United States Patent ,9]
[11]
McMullen
[45] NOV. 23, 1976
[54] PRODUCTION OF OLEFIN OXIDES
[75] Inventor: Charles Henry McMullen,
Scarsdale, N.Y.
[73]
2,231,374
9/1973
Germany
Primary Examiner—Norma S. Milestone
York, N.Y.
Dec. 29, 1975
Attorney, Agent, or Firm-Bernard Lieberman
[21] Appl.'No.: 645,038
Related US. Application Data ‘ '
Continuation-in-part of Ser. No. 553,583, Feb. 27,
1975, abandoned.
[30]
[52]
[51]
[58]
FOREIGN PATENTS OR APPLICATIONS
1,942,502
2/1970 Germany
Assignee: Union Carbide Corporation, New -
[22] Filed:
[63]
3,993,673
‘
Foreign Application Priority Data
Feb. 26, 1970
Germany . . . . .
. . . ..1942502
Sept. 27, 1973
Germany ................................ ..2231374
US. Cl ......................................... .. 260/3485 L
Int. Cl.2 ...................................... .. C07D 301/12
Field of Search ............................ .. 260/3485 L.
[56]
[5 7]
ABSTRACT
A catalytic liquid phase process for the production of
ole?n oxides comprising admixing an ole?n and hy
drogen peroxide in the presence of an arsenic catalyst
which is provided to the reaction as either elemental
arsenic, an arsenic compound or mixtures thereof, the
arsenic content of said compound being present in
catalytically active amounts, said compound being es
sentially free of tungsten, molybdenum, vanadium and
chromium; and the temperature of the admixture is in
the range of about 25° to about 200° C.
References Cited
UNITED STATES PATENTS
2,786,854
2,833,787
3/1957
5/1958
Smith et al. ................ .. 260/3485 L
_Carlson et al. ............. .. 260/3485 L
15 Claims, No Drawings
3,993,673
1.
Those skilled inthe art will appreciate that arsenic is
raonucrron orowrrn'oxrmis
generally groupedwith the non-metals in the Periodic >
snckonouno or: THE-‘INVENTION
Chart of the Elements. See, for example, Lange's
j Handbook of Chemistry, Revised Tenth Edition.
_
This application is a continuation-in-part ofmy co
DESCRIPTION OF THE PREFERRED
pending application'Ser. No. 553,583, ?ledlFeb. 27,
1975 and now abandoned.
EMBODIMENT
.
This invention relates to a process for the. production
of ole?n oxides and, more particularly, to a catalytic
‘The process can be carried out by feeding a mixture
of ole?n and‘ hydrogen peroxide into a reaction vessel.
liquid phase process for the production of ole?n oxides 10' A liquid phase‘must be established and, depending on
by' the transfer of oxygen from‘ hydrogen peroxide to an
the" nature of the ole?n, pressure or a solvent may be
necessary-The reaction vessel can be glass, glass-lined
olefin‘ substrate.
.
’
‘
'
i
'
.
or made of aluminum or titanium. A glass-lined polytet
Ole?n oxides are of considerable importance in the '
chemical industry as intermediates in the preparation
ra?uoroethylene coated stainless steel autoclave is
of urethanes, glycol'solvents, coating compositions,
molded‘ article's,‘ surfactants, plasticizers "and many
‘found to be advantageous and unlined stainless steel
can also be used effectively. A tubular reactor made of
similar materials can also be used together with multi
point injection to maintain a particular ratio of reac
other products. Consequently, for many years, produc-v '
ers of ole?n oxides ‘have been seeking process-routes
wherein the reactants are favored with highselectivity,
high efficiency, and'commercially acceptable reaction ‘
rates and there is a minimal'by-product‘production. In
the case of ‘catalytic’ reactions'it-is preferredjthat inter
mediary epoxidizing species are; avoided and that the
catalysts are relatively‘ easy‘ and ‘inexpensive to pro-.
tants.
Someform of agitation is preferred to avoid a static
system and can be accomplished by using a mechani
cally stirred autoclave, a multi-point injection system,
or a loop reactor wherein the reactants are force circu
lated through the system. Sparging can also be used. It
25
should be pointed out that agitation is inherent in con
tinuous processes, but is enhanced by the use of the
Various catalytic processes have been suggested to
meet industrial needs 'such‘a‘s‘ olefin reactions with
~:,s,l|1ggestecl modes of operation/In subject process, it is
found that increased rates of reaction are obtained by
hydrogen peroxide" in'the presence of heteropolytung
stic acids of arsenic, antimony or bismuth or the acid 30 “good gas-liquid ‘contact throughout and that this
‘contact is provided by agitation. The homogeneity of
salts of heavy metal peracids; with molecular oxygen in
the presence of arsenic catalysts; ‘and with organic
hydropeifoxides in the presence of catalyst compounds
or mixtures of compounds wherein at least one element
the reactants, provided by the agitation, is also advan
tageous.
,
_
,
The'ol?n can be broadly de?ned as an epoxidizable
from groups 4bto_6b and atleast one element groups 4a 35.. ,olefinically unsaturated hydrocarbon compound. Thus,
to 6a_.ofthe Periodic‘Qh‘art of the Elements are present
the ole?n can include terminal ole?ns such as mono
(the'Periodicr Chart referred to herein is the one ap
func‘tional and difunctional ole?ns having the following
pearing in Lange’silrlandbook of Chemistry, Revised
structural ‘formulas, respectively:
Tenth Edition). l_t wasfound, however, that none of
these routes to olefin oxides met commercial needs, the 40
organichydroperoxide route producing large amounts
of by-product and the other catalytic routes mentioned
either signi?cantly. promoting ring-opening of the epox
ide or other rearrangements, the production of inter
kilwherein R‘ and R2 can each be hydrogen or an alkyl
mediate peroxy compounds,,and/or necessitating the v45 Kradicahstraight or branchedzlchain, having 1 to 20
useof expensive catalysts as well as‘ lacking optimum carbon atoms; ,and
‘
'
selectivities, efficiencies, orreaction rates.
SUMMARY OF THE‘INVENTION '
- '-~An~object ‘of-the inventiomtherefore, is to provide a: 50
new process for the epoxidation of ole?ns which avoids
the de?ciencies heretofore mentioned and can be par
ticularly counted on for highaselectivity as well as high
‘ ‘wherein R‘ and R2 can each be hydrogen or an alkyl
_ “radical having 1- to 10 carbon atoms and R’ is from 0 to
1.0 methylene groups. The broad de?nition can also
v~Other“'0bjects and advantageswillbecomeiapparent' 55 include cyclicI ole?ns and internal ole?ns. The ring
efficiency.
hereinafter.
‘
‘
»
'
'
-
>
>
-.
-
According to the present invention-,a high efficiency
and high selectivity catalytic liquid phase process for
, portions of the cyclic ole?nsvcan have up to 10 carbon
.atoms and one unsaturated bond and can be substituted
with one or two alkyl radicals having 1 to 10 carbon
atoms. The cyclic olefins can be represented by. the
the production of olefin oxides has been discovered
which comprises admixing an ole?n and hydrogen pe- 60 following structural formula:
provided
roxide in to“,
thethepresence
reactionlas
of an
either
arsenic
elemental
catalystwhich
arsenic, an
,is
arsenic compound or mixtures thereof, the' arsenic ‘
content of said compound being present in catalytically
active amounts, said compound being essentially free 65'
of tungsten, molybdenum, vanadium and chromium;
wherein R‘ and R2 each can be alkylene radicals having
and the temperature of the admixture is in the range of I 7 ,1 to 4 carbon atoms and R3 and R‘ each represent
about 25° to about’ 200910.. .
. hydrogen atoms or alkyl radicals, straight or branched
3,993,673
3
4
chain, having I to ID carbon atoms. The internal ole
The catalyst can be used in homogeneous or hetero
geneous systems; however, in the latter case the system
?ns can be represented by the following structural
formula:
should be adapted to provide sufficient contact be
tween the reactants and the catalyst. Although this is
accomplished by conventional techniques, the stirred
reactor use in the homogeneous system is simpler and
wherein R‘ and R3 each are straight chain or branched
chain alkyl radicals having 1 to [0 carbons atoms and
more economical.
R2 and R“ each can be hydrogen atoms or the same as
catalyst in conjunction with compounds having no cat
alytic effect on the ole?n epoxidation reaction. For
example, the arsenic catalyst may be combined with an
additive intended to stabilize hydrogen peroxide in the
reaction medium, e.g. zinc octanoate.
R1 and R3. The broad definition can further include
olefins derived from aromatic compounds, such as
styrene and stilbene which can be represented by the
The invention also contemplates the use of arsenic
0
following structural formulas:
The arsenic can be provided to the reaction in any of
its commonly available forms, such as elemental ar
senic wherein the oxidation state is zero, arsenic trio
tide where arsenic is present in the plus three state, or
arsenic pentoxide where the oxidation state is plus ?ve.
It is recognized that arsenic in any of the above
wherein R is a monovalent alkenyl radical having 2 to
10 carbon atoms and R’ is a bivalent alkenyl radical
having 2 to 5 carbon atoms.
0
'
described forms may be converted under reaction con
ditions to a catalytically active species.
Generally, the inorganic derivative contains at least
Representative ole?ns are ethylene, propylene, bu
one arsenic-to-oxygen bond or is converted to a species
containing such a bond under reaction conditions. ll
tene-l, butene-Z, isobutylene, pentene-l, hexene-l,
pentene-2, octene-l, cyclopentene, cyclohexene, cy
clooctene, Z-methyIbutene-l, 3-methylbutene-l, hep
tene-l, hexene-2, hexene-3, octene-Z, heptene-3, pen
tadecene-l, octadecene-l, dodecene-Z, Z-methylpen
lustrative of inorganic derivatives of arsenic are arsenic
oxides, oxyacids of arsenic, salts and esters of the oxy
acids of arsenic, arsenic halides, arsenic oxyhalides,
and arsenic sulfides. The ester of the oxyacids of ar
tene-2, tetramethylethylene, methylethylethylene, cy
senic can be considered to be a combination of inor
clobutene, cycloheptene, Z-methylheptene-l, 2,4,4,
ganic and organic derivatives.
trimethylpentene-l, 2-methylbutene-2, 4-methylpen
The organic derivatives generally contain at least one
carbon-to-arsenic bond.
tene-2, and 2-ethyl, 3-methylbutene-l.
Heteroatom~containing olefins such as allyl alcohol
Illustrative of organic derivatives, i.e. organometallic
compounds, containing arsenic in the plus three oxida
and allyl chloride and other substituted ole?ns can also
be used in subject process provided that the substitu
tion state are those of the general formula RAsXY
wherein R is an alkyl, aralkyl, or aryl radical and X or
_ents are inert to hydrogen peroxide under the pre
scribed reaction conditions. l-lydroxyl, halogen, and
Y is hydrogen, alkyl, aralkyl, aryl, halogen, hydroxyl,
alkoxy (--OR'), acyloxy (—.OCOR'), —AsR'R",
ether substituents can be used here as well as, e.g.,
RCOO—, —Si(OR)3, —COOR, and aromatic substitu
ents such as phenyl, etc. Additional examples of olefins
A
are soya oil, linseed oil, 4-vinyl cyclohexene, butadi
ene, and polycyclic olefins such as norbornene.
The hydrogen peroxide can be used in aqueous solu
tions ranging from about 20 percent or 30 percent by
weight hydrogen peroxide on up to anhydrous hydro
—OAsR'R", a nitrogen containing group, e.g., —N
R'R", a phosphorus containing group, e.g., —PO(O
R’), a silicon containing group, e.g., OSiR'3, or a sulfur
containing group. Compounds such as the arsenoso
compounds, (RAsO)n, primary arsine oxides, RAsO,
or heterocyclic derivatives of arsenic such as the arso
lanes AsR or arseno derivatives, (RAF)n, can also be
gen peroxide which can, of course, also be used. It is
used.
preferred to use less water rather than more. Solutions
groups and n is an integer representing the number of
of hydrogen peroxide in the solvents referred to below,
recurring units in the polymeric structure.
Compounds containing arsenic in the plus five oxida
tion state are exemplified by the general formula R'R'A
formed either by addition to the solvent or by reaction
to provide both hydrogen peroxide and solvent, are
useful for incorporating the hydrogen peroxide in the
process.
The catalyst may be provided to the reaction as ele
mental arsenic or an arsenic compound essentially free
of tungsten, molybdenum, vanadium and chromium, or
mixtures thereof. The term ”mixtures" includes mix
', R", and R’” can be alkyl, aralkyl, or aryl
'R"'AsXY where R’, R", and R'” are as de?ned above
and X or Y is alkyl, aralkyl, aryl, halogen, hydroxyl,
alkoxy, --NO,,, or —SO4H. Other useful classes of com
pounds have the general formulae R'R"As (=O)X and
R"'As(=O)XY with R’, R" and R’” as defined above, _
tures of elemental arsenic with one or more of the
and X and Y as de?ned above in this paragraph.
Speci?c examples of the above derivatives are as
above-described arsenic compounds as well as mixtures
of two or more of such arsenic compounds.
follows:
Name
Formula~
Arsenic trioxide (Arsenolite)
Arsenic pentoxide
Arsenious acid
Arsenic acid
Arsenic triethoxide
Asp,
As,0,,
As(Ol-l).
H,As0.
As(OC,H,),
Arsenic triphenoxide
A5(oC|Hl):
3,993,673
-c0ntinued
Name
Formula
2,2'-ethylenedioxybis( 1,3,2-dioxarsolane)
O
'
O
AsO(CH2)2OAs
O
2,2'-oxydi-l ,3 ,2»dioxarsolane
O
O
o
As—O_As
O
l ,4,6,9-tetraoxa-5-arsaspiro[ 4.41-
nonan-S-ol
.
0
O
Arsenic trichloride
OH
AsCla
Arsenic oxychloride
Arsenic trisulphide
Triphenylarsine
O
0
O
‘
AsOCl
'
-
Triphenylarsine oxide
Hydroxybis(tri?uoromethyl) arsine
A525:
(CsH5)aAS
(C8H5)3AsO
(CF3)zAsOH
Oxybis( dimethylarsine)
Phenoxydimethylarsine
[(CH3)2As]2O
(CH3)¢AsOC¢H5
Benzenearsonous acid
C,H5As(OH),
Bis(oxoarsino) methane
CH2(AsO)2
Sodium arsenite
NaAsO,
Sodium arsenate
NaJAsO4
'
Pharmacolite
CaHAsO4.2 H2O
Aluminum arsenate
AlAsO,
Ammonium magnesium arsenate
Adamite
MgNH4AsO46 H2O
Zn(ZnOH )AsO,
Bismuth arsenate
BiAsO4.l/2 11,0
Bismuth uranyl arsenate
551,0,3‘ uo,. 2 mo. l2 H2O
(Walpurgite)
Zirconium arsenate
Thallic arsenate
Thiobis(dimethylarsine)
Dimethyl(dimethylarsino) phosphonate
Dichlorotris(tri?uoromethyl)-arsenic
Methylphenylarsinic acid
l(CHa)zA$lzS
(CHS)ZASPO(OCHII)2
(CFa)3A5Cl2
/
CH_-|(C5H5)AS
)
\
OH
Poly(methylenearsinic acid)
'
o
u
,
CH|1|\s
o
I
Bis(4-nitrophenyl) arsinic acid
//
(4"‘O,NC.H,),As
Phenoxarsinic acid
O
\
: :0 I : -
OH
As
// \
O
Butanearsonic acid
4-Bromobenzenearsonic acid
l-Phenylarsolane
OH
C4H,AsO,H=
4-BrC.H4ASo=H:
bone such as a polysilane, again, by conventional meth
As noted, mixtures of any of the aforementioned
ods.
catalysts can be used,
The arsenic catalyst can be soluble, partially soluble,
Where supported heterogeneous catalysts are de- 60 or insoluble. Of course, contact of the reactants with
the catalyst is essential, and different conventional
sired, they can be loaded onto a support by any of the
techniques are used to provide this contact.
known conventional techniques such as impregnation,
precipitation, etc. The support can be a naturally oc
curring material, e.g., a clay or aluminosilicate, or a
The reaction medium must be one in which the ole?n
and the hydrogen peroxide solution are soluble under
synthetic material such as zeolite, silica gel, or alumina 65 reaction conditions, i.e., it must be capable of main
taining a liquid phase throughout the reaction. it should
having a surface area in the range of about one square
also be inert to the reactants and the catalyst. Gener
meter per gram to about 800 square meters per gram.
ally, a conventional inert organic solvent is used as the
' The catalyst can also be attached to a polymeric back
3,993,673
7
8
ratio of about 0.001 gram atom to about 0.1 gram atom
reaction medium. A very wide choice is, permitted
which includes ethers, esters, alcohols, glycols, other
oxygenated solvents, chlorinated solvents including
chlorinated hydrocarbons and chlorinated aromatics,
of arsenic per mole of hydrogen peroxide is preferred.
The ratios of ole?n and hydrogen peroxide can be
kept fairly constant by the use of a continuous process
and by analyzing the outlet ratio and adjusting the feed
and sulfolane. Where gaseous ole?ns are used, it is
desirable that a solvent be selected that will increase
ratio. In a backmixed reactor, the feed is adjusted until
the outlet ratio is within the prescribed range. Where
the solubility of the ole?n. A representative list of sol
vents appears in examples 31 to 41. Other useful sol
two or more reactors are used in series or the reactor is
vents are ethyl acetate, tetraethylene glycol, dimethyl
tubular with multi-point injection, the reactions taking
formamide, nitromethane, tetrahydrofuran, acetone,
place are considered to be a series of batch reactions
and are carefully monitored to insure for the most part
that the molar ratio in any one reaction is not permitted
phenyl acetate, diphenyl CARBITOL, propylene glycol
diacetate, cyclohexylacetate, triethyl phosphate, and
to go below or rise above a desired range.
The amount of reaction medium or solvent is deter
2,2-dimethoxypropane. Co-solvents such as toluene,
benzene, chlorobenzene, ortho-dichlorobenzene, nitro
benzene, l,l,2,2-tetrachloroethane, n-pentane, cyclo
15
hexane, and anisole can also be used. Mixture of sol
vents as well as co-solvents can also be used. There is
an exception to the use of a solvent inert to the reac
mined by the amount needed to maintain the liquid
phase. Generally, the amount is in the range of about 5
percent byv volume to about 95 percent by volume
based on the volume of the total reaction mixture in
cluding ole?n, hydrogen peroxide solution, catalyst and
tants and that is where a liquid ole?n reactant is used to
20 solvent. It is preferably in the range of about 25 percent
provide the liquid phase.
by volume to about 75 percent by volume. Other quan
The reaction can be conducted in an atmosphere of
air or oxygen since the ole?n selectively reacts with the
hydrogen peroxide in preference to the molecular oxy
gen; however, the reaction is preferably conducted in
an essentially oxygen-free atmosphere. This is provided
by conventional means, e. g., by using an inert gas such
as nitrogen, argon, or helium as the atmosphere in
which the process is carried out.
The pressure is generally in the range of about atmo
spheric pressure to about 1500 psia. Pressure is se
lected according to the ole?n used since it will de?ne
the concentration of gaseous ole?n which can be main
tities of solvent can be used, however, so long as there
is a suf?cient amount to maintain the reaction in the
liquid phase.
One of the features of this invention is that the sol
25
vent is not degraded during the reaction as in the case
where molecular oxygen is used to epoxidize ole?ns in
the presence of arsenic catalysts.
Recovery, separation and analysis of products and
30
tained in the liquid phase at reaction temperature.
The temperature of the reaction can be in the range
unreacted materials are accomplished by conventional
means.
The reaction is found to be clean, i.e, having minimal
by-product formation. Ole?n ef?ciencies approach 100
percent and hydrogen peroxide efficiencies approach
'
of about 25° to about 200° C. and is preferably in the 35 80 to 95 percent.
The following examples illustrate the invention. Per
range of about 60° to about 130° C. Lower tempera
tures than 25° C. can be used if reaction rates are sacri
centages are by weight unless otherwise _ speci?ed.
?ced.
The time of the reaction is simply that in which one
or the other reactants, usually the hydrogen peroxide,
is used up. This is applicable in batch and semi-continu
Moles and percentages of hydrogen peroxide are calcu
lated on an anhydrous basis and those of catalyst are
calculated for arsenic.
EXAMPLES 1 TO 14
ous processes to which subject process can be applied.
In continuous processes, which are preferred for com
The ole?n is reacted with a 95 percent aqueous solu
mercial use, the reactants are continuously fed so that
tion of hydrogen peroxide (95% H202 + 5% water) in
time of reaction is merely the measure of the length of 45 the presence of an arsenic trioxide catalyst in 1,4-diox
ane solvent. The ole?n, hydrogen peroxide solution,
each cycle.
A molar ratio of about 0.5 moles to about 200 moles
catalyst, and solvent are mixed together in a 100 milli
liter Pyrex ?ask at room temperature under one atmo
of ole?n per mole of hydrogen peroxide can be used;
sphere of argon. The reaction mixture is then heated to
however, a molar excess of ole?n is suggested. The
preferred molar ratio is in the range of about 2 moles to 50 90° C. Samples are withdrawn periodically and ana
lyzed for residual peroxide by the iodometric method
about 20 moles of ole?n per mol of hydrogen peroxide.
and for epoxide by gas-chromatography or by titration
As noted, a catalytically active amount of catalyst is
using the tetramethylammonium bromide-perchloric
required. There is really no upper limit except the
acid method.
bounds of economy. Generally, a molar ratio of about
0.0001 gram atom to about 1 gram atom of arsenic per 55
Variable conditions and results are set forth in Table _
mole of hydrogen peroxide is satisfactory while a molar
I.
Table I
mo,
Ex.
l
2
3
4
5
6
7
8
9
Ole?n
(millimoles)
H2O,
(millimoles)
Asp,
(millimoles)
l,4-dioxane
(milliliters)
Reaction Time
(Hours)
Epoxide
(millimoles)
Convened
(mole %)
Octene-l
Styrene
2-Octene‘
cis-2-Octene
trans-2-Octene
330
I65
165
67
67
54
27
27
ll
ll
0.54
0.27
0.27
O.l l
0.1 l
44
29
22
8
8
5
4
6
2
3
4O
24
24
10
9
88
95
94
95
89
Cyclohexene‘
Allylpentyl ether
Allyl alcohol
Soya oil
82
82
165
22"’
27
13
27
27
0.53
013
0.27
0.27
80
I0
36
24
5
2
l
4
17
l
3
25
80
58
30
l00
Ole?n
131,993,673
"
‘ “Table l-continued
Ole?n
(millimoles)
Ex. Ole?n
l0
Linseed oil
ll
Z-Ethylhexyltallate
12
Vinyltriethoxysilane
I65
I3
l4
Allyltrimethoxysilane
4-Vinyl cyclohexane
165
l65
H2O,
(millimoles)
As,0;|
(millimoles)
l,4-dioxane
(milliliters)
Reaction Time
(Hours)
H202
Epoxide
(millimoles)
Converted
(mole %)
I00
223
27
0.27
24
' 3
25
22“
27
0.27
24
‘3
23
94
27
0.27
14
3.5 '
10
7
98
27
27
0.27
0.27
22
21
1.5
l
20
23
I00
89
‘85:15 cis-trans mixture
‘reaction temperature 70" C
‘Weight in grams
hours the tube
' is removed from the bath and anal y sis of
15 the contents shows that 72 mole percent of the perox
EXAMPLE 15
2.0Xl0‘3 mole of arsenic trioxide, 300 ml. ‘of 1,4
ide is consumed and the yield of epichlorohydrin is 50
dioxane solvent, 15 ml. of n-nonane internal standard,
mole percent.
4.1X1O‘l mole of hydrogen peroxide (95 percent aque
EXAMPLE 19
ous solution) and 3.1 moles of propylene are charged
to a one-liter, 316 stainless-steel, stirred autoclave,vat 20 5.0Xl0‘4 mole of arsenic trioxide catalyst, 8.0X1O'2
room temperature. The reactor is pressurized with 200
mole of cyclohexene, 80 ml. of 1,4-dioxane and 2.5 ml.
psig of argon and is then heated to 90° C. Samples of
of 28 percent aqueous hydrogen peroxide solution
the liquid-phase are withdrawn at intervals and ana
(28% H202 + 72% H2O) are mixed at room tempera
lyzed for residual peroxide by the iodometric method
ture in a 100 milliliter flask (under argon at atmo
and for epoxide by gas chromatography. After 6 hours, 25 spheric pressure) which is then immersed in a bath at
2.7 X 10-1 moles of propylene oxide are produced and
90° C. After 35 minutes of reaction, cycohexene oxide
79 mole percent of the initial peroxide is consumed.
'
.is detected in the mixture.
Examples 20 to 30
EXAMPLE 16
Example 15 is repeated except that 2.5 moles of 30
Octene-l (3.3 moles) is reacted with 95 percent
aqueous solution of hydrogen peroxide (5.4 X 10'1
mole of H202) in the presence of various arsenic cata
lysts (5.4 X 10‘3 mole arsenic compound) in 1,4-diox
isobutylene are substituted for propylene. After 6
hours, at 90° C, 3.2)(10‘1 mole of epoxide is produced
and 95 mole percent of the peroxide is consumed.
ane solvent (45 volume percent based on the method of
'
35 the reaction mixture) at 90° C. by the method de
scribed for example 1. The epoxide efficiency is de
EXAMPLE l7
Example l5 is repeated except that 3.2 moles of
ethylene are substituted for propylene and 4.0><l0““
?ned as:
mole of arsenictrioxide catalyst is used. After 3 hours, _
II
at 90° C, 40 mole percent of the initial peroxide is‘
I
'
I
'
I
moles of peroxide consumed
- consumed and ethylene oxide is the major product
detected.
Variable conditions and results are set forth in Table
-. II.
Table ll
Example Catalyst
Reaction
Time
Epoxide
Ef?ciency
H2O,
Conversion
(hours)
(%)
(mole %)
2O
Arsenic triethoxide
4
96
76
2|
2,2'-Ethylenedioxybis( l ,3,2-dioxarsolane)
5
98
74
22
Elemental Arsenic
4
80
84
23
24
Phenyl arsine oxide
Arsenic pentoxide
4
6
90
86
64
76
25
Arsenic acid
3
73
66
26
Arsenic trichloride
4
82
75
27
Benzene arsonic acid
28
n-Propyl arsonic acid
29
3O
Triphenylarsine
Triphenylarsine oxide
'
4
70
67
19
37
83
23
23
42
38
17
19
EXAMPLE 1s
2.7Xl0
_4
.
.
.
.
_
mole of arsenic triethoxide catalyst C118 60
.
I
EXAMPLES 31 To 41
solved in L1 ml. of 1,4-dioxane, 2.0 ml. of n-undecane
internal standard, l.65><l0"l mole of allyl chloride,
32.9 ml. of 1,4-dioxane, and 2.7 X 10'2 moles of a 97 .
percent aqueous solution of hydrogen peroxide (97%
B10, + 3% H,O) are mixed together in a 100 milliliter 65
?ask at room temperature. A 2.0 ml. aliquot of thisv
mixture is frozen, evacuated and sealed under vacuum
in a thick-wall Pyrex glass tube (pressure = autoge
nous) and the immersed in an oil bath at 90° C. After 8
Octene-l (3.3 moles) is reacted with a 95 percent
aqueous solution of hydrogen peroxide (5.4 X l0‘l
mole of H202) in the presence of arsenic trioxide cata
lyst (5.4 X 10*“ mole) in various solvents, each in an
amount of 45 volume percent based on the total vol
ume of the reaction mixture. For the solvents boiling
below 90° C, the method described in example 18 is
used, and for the solvents boiling above 90° C, the
3,993,673
11
3. The process de?ned in claim 2 wherein the molar
ratio of arsenic to hydrogen peroxide is about 0.0001
method described in example 1 is used. Variable condi
tions and results are set forth in Table III.
Table Ill
Epoxide
Reaction
Time Hrs.
Example Solvent
31
82
16
32
Z-Propanol
2
66
12
33
t-Butanol
2
74
8
34
35
36
37
Methyl CELLOSOLVE
1,2-Dimethoxy ethane
Diethyl CARBlTOL
1,4-Dioxane (35 vol. %)
‘Chloroform (10 vol. %)
l
l
l
l
96
78
75
84
19
44
66
38
38
39
40
41
Ethanol
H2O,
Ef?ciency Conversion
(%)
(mole %)
1
1
83
48
acetate
Methyl acetate
1
90
7O
Glycol diacetate
l
92
69
5
96
95
Methyl CELLOSOLVE
Diethylene glycol
diacetate
20 gram atom to about 1 gram atom of arsenic per mole of
EXAMPLE 42
hyd ogen peroxide
4. The process de?ned in claim 3 wherein the process
l‘
.
is conducted in an inert organic solvent.
5. The process de?ned in claim 4 wherein the tem
of H202) in the presence of sodium arsenite catalyst 25 perature is in the range of about 60° to about 130° C.
6. The process de?ned in claim 5 wherein the molar
(1.0Xl0‘4 moles) in 80 ml. of 1,4-dioxane solvent at
ratio of arsenic to hydrogen peroxide is about 0.001
70° C by the method described for example 19. The
gram atom to about 0.1 gram atom per mole of hydro
catalyst is substantially insoluble in the reaction mix
gen peroxide.
~
~
.
.
ture. After 30 minutes of reaction, cyclohexene oxide is
detected in the mixture.
30 7. The process defined in claim 6 wherein the ole?n
Cyclohexene (8.2><l0'2 moles) is reacted with 93
percent aqueous hydrogen peroxide (2.1)(10‘2 moles
is propylene.
EXAMPLE 43
8. The process de?ned in claim 7 whereinthere is a
molar excess of ole?n over hydrogen peroxide.
9. The process de?ned in claim 8 wherein the molar
Octene-l (1.7)(10‘1 moles) is reacted with 95 per
cent aqueous hydrogen peroxide, (2.7X1O'2 moles of
H202) in 1,4-dioxane solvent, (45 volume percent), at 35 ratio of ole?n to hydrogen peroxide is about 2 moles of
ole?n per mole of hydrogen peroxide.
90° C, in the presence of arsenic trioxide (2.7X10“
moles) and zinc octanoate (l._1><10‘ moles), by the
method described for example 1. After 2 hours 6 per
10. The process de?ned in claim 1 wherein the hy
drogen peroxide is present in the form of. an aqueous
solution containing at least about 20 percentby weight
cent of the octene-l is converted to epoxide.
hydrogen peroxide based on the weightl‘of the aqueous
EXAMPLE 44
solution.
.
11. The process de?ned in claim 1 wherein ‘the pro
Example 43 is repeated except that magnesium ace
cess is conducted in an essentially oxygen-free atmo
tylacetonate (5.4Xl0“ moles) is used in conjunction
with arsenic trioxide catalyst (2.7Xl0“ moles). After 3
sphere.
hours, at 90° C, 1 percent of the octene-lis converted 45
to epoxide.
What is claimed is:
l. A catalytic liquid phase process for the production
-
,
“
,
'
12. The process defined in ‘claim 4 wherein, the hy
drogen peroxide is present in the form of, an aqueous
solution containing at least about 20 percent by weight
hydrogen peroxide based on the weight ofthe aqueous
solution.
.
t
"
', ' .
of ole?n oxides comprising admixing an olefin and
hydrogen peroxide in the presence of an arsenic cata 50 13. The process defined in claim 9 wherein the hy
drogen peroxide is present in the form. of a aqueous
lyst which is provided to the reaction as either elemen
solution containing at least about 20 percent by weight
tal arsenic, an arsenic compound or mixtures thereof,
hydrogen peroxide based on the weight of theaqueous
the arsenic content of said compound being present in
catalytically active amounts, said compound being es
sentially free of tungsten, molybdenum, vanadium and 55 14. The process de?ned in claimv3 wherein the pro
cess is conducted in an essentially oxygenifree atmo
chromium; and the temperature of the admixture being
solution.
in the range of about 25° to about 200° C.
2. The process de?ned in claim 1 wherein the molar
.
i
,
sphere.
‘
i
t
‘
'
,
.
t
15. The process defined in claim‘ 13 ‘ wherein the
process is conducted in an essentially oxygen-free at
ratio of olefin to hydrogen peroxide is about 0.5 mole
to about 200 moles of ole?n per mole of hydrogen 60
1k
IR
mosphere.
‘
s
peroxide.
65
»
it
t
w
.
‘
'
-