
.ig
“,‘:
h53 ‘ 1“.5
grams48-percent
hydroI
..
:....-. ;:
.. /
,.,.
.lwomic
acid
., >
.’.”’
2. “ .500” 5.0grenmp-naphthal’ene
eul- 36 .’: 34
/.<,...,:,
..,.
... .~...
“f.onic
.aoid
,,. ..’
..
. ., ,.. -.”.’.
5.0.
gramsp-tdu.ene
Lsulfonic “’&. ,: ., -,.31
.,,
,... .,.
,.......,.....II. .,,. ,.
“’”
I
‘mid:
‘: ~L
i.,
.‘r3”’’l”5m
I
-
18
15
‘.
:
:.
.
,’
.’.
,
,,
... .’.
..
.
..
... ,
.,
. ‘.
thepin~olwas,ref’l~e~
with,
the,q,a@l&st
inColIn these
&perfments,
.;:,.unms5.
~or7. Theproduct
of eachrunwaswashed.
drie&an&.
distilled
in
.ColuL&
6
~m
analyele.
:Fromtheresults.
0+,
,
the&
exper@nts,
itwas
..
J. “concluded
that.48-@ercent
[email protected]
-.aoi~
-was
:.the.
%e.st
@talystofthose
:. tried
for thts’
dehydration.
:By deh@rating
.,sever~
Mtqheqofpinaool
.-~(.2,5
to.,3.0
kg~erbatch),17.4,l\ter@
of.2,3?,dimetjl@-lr3-tn@adiene
was .
prepared
whichboiled
68.5°to‘j’l..5,0
Cla$758.
mi.1.limgters..,.
~..
...
,-.
...’
4. ,.;5007iOgraMsani>tie
hydro.lmomide:“...
..
I
I
L .,
.,
..’,
t.
.,.7,.
,.,
..,-/.
.
:.
.,
. . ..,-&
Chloro-2,3;dtiethyl-2-bu%ene
.-Thqaddition
o?hydrogen
chlorlde
.,...to:2,
~*dimthylFl,3-butdtene,
ms dccompltshed~in
theapparatus
described
,,. in”reference
.2,.Thereaotfon
chamberswere
keptat.-30°C, anddryhydrogen
chloride
andalkadiene
addedsimultaneoud~, The dailyoutput
of
theapparatus
was1.0to1.5llters
ofchloride.
Theproduct
wasfreed
ofdissolved
hydrogen
chloride
by aeration
withcarbon
diexide
endstored
oversodium
carbonate.
Distillation
analysis
showed
thattherea.otion
waspraotical~
quantitative.
Theproduot
used forfvrther
s~thesis
hile~at32° c at45millimeters
ofmercury.
\
,1
16
.
NACATNNO.1247
.
thyl-2-hexene,To anethersolution
2,3.?H?rime
of62~ld~ ofISO-’
propyhagnesium
chloride
wasadded7,32kilograms
of l-chloro-2,3-dimethyl2-butene.
Thereaction
mixture
became
veryviscous.
snditwasnecessam
totid~re etherat intervals.
Thereact~mwaaw&cedup afterb dayssndtheorganic
mate@al.
wasdried,
theether removed,
andthecruderesiduedistilled
through
Colwm3 (b.p,70°to71.0
C at$Xl
m,
nD20u 1,4299),
Although
therewasno appreciable
forerun,
a largeamount
ofhigh-boiltng
material
(175°to2000C)waspresent.
Thismaterial
was
notidentified,
butispresumed
tobepolymers
(climers
andtrimers)
of
thealkadiene
formed
undertheInfluence of theGr@nardreagent.
Thecrude2,3,5-trimethyl-2-hexene
contained
a considerable
quantity
ofchloride,
.thegreater
partofwhichwasremoved
byboiling
withalcoholicpotassium
hydroxide~
Hydrogenation
ofthecrudealkene
gave2,3,~trimethylhexsne,
whichwasfiltered
through
siltca
gelanddistilled
in ,
6olumn3. I%n2500ml ofmaterial,
therewereobtained
900mlwhich ‘
boiled
131-.9°
C (nD20
= 1.4060
to1,4061)
andSOml’ofa hydrocarbon‘
whichboiled
lkli9°
C (~20 = 1~4218)
, Thelatter
wasUlentified
ad
2,3,3,4-tetramethylpentsne
by comparison
witha sample
prepared
inanother
manner.A residue
ofabout1 literwhichboiled
above1650C resulted
fromthisdlstlllatlon.
Thisresidue
wasprobably
formed
by tieaction
of potassium hydroxide
orhydrogenation catalyst
onthe’
unsaturated
halide
whichwaspresent
inthecrudeolefin.Obvfously,
mostof theGrignard
reagent
was.
dissipated
insidereactions
rather
thanbycoupll.ng
wil@the
chloride
Intheexpected
manner.Thistendency
couldpossibly
havebeen:
decreased
bycarrying
outthereaction
ina moredilute
Solution,“
Thispreparation
wasmadein1939atthesuggestion
of Dr. C. E.
BooniofOhioStateUniversity.
Thegoalwasthepreparation
of2,3,5+
trhnethylhexane
and2,3,3,h-tetramethylpentane.
Thereactfon
yielded
abouteighteen
partsof theformer
toonepartofthelatter.Thesetwo
hydrocarbons
probably
resulted
frcmtheaction
oftheGrQmrd reagent
on
twoZsomersof2,3-dimethylchlorobutene.
Thesetwoisomers
probably
were‘
l-chloro-2,3-dimethyl-2-butene,
fohmed
by1,4addition
ofhydrogen
chloridetothediolefin,
and3-chl.oro-2,
3-dWthyl-l-butene,
formed
by 1,2
addition.
Theformer
chlorlde
wouldbe expected
to react withisopropyl-s~~chl~ride togive2,3,5-trtmethyl-2-hexene,
andthelatter
chzoridetotogive2,3,3,4-tetr~thyl-l-pentene.
..
E.T.Clinehasmadea &udy ofthisreaction
(reference
24),in
whichhydrogen
bromide,
rather
thanhydrogen
chloride,
wasused,Ee obtained
a ratioofalkenes
of1,6partsof2,3,5-trimethyl-2-hexene
to1
Pat%of2,3,3,”4-tetrsxnethyl-,17pentene.
.
.
.
.
.
.
17
NACATN tiOi 12k’7
,.
2,2,4-Tr@ethyIhexsne
“In 1937,Brooks,
Cleaton,
endCarter
(reference
1) isolated
enunlmowmnonene
fromtheresidue
o%ta.ined
inthedistillation
of isooctane
(2,2,
4-trimethylpentane),
whichwastentatively
identified
as2,2,
ktrimethylhemme.
In ordertoextablish
theidentity
ofthishydrocarbon.
a sample
of2,2jk-trimethylhexene
wasprepared,
anda comparison
ofphysioal.
properties
made.
Diisoln@lene
wasoxidized
by sodium
bichromate,
asdescribed
in
reference
15byWhitmore,
Homeyer,
endTrent,
togivetrimethylacetic
acidandk,4-dimethyl-2-pentenone
(methylneopentyl
ketcne),Thgoxidationofdiisobutylen~
ismersISfilBcussed
tireftiy inlatersections.
.
TO 790molesof ethyxesium chlortde
in1400mlofethersolution
wasadded742grsms(6.5.
males)
.ofk,4-dfmethyl-2-pentanone
(b.p.12~L”
C
at760~@, nD20= 1.4038)
in~ ml ofdryether.Thereaction
mixture
wasallowed
to stendat~oomtemperature
for35hours,
refluxed
for6
hours,
endthenworked
up inthestand@ menner.Theorganic
material
waswashed,
dried,
enddistilled
inColumn
h. n. addition
toetherand
recovered
ketone,
409grams(2.9moles)of 3,5,5-trimethyl-3-hexanol
end
84grains
(0.6mole]of’nonenes
resulting
frcm-premature
dehydration
of
thecsrbhol were obtained.
Thepurified
csrbtiol
*S dehydratedby
heatingwith~-naphthelene
sulfonic
acid(1gram)togivea mixture
of slkenes
whichboiled
1270to13P C. Theyieldwas335gruns(91percent).
This
alkene
mixture
hasbeensnalyzed
byWhitmore
endCook(reference
16)who
foundby ozonolysia
thatitcontained
approximately
threepartsof 3,5,5trimethyl-2-hexene,
onepartof2-ethyl-k,4-dlmethyl-l-pentene,
anda
traceof’3,5,5-trimethyl-3-hexene.
Allthesecompounds
gfvethesame
alkane
whenhydrogenated,
sono attempt
wasmadetoseparate
them.
“Thealkenes
werehydrogenated,
andtheproduct
filtsr?d
thro@”
silica’gel
enddistilled
inCQlmn~.~Themiddle
.70percent
ofthqdistillata,
whichdistilled
ata constant
temperature,
wasretiistilled$in
thesame.colunm,
themiddle
25percent
ofthedistillate
fromthelatter
distillation
wasusedinthemeasurement
ofphysical
prope@es. The
properties
ofthesynthetio
material
aregiven in table2 andarecompared
inthefollowing
tablewiththeproperties
of,
2,2,k-tr~thylhexene,
which
was3.solated,by
thepresent
authors.
Theidentity
ofthetwoisproved
by dataonthefreezing
point.of
the50:50mixture.
.,,
. .
.
..
.
..
.
...,.
.
.
I
!
1
18
NACATNNo.1247
Property~
from
Synthetic
material. ZYaction
2,2;
4-trlmethylhexene
Asooctane
residue
(reference
1)
Boiling
potntat760mmHg,‘C
126.54
Chemgein
%oilfng
pofntwith
pre8sure,
OC/&nHg
00.0503
126,51
-..
Freezing
point,‘C
-123.h(rep) -
-129.53
Freezing
pointofmixture,‘C
-124.19
-124.19
Retractive
index,~20
%=
Donstty,
gin/ml,
d20
d.=s
1.4033
,.
1.40312
1.4010‘
---
o.n$
% .7153
---
O.71X8
..
%he published
density,
0.7048
(reference
1)ofthemateriai.
isolated
fromieooctane
residue
wasinerror.A recalculation
oftheoriginal
data
gave0.7153,
redetermination
gave0.7154.
.
.
2,2-DhMAhyl-3
-Ethylpentene
Thesynthesis
of’
2,2-dhethyl-3-ethylpentane
wascarried
outinthe
following
steps:(a)Reaction
oft-butykgnesium
chlorlde
withcarbon
dioxide
togivetheGrignard
complex
oftrimethylacetic
acid,(b)reactionof thiscomplex
withethyl.magnesium
chlorlde
toproduce
2,2-dimethyl3-ethyl-3
-pentanol,
(c)dehydration
of thecarblnol
to4,4-dh@hyl-3‘ethyl-2-pentiene,
and(d]hydrogenation
oftheolefin
to2,2-dimet~l-3etliylpehtane.
“
,..
To 50.2 moles of~-butylma~esium
chloride
in1.8liters
ofether,
cooled
to5°C,was~dded3 kilograms
of solidcarbon
dioxide
insmall
pieces
whilethe”
reaction
mixture
wasbeingstirred.
Stirring
wascontinued
whilethemi’xture
cametoroomtemperature
andwhileitwasheated
b reflux
for2 hours.Itwasthencooled
and104molesofethylmagnesiumchloride
in20liters
ofetherwasaddedslowly.Afteraddition
was
.
complete,
themixture
wasstirred.
for6 hoursandallowed
to standat
roomtemperature
for2 days.Theproduct
wasdistilled
Incolumn
6.
Fromthisdistillation
wasobtained
3485grams(48.2percent yield)
of
.c=binol(b.p.go”ta95°c at~0m I&,.151°
to176°C’at756mm Hg,
nD20= 204417,d=o= 0.8’jl).
Thecarbinol
wasdehydrated
byheating
,
NACATNNO.1247
19
&th f3&phthal.ene
sulfonic
acidtogive3600ml ofalkene.Fractlona%ionof thecrudealkene
lnColumn
5 gave26&)ti of.purlfied
4,kMmethyl-3-ethyl-2-pentene.
,TheQlsene
washydrog&natedY
andtheproduct
filtered
through
silica
gel”end
distilled
inColumn
1. Fromthisdistillation
3.650
ti of.constent-tiiling
2,~-dimetiyl-3-e~lpentene
to1.41230)
wasobtained.
(W’”= 1.41225
2,&-D~ethyl3-Ethylpentane
.. r, Preparation,
of2,k-dlmethyl-3:ethylpentan&
wasacc~plished
byhy&o..”~.genation
ofthealkenes
which-resulted
fromthedehydration
of2,4~ ~’Wmethyl-3-ethyl-3-pentanol:
Thec~blnolresulted
fromtheaction
of
ethylmaguesium
chlorld~
on2f&dimethyl-~-pentanone
(~iisopropyl
ketone).
,.
.
To 76.2,.moles
ofethylmagnesium
chloride
wasadded75molesof2,4Mmethyl-s-pon>enone
during
2 days.Theproduct
wasrecovered
by add2tionof iceendammonium
chloride”to
the.
reaction
mixture,
endby subsequentdistillation
gave5650grams(52.3
percent)
of”2,@limethyl-3-ethyl3-pent~ol.A puresample
wasobtained
by redistillation
ofthebest
Portion
ofthecrude. >
Thecarbln#ol”was
de~rdrated
with~-naphthalene
stifonic
acidto give
~6110tiofcrudealkene
Mxtwe. A charge
of2 liters
ofthedehydration
product
wasfractionated
inColumn
5 formaI~sis.Theindividual.
olefins
wererecovered
intheratioof77percent
of thelower-boiling
2,4dimethyl-3-e~hyl-2-pentene
to23percent
ofthehfgher-lmiling
&methyl3-isopropyl-2-pentene.
A semple
ofeachoftheseieomers
wasredistilled
fordete~nat~on
ofphysical-constants.
Thevelues.,olN@nedwere:
2,k-Dimethyl-’ 4-Methyl-3. .
Property
3-ethyl-2tsopropyl-2.,
pentene
pentene
Boiling
pointat760mmHg, ‘C
.
.
“130.5
%fractive
hdgxj nD20 .
.,
1.4227
%25
1.4204
138.7 . “’
1.4349
Density,”
d20 L
0.7433
0.7584
25
..:
d.
0.7385
0.7550’”.
1.
Hydrogenation
of smplesofbothalkenes
yielded
thesamealkane.
The~ene mixture
(b.p.12& to140?C]washydrogenated
andtheresultingproduct
d+stilled.in
Columu
4. The.portiofi
boiling
136°tO.1390C
wasfii%~red
through
silica
gd
qxt refr&tionqted
in.Col&n
2. ‘~
,.
,,
,.
,.
... ,
,.
,..
20
NACATNNo.H?47
.
In1945thepreparation
wasrepeated
ona somewhat
larger
scale.
Forthispreparation,
2,4-dimethyl-3-pentanone
wasfractionated’in
Still
11. “Only
$hepurest-”fr&tions
obtained
(b.p.
124.60
to124.7°
C,
nD20= ~.40~5
to1.~017)
wereusedinthesubseQ~~ent
@thesis.-The.
carbinolwa~theproduct
of’reactfon.
ofthe,Grignard
Yea”gent
prepbred
from
260moles@ ethylehlorfde
with223”mo16s
of r6distill@d
ketone;.Tho
re”tiction
prcduct
wa~.distilled
inColw&21:imtll
theheadtem~erature
was130°C. ‘Asamp16
(1600grams)
oftheresidue’
was~.di.stilled
inColumn
h. Fromthisdistillation,there”were
obtained
1130grams,of,
purecar%inol(2,&dhethyl-3-ethyl-3-pentmol,
b.p.94.5°to95.0°C at 47mmHg)
andabout200gramsofIec+s
puremateriel.
A sample
fromthemiddle
cut
of thisdistlUatlon,was
&sened for~physica.1.’
constants
measurements,
‘Therestof thevndistflled
residue
wasdeh@rated,with.,Bi7naphththe,lm
sulfonic
acid,andthedehydration
products
were.washedj
drl,e~j<,~d.distilled
inColumr”ll..
Analysls
ofthedistillation
curve
shawe~thepr
esenceof77volume
percent
(13.4”
llters):of
lower-boilingg
let3ny’,@23
volume
’pebctint
(4.0liters)
ofthehigher-boiling
isomer.Inthisdistillation
a bestsample
fromeach.of
tlte,plateaus
wasrem?rvet
andredlstil.led
inColumn
17”for
phystcal*constants
measurements.
Eydrogena.tibn
of.the
olefins
wascarried
outaspreviously
descri%ed.
The pai%ffin
was
fractionated
inColumns
17,18,19,and20. Therews obtained
ll@O ml
ofpizre
hydrocarbon
forengine
tests.Physic~constants
ofmaterials
synthesized
inthislaterpreparation
aregiven in table 2.
‘ .
.
,,
., ...
.... . .
‘*2,2,3-3~Tetramethylpentane
{Tetrene)l ~ :, “.,
Thesynthesis
of2;2,3’,3-tetremethylpentane
(anew compound
designatedteln%he)
wasfirst&c&omplished
in1940(October-December).
.’The
re‘“-iiction
invblved
(a)preparation
of2,3,3-trimet~-l-2-butqnol
(t~pt~ol)
“from3,3-’d~~et@l-2-%ut/~none
(-pinacolone)
andmethylmagmsivmbromide,
“ (b)reaction
ofthiscarbinol
withhydrochloric
.Ewid
to,
give2:chloro“:2,3,3-trimetfi.ylbutane
.(triptyl
chlorfde),
end(c)reaction
ofthechloridewithethylaqgesiumc
hlotiide
togivethenonane
and2,3,3-trimethyl.l-butene
(triptene). .
..
..
..
FrOM82m?lesofpinacobne
and84meleeofrne~lmagnesivm
bromide,
56:5molesof’
2,3,3-trZmethyl-2-butanol
wasprepared.
~is carbhol was
dissolved
inether,
andthesolution
shaken
withseveral
portions
.ofcon;centrated
hydrochloric
acid,Samples
of theethersolutlon
wereremoved
periodically.
Thesublhiktlon
pointofthecrudechloride
fromthese
ssnlples
roseto131°to133°C. Recrystallized
chloride
wasfoundtosublimeat133°C. Thechlotide
solution
waswashed,
dried,
pndaddedto115
molesof ethylhagnesium
chloride.
Themixtmewasstirred
for~ hoursand
thensUowedtbstandfor.1
weeksatroomtemperature.
—.
~CompoWds
designated
@th asteri~s:~e,belie.vpd
-@’be:pew
compounds.
,,,. . ,,;t*;.
,,..
,,.
.
1,
,.
-, ;)!.
~,, !“:!”
‘, ..
..~.,
‘,
..:1,.
.,,
.,
.,
’,.,,
.
.,...”
,.’
. ,:,
. ,,
.
.,.
,’,
... . ., ;
. ..,. . .,... . .
,’
1
. .
.
.,.
.
,,
,
NACATNNo.1247
21
Afterthere&tlonmixture
wasworked
up,theorganic
material
was
distilled
incoIumn
6, andyiblded
?300mlof recovered
triptene
(trimethylbutene)
and1900ml of crude2j2j3,s-tetramethylpentane,
whichwas
contaminated
by a oonsiderablq
amount
of triptanol.
Thecarbinol
was
filtered
offas the.hy~atq,
E@ the’ftltra~e
drieii
andfiltered
through
Silica
gel.me volume
ofnonane
recovered
was1~0 ml,whichrepresents
a yi.el~
of9 peroent,
baseaon”the
original
pinacolone.
Distillation
of
thismaterial.
inColumn
4 gave10& ml ofhydrocarbon
whichwascollected
at 88.6°to 88.70c at159mill~etersof
mercury.A portion
ofthismaterial
wasrecrystallize
repeatedly,
untilthe,refractive
indexand
freezing
point:were
unchanged
by further
crystallization.
Physical
constants
weremeasured’~n
this,sampleg
A’second
runofthispreparation
w&smadeinMtich1941;inWhich”
recrystallize&
triptyl
chl~ldewas
reactetl
withanequimolar
quantity
[email protected] thiscase
theyielil
wasincreased
to22percent,
baseaonthechloride.
.
Procurement
of10 gellons
’ofthis‘hydrocarbon
wasundertaken
in
1941.Partofthis(2.9gal)wasprepared
atOhioStateUniversity
the
restwasprepared
intheselaboratories.
Thislarge-scale
preparation
‘wascarried
outby a modification
ofthetechnique
developea
atOhio
StateUniversity.
Thechloride
wasaddetl
totheGrignard
reagent
in
etght’equsl
portions,
in8 successive
@ys, whilethereaction
mixture
waskeptat 35°C.
An improved
methcd
wasdevised
forthepreparation
ofthelargequantities
oftriptyl
cliloriae
necessary
forthissynthesis.
Theequipment
consisted
of threereactors;
madefrom30-inch
lengths
of12-inch
pipe,
closed
atbothendswithcompanion
andblindflanges.
.Oneen~ofeaohreactorwasfittecl
witha smallsteelvalve(1/4~n.).Thesereactors
were
refrigerated
(-30°C) anawereconnected
to a manifold
through
whichhydrogen
chloride
co~d be admittecl
tO.eaGh.
Thermotorswerechatiged.with
triptene
inwide-mouth
bottles.Theflanges
of thereeptors
weresec,ured
byboltsendthereactors
wereallowed
to standuntilcold.Hydrogen.
chloride
wasthenadmitted
mtll thepress~ewas100to120psi. The
pressure
gradually
fellas thegasreaQted
untilthepressure
wasabout
50 to60 psi..Thentheprocess
wasrepeated
untiltherewasno,appreci,able,
change
inpreesure
during
enhour.Theexcess
gaswasreleasea,
the
system
purged
withdryair,andtheproduct
removed.Theyieltwaspractically
quantitative.
Thepro~uct
wasuncolorea
ma contained
a.small
amount
ofexcess
hydrogen
chlortd.e.
Thisexcess
wasconverted
toa3@l
chlorfae
by a&Mnga smellamount
ofolefin
to each@ S@ ~lowing~
.
standuntilreaotea.
By meens ofthistechnique,
20 to 35liters
of
triptene
wasconv@@ tothechloriae
@ 1 working day.
To 300 moles”of’
ethylmagnesium
chloride
therewasaaded300molesof
triptyl
chloride
inefghtequalportions
during
8 days.During
thistime,
thereaction
mixture
washeated.
to re~lux
temperature
endstirred.
At the
endof2 to4 additional
days,whenalltheGri~ardreagent
hadrsaoteil,
22
NACATNNO.1247
acidand,washed
four
themixture
wasworked
upwithIceandhydrochloric
timeswithwater.Distillation
oftheether,
endofmostof thetriptene
wascarriecl
outfroni the &actIonkettle,tiedistillate
wasdx~edand
redistilled
inColumn
3.2or13forrecovery
of triptene,.
,~eresidue
inthereaction
kettle
was”boile’d
withsodium
propylate
inpropyl
alcohol
titiltheproduct
wassubstantially
freeofchloride.
Aftertheproduct
waswashedf
itwassteamdistx?lled,
andthedistillate
&rfedandboiled
withalcohdlic
silver’nitrate
tormnove
thelasttraces
ofchloride.
Thentheproduot
wasfiltered,
washed
several
times,
driefl,
anddistilled
inColumns”ll,
18, 19,end20, Fromtworunsasdo”scribed,
whichwereworked
uptogether$
therewas,
obtal~ed
14.P2kilograms
(116.6
moles)
oftetrane
whichwas99.6 molepckcent
pure.Thtsrepresents
a
yieldof19.hperoent.
A totalof21.7kilograms
wasprepared
by this
method.
,.
‘*2,2,3,h-Tetramethylpentene
‘end
2,~,3,h-Tetramethylpentqn,e
Thefirstpreparation
ofthesetwonc)nanes
wasaccompl+shea
in&zne
1941byhydrogenation
ofthed.kenes
(reference
17)formed,by
thedehydra.
tionof2,2,3,k-tetramethyl-3-pentanol.
Thecarbinol
wabprepared
by the
reaction
%etween
methylmagnesium
bromide
and2,2,k-trimethyl-3-pentanone.
Thisketone
wastheresult ofoxidation,of
2,2jh-trhnethyl-3-pen-lmnol,
oneoftheproducts
resulting
fromtheu,otion
oft-butylmagnesium
chloride
on isobutyraldehyde.
.
Themethod
ofrefetience
17wasusedtoprepare
2,2,4-trime,thyl-3pentmol.To 55molesoft-butylmagnesium
chloride
wasadded3960 grams
Distillation
of theorganic
redction
(55 moles) of ~sobutyraldehyde.
products
gave4290grams(33moles,
60-percent
yield)
of2,2,&trimethyl3-pentenol.
Thecarblnol
wasoxidized
topentsmethylacetone
(2,2,4trimethyl-a-pentanone)
wf,th
potassim
di’chromate
andsulfuric
acid,by
method
ofFawors&.(Seereference
18.} From32molesofcarbinol,
therewasobtainod
3150giams(24.6
moles,
77-percent
yield)
ofketone,
.which’
wasdistilled
inColumn
5. ‘
The2,2,4-trimethyl-3-pen&mne
(24.6 moles)
in6 liters
ofether
waareacted
with26molesofmethylmagnesium
bromide,
andtheproduct
dtsW1.led
h Column~ until thetemp&atvfle
reached
lh30C. At this point
dehydration
ofthecarbinol
wasbeginnl~totakeplaoe,
sothedistillationwasinterrupted,
andtheclear,
slightly
yellow
residue
(29?0ml)
wasdehydrated
With~-naphthal.ene
sulfonic
aoid.
;l?r~thedehydration’~here
resulted 2h10ml ofalkene
&ixtwe,which
wasdriedanddistilled
inColunn
3. Thefollowing
fractions
wereobtained:
.
23
NACATNNo.1247
3Wction
gl *O119
119to124
r
23 Forerun
1550 3,3-Dimethyl-2v
isopro~~l-1-b,utene
124 to 129
ZOo Ihtezmediate ‘
600 2,3,3,k-Tetramet~J.;
130to135 “
l-pentene
>135
120 Restdue
..
1
1
2
5
IYactions
2, ‘3, and 4 represent
a combined
yieldofalkenes
of15.9
moles(65percent,
basedon2,2j4-trimethyl-3-pentenone)
. Samples
from
themiddle
oftheplateaus
represented
by fractions
2 and.kwerereserved
forphysical-constants
measurements.
No attempt
wasmadeto isolate
2,3,4,k-tetrsmethyl-2-pentene,
a verysmallquantity
ofwhichwasfound
byllhitmore
andLau@linin’reference
17.
Theallsene
fraction
whichdistilled
119°to124°C washyd,rogpna~ed,
andtheproduct
wasfiltered
through
silica
gelanddistilled,in,”,polamn
3. Therewasobtained
1G7Qml ofhy&ocdrbonw
hich%oiled133.7°
to
3.34.1°
C, ~20 (uncorrected)
= 1.4147
to1.4150.(l’Uhcorrect&d”
means
no correction
forpoesible
instrument
error;’)
Redistillation
ofthismaterial
gave93Jw collected.
at133.8°
C. Physical.
constants
were”determinqd,on.a
sample
fromthe,cent:r
of,thisfr~tion~ t.
.,
The’i&ken&
fr~t~onh ti&{reafqdfl~~like
mc&er,’an’’”yielded
347ml
oftiter$~”qoll+cted
‘at
l’42~
C’
(uncoirec”te&),
fractions
~’ofptihich
showed
,, .. .
‘=o’(Wcorrect.ed)
of1.42?.9,to
,1.4220.
A,,
.a$~frqc,t~~e’-.~d~~
r-e ~D
sqmple
fro~’~his,
d,i,st~llation
~S “re&z-@.’
for-d,6te~n&ti~on’
ofphysfc”al.
ccnstsxits.
.All”<inte~diate
,frcict~ons,
fore&u@,
,redidueti,
a@ niaterial
eluted
frm ‘sflica
gel“were
hydr~genated
andd+stille.d
inColumn
8, In
thisway,fherewereobtained’”~
additjion&l
200~.o<2;2,3~4-t6tr~thylpentqne
end14.5”nil
o?2,~,3,4-te;tremet~lpantane
~. . .. ..;..
‘..’
Testsonthesetwohydrocarbons
demonstrated
thetivikability
ofpreparing
larger
quantities.
Consequently,
10gsllons
ofe’ach
wassynthesizedatPennsylvania
StateColleqe.T1’+ese
hydrocarbons
werepurified
in
I
theselaboratories
forengine
testsby.distillation
inColumn..,l.
New
puresamples
forme%urememt
ofphysical.constants”were
obtain6d
concurrently.The,
improved
data’are
giveninta%le2.
. .
:..
.,,
\
!.
I?ACA
TN No.1247
l’Mrnethyl.-Zinc
Synthesis
ofThreeTetramethylpentenes
An olefin
co-polymer
fraction
contai~ 3,4,4
-trimet~yl-2-pentene
and2,3,&trimethyl-2-pentene,
wasreacted
withdr,y
hydrogen
chloride
untilabout60percent
of,the
oloffn
wasconverted
tochloride.
This
chloride-olefin
mixture
wastreated
withdimet~lzincina solvent
OT
hydrogenated
co-dimer,
whichcontainefl
2,2,3and2,3,&trimethylpentenes.
ThQresulte,nt
yroduct
washydrogenated
toa mixture
ofhydrocarbons,
all
knowntohavesuperior
characteristics.
Thisstudylbd’tb”’theqswthesefl
of thesecompo~dsina purestate
by thismethcxi.
Secondary
andtertiaqbutylalcohols
wereco-polymerized
inthe
presence
of sulfuric
acidinthemanner
described
inreference
19. A
portion
ofthoproduct
wasanalyzed
bydistillation
inColumn
1 endwas
foundtocontain
thedilsobutylenes,
2,k,&trimett@-1and~2-pentenes
(~ Percent),
3,4,4-trimethyl-2
-pentene
(23percent),
2,3,4
-tr~.methyl-2pentena
(37percent),
andhigher-boiling
material
(15pei-cent).
Therest
of,the
olefin
mixture
wasroughly
sep~ated
by distillation
In’Column
7.
Thefractions
whichboiled
107°to120°C amounted
to9740gram andconsisted
of2,3,&trimethyl-2-pentene
and3,f+,&-trimetll@-2-pentene
asma,jor
components.
partof thisfraction
(6300gr~) wasfract~o~ted
incol..
umn2. By thisdistillation
therewereobtained;
1150@%ms of3,4,4trhethyl-2-pentene
(nD20= 1:4230,,
n 25u 1,4205,
d20= 0.7392,
d25u,o.7350,
b,p.112.1°
tou2.80C,,and
@
65
&sms
of 2,3,4-trimethyl- .
Y
2-pentene (n20= lrh275,
d20=,0.7434,
~=5= 0.7391;
b.p.
%25 = 1.4250,
,.
116.3°
to.~~;5°c).
Thesetwoalkends
were’
reacted
separately
%rith
hydro~en
chloride
at
-6ooc inQZI
apparatus
descrfbqd
inreference
2 untflapproxi~tely
60
percent
of the+Lke;e
hadbeer+
converted.,to
alkylchloride.
,The
~roducts
werewashed,
,dried;
am?.
fz’actionated
in.Columen
3. In”th%s
wqy,‘/16 grsms
ofconstant-b~fliag
3-chlo&o-2,2,3-.trimeth.ylpentane
wasobtained
fromthe
3,,4,4-trlmethyl-2-yentene.
Thechloride
“froln
2,3,4-trimetl@-2-pentene
(1410grams)
wasprobably
a mtxture
of2-chloro-2,
3,&trhnet@lperr&ne
and3-chloro-2,3,&tz%ethylpentan?.
Sincethesetwochlorides
werecxpetted
toyieldtwodifferent
nonanes
(b~reaction~th
dimethyl
zinc]+
withboiling
points
differing
by about& C;tioattempt
wasmadeto separatethechloride
mixture.Physical,c,onetants
measured
onthechlorides
are,
i.ncltided
intable2. ,,
.
,.
2,2,
3,3-Tetr’smethvlpentane.In theapparqtus,
andby thetechnique
described
previously,
4.Kiis,(614 WSM6),
of 3-chloro-2
2,3-trimot~lpentaie
inTOOml of isooctqne (2,2,4-trimethylpent~e,
‘S
-4refei-ence
.
fuel)wasallowed
toreactwiththe?iimethyl
zincfrom7.75 moledof
methyliodide.Thedimethyl
zincwasina aolutlon with500ml of isooctane-Thebathtemperature
forthereaction
was70C. Theproduct
was
.
‘boiled
for2 hourswith5-percent
potassimn
hydroxide
inalcohols
washed,
andfractionated
inColumn
4. Thisdtstlllatlon
gave:
..*
NACATNNo,1247
.
... .
.,,
7
.“
Boillng
rmge
‘
Refractive
index,nD20
Fmiction(Headtem;fra@re)
1 ‘;~~
“
.“
—.
g6to100
1.3918
i
1130
65. .
1.4059
100to110
110toU6
231
i.41~t&.422s
3%04
116to138.6
27
5
138.6to140.3
I:4226
6
39
150 ‘
1.4233
140.3
7“
)istil.lation.
oftheresidue
wascontinued
inStill8 andgave:
J
8i
1;4232,
140m3
77
1.4379,
10
.’
9 (Residue)
s 340.3
L
Alkene”
by-products
ofthereac““Fraction
1 was,
recovered
solvent.
tion,formed
by deh@rochlorination
of the4kyl chloride,
werecontained
.infractions
2 to5. By thelowrefr~tive
indices
of”thess
fractions,
it isindicated
thatthismaterial
consisted
mostly
of 3,4,k-trime%hyl2-pentene.
Theyieldof 2,2,3,3-tetremethylpentane
(fractions
6,7,.
and
8)amounted
to 37.7-percent
based,on
alkylchloride.
3?raction”7,
after
filtration
through
silica
gel,kadthefollowing
properties:
freezing
140.20°
[email protected] at76omillimeters
point,
-ll.@”C,boll.ing
point,
“ofmercury;
refrtictive
index,n~20=1.4233,nD25= 1~4211~
density,
d20= o,7565,’aas
= 0.7527.
’Itmaybe seenthattheproduct
wasofhigh
purity
whentheiie
prope~ies
arecompare-d
withthoseofthe-pure
sample,
aslisted
intable2. Thefreezing
pointindicates
a purltyof,a?xmt
r
99.5 molepercent. ~
. . ,
,...
..
2,2,3,&. ”and2,3,3,4-Tetramethy
lpentanes:Byu&e;ofthe“&meprocedureas.described,
tworunsweremadeinwhicha totalof 8.35rnqles
of
themixture
of2-,aid3-chloro-2X3,4-trimethyl’pentanes
wasreaotsd,,
at
10°C,.with
thedimethyl
zincfrom15.5molesofmethylIodide.Thecombinedproducts
w&e refluxed
withalcoholic
potassium-hydroxide,
washed,
dried,
enddistilled
inColmnk. Thisopera.tlon
gave: .
..
.. ..,O
-.
!,.
*
..
,..
..
..
..
..
,.
.
26
NACA’TN
No.1247
.,
,
“1 I
Boiling
range
index,nD2c
Fractfon (Headt
eTrature) Volume Refractive
(ml)
,
#
.
~ to 100
1.3917
1.“
20;:
’100to11~
1.4080
3:04 ‘, u? toSL9
~ 440
‘1.4269
to1.4267
31
1.4219
119to130
6~8
130.0to133,5
139
1.4158
to1.b150
138
L
1.4152
“,133
.5td134.0
9
64
10
1.4183
134to140
Theresidue
wasdistilled
inStill8,andgave:
11
140.0to141.5 v .10,
.12
141.5tO142.0
60
142.0to143.o
20
13
14
10
143to165
?n~avle)
”-----------R?
15 (RL-,
‘
I
.
,.
-4 II
! ..
‘
1.4212
1.4218
1.4221
“1.);~l
1.L57n
-.,<I“
J
Fraction
1 wasrecovered
isooctane;
fractions,3
to4 werealkene
byproducts,
tndicated’to
bemostly
2,3,4-trimethyl-2-pentene
bytherefractivelndtces.
Thetotalyieldoftetramethylpentanes
(fractions 6 to14)
“
mountedto30percent,
basedonalkylchloride.
Thesetetr@ethylpen“~es consisted
of al)out
71percent
of2;2,3,4-tetrsmethylpentane
and
about29percent
of2,3,3,4-tet_thylpentsne.
‘,
,“
Fraction
9, afterfiltration
through
sflica
gel,hadthefollowing
, properties:
freezing
point,
-122.54°
C,boiling
petit,
133.3°
to133.k°C .
at760mil~imeters
ofmercury,
refrtitive
index,n 20=,1.4148,
denst%f,
d20= 0.7397,d25= 0.735
B: Thesevalueu
arein
nD25= 1.4127;
agreement
withthosereported
forthepure2,2,~,&tetrkmethylpentsne
In
“ table2. Fraction
12wasfiltered
through
silica
gel,andtheeluent
used
forMasuremont
ofphysical
properties.
Theseproperties
werefound
to
be: boiling
point,
141.3°
to141.4C at760millimeters
ofmercury’j
refractive
Index,nD20= 1.4217,
nD=5= 1.4196,
density,d20= 0.7545,
ii25
= 0.7S12.Thesedataagreewtththosereported
forpurer2,3,3,4tetremothylpentane
intable2.
A tetramthylpentane,
assumed
tobe 2,3,3,4-tetramethylpentane,
was
prepared
byDinerstein
(reference
20]in1940,by action
ofdimethyl
zinc
on 3-chloro-2,3,&trimethylpentsne.
LaterworkbyEnyeart
(reference
21
andby thepresent
authors
showsthatthehydrocarbon
described
by
Dineretein
was2,2j3,&tetramethylpentane,
.
NACATN ~Oa 1247
27
*2,4
-?)imethl-3-IsopropyIpemtene
(Triisopropylmethne)
Therecent
preparations
oftrtiso~ropylcarbinol
by theaction
of
isopropyl
lithiumon
2,4-dimethyl-3-pentanone
(fliisopwopyl
ketone)
(see
reference
22)andby theaction
of isopropyl
chloride
ondilsopropyl
ketone
inthepresence
of sodium
(seereference
23)havemadeavailahl.e
a method
forsynthesizing,triisopropymthane
(2,4~dim~l-3-i~opYgpylpentane).
A quantity
ofthiscompound
hasbeenprepared
by theuse of
isopropyl
lithium.
Preliminary
workonthisreaction
wasperformed
inseveral
smallscaleexperiments,
ineachofwhich10 gramatomsoflithlum,
6.5 moles.
of isopropyl
chloride,
5.4molesofdiisopropyl
ketone,
and2000ml of
solvent
wereused.Durtng
thisstudy,
itwasfoundtlmttechnical
2,2j4trimethylpentsne
(isooctane)
served.
admirably
asa sol~ent
whenitsuse
wasaugmented
by efficient
stirring
and,
er!!ernal
cooling
ofthereaction“
mixture.No preliminary
purification
of thesolvent
wasnecessery
end
thehaz=dsaccompanying
itsusearemuchlessthanthoseofpetroleum
(Seereference
22.)
ether,
usedby theoriginti
investigators.
Thepreparation
oftheconsiderable
quantities
offinely
divtded
lithtarequired
wasexpedited
by theuseof a smallIaboretor.r
rolling
mill.Whilethelithium
wasbeingworkedinthemillitwas-luhr$cs.ted
andcoated
witha mixture
of ti-percent
isooctane
and20-percent
light
mineral
oilappl~ed
%ymeansofanoilcan. Th~stechnique
ten.~.ed
to
prevent
thelithium
fromsticking
totherollsan~alsoprevente~
excessiveoxidefomnation.
Therolled
pieces,
about0.003inchthick,
were
cutintoribbons
enil
thenin%osqwes fnlargeshallow
panunderisooctane,
.’
.. Theyields
inalltieprellmimqrunse@nted to18 to:22percent
ofcarbinol.
No appreciable
change
@ yielfl
wasexperienced
whenthe
reaction
between
isopropyl
lithium
snd,
dlfsopropyl
ketone
w.zs,
carried
o“ut
at99QC; thetemperature
ofImiling
isooc~sne,
rather.
thanai 35°C,
thetemperature
usedby theoi*i@M
investigators.
..
‘After
thetechnique
of”handling
thereaction. @d been sufficiently
developed,
alargerunWascarried
outinthe50-gallon
stainless-steel
kettle.Thatotal’
qyb,ntiky
of reactants
usedwas: 159gramahms (1.10
kg)cflithium,
115moles(9.03kg)of isopropyl
chlori,de,
~ moles(9.13
kg)ofdiisc.propyl
ketone,
Thequantity
of
and55 litersofisooctsne.
isopropyl
chloride
wasrelatively
larger
thenthatusedby thecriginel
Investigators
inorderthata minimum
smmunt
oflithimnbe
leftunreacted.
endthatanylossoccurring
through
thereflux condeneer
be replenished.
“The
diisopropyl
ketone
wasconsknt-boilinq
material
obtained,
by redistillation
of thecormnerctbl
product
inStillU.
,
I
1
1
28
NACATN~!O
.1247
Thekettle
wasflushed
withnitrogen
andcharged
with31liters
of
isooctane.
Abouthelfthelithium
wasaddedandthereaction
started
%y
theaddition
of1 literofIsopropyl
chloride
in1 literofieooc%ne,
andbywarming
thejacket
to35°C. Theremainder
of,the
lithimn
was
addedfnth~eeadditional
charges
during
thenext2*days.DtUiinR
the
first3 days,a mixture
of theremainder
oftheiso~dopyl
chloride
inan
equalvolume
ofisooctane
wasaddedinfourcharges.
A solution
ofdiisopropyl
ketone
in11.4liters
ofisooctane
was
added during
8 hours,
whilethereaction
temperature
washel~atk5°to
600C. Afteraddition
wascomplete,
themixture
waswarred
andstirred,
for5 hours,
afterwhichitwhscooled.Decomposition
ofthereaction
mixture
waseffected
%y theaddition
of25pounds
ofcracked
ice,followed by a solution
of11pounds
ofamnonium
chloride
in5 gallons
of
water.Theaqueous
le,yer
wasremoved,
andtheorganic
layerwas$ed
five
times,
eachtimewith3 to5 gallons
of’
water,
titerwhichitwaswithdrawnanddriedovernight
withpotaseiua
carbonate.
Fractionation
oftheproduct
incolumn
6 gave:recovered
isooctane,
diisopropyl
ketone,
bofling
point121°to126°C,2375~~~j intermefltate
fractions,
240grams;
endtriisopropylcarbinol,
boiling
point104°to
110°C at50 to55millimeters
of~:~c~, 2576grins.~1i8~epreaentn
a
yieldof 20.4percent
%asedonthediieopropyl
ketone
added.A pFrtof
thetriisopropylcerlinol
wasredistilled,
anda puresample
col:.,,cked
I’roln
themiddlo
ofthisdistillation
forthemeasurement
ofphysical
cmutants.
Thecarhinol”wasdehydrated
by distillation
fromanhydrouscopper
sulfate.
From16molesoftriisopropylcarbinol,
14.4moles(9Opercent)
ofcrude2,4-dhnethyl-3-ieopropyl-2-pentene,
wasobtained,
Waterrecovery
amounted
to ~ percent.
Thecrudeolefin
wasdriedovercalcium
chloride
anddistilled
inCQlumI
6, fromwhich1372gramsofmaterial
-which
boiled
1~3.2°
to153.6o
c at756to759miilimetere
ofmercury,nD5”=1.4360
to1..4371
(allvalues
uncorrected),
wascoll~cted.
A sample
wasremoved
fromthemiddle
ofthedistillation
fo~themeasurement
ofphy~lcal.
constants
o
Theolefin
washydrogenated,
anddistilled
InColumn
6, andgave
1100grams(8Opercent)
ofconstant-hoilinC
material,
boiling
point
156.5*
C at749mllltmeters
ofmercury,nD20=1.4234
to1.4236
(allvaluesuucorre’cted).
Thismaterial
contained
a traceofole~in
whichwas
removed
%y repeated
filtration
through
silica
gel, Refractionaticm
under
reduced
pressure
nfforded
themesnsofo%talntng
a puressmple
for
physical-constemts
measurements.
.
.,,
,,
..
.
.’
.,
..
,..
NAOA~ NO.12&7
29
.
..-.
.:
*Pent~thylpentan&
2,2,3,3, 4-Pentsmethylpentane.Thefir8tpreparation
of2,2,3,3,4pentxamethylpentsnewas
carried
outinFeb_ ,1942
by thereaction
between
2-chloro-2,3,3-trim&hylbutane
andisopropymesiumchloride.
To 30.5molesof isopropyl
ka@n&~m chloride
in10.53liters
of
ethersolution,
therewasadded,
atro,om:temperature,
26.4molesof2chloro-2,3,3-trimethylbut~e
(subliirtation
point132.Pto134°C) in3.5
liters
ofether.Afterstanding
for3 weeksat15°to.20°
C, the.reactionmixture
wasworked’”up
intheusualmanner,,
Theprcd@, distilled
inco1um~6;gave:
.1.
... . .
14,8mclesof 2,3,3-trlmethyl-l-b@ene,
for&dbydehydro. chlorination
of2-chloro-2,3;3-trimethyl?)utsne
. .
O*1moleof2-propanol,
fo~edbyox~dation
oftheGri@ard
reagent,
foundinanazeotrope
with2,3,3-trimethyl-lbutene .“
2.2 nmles ofrecovered
2-chloro-2,3,3-tMmethylbutane .,
S.lmclesof2,3,3-ttimtiyl-2-hutml,
pre&nablyby
hydrol-,
.ysisofthechloride
,.
,.
..
1.05molesofcrude2,2,3,3,4-pentamethylpentene
Thtsrepresents
a yieldof4.0percent.Another
run,inwhich19.\3
moles
ofthe’chloride
wasusedandwhichwas’kept
at.5°C for.3.
weeks,
thenat
roomtemperature
for2 weeks,
yielded
~le ofadditional.
crude(3.1., 0“.6
percent’yield).
,.
,,
.
.
Thecombined
yieldofcrudematertal
(300.ml.)
wasfractionated
in
Colmn8. Frcmthisdistillation
.there.was
obtained
226ml ofmaterial
whichboiled
163,70
to164°c (tieoirqcted).,
~is proauct
wasrodistilled
inthese&”coluxm,
endthere’
was@llected186ml ofconstantboiling,
constant-refractive-fndex
mkterisl.
Thephysic4constents
of
thisproduct
afterfiltration
through
silica
gelwere:freezing
point
“-37●
5°c,n 20= 1.4361,
da = O.78Q3,
boiling.
point 165.54° to I@i56° c
at750”.5
M ?liuktbtis
ofme’rc&y,
, ,.,., .’
,.,
..
‘>
Later,
twoother’
~thodbfor”the
preparation
of&is decane
were
lnveBttgated.
Bothof thesemethods
fnvolved
thenethylationof
2,2,3,4tetramethyl-3
-chloropentane.
Thischloride
wasprepared
ingoodyield
fromthecorresponding
alcohol
by reaction
withconcentrated
hydrochloric
sold.The”
chloride
decomposed
eastly
whena boiling-point
determination
wasattempted
atatmospheric
pressure.
Itwouldnotcrystallize
atdryicetemperature
andhadan indexofrefraotlon
nD20 of1.4389.The
1
,
:: .,,.
30
?;.
.,.
,
.
NACATN ~Os 1247
,.
. . .,.’. .
,. .,-.,
.,
carbinol
wasprepared
bythereaction
between
,~,~~gn~s,ium
bromide
.;,;,.
ad 2,2,
h-trimet~l-3-,pen@one.
“ ...
.,.,“,. ..
..
....
......
..;“,:’,.~
.,;,
-:,,
:
r,.
.
..
,1. “
In qneexperiment (Novdmber1943)b’k’
th6me%hykti’oh of‘&is’”
c~’o-:“
ride,1.7molesofthechloride
in320ml ofbenzene
was,
added.,
to$?.5
molesofdimethyl
zinc
j usfngt
thepreviously
described
“ted~que..”
.Dfs.tillation
analysis
of,theproduct
of‘rbaction
eho~@’
t++presence
0$0..4
mole(23.5percent
):’.of
2-fsopropyl=3y
~-d3meth@-l-but~ne
dnfl.
0.81tile.
.
(47.5percent)
,of‘2;
3;3;4~tetrsmethyl-1
-p&&ene,
“both”
fo’lnned”
by.dehjdro:
chlorinat~op
oftlw?
a,lkylt
chlorfde.
‘Intidi+i’ini,
‘thei+
wasfoun$i’.
0.38
mole(assuming
CIOH22)
of’
material
whichboiled
150°to160°:
C,andi%’m
whfchno purematerial
couldbe isol@ed
~,,.
, :~, ,.
:,,. J.
,.,
..,.’ .,
.,. ,,..;.,:,.
Inanother
ex&rln&nt
(MaY’19~)j’
10.~:~l~s’”6f
:2j2,~i&~tetr~t~l3-chZoropmtsne
wastreated
with11.0,
molepofmethylmagnesium
..br@de
inether
solution.Theretitfofi
waiallowed
to’takq,
p~ace.
qwei,aperiod
of 3 weeksat.l~,”
to22°C. Theproducts
ofthereadtion,
.asdetermined
bydistillation
analysis,
consisted
of 3.omoles(28percent)
“of2-isopropyl-3,
3-dimethyl-l-butene,
and5.7I@ps .(53
percent).
of2,3,3,,4tetr@t@l-l-pent@e’;
&ofidby,de~
d&tihIorina*~’mof thti
al~l chloride.Inadditton,
therewasfoundO:?mo~e,
(4.
pe~ent)
,of
.cr~e
2,2,3,3,4
-pentet~lpentsae
(15@tio167°Cy.~z
0..
=.1.?k354’ti
”I,:4369).
;..’.,
It isInteresting
tonotethatinbothofthesq.
dtrlala,
we .d@ydrochlorlnation
ofthealkyl’”chlbtiide
j”l’ed’%o
approxim&&ly
the8* relative
proportions
of’
thetwononenes;
namely,
one,,,
pa.r$
of,?7JSOPX’OPY1-3$3.
d@thyl-l-but,ae,,
@::tw.p~t8 &:2,3y~,
+-t6tr-t~l~l-w’q~enp..
,~i’e”.
propor$lo~.
isnottheBeiue
&Ieoc~in%.when
the’
c&rb~nol’.itself
‘Is,
d,ehf:
..
d?%+e~.Inthatcashthe:
Prbp’drtions
tie:
thr&eparts’
of2-$sopropyl-~,
3dlmethyl-1-butene
endonepartof2,3,3,4
-tetrsmethyl-l-pehtene.
‘(See
reference
15.)
...:....,
. ,.
’.1.,
,.
.. .....”’ ,.
.... ..,,,
t,’.:, !.....:.J.
~-.~..~’~
,.
. Pents.methy@e
ntanes.
fr&’2;42,
3,h;k-fi~~***~i-3-&~*&ol
aiattempt
to.
pre,p~e,,P
i2,3;4J4~~nt~t~lp&t~~).ithA,~
beeti
$o~d “,:
that.2,,2,
~.,k,,~-pen,t~t~l-3
-@mt*lwlll dehy~te.~qr,~he:.
influence.”
ofi.odine.
to::,q
m$xt~ of.two.dedene-s;
which,”
‘@ h@&gen&ttofix
yields
botho?.the.:~ntmtwltieti-es:
:}-~:
;,,”
J’’::’
,,;:’
:,; .,.
::,-:,’,’: ... .
,.,
.
,,. ...
...’-’..
!.,;,~
,.
k 193il&~re endLa&in (nferenti’
17)’&@o~~~”t~e’~
sfiydra-”
‘“
tfonof2,2,3,4,4
-pentemethyl-3-pentanol
bymeanaof,~-~aphthplene
sulfonic,
acidto@ve\.2~tYtutyl-~
~~~dimet~I-l-buteh&,
"wi,tho,ut:,
app,rec~~le
rearrangement.
Wey.dso.Yepbrted
a“mallfl,,nnobn~’of
low-boil~ng,’.
~$den-,
‘,
!,. .: :,.”.”.
tified.
material.
. :,,.
,,;:.,
:
: . ,,,
/{: ;-i,’:”,”, “’.’”
,..
;,,.
....,,,,.
;..,,..
,,
:.,. . ‘,”:,
.1
.,..
: Sincethfsr,eagt@n
~ffered
a.meah&of’
p&6p&fi$”
2,2ijx~~4~~eh$a~’.:
methylpentane~
a tr$sl)~-l%s.mblib..’
Wti’’t~e”.
ctib$n@wasd@#rht@
.
with”p,:~phthalqne
@tifonfc
acid~at”.’a~epherie
preiktiby
“the
products
ofthe’
reaction
consisted
ofisobutybne,
2,3-dimethyl-l-butene,
.!.
.
.,
.
NACATNNO.124~
.-
31
.
2,3-dimethyl-2-butene,
andonlya small~u@. of’
higher-lmillng
material.
No 3~3-dimethyl-l-butene
WQSfoundinthereaotioq
products.
Dehydration
ofthecarbinol
withiodine
wasfoundto”
yield..a
mix%ure
ofdecenes,
composedof2-t-butyl-3,3-dimet@l-l-butene
@ 2,3,3,~,k-pentamethyl-lpentene.
.
.“.
Jl)Preparation
of2,2,4-trimethyl-3-pent&none
and
2,2,4,
4-tetrame+&yl3-pentsmne
.
.,,
Preptiation
of2,2,4-trhthyl-3-pentanone
vasmadeby theEellerBauersynthesis
(reference
24)intoluene
solvent
by theaction
of sodium
amideandthenmethylsulfate
on2,4-dimethyl-3-pentenone.
Sodiumamide
wasmadeingo-to9&percent
yieldby’the
method
described
inreference
a. Thecrude2,2,4-trfmethyl-3-peatenone
wasmethylated
a second
time
by thesanemethod
togive2,2,4,.$-tetramethyl-3-pentsnone..
“The
manipulative
details
of thesereaotions
&e described
byl,%itmore
andLaughlin
inreference
17. me over-~ yieldwas58percqnt
ofthattheoretic~y
possiblecalcul.ate~
without
includinrecovered
2,4-d@ethyl-3’penttione
and2,2,~-trimethyl-~-$entanofi6,
whit
in thesynthesis.
A
f wererecycled
chemge
ofthisketone
wasfractionated
inColunm
1, fortheisolation
of
a puresample
forphysical-constants
measurements,
Intile
sanecolumn,
a sample
ofthe2,2,4,4-tetramethyl-3-pentenone
wasalso.
distilled
foi,.
them
ssme.purpose.
..
12) Preparation
of2,2,3,
4,4-pentame%hyl3-pentanol
1
Absolution
of10molesofmethylmagne,slum
brcmide
wasreaoted
with’
8.75molesof2,2,4,4-tetrsmethyl-3-pentancrie
andtheproduct
worked
up
intheusualmsnner.Fractionation
oftheproduct
inColuam
4 ata pres‘
sureof57mtil~meters
ofmercury
gavea forerun
of 307””ti
ofmaterial
whichboiled
below105°C. At thispointthecarbinol
beganto soltdify
inthecondenser
andthepaleyelloy
material
remaining
‘in
thepotwas
fouQdtobe quitepm-ecarblnol
(me,ltfng
pcl::t
above37°C). A portion
wa~recrystallized
frometherforuse@ thedetermination
ofphystcal.
properties;
Theyield
mounted
to75perceht
of
the.theoretical
quantity.
.
3,4’,U-pGntmnetl@~-pentsnol
of2,2,
(31 Dehydration
. .
with13
-naphthalene
sulfonfc
acid ..,
,“
.,
Dehydration
of 897grams(5.7rnolee)
of’2,2,3,4i&pentsn&kyl-3yentanol
with8 gramsof~-naplrthelene
sulfonic
aoidundera fractionatingcolumn
resulted
inthedistillation
ofa waterlayer,
ano~ganic
layer(855ml),andabout50ml ofmaterial
collected
Ina dry-ice
trap.
Theorganic
iayer,
whichsmelled
strongly
of sulfur
dioxide
andhydrogen
sulfide,
waswashed,
dried,
anddisttlled
fromsodium,
emdgatethefollowing
fractions:
&-
.
.
32
NACATNNo.1247
,. ,., , ,,,
BolZing
rsnge
Fracticn (Head
index,“nDRo
~g~erature) TdZume Refractive,
“ ,“(ml)
~~~ 1
..
e----54
1
6;
3..3908 .
54 to57
1.4033
51 to71
26
~
“1,4084
71”to73
1.4100
3:;
“
73 to.
75
z
75 to150
1.4223
150tO 153.2
;?
.1
A375
7
8
153.2to156s5
1.4400,’ ,“
156.5*O 157
:?
“ . 1.4411
9
-----22
Residue
157
~
,1
.,
.
.
aDistillation
interrupted.
I
A considerable
quantity”nf
gaswasevolved
during
thedistillation.
Thisgasboiled
atabout-4°C,wasreadily
absorbed
insuldlmic
acid,
and absorbed
bromine.
Regeneration
from‘svlfurlc-aciti
solution
@yneutrslization’remilted
int-lutyl
alcohol.
Tht6’
identifies
thq~i~.g
as isobutylene.
Theotherprincipal
produ~ts
oftherqaction
were,f~~ciion
2(2,3-dimethyl-l-butene),
f~action
5 (2,3-dimethyl-2-bute]le),
&i,5,fractions7 end8,whichpro~ahl~
qontained
a mixtuzze
of2,3,3,k,4-pente’Methyl-1-pentene
and2-t-butyl-3,3-djzneth@-l-b~te~le.
Sincetheprcducts
ofthisdistillation
didnotyieldthedesired~co~po’thdB
inanyappreciablequantity
moreelaborate
analysis’
wtie
notunkrtaken.
,..
,.,,.(4)Deh@r@16h,of
-pentanol
‘~.
2i2,3,h,h-pentsmeth~l-3
‘
,,
withIcd,ine
;.
.,
A ch~geof2 2,3,4,h~pentekkt111-3~fier,imol.
(640grems,
h.1mo~es)
Wasrefluxed
wi.th
Lgams ofiotihe
~dth~pioductd~di~.led
throu@ia
shortfractionating,c
olum, yieldi’ng
70ml of’
water.and
7C!0
ml oforganic
material.
Theorganic
layerwaswashed.j
driad,
andfractionated
roughly.
Thedistillates
fromthreerunswerecombined,
yielding
1950ml.ofniaterialwhich,
onfurther
fractionation}
gavel&10ml botling
140°to155°C.
Theresidue
wassemisolid
andhad# odorsimilar
tothatofa carbinol.
The140°to155°C!fraction
wa~redis$C1.led
intothefollowing
fractions:
s
.’
.
.
.4
NACATNNo.1247
‘33
Boiling
ranga
Fraction (EeadteTture}
1
2
5
6
‘7
8
.
.
.
55
43
283
k60
190
55
50
26
A constmt-’boil-lng
portion
offraction
3 wasreee~edfordete~iAt 157°C, solid.materfal
nation
ofphysical
constants
aud0zonoiy8iS.
started
toforminthecondenser;
sothedistillation
[email protected]
cooled
residue
intheflaskwassolid,
melting
at34.5°to:37.5°
Cy-lnrh
a mixture
ofthisCO~Q’~d~~ theoriginal
carbinol
wasllqUid
&troom
temperate.Thematerial
wassoluble
inether,
insoluble,
inwater,
slightly
soluble
in @-percent
phosphorj.c
acidandwas.unaffected
by
sodium.
..
Analysis
showed
thepresence
of63.1percent.oarlxm
and13.8per-”
centhydrog~n.
I%cause
of thevolatility
ofthecompound,
theseresmts
.lkaybelow. By extending
theCH content
to totallCOpercent,
thesnal.ysiswascalculated
to 85.8percent
carbon
and14.2percent
hydrogm,
whichagrees
witia
thean&lxsiE!
of analkene.Themo+ecular
weight
was
foundcryoscopical.ly
tobe 142.4(theory
for C#=o = 140.1).
.. . . . .
,,, Atthispo’int
thedistffiation
ofthesolidolefln
wascontfnued
after-provisiorhad
beenmadeto.prevent
soiidlficaticx
’ofmateriel
@
G.the.condenaer.
Thisdistiilattcm
gavethef~,;iowing
fractiona:~ L“,
,...,, .,
.,
..,.
,,
,.
,., .
,.:”.,
Bofling
rsnge
Fraction @@ ;g:’erat~e)~.
~;p;l
..
.
100tOM8.2
148.2to14900
149.otoJ.4gs6
149.6tO151.0
1~1.oto152*O
152,0to153.0
1’53.0
to155.0
155.0to157.0
index,nD20
V-ctlmie~efr=tf~e.
(mcorrectdd)
(ml.)
9.
10,
u
12
13
14
15
Residue
157.0to 157,.2.‘,:30.1
“
.18,6
157.2to158.0
18.4
158.0to158.2
158.2toL58.2
27.7
158.2to158.9
28.1
28.3
158.9to159.0
28.2
159*Oto159.O
3901 j
Ozonolysis
wasyerformdonfraction
15.
34
NACATN NO.1247
~
Ozonolysis
—-ofAlkenes
Ozonizaticm
of0.21moleofalkene
in 300‘hil.
isopentane
at -5°to
-10°C wasaccomplished
in12hovrs.Oxygen
containing
7.5percent
oznx.e
waeusedattherateof7’500
ml.perhouriThesolvent
wasnotremove~
prior,to
decomposithn.
because tiie ozonlde
proved-to
be a solid,.
llecanposition
waseffected
bymsansefthetechnique
developed
byWhitmore
an~
Church
inrefsrence
26, Thereaction
wasofmedium
violence
andgave
of,the
water
riseto 36.5ml ofoiland150ml ofwateylayer.Analyaia
layershowed.
thepresence
of0.18moleofformaldehyde
an~no otherlowmolecular-weight
aldehyde
orketone.Theoilwasdf~tilled
toyield
24.3ml of2,2,k,4-tatr~thjl-3:~entmme
(b.p.150°t~1550C)jwh~ch,
whentreated
withmathylmagnesium’b
rcmide,gave2$2,3,4,4-pentamethy2-.3pentanol,
theidentity
ofwhichwasproved
by a mixedmelting
pointwith
a ?mownsample.
(b)E2@3er-boilln
galken’e
(2,3,3,4,
k-Tentamethyl-lpentene)
Tn thesamemanner
asdescribed,
0,11moleofthehigher-boiling
alkene
wasozonized
in~00ml.ofisopentae
et -10°to-20°C toyield
0.071moleot.fomaIdeh@e
and9 gramsofanoil.(b.p.
1~2°C;
nD24= 1.4149).
Thisoi,l
gavea positive
io~oform
test,and-was
oxldizefl
‘
by50-percent
nitric
acidto2,2,s,3-te%ra~t~lb~~tmolc
aci~.(Seereferences
27and28,) Afterseveral
crystallization
fromalcohol,
this
acidmalted
ati19@to197°C, thessmevaluerbpdrted
inreference
29.
Theneutral
equivalent
wasfound.
tobe 147.3.Theamidewasprepared
and
fo~d tomeltat201.50
tO2c2.2°
C,whichagrees
withthe&61ting
point
Theketone
gavea 2jh-fl~nitro(231°t02020’C)
fouad’in
reference2~.
phsnylhyQrazone
whichmelted
at182°to18~0C. Thekgtone
wastherefore
considered
to%e 3,3,k,4-tetrameWyl-2-pen%auone.
(~dySiS: ~~ fo~dj
17,20,
17.28percent;
c~clfiated
for C~@.@aO~j17.27percent.]
Thecrudelower-boilin~
alkene
fromthedehydration
of2,2,3)4~4pentauethyl-3-pen@ol
(fractians
2 to 8)washydragenateil
andfiltered
through
sil$ca
gel..Difl$illtiti.on
inColumn
5’@ave:
i
.
.
,,
,,
,
.,
,,
.
.
.,
NACATNNo.12b7 “ ~
.
.
:.
.
.
35
.,.
‘3
.,:
Boiiing
renge
I
.,Fractton-(Headtemperature)
~
~
n~~
~
“.~:~y” Rek~tlveIndex;
..:
(Oc)
1.4296
to1;4304
. 1.4306
to”:l.4307
1.4307
to1.4313
1.4320
to-1.b341;‘
1.4360 ‘.,
1
An anslysis
ofthedistillation
ciuveshowed
thepre~ence:of
735ml’of :
2,2,3,4,4-pentam@hylpentane
and112ml of?,2,3,3y4-Pent~thYIPen~~~.
lto2
153.4tO158.4
3%08
1s8.4 ~
158.4to159.8
9 to14
15to16 . 159.2to161.7
..............
Residue
160
. 300
303,
, 97
47
H@rogenatlon
of’the
htgher-boiling’alkene
wasoarried
Outiin-s
~
solvent
(2,2i4-trimethylpentane)
.;Distillation
gave,Intidttion
b the
solvent,
a small.
fore&vn.
@l 247~ of-fractions
collected
at163°-tQ:
‘;
164°c(~20= l,4358to1.4361).Thebest~
samples
ofboth,dec~es
were:
:.,. ,. ,,
reserved.
formeasurement
ofphysical
constants.
.“’.
.
.
.
Theyieldoffiktied
tsola%ed
inthe::ptie
state(celc~ated”on.”
:
2,2,4,4-tetrmethyl-3’pentanone)
tiuntedto25.8percent
:o~,2~?13,J+,4pentwethylpentane
and.11.k
perce@of2j2,3,3,4@p4fit~tw~perit~e~
.
Theseyields
could”rio%
he usedtof’orma
definite-”opinicm
ofthereac-’
tion,norcanmuchwelght%e.placed.on
therafi’aof:products
fo~d,
sincea lossexperienced
inthedistillation
andhandlhgofthehigher
boiling
decene
isnot”accounteti
for:
‘‘-‘“:’
:’-”
’”.:
....
..,, ‘ “..,
,, : $
:.
...,,..
,,
.....
..
Pentanol.“l1.Pentamethylpenten6s
frorn’’2~2;3,k,@pentemetQ?~-3Thesecondrun
ofthis,series
oftietitfons
wasmade’
%0 increase:ths’~
stockofliydrocarbons”and
h obtain
more’
inforrdlon:on”
theratie
‘of
““
>,..:,
.,,-...
:,
prbducts
fozmgd
b
ydeliydration”of
thec%rbinol.
~”.,;”
’’-:,
.
;!.
.,
,,:...
. ..
,’ ., ., ,. ,,:,.
,... ,,j~)~prePwatiion~o
f’2,2”4=trimthYT-3-pentti0n8”
‘ .,.
...;.
. “:.
..
,, .....
.,.,,.
,.. ..?. ..,.
.,.
.,,....... .-,.
.,,
,.
..”. s:.
‘Fort
his”second-s~tiost~j.rm”e
dtiler
m&thodwaSd~tiised
~ormaking
2,2,4-trfmethyl+pentknone.
.Thi~’’uthod
Ws””ti’dapWtfon
ofthatde-’
eeribed:by
Nef.
inreference
’30
whobb%ained’tlifs
:lie~ofie’
by %he+~~austive
methylation
ofacetone,
methylisopropyl
ketone,
Metml ke+bie;
“or “
pinacolono
withmethyliodide
enfl
potassium
hydroxide
ina sealed
tube
at140°C. .The.@ethod
used.
ti:ths,~ep,ent.,ti.o~~
su~stttuted.the
lessexpensive
methyl
bromide
formethyliodide
inthemethylation
ofco~rci$%l
2j4-d@th$l-~-penbnorle
.’” ~ ‘{fi.:~..~:’
-:’‘“”’
“:‘ ..
““’:
‘:””.”.
.,.,.
....
.,..,
,.....
.,.:
. .......,.
..
..... . ......
.....
. .,~...
..‘ ,,,.. ‘.,
,Seviiral.dubs
ofvmioW~Mzeswe%et@ddm&
’t H8&e
Stitsare”
S~“’
marized
in-the
fdllowttig
table:
‘“““i ‘~“.’~~t
““’-~
:; “’”’.
“-“
36
~ACATNNo.1247
.,
MIWHYLATION
OF2,b-DIMETHYL-3”~PENTANO~
,.
,.
Yield of 2,2,4.
trfmethyl-3lethylattng
“2,4
-DimetbylPotassiti
Temperatti&
Duraticmpentanonel
3-pentanone
hydroxide
agent
(percent)
(h)
(moles) “
(moles) (moles) (Oc)
.
—
CH~I(105)
1.2
CH~)
4504(1
.5),
1.2
“s
CE#r (4) ‘“ ‘4,
3●
5
“ yey
12
C~Br (4)
k
‘ 12
CE3Br(k)
4
12
CHaBr(4)‘
4;
140,t0
160
7.0
55
~4a’to
160 .7.2
.
‘ 160*O170 6.0
0
140to150
9.1
390to2m” “11.7
6(CaO)190to200
8.0
35
15
35,
0
CH~r (47.7) . 39.6
120
“200to215 .8,0 i
57
CH3Br(47.7]
3906
120
“ 10,0
l~,to200’
54
CH~Br(47.?)
39.6
120
s
.
. 200tO230
8.0
%asedon2,4-dhet~l-3-yentanone
consumed.
47
‘—
“
.
Thesereactions
werecarried
outinhydrogenat~pnb
ombs. Thebomb
waschilled
by solidcarbon
dioxide
andcharged
withthe,
reactants,
then
sealed
andhe~ted
tothetemperature
indicated.
“Since
therdaction.is
exothemnfc,
it.was”’found
d~fficul.tto,hold
a predetermined
narrow
’temperaturerange.(Theoperation
could
“probab~~
bem@e:moreefficient
by
pwqpin~
themethyl.
’bromide
intothereaction
vessel
asitisconsumed
by
ther6actiti
inorder..to,obtain
morestable
reaction
conditions.)
When
thereaction
*S complete
thebdmbwascoolti”
endthe.contentm,washed
..well
with~terj.
dried,
endfractionated.
Tn’ofieexperiment
an’attempt
was madetodistill
theresidue
(247gramB).Itwasfoundtocontain
lachrynatary:.materials.,
butlittle,
ifany;2,2,4’,4-t6tramethyl-3pentaaone,
Noneofthiscompound
wasfoundbjNofinany.of
hismethyla,,
tionproducts.
>
-penta%rie
\2) Preparation
’of2,2,4,4-tetrametyhyl-3
Whilethopreparation
of2,2j4-trimethyl-3-pentenone
‘was
inprogress,
a nowendsimpler
method
forswthesizing
2,2,4j4-tetr=t~l-3-Pent~one
wasdescribed
byBartlett
andSchneider!
(Seereference
23.) Thisnew
procedure
eliminated
entirely
thenecessity
ofusin~sodium
emideinthe
,
.
.
NACATNNo.12b7
37
synthesis.
TheBartlett
andSchneider
reaction
involvod
interaction
betweent=butyl
ghlo~ide,
methyltr~tl@acotate$
andsodium
sandto give
,amixtureof2,2,4,4-tetramethyl:3-yentmncmq”
and:
2,2,4j4’-tetramethyl-3
,,
.:,.
,,
,... r
pentariol.
as,major
proiiucts.
.
>.- :, ,.
“.
., “..
,.
Several
emall~scale
rtis(1.6 toz?;(3
molds)
ofthisreaction
were.
made.Therewasno appreciable
difference
~ntheyields
ofditertiarylnztyl.
compounds
fromreactions
’inwhich:technical
isoocttie
(2,2,ktrimethyl~entene)
wasusedasa solvent
andthoseinwhichisopehtane
wasused.Sincetheformer
solvent
isconsidered
safer,
itwasusedin
themajority
ofthetrialtis andintheIarg@-Scale
run. Slightly
larger
(2to5 percent)’yields
werecbtafned-when
sodium
sand’was
used
rather
thensodium
wird.Innoneofthesmill-scale
runsdidtheyield
of.oombined
ditertiary-butyl
cornpo~ds”dficebd
53percent~(Bartlett
andSchneider
report
ytelde.up
to71p@cent,)
“Afterthetechnique
for
handling
thisreaction
hadbeensuffiofently
developed,
a largerunwas
mafle
inthestainless-steel
kettle~
(a)Methyltrimethylacetate
,,
*
*
.
Tok solut~on
of 53 kilograms
(177moles)
of sodimhdfchromate
dihydrate
(technical)
in98 liters
ofwaterintheglas~-llned
reactor
was
added39.9liters
ofconcentrated
sulfuric
acid.The’soltitfon
washeated
to 82°C and6.6kilograms
(59moles)
of’
2,&,k-trimethyl-2-pentene
(97
percent
pnre)wasaddedovera period
of5 hours.Therateofaddition
wasre@ated sothatth~temperature
of.tho’mixture
dtd-not
“e%ceetl
88°C.
~henabout3 ltters
ofmethyl
alcohol
wasaddedtousetheiexcese
dichroute,andthemixture
wassubjected
to steamdistillation.
There’
were.obtainpd
5.76kilogrsms
oforganic
layer”
andabout30 l-fterb
ofaqu”~us””
layer.Theaqueous
layerytelded,
ondistillation;
anadditiional
0.82
ktlogrsm
oforganic
material..
Thecrudeproduct
wasdistilled
tnCol-unns4 and5, andyielded
3.93kilo@amso? trfmethyl
acetic
actd”
(b-p.
160°to165°C]65.0 percent
yie~d).17ie
metlqvl
e=terof trimethylacetic
soldwasprepared
fntheususlmanner
by”refluxlng
a solutioh
ofthe’“’
acidinflmethyl
alcohol.
Sulfuric
aci~wasused:
asthecatalyst.... “
. .
:.
,
(b)2,~,
$,4-Tetrao~l-3-@entiaone
“ ‘ ,+~
v
.
.
Sodium
SS..Il&,
from6.!3kflogmme(300moles)
of sodiun”was.
prepared
tmder.toluene
(22 llters)
intheusualmsnner.Themixture
wascooled
to3.5°
C end16liters
O* technical
isooctsne
(2,2,4-trhWlylpentane)
and16kilogrsms
(173moles)
of t-butylcMoride
were~dded.
.Afterthe
reaoticm
wasinitiated
by the-addition
of’a smallquantity
ofester,
the
remainder
(total
7.98kg,69.5w@e&) *S addedduring-h
hours,
wMlo
~$he@nperature
wasmalntaintid
titX* to’kOO
C. ~tirring
wascontlntied
,,for
5 hours,
thenthff
mixture
~s allowed
“h standoveinight.
Theproductwaswor~ea
UQ In.the
menher
desc~ibd
byllartlstt
endSchneider
in
reference
23. Distillation”gave
2.57kilc@am6(18.lmo~es)
of~2~2,bjk-
“38
I?ACA’@
No,1247”
0 to156.00
c),666~emq of intertetramethyl3-pentanone
(b.p.151.5
mediate,
:mi 2.72‘ktlogrsms
(18.9
moles)
of2,2,4,
k-tetrtiethyl*3
-pentenol
(b,.p.
1670to173°c)..Including
the?.ntenmdlatef
thiBrepresents
a
yieldofapproximately
61percent,
basedonmethyl
trimethykcotate*
.
-
Thecar’binol
fraction
md theInter.aediate
containing
carbinol
were
combined
andoxidized
intwobatches.Xn eachbatch1.36kilograms’
(9.45
moles)’
ofcarbinol
and333gramsof Intermediate
weresuspended
in
a solution
of1275gremsof sodimnd
ichromate’d
ihydrafie
in1170ml of
water.
-Whilethereaction
tiixture
washeldat45°to”60°
C, a solution
of2300ml concentrated
sulfuric
ac}din2170ml o’f
titerwasaddd d~Ing2 days,afterwhichthereaction
mixture
wasstirred
andheated
to
500C’for1 day, Theorganic
material
wasthensteamdistilled,
dried,
andf’raotionateil,
ThereWs obtained
1.35 kilograms
(9.72
moles)
of
ketone
(b.p.151°to 154°C; 78 percent
yield).
In thesamemenner,
allthe2,2,4,h-tetramethyl-3-pentanol
obtained
h theseveral
preliminary
runswasoxidfzed
toketone,
andallthe
ketone
fromtheseveral
sources,
wascombined.
Thisinclufled
a small
(Seereference
24.)
amount
prepared
by theHaller~Bauer
reactton.
(c)Preparation
anddehydration
of2,2,3,4,4pentamethyl-3pentanol
*
The ,pentsmethylpentanol
wasprepared
inthemanner
altieady
described, .
mom 6*96kilograms
(49.c
moles)
of2,24j4-tetremethyl-3-pentdnone
there
wasobtained
4.84kilograms
(30,6
moles
pentemethyl-3-pentanol
~ of2~2,3,4,4“ (62.6percent
yield).Dehydraticm
ofthecarbinol
wascaused
by rsfl~ing
withiodine.’
~ a trim run,332w+ (1.98
ti1es]
ofcarbinol
was
2 hours,
93percent
ofthetheoboiled
with3.3grsmscf”
iodine.During
The,
organic
layer
retical
quantity
CNwahr’”was
eliminated
endcollected.
waswashed
w~thmtinm.thios~dfate
solution
endwithwater,
dried,
and
distilled
inColunl
17. ~~ec~mrge
was246“~ams.Thedeccpfracticns
(b.p.
145°-to 158.9°C)weighed
216.6gram (1.54 moles;
78 percent).
Analysis
of thedistillation’
curveshcwed
thatthesefractions
consisted
ofequalpintsofthetwoisomrs,3,3,-dlmet~l-2-t-butyl-l-hutene
end
Treatment
ofthemainportion
cfthe
2,3,3,4,4-pentaethyl-l-pentene.
carbinol
forthepreparation
ofthepentemethylpemtsnes
followed
theprocedure
already
described. “ :
.,
,,
.’
2,2,5,5-Tetremethylhe%ane
and2,2,b,5-Tetn%unethylhexane
,!
..
Thesynt~esis
of2,2,5~5md 2;2,~X5-tetramethylhexenes
wasaccora‘~
pltshecl
%y thefallowing
reactions:
(a)‘oxidation
of2,4,4
-trimethyl,-l,,,
pentene
to4,&-dimethyl-2-pentanon6
‘(methyl
qeopentyl
ketone),
(b)6Aida~
tlonofthisketone
tot-lnrtyhc’e’tic
acid,(c)conversjiofi
”of,the
‘acfd
to
.
methyl.
t-butylaceta%e~
:(d)
“.heaction
oftheester
with”t-.bu~ytignes!um
,.,
,.
..;
,.,
f
!.
,..,
.:
m
,
NACATNNO.Z247
39
ohloride
togive2,2,5,5
-tetramethyl-3-hoxanol~
(e)de~~ati.on
of’
tie
carbfnol
to a mixture
of2,2,5,5-tetrme?~l:3-hexone~
2~3~5~5-tetramethyl-2-hexene,
and2,3,5,[email protected]~
~fi~
(f)hYdro=~tfon
ofthe?irst-nemed
alkene
to2,2,5j5-tetremethy~hex~e
~d of fielast
MO alkenes
to2,2,4,5-tetramethylh6xexleP
Oxldatlonof
2,4,4.-trimethyl-l-pentene.The”
oxidation
of2,4,4trimethyl-1-pentene
wascarried
outessentially
inthemannerdisclosed
byllhitmore,
Eomeyer,
emlTrent-ti”ief6renoe
15. Several
runsweretie
usingolefinof~-percent
orhigher
pwcity.(Theisolation
ofthis
oleffn
isdescribed
later.)In a typical
run,101molesofallsene
was
oxidized
during
10dayswithsodium
dichronhtq
by theslowaddition
of
snlfuric
acid.There,were
obtained
180Qgramsofacidic
material
end
9360XL ofneutral
otlwhichupondistillation
inColumn
3;gnve2154
“mlofforerun,
4150grams(3~.4
nnles)
4,4-dimethyl-2-pentencme
(bopk
“This
yfeldofketone
isequiv1$23°
to1.26°
C),= 2000@ a$ residue.
~ent to36percent
ofthetheoretical
amount.The‘aoidfc
material
was
foundtobe a complex
mixture
contain$rig
onlyminorquantities
oftrimethyl~et~c
sndt-lmtylacettc
acid,.
andwasnotfurther
investigated.
Oxidation
oftmethylneove-ntyl
ketone-Thehypohalite
oxidation
of
themet,hyhieopsntyl
ketone
to~:bntyhcetic
acidwasaccompl.ished”by
a
modification
ofthereaction
disclosed
in,
reference
15.There,sc@ium”
hypobromlte
(prepared
frombromine
andsodiwn
hydroxide)
wasusedywhile
inthepresent
work’
the.less
expensfve,
co-rci~~ avatl~ble
c~Oi~ ~
small
”preliminsry
runsweremadeto’‘
hY?W~orftewasused.Sever.@.
develop
familiarity
~%h thqreacttoh
before
a largemm wa~mder.taken.
.
Tbe&,.,
@rge runswere
mad?,oneofwhichis4descrtbed.
“A’solukia.of
Z4.Okflogrbsoftechg~dal
stilti”~ydroxidivti
38
Iitors’of
waterwasprepared,
Tht8.solution
wascooled
to19°C,andto
itwereadded.about
90kilograms
ofcracked
Iceand13tiogr@ms.
of.commercial
cslcfwn
hypoc’hlorite
70#percent
chlorine).
Thetemperature
wasthe~added
thereby”obtafned
wasabout-k& C. Theketone(50moles)
during
~liours.
Thetemperature
ofthereaction
mixture
remained.
below‘‘
+5°C during
thisaddition.
An additional
25kilogremm
ofcracked
ice ,,
wasaddetl
andthemixture
‘stirred
fop10,houm,afterwhiohitwas
heated
to”65°
to70°C for5,hours.
Aftercooling
themixture
to20°C,
19.7liters-of
sulfurtc
tiidwasaddedslowly
andtheproducts
steam
distilled.
Thecrudeproduct’
wasd~stilled
in several
batches
froma
3.-liter
Claisori
flask.Therewasobtained
4070’grsms
(3103
moles;
63-“
percent)
of~cid’colleoted
between
lti”andlgO°C. No further
purif~-~ ‘“
i
cation
of theacidwasmade* .
.
Conve&sion
oft-butylacetic
acfd.to
methyl
t-butylacetate.The.
methyl
ester of t-butylacbtics~id
wasude intheorthodox
manner.’.
In
a tfiioal
~,:a solutionof
4140grams(35.7
melee)
~~.midand300d
‘
ofoonoentratOd
e~f~lc atitd
in10liters
{270moles].
of’methanol
was
40
NACATNNo.1247 ‘
heated
tor6fluX
fortwoperiods
of7 hourseach.Thecrudeproduct
obtained
was’
distilled
inColumn
5 andgave356ograms(27.4
moles;
76.7
percent)
ofester,
whichwascollected
at125°$01270C.
Preparation
of2,2,’5,
5-tetremethyl-3
-hexanol.Thepreparation
of
2,2,5,5-tetremethyl-3-hoxanol
wascarrie~
outb~theuseofthereaction
described
byMoersch”
(reference
31)whichisenadaptation
ofthatused
by .Heyd
(referenoe
32). ““
,.
TO theGri&nard
reagent
prepared
from326grsmatomsof,magnesium
and325molesoft-lxxtyl
chloride,
therewaeadded68Yj grems(52.4
mixture
moles)
ofmethyl
t-butylacetate
dtiing
8 hours.Thereaction
wasrefluxed
7 hourseachdayfor3 daysandallowed
to stendeach~iglit.
Decomposition
wascaused
by d~l.nte
sulfuric acid(17kgconcentrated
aoidand20kgwaterandice).The”
product”was
steamdistilled,
endthe
aqueous
layerextrmted
withether.Theorganic
layers
werecbmbined
andtheether
removed
inColumnF1l.
Theresidue’
was redistilled
inCol-’
uans24tid7,yielding
65o7gramsofcarbinol
collected
at166°to
170°C..This’is
equimlent
to41.2’moles
or79percent
yield.Moersch
reported
@ percent
yield(reference
31).
Dehydration
of2,2,5,’5
-tetramdthyl-3-hexanol.Threepreliminary
——
experiments
weremadeonthedehydration
ofthiscarbinol
andontherearrangement
oftheresulting
olefins.
Inone
grams(0”.70
mole)
ofcarbinol was-passed
over256grams(330ml.)
of altina (B*er Wdr+O~
lot 91942)at 300°to”305°C attherate’of47
gramsperhour.T“ecatalysttubewas‘2.5
centimeters
indismeter.
Thewaterrecovered
emounted
to10.8mI(0.6mole;86percent].
The prductwasdrie~endfractionatedinColumn
17. Theyieldofdecenes
amounted
to70percent
(78percentonbasisofcarbinol
consumad),
andcon~isted
of 34,5molepercent
2,2,’j,5-tetramethyl-~-hekene,
35.2percent
2,3,5,5-tetremethyl-l-hexene~
end30.2percent
2,3,5,5-tetramethyl-2-hexene.
2W1’lj
117
i18gramsofcarblnol
wasdehydrated
under‘ L
Inanother
experiment,
thesameconditions,
except-that
theratewas98 gramsperhour.~
thiscase,a yieldof46percent
olefin8’’(73
percent
on basis ofcarbinol
consmed)
wasobtained,
Themixture
ofolefins
contained
34.8 percent
,
2,2,5,5-tetramethyl-3-hoxene,
42.opercent”2,3,5,5-tetrsmethyl-l-hexene,
and23.2percent
2,3,5,5-tetramethyl-2-hexene.
.
To determine
theextent
ofrearrem~exaent
‘ofthe‘clefIns,
a mixture
ofdecenbs
waspassed
overthecatalyst
“at30@oto310°C attherateof
44grsmsperhour.Analysis
oftheresultant
mixture
showed
thatthe
.
original
mixture
wasisomerlzed
asfollows:2)2,5,5-tetmmethyl-3-hexenej
from13.5percent
to16.8 percent;
2,3j5,5-tetrami@yl-l~hexene;
from
46.2pe%cent
to 31.2percent;
2,3,5j5-tetrsmethyl~2-hexene,
frcm40.O
‘ .
percent
to52.0 percent?
‘‘i
.
,.
,.
NACATNNo.1247
41
Inthemanner
usedinthe
Thebulkd’thecarbincit
wasdehydre.te?l
inColfirstexmriment.Theresultant
nlixture
wasdriedanddtatilled
mn 5. fiecarbinol
recovered
wasrecycled
fordehydration.
~ this
way,4999gramsofcrudeolefinmtxture
wasobtained
(86.6
percent
yield).
Thfsmixture
wasseparated
roughly
inColum5 Intoconcefitrates
boiling
121°to12P C, 239°to145°C,andZ52°to1580C,sndintermediate
fractions.
A sample
(~ d) ofeqchhydrocarbon
wasredistilled
inColTheimpure
fractions
fromeaoh
umn17forpreparation
ofpurecanpounds.
ofthesedistillations
werereturned
to theappropriate
concentrate.
Theseolefins
havebeenidentified
previously.
(Seerete~nces
31anti
32.-)”
Eydrogenatfon.EqOhoftheolefin
concentrates
“was
hydrogenated .
?Xelast“%wo
olefin
conseparately,
EMwasthe”
combined
intermediate.
centrates
gavethe“isme
paraffin
andwerecombtned
fordistillation?
Purification
ofbothparafftns
wasaccomplished
in~ol~ 18. Thebest
500ml samples
fromeaoh,
distillation
wereredistilled
inColumn
17,end
physical
const~tsweremeasured
onthebestssmplqs
fromthesedistilla.,
tions. .
,.
..
“.
,,.
.“
..
,-.’
22213,3-Tetrmt~Uexane
‘;.,
.’,
Thishydrocarbon,
whtchwassynthesized
atPennsylv~ia
StateCollege,
~en received,
thesample
(2gel)
waspurifted
in~ese Iabaratories.
contained
chlorides
whichwereremoved
byboiling
withalcoholic
“alkeli.
Theproduct
waswashed,
dried,
and”fractionated
in”CoWMns
19.sn&
20. The
bestportion
fromoneofthesedistillations
wasrefractio~ted
inColumn ~~:
17. Physical
c~stants
were’determ@ed
onthebestfractions
fromthis
distillation.‘
,.,
I
.,
,..
,
*3,3,4,4-TetrmtMWexme
.“’
Themethorl
0$prqparat16n
ofthfsdeckne
is ~imilar
to thatusesin
thepreparation
of2,2j3j3-tetmmethylpentsne,
&nil
involved
thereaction
.“::
between
ethylmagnesium
chloride
end2,3,3-trimethyl-2-chloropentane.
.
2,3,3-trimethyl-l~pentene
(b*P_1080340 ‘ ,
In theexploratory
synthesis
to1.08.400
C,nD20=1.4170
4 wasconverted
to1.172)
tothechloride,
2,3,3-trimethyl-2-chloropentene,
by react;on
withdry~drogenchloride
at -30°C. Theproduct
wasfractionated
inColmnu
4. Theforeruofun- “ - .
chsnged
olefin
wasused”fn
thepreparation
of“more
chloriae.
Thechloride
usedinthecoupling
reaction
wasthatoollbcted
between
81°and82°C at
!57millimeters
ofmercuryo
,,
theGrignard
solution
prepared
from10grm at- ofqest~
‘,
and10molesofethyl
%rcmide,
therewas.
added,”
tluring
7 days,903m@es
(1382grsm)of thechloride
.-On thetwelfth
@ themixtuxe-was
worked
up. Theetherwap,
removed
from%heorganic
layerandtheresidue
refluxed
6 hourswithalcoholfc
alkali
(10percent
~H) to retive
ohloridesg
cThe
TO
.
42
NACATNNo.1247
washed,
dried,
chloride-free
material
wasdistilled
inColumn
27. A
largerunofthepreparation
ofthislxydrocarbon
isinnro~ess,From
thisruna considera~ly
purercompoundisexpected..
2,3-Dimethyl-l-Butene
and2,3-Dimethyl2-Butene
Thepreparation
andproperties
of 2,3-dimethyl-2-bntene
8.nd
2,3dimethyl-1-butene
havebeenreported
previously
inreference
7. While
the2,3-dhethyl-l-butene
reported
wasrelatively
pure,the‘2,3-dimethyl2-butene
wasdecidedly
@me. Theboiling
mng’eofthebestsample
of
%helatter
W8,S
a?)o~t
O.kOC, evenafterrepeated
fractionation
whereas
otherhydrocarbon
prepsred
andreported
Inthesenepaperhadboiling
ranges
oflessthanO.O1°C. Thewideboiling
rangehasbeenattributed
tothepresence
ofperoxides
inthesample.Thistendency
toformperoxidesismuchmorepronounced
in the2,~-dlmethyl-2-butene
theninthe
oneisomer.Sincebothalkenes
result
fromthesamereaction,
thestudy
ofbothcompounds
wasrepeated.
Themethod
ofpreparing
thealkenes
was
dehydration
of2,3-dhethyl-2-butanol
bymeansof iodine.Thecarbinol
wasprepared
by actfon
ofmethylmagnesium
bromide
onmethyl
isobutyrate.
Several
batches
ofmethyl
isohrtyrate
weremade,ineachofwhich
Xmoles ofmethanol
and30molesof isobutyric
acidwerere??luxed
for
6 to 8hourswith15ml ofconcentrated
sulfuric
acid.Theprsduct
was
recovered
by adding
water,
extracting
theunchanged
acidby sodium
carbonate
solution,
andsaturating
theaqueous
layerwithselttorecover
unused
alcohol
anddissolved
ester.Thecombined,
nonacidic
orgsnic
layerwasdfstilled
inColumns
3,.4,5, and6. Onlyconstant-boiling
(~O.l°
C)materia3.
wasreserved
forsubsequent
steps.Theyleldamounted
to71percent
ofthetheoretical
basedonoriginal
isobutyric
acid.
Ina typical.
runofthepreparation
of2,3-diruethyl-2-lmtanol
42
molesofmethyl
isohutyrate
wasaddedtogomolesofmethylmagnesium
bromidein12hours.Af’ter
thereaction
mixture
hadbeenallowed
to stsnd
for15hours,
itwaswarmed
forh hoursendthentreated
withiceand
dilute
hydrochloric
acid.Theorganic
material
wasdriedenddistilled
inColumn
6. Afteretherandunchanged
esterhadbeenremoved,
thocarbinolwasdistilled
at76.40to76.6oc at152millimeters
ofmercury.
Theyieldwas3120grams(73percent,
basedonester),
Thedehydration
of2,3-dimethyl.-2-butsnol
wasaccomplished
byheatingitwith1 gremofiodtne
perliterofcarbinol,
Theolefinic
materialthereby
obtained
wasroughly
separated
inColumn
4 andconsisted
of
approxlmekely
threepartsof2,3-dtmethyl-2-butene
andonepartof2,3dimethyl-2-%utone.
Theresidue
frm”thisdistillation
consisted
ofvm.ohsnged
carbinol
whichhadsteamdistilled
during
thedehydrattnn
step,
Thiscerblnol
wasreturned
to thedehydration
process
as ftaccumulated.
In thisway,a practically
quantitative
yieldofalkenes
wasobtained.
.
43
.
l?ACA
TNNo.12~7
.
Twocharges
ofcrude2,3-dtmethyl-2-lxrkne
werefractionated
inColmn 1. Themiddle
cutsfromthesedfstilllations,
theRracticms
ofwhich
hada constent
~efractive
hdex (~,00005),
werecabined,andamounted
to3.6liters
ofmaterial..
The”2,3-dimethyl-l-butene
wasfractionated
in
likemanner,
a@ 3.5lfters
ofmaterial
wasobtained.
Thetwohydrocarbonswerethen,subdected
tod~still.atlon
tnColumn
5 underconditions
dest~edtodestroy
anyperoxides
present
andtopre,vent
theirformation
in
thedistillate.
Thiswase.ccomplished
byadd.i~hydroquinone
tothedisti~ationcharge
andby keeping
thecolunn,
take-off,
anddelivery
systems
flushed
withnitrogen.
Tnthisw~v,thirty-three
100-ml
fraotions
of each
hydrocarbon
wereobtainel.
For~easurhgthephysical
properties
oftheseolefins
thesameapparatusandmsthods
previously
describe~
wereused,hutcarewasexercl.sed
toflisplace
airintheapparatus
withnitrogen
’during
thedeterminations.
“
Refractive
indices
weremeasnred
intheusualmanner.Peroxide
numbers
(moles
ofactive
oxygen
in1000liters
of solution)
weredeterminedly
themethod
ofYuleandWilson(reference
33).
For2,3-dtiethyl-l-butene,
fraction
17wasusedfordetermination
of
refractive
Indexanddensity.Theperoxide
nuniber
ofthisfraction
was
0.03.Measurements
of%oiling
points
ofthisolefin
weremadewithfractmns 16end3.9.Thedistillate
fromthesedeterminations
contafned
en
P
unmmsurably
smallamount
ofpe~oxide.
Thefreezing
pointof2 3dlmethyl-2-tiutene
~s madeon fraoticm
17 (0.07peroxide
number
~.
Refractive-fndex
anddensity
measurements
weremadeonfraction
21 (0.03
peroxide
number),
endboiling-point
measurements
onfractions
18, 19, end
20 (0.04 to 0.06 peroxide
number).Themeasured
values
oftheproperties
aregiven h table20
.
.
Considerable
difference
ofopinion
exists
regtiding
thefreezing
pointof21,3-dimethyl-l-butene.
Schurman
endBoord(refe~ence
34)report
a ‘*melt@pointof -120°to -123°
C cnmaterial
having
a boiling
range
ofo,4~c. Brooks,
Howard,
andCrafton
(reference
5) report
a freezing
poinkof -lb.l,”
C!on.asample
ofhighpurity
which,
however,
mdoubtedly
containdd
someperoxide.”
Kiatiakowsky
.mxlcoworkeri
(refm?ence
35);
usinga eample
having
a boiling
remge”of
O.O1°C foruseindetermining
theheatofhydrogenation,’
reportetl
thatthematertal
congealed
tod glass
atlowtemperatures.
Twoattempts
yeremadeinthisworktofreeze
sampleswhichwereperoxide-free,
but.both
wereUnsuccessfti.
An attempt
to
freeze
sampleq
recovered
fromtheboiling-point
distillates,
whichhad
beenexposed
toalrfor2 weeksalsofailed.Attempts
weremadeto freeze
samples
containing
smallsmcmnts
of2,2,k-trimethylpentanej
thopestiples
containing
0.58en~2;4molepercent
ofthisimpurity
~alledtofreeze.
Onessmple
containing
1.43molepercent
2,2,4-trimetl@pentane
gavean
indefinite
freezfng
pointat -145.4°
C. Thisvalueseemsto substantiate
theprevious
velueof -140.1°
C (reference
5) end.
wouldindicate
a very
lowheatoffusion,
whichmaybe-acontroll~ng’fac%or
inthedetermination
ofthefreezing
point.
..-.
.’
f
44
NACATN NO. 1247
Thepresence
ofperoxides
caused
a marked
change
l-n
theboiling
men s~p].es
ofpure2,3-Rimethyl-l-butene
ranges
of theseolefins.
weredistilled
inthetoiling-point
apparatus,
theobserved
temperature
changes
(from20to &)percent
distilled)
were less than 0.004° C. The
samematerial,
afterexposure
toair for2 monthsshowed
a distillation
istheeffect
rsmge(20to,@percent)
of0,11°C. Stillmorep~tonounce~
Ssmples
containing
a smallquanofperoxides
on2~3-dtmefhyl~2-butene.
tityofperoxide
(peroxide
nraober
0.04)distilled
overa rsngoof
hadaccumulated
peroxides
for
0.007°
C orless,butafterthismaterisl
10daysthedistillation
rangewasfoundtobe1.03°C.
Tn ordertodetermine
the.rate
ofperoxide
fomuatfon
undernormal
laboratory
conditions,
samples
of purified
alkenes
wereallowed
to stand
portions
were
atroomtemperature
incontact
withair- Periodically,
Theresults of these enalyses are
tithdrawn.and
analyzed
forperoxides.
given in figures
3 andh. Thegreatdlfferencein
ratesofperoxide
formation
in thetwocompounds
maybe seeninthecomparison
giveninfigure3.
3-Methyl-2
-Pen~ene
(cisandtrsns)
,.
Thetwogeometric
isomers
of 3-methyl-2-pentine
wereprep~edbY
whichwasformed
by action of ethyldehydration
of3-methyl-3-pentenol,
magnesium’
chlorlde
on2-butanone.
To 53.8molesofethylmagnesium
chloride
wasadded55.8molesof2(b.p.75° to&)”C
tmtsmone
in5 liters
ofether.Theyieldofcarbinol
Thecarbinol
wasdehyat142mm IQ)was40percent
ofthetheoretical,
drated
withP-naphthalene
sulfonic
acidtoyielda mixture
ofol.efins.
A
driedolefin
mixture
wasfractionated
in
charge
of2240ml ofthewashed,
Columm
2,whichgave24oml ofthe.lower-boiling
(cis?)
and960ml ofthe
Physical
.constents
weremeasured
onthe
higher-boiling
(trsns?)
isomers.
ofthedistillation
curveshowed
bestsemples
ofeachiscmer.Analysis
thattheorigtnal
mixture
contained
26percent
(by’
volume)
oftholoworboiling
and74percent
ofthehigher-boiling
forms.
Theidentification
ofthesetwoolefins
ascisandtrans3-metlzyl2-pentene,
rather
thantheiso~ers
3-met~Vl-2-pentene
and2-ethyl-lbutene,
isbasedprinmvily
onmassspectrometer
studies.
Thetwopatternsformed
by analysis
ofthecorQpounds
ob~afned
ar~verynearly
identical.No thirdcomponent
wasisolated
fromthedistillation,
although
itisprobable
thatonewaspresent
insmqllquantity.
.
.
liwe~tigation
ofDiisobutylene
,.
R wasnecessary
toisolate
l.~gequamtities”of
thetwodiisolmtylenosj2,4,k-trhethyl-l-penteno
and2,4,4-trimethyl-2-pentene,
inorder
toprovide
samples
forengines
tud~esandforthesyntheses
of4,41
NACATNNo.1247
.
45
oxidation,
Forthis
dimethyl-2-psntanone
andtrimethylaoetic
aoitt%y
Purpose,
a considerable
quantity
(k50liters) of thecmrctal mixture
wasaystematloslly
fra0ti0natf3d.
Theoriginal
nmterial
wasseparated
intofive“cuts”
orconcentrates
ofthelimlted
potcapacity,
it
byfractionation
inColumn
11. Because
cuts
wasnecessary
toperform
thisoperation
inbatches.Corresponding
fromeachbatohwerecombined.
Thedataonthesedistillatims
aresummarized
intable40
:,
a smallquantity
CutA (forerun)
comprised
anazeotrope
containing
“of2,4-4-trimethyl-l-pentene
withlmtylalcohol,
alongwithotherpoler
compounds.
Thiscutwasnotextensively
investigated.
,
CutC (58 llters),
theintemnediate
between
cutsB eadD,wasrefractionated
inColcdmn
11toyielil
34liters
of2,k,4-trimethyl-l-pentene
whichwascombined
withcutB, 14ltters
of intermediate whichwasnot
further
investigated,
and9 liters
Gfresidue
whichwasaddedtocutD.
Theaugmented
cutsB andD werethendesignated
as3-1,andD-1,respectively.
CutB-l(298liters)
wasfoundtobe about96.7 percent
pure2,4,4trtiet@l-1-pentenej
itsfreezing
pointwas-$J6.50
C. A 170-liter
porttonfromthemiddle
ofthfscutwasrefraotionated
inthreerum sad72
liters
ofpurified
2,k,4-trimethyl-l-pentene
wasobtained,
comprising
fraotions
withfreezing
points
intherange-93.59°
C to -93:57°
C.
Physical
constants
weremeasured
ononeofthefrac:ions
of -930550
C
material.
Theseconstants
agreewfththosereported
byTong%erg,
Pickens,
Fenske,
andllhitiore
(reference
36). Thiscompoundhas
%een
identifiedby
ozonolysis
byllhitmore
-andChurch
(reference
26).
.
.
-
Cut D-1(g5liters),
a concentrate
of2,4,4-trimethyl-2-pentene,
wasrefraotionated
intworpns.Fromthesedistillations,
therewasobtained
49.3liters
ofhighpurity
2,4,4-trimethyl-2-pentene,
composed
of
fractions
withfreezing
points
from-106.62°
to -106.5~C. A p~rtion
wasrefractionated
in.Column
1 forisolation
of a sample
forphysicalconstants
measurements.
Thiscor@ound
wasalsocharacterized
byTongberg
andothers
(reference
36),andidentified
byWhitmore
andChuroh(reference26).
.,
The”residue
fromdistillation
ofcutD-1was*fraotionated
inCol-,
umn1. Fromthisdistillation
therewereobtained
twoconcentrates,
designated
asD-2endD-3.
.
~. GutD-2(745ml,b.p.10608°
C,nD20= 1*4149
b 1.4152,
d = 0.7265)
wasprobably
an impure
sample
of2,3,4-trimethy~-~-pentene.
Kuykendal.1
(reference
37)obtained
the.
follgtiqg
pmggfi~es for fiis
~~
compo~d:b.p.106.7° tO 107.7Oc, W25 = 1.4146,d = 0.726.
46
IVACA
TN No, 12k7
.
CutD-3(tikml,b.p.198.0°
C,~20= 1.4162
tO1.4171,
d20= 0.733)
wasa complex
fixture
inwhich2,3,3-trimethyl-l-pentene
wasthepro’bable
ma$orcomponont.
Thispartial
identification
ismadeby a comparison,of
thephysical
pro’pertfes
ofcutD-3withthoseofthe2,3,3-trimethyl-lpentene
isolated
fromShellHot-Acid
Polymer,(Seenextsectdon.)
Since
onlysmallquantities
ofthesecuts(D-2andD-3)wereavailable,
no extensive
invef3tigation
wasmade,
onthem.
,4
CutE wascombined
withth.s
residue
fromthepreliminary
fraotionations.ThecomMnedmaterial
(27liters)
wasfractionated
inColumn
11,
andyielded
3.8liters
of 3,44-trimaWyl-2-pcmtene
(cisandtrans)
(b.p.
112.G0
to112.6°C,n 20= 1.~235,
d20= 0.739)
and4.’3
liters
of2,3,4trimethyl-2-pentene
(B.p.11$.1”
toD6.20C,nD20= 1.4275,
&QO= 0.7428).
TheEietwo compo~ds
wereidentified
by comparis~n
ofthefrphysical
properties
withthoseofpure3,h,.$-trimethyl-2-pentene
and2,3,4-trimdhyI2-penten.e.
Thepurecompounds
wereobtaineflhy
thedistillatiaa
analysis
ofShellHot,-Acid
Polymer
andby dimethyl-zinc
synthesis.
Partofthis
sample
of 3,4,4-trtiethyl-2-pentene
wasoxidized
topinacolone.
The~ntiresample
of2,3,k-trimethyl-2-ponteue
was droflenated
to2;3,k,#
~
trimethylpentane
(b.p.113.41°
C,nD20= 2;40%to1.4040)
An approximate
amlysisof th9 original
dilsolmtylene
(gas-free
basfs)
wasmadeby examination
ofthedistillation
curve”a.
Thismixture
wasfoundtocontain:
,:
,
.
2,4,4-trimethyl-l-pentene
~.~ percent
(Byvolume)
2,k,k-trimethyl-2-pentepe
,,
4:6
3,4,4-trimethyl-2-pentene
2,3,4-trimethyl-2-pentene
“a3.7
2,3,4-trimethyl-l-pentene)
2,3,3-trim&thyl-l-pentene
1.0
)
Othero~tene(s)
pol~ compouiids
2;0 ‘
‘Mvestigktion
ofHot-Acid,Polymer
(Shall
Oil(M&my)
(Unfinished
project)
Theinvestigation
ofHot-Acid
Polymer
wasundertaken
toisolate
and
purify
someofthemajorconstituents.
Thegeneral
method
ofoperation
wasthemm asthatusedintheinvestigation
of’diisolnztylenes,
butfor
thisworkmoreefficient,
higher-capacity
sttlls
(12, 13, 14, and16)
were available.
Atotal”of,1041
Ifters
ofcrudepolymer-was
mzbsected
toPreliminaq
frmtionation
infivebatches.Corresponding
cutsfromtheaeper~
m
.
.
.-
k7
NACA~.NO.1247
hatches
werecombined.
Tnthiswey,thepolymer
wasdivided
intofive
yortions.
Thedataonthesefracti~tio~s
tiegivenin table5.
investigated.
LikeCutA,whtchcontained
lnrtanol-2
wasnotfurther
wise,theresidue
hasnotleenstudied.
thefollowing
mateBy refiactionation
ofcutB,therewereisolated
rials:
CutB-l- 1C3liters,
2,h,4-trimethyl-l-pentene,
b.p.101.1°
to
lC1.3°
C/755mmHg,nD20=1.4084
to1.4086
CutB-2”-9.5ltters,
a mixture
ofclose-lm~ling
olefins,
b.p.
to1.4246
107.0°
to107.1°
c/756mmHg,nD = 1.4144
2,3,3-triuthy~-~-pentene,
~.p.108.oo
to
CutB-3 - 8.o liters,
108.I.o
C/753,nmJHgj
nD20= 1.4173
to1.4175
A considerable
amount
ofmaterial
between
B-1sndB-2hasnotyet
beeninvestigated.
Thisintermediate
contains
2Jk,h-trimethyl-2-pentene,
associated
withatleasttwoothercompounds
tithboiling
points
near
1050c.
.
.
CutB-2wasrefractionated.
.Thepresence
of several
campo.nnds
is
ofB-2MS hydrogenated.
indiqated
by thedistillation
data.A sample
hmlysisoftheproduct
showed.
tihe
preeence
ofabout30percent
2,2,3and70percent
,2,3,4-trtmethylpentanes.
CutB-3wasrefractionated
forisolation
ofa sample
suitable
for
A sample
of thismaterial
wasoxidized
physical-constants
measurements.
tomethyl
t-amyl
ketone(b.p.130.2f’
to131.2°
C,nD=o= 1.4201),
of
“ whichthe2,k-dinitrephenylhydrozone
meltedat111°.to1.12°
C. Hydrogenation ofa sfiple
yielded
2,3,~-trhethylpentane
(b.p.114.5°
C,
=
1.4073).
%20
.
Purification
byrefractio~tion
ofcutC gave100liters
of’
purified
3j4,4-trimethyl-2-pentene
(b.p.111.7°
to111.9°C/751
mmHg;nD20= 1.4231
Thebestssnple
fromthisfraction
wasused’to
determine
to1.4233).
thephysical
constants.
Thepresence
ofcisandtransisomers,
which
wereonlypartially
separated
by thefractitiation,
causes
thewideboilingrange.It isthought
thatthesample
reserved
forphysical-constants
measurements
contained
moreoftheh$@er-boiling
(trsns?)
isomer
themof
thelower-boiling
compound.
(Oxidation
,ofthis
;compound
by sodium
&ichromateproduced
pinacolone
in 30percent
yield.}
..
. .
.
NACATNNo.1247
48
.
ofI@ liters
ofcutD Gave45liters
of’
2,3,4Redisti~ation
trimethyl-2-pentene
(b.p.116@c/7s4mm
Hg, nD20=l.h271
tol.4272).
,.
“
Nationsl
Bureau
ofStandards,
Washington,
D.C.,July15,IP46
RE.EERENCES
.,
1.Brooks,
Donald
B.,Cleaton,
Robetta
B.,endCarter,
TrankR.:
Paraffin
H@rocarbons
Isolated
fromCrudeSynthettc
Isooctane
(2,2,
~+-Tfimethylpmrtane)
, Res.Paper1027,Nat.Bur.
ofStend@s
vol.19,Sept,1937,pp.,319-337.
Jour.
,Res~,
2.Howard,
FrankL.: Preparation
endSomePhysicsl
Properties
of2,2,4,4Tetammethylpentsne,
Nat.Bur&ofStandards
Jour,Re~.,:~li
24,
June1.940,
pp.677-684.
3.Brooks,
Donald
B.: Properties
ofPurified
Normsl
Heptene
exil
Isooctane
(2,2,
4-Trimethylpentane)
. Res.Paper1160,Nat.Eur.ofStandards
Jour,Roe.,vol. 2s,Dec.~938,pp.&7-@i2. .
.
4;Brooks,
Donald
B.,Howard,
FrankL.,aadCrafton,
HughC.,Jr.:
Fhysical
Properties
ofPurified
2,2,~-Trimethylpentane.
Res.Paper
PP.6371259,Nat.Bur.Of Standards
ifOLW.
T/es,,VO1. 23, Dec.194o,
64~.
5.Brooks,
Donald
B.,Howard,
FrankL.,endCrefton,
Hu@IC,,Jr.:
Physical
Properties
ofSomePurified
Aliphatic
Hydrocarbons.
Res.
Paper1271,.
Nat.Bur.ofStandards
Jour.Res.,‘vol.
24,Jan.1940,
Ppc33-450
6. Adkins,
Homer:Reactions
ofHydrogen.
Wniv.ofWis.Press,
1.940,
ch.3,pP.29-43.
7. Brunn,
Johannes
H.: Laboratory
Bubble-Cap
Colum6ofGlass.Ind.Eng,
Chem.,
Anal.cd.,’
VO1. 8,MRY1936,
pp.22b226.
8.Whitmore,
FrankC.,andLux,Albert
R.:,TheAbsence
ofReemengemont
oftheIsobutyl
Groupduring
theFormation
ofIsobutylaagneslum
Bromide
endItsRelation
totheTheory
ofRearrangements.
Jour.
Am.Chem,Sot.,vol.54, no.8, Aug.1932,pp.3448-345~.
B. J.: TheSynthesis,
Purification
andCertain
Physical.
Constants
oftheNormal
Hydrocarbons
framPentmetoDodecane,
ofnAmylBromide,
andofn-Nonyl
Bromi.de.
Nat.Bur,ofStandards
Jour.Res.,VO~. 9,Oct.1932,Pp.457-472.
.
9.Mair,
●
NACATNNo.124?
49
.
10.Whitmore,
FrankC.,andBaiknAxmher,
D.E.: TheYieldsofSomeKLiphatic
Tertiary
Gri@ardReagentE.
andtheLimits
ofTheir‘Usefulness
asSynthetic
Re~ents,Jour.Am.Chem.SOC.
j vol.55,no.k,AprQ
1934,~. 1539-1567.
11.Whi%nmre,
FrankC.,andFleminG,
George
H.: Preparatim
ofTetramethylmsthane
(I?eopentene)
andDetermination
ofItsPhysical
Constants
. Jour.Am.Chem.Sot.,vol.55,no.9,Sept.1.933,
pp.3&133806
●
12.
Hartman,
W. W.: MethylT.odide
fromMethyl
Sulfate.Collective
vol.
●
ed.;
j JohnWiley& Sons,Ihc.
IIofOrganic
Symthesee,
A. H.Blatt,
(NewYork,N. Y.)1943,pp.k04-405.
andEntro13. Aston,
JohnG,,andMesserly,
George
E.: HeatCapacities
TiesofOrganic
Compounds.
IT - Thermal
andVaporPressure
Datafor
Tetramethylomethane
from13.220
K totheBoiling
Point.TheEntropy
fromItsRomanSpectrum.
JOLIT.
Am.Chem.Sot.,vol.58,no.12,
Dec.1936,pp.2354-2361.
14.C13ne,
Edwazzd
Terry:TheSynthesis
ofTypeIITandTypeV Oleftns
fromDimethylbutadienemonohydrobrom15e...
OhioStateUniv.,
Ph.D.
Thesis,
1939.
15.WhitMore,
FrenkC!.,
Homeyer,
A. H.,andTrent,
W.R.: Tertiary
Butyl
Acetic
Acid,U. S.Patent
No,2,004,066,
Juneh,1935.
16. Whitmore,
FrankC.,andCook,Newell
C.: me Decomposition
of
Ozonides
withRaneyNickel.Jour.Am.Chem.Sot.,vol.63,no.12,
Dec.1941,p. 3540.
17.Whitmore,
FrankC.,andLanghlin,
of
Kenne*h
C.: TheDehydration
Tertdazz
Alcohols
Containing
a Neopentyl
System.II - Methylisoprbpyl-tert-butylcarbinol,
Methyldi-tert-butylcsrbinol,
andMethylethylneopentylc
arbinol.Jour.Am.Chem.Sot,,vol.55,no.9,
Seyt.1933,Pp.3732-3738.
18.Fawurskyj
AI.: tierdieEinwirkung
vonPhosphorhalogenverbindungen
aufketme,
BYomketme
undketon~kokole.
” Jour. Praktische
Chemie,
QO1. 88,Nov.1913,
pp.641-698.
.
.
19.~ihore, Frank C., ~u@lfn, Ke~eth C., ~tuszes~, JO~I F., @
ofOlefins.TX - T&eCopolysUYZUdis,J. D.: ThePolymerization
merization
of s-Butyl
emdt-Butyl
Alcohols
by Sulfuric
Acid.Jour
Am.Chem.Sot.,vol.63,no.3,March1941,pp.756-757.
●
~c Dinerstein,
Robert
Alvin:Synthesis
ofIsomeric
Nonanes
Employing
ZincAlkyls.2,2,4
j4-Tetramethy@entane,
2,3,3,4
-Tetremethylpentane.
Pennsylvania
StateCollege
Thesis,
1940.
50
NAC!A
TNNO.1247
.
22.,E&eart,Charles
of2,3,3,
h-Tetramethyll?entane*
.
R.: Z.TheSynthesis
11.TheSYmkhesls
of3,3-IMmethyl-l.-Chlorobutane.
IIT.Misce$laneouff.
Pennsylvania
StateCollege.
Ph.D.Thesis,
19~L2.
22 Young,
JohnD.: Highly-Branched
Ccmpounds.
Willtam
G.,andRoberts,
ThePreparation
ofTriisopropyl
Carblnol
andDiisopropyle-3utylcarbinole
Jour.Am.Chem.Sot.,vol.
66jno.9,Sept.
1944,
,,
pp.1444-1445.
●
23.Bartlett,
PaulD,,andSchneider,
Abraham:TheSynthesis
ofTri-tButylcarbtnol
andOtherHighly
Branched.
Alcohols
byMoansofSodium.
Jour.h. Chem.Sqc.,vol.6’1,
no.1,Jan.1945,pp.~k~-U4.
24,Hal.ler, A., sndBauer,
Ed.: Alcoylation
desc~tones
aliphatfques
par
ltintermediafre
deltsmidure
de sodium.Comp%es
Rend.us,
vol.150,
MarchI91o,pp.582-589.
F.W.: Sodium
Amide,Organic
S;mtheses,
VOIC20~
em Bergstrom,
C.F. H.Allen,
ed.jJohnWiley& Sons,Xnc.(NewYork,N.Y.)
1940,pp.86-91.
FrankC.,andChurch,
JemesM.: TheIsomers
of “Ditso26.Whitmore,
butylene.f’
111~ Determination
ofThe~rStructure.
Jour.Am.Chem
Sot.,vol.54, no.9, Sept.1932,pp.3710-3714.
:
.
.
R,,andSung,W.: “Penncme”
ouTltramethyl-2-2-3-327*Locquin,
Pentanone-4.
Comptee
Rendus;
vol.178,May1924,p,.
1179.
,.
28.Locquin,
R.,andSung,W.: Surla “pennone’t
outftramethyl-2-2-3-3pentancme-4.
Bulletln
de laSociete
Chemique
deFrance,
ser.~k,
vol.35, April1924,pp.753-7620
29 Whitmore,
FrankC.,Marker,
R.E.,andPlauibeck,
Louis,
Jr.: Studies
onHexamethylethane
andRelated
C~ounds. Jour.Am.Chem.Sot.,
vol.63, no. 6, June1941,Pp.1626-1630.
●
J.U,: ber dieAlkylkrung
derKetone.Justus
Llettigs
Annslen
w- IVef,
derChemie,
vol.310,11399,
PP.3~6-335a
31 Moersch,
George:Syhthetic
Aliphatic
Qydrocsrbons
ofNj.ne
toTwelve
Carbons.
Pennsylvania
StateCollege,
Ph.D.Thesis,
1942.
●
32.Eeyd,JosefWillt~:“A Studyof‘Compounds
Containing
a NeoCarbon.
Pennsylvania
StateCollege,
Ph.D.Thesis,
1937.
andGuminGasolfne.
andWilson,
C.P.,Jr.: Peroxides
33 Yule,J.A. C!.,
VO1.23, no. 11, NOV. 1931,
pp.1254-12~9,
Ind.Eng..Chem.,
!,.
.
●
●
T?ACA
TNEO.124’7
51
34. Schumsn,Ihan,snaBoord,
CecilE.: Syntheses
intheOlefin
Series
T - Com@et@ theSurvey
oftheEuxenes
andIncluding
Certain
Eeptenes
~a Octenes.Jour,Am.Chem.Sot.,VOI*55,no.12,Deco
1933,pp..493@4935.
.
35. Kistkkowdcy,
G.B.,Rvhoff,
JohnR.,%xlth,
Hilton
A.,andVau@an;
W.E.: EeatsofOrganic
Reactions.
IXI- H@rogenation
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Higher
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36. TonghergY
C.O.,Plckens,
J.D.,Fensks,
M.R.,andWhitmore,
FrenkC.:
l%eIsomers
of l~I)iiso’butylene
.t*II.Jour.Am.Chem.Sot.,vol.54,
no.9,Sept.1932,pp.3706-371o.
intheClc’cene
Seri~sj Octenes
of
37. Kuykendall,
Sidn.ey
Benson:Syntheses
TypeIII...OhioState~iv.,Ph.D.Thesis,
1935.
52
NACA TN No. 1247
TABIZ 1.-”
still
DBIIUATI
mlcommS
Size
w
2
603by4.0
Total
reflux,
illtamlttent
take-cm
.......do-------- (s00
tort)
3
Totel
4
------tlo
5
6
7
8
-------ao
--------150by 2.2
-------------150by2.2
do
-------do
--------q by2.2
-------do
-------- 70b~1.1
9
-------------h ~ 1.0
do
1
10
11
2*13
14
M5
17
18
9&20
-a
2t025
5tu27
Paoklng
(em)
reflnx,
m
m
2ooto
5000
150 ~
2.0
3/16-lnoh
glass
helloes
150 by
2.0
Doe
3&-kh steid.eies-eteel
helloos
frca
O.OIO-lmh
tire
--------------do---------------%.
.Do. ”
3/16-iuoh
glares
helloes
---------------do
---------------Do.
Do.
l/16-lnoh
fiohrme
helioea
*
%.
tire
O.OIO-tih
~able take-off
“
--------
3/16-hh
PYMX
helloes
PotOapaelty
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tire
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600
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1600
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rings, f ollowd b~ 1550
------do----.---1600
b~2.7
oentimetar
3/32-imh
mta?nleeneteel
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from
0.010
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wire
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m to5000
0.8 Kell-grlQ
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Dephlegnator
120 by 3.5
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glass
hellcea
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controlled
takeoff
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variable
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3/16-inah
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5000
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NATIONAL ADVISORY
COMMITTEE
FORAERONAUTICS
NACA TN No. 1247
53
TABLE
2 .- PHYSICAL
PROP2RTIE6
OF @XPOUHD
PREPAREO
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point
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o.7117s -o.mo76 1.4032i
0.011
0.70333
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;:%%
0.71792 :%
0.021
1.4123j
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0.037
0.73537
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0.73165 -0.UM75 1.b1321
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1.4366
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1.4326
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July l@K?
Julr 19b3
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-----October1*
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-0.OW* &w.lst19W
-0.0W47 Aneust1943
1.42%5 .O.OW* Au@St194i
1.41431 -o.om4e Oatobtr1941
1.4203 -0.0W46 Ju 1943
1.4351 -o.om4e Jn.lr1945
1.422* dW3m52 Julr 1945
;%
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1,4339 -o.ccdto :ti%;i&g
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0.039
0.30
0.s226
0.s243
~.om66
L41a6
1.4163
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2,3-rIica.b,Y2-&til
-20.4
0.037
0.042 0.8236
0.6193
----
---0.70
52.3-71.5
----
------
w w~
4.WX6
1.4170
1.4142
-o.Wm4
Ott.bm 1943
-----0.2354
o.a5gs
-----a.omeg
1. 52
1. z 39
----1.44i6
-----4.maw
Ju3r1943
J&r lgkl
-o.mcgl 1.4423 1.44J5 -o.0m47 J* 19’4J
-J.W025 1.4405 1.4WW -0.UW7 July 1941
-l&o
0.042
2,2-DidbYI-3-btbvh3-p8utiL
-19.0
0.05
1.55
0.2572 0.2526
2,2,3, 4-TetrnnetW->pf5hon.01
+12.a
o.&7
0.5
0.2.565 0.2523
2,kDimtb.yl-+iuapropyl+per,tar,l
2,2,3,4,h-tiOW-3-pd_l
2,2,4-5rinetby1-J-p
ezwwnO
2,2,4,M!~trnnethyl-3p9ntnnone
2tbrl !h-inotbylnmtate
-14.7
O.m
O.n
0.2632
+42.1
O.m
0.3s
-29.02
-25.24
-29.55
136.190
153.W
0.0425
0.0521
o.m7 o.eo654 o.tm2g -0.0W25 1.40596 1.433.s9 -0.WN12 Juu 1941
Jemary1944
0.010 o.82k09 0.s2227 -0.w076 1.41927 1.41712 -&mob
n2.35
3C:;:2:3..tiimtk@pmt=a
pl%thv,p.ntul.
Trimtulp-t~
2-obb_2,3,
-17.9
+10.G
---
0.C450
-----
0.061 0.s5467 0.3%52 4.032.03I
--------- 0.9066 -----0.9105 0.9365 -o.oam
------.------- 0,222
J-OhlOrc-2,3,4-TrinOthylpentone
}
l-ob10rc-2,
~n0thyl-&bubena
---
nfmzt
erl.22
1)---------
----
0.2543
0.
LW91*
-o. omqs
1.WO
1.4452
-o.cm43
Dmmbor1944
raw
-----
1.39062 Wsga
1.4441 -- . . . .
@l.57
1.W36
-----1.4Jt!
----b- ------1
-----------
-3Xde
------xlo043
------
1944
Juw 1941
Jn.lr 1942
Jnn*lqlq
1932
AIu$IBt
-. -.. . Kay194)
= Symboln:
becamevery Viecoueor @22+8ywitbout :reezing
Weznt
to a oryot~line aolidmnd, materimlocmidered too i
j-or-boiling
determination of free= w oint; U, aelting point; L.“W,t;
&eometrioiaomerjH.B.~. , ~i&ner-boiling geometric I,omer! C , mixture
of geometrioioomers.
b
seerererenoa5.
0
See refermoe 4.
d Oaloulatedfroz data @VW
s
.
NATIONALADVISORY
in rOfOrCUIOe
13.
e The rofraotive In,iicoe of 2, 2,3,3 -tetramethylDentane were determined
bv k. Leroy Tiltonon tho @tioal In~trumentaSectionof thiE Bureau.
COMMITTEE
FORAERONAUTICS
●
4
,.
,
,
.
Boillng
Wmcarhn
at
Refraotlve
7601mEg
Index,
~=’
(%, Cottill)
Vollml
point
leolatea
(d)
728
Voltm
(peroent)
oftotal
Butene
Alkylatel
Isopentane
8.9
1.3531 to 1.3533
2,3-Dirwthylbutaue
57 ●9
l*q@ to1.3752
2-Metbylpmtans
60.2
1.3714
to1.371,6 224
3-MeMlylpaltana
63s
1.3761
to1.3763
2,4-D&thylpentane
all.5
1“381!3
to1.382’02,610
3.44
2,3-Dmw1~~
89.9
1.391.2
to1.3920 1,034
1 ●y
2,2,4
-Trirlethylpentenl
99 ●3
1.~w to1.3915 11,727
2,213
o .g7
2.g7
.30
224
.30
15.48
%%0 data in this Colm ~6eut
the emunt Isolated having the properties
ehovn. It does not mnstltmte an exaot enalyais of W
crule.
NATIONAL ADVISORY
COMMITTEEFORAERONAUTICS
Pol- perWIIt Ora
Boiling l-angel hfraoti~
(%)
%
inaux,
Ma@r Ccmstltwxlte
3J.
101.s
I Below
264
57.8
1o1.5 to lo2
38
E?&
102 to 104
1.4094
to1.4127
18.7
1.04
tolo7
1.4150to 1.4160 2,4,k-TrlmW@-2-pentane,
ml W
quantitiesof 2,3,bd 2,3,3-txIiwJtJIyl-lpentenea,d
other ootemm
lo7tol17
1.4207to 1.4238 2,3,4—wimtkyl- d 3,4,4tr’het#lyl-2-pentmle13
14
6.0
1.392
b 1.m82
1.4084
to1.40882,4,4~u1-PI=M
L.
G4M ana
loee
%ottrell 8ollY.ng-pomt
meamaamnt s ml
2,4,4—wIMwvl-~,
butyl aloohol,other polm
Cmplnm!ll?l
.—
first
In~ati,
mtrke of
2,4,4-trlmethyl-la 2Pemalles
—
alla
laetrraot.lmso
NATIONAL ADVISORY
COMMITTEEFORAERONAUTICS
.
.
>
,
*
-.
.
>
-5.-
DrvImX?oFm
Tolw
cut
pltera)
A
38
B
200
AcIDPoLYMm
BYPmLnm&WmMc’mmmcm
Voluwper- lloll~c$md
centof*
<1.408
<101
3.7
10100 to 1o1.7
24.9
RofreotiveWox,
%=
1.408
to
Forerun
1.420
2,4,4-Trimthyll-pentlme
2,3,hl%lmthyl-
l-pentona
2,3,
3-lwmwl@l-mtene
c.
246
2306
I.1o.1 to lu!.o 1.b21 ta 1.423
D
M!
16.2
113.0 to
E
208
m .0
GM d
los82
pmlidnary
2,3,4-Trlmetl@2-pentene
U6 .0 1.425to1.4%
>116
Ree!lilue
-----------------
n%
‘oOttrell
bofmlg-poillt
%
3,4,
Wrimethyl2-psntene
~tu
dlstKUatitm
on ffrat and hat fraotlm.
of 2 Mters imlicated mm 10 pement
~.
NATIONAL ADVISORY
COMMITTEEFOQAERONAWICS
o-l
m
B
.*
24.31
I
24.30
;/
I
.
84.22
24.28
~
%4.27
j
a.63600
44.26
:
Qoo.a
0.
;
a4. Ei3
24. a5
24.24
0000
0000
,00
00
.
I
2.b.2~
o ‘o
20
Figure
1.-
Meezing
NATIONAL ADVISORY
COMMITTEEF~ AERONAUTICS
_J—..
40
. —xl
Time, min
point
of 2,2,5,5-t
otramethylhexane.
.--..
60
Fig.2
XAOATN~0.~i347
135.5ar
a,a,5,
5-Tetr&n
ethylhex
ane
P=7 60.90
mm hg
136.51
c
0
0
135.50 ~“,,
0
c
(b 0
,>
0
c
()
0
0
c
0
0
135.490
,
40
60
Reaovery,
peroent
20
100
80
125.f3a
2,2,4
Trinethy
lhexane
P-7,.5.91
mmlag
la5.81
,
<> 0
125.80
(>
0
0
c
0“
4>
0
(I
(
c
0
ct
co
0
g
.
la5.
79
0
40
60
Reoovery,
pera,ent
ao
5
100
80
sw
~la5.lch
:
a,3,6,6-Tetram
ethyl-3hexene
P- 747.11
mmhg
la5.oi3
1)
<I 0
124.90
00
c
0
0
<,
a
0
t) 0
(>
0
1>
06
1)
>.
0
la4.800
40
20
60
100
80
Reoovery,
percent
101.54
a,4,4trimethyl-1-pent
ene
P=? 61.81mmhg
101.53
0
101.52
101.510
~ooo
<>
GP
0
0
,I
1I
0
0
1~
0
1)
tb
.
20
40
60
80
100
percent
representative
hydrocarbon. .
~iguze
2.-&ilingpointoffour
Recovery,
NATIONALADVISORY
COMMITTEE
FORAERONAUTICS
E
94
w
~
.
l.a
48
g
●
:40
;l.Q
~
d
2
l-l
/
g
/
0
.8
/
;
/
:
g
5
/
~
<
~
&a
h
K
/
~4
.5
/
&dimethyl+bmt
o
8,
0
a,Lf-dimethyl-l-but
●
ne
;
/
m“
❑
2
:
One
9
y
6
/
“
.
/
i
/
j 16
1“
:
n
~
g
&
;
‘8
4
/
.
/
o
0
10
30
?irne,
~igura
3.-
fist en of
peroxide
fo=tion
and 2, 3-dimethyl-l-Wtae.
40
So
hr
in
2, 3-dirnethylAtit
m
me
30
10
o
Pigum
4.-
aate
of
peroxide
30
Tim , hr
formation
49
50
3
In a, 3-dimethyl-l-bUtae.
NATIONAL ADVISORY
COMMITTEEFORAERONAWW
~.
w
“+