m a tu r e o f M a l t o s e
d It s
a ti o n P r o d u c t s w i t h A I
k a li n e P e r oxid e o f
H yd r o g e n
an
A D I SS E RTATIO "
0 TH E
1 TH E
OA R D O F G R A D U A T E S T U D I E S I " CA" D I D A C"
D E G R EE O F D O C T O R O F P H I L O S O P H "
B
B"
SI E GE L
A
.
E
U C K B O RO U G H
E A S TO " P A :
E S CH E " B A C H P R I " TI " G C O M P A ""
,
1
.
914
.
of
Th e St r u c t u r e
Ma l t o s e
Al k a l i n e
" ei
d I t s Ox i d a t i o n P r o d u c t s wi t h
P e r o x i d e o f H y d ro g e n
an
.
and his students have established the methods for oxidizing t h e
sugars with various agents and for separati n g and identifying the resulting
2
pro d ucts " e f has recently submitted a complete system of dissociation
of the sugar mol ecule in explanation of these oxidations and in explana
tion of the reciprocal conversion of certain sugars under the influence of
dilute alkalies
3
L ewis investigate d the pro d ucts formed when maltose is oxidize d
with al kali n e cupric su l fate This work brought out t hat maltose is
oxidized largely as an unh ydr olyzed disaccharose forming g l u c o s id o
acids whose subsequent hydrolysis gives dextrose and simpler acids
There were thus obtained from 1 00 g of anhydrous maltose
g of
hydrolyzed dextrose
g of hexonic acids
g of glycollic
g of oxalic
g of formic acids and
g of carbon dioxide O f
unidentified material believed to contain g l y c er i ni c and t r i o xy b u t y r i c
acids there remained
with
g lost during the various
g
manipulations The ratio of the various products found was quite
diff erent from that observed by " e f in a study of the oxidation products
of the simple hexoses dextrose levulose and mannose especially in
respect to the larger amount of mannonic lactone
g ) formed from
the disaccharose This investigation of maltose however failed to throw
any light on the constitution of that sugar largely because the amount
of oxygen taken up by each molecule was i n s u fli c ie n t
The present study was therefore undertaken in the hope that the more
complete destruction of the maltose molecule under t h e influence of
alkaline hydrogen peroxide might permit a better quantitative separation
of the products thus reflecting the point of the g l uc o s id o union between
l
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I bi d
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3 57 .
2 1
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Chem
.
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3 57.
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4 3 3
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30 1
— 1
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259
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,
4
the two constituent dextrose groups in malt sugar The resu lts c on
firmed the previous findings that maltose oxidizes l arge ly without h y
d r o l y s is and that saccharinic acid formation d oe s not take p l ace und e r
the c onditions A larger amount of oxygen is t a ken u p with al kal in e
peroxide as evidenced in the larger y ield of acids containing few carbon
atoms O ne hundre d grams of anh ydrous mal tose gave by th is metho d
g of hydrolyze d dextrose (corr
g)
g of mannonic lactone
g of glycollic
g of oxalic
g of formi c acid and
g
of carbon dioxi d e O f unidentifie d material there remaine d i 1 8 g
bel ieved to contain er y t hr o nic an d l -threonic acids O ne gram of ma ~
t e r ia l was used up in titrations and otherw ise lost in manipulation
E specially noteworthy are the larger amounts of formic an d glycollic aci d
f ound in comparison with the previous w ork using a lkalin e copper sulfate
1
H erein it is be l ieved are to be f oun d the proofs indicate d by " ef which
2
establish the str ucture of maltose as ori ginally assume d by F is c h e r as
a y-d -gl u co s i d o d -gl u cose hydrate
.
‘
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,
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,
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,
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,
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,
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,
— C
C HO
r
l
C H OH
C HOH
C HOH
I
0
2
I
0
— H
C
L
H
C HOH
0
I
.
C HOH
C HOH
C HOH
C H 20H
in which the primary alcohol hydroxyl functions in the g l u c o s id o union
3
3
Fischer established the structure of maltose as a disaccharose com
posed of two molecules of d -glucose and containi ng a 7 ~lactone ring
4
similar to his synthetic al kyl glucosides According to Armstrong
maltose is an a -glucosi d e as established by selective enzyme action
.
.
.
.
,
5
The res u lting formula
does not
however determine which of the carbon atoms 1 2 3 4 and 5 holds the
hydroxyl gro u p taking p art in the gl u c o s i d o un i on C arbon atoms 1
2 a n d 3 ma y be at once eli minated as possibilities from the following
consideration : d -M al tose with
molecules o f calcium hy d roxide at
ordinary temperature gives a very large quantity of g l u c o s i d o a and
-d -i s o sa c c h a r i n i c acids 5
B
,
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1
A nn
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—
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2
4 3 , 9 9 3 03
,
2 7,
3
4
5
I bi d
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35, 3 1 4 1 ;
,
Tr a n s
2 98 8
.
Chem
K il ia n a B e n
,
45 ; " e f A n n
2 8, 1 1
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85,
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3 57 ,
3 06
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—
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37 , 5 4 5 6
.
C OO R
C OOH
H O— C— C H o
— C
CH o
‘
"
OH
CH2
CH 2
C HOH
C HOH
a nd
C H 20 H
(: 11 o
This product can only come about th rough enolization of malt sugar
with subsequent addition and splitting o ff of water forming i nt e rrn e d ia t e l y
O
fructose C 6 H 1 005 C H 20H (C H O H ) 3 C C H 20H
after
the analogy of the interconversion of simple hexoses under the influence
1
of alk alies
This product similarly goes over into y d -g l u c o s i d o ortho
O O
'
-d -
g
y
l u c o s id o -d -
—
,
“—
.
,
'
-
:
.
h C XO S Ol l
Wt
'
,
h
the
,
benzilic acid rearrangement can give the final product y -d -g l u c o s i d o
a
and B-i s o sa c c h ar in ic acids H yd r olysis of the latter yields d -glucose
and a and 6-isosaccharin It may be seen that these transformations
involve the th ree hydroxyl gr oups attached to carbon atoms 1 2 and 3
which therefore must be pres e nt as such i n the origi na l maltose molecule
The participation of any one of these in the gl u c o s i d o union is therefore
preclude d
The selection of the correct hydroxyl group as between the two remain
ing is fixed upon that attache d to carbon atom 6 by the following
considerations
2
3
" e f and G l a t t fe l d have shown that when glucose is treated with alkali of
a certain concentration there results six sugars ; i e d -glucose d -mannose
d -fructose d -p s e u d o fru c t o s e an d a an d B-d -glutose
The intermediate
—hexose d i e n o l s
of this transformation undergo dissociation into
hydroxy meth ylen e and me t h y l e ne o l s of the pentoses There result
final ly through further dissociation various sugars containing one two
three four and five carbon atoms (C H 20) the oxidation of which a c
companied in some instances by the benzilic acid rearrangement produces
the ultimate products found in suga r oxidation
It is altogether probable that maltose under the influence of alkalies
enters into a similar equilibrium of the six gl u c o s id o hexoses of the
glucose series The intermediate gl u c o s i d o h e xo s e d ie n o l s undergoing
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1
2
3
2 8,
B en ,
A nn
3078 ;
Rec t ra v
.
.
c hi
m
4 03 , 3 6 2
A m Chem J , 5 0, 1 3 7
" e f , A nn 4 03 , 3 00 3 8 1 -3 8 2
.
,
.
.
,
.
.
,
.
.
P a ys
1
9,
,
1
6
dissociation oxidation etc woul d produce the gl u c o s i d o acids whose
hydrolysis w oul d give the fin al pro d u cts found in this study
The step -b y -step splitting off of oxymethylene with the formation of
for mi c and carbonic acids as t he main course of the reaction coul d not
go bey ond the carbon atom whose hydroxyl enters into the g l u c os i d o
u nion otherwise gl u c o s id o acids would not be the principal product of
the oxidation In the following equation it may be seen that if F ormula
I were correct for maltose the principal product of the oxidation wou ld
be gl u c o s i d o gl y c e r in ic acid :
,
,
.
,
.
,
,
,
.
C H O I MD
C HOH
C H OH
C HOH
C H OH
h
C HOH
C)
—~ C H
H OH
—
C H OH
CH
C O OH
C HOH
CH
C HOH
C H 20 H
C H ZO H
C H 20 H
“
If F ormula I I were correct the
glycollic acid
,
p rincip al
C H gO H
product would be
gl u c o s i d o
.
CH OI h O
n
[
—
CH
C H OH
C HOH
C H OH
C HOH
C HOH
C HOH
C HOH
C HOH
C HOH
C HOH
C OO H
C HxH I
CH 2
C H xnr
CH 2
O ne hundred g rams of maltose with alkaline peroxide gave finally
g of pure crystalline glycollic acid while g l y c e r in i c acid was not found
present
The ratio and nature of the oxidation products of d -glucose with alkaline
hy drogen peroxide are quite di fferent from those of maltose especially
‘
in respect to the small amou n t of glycollic acid
from 1 00 g ) and the
2
—
presence of d a r a b o n i c lactone in the former These di fferences must
be due to the eff ect of the above g l u c o s i d o bond
R egarding the source of the o t her products found the large quantities
.
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,
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,
1
S p o e h r A m Chem J
,
2
G l a t t fe l d ,
.
I bi d
.
.
,
5 0,
.
1
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43 ,
35
—
1
23 8
57
.
.
of carbonic and formic acids undoubtedly result from the oxidation of
dissociated h y d r o xy me t h y l e n e " C H O H
O xalic acid could result
1
<
from a more complete oxidation of diose me t h y l e n e o l H O C H 2C 0H
—threonic acid were indicated in the results but not
and
h
r
n
l
t
o
i
c
E ry
established because of the small amounts Their formation is most
glucose d ie n o l
l
i
2
d
u
c
o
s
d
o
probable from the dissociation of g
3
.
,
.
,
.
,
,
-
r
OH
011 0 11
01 1 011
C OH
011 0 11
C OH
011
11 00H
0HOH
H 0011
C H 20H
011 2
into the me t h y l e n o l s of diose H O C H 2C (O H ) < and of gl u c o s id o -ah
erythrose The osone of the latter formed by oxidation could undergo
the benzilic acid rearrangement (asymmetric in part or entire) to give
C 4 acids
M annonic lactone on the other hand has been prove d to arise from th e
hydrolysis of gl u c o s id o mannonic acid through the action of dilute alkalies
2
on ma l t o s o n e
That the benzilic acid rearrangement often takes place
"
asymmetrically has been pointed out by " e f in explanation o f the pre
ponderating gluconic acid in oxidation of the simple hexoses and of
mannonic acid when maltose is acted upon by Fehling s solution
4
L ewis has obtained mannonic lactone in quantity from the oxidation of
lactose with Fehling s solution In the oxidation of maltose with alkaline
peroxide there is formed intermediately therefore some ma l t o s o ne
E xp e rim e nta l P a rt
A solution of
g of K a h l b a u m s maltose in 8 0 cc of 3 % hydrogen per
oxide (6 5 molecules ) was prep ared and added with vigorous shaking through
a period of ten minutes to a solution of
g of
potassium h y
d r o xid e (equivalent to
g of potassium hydroxide net being
molecules ) in 1 00 cc of water The total volume was then increased to
2 00
making the concentration of the alkali approximately half normal
U nder similar conditions
g of maltose were dissolved in 1 6 0 00
hydrogen peroxide and th e mixture poured with vigorous shaking through
a period of ten minutes into a solution of
g of potassium hydroxide
in 4 0 cc water
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1
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C f A n d er s o n A m Chem
2
3
4
L
e wi s
A nn
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,
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42 ,
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2 3 1 —2 ,
3 5 7,
U n p u b l is h e d
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—
3 5 319
1
n o te s
2 84
.
4 2 , 40 6
.
.
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8
Three solutions of each concentration were prepared and kept at room
temperature being protected from the carbon dioxide of the a ir by means
of soda lime tubes
In none of the above mixtures was any change in tempe rature or a p
The final solutions were in all cases
p e a r a n c e of the solution noted
colorless
B y testing with Fehling s solution the oxidation was found in the
first three trial s (8 0 cc hydrogen peroxide ) to be complete after seven
to ten days and in the last three (1 6 0 cc hydr ogen peroxide ) after fourteen
to seventeen days as evidence d by the absence of reduction While the
solutions were standing as well as at the conclusion of the oxidation the
continued presence of an excess of hydrogen peroxide was proved by
frequent tests with starch potas sium iodide paper The excess of hydrogen
peroxide was finally removed by the addition of a little platinum black and
" igorous stirring
(I ) "u a n ti ta ti ve D eter mi na ti on of th e A mou n ts of Ca r bon D i oxi d e F or med
i n th e Oxi d a ti on — To determine the amount of carbon dioxide in each
case an apparatus was set up in which a wash bottle of concentrated
potassium hydroxide was connected with a large U -tube filled with soda
lime and this in turn with the flask containing a sugar solution To the
other side of the flask was attache d a reflux condenser in series with six
towers containing a saturated solution of barium hydroxide The
calculated amount of hydrochloric aci d was then added to the alkaline
reaction mixture by means of a dropping funnel and air free from carbon
dioxide was slowly and continuously drawn through the apparatus
The flask was finally heated in an oil bath at 1 1 0 to 1 2 0 for one hour
The barium carb onate precipitate was then thoroughly washed dried at
and weighed
1 00
B lank experiments were also made to d etermi ne the amount of carbon
dioxide in
g of potassium hydroxide Three determinations gave
respectively
g and
g of barium carbonate
g
The three solutions of maltose with 8 0 cc of hy d rogen peroxide after
the correction was made for the potassium hydroxide gave res pectively
g an d
g of barium carbonate Two of the
g
solutions prepared with 1 6 0 00 hydrogen peroxide after the correction
gave
g and
g of barium carbonate
TA B L E I — SU M M A R" O F R E S U L TS F O R C A R B O " D I O X I D E
T i me for
G rams of
A mo nt
A mo nt of h y
of ma l tose d ro g en p ero id e o id at i on
carb on
P
cent of P cent of
di o id e
t h e ret i cal yi e l d
total
D ays
C
G rams
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°
°
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°
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,
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,
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,
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,
,
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u
u
x
.
c
.
3
22
.
x
.
.
80
—1 0
7
80
—1 0
7
80
-1 0
7
1
60
1
1
60
1
’
er
.
—
4 17
4
—
1
7
x
.
o
er
.
.
.
.
9
As
(2 ) "ua nti ta ti ve D eter mi na ti on of th e A mou n ts of
before three lots of
g of mal tose with 8 0 cc hydrogen peroxide
were set aside under like conditions also three lots with 1 6 0 cc hydr ogen
peroxide The time periods for complete oxidation were the s ame as in
the first series Aft er adding the platinum black to the solutions and
heating the flasks to remove the excess of hydrogen peroxide theoretical
amounts of hydrogen chloride were added E ach soluti on was then
separately distilled from a flask provided with a K "
eldahl bulb to prevent
A press u re of
t h e vol a tilization of p ossible glycollic acid
5 mm
was maintained and the flask finally heated for some time in a boiling
water bath The residues were several times dissolved in 1 00 cc of water
and the distillation repeated The distillate which proved to be free
from hydrogen ch loride was then made up to a definite volume and the
formic acid determined by titrating an aliquot part with
N sodium
l
hydroxide The Jo n e s method was also used in which the formic acid
was oxidized to carbon dioxi d e with
N permanganate The two
methods agreed perfe c tly thus proving formic the only volatile acid
present
TA B L E I I S U M M A R" O F R E S U L TS F O R FO RM 1 c A CI D
A mo nt of
F orm i c ac id F orm i c ac id
T i me for
b y so di m
P
cent of P cent
by p
A mo nt of
h yd ro g en
mal tose
o id at i on man g an ate h yd ro id e t h eoret i cal of total
p ero id e
yi e l d
we i g h t
D ays
C
G rams
G rams
G rams
"ol a ti l e A ci d s
.
.
.
,
—
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,
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.
,
.
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.
.
.
,
.
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,
.
.
,
.
—
.
.
u
er
u
x
.
c
.
.
x
.
.
80
—1 0
7
80
7
—1 0
—1
60
1
4
1
60
1
4 1 8
1
60
1
4
1
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.
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8
1
—
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8
(3 ) Th e " onvol a ti l e A cid 5 I n the determination of the nonvolatile
acids left behind with the salt residue after the distillation of formic acid
it was decided to use l a rger quantities of the materials in the same pro
portion as in the preliminary experiments in which 8 0 cc hydrogen
peroxide were used E ight
g lots Of maltose (equivalent to
g of anhydrous sugar ) were thus set aside In each case the strength of
the hydrogen peroxide was again determined "
ust before using and c o r r e c
tion made so as to keep the concentration uniform " 0 change in t h e
temperature or color of the solution was ever noticed on addition of the
hydrogen peroxide solution to the sugar There were only sli g ht di ff er
e n c e s in the time required for complete oxidation the average bei ng eleven
days After no reduction was shown with Fehling s sol u tion the con
tents of each flask were heated for a half hour and shaken repeatedly
with platinum black to remove the excess of hydroge n peroxide Then
6 % in excess of the theoretical amount of hydrochloric acid was added
and the solution distilled at a temperature of 4 5 to 5 0 under a pressure
—
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,
,
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,
’
,
.
-
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.
,
°
1
Am
.
Che m
.
J
.
,
1
7, 5 3 9
.
10
°
of 1 5 2 5 mm The residue in the flask was dried at 8 0 for hal f an hour
redisso l ve d in 1 5 0 cc water and again d istilled This process of r e
distillation was continued until t h e nonvolatile aci d s were entirely free
from hydr ogen chloride
The amount of formic acid in the fi l trate from each lot w as determined
by the Jones method the yields being as follows :
g
g
respe
c
tively
These
g
g
g
g
g and
g
results are nearly 2 5 % higher than those obtained with small quantitie s
of sugar
The salty residues of acid gum from each lot of sugar were taken up in
The 95 %
95 % alcohol thus separating most of the potassium chloride
alcohol residues from each lot were then combine d an d refluxed with
absolute alcoho l thus eliminating more of the salt After filteri n g and
concentrating somewhat the fi l trate was l eft at a l ow temperature for
twenty -four hours A little more of the sal t separated out together with
a small amount of materia l which re d uce d Fehling s solution an d which
apparently was hy d rolyzed sugar
The fina l product dried at 75 and 2 0 m m weighed 1 0 5 g which is
of the weight of the sugar u se d
The gu ms which were slightly d arkened wer e dissolve d in five parts of
5 % sulfuric aci d an d heated on the bo ili ng water bath for ten hours under
the reflux Then the theoretica l amount of barium hy d roxide necessary
to remove the acid was dissolved in 3 00 cc of hot w ater and slowly
a d ded After heating on the boiling water bath f or another half hour
the mixture was filtered O n concentrating the solution to two l iters
1
the amount of split o ff sugar was determi ned by the M unson and Walker
method and a l so by the F ehling solution m etho d The resu l ts by the
former in two determinations were
g an d
g of c uprous
oxide This weight of cuprous oxide from 8 cc of the solution cor responds
to
mg of dextrose equivalent to
g of this sugar in the 2 000
cc B y the l atter meth o d 2 0 cc of the sugar solution were diluted to 1 00
cc and
cc of this were required for 1 0 cc of Fehling s solution
corresponding to a total of
g of dextrose
In order to d etermine to what extent d extrose was destroyed during
the ten hours hydrolysis with five parts of 5 % sulfuric acid an in d e
pendent experiment was conducted in which 1 00 g of C P dextrose
hydrate
anhydrous ) was refluxed on the boiling water bath ten
hours with 5 00 cc of 5 % sulfuric acid The solution darkened an d
showed a final content of
g of anhydrous dextrose
g hy d rated )
or a loss of
The solution was now ad "
uste d so that a fe w drops gave the slightes t
precipitate with a 2 % solution of sulfuric acid filtered and concentrate d
—
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"
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,
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,
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,
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,
’
.
°
,
.
,
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,
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,
,
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,
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,
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,
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.
.
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,
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’
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,
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,
J A m Chem
.
.
.
.
.
.
1
.
28,
663 ;
2 9,
541
.
I I
to about 1 5 00 cc To remove the dextrose the solution was heated
in a boiling water bath with 6 0 g of calcium carbonate for ten hours and
filtered The filtrate was of a golden red color and syr upy odor Th ir t y
eight grams of calcium carbonate were filtered o ff and digested with 5 %
acetic acid An insoluble residue was left which was dissolved i n hydro
chloric acid and r e p re c ip i t a t e d with ammonia several times until per
This gave
g of calcium oxalate When dried to a
fe c t l y white
constant weight at 1 00 and analyzed the following result was obtained :
g of the salts gave on ignition
g Ca O
fo u n d
C a l c u l a te d fo r C 3 C O H 0 1 C a O
The aqueous solution of lime salts and dextrose was then concentrated
in two hemispherical evaporating dishes on steam baths C old dilute
alcohol was added with much stirring and decanted several times The
darkened lime salts thus obtained were t ak en up in water and decolorized
with animal ch arcoal O n repetition of the above process the lime salts
became granular in appearance and so free from su gar that
g showed
no reduction with Fehling s solution The air -dried lime salts weighed
g and on ignition
g of calcium salts gave
g or
calcium oxi d e
The calcium was split o ff by treating the lime salts in a hot dilute solu
tion with a slight excess of oxalic acid After filtering the aqueous
solution was distilled under reduced pressure as usual and the residue
dried The thin syrupy acids which weighed
g dissolved with the
exception of
in 5 0 0 cc hot absolute alcohol This solution was
g
concentrated several times and set aside in the ice box but n o crystals
formed Finally it w as concentrated to a weight of 8 0 g representing
There were now added slowly 2 5 0
4 0 g of gums and 4 0 g of alcohol
cc of absolute ether with much shaking and the whole mixture placed
in the ice box over night O n decanting the ether solution a nd distilling
g mobile light brown resi d ue Fraction A was obtaine d
The
portion insoluble in absol u te ether was darker and thicker and weighed
g To the latter was added acetic ether in repeated portions of 3 00 cc
each and the mixture refluxed till no more of the gum went into solution
The acetic ether solution was concentrated and set away but no cry stals
formed F inally the ether was removed by distillation and 8 g of gum
Fraction B obtained
The remaining gum Fraction C soluble in a b
solute alcohol weighed
g
F r a cti on A — Ou standing for some time after careful drying the entire
ether residue weighing
g solidifie d to a homogeneous mass of leafy
c r ystals characteristic of glycollic acid Its identity with this acid was
established in five diff erent ways
1
The melting point of the crystals w as found to be 8 0
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3 57,
223
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1 2
A portion was carefully dried in a vacuum desiccator weighed an d
dissolved in water A part of this solution equivalent to
g of
crystals on titration required
cc of
N sodium hy droxide or
The theoretical amount required for o 5 g of glycollic
00 for 0 5 g
00
aci d is
To
g of A was added 4 00 5 0 % alcohol and
g of phenyl h y
After standing three or four d ays at roo m temperature the
d r a z in e
mixture suddenly became a mass of fine crystals These were filtered
Three and one -tenth
o fl and recrystallized twice from 3 0 % alcohol
grams of shiny hexagonal plates with a me l ting point of
were o h
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t a ine d
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and six -tenths grams of the crystals from the residue A were
digested eight hours on a boiling water bath with 5 g of quickl ime An
O n concentration
excess of 5 g of calcium hydroxide was filtered o ff
of the filtrate
g of crystals of calcium glycollate were obtained and
recrystallized
g of air -dried salt lost on drying to constant
g of water
weight at 1 00 to 1 2 0
fo u n d
C a l c u l a te d fo r C 3 (C H 0 ) 4 H 0 2 H 0
The remaining
g of anhydrous calcium salt gave on heating
g of C a O
fo u n d
C a l c u l a te d fo r C 3 (C H 0 ) : C a O
F our an d fiv e -tenths grams of the resi d ue A on being treat ed with an
excess of strychnine in the usual manner gave on cry stallization
g
strychnine glycol l ate melting at 1 8 5 to 1 90
O n heatin g the strychnine glycollate with an excess of quickli m e for
ten hours there was obtained
g of calcium salt
g of air -drie d
salt lost on being dried in the air bath to constant weight as above
g of water
fo u n d
C a l c u l a te d f o r
The remaining salt
gave on further heating
g of
g
F our
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Ca O
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C a l c u l a te d fo r C a (C 2H 3O s)
B
:
C a O,
fo u n d
,
This residue of
g was diluted with water to 2 5 0 cc
Ten cc of this solution containing
g of the original gum was dilute d
to 1 00 cc and treated with
cc
N sodium hydroxide This was
heated for ten minutes on the boiling water bath an d the excess of sodium
hydroxide titrated with
N hydrochloric acid A total of
cc
N sodium hydroxide was thus used to neutralize
g of the acid
O n the basis of this titration the calculate d amount of brucine
g
was a d ded to the acid solution together with a small amount of alcohol
F r a c ti o n
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1
A r m 3 5 7 . 2 33
" e f I bi d 3 57 ,
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238
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1
3
This w as d igeste d on the boil ing water bath one ho u r after the complete
solution of the brucine O n concentrat ing the solution under red u ced
pressure a white precipita te of
g f ormed whi ch was filt e re d off an d
l
prove d to b e b ru c i ne
The water was removed by distillation an d the
resi d ue taken u p in ha lf its w e ight of water and five times its weight of
absolute alcoho l after whi ch seven crops of c ry stals tota ll ing 2 0 g w ere
g and 1 g of transparent plates
obtained as fo ll ows : 5 g
g
—
—
2 0 2 2 05
1 95 2 0 2
me l tin g respectively at 1 9 8
and
8 g
g and 1 g of small cubes a ll melting at
— T his alcoho l -soluble residue o f
g was dilute d with
F r a cti on C
water to 1 00 cc and titrat e d as above Ten cc of the solution required
cc of
N sodium hydroxide To the remaining solution was
O n taking up the salts
added the cal culated amount o f brucine
5 g
g melting at 1 8 5 cr ystallize d
in alcohol
g melting at 1 84 an d
out After concentration a resi d u e of
g was left which combine d
with a correspon d ing residue from G u m B ma d e
g In order to
convert t his combined residue into free brucine an d aci d sodium hy d roxide
was a dd e d on the basis of one an d on e -hal f mo l ecules of sodium hydr oxide
to one mo l ecule of the brucine sa l t of an assum e d four -carbon atom acid
To neutral ize the sodium
E ight grams of b r ucine were filtere d o ff
hydroxide a slight excess of hydrochloric aci d w as added an d the solution
distil led to dryness The sa l ty resi d ue was dissolved in water and r e
distilled to remove all traces of hy d rogen chloride The aci d was then
taken up in absolute alcohol an d after the removal of the a l cohol
g of gu m were obtained This residue was titrated as before in a 2 %
cc
N so d ium hy d roxide
solution and o 5 g was found to require
The remaining portion of the solution was digested eight hours on the
boiling water b ath with
g of quickl ime The fi ltrate on standing
gave
g of crystals O n heating these to a constant weight
g was O btaine d After ignition
or
of calcium oxi d e
g
was left
The high melting salts including t h e first four crops from B and the
two smal l crops from C were combined makin g
g in all L ikewise
the remaining low melting salts from B were combined making
g
O n treatment with sod ium hydroxide in the usual way the high melting
salts gave
g of acid gum an d the low melting salts
g O n stand
ing after having been freed from abso l ute alcohol by distillation the
low melting salts gave
g of leafy crystals resembling in appearance
glycoll ic acid and melting at
This was boiled with strychnine and
after filtering o ff the excess gave on concentration
of st ry chnine
glycollate crysta l s mel ting at 1 8 5
The remainder of the solution of
this residue was added to a similar residue from the high melting salts
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1
A n d er s o n A m
,
.
Chem
.
42 ,
41 0
(fo o t -n o te )
1
4
The
g of gu m from the low melti ng salts on being taken up in alcohol
and allowe d to stand for some time gave
g of the characteristi c
cry stals of mannonic l actone melting at
S ome of this was mixe d
with p ure mannonic lactone with no change in melting po int
After various futile attempts at identification t he remaining portion
from the low melting salts was combined with that from the high melting
salts givi ng
g An optical d etermination of the l atter gave : d
2 ; i
e
g substance and
g w ater ; [ a "in a
p
O
1 d cm
tube equals
whence [ a n
O f the resi d ual
gum o 5 g was foun d to require
cc
N sodium h yd roxi d e With
quick l ime the final portion gave
g air -drie d calcium salt This
on dry ing to constant weight lost
g or
water O n ignition
g or 1 7 % of C a O was obtained
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S u mm ary
.
S accharinic
acid formation does not take place at room temperature
when maltose is treated with an alkaline solution of hydrogen peroxide
with an a lk alinity of
"
2
The ratio and nature of the oxidation products from maltose with
a lkaline peroxide are quite diff erent from that of gl ucose w ith the same
reagent a fact which must be attributed to the effect of the g l u c o s id o
bon d
3 Approx imatel y ha lf of the maltose in the reaction m ixture use d
oxidizes as s u ch The remainder is apparently hydrolyze d before oxida
tion
4 The formation of g l u c o s i d o acids in the oxidation of maltose ex
plains why a molecule of dextrose requires 2 4 8 atoms of oxygen by
Fehling s solution while the larger maltose molecule requires but
atoms with the same reagent
-d -i s o s a c c h a r i n i c acids from maltose under
The
formation
of
and
oz
B
5
the influence of mild alkalies invol ves free h y droxyl groups on the first
second an d third carbon atoms from the free aldehy d e group These
carbon atoms are therefore eliminated as having t ak en part in the
l
g u c o s i d o bond
6 The formation of relatively large amounts of y-d -g l u c o s id o g l y c o l l i c
aci d in the oxidation of maltose rather than y -d -gl u c o s i d o gl y c e ri n i c aci d
in d icates that the terminal or primary alcohol carbon atom functions
in the g l u c o s i d o union of the two d -glucose molecules which go to make
up maltose
-d - l u c o s i d o -d glucose with the
The
formula
of
maltose
is
that
of
a
y
7
g
g l u c o s i d o union on the primary alcohol carbon
1
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G l a t t fe l d
,
A m Ch em
.
.
5 0,
1
50
.
of alkalies enters
the glucose series the
hexose -d i e n o l s result
ace
,
ewis grateful
gement is here made
L
ee
L
,
.