Professional Documents
Culture Documents
hand, dodee-2,4-dienal in the current work has been 3. Ellis, R., Gaddis, A.M., and Currie, G.T., Anal. Chem., 30, 475
(1958).
consistently found in linoleate and in most of the fats. 4, Ellis, R., and Gaddis, A.M., Anal. Chem., 31, 1997 (1959).
5. Ellis, R., Gaddis, A.M., and Currie, G.T., Food Research, in press,
The possibility has been considered that undec-2,4- (1961).
dienal and dodec-2,4-dienal might be mistaken for one 6. Farmer, E.tt., Koch, tt.P., and Sutton, D.A., J. Chem. Soc., 1943,
541.
another, but this is not believed to be the case (4). It 7. Fritsch, C.W., and Deatherage, F.E., J. Am. Oil Chemists' Soc.,
m a y be that both compounds are present but approach 33. 109 (1956).
8. Fugger, J.. Cannon. J.A., Zilch, K.T., and Dutton, H.J., J. Am.
trace amounts in proportion to the other aldehydes Oil Chemists' So('., 28. 285 (1951).
9. Gaddis, A.M.. and Ellis, R., Science, 126, 745 (1957).
(12). H e a t i n g the oxidized b u t t e r f a t produced over 10. Gaddis, A.M., Ellis. R.. and Currie, G.T., Food Research, 24,
17% 2-alkanone class consisting of C~, C7, C9, Cll, Cla, 283 (1959).
11. Gaddis, A.M.. and Ellis. R., Anal. Chem., 31, 870 (1959).
and C15 ketones. These compounds are not due to 12. Gaddis, A.SL, and Ellis. R.. Food Research, 24, 392 (1959).
oxidation as their formation in heated fresh b u t t e r f a t 13. Gaddis, A.M., Ellis. R., and Currie, G.T., Food Research, 25.
495 (1960).
has been described by P a t t o n and T h a r p (17). 14. K a w a h a r a , F.K., and Dutton, H.J., J. Am. Oil Chemists' Soc.,
Composition of volatile monocarbonyl compounds 29, 372 (1952).
15. X a w a h a r a , F.K.. Dutton, H.J., and Cowan, J.C., J. Am. Oil
found in the more highly u n s a t u r a t e d peanut, soy- Chemists' Sot., 29, 633 (1952).
16. Morris, S.G., J. Agr. Food Chem., 2, 126 (1954).
bean, and linseed oils is shown in Table V. Amounts 17. Patton, S., and Tharp, B.W., ,l. Dairy Set., 42, 49 (1959).
of the m a j o r characteristic aldehydes reflect the larger 18. Patton, S., Barnes. I.J., and Evans, L.E., J. Am. Oil Chemists'
Soe., 36, 280 (1959).
proportions of linoleie and linolenie acids in these oils. 19. Privett. O.S., and Xickell, E.C., Fette, Seifen, und Anstrichmit-
tel, 61. 842 (1959).
REFERENCES 20. Witting. L.A., and Schweigert, B.S., J. Am. Oil Chemists' Soe.,
35, 413 (1958).
1. Badings, I-I.T., J. Am. Oil Chemists' Soc., 86, 648 (1959).
2. Chang, S.S., and Kummerow, F.A., J. Am. Oil Chemists' Sot'., 30,
251 (1953). [ R e c e i v e d D e c e m b e r 6, 1960]
A polyaldehydic product called aldehyde oil was prepared by ylation with hydrogen peroxide, cleavage with lead
the ozonization of soybean oil, followed by reductive decompo- tetra-acetate, followed by oxidation with hydrogen
sition of the ozonolysis products. Reductive decomposition by peroxide, then by saponification.
chemical means gave 85-90% yields of carbonyl in the alde-
hyde oil. Catalytic reduction gave 75-80% yields. Partially- This p a p e r describes a relatively simple method of
hydrogenated soybean oll gave more efficient results than did p r e p a r i n g an aldehyde oil in good yield fronl soybean
unhydrogenated oil. The polyfunctional aldehyde oil was found oil and also describes some of its properties. The
to undergo condensation reactions with phenolic compound~, effects of solvent and the method of reduction were
urea, amines, and polyols to give cross-linked polymers. studied in some detail in order to obtain high yields.
The course of the reaction m a y be illustrated with
ZONE IS ONE Of the most attractive reagents for an idealized triglyceride structure for soybean oil:
TABLE I
The Ozonization of S o y b e a n Oil
Ozonization A l d e h y d e oil
Total I Yield i Yielder
Exp. Con-
carbonyl i , water
No. Solvent a Temp. sumed, Not
'.,onsumed, yield % vol~ Crude Carbonvl i C a r h o n v l r soluble
% of ~} of i before i aldehydes yield yield" [i c o n t e n } ~aldehyde
theory theory ! isolation
i / ,
A, Chemical R e d u c t i o n % % mmoles, g. ] G
1 M e t h y I e n e chtoride --2O t25 2.9 45 ~ 44 112 78 3.00 I ......
2 Methanol +14 135 3.1 48 55 94 77 3.57 ......
3 Ethanol +S 124 2.7 59 78 101 86 3.69 2.0
4 n-Butanol +14 120 4.2 54 68 115 86 3,28 ......
5 M e t h y l e n e chloride ( 5 5 ) - m e t h a n o l (45) --15 130 3.2 60 49 102 91 3.91 8.0
6 E t h y l acetate ( 8 0 ) - m e t h a n o l ( 2 0 ) --11 127 3.0 56 55 100 92 4.00 ......
6A b E t h y l acetate ( 8 0 ) - m e t h a n o l ( 2 0 ) --18 117 4.7 51 76 109 100 4.02 ......
7e M e t h y l e n e chloride ( 5 5 ) - m e t h a n o l (45) -- 9 129 2.1 75 63 114 91 3.48 ......
8a M e t h y l e n e chloride ( 5 5 ) - m e t h a n o l (45) -- 4 129 3.1 84 79 105 85 4.36 ......
B . Catalytic ~ e d u c t i o n
9 E t h y l acetate --20 120 3.4 44
10 M e t h y l e n e chloride e --64 102 3.3 47
11 E t h y l alcohol +10 117 3.0 54 115 72 2.70 4,4
12 Isoprol)yl alcohol -- 3 116 4.5 55 85 124 79 2.79 1.8
13 Ethyl acetate (80)-acetic acid (20) --11 118 4.0 57 107 76 3.10
14 M e t h y l acetate ( 8 0 ) - m e t h a n o l (20) --20 154 2.9 69 7O 102 68 2.88 24.9
a Except where noted a concentration of about 1 0 w t . % of soybean oil in t h e solvent w a s used.
The concentration of soybean oil in the solvent w a s increased to 3 0 wt. ~?).
e Marffarine.
d Triolein.
e The methylene chloride was replaced with methanol before hydrogenation.
Analysis for aldehydes on the solution containing all I[, chemical reduction of the ozouolysis products was
reduction products is reported as the total earbonyl used.
yield before isolation. Because of the loss of malon- Similar results, obtained when the ozonolysis prod-
aldehyde, which is subject to ozone attack, the maxi- ucts were reduced catalytically with hydrogen, were
mum production of useful carbonyl compounds should not as clear-cut as with chemical reduction because
be about 57 mole %, or 31.8 + 67.5 = 99.3 weight % of lower yields. In this series isopropyl alcohol is
(see method of yield calculation in Experimental). equivalent to ethyl alcohol, but hydrogenation at
The expected earbonyl yield of 57 mole % was about atmospheric pressure was difficult to achieve. Re-
the value actually obtained with the soybean oil raider duction took place more readily at 40 p.s.i.g.
optimum conditions. In isolating the reaction prod- Alcohol as the solvent is clearly superior in obtain-
ucts, no attempt was made to separate pelargonalde- ing high earbonyl yields but has the minor disadvan-
hyde, caproaldehyde, and propionaldehyde; these are tage of causing iuereased consumption of ozone. Such
reported as volatile aldehydes. Crude yields and car- solvents as methylene chloride, acetic acid, and water
bonyl yields of the products are based on the weight have been reported to be essentially nnreaetive to
and earbonyl content theoretically expected, respec- ozone whereas niethanol does react (5). However
tively. In some experiments, earbonyl analyses were reaction of ozone with carbon-carbon unsatnration
made on the aqueous solutions and are reported as is so rapid that very little of the ozone reacts with
yield of water-soluble aldehyde, chiefly malonaldehyde.
Factors Affecting Ozonization TABLE II
Effect of Solvent on Carbonyl Yield in the A l d e h y d e Oil
Solvent. Reactive solvents in general, such as meth- (Chemical R e d u c t i o n )
anol, ethanol, and acetic acid, are superior to non- ~ta~ I
1 IAhIehvde
reactive solvents (4). The alkoxy- or aeyloxyhydro- E x p . No.
caroony oil"
Solvent yield carbo'nyl
peroxides formed are easily reduced or oxidized and before yield
isolation "
lead to a minimum of by-products. 5{ethanol is a
good solvent for the ozonization of methyl oleate (3). I r r
] ....................................... ] M e t h y l e n e chloride i 45 78
The total carbonyl yield before product isolation is 2 ...................................... i Methanol ' 48 ~ 77
as high as 92% when methanol is the solvent, and the 3 ....................................... i Ethanol 59" 86
n-Butanol 54 86
isolated yield of the methyl ester of azelaic semialde- o . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . [ M e t h y l e n e chloride ( 5 5 ) - I 605 91
methanol (45)
hyde is 88%. Ethyl acetate ( 8 0 ) - I
methanol (20) ! 56 92
In the ozonization of soybean oil, methanol gives a
a Includes 2% water-soluble aldehydes.
relatively low earbonyl yield in the aldehyde oil b Includes 8% water-soluble aldehydes.
comparable with that obtained with the nonreactive
solvent methylene chloride. This low yield results
from the relative insolubility of the oil in methanol the solvent. Ill these experiments consumption of
to give a two-phase system. The ozonolysis products, ozone exceeded by about 25% the amomlt expected
which are soluble, were present in solution in much on the basis of the unsaturation.
higher concentration than the oil and hence were The concentration of oil in solvent was 10 wt. %
subject to oxidation. Both ethanol and n-butanol were in the majority of experiments. Equivalent results
better solvents and gave better results. Butanol pre- were obtained at 30 wt. % (Exp. 6A, Table I).
sents some disadvantages because of the difficulty in Reduction Method. Previously it had been found
separating layers during washing operations. Best that catalytic reduction of the ozonolysis products
results (aldehyde oil carbonyl yields of 90% or bet- from methyl oleate with 10% palladium-on-charcoal
ter) were obtained when a good solvent (methylene gave earbonyl in lower yields than did reduction ~dth
chloride or ethyl acetate) was used in combination zinc and acetic acid (3). This difference was con-
with methanol. In all the experiments listed in Table firmed with soybean oil (Table III). In spite of
JULY, ]961 PRYDE ET AL.: OZONIZATION OF SOYBEAN OIL 377
TABLE VI
P h y s i c a l C h a r a c t e r i s t i c s of A l d e h y d e Oils
Physical Characteristics
E x p . No. Material Method of
Source reduction 30 Mol w t Gardner Gardner
n o " " viscosity color
TABLE IX
soluble products, depending upon the reactant ratio.
Theoretical Composition of AMehyde Oil
An aldol condensation occurred almost immediately ( B a s e d on Soybean Oil C o m p o s i t i o n )
when the aldehyde oil was treated with an amine, such
as n-octyl amine, ethylene diamine, piperidine, mel- Component Mole %
amine, and aniline. These condensation products were P a l m i t i c ......................................................... 10.9
S t e a r i c ........................................................... 3.3
rubbery, insoluble, and infusible gels. Mixtures of Azelaic semi-aklehyde .................................... 85.8
pelargonaldehyde with aldehyde oil were condensed Molecular w e i g h t ~ 600
in the presence of diamines to form soluble products, Carbonyl value ~ 4.29 mmoles g. I
which could then be cross-linked with the further ad- C o n s t a n t s for D i m e t h y l Aeetal Oil
dition of aldehyde oil. ~Iolecular w e i g h t ~ 719
Carbon)" v a l u e ~ 3.58 m m o l e s / g .
Heat alone also caused aldehyde oil to form a
brown, insoluble, and infusible but soft resin.
It is quite evident from these reactions that the chromatography (GLC, on 10% Craig succinie poly-
polyfunctionality of aldehyde oils is sufficient to cause ester on Chromosorb at 175~ Compositions of the
cross-linking (Table V I I ) . This property, in addi- original soybean oil and the aldehyde oil derived from
it are given in Tables V I I I and IX.
TABLE VII
The aldehydes theoretically produced front one mole
Functionality versus Carbonyl C o n t e n t of Aldehyde Oil
(889 g.) of soybean oil include, as shown in Table X:
N u m b e r of
Source Carbonyl aldehyde
content groups/mol. TABLE X
Theoretical Yields of Aldehydes (other t h a n Aldehyde Oil)
A. As free aldehyde meq./g, P r o d u c e d from Soybean Oil
Theoretical .................................................... 5.41 3.00 [ B a s e d on 1 Mole (889 g.) of Soybean Oil]
T r i o l e i n a ....................................................... 4.36 2.41
Soybean oil a................................................. 4.00 2.22 Aldehyde produced, m o l e s / m o l e
Soybean oil b ................................................. 3.60 2.00 Compo- soybean oil
F a t t y a .id sition,
B. As d i m e t h y l acetal origin 'i mole ~/c Ca C6 Malon-
Theoretical .................................................... 4.34 3.00 I c~ aldehyde
Soybean oil ~................................................. 3.04 2.10 1 I
Soybean oil b .................................................. i 2.90 2.00 0.78
Oleic ............................... [ 26.0 ....
a A c t u a l sample. Linoleic. .......................... j 53.6 1.608 i:~08
b Calculated carbonyl c o n t e n t to give a f u n c t i o n a l i t y of 2. Linolenic. ....................... 6.2 0']i'86 , .... 0.372
TABLE XI
A h l e h y d e Oil C o n d e n s a t i o n s
formation of acetals. The third is the most probable bonyl as volatile aldehydes was 79%, crude yield of
cause of high-oil yields in these experinlents. aldehyde oil was 105%, and the carbonyl yield in the
aldehyde oil was 85%.
Procedure Catalytic Hydroge~ation. Soybean oil (28.9 g., 0.15
The general ozonization procedure employed has mole of unsaturation) was dissolved in 250 ml. of
been previously described in some detail (3). Of all absolute ethanol. Oxygen containing 1.12 m moles of
the experiments summarized in Table I, one suffices ozone per liter of oxygen was passed through the solu-
to illustrate chemical reduction of the ozonolysis prod- tion, which had been chilled to 10~ at a rate of
ucts and another, to illustrate catalytic hydrogenation. about 1.81 1./rain. for 89 mill. The end-point of the
reaction was determined by the same means as before.
Chemical R~duction. Triolein (150 g., 0.498 mole of
The amount of ozone found to have passed through
unsaturation) was dissolved in a solution of 800 ml.
the reactor was 3.0% of the theoretical anlount. The
of methanol in 1,000 ml. of methylene chloride. Oxy-
amount of ozone absorbed by the reaction mixture
gen containing 1.24 mmoles of ozone per liter of oxy-
was 117% of the theoretical. The solution and v a p o r
gen was passed through the solution, which had been
space above the solution were flushed with nitrogen,
cooled t o - 4 ~ at a rate of about 2.8 1./rain. for 190
and 0.20 g. of 10% palladium-on-charcoal catalyst
rain. The end-point of the reaction was determined
was added. H y d r o g e n a t i o n was carried out at atmos-
as the point at which the ozone concentration in the
pheric pressure and room t e m p e r a t u r e for about 7
exit gases f r o m the reactor began to rise as deter-
hrs., at the end of which time the test for peroxide
mined by the Welsbach ozone meter. The amount of
was negative. A solution of hydrogen iodide in glacial
ozone that was unreacted and found to have passed
acetic acid was used for this test. The use of isopropyl
through the reactor was 15 mmoles, corresponding to
alcohol as a solvent required a pressure of 40 p.s.i.g.
3% of the amount of ozone theoretically expected to
of hydrogen to obtain a product free of peroxide. The
be absorbed. The amount of ozone absorbed by the
solution was filtered, then washed in much the same
reaction m i x t u r e was 129% of the theoretical. The
m a n n e r as before to renmve small amounts of malon-
ozonolysis products were reduced with zinc powder
aldehyde. I f this step was omitted, the aldehyde oil
(75 g.) and glacial acetic acid (150 ml.). The excess
p r o d u c t was considerably darker in color. There was
zinc and the precipitated zinc salts were renloved by
obtained 12.8 g. of volatile aldehydes and 21.38 g. of
filtration. The solution was evaporated under a slight
aldehyde oil. The total yield of carbonyl in the vola-
v a c u u m to a volume of about 500 ml. W a t e r (350 ml.)
tile aldehydes was 81%, the crude yield of aldehyde
and methylene chloride (250 ml.) were added, and the
oil was 115%, and the carbonyl yield of the aldehyde
layers were separated. The aqueous layer was ex-
tracted twice more with methylene chloride, and the oil was 72%.
Resin-Forming Reaction, s. These were carried out
extract then ga.ve a negative test for earbonyl. The
on a small scale on a purely exploratory basis and are
methylene chloride solution was washed first with
summarized in Table X I .
water, then with diluted sodium bicarbonate solu-
tion, and again with water, backwashing each wash REFERENCES
with a small amount of methylene chloride. The com- 1. A n o n y m o u s , Chem, E n g . News, 3 7 , No. 36, 25 ( 1 9 5 9 ) .
bined methylene chloride solutions were dried and 2. S c a n l a n , 5 . T . , a n d S w e r n , D a n i e l , J . Am. Chem. Soc., 6 2 , 2 3 0 9
evaporated. The residue weighed 202 g. and contained (1940).
3. P r y d e , E . t t . , A n d e r s , D . E . , T e e t e r , H . M . , a n d C o w a n , J.O., ft. Org.
4.15 mmoles of carbonyl per g r a m for a earbonyl Chem., 2 5 , 6 1 8 ( 1 9 6 0 ) .
yield of 84%. The volatile aldehydes were then re- 4. B a i l e y , P . S . , Chem. Revs., 5 8 , 9 2 5 ( 1 9 5 8 ) .
moved u n d e r vacuum. There were recovered 15.1 g. 5. G r e e n w o o d , F.C., J. O r g . Chem., 1 0 , 4 1 4 ( 1 9 4 5 ) .
6. T h e f o r m a t i o n of e a r b o x y l i c a c id s a n d e s t e r s by t h e u s e of pal-
of material in a d r y ice t r a p containing 0.39 mmoles l a d i u m - o n - c h a r c o a l c a t a l y s t s is to be t h e s u b j e c t of a f o r t h c o m i n g pub-
of carbonyl/g., 54.7 g. of volatile aldehydes contain- lication.
7, D o b i n s o n , F,, Chem. a n d I n d . , 1 9 5 9 , 8 5 3 .
ing 6.33 mmoles of carbonyl/g., and 86.2 g. of residue
containing 4.36 mmoles of carbonyl/g. Yield of car- [Iteceived February 10, 1961]