548 T ~ E JOURNAL OF THE A M ~ m A N OIL CHEMISTS' SOCIETY VOL.

31

retical principles of liquid t h e r m a l diffusion have not 3. Kis$1er, g . E., 3]£uckerheide, V. J., ~/[yers, L. D., J. Am. Oil
Chemists' Soc., 23, 146-150 ( I 9 4 6 ) .
been fully developed. Factors which affect the degree 4. Myers, L. D., 2¢Iuckerheide, ~r. j., U . S . Pat. 2,293,676 (1942)
a n d U . S . Pat. 2,421,157 (1947).
of separation in the t h e r m a l diffusion process are 5. Brown, A. C., U . S . Pat. 2,352,160 (1944).
u n i f o r m i t y of size of the a n n u l a r space, t e m p e r a t u r e 6. Schlenk, H., Holman, R. T., Science, 112, 19-20 (1950).
7. Newey, I t . A., Sho.kol, E. 0., ~Iueller, A. C., Bradley, T. F., and
differential, and time required for diffusion. I t ap- Fetterly, L. 0., Ind. Eng. Chem., 42, 2538-2541 (1950).
8. Jones, A. L., and Foreman, 1~. W., Ind. Eng. Chem., 44, 2249-
pears that this method m a y be adapted for continuous 2253 (1952).
operation. 9. Pool, W. 0., U . S . Pat. 2,543,055 (1951).
REFERENCES 10. Eckey, E. W., Ind. Eng. Chem:, 40, 1183-1190 (1948).
11. Nicholsen, R., and Formo, M. W., g. Am. Oil Chemists' Soc.,
1. Stingley, Dale, Chem. Industries, 48, 50-52 (1941). 26, 329-331 ( 1 9 4 9 ) .
2. Eoster Wheeler Corporation Bulletin 1D-46-10 and :F'otfus, R. tt., 12. Swern, Daniel, and Parker, W. E., J. Am. 0il Chemists' See.,
and Whit~ F, B., J. Am. 0il Chemists' See., 30, 49-53 (1953). 29, 431-434 (1952).

Ester Reactions of Fatty Materials

MARVIN W. FORMO, Archer-Daniels-Midland Company, Minneapolis, Minnesota

E A C T I O N S involving ester linkages of fats and R C O O R ' -~- R " C O O H ~ ' R " C O O R ' -1- R C 0 0 H
R oils are among the most i m p o r t a n t in the chemis-
t r y of f a t t y acid derivatives. Hydrolysis of esters 4. Interesterification, sometimes termed ester inter-
under alkaline conditions, the familiar saponification change or trans-esterification, is the exchange of acyl
of fats and oils, has been practiced for centuries. This and alkyl groups between a p a i r of esters.
p a p e r will cover the non- RCOOR' q- R " C O O R ' " ~ ' R C O O R ' " -~- R " C O O R '
hydrolytic ester reactions:
esterification, a l c o h o l y s i s , There has been some confusion in the literature
acidolysis, and interesteri- regarding the nomenclature of these related reactions.
fication. These reactions are Some authors use fhe terminology, "trans-esterifica-
of f a r more recent origin tion reactions," broadly to describe a]coholysis, acid-
and have been recognized olysis, and interesterification. Others use the t e r m
for a p p r o x i m a t e l y one cen- "interesterifieation r e a c t i o n s " in a similar broad sense
tury. t t o w e v e r it has only ( G e r m a n " U m e s t e r u n g " ) . I t is becoming more com-
been within the past few mon practice to use the term "trans-esterification" as
decades that they have a synonym for interesterification or ester-interchange
a s s u m e d t e c h n i c a l impor- to describe the exchange of acy] and alky] groups
tance. Alkyd resins, rub- between a p a i r of esters. Such terminology will be
b e r - l i k e , polyesters., im- adhered to in this discussion.
proved lard for shortening, The close relationship between esterification, aleo-
and nonionic surface active holysis, and interesterification is illustrated b y com-
agents, to improve shorten- parison of the equilibrium constants for homogeneous
i n g efficiency a n d s o f t e n reaction. Normally we do not have sufficient data to
bread, represent only a few calculate all equilibrima constants, b u t theoretically
of the products dependent the point of equilibrium in both alcoholysis and inter-
M. W. Formo upon these ester reactions. esterifieation reactions can be calculated f r o m the sim-
ple esterifieation constants.
General Scope and Chemistry of S t u d y of esterifieation and hydrolysis provided some
the Ester Reactions of the earliest classical examples of reversible equilib-
ria. A t equilibrium in a homogeneous reaction the
There are f o u r closely allied reversible reactions ,relationship between concentrations of reactants and
involving addition or interchange of alkyl radicals on products is represented b y the familiar esterifieation
the earboxyl residue of f a t t y acids. These reactions, constant.
which have much in common, are as follows :
1. Esterifieation is the condensation ~f an acid and Acid -[- Alcohol , ~ Ester .4- W a t e r
an alcohol to give an ester and water; the reverse [Ester] X [Water]
reaction is hydrolysis. [Acid] X [Alcohol] ---~K esterification
RCOOH @ R'OH , ' RCOOR' @ IIOH Table I illustrates tile relationship of the esterifiea-
tion equilibrium constant to the aleoholysis and inter-
2. Alcoholysis involves the replacement of the alkyl esterifieation equilibria. Knowledge of esterification
group of an ester b y another through interaction of constants would p e r m i t calculation of the equilibria
the ester and an alcohol. The reaction is frequently in both alcoholysis and interesterification reactions.
described in terms of the added alcohol, e.g. methan- Several reviews are available covering the ester
olysis, glycerolysis, etc. reactions (1, 2, 3, 4, 5).
I~COOR' @ R " O H ~ ~ R C O O R " -~- R ' O H Esterification Reactions
3. Acido]ysis, in an analogous way, is the substitu- There are f o u r p r i m a r y methods for direct prep-
tion or exchange of aeyl groups of esters through the aration of esters:
reaction of an ester and an acid. 1. reaction of an alcohol and an acid with elimina-
~ T e c h n i c ~ l P~per No. 130 from the Areher-Daniels-SIidland Company. tion of w a t e r ;
 NOVEMBER 1954 FORMO: ESTER ]{EACTIONS 549

TABLE I two to four times their weight of Mcohol in the pres-

E Q U I L I B R I U M CONSTANTS IN ESTERIFICATION ALCOHOLYSIS
ence of 1% to 3% of sulfuric acid or dry hydrogen
chloride. Using such large excesses of methyl alcohol
AND I N T E R E S T E R I F I C A T I O N REACTIONS (15 to 35 moles per mole of fatty acid), ester yields
of 95% or higher are obtained.
ESTERIFICATION REACTION:
The equilibrium and velocity constants of esterifi-
REACTION OF ACID, RCOOH, WITH ALCOHOLS ReOH AND RSON
cation of f a t t y acids with methyl, ethyl, and other
monohydric alcohols have been the subject of classi-
RCOOH + ReOH q: ) RCOORt 4- HtO
cal investigations (8, 9, 10, 11). Sudborough (11)
K , - (RCO°Re) ~H~°-L and his co-workers demonstrated that the velocity of
(RCOOH) (RIOH)
esterification of various f a t t y acids from butyric to
RCOOH ÷ R~OH - ~> RCOOR= + H20
(RCOOR'~ (R=O)
stearic was practically constant. The rate for unsatu-
K 2" (RCOOH) (RaOH} rated acids such as olMc, elaidic, erucic, and brassidic
SIMILARLY FOR ACID, ReCOOH,WITH ALCOHOLS, RZOH AND RIOH
were similar and somewhat less than half that of the
KI,(R/COOR=) (H~_L i K4= (RtcO01~) (HtO) saturated acids. It is interesting that the esterifica-
(R"COOH) (RZON) (RtCOOH} (RSOH-'T- tion rates of the cis- and trans-isomers are virtually
ALCOHOLYSIS REACTION:
identical.
Analysis of fats for component acids usually in-
RCOORz .¢. I~OH <. "'> RCOOR3 .1- ReOH volves fractionation of esters. The fat sample is con-
{RCOORa) (ReOH)= _.Ke_ verted to methyl esters by alcoholysis, or alternatively
KAL-I,t (RCOOR=) (RaOH) KI
the sample is saponified, extracted with solvents to
RICOOR¢'I" RIOH~. > RIcooR 3 -I. R20H remove unsaponifiable constituents, acidified, and es-
KAL-2 = ~RtCOORS) [RIOH) = ._.~K4_ terified with methyl or sometimes, ethyl alcohol. F o r
(R'COORz) (R3OH} Ka analytical work it has been suggested that methyl
esters be formed by reaction of soaps with an excess
I NTERESTE RIFICATION REACTION : of dimethyl sulfate in the presence of potassium car-
bonate (12). This reaction is convenient and quanti-
RCOOR2+ RICOOR3( ) RCOOR3 + I~COOR$
t a t i v e . Vacuum-distillation is used to separate the
methyl esters into fractions of varying boiling points
K-~NTERESTERtFtCATtON = ~RICOOR~ {RCOOR3) = KAL-t = K I k K . ~ - and molecular size. Such determinations as refractive
(RCOORz) (RICOORs) KAL-e Kt K#
index, iodine value, and saponification value are used
to characterize the fraction and permit calculation of
2. reaction of an alcohol and an acid anhydride to the fatty acid composition. L ongenecker (13) and
form an ester and an acid; Hilditch (14) have reviewed the literature on ester
3. reaction of an alcohol and an acid chloride with fractionation as an analytical tool. The quality of the
elimination of HC1; still and the technique of operation are of major im-
4. reaction of an alkyl halide and a metal salt of portance in application of ester fractionation for de-
an organic acid with elimination of the metal termination of fat composition (15, 16).
halide. F a t t y acids esterify far more rapidly than rosin
acids with low molecular weight alcohols such as
Indirect methods for ester formation involving alco- methyl, ethyl, pro pyl, and butyl. This difference is
holysis, interesterification, and acidolysis will be con- the basis for the analytical determination of fatty
sidered later. Of the direct methods the only process acids and rosin acids in tall oil. The mixed tall oil
of technical importance involves direct formation of fatty acids are refluxed with methyl alcohol contain-
the ester from alcohol and acid. ing dry hydrogen chloride gas. The fatty acids esterify
Esterification of earboxylic acids, involves loss of whereas rosin acids are virtually unesterified. Differ-
water between the hydroxyl group of the acid and the ences in A. V. before and after esterifieation permits
hydrogen of the alcohol. calculation of both the f a t t y acids and the rosin acids
0 0 (17, 18, 19). This difference in ease of esterification
// H÷ // has been suggested as a basis for separation. Gloyer
RC-OH -+- H OR ~ ~ RC-OR -[- HOH esterified tall oil and fractionated, using a combination
of a non-polar solvent, such as. petroleum naphtha,
The rate of reaction is proportional to the hydro- which preferentially dissolves the f a t t y esters and fur-
gen ion concentration over lower ranges of acid cata- rural, which is more polar and dissolves the rosin acids
lyst concentration. Strong acids such as H~S04, tIC1, (20). Rosin acids can be esterified with methanol un-
H~POd, toluene sulfonic acid, Twitchell acids, etc., der drastic conditions by autoclaving an excess of an
catalyze esterification. The reaction is bimolecular, alcohol with rosi~ acids at temperatures of 280-290 °
but if a large excess of either acid or alcohol is used, C. and pressures of approximately 1,000 lbs./sq, in.
the reaction is pseudo-first-order. Modern electronic (21, 22, 23).
concepts of the reaction mechanism are discussed by Because the esterification is an equilibrium reaction,
Alexander (6) and Remick (7). it can be driven to conclusion by removal of the water
Esterification of Fatty Acids with Low Molecular of reaction. I n the esterifieation of lower alcohols,
Weight Monohydric Alcohols. The esterifieation of removal of water is difficult because of the closeness
fatty acids with lower molecular weight monohydric of boiling point of water and the lower alcohols. Aze-
alcohols is normally carried out, using a large excess otropic procedures likewise are not applicable because
of the alcohol in the presence of an acid catalyst. For of the mutual solubility of alcohol-rich water-alcohol
preparation of methyl and ethyl esters, fatty acids mixtures with normal azeotroping solvents.
are commonly refluxed for several hours with from Cation exchange resins of the phenol-formaldehyde
550 THE JOURNAL OF THE AMERICAN OIL, CHEMISTS' SOCIE~T¥ VOL. 31

sulfonie acid type have been used to catalyze esterifi= ling is used for collection of water. Measurement of
cation of oleic acid by n-butyl alcohol b u t offer no the water distilled during reaction offers a convenient
advantage over conventional acid catalysts (24). method for following the course of the reaction. The
Methyl and n-butyl esters of unsaturated acids are temperature of azeotropie esterifieation can be closely
used as lubricating oil additives in the form of sul- regulated b y control of solvent quantity (36). Com-
furized esters (25, 26). mereially azeotropie esterification is used, particularly
for alkyd resin production. Phthalie anhydride sub-
Esters of Higher Monohydric Alcohols limes readily at esterification temperature, and the
azeotropie solvent (usually xylene) tends to dissolve
Esterification of higher alcohols from hexyl u p w a r d
and flush the sublimate back into the reaction kettle.
can be carried out conveniently, using stociometric
2. Esterification using an inert gas sparge. Rate and
quantities of alcohol and f a t t y acid u n d e r azeotrope
degree of esterifieation with polyols is. improved by
conditions with benzene, toluene, or xylene as a sol-
blowing an inert gas, such as carbon dioxide or nitro-
vent. Direct esterification of higher f a t t y alcohols is
gen, through the reaction mixture (37, 38). Water
practical, using a stream of inert gas such as carbon
is carried off b y the gas stream, b u t losses of both
dioxide, nitrogen, or even steam to sweep out the lib-
polyol and f a t t y acid occur.
erated water, or alternatively a partial vacuum may
3. Vacuum. esterification. Esterification under re-
be used to remove water while retaining the acid and
duced pressure offers the most efficient and practical
alcohol. Higher f a t t y alcohol esters of saturated acids
method for esterification with polyhydric alcohols (39,
are waxy solids.
40). A moderately rapid reaction is maintained at a
lower temperature than for the other processes with
Other Monohydric Esters
good preservation of Color. Glycerol, which is prob-
Vinyl esters are p r e p a r e d in an unusual manner. ably the most important polyol used for esterification,
Vinyl alcohol is unknown, but vinyl esters can be is moderately volatile at vacuum esterification tem-
prepared by direct addition of acetylene to f a t t y acids peratures. Partial condensers help minimize glycerol
at high temperatures, usually in the presence of a losses. A combination of vacuum esterification and
basic catalyst, such as zinc oxide (27, 28). sparging with CO2 or even steam gives the most prac-
1%COOH -}- HC ~ CH > RCOOH = CH2 tical reaction from the standpoints of rate, complete-
ness, and product color.
An alternative process more suitable for laboratory Catalysts can be used for speeding up esterification
preparation involves acidolysis of vinyl acetate with b u t usually to the detriment of color. Konen (41) in
f a t t y acids in the presence of a mercury salt (29, 30, a study of the esterification of unsaturated acids with
31, 32). a series of polyols concluded that, in " q u i t e an ex-
Copolymerization of vinyl esters of saturated acids tensive study of catalysts, none was found that gave
with vinyl acetate has been suggested for preparation sufficiently good results to w a r r a n t use either com-
of internally plasticized resins (33). mercially or in the laboratory. In all cases the use of
Teeter and Cowan prepared allyl, methallyl, and a catalyst increased the initial esterification rate; but
chloro-allyl esters by direct esterification and also b y if a low final acid value (2-5) was desired, the time
aleoholysis (34). necessary to arrive at this acid value was the same
T e t r a h y d r o f u r f u r y l and cyclohexyl esters have been with or without catalyst." There is an extremely volu-
prepared azeotropieally, using benzene as a solvent minous literature on catalysis of the esteriflcation re-
(35). T e t r a h y d r o f u r f u r y l oleate is marketed as a vinyl action. Among catalysts which have been described
plasticizer. are a variety of acidic materials, such as sulfuric
acid, hydrochloric acid, p h o s p h o r i c acid, sulfonic
Esters of Polyhydric Alcohols acids, Twitchell reagent, trifluoroacetic acid, boron
Commercially the esters of polyhydric alcohols are trifluoride, alkyl acid phosphates, etc. Catalytic ac-
f a r more important than the monohydric esters. In tivity has been ascribed to practically all metals, in
the case of monohydric alcohols it is possible to use a the periodic table in the form of acetates, abietates,
large excess of the esterifying alcohol, removing it alkoxides, carbonates, chlorides, fluorides, hydroxides,
at the conclusion of the reaction. With polyhydric oxides, naphthenates, and soaps of f a t t y acids. Metal-
alcohols this is impossible. With an excess of polyol lic salts mentioned most commonly are lead, zinc, and
the f a t t y acid residues are distributed randomly, leav- calcium. Many of these esterification catalysts are
ing some free hydroxyl g r o u p s and giving a product also catalysts for alcoholysis, interesterification, and
containing all possible mono-, di-, tri-, etc., esters to- acidolysis reactions.
gether with the fully esterified polyol. In order to Good agitation during large scale esterifieation is of
carry esterifieation to completion it is necessary to use great importance. Paddle agitators are not normally
only the theoretical amount or a slight excess of the satisfactory, and propeller or turbine types are needed
alcohol, using reaction conditions u n d e r which water to draw the heavy, f a t t y acid immiscible polyol from
is efficiently removed. Esterification by use of heat the bottom of the reaction vessel. This is particularly
alone without special provisions for removal of water important in order to avoid charring with high melt-
gives poor results, both with respect to the rate and ing polyols, such as pentaerythritol (42).
extent of esterifieation. Several methods are used for
water removal : Esterification with Glycerol
1. Azeotropic esterification. The theoretical amounts F a r more work has been devoted to the study o f
of polyol and f a t t y acid are heated in the presence of esterification of f a t t y acids with glycerol than with
refluxing xylene which carries away the water formed any other alcohol, either monohydric or polyhydric.
during the reaction. F o r laboratory preparations a Lower molecular weight f a t t y esters are f a r l e ~
simple trap such as the Dean-Stark or Bidwell-Ster- important than the higher f a t t y acid esters. Reac-
 NOVEMBER 1954 F O ~ O : EST~a R~ACTm~S 551

lion of acetic anhydride with glycerol to form tri- using nitrogen sweeping and standardized agitation
acetin is used as a basis for the familiar " a c e t i n " at various temperatures (49). The rate of esterifica-
method for determination of this important polyol lion increases sharply with temperature (Figure 1).
(43). Reaction of acetic anhydride with hydroxyl The reaction was found to be bimoleeular but pro-
groups is used as an analytical determinatio~ l o r ceeded in two stages with heats of activation of 12,300
hydroxyl content (% hydroxyl, acetyl value, or pref- and 10,800 cal. per mole respectively.
erably hydroxyl value) in oils and fats as well as in Experimental evidence indicates that the esterifica-
polyols (44). lion of f a t t y acids gives a statistical or random dis-
Reaction of monoglycerides with acetic anhydride tribution of f a t t y acids among the glyceride types.
gives " a c e t o stearins," non-greasy, highly flexible I n the simplest sense, fats may be c o n s i d e r e d as
f a t t y m a t e r i a l s having promise as plasticizers, coat- composed of two acids, saturated and unsaturated.
ings for food products, and temperature-resistant Figure 2 gives the composition of component tri-
spreads (45, 46, 47). glycerides having s mole-fraction of saturated acids,
Esterification of glycerol is a stepwise process. S, and u mole-fraction of unsaturated acids, U.

CH~OH /
GHOH
CHoOH
.[
CH~O0(~R CH~O'GOR.
I
9o
(/1
~l-I0'001~ ~1 80
RC'00H + °HOH
CHeOH \
l
I
tt a
n,-
td 7 lU NSATURATED TRISATURAT
~HOCOR - - - ~ C:HOCOR
I /
C'H20H CH~0H
a a n d fl M o n o g l y c e r i d e s Diglycerides Triglyceride
° ,0'2
I-
~l• MONOSATURATED DISATURATED
1, 3 a n d 1, 2 0
Z 40~ rIU~T~AT[D
~ MON(~N,~rUR
D.
2
The p r i m a r y initial product is the a monoglyceride 0
although some fl isomer also is formed but probably
rearranges to the a-form. Similarly, the 1,3-dig]ycer-
ide is the principal form on continued esterification
leading finally to the completely esterified triglyceride.
o
The first comprehensive classical study of esterifi-
cation of glycerol was carried out 100 years, ago by
Berthelot, who. systematically prepared mono-, di-, and MOLE-% OF SATURATED
triglycerides from practically all f a t t y acids known at FATTY ACIDS
that time (48). Such esterifieation of f a t t y acids with FIG. 2. C o m p o n e n t g]ycerldes a t s t a t i s t i c a l d i s t r i b u t i o n .
glycerol is sometimes termed re-esterification since it
gives the glyecrides from which the acids, and glycerol
were originally derived. The composition of glyceride types is given b y the
Feuge, Kraemer, and Bailey studied the esterifica- following equations (49) ~
lion of p e a n u t oil acids with glycerol at 20 ram.,
T r i s a t u r a t e d , GS~ = s~ X 100, m o l e - p e r c e n t a g e .
D i s a t u r a t e d - m o n o u n s a t u r a t e d , GS~U = 3s~u X 100, mole-
IO0- l percentage.
M o n o s a t u r a t e d - d i u n s a t u r a t e d , GSU2 = 3su 2 X 100, mole-
9
percentage.
Triunsaturated, GUs = us X 100, mole-percentage.
8
Bhattacharya and IIilditch esterified various com-
b i n a t i o n s of saturated and unsaturated acids (50).
The trisaturated glyceride co~ltent b y permanganate
oxidation fell very close to the trisaturated glyceride
curve of F i g u r e 2. Other studies involving interesteri-
fication of glycerides in homogeneous systems indicate
that within experimental error the content of fully
saturated glycerides corresponds to the amount cal-
culated for r a n d o m distribution (51, 52, 53).
Esterification of f a t t y acids with an excess of glyc-
erol gives a mixture of mono-, di-, and triglycerides.
U. The composition of the reaction mixture has been
calculated on the basis of homogeneous reaction and
The a.bove distribution is a special case of the generalized random
distribution theory. With a mole-fraction of acid A, b mole-fraction o.f
B, c mole-fraction of C, d mole-fraction of D, etc., glyceride types are
I ¢' 5 4 5 6 T 8 as follows :
aR (All values as mote-percentage.)
Single component acid glycerides:
GAz~----as X 100; G B z : b s X 100, etc.
T w o component ucid glycerides:
T I M E (HOURS) GArB = 3 ~ b X 100; GAeC ---- 3 a~c X 100; GABz = 3 ab.~ X 100,
etc.
FIG. 1. Esterifieation of equivalent quantities of peanut oil Three component acid glycerides:
GAB0 ---- 6 abc X 100; GABD ---- 6 abd X 100; GBCD = 6 bad X
acids and glycerol a.t various temperatures. 100, etc.
552 TItE JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY VOL. 31

The logarithm of the percentage of added glycerol is

plotted against the temperature. Between the temper-
,.o atures of 175°C. and 250°C. there is a linear relation-
ship between the temperature and the logarithm of
I I the maximum amount of glycerol in solution.

50

40 J

~30 J
J
o o~ I ].s ~ 15 $ 3.S 4 iI5 ° I0
MOLES OF ADDED ELYCEROL REACTING WITH ONE MOLE OFFATOF M.W. 8?0
5.2 10~57 21.14 31.71 42,28 52,85 105,,7
WEIGHT-% OF GLYCEROL AOD[O TO I MOLE OF FAT

Fro. 3. Equilibrium between fats and glycerol assuming

homogeneous reaction and statistical distribution. ~20 J
J
8 MONOGLYCERIDE
/ t I

11'5 200 225 250

TEMPERATURE uC

FIa. 5. Glycerol miscible and reactable with fat at

various temperatures.

Referring back to Figure 4, at 175°C. the maximum

°o 0.5 I 2 3 4 5 10 content of glycerol which can be added while main-
MOLES OF ADOED GLYCEROL REACTING WITH I MOLE OF FAT
taining homogeneous reaction conditions is 17% cor-
5.Z 10.57 21,14 31.71 4E,:~8 5E.85 105.7 responding to a maximum monoglyceride content of
WEIGHT-% OF GLYCEROL REACTING WITH I MOLE OF FAT slightly over 40%. At 250°C. up to 40% of glycerol
Fro. 4. Equilibrium between fats and glycerol after removal can be added to give a mixture at equilibrium con-
of excess glycerol taining 65% of monoglyceride. Practically, this tem-
(Assume homogeneous system and statistical distribution) perature is too high, and intramolecular dehydration
of glycerol or partial glycerol esters occurs to give
polyglyeerol and its esters (54, 56). Limiting tem-
statistical distribution of fatty acids among available peratures of 200°C. to 225°C. are normally used, giv-
glycerol linkages (54). Figure 3 gives the statsitical ing approximately 50%. monoglyceride content as a
composition on mole-% and weight-% bases for alco- maximum for technical monoglyceride either by di-
holysis of a triglyccride of 870 M. W. (correspond- rect esterification or by alcoholysis.
ing to soybean oil) by varying proportions of added The data of Feuge and Bailey indicated that very
glycerol. The figure also applies to esterification reac- close approach to the statistical distribution was ob-
tions, assuming complete esterification of a stoichio- tained when lower levels of glycerol were used. Esteri-
metric amount of glycerol followed by addition of fication of fatty acids by excesses of other polyols also
excess glycerol over the range in Figure 3. Figure 4 has been demonstrated to give an approach to statis-
gives the equilibrium composition of f a t t y compo- tical distribution (57).
nents after glycerol removal. Normally the observed Addition of a mutual solvent permits higher mono-
quantity of monoglyceride falls below the theoretical. glyceride content by maintaining homogeneous reac-
For instance, Hilditch and Rigg (55) esterified fatty tion conditions at high glycerol levels. Hilditch and
acid with excesses of glycerol up to 10 moles but ob- Rigg (55) used phenol as a mutual solvent for esteri-
tained monoglyceride yields under 50% instead of the fication, an d Eckey and Richardson used dioxane as a
anticipated yield of approximately 85%. mutual solvent for glycerolysis (58). Mattil and Sims
The limiting factor determining the product com- used pyridine as a solvent (59). In the reaction of fat
position is the comparative insolubility of glycerol in with 50% by weight of glycerol in 4 parts of pyridine,
the reaction mixture. The reaction is homogeneous using sodium methoxide as a catalyst at steam bath
only over the lower ranges of glycerol addition. Feuge temperature, maximum conversions of monoglyceride
and Bailey determined experimentally the maximum of approximately 65% were observed. A 1:1 ratio of
quantity of glycerol which would react with and be fats to glycerol gave a monoglyceride yield of 78%.
soluble in hydrogenated cottonseed oil at various, tem- These yields are close to the amounts predicted for
peratures (54). Their results are given in Figure 5. statistical distribution in Figure 4.
NOVEMBER 1954 FOaMO: ESTEt¢ REACTIONS 553

Non-Glycerol Polyhydric Alcohol Esters

Non-glycerol esters are of very real importance, par-
ticularly for protective coatings. Goldsmith published I00
a comprehensive literature review covering prepara-
tion, physical and chemical properties, and industrial
applications of f a t t y esters of polyhydric alcohols 8(1
(60).
Glycol esters are p r e p a r e d b y direct esterification bJ
as for glycerol esters with care to avoid loss. of the 60
more volatile glycol. Ethylene glycol, propylene gly-
col, and butylene glycol with other higher polyols are
sometimes used as viscosity modifiers for alkyd resins. -~ 4o

Propylene glycol maleates and phthalates have re-

ceived recent attention as components of polyester
resins for laminating and flexible foams. 20 ~ $ORBITDL

Polyethylene glycols of general formula, gPENTAERyTHRITOL

HOCIt2CH 2( 0 CH2CH2) nOH, 0 ".i ........ !

2 4 6 8 I0 12 4
where n has a value from 1 to approximately 15 are TIME IN HOURS

esterified to give surface-active monoesters and, using :FIG. 6. Esterifieation of linseed fatty acids with stoichiomet-
low molecular weight f a t t y acids, they give diesters tic quantities of glycerol, pentaerythritol and dipentaerythritol
which are vinyl plasticizers. Saturated esters mar- at 232°C. and with sorbitol doillg a 4:1 molar ratio of fatty
keted as polyoxyethylene stearate haxe been used as acid to polyol.
bread softeners, b u t their application for this pur-
pose has been currently banned, pending accumula- esterification of pentaerythritol (42), dipentaerythri-
tion of additional toxicity information. Although the tol (62), and sorbitol (63). Both sorbitol monoesters
monoestcrs may be prepared b y direct esterification, and sorbitol monoesters reacted f u r t h e r with ethylene
a more elegant synthesis involves direct addition of oxide are marketed as nonionic surface-active agents.
ethylene oxide to the f a t t y acid in the presence of an The esterification of erythritol (41, 42, 64), trimeth-
alkaline catalyst (61). ylol propane (42), and inositol (64, 65) have been
I~COOH -~- CH2-CH2 , RC:OOC!H2CIt~OIt - - - - - - --> considered in papers dealing primarily with other
\/ polyols. Tetramethylol eyclohexanol (TMC), a penta-
O h y d r o x y alcohol derived from reaction of formalde-
RC!O,OCH~CH~(O CIt..CH~)nOH
hyde with cyclohexanone, shows an initial rate of
A mixture of mono-, di-, tri-, tetra-, etc., ethylene esterification similar to glycerol during the stage of
glycol monoesters are formed, the mean chain length p r i m a r y h y d r o x y l reaction. D u r i n g later stages of
is determined by the molar ratio of f a t t y acid to reaction the secondary h y d r o x y l of glycerol esterifies
ethylene oxide. more rapidly than the hindered secondary h y d r o x y l
H i g h e r polyol esters of unsaturated f a t t y acids are of TMC (66).
of particular importance in drying oil technology. Xylitol (67, 68), alpha methyl D-glucoside (65),
The principal polyhydric alcohol is pentaerythrit~l, and the hexitols, inositol (69), pinitol, and quebrach-
but a wide range of polyols has been considered. itol (64), have all been esterified with drying oil acids.
When highly unsaturated f a t t y acids are esterified The latter paper (64) compares esterification of a
with polyhydric alcohols, especially alcohols having number of polyols, using xylene as an azeotrope.
more than three reactive hydroxyl groups, the result- Sugar esters cannot be prepared by direct esterifi-
ant ester will polymerize if temperatures are too high. cation because of earamelization of sugar at normal
The polymerization can lead to high viscos~kv or even esterification temperatures. Fatty acid chlorides in
gelation before an adequate reduction in acidity is tertiary amines have been used for preparation of
attained. Konen, Clocker, and Cox (41) esterified lin- such esters (70).
seed acids with a group of polyols and selected 232°C. Polyvinyl alcohol esters cannot be prepared di-
(450°F.) as an optimum temperature. A t higher tem- rectly because of the insolubility of the polyol in
peratures the rate of polymerization increased quite f a t t y acids. Rheineck used phenol as a mutual sol-
sharply without appreciable increase in the rate of vent for esterification (71). Polyvinyl esters have
esterification. Figure 6 illustrates the esterification also been prepared by interesterification of methyl
of linseed acids with several polyols, using vacuum- esters and vinyl acetate (72).
processing at 232°C. with a stoichiometric amount of Phosphite esters have been described as catalysts
polyol. The rate of esterifieamtion is a function of the for esterification of phenolic resins with f a t t y acids
type of hydroxyl groups. Pentaerythritol and dipen- (73). Similar catalysts have been claimed as color-
taerythritol having only p r i m a r y hydroxyls esterify stabilizers in esterifieation of dibasic acids (74). Ki-
most rapidly. Glycerol having two p r i m a r y and one netics of esterification of poly-alcoholic resins with
secondary hydroxyl esterifies more slowly. Sorbitol f a t t y acids have been reviewed b y Rubin (75).
has six hydroxyls, two p r i m a r y and four secondary, Esterification of tall oil presents a difficult problem
b u t u n d e r esterification conditions internal dehydra- because of the drastic conditions required to accom-
tion occurs and from a practical standpoint only four plish reaction of the rosin acids. Dunlap investigated
hydroxyls are available, one p r i m a r y and three sec- the selective esterification of tall oil, using glycerol
ondary. In line with the hydroxyl type this polyol and pentaerythritol (76). B o t h f a t t y acid acidity and
esterifies still more slowly. Specific papers cover rosin acid acidity were determined during the esteri-
554 THE JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY VOL. 31

fication at various temperatures of a tall oil having 8OI IUO°C

approximately half of its acidity as. f a t t y acids and

half as rosin acids. Results are shown in F i g u r e 7. : VOi\ ~ . . . . . . "C RESIN ACIDS
A t 180°C. virtually all reduction in acidity is
accounted for b y esterification of f a t t y acids, and
reaction of rosin acids is n e g l i g i b l e . A t 220°C.
z
esterification of f a t t y acids occurs p r i m a r i l y , with
Q:
limited esterification of rosin acids. At 250°C. and
275°C. there is relatively little change in the rate of
f a t t y acid esterification, b u t appreciable reaction of FATTY ACIDS

rosin acids takes place. I n order to prepare tall oil > 2o

esters of low acidity (5-10 A.V.) it is necessary to a °¢

operate at high temperatures (240°-260°C.) during

the latter p a r t of the esterifieation, using an appre-
ciable excess (10-20%) of polyol to counteract the 60 120 lao 240 300 ]60 420
effect of polyol decomposition and intermolecular de- TIME IN MINUTES
hydration (77, 78). F'm. 7. Esterification of fatty acids and rosin acids at vari-
Tall oil esters are used in protective coatings and ous temperatures, using 10% excess of pentaerythritol.
particularly in f o u n d r y core binders in conjunction
with petroleum resins. Esterification of rosin acids
under similar esterifieation conditions with glycerol mendously increased functionality of the maleinized
gives ester gum and with pentaerythritol gives P E oils, caution must be exercised d u r i n g esterifieation to
ester gum. Modification may also be carried out, using avoid excessive viscosity increase before the acidity is
maleie anhydride as an acid to give a series of var- reduced to a desirably low level.
nish and lacquer resins. A n alternative method for preparation of maleic
Esterification of combinations of f a t t y acids and modified oils involves alcoholysis of the oil with a
phtha]ic anhydride with polyols gives the familiar polyol (usually glycerol or pentaerythritol), followed
and very important oil-modified alkyd resins. Closely b y esterifieation with maleie anhydride (82).
related is the production of maleie modified oil (79).
Maleic anhydride adds to u n s a t u r a t e d f a t t y acids or Alcoholysis
esters probably to form /dkenyl succinic anhydrides
(80, 8]). Alcoholysis is the most common of the exchange
reactions and was applied as early as 1846 when
R CH2--CH -- CH COOR' Rochleder described the preparation of glycerol by
#
O ethanolysis of castor oil (83). Aleoholysis is catalyzed
+ HC--C by a variety of materials of which the alkali metal
alkoxides are most effective. Technically, the aleo-
il O holysis of fats with polyol, such as glycerol and pen-
II / taerythritol, is a common procedure in the manufac-
HC- C
ture of oil modified alkyd resins. Catalysts effective
JO in promoting alcoholysis are also effective in interes-
$
R cH - OH ~ CH - - - - - - COOR' terifieation reactions.
IT #
o Alcoholysis by Monohydric Alcohols
CH -- C The mechanism of alcoholysis of glycerides by mono-
I \
I 0 hydrie alcohols was investigated b y m a n y early work-
I / ers., who demonstrated that the reaction is catalyzed
CH~ C
b y both acids and bases (84, 85, 86). The reaction is
0 very r a p i d in homogeneous systems in the presence
Simultaneously under conditions of addition at 200- of alkaline catalysts. Reid concluded that alcoholysis
2400C., there may be some conjugation of f a t t y acid using sodium alkoxides took place a p p r o x i m a t e l y
unsaturation followed by Diels-Alder type addition 4,000 times as fast as alcoholysis using an equivalent
to the conjugated structure. amount of HC1 (87). D u r i n g the course of the saponi-
fication-value determination, using alcoholic alkali,
R --- CH~ -- C:H ~ CH--C'H2--C!H--CH- - - COOR' alcoholysis proceeds far more rapidly than saponifica-
]
$ tion with the result that the alkali reacts primarily
R - - - - CH2 -- CH : CH--CH-- CH--CH2 - - - - COOR'------> with ethyl esters rather than triglycerides (88). An-
CH ~ O H derson and Pierce concluded that aleoholysis is about
/ \ 1,500 times as fast as Saponification (89). As an indi-
R - - - - C!H~-- CH CH --C'H~- - - - COOR'
\ / cation of the speed of the alcoholysis reaction Feuge
CH -- OH and Gros in an investigation of the ethanolysis of
/ \
O~C 0~0 peanut oil reported that turbi.dity, because of glyc-
\ / erol separation, occurred within 1.5 rain. after addi-
\ / tion to the oil of alcoholic alkali containing 2 equiva-
o lents of ethyl alcohol and 0.2% of N a O H based upon
Esterification of the maleic adducts of glycerides the oil (90). A n optimum temperature of 50°C. was
with polyols is carried out, using v a c u u m processing observed, and reaction p r o c e e d e d rapidly at lower
or by azeotropic esterification. Because of the tre- temperatures.
 NOVEMBER 1954 FORMO: ESTER REACTIONS 555

In the methanolysis of oils at moderately low tem- Feuge and Bailey demonstrated that the glycerolysis
peratures smaller proportions of methyl alcohol give of triglyeerides in the presence of sodium hydroxide
higher conversions to methyl ester because of the fa- as a catalyst gave essentially statistical distribution
vorable effect of glycerol precipitation, which would of mono-, di-, and triglyeeride (54). Figure 3 illus-
remain in solution using higher proportions of methyl trates such composition. As was pointed out in the
alcohol (91). discussion of esterifieation of fatty acids by glycerol,
W r i g h t studied alcoho]ysis of methyl ester by the limiting factor in determining the composition of
higher alcohols, such as furfuryl, tetrahydrofurfuryl, the reaction mixture is the solubility of glycerol at
benzyl and methyl cellosolve, removing the liberated reaction temperature. Dioxane and tertiary amines
methyl alcohol by distillation (4). Using lead soaps have been used as a mutual solvent to permit higher
as catalysts, relatively high temperatures of 200°C. monoglyceride yields (58, 59).
were required in alcoholysis of glycerides, which pro- If the homogeneous aleoholysis mixture containing
ceeds readily even at room temperature with alkali alkaline catalyst is cooled slowly, glycerol separates,
metal hydroxides. upsetting the equilibrium composition. Re-equilibra-
The aleoholysis procedure is normally much sim- tion occurs to give a new distribution of partial esters
pler than esterifieation for preparation of lower alkyl corresponding to the amount of glycerol remaining in
esters. In some eases it permits ester formation which the solution phase. During gradual cooling in the
could not be accomplished by direct esterification. presence of catalyst the quantity of monoglyceride
For instance, furfuryl alcohol cannot be esterified di- can be seriously .reduced. It was pointed out that
rectly in the presence of acid catalysts because under addition of strong phosphoric acid at the optimum
these conditions rapid polymerization of the alcohol alcoholysis temperature destroys the alkaline catalyst
takes place. Aleoholysis of oils with furfuryl alcohol and permits maintenance of maximum monoglyceride
proceeded readily, using 0.5% of sodium metal as a content during cooling (99, 59).
catalyst (92). At high temperatures monoglycerides decompose to
Methanolysis of triglycerides, using an anion ex- give glycerol, and under vacuum steam-distillation
change resin, has been suggested (93), and cation conditions glycerol can be removed nearly completely,
exchange resins have also been checked but found to leaving a still residue of triglyeeride. The deeompo-
be relatively ineffective (94). sition is accelerated by traces of alkaline catalysts and
The alcoholysis of fats and oils with low molecular to a lesser extent by acids. Arrowsmith and Ross
weight alcohols, followed by distillation of the ester report that, if an aleoholysis mixture is carefully
fraction, has been suggested for concentration or puri- adjusted to a pH of 6-7, the monoglycerides in a
fication of vitamins and sterols (95). Alkyl esters technical monoglyceride (approximately 50% mono-
have been suggested as intermediates in soap making glyceride content) can be distilled under vacuum
(96). The a]eohotysis procedure permits relatively (100, 101). Distillation using normal high vacuum
simple recovery of glycerol in high6r concentrations technique has been extended commercially to molecu-
than are obtained in regular aqueous saponification. lar distillation (102). Starting with a technical prod-
uet containing 40-50% of monoglyceride, distillates
Alcoholysis by Polyhydric Alcohols of 90-97% monoglyceride content can be obtained at
Alcoholysis of fats and oils with polyhydric alcohols sufficiently low t e m p e r a t u r e s and in a sufficiently
is far more important technically than reaction with r a p i d time to limit decomposition. By use of three
monohydric alcohols. Acidic materials are quite in- stages of centrifugal short-path distillation Kuhrt re-
effective as catalysts, and reaction in the absence of ports that almost instantaneous removal of monoglyc-
catalyst is inappreciable at practical operating tem- eride is observed with limited decomposition (103).
peratures. For instance, alcoholysis of soybean oil The time factor is important since it was indicated
with pentaerythritol in the absence of catalyst re- that at 100°C. a 10% loss in monoglyceride content
quired a temperature of 280°C. (42). Alkali metal required a heating period of more than 8 hours
hydroxides, carbonates, and alkoxides are very effec- whereas at 230°C. 10% reversion will occur in as
tive as catalysts, and the oxides and oil-soluble soaps little as 5 rain.
o f calcium, barium, lead, lithium, zinc, cadmium, and Alcoholysis of glycerides by other polyols utilizes
strontium are somewhat less effective but may present essentially the same procedures developed for glyc-
some advantages in color of products. Because of the erol. Burrell (42) studied the pentaerythritolysis of
relative insolubility of higher polyol in fats it is. nec- linseed and soybean oils. A variety of metal salts as
essary to operate at relatively high temperatures of naphthenates, stearates, or abietates were examined as
200-230°C. in order to maintain homogeneous reaction catalysts at a 1% level in the alcoholysis of soybean
conditions. oil with 24% of pentaerythritol at 230°C.
Alcoholysis with glycerine is an important indus- The solution of pentaerythritol in the reaction mix-
trial reaction for preparation of a variety of partial ture was taken as an end-point to indicate alcoholysis
esters. ~ Sodium hydroxide has been a favored cata- and was found to correspond closely to the familiar
lyst for alcoholysis to give edible products (97, 98) alcohol solubility test. Calcium naphthenate was par-
whereas calcium o.xide and litharge, which give cal- tieularly effective, giving clarity in 5 rain. with bet-
cium and lead soaps, are favored for alcoholysis dur- ter color than could be obtained using lead naphthen-
ing manufacture of alkyd resins and modified drying ate or litharge. Burrell then compared the reactivity
oils. As alcoholysis proceeds to give a mixture of of various polyols in the alcoholysis of soybean oil at
glycerol and mono-, di-, and triglycerides, the prod- 230°C., using 1% of calcium naphthenate.
uct becomes progressively more soluble in polar sol- The speed of aleoholysis appears to be partially a
vents. Solubility in 4 to 5 volumes of methyl or ethyl function of type of hydroxyls; the primary reacts
alcohol is frequently used as a criterion for complete- more rapidly than the secondary. The rate is also
ness. of alcoholysis. undoubtedly a function of polyol solubility in oil.
556 THE JOURNAL OF THE AMEI~ICAN OIL CHEMISTS' SOCIETY VOL. 31

Polyol used Aleoholysistime in rain. described interesterification was a thermal non-cat-

alytic interchange between ethyl benzoate and amyl
Trimethylol propane 0.5 acetate. Interesterification involving' glyeerides was
Ethylene glycol 1.0
Tetraethylene glycol 2.0 not recognized until the 192'0's when Van Loon (116)
]?entaerythrltol 5.0 and Normann (117) independently demonstrated that
Glycerol 6.0 the reaction could be effected by merely heating oils
Mannitol Not in 4 hours and fats at high temperatures or more readily at lower
Polyvinyl alcohol Not in 4: hours
Sucrose Not in 4 hours temperatures in the presence of catalysts.
The distribution of f a t t y acids in naturally occur-
Partial replacement of glycerol b y a higher polyol ring glycerides is selective rather than random. The
can be obtained u n d e r conditions of vacuum-distilla- quantities of trisaturated glycerides present in seed
tion. W r i g h t obtained partial replacement of glycerol fats, especially, falls considerably short of tile sta-
by pentaerythritol, by heating under vacuum at 200- tistically expected quantity. Referring to Figure 2,
250°C. in the presence of a lead salt catalyst (4). c o t t o n s e e d oil c o n t a i n i n g approximately 25% of
Preparation of pentaerythritol esters (4, 104) and saturated acids should have 1.6% of trisaturated
glycerol esters (68) from methyl esters by alcoholysis glycerides according to statistical distribution, but it
has also been described. contains at most a few tenths of 1% of the fully
saturated glycerides. Cocoa b u t t e r containing 60%
Acidolysis of saturated acids should have 22% of trisaturated
Aeidolysis., the replacement of an aeyl group of an glycerides b u t contains only a few per cent. In
ester by the acyl group in an acid, is less important classical research studies Hilditch investigated the
than the other ester exchange reactions. E a r l y liter- relative distribution of saturated and unsaturated
ature reported that lower molecular weight acids tend acids in a large variety of natural fats and oils and
to replace higher acids, but later investigation indi- proposed his " R u l e of Even D i s t r i b u t i o n " to explain
cated that there is little tendency for one acid to be the observed glyceride distribution (118). More re-
snore active than another in acidolysis. Tile equilib- cently, K a r t h a proposed the " R u l e of Glyceride Type
r i u m constant is 1.0 even with acids as. widely sep- Distribution," which, based upon relatively simple
arated as acetic and stearic (106). Reaction of acetic analytical data, permits calculation of glyceride com-
acid with coconut oil, using sulfuric acid as a catalyst, position based on statistical formulas (119). Inter-
gives mixed aeeto glycerides which are reported to esterification of natural triglycerides at temperatures
be nitrocellulose plasticizers (107). Introduction of above the f a t melting point shifts the distribution of
butyric acid into tallow by acidolysis followed by component glycerides from the observed selective ori-
re-esterifieation of glycerol, has been suggested for entation to a statistical or random arrangement (51,
preparation of butter-like fats (108). 120).
Triglyceride compositions can be modified by acid- A variety of metallic salts, oxides, and hydroxides
olysis reactions by heat alone or in the presence of have been described as interesterifieation catalysts.
zinc oxide, using vacuum distillation to remove lower These are relatively ineffective, requiring" rather high
molecular weight acids (109). When a mixture of temperatures with consequent thermal breakdown.
pahn acids and palm oil are heated under vacuum The reaction between ethyl benzoate and benzyl ace-
distillation conditions, acidolysis occurs and the lower- tate of Friedel and K r a f t s proceeded slowly at 200-
molecular-weight palmitic acid is removed by distil- 250°C. and required a temperature of 300°C. to give
lation from the 18 carbon acids. A similar reaction is an appreciable rate of interchange (115). Normann
suggested for upgrading of fish oil and soybean oil for found that at least 24 hours at 250°C. were required
coating purposes. Analogously, vacuum-distillation of to give relatively complete interchange equilibrium of
a mixture of oils and dimer acids from heat polymeri- a mixture of 10 parts of tristearin and 90 parts of
zation results in replacement of monomeric acids and soybean oil (117). Even at 270°C. Van Loon found
improvement of quality for coating application (129). that more than 8 hours were required to reduce the
Kaempfe reports, improved heat polymerized fish melting point of a mixture of beef stearine and soy-
oil by blowing with steam at temperatures above bean oil to its final melting point (121). Hilditch
260°C. (110). Hydrolysis, followed by acidolysis, heated synthetic beta oleodistearine at 3000C. for 10
apparently occurs. Fish oils contain about 25% of hours to give an equilibrium mixture of tristearin,
saturated acids, chiefly palmitic, together with C~s-2~, distearoolein, monostearodiolein, and triolein (122.).
and even higher-molecular-weight unsaturated acids. Earlier catalysts, such as tin and stannous hydroxide,
Preferential removal of palmitic acid improves the permit reduction in temperature and time but are far
bodied oil for coating use. less effective than alkali-metal derivatives.. Norris and
Acidolysis occurs during varnish cooking in which Mattil (52) reacted mixtures of synthetic triolein and
glycerides are heated at temperatures of 260-315°C. tristearin in the presence of stannous hydroxide, first
with acidic resins (111, 112, 113, 114). Retardation introduced b y Van Loon (116, 121), for 1 to 3 hours
of gelation of tung oil b y rosin is ascribed to the at 225°C. to obtain a mixture containing trisaturated
acidolysis reaction in which resin acids enter the glycerides c o r r e s p o n d i n g to statistical distribution
glyceride structure. within experimental error of their crystallization an-
Monomeric v i n y l esters have been prepared from alysis procedure.
f a t t y acids and vinyl acetate using mercury salts as The most effective catalysts for interesteriflcation
catalyst (29, 30,31, 32). are alkali metM derivatives of extremely weak acids
(51, 123). Included in this category are alkali metal
Interesterification alkoxides, alkyls, and aryls. Alkali metals themselves
Priedel and Crafts first recognized the interesterifi- (as powder dispersion in solvents) (123) and alkali
cation reaction in 1865 (115). Historically, this first metal hydrides (124) are also highly effective, prob-
NOVEMBER 1954 FO~MO: ESTER REACTIONS 557

ably reacting with free hydroxyl groups in fats to s a t u r a t e d g l y c e r i d e , crystallizes from the reaction
form complex alkoxides. With such catalysts random mass. This removal of an insoluble component upsets
distribution is obtained in a matter of minutes at low the equilibrium, and more trisaturated glyceride is
temperatures of 50-60°C. Appreciable catalytic ae- formed in an attempt to reproduce statistical distri-
tivity is even observed at sub-zero temperatures. bution in the homogeneous liquid phase. Precipita-
The r e a c t a n t s in esterification, alcoholysis, a n d tion continues as determined b y the solubility of the
acidolysis reactions are all catalysts for interesteri- fully saturated glyeerides at the final reaction tem-
fication although they are relatively inefficient and perature. F o r oils such as cottonseed and menhaden,
function only at relatively high temperatures. A small containing approximately 25'% of saturated acids, as
amount of water (125) hydrolyzes triglycerides to much as 18 to 24% of the total acids of the oil can be
give f a t t y aeid and diglyceride. If re-esterifieation separated as trisaturated glycerides in an interesteri-
occurs, involving a different f a t t y acid f r o m t h e one fieation period of approximately one week at gradu-
originally split off, a new ester is formed together ally lowered temperatures down to 10°C. I f such an
with water, which can go through the hydr<>lysis- interesterified product is warmed in the presence of
esterification cycle. Volatility of water under atmos- the catalyst to a t e m p e r a t u r e above the melting
pheric pressure limits the potential of this reaction, point, the mixture reverts to statistical distribution.
but in an autoclave at high temperature it repre- In order to retain the directed distribution =with high
sents an effective method for interesterifieation. The content of fully saturated glycerides, the catalyst is
alcohol split off (a diglyeeride in the case of fat hy- destroyed at low temperature by addition of acids or
drolysis) may react with a triglyeeride by way of the water. Subsequent washing, crystallization (with or
aleoholysis reaction to form a different triglyceride without solvent), and filtration separates the inter-
and a new diglyceride. Use of monoglycerides for esterified oil into a solid fraction, having a high satu-
catalysis of interesterification, p a r t i c u l a r l y in the rated acid content and low iodine value, and a liquid
presence of alkaline catalysts., has been described b y fraction, having a lower saturated acid content and a
several investigators (126, 127, 128). Similarly, the higher iodine value.
acid may displace a different f a t t y acid from a tri- Application of this directed interesterification with
glyceride to form a new gtyeeride molecule, liberating subsequent separation of solid glycerides has potential
a different f a t t y acid to continue the interchange value for upgrading of drying oils. Soybean oil, for
reaction. instance, contains about 14-16% of saturated acids,
Such interesterifieation through the aeidolysis reac- which are held almost without exception on glyeer-
tion is of particular importance during heat bodying ides containing two unsaturated acids (136). On a
of oils. F a t t y acids are liberated partially through mole % basis about 45-50% of soybean oil consists of
hydrolysis and partially through eracking and ther- these monosaturated-diunsaturated glycerides, which
mal breakdown. Simultaneously the p o l y e t h e n o i d during drying can form only linear polymers, if it is
acids undergo polymerization chiefly to give dimers assumed that each unsaturated acid has. a function-
although higher polymers are also formed. Inter- ality of only one. By removal of all of the. saturated
change of acyl groups between glyeerides and liber- acids the iodine value of soybean oil would be raised
ated acids produces new esters and new acids until from an average value of approximately 135 up to
ultimately a random or statistical distribution of sat- appro.ximately 160. In practice the maximum iodine
urated acids, unpolymerized unsaturated acids, and value practically attainable is about 148 to 154. This
polymerized acids is obtained on glyceride molecules requires appreciable removal of saturated acids and
(126, 129, 130, 131). results in an oil of improved drying potential.
In another modification of the same principle of in-
Directed Interesterification
teresterification with precipitation of glyceride, alka-
In the absence of a directing influence, interesteri- line catalyst is added to chilled oils containing a
fication can give only a statistical glyceride distribu- solid crystalline grain (137, 138). In the ease of most
tion. This reaction is commercially important in the oils the crystals present i n the chilled product con-
case of lard. L a r d has a narrow plastic range, that tain a preponderance of disaturated-monounsaturated
is, there is a relatively short temperature range in glyeerides, and these act as crystal nuelei or seed in-
which lard has good working properties as a shorten- ftneneing subsequent interesterifieation to give contin-
ing. Above this range the consistency is too soft and uing separation of the disaturated-mononnsaturated
below, lard is too firm. L a r d creams poorly and gives glycerides. With long storage there is gradual re-solu-
poor cake volume (132). Interesterification of lard tion of the disaturated glycerides and precipitation
widens the plastic range, increases creaming and cake of the less. soluble trisaturated glyeerides. The method
volume and improves appearance (133, 134, 135). The has potential value in the edible oil field for produe-
rearrangement of lard coupled with application of tion of margarine oils and puff pastes, b u t there is
butylated hydroxyanisole as an antioxidant makes only limited potentiality in the drying oil field since
lard more competitive with hydrogenated vegetable the conversion of saturated acids to insoluble glycer-
shortenings. ide forms does not proceed to a sufficient extent to
Several methods have been described for obtaining remove a large proportion of the saturated acids.
non-statistical orientation. The "Directed Rearrange- A closely allied reaction involves aleoholysis under
m e n t " process of Eekey (51, 123), in which interes- conditions similar to those used in the directed inter-
terification takes place with simultaneous crystalliza- esterification. I f glycerol is added to an oil which is
tion, represents a partieular!y valuable extension of undergoing interesterification, the process becomes a
the interesterification reaction. If a liquid reaction mixed one of aleoholysis and interesterification since
mixture of a glyceride and an alkaline catalyst (so- the same catalysts are active for both reactions (139,
dium alkoxide, sodium metal, sodimn hydride, etc.) 140, 141). This ester-alcohol exehange produces an
is gradually cooled, the least soluble component, tri- equili.brimn mixture containing glycerol, monoglycer-
558 THE JOURNAL OF TI-IE A M E R I C A N 0IL CHEMISTS' SOCIETY VOL. 31

ide, diglyceride, and triglyceride. At lower levels of modification of fats and oils. Very real potential ex-
glycerol up to 5% selective crystallization of diglyc- ists for more widespread industrial application of this
eride takes place, and at higher glycerol levels of method.
10% quite pure monoglyceride precipitates. At an REFERENOES
intermediate level both partial esters separate. This 1. Eckey, E. W., "Vegetable Fats and Oils," pp. 134-149, Reinhold
selective precipitation of partial glycerol esters is Publishing Corporation, New York (1954).
2. Markley, K. S., "]t~atty Acids," pp. 254-313, Intorscience Publish-
mpre nearly complete than the triglyceride precipita: ers Inc., New York (1947).
3. Norris, F. A., Oil and Soap, 17, 257 ( 1 9 4 0 ) .
ti0n and permits removal of virtually all saturated 4. Wright, H. J., Segur, J. B., Clark, H. V., C'oburn, S. K., Lang-
acids from the rearranging fat. don, E. E., and DuPuis, R. N., Oil and Soal~, $0, 145 (1944).
5. Van Loon, C., Chem. Weekblad., 47, 494 (1951).
Directed interesterification reactions can also be 6. Alexander, E. R., " I o n i c Organic Reactions," p. 224, John Wiley
and Sons, New York (1950).
effected by removal of a volatile component. Trieleo- 7. Remick, A. E., "Electronic Interpretation of Organic Chemistry,"
stearin cannot be prepared by" direct esterification of 2nd ed., pp. 408-419, John Wiley and So,ns, New York, (1949).
8. Smith, H. A., and Reichardt, C. H., J. Am. Chem. So c., 63, 605
the acid with glycerol since polymerization occurs (1941).
9. Hinshelwood, C. N., and Legard, A. R., J. Chem. Soc., 1935, 587.
simultaneously with esterification. The glycerol ester 10. Fairclougb, t¢. A., and ttinshelwood, C. N., J. Chem. Soc., 1989,
can be prepared by interesterification of methyl eleo- 593.
11. Thomas, E. R., and Sudborough, J. J., J. Cllem. Soc., 101, 317
stearate and triacetin in the presence of sodium me- (1912).
12. Youngs, C. G., and Craig, B. M., J. Am. Oil Chemists' Soc.,
thoxide l:lnder vacuum (41). As methyl acetate is 28, 521 (1951).
formed by the interchange, it is removed, ultimately 13. Longenecker, H. E., Oil and Soap, 17, 53 (1940).
14. Hilditch, T. P., "The Chemical Constitution of Natural Pats,"
giving relatively pure trieleostearin. In an analogous 2nd ed., pp. 474-512, John Wiley and Sons, New York (1947).
15. Wyman, F. W., and Barkenbus, C., Ind. Eng'. Chem., Anal. Ed.,
way Eckey prepares fatty polyvinyl esters by inter- 12, 658 (1940).
esterification between polyvinyl acetate and methyl 16. Norris, F. A., and Terry, D. E., Oil and Soap, 22, 41 (1945).
17. McNicoll, D., J. Soe. Chem. Ind., 40, 124T (1921).
esters of fatty acids (72). 18. Anderson, R. H., and Wheeler, D. H., Oil and Soap, 22, 137
(1945).
A somewhat related displacement is obtained when 19. American Oil Chemists' Society, Official :Method D~ 12-48.
methyl esters of higher molecular weight acids arc 20. Gloyer, S. W., Ind. Eng. Ohem., 40, 228 (1948).
21. Butts, D. C., U. S. Pat. 1,979,671 (1934).
heated with glycerides of lower average molecular 22. Karser, H. E., U. S. Pat. 2,074,963 (1937).
23. Johnston, A. C., U. S. Pat. 1,840,395 (1932).
weight in the presence of an interesterification cata- 24. Lovesgue, C. L., and Craig, A. :M., Ind. Eng. Chem., 40, 96
lyst (142, 143). Lower molecular weight methyl es- (1948).
25. :Musselman, J. M., U. S. Pat. 2,399,243 (1946).
ters are removed by vacuum-distillation, leaving a 26. :Morway, A. J., and Zimmer, J. C., U. S. Pat. 2,217,764 (1940).
27. Reppe, W., Ger. Pat. 588,352 ( 1 9 3 3 ) ; U. S. Pat. 2,066,075
glyceride of changed composition. (1936).
Interesting possibilities exist for interesterification 28. Powers, P. O., Ind. Eng. Chem., 38, 837 (1946).
29. Swern, Daniel, a.nd Jordan, E. F., J. Am. Chem. Soc., 70, 2334
involving combinations of fats or combinations of fats (1948).
30. Jordan, E. F., and Swern, Daniel, J. Am. Chem. Soc., 71, 2377
with simple esters. Tung oil is subject to crazing and (1949).
wrinkling during film drying unless it has been heat 31. Barnitz, E. S., J. Am. 0ii Chemists' Soc., 26, 104 (1949).
32. Port, W. S., Hansen, J. E., Jordan, E. F., Dietz, T. J., and
treated partially to isomerize and polymerize the eleo- Swern, Daniel, J. Polymer Sci., 7, 207 (1951).
33. Port, W. S., Jordan, E. F., H~ansen, J. E., and Swern, Dwniel,
stearic acid. This drying defect is probably caused J. Polymer Sci., 9, 493 (1953).
by trieleostearin, which would statistically be present 34. Teeter, I-I. M., and Cowan, J. C!., 0il and Soap, 22, 177 (1945).
35. Van Sehaack, 1~. H., U. S. P a t 1,820,623 ( 1 9 3 1 ) ; U. S. Pat.
to an extent of not less than 60%. Simple blends of 1,697,295 (1929).
36. Earh~art, K. A., and Rubin, B. U., U. S. Pat. 2,308,498' (1943).
tung oil and soybean oil which might be used in house 37. Seheij, L. T. C., l%e,c, tray. chim., 18, 169 ( ] 8 7 9 ) .
paints also showed this deficiency in the dried films. 38. Gaerner, T. L., J. Soc. Chem. Ind., 47, 278T ( ] 9 2 8 ) .
39. Bellueci, I., Gazz. chim. itaI., 42, I I , 283 ( ] 9 1 2 ) .
By interesterification to give a redistribution of tung 40. Long, J. S., Kittelberger, W. S., Scott, L. K., and Egge, W. S.,
Ind. Eng. Chem., 21, 950 (1929).
acids and soybean acids, "gas-proofing" can be at- 41. Konen, J. C., Clocker, E. T., and Cox, R. P., Oil and Soap, 22,
tained at low temperatures. A simple blend, for in- 57 (1945).
42. Burrell, H., 0il and Soap, 20, 206 (1944).
stance, of 1 part of tung oil and 2 parts of soybean 43. American Oil Chemists' Society, Official Method Ea 4-38.
44. Mehlenhaeher, V. (~., Determination of Hydroxyl Groups, "Or-
oil, would contain approximately 20% of trieleoste- ganic Analysis," voh I, 1-65, Interscience Publishers Inc., New York
arin. An interesterified mixture of the same compo- (~953).
45. Feuge, R. O., Vieknair, E. J., and Lovegran, N. V., J. Am. Oil
sition would contain only 2.3% of trieleostearin, an Chemists' See., 29, 11 (1952).
46. Baur, F. J., J. Am. Oil Chemists, Soc., 31, 196 (1954).
amount insufficient to affect film characteristics. Such 47. Baur, F. J., U. S. Pat. 2,615,160 (1952).
interesterified tung-soybean combinations were mar- 48. Bertheh)t, M., Compt. rend., 36, 27 ( 1 8 5 3 ) ; 88, 668 ( 1 8 5 4 ) ;
Ann. chim. phys., 41, 216 (1854).
keted for house paint use when both tung and soybean 49. Feuge, R. 0., Kraemer, E. A , and Bailey, A. E., Oil and Soap,
22, 202 (1945).
oils were lower in cost than linseed oil. Calcium soaps 50. Bhattaeharya, R., and Hilditch, T. P., Proc. Royal Soc. (Lon-
have been preferred catalysts for such reactions, and den), A1~9, 472 (1930).
51. Eckey, E. W., Ind. Eng. Chem., 40, 1183 (1948).
Reutenauer suggested interesterification of linseed oil 52. Nerris, F. A., and :Mattil, K. F., Oil and Soap ~3, 289 (1946).
53. Kawai, S., J. Soc. Chem. Ind. Japan, 44, Suppl. Bind., 244
with rape and safflower oils as a means of extending ( 1 9 4 1 ) ; C. A. 44, 8137 (1950).
linseed oil supply during periods of shortage or high 54. Feuge, R. 0., and Bailey, A. E., Oil and Soap, 23, 2 5 9 (1946).
55. Hilditch, T. P., and l~igg, J. G., J. Chem. Soc., 1935, 1774
cost (144). 56. Petit, J., Am. P a i n t Journal, 38, 82 ( ] 9 4 8 ) .
Fats can be interesterified with simple esters such 57. Savary, P., Oleagine~ux, 4, 155 (1949).
58. Eckey, E. W., and Richardson, A. S., U. S. Pat. 2,251,693
as acetates, butyrates, etc., to give mixed glycerides. (1941).
59. Mattil, K. F., and Sims, R. J., J. Am. Oil Chemists' Soc., 29,
There is both industrial and edible significance for 59 (1952).
such modifications. Interesterification between fat tri- 60. Goldsmith, H. A., Chem. Rev., 33, 257-349 (1943).
61. Scholler, C., and Witwer, M., Get. Pat. 694,178 (1940).
glycerides and triacetin may be used for preparation 62. Burrell, H., Ind. Eng. C~hem., 37, 86 (1945).
63. Brandner, J. D., Hunter, R. H., Brewstor, :M. D., and Bonner,
of acetoglycerides (46, 47). Use of a large excess R. E., Ind. Eng. Chem., 37, 809 (1945).
of triacetin (0.5 parts per part of fat) gives prima- 64. ]~heineck, A. E., and Brice, R. M., "Pinitol and Quebrachitol
Esters of Linseed Patty Acids," presented at 27th Fall Meeting of the
rily diaceto g]ycerides, waxy, translucent fats having American Oil Chemists' Society, Nov. (1953).
pronlise as plasticizers, high temperature spreads, and 65. Gibbons, J. P., and Janke, R. A., J. Am. Oil Chemists' Soc., 28,
456 (1951).
edible protective coatings for foods. 66. Wittcoff, I-I., J. Am. Oil Chemists' Soc., 26, 157 (1949).
67. Carson, J. P., and :Maclay, W. D., J. Am. Chem. Soe., 66, 1609
Although interesterifieation was recognized long (1944).
ago, it has only been in recent years that intensive 68. Teeter, I-I. :M., Bell, E. W., and Cowan, J. C., J. Am. Oil Ohem-
ists' Soe., 28, 299 (1951).
study has been given to the reaction as a means of 69. Bolley, D. S., Ind. Eng. Chem., 41, 287 (1949).
 NOVEMBER 1954 FORMO.' ESTER REACTIONS 559

70. Rheineck, A. E., Rabin, B., and Long, J. S., U. S. Pat. 2,077,- 106. Barkenbus, C., Roswell, C. A., and Mitts, A . E . , J. Am. C.hem.
371 (1937). Soe., 62, 1251 (1940).
71. P~heine~k, A. E., J. Am. 0il Chemists' Soc., 28, 456 (1951). 107. Schwartz, G. L., U. S. Pat.. 1,558,299 ( 1 9 2 5 ) .
72'. Eckey, E. W , [L S. Pat. 2,558,518 (1951). 108. Norman, W., Gor. Pat. 407,180 (1929).
73. Harrison, S. A., U. S. Pat. 2,622,071 (1952). 109. Eckey, E. W., U. S. Pat. 2,378,006 (1945).
74. Jundson, B. E., U. S. Pat. 2,612,515 (1952). 110. Kuempfe, G-., Farben-Ztg., 40, 1009 (1935).
75. l~ubin, W., J. 0il and Colour Chem. Assn., 35, No. 386, 418 111. Powers, P. O. Ind. Eng. Chem., 42, 146 ( ! 9 5 0 ) .
(1952). 112. Albert, K., Ger. Pat.. 555,812 (1932).
76. Dunlap, L. I-I., Hassel, L. V., and Maxwell, J., J. Am. Oil Chem- 1 1 3 . Greth, A., and Lemmer, F., U. S. Pat. 2,217,363 (1940).
ists' Soc., 27, 361 (1950). 114. Scheiber, J., Farbe u. Lack, 1929, 393, 404, 418.
77. Gourley, S., J. Oil and Colour Chem. Assn., 33, No. 358, 175 115. Friedel, C., and Crafts, J. R., Ann., 133, 207 (1865).
(1950). 116. Van Loon, C., Dutch Pat. 16,703 (1924).
78. Mueller, E. R., Eness, P. L., and ~[cSweeney, E. E., Ind. Eng. 117. Normann, W., Gex. Pat. 417,215 (1925).
Chem., 42, 1532 (1950). 118. Hilditch, T. P., "The Chemical Constitution of Natural Fats,"
79. Clocker, E. T., U. S. Pats. 2,188,882 to 890 (1940). 2nd ed., p. 15, John Wiley and Sons, New Ym-k (1947).
80. Teeter, H. M., Geerts, M. J., and Cowan, J. C., J. Am. Oil 119. Karth~, A. R. S., "Studies on the Natural Fats," vols. I and I [ ,
Chemists' Soc., 25, 158 (1948). Ernaeulum, I n d i a (1951).
81. Bickford, W. G., Krauczunas, P., a n d Wheeler, R. H., Oil and 120. I)esnuelle, P., and Naudet, M., Bull. Soc. chem., 1946, 90, 595;
Soap, 19, 23 (1942). 1947, 323.
82. Schwarcman, A., U. S. Pats. 2,412,176; 2,412,177,(1946). 121. Van Loon, C., U. S. Pat. 1,873,513 (1932).
83. Rochleder, F., Ann. 59, 260 (1861). 122. Barker, C., Crawford, R. V., and Hilditch, T. P., J. Chem.
84. :Hailer, A., Obmpt. rend., 143, 657 (1906). S~c., 1951, 1194.
85. Jones, M., and Lapworth, A., Proc. C~em. Soe., London, 36, 123. Eekey, E. W., U. S. Pats. 2,442,531, 2,442,532, 2,442,533,
141 (1914). 2,442,536, 2,442,537 (1948).
86. Belier, E. M., Compt. rend., 193, 1020 (1931) ; 194, 1655 (1932). 124. Eckey, E. W., U. S. PaL 2,558,547 (1951).
87. Re~d, E. E., Am. Chem. J., 45, 506 (1911). 125. Eckey, E. W., U. S. P a t 2,378,005 (1945).
88. Pardee, A. M., and Reid, E. E., Ind. Eng. Chem., 12, 129 126. Royce, I{. I)., U. S. Pat. 2,015,606 (1935).
(1920). 127. Bailey, A. E., Oil and Soap, 20, 132 (1943).
89. Anderson, E., and Pierce, I~. B., J. Phys. Ohem., 22, 44 (1918). 128. Gooding, C. M., U. S. Pat. 2,309,94.9 (1943).
90. Feuge, R. O., and Gros, A. T., J. Am. 0il Chemists' Soe., 26, 129. Cowan, J. C., J. Am. Oil Chemists' Soc., 27, 492 ( ] 9 5 0 ) .
97 (1949). 130. Pasehke, R. F., and Wheeler, I). H., J. Am. Oil Chemists' Soc.,
91. Bradshaw, G. B., and Meuly, W. C., U. S. Pat. 2,360,844 (1944). 31, 208 (1954).
92. Norris, ]~. A., and Terry, I) E., 0il and Soap, 20, 193 (1944). 131. Anderson, L. ~J., and Porter, J. V., Ind. Eng. C:hem., 41, 741
93. Schlenk, H., and Holman, R. T., J. Am. Oil Chemists' Soc., 30, (1949).
103 (1953). 132. Bailey, A. E., " I n d u s t r i a l 0il and F a t Products," 1st ed., pp.
94. Sussman, S., Ind. Eng. Chem., 38, 1228 (1946). 280-284, Interseience Publishers I n c . , New York (1945).
95. Trent, R. T., U. S. Pat. 2,432,181 (1945). 133. Ibid., p. 682.
96. Holmberg, J., Acta Polytech., 45 (1949). 134. Mattil, K. F., and Nelson, I)., U. S. Pat. 2,625,483 (1953).
97. Edelev, A., and P~ichardson, A. S., Can. Pats. 340,803-05 (1934). 135. Vanderwal, R. J., and Akkeren, L. A., U. S. Pat. Reissue
98. Christ~nson, C. W., U. S. Pat. 2,022,493 (1935). 23,499 (1952).
99. Eckey, E. W., and Clark, C. C., U S. Pat. 2,065,520 (1936). 136. ~Iilditch, T. P., Meara, M. L., and Holmberg, J., J. Am. Oil
100. Arrowsmith, ~. J., and P~oss, J., U. S. Pat. 2,383,581 (1945). Chemists' See., 24, 321 (1947).
IOl. l~oss~ J., Bell, A. C., Arrowsmith, C. J., and Gebhart, H. tI., 137. Abbott, A. I)., U. S. Pat. 2,442,538 (1948).
Oil and Soap, 23, 257 (1946). 138. Eckoy, E. W., U. S. Pat. 2,442,535 (1948).
102. Kuhrt, N. H., Welch, E. A., and Kovarik, F. J., J. Am. Oil 139. Eckey, E. W., and l~ormo, M. W., J. Am. Oil C.hemists' Soc.,
Chemists~ Soe., 27, 310 (1950).
26, 207 (1949).
140. Eckey, E. W., U. S. Pat. 2,442,534 (1948).
103. K a h r t , N. H., U. S. Pat. 2,634,278 (1953). 141. B a u r , F. J., and Lunge, W., J'. Am. Chem. Soc., 73, 3926
104. Chipault, J., and Lundberg, W. O., Ann. R ep. Hormel Inst. (1951).
1946-47, 42. 142. Eckey, E. W., U. S. Pats. 2.378,005 and 2,378,007 (1945).
105. Gros, A. T., and Feuge, R. 0., J. Am. Oil Chemists' Soc., 26, 143. Naudet, M., I)esnuelle, P., Oleagineaux, 7, 335 (1952).
704 (1949). 144. Reutenauer, G., and Sisley, J. P., Oleagineaux, 3, 305 (1948).

Nitrogen-Containing Derivatives of the Fatty Acids

H. J. HARWOOD, Research Division, Armour and Company, Chicago, Illinois

HE chemical literature describes the application

T of almost all reactions of organic acids to the
higher fatty acids. Among these reactions are
Usually nitrogen is introduced into the fatty-acid
molecule through the reaction of the carboxyl group
with ammonia or amines. By this means are obtained
many by means of which the n i t r o g e n atom is intro- amides and nitriles and, from these, amines and qua-
duced into the molecule. Although the present dis- ternary ammonium salts. Modifications and deriva-
cussion will emphasize tives of these major classes make up the greater pro-
. . . . . . . those processes which are
. . . . . . .
portion of the material to be presented here. Methods
applied commercially, of preparation and chemical reactions of various de-
many other typical reac- rivatives will be discussed. Properties and uses will
tions will be mentioned. be mentioned briefly.
Within the past two dec- Throughout the following discussion chemical reac-
ades an important indus- tions will be presented in general terms. The symbol
try has developed based R will be used to designate either saturated or unsat-
u p o n d e r i v a t i v e s of the urated normal aliphatic chains.
higher fatty acids which
c o n t a i n n i t r o g e n . To a Amides
very large extent the use- Simple amides arc produced through the reaction
fulness of these products of a molecule of fatty acid and a molecule of ammonia
results from the properties with the elimination of one molecule of water (1) :
imparted by the nitrogen
RCO'OH + NH3 .--> I~CONH,_, + H,_,O
atom, in combination with
the h y d r o c a r b o n c h a i n . This process is employed for the commercial prepara-
Generally these useful tion of the higher aliphatic c o m p o u n d s . The fatty
p r o p e r t i e s can be de- acids are heated in a closed vessel to a temperature of
ll. J. Itarwood scribed in terms of the about 200 ° and are then subjected to a stream of
s u r f a c e a c t i v i t y of t h e ammonia gas under slight pressure; continuous vent-
molecule. Frequent references to this property will ing removes excess ammonia and water as, it is
be made throughout the following discussion. f o r n l e d . . T h e resulting product consists of approxi-