202

OIL

&

FAT

INDUSTRIES

July, 1928

Avocado Oil
The Composition and Constants of a Little-Known Pericarp Oil
BY GEORGE S. J A M I E S O N , W. F. B A U G H M A N AND RAYMOND M. H A N N

V O C A D O g r o w i n g 1 is one of t h e m i n o r i n d u s t r i e s of California and Florida. One of the p r o b l e m s of t h i s i n d u s t r y is to find use f o r t h e l a r g e quant i t i e s of cull f r u i t which a t p r e s ent go t o waste. I n c i d e n t a l l y , l a r g e q u a n t i t i e s of t h i s f r u i t a r e produced in c e r t a i n r e g i o n s of t h e W e s t Indies, C e n t r a l A m e r i c a , a n d Lropical S o u t h A m e r i c a , f r o m which i t is not f e a s i b l e to s h i p t h e f r u i t in f r e s h condition to n o r t h e r n m a r kets. W i t h t h i s in view, t h e aut h o r s have m a d e an i n v e s t i g a t i o n of the f a t t y oil c o n t a i n e d in t h e pulp of t h e f r u i t . The edible p o r t i o n or pulp of the different v a r i e t i e s of avocado g r o w n in C a l i f o r n i a c o n s t i t u t e s from a b o u t 68 p e r cent to 85 p e r cent of t h e f r u i t a t m a t u r i t y . 2 T h i s pulp is rich in fat, some v a r i e t i e s containing, on a w a t e r - f r e e basis, a t l e a s t 70 p e r cent of t h i s c o n s t i t u ent. T h e large seed of t h e f r u i t c o n t a i n s v e r y little oil, an a i r - d r i e d c r u s h e d sample of seed c o n t a i n e d only 2.2 p e r cent of oil.

Extracted by Ether The oil has been e x t r a c t e d w i t h e t h e r f r o m several s a m p l e s of deh y d r a t e d avocado pulp and e x p r e s s ed f r o m several o t h e r d e h y d r a t e d samples b y E. M. Nelson of t h e
1C. G. C h u r c h and E. M. Chace, " S o m e C h a n g e s in t h e C o m p o s i t i o n of C a l i f o r n i a A v o c a d o s D u r i n g G r o w t h , " U. S. D e p t . of A g r i . Bull. No. 1073; W i l s o n P o p e n o e , " T h e A v o c a d o in G u a t e m a l a , " U. S. D e p t . of A g r i . Bull. N o . 743. 2C. G. C h u r c h a n d E. M. C h a c e , ibid.

Protein Investigation Laboratory. P r e v i o u s a t t e m p t s to express the oil f r o m the fleshy p o r t i o n of the avocado gave only a stable emulsion of oil a n d juice, consequently it i t necessary, to d e h y d r a t e the pulp b e f o r e i t is pressed. In all cases t h e oil was d a r k g r e e n b y t r a n s m i t t e d l i g h t and r e d by reflected light, b u t the e x p r e s s e d oil was l i g h t e r in color t h a n t h e e x t r a c t e d oil. The e x p r e s s e d oil had b u t little odor and a p l e a s a n t f r u i t y flavor and p r o b a b l y could be used as a c o m m e r c i a l edible oil if it w e r e not f o r its color. A sample of the e t h e r - e x t r a c t e d oil w a s refined by the caustic soda process and bleached w i t h 6 p e r cent f u l l e r ' s e a r t h . The r e s u l t i n g product was c o n s i d e r a b l y l i g h t e r in color, b u t it still had too d a r k a g r e e n i s h hue to be used as a commercial edible oil. A boiled s e t t l e d soap m a d e f r o m the crude oil b y R. S. McK i n n e y of t h i s l a b o r a t o r y was of m o d e r a t e h a r d n e s s . I t had a pale g r e e n color b u t on exposure to s u n l i g h t for t h r e e or f o u r days the s u r f a c e of the soap bleached to a c r e a m color. This experiment shows t h a t the oil could be used in combination with other fats for the m a n u f a c t u r e of h a r d soap. Kept for Year The oil has good keeping qualities. Several s a m p l e s of t h e crude oil were kept in p a r t l y filled bottles on a l a b o r a t o r y table f o r a year. T h e y were low in a c i d i t y

July, 1928

OIL

& FAT

INDUSTRIES

203

when first extracted (7), being around 1.0 in acid value (1 rag. of KOH was required to neutralize the free f a t t y acids in 1 gm. of oil), and their acidity did not increase much. The acid value of one sample at present is 3.0, having increased two units, but the acid values of the other samples increased only 0.2 or 0.3 of a unit. They show no symptoms of rancidity. Chemical Composition The chemical composition of a sample of the oil extracted with ether from the dehydrated pulp of the F u e r t e s v a r i e t y of avocado has been determined, and is reported below. The more i m p o r t a n t chemical and physical characteristics of this oil are recorded in Table I. The percentages of s a t u r a t e d and u n s a t u r a t e d acids were determined by the lead salt-ether method, a and corrections were made f o r the small q u a n t i t y of u n s a t u r a t e d acids t h a t separates with the s a t u r a t e d acids fraction. It was also taken into account t h a t the unsaponifiable m a t t e r separates with the unsaturated acids fraction. The iodine number of the unsatu r a t e d acids fraction is 101.2, indicating t h a t this fraction consists of oleic acid (iodine number 90.1) and linolic acid (iodine number 181.4). The following percentage composition of the u n s a t u r a t e d acids fraction was calculated from these figures.
Glycerides in original In original oil oil cent cent Per Per 74.0 77.3 10.3 i0.8 84.3 88.1 (1920):

The s a t u r a t e d acids were sepa r a t e d from the oil by the lead saltether method and esterified with methyl alcohol. This m i x t u r e of methyl esters, which weighed 102.2 gm., was fractionally distilled under diminished pressure. The data for the distillation are given in Table II. The preliminary, distillation was made from a l - l i t e r Claissen flask and divided the mixture into five fractions and a residue. These were redistilled from a 250-cc. Ladenburg flask according to the manner indicated in the table. F i v e final fractions were obtained. The iodine numbers and the saponification values of these five final fractions were determined and are recorded in Columns 2 and 3, Table I I I . The small final residue consisted of decomposition products and was disregarded. The iodine numbers are measures of the cont a m i n a t i n g unsaturated acids, and from these values the percentage of u n s a t u r a t e d acid esters in each fraction was calculated. From these percentages and the saponification values the mean molecular weights of the s a t u r a t e d acid esters in the different fractions were calculated as recorded in Column 6. ~ Results I n d i c a t e Esters The results in Column 6 indicate what s a t u r a t e d acid esters m a y be present in each fraction. Thus, the mean molecular weight of the s a t u r a t e d acid esters in fraction 1 lies between the molecular weights of methyl myristate (242.3) and methyl p a l m i t a t e (270.3), and suggests t h e r e f o r e that this fraction contains these two esters. The results for fractions 2, 3 and 4 suggest t h a t these
~J. A m . (1920). Chem. Soc., 42, 152, 1197

Oleic acid, . . IAnolic acid,.

Per cent. 87.8 12.2 100.0

.~J. A m . C h e m . Soc., 42, 2398 C o t t o n Oil P r e s s , 6, 1, 41 (1922).

204

OIL

& FAT

INDUSTRIES

July, 1928

f r a c t i o n s a r e composed m o s t l y of m e t h y l p a l m i t a t e , b u t c o n t a i n also small p o r t i o n s of m e t h y l s t e r a t e (298.4). The i n d i c a t e d s a t u r a t e d a c i d e s t e r s in f r a c t i o n 5 a r e m e t h y l s t e a r a t e and a small a m o u n t , less t h a n 1 p e r cent, of m e t h y l a r a c h i d a t e (326.4). Recover Fatty Acids I n o r d e r to t e s t t h e Correctness of t h e s e deductions, t h e f r e e f a t t y a c i d s w e r e r e c o v e r e d f r o m some of t h e s e f r a c t i o n s b y s a p o n i f y i n g w i t h alcoholic p o t a s h a n d decomp o s i n g t h e soap solution o b t a i n e d w i t h h y d r o c h l o r i c acid. The cons t i t u e n t s a t u r a t e d acids w e r e isolated by fractional crystallization f r o m ethyl alcohol. T h e i r i d e n t i ties, were e s t a b l i s h e d by d e t e r m i n i n g the m e l t i n g p o i n t s a n d b y obs e r v i n g w h e t h e r or n o t t h e s e m e l t ing points were lowered when the s u b s t a n c e s w e r e m i x e d w i t h equal q u a n t i t e s of t h e r e s p e c t i v e a c i d s w h i c h t h e y w e r e suspected of being, t h e p u r i t y of w h i c h h a d been e s t a b l i s h e d p r e v i o u s l y by element a r y analyses. T h e deductions d r a w n f r o m t h e m e a n molecular w e i g h t s w e r e confirmed as follows: A r a c h i d i c acid, C2oH4o02, m e l t i n g a t 77 ~ w a s isol a t e d f r o m f r a c t i o n 5. P o r t i o n s of s t e a r i c acid, ClsH3602, identified b y the m e l t i n g p o i n t 68-69 ~, w e r e o b t a i n e d f r o m f r a c t i o n s 5 and 4. A s was to be expected, it was not difficult to o b t a i n p u r e p a l m i t i c acid, C16H3202, m e l t i n g at 63 ~ f r o m f r a c t i o n s 4 a n d 1. On account of the s o l u b i l i t y of m y r i s t i c acid, C14H2sO 2, in alcohol a n d t h e l a r g e q u a n t i t y of p a l m i t i c a c i d p r e s e n t , it is not s u r p r i s i n g t h a t i t w a s not possible t o s e p a r a t e t h i s acid in a p u r e condition f r o m f r a c t i o n 1. Seven crops of c r y s t a l s w e r e o b t a i n e d f r o m t h e alcoholic

solution of f r a c t i o n 1 b y g r a d u a l l y e v a p o r a t i n g t h e alcohol a n d adding w a t e r . The m e l t i n g p o i n t of the small s e v e n t h crop w a s 56-57 ~ and since t h e m e l t i n g p o i n t of p u r e m y r i s t i c acid is 54-55 ~ i t w a s cons i d e r e d to be a m i x t u r e of m y r i s tic a n d p a l m i t i c acids. The q u a n t i t i e s of s a t u r a t e d acids in t h e v a r i o u s f r a c t i o n s w e r e calculated f r o m t h e m e a n m o l e c u l a r w e i g h t s of t h e i r esters (Columns 6, Table I I I ) and the t h e o r e t i c a l molecular w e i g h t s of the t w o esters in each f r a c t i o n . T h e r e s u l t s a r e given in Column 7-14, Table I I I . I n Table I V t h e p e r c e n t a g e comp o s i t i o n of t h e s a t u r a t e d acids is given in Column 2. These values have been c a l c u l a t e d to t h e b a s i s of t h e o r i g i n a l oil a n d a r e recorded in Column 3. I n Column 4 a r e t h e equivalent p e r c e n t a g e s of glycerides. Summary I t m a y be p o s s i b l e to utilize t h e cull avocado f r u i t , which a t p r e s e n t goes to waste, b y m a k i n g use of the f a t t y oil c o n t a i n e d in it. This oil p r o b a b l y would not find a m a r ket as an edible oil on account of its color, b u t e x p e r i m e n t s have shown t h a t it would be valuable for t h e m a n u f a c t u r e of soap. The composition of t h i s oil has been det e r m i n e d a n d is recorded below. Per cent Glycerides of: Oleic acid . . . . . . . . . . . . . . . . . . 77.3 Linolic acid . . . . . . . . . . . . . . . 10.8 Myristic acid . . . . . . . . . . . . . . trace Palmitic acid . . . . . . . . . . . . . . 6.9 Stearic acid . . . . . . . . . . . . . . . 0.6 Arachidic acid . . . . . . . . . . . . trace Unsaponifiable matter . . . . . . . 1.6

July,

1928

OIL

&

FAT

INDUSTRIES

205

TABLE I A v o c a d o Oil Chemical and Physical Characteristics 25 ~ Specific g r a v i t y - . ............................. ......... 25 ~ R e f r a c t i v e i n d e x 20 ~ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acid value . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Saponification value . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Unsaponifiable m a t t e r (per cent) . . . . . . . . . . . . . . . . . . . . . . . . . . . . Iodine n u m b e r ( H a n u s ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acetyl value ............................................... Reichert-Meissl number ..................................... Polenske n u m b e r . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Saturated acids (corrected) (per cent) . . . . . . . . . . . . . . . . . . . . . . . U n s a t u r a t e d acids (corrected) (per cent) . . . . . . . . . . . . . . . . . . . . . Iodine n u m b e r of u n s a t u r a t e d acids . . . . . . . . . . . . . . . . . . . . . . . . . . . T A B L E II A v o c a d o Oil F r a c t i o n a l D i s t i l l a t i o n of M e t h y l E s t e r s of S a t u r a t e d A c i d s (102.2 g. s u b j e c t e d to d i s t i l l a t i o n ) Fraction Temperature ~ 192 (Preliminary distillation under 15mm. pressure) A 192-3 B 193-4 C 195-9 D 200-15 E Residue (Final distillation under 2 mm. pressure) 154-5 F r a c t i o n s A a n d B added . . . . . . . . . . . . . . . . . . . . . 1 155 F r a c t i o n s C a n d D added . . . . . . . . . . . . . . . . . . . . 2 156-7 Fraction E added ........................... 3 157-164 4 178-205 Residue added . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 Residue TABLE III Weight Grams 20.0 24.0 23.52 23.20 7.44 3.84 11.00 46.80 24.00 12.50 7.27 0.34 0.9132 1.4700 2.8 192.6 1.6 94.4 9.2 1.7 0.2 7.2 84.3 101.2

A v o c a d o Oil R e s u l t s of A n a l y s e s of F r a c t i o n s O b t a i n e d b y D i s t i l l i n g M e t h y l E s t e r s of Saturated Acids

1 2 3 4 5

3.7 6.2 10.2 22.4 36.8

208.2 205.9 205.0 202.7 188.5

269.4 272.5 273.6 276.8 297.6

Per cent 3.84 6.43 10.58 23.24 38.17

2(~8.5 2710 271.1 271.4 298.6

Per Per cent G cent 5.82 0.64 85..~2 ........ 86.51 ........ 82.37 ........ 69.94 .................. 0.64

G 9.3.q 40.49 19.77 8.74 78.39

Per Per cent G cent G ................ 2.22 1.04 ........ 2.43 0.58 ........ 2.86 0.36 ........ 58.51 4.25 0.42 0.03 6.23 0.03

206

OIL

&

FAT

INDUSTRIES

July, 1928

Acids Myristic . . . . . . . . . . . . . Palmitic . . . . . . . . . . . . . Stearic . . . . . . . . . . . . . . Arachidic . . . . . . . . . . .

TABLE IV Avocado Oil Saturated Acids Acids in saturated acid fraction Grams Per cent 0.75 0.64 91.91 78.39 7.30 6.23 0.04 0.03 85.29 100.00

Acids in original oil Per cent .05 6.62 0.53 trace 7.20

Glycerides in original oil Per cent trace 6.9 0.6 trace 7.5

Recommends Benzoate Test for Olive Oil

The Olive Oil committee of the A m e r i c a n Oil Chemists' Society, headed by Louis M. Roeg, chief c h e m i s t for B r e w e r & Company, Worcester, Mass., recommended to the recent c o n v e n t i o n of the Society the use of the silver benzoate method for t e s t i n g olive oil ext r a c t e d by carbon disulphide. D u r ing the year the committee members t r i e d other methods, b u t came to the conclusion t h a t the silver benzoate one shows the best reaction. E x t r a c t s f r o m the c o m m i t tee's report follow: P r o b l e m Stated

and the silver benzoate test. The following results were noted: "Coin Test: W i t h 100 per cent extracted olive oil, a s h i n y new dime was very definitely blackened. W i t h t e n per cent extracted oil a n d n i n e t y per cent edible olive oil by volume, the dime was not blackened to a n appreciable extent. Acetic Test Wfth 100 per cent extracted olive oil, a definite, rosy-red coloration was secured. W i t h t e n per cent extracted oil and n i n e t y per cent edible olive oil, a s l i g h t p i n k coloration was noticed. This shows a b e t t e r reaction t h a n u n d e r the coin test. "Silver Benzoate Test: F o r this test we make the silver benzoate f r o m silver n i t r a t e and sodium benzoate by p r e c i p i t a t i o n f r o m hot aqueous solutions. A f t e r cooling, w a s h i n g with cold w a t e r and drying, t w e n t y m i l l i g r a m s of silver benzoate were added to five cc. of mixed olive oils and the m i x t u r e heated to 150 degrees C. in an oil bath. W i t h t e n per cent extracted oil a n d n i n e t y per cent edible oil, a dark b r o w n coloration was obtained. W i t h five per cent extracted oil a n d ninety-five per cent edible oil, a b r o w n coloration about half as dark as the first was

"Acetic-Anhydride Test:

"On October 25, 1927, the chairm a n of the committee sent to its m e m b e r s a s t a t e m e n t of the prob-lem, saying t h a t it was n e c e s s a r y to detect in edible olive oil the small q u a n t i t i e s of extracted olive oil containing sulphur from the carbon disulphide solvent, and t h a t his own l a b o r a t o r y had tried the t h r e e methods for doing this t h a t were outlined by Mr. F. Lauro in the September, 1927, issue of OIL AND FAT INDUSTRIES. "These three methods are the coin test, the acetic-anhydride test ( I t a l i a n test of P a c h i n i or B r a c c i ) ,

July, 1928

OIL

&

FAT

INDUSTRIES

207

secured. W i t h one p e r cent ext r a c t e d oil a n d n i n e t y - n i n e p e r cent edible oil, a definite b r o w n coloration, d i s t i n c t l y d i f f e r e n t f r o m 100 p e r cent edible olive oil, was produced. " T h e s e r e s u l t s w e r e secured in the l a b o r a t o r y of the c h a i r m a n of the c o m m i t t e e . The r e s u l t s were sent to all m e m b e r s of t h e committee w i t h i n s t r u c t i o n s to m a k e s i m i l a r t e s t s on s a m p l e s of e x t r a c t ed a n d edible oils m a i l e d to them. On O c t o b e r 31, G. S. J a m i e s o n s t a t e d t h a t he supposed t h a t the sample m a r k e d ' e x t r a c t e d oil' had s u b s e q u e n t l y been refined, b a s i n g his opinion on its l i g h t color. Others including the chairman are of t h e s a m e opinion. T h i s is an i m p o r t a n t point, f o r it shows t h a t a light colored ( a n d p r o b a b l y refined) olive oil e x t r a c t e d by c a r b o n disulp h i d e m a k e s a definite brown c o l o r a t i o n w i t h silver benzoate, even w i t h one-half of one p e r cent

e x t r a c t e d oil a n d n i n e t y - n i n e a n d o n e - h a l f p e r cent edible oil. "W. H. D i c k h a r t in his l e t t e r o f D e c e m b e r 29, 1927, s t r e s s e d t h a t t h e above t h r e e t e s t s when a p p l i e d to olive oils e x t r a c t e d b y carbon d i s u l p h i d e show t h a t s i l v e r benzoate is a m o r e definite r e a g e n t t h a n t h e I t a l i a n a c e t i c - a n h y d r i d e test, b u t t h a t t h e l a t t e r t e s t will act p o s i t i v e w i t h oils e x t r a c t e d by o t h e r solvents, w h e r e a s silver benzoate f a i l s with oils e x t r a c t e d by solvents o t h e r t h a n silver benzoate. However, since the m a j o r i t y of c o m m e r c i a l oils a r e e x t r a c t e d by c a r b o n disulphide, we shall continue t h i s r e p o r t as p e r o u r o r i g i n a l problem. "On J a n u a r y 31, M. L. Sheeley s e n t his r e s u l t s f r o m t h e use of t h e t h r e e tests, a n d since t h e y also a g r e e d w i t h the conclusions of t h e others, the c o m m i t t e e r e c o m m e n d s t h a t the silver benzoate t e s t be a d o p t e d f o r t e s t i n g olive oil ext r a c t e d by c a r b o n d i s u l p h i d e . " carbon in addition to the regular g r a d e s h e r e t o f o r e handled.

Jackson Becomes Sales Manager for "Purit"

Purit Company, Amsterdam, T HE Holland, manufacturers of "Purit" activated carbons, and the Glidden Food Products Company, United States Depository Agents for "Purit," announce the appointment of A. A. Jackson as General Sales Manager. Mr. Jackson's headquarters are at 82 Wall Street, New York, with the Glidden Food Products Company. Mr. Jackson has been closely identiffed with the activated carbon business for the past several years and enjoys a wide personal acquaintance with the consuming trades in this line throughout the country. He has returned recently from an extensive visit with his principals in Holland, during which arrangements were completed for carrying in stock at convenient American distributing points a new grade of decolorizing

Society Gains 55 New Members

R O W T H of t h e A m e r i c a n Oil C h e m i s t s ' Society is shown b y the r e p o r t of t h e M e m b e r s h i p C o m m i t t e e at the recent convention held a t N e w Orleans. D u r i n g t h e p a s t y e a r fiftyfive new a p p l i c a n t s w e r e s u b m i t t e d to t h e Society b y t h e Committee, which is composed of Miss Rosalind U. N o r r i s a n d Messrs. W. G. McLeod, P. W. T o m p k i n s , L. C. Howe, W. A. P e t e r s o n , a n d A. W. P u t l a n d . T h a t t h i s g r o w t h was due to "reco g n i t i o n and a p p r o v a l of t h e Society's work and activities" r a t h e r t h a n to t h e efforts of t h e C o m m i t t e e was expressed.