T H E STALING O F COFFEE

SAMUEL C. PRESCOTT; ROBERT L. EMERSON, AND L. VERNON PEAKES, J R . Department of Biology and Public Health, Massachusetts Institute of Technology, Cambridge, Massachusetts (Received f o r publication, December 4 , 1936)
INTRODUCTION

Broad investigations on the chemistry of coffee from many angles have been carried out by various workers and a vast literature has accumulated. The present work deals with but one phase of the study, namely, substances involved in changes which the roasted product undergoes when kept for extended periods whereby the modification of flavor known variously as ((flatness, staleness,) or rancidity results. Since these changes are more marked in ground coffee than in the roasted whole bean, and more readily observed in coffee freshly exposed to air than in coffee not so exposed, they are commonly regarded as oxidative in character. I n recent years it has been assumed in some quarters that it is oxidation or saturation of fats normally occurring in the bean which has been the principal cause of staleness o r rancidity. However, there are reasons for believing that the oxidation theory is inadequate to explain all changes which are brought about. Since the literature of coffee is so voluminous, reference can be made to only a few papers which have dealt with the aspect of the work Kith Khich this article is concerned. At the present time the knowledge as to chemical changes responsible for loss or modification of flavor as exhibited i n freshly roasted coffee is f a r from complete. We find statements such as that of Wendt (1930) who says that rancidity is due t o oxidation of f a t of the coffee bean, and that of Trigg (1919) claiming that deterioration is due t o hydrolysis, alteration, and volatilization of its aromatic principles. More recently statements from the Continental Can Research Fellowship a t the Mellon Institute (Weidlein, 1934) attribute staleness to oxidation and volatilization of substances causing aroma and to oxidation o r rancidity of coffee oil. While such statements may contain considerable truth, no experimental data are given t o support them, and they are too general to provide a satisfactory explanation. A systematic investigation of the chemistry of deterioration of coffee has been carried on for many months by Bengis and Anderson (1932, 1934) and they have reported isolation of a constituent of the unsaponifiable matter which they term Eahweol. This is an
This investigation was made possible through a generous contribution from the American Can Company. 1 FOOD RESEARCH, VOL. 2, No. 1.

S. C . PRESCOTT, R. L. EMERSON A N D L.

V .

PEAKES, J R .

unsaturated substance which changes very ra.pidly in presence of air or acids. They have also attempted to follow changes taking place in coffee f a t during a period of sixteen months, but could detect only very slight changes in the amount of extractible fat, unsaponifiable content, iodine value, and saponification value of the fat or in the ratios of the various acid components of these glycerides during this period. Several years ago some preliminary studies on rancidity of coffee were undertaken by the authors, results of which appeared in a Report on an Investigation of Coffee published by the Joint Coffee Trade Publicity Committee. After a considerable hiatus during which it was our intention to resume the investigation, and before the appearance of the papers of Bengis and Andersou (1932, 1934) on changes in coffee fat, investigations were resumed in this labora-tory. At that time it seemed likely that fat played an important role in staleness of coffee, and this was the first aspect of the problem to be considered.
EXPERIMENTAL WORK

During the earlier work carefully prepared samples of coffee extracts had been made. Instead of waiting f o r cofee to age, therefore, these samples, which were undoubtedly in a more advanced state of deterioration than those examined by Bengis and Anderson (1932, 1934), were subjected t o certain chemical %tests. The samples gave clear evidence of deteriorative change and were investigated with reference to acid value, saponification number, percentage of unsaponifiable matter, iodine value, and peroxide content. These were compared with fresh coffee extracts prepared in a similar ma.nner, with extracts five and one-half months old, and also with freshly prepared extract of ground coffee which had been kept in ground condition for five and one-half months. The comparative results of these examinations are summarized (Table 1). I n order to place on record the methods followed in this investigation the following descriptions of the extracts are presented :
Description of Extracts
Extract A was obtained by continuous extraction of freshly roasted and ground coffee with petroleum ether which had been freed from unsaturated hydrocarbon by refluxing over concentrated sulfuric acid, washing with water, and distilling over stick sodium hydroxide. Only t h a t portion of the petroleum ether which boiled f r o m 42 t o 80C. (107.6 to 176F.) was used. After extraction of the .fat, the petroleum ether was removed by distilling o n a water bath. The final stages of distillation were carried out under reduced pressure. The temperature of the water bath never exceeded 70C. (158F.). The weight of the extract was 8.2 per cent of that of the coffee used. It was a dark brown liquid of fairly low viscosity and surface tension and had a pleasant coffee odor.

T H E STALING O F COFFEE

Extract B was a five and one-half months old petroleum ether extract of Santos coffee. It had remained on a laboratory bench protected from dust and unprotected from light or air during t h a t time. It was a dark brown liquid of fairly low viscosity and had a slightly rancid coffee odor. Extract C was a fresh extract of the same lot of coffee from which extract B was prepared; it had been aged in the ground condition for five and one-half months. The extract was prepared in the same manner as A . It weighed eight per cent as much as the ground coffee used. Extracts 0, E, F, and G were similarly prepared extracts which had aged a much longer time. Their exact age is not a matter of record. They no longer
TABLE 1

Changes in the Chemical Characteristics of Coffee Fat Owing t o A g e __ ___

~ ~ ~ ~

Fresh coffee

extract 5 % mo. old

An

)f coffee

Fresh extract

5 % mo. old

Extracts much older

~~

Acid value in milligrams of KOH/gm.

3.3

__

4.9

5.2

18.7

29.9

50.4

47.2

Saponification No. in milligrams of KOH/gm .................. 171 Unsaponifiable per cent..................... Iodine value (Hubl) in centigrams of iodine/gm ................. Peroxide content in millimoles/kg ...........

174

172

197

192

206

200

9.5

7.5

.......
90.7

.......
54.2

5.0

4.2

.......

90.9

84.7

49.1

34.3

80.5
~

.......

199

138

49

had the odor of coffee. They were chosen in the order of increasing deterioration as well as could be judged by their appearance and odor. A brief description of each is as follows: D. A light-colored extract; solvent used unrecorded ; consistency about the same as heavy-bodied linseed oil; no crystals in the liquid. E. A dark acetone extract; more viscous than D; containing some gummy material settling on the bottom of the flask. F. A fairly light-colored petroleum ether extract; more viscous than A or B, but still possible to pour; contained a large amount of crystalline material. G. A dark, gummy, semisolid extract; solvent unrecorded; contained a large amount of crystalline material.

The results show clearly that the f a t in coffee is susceptible to oxidation, but that this change has been only partial in five and

S. C . PRESCOTT, R. L. EMERSON AND L. V. PEAKES, J R .

one-half months. This fact is quite contrary to the opinion of at least one writer, Bredt (1934), who claims that while extracted fats of coffee grow rancid rather slowly in the mass and under ordinary conditions, the alteration occurs rapidly when they remain in contact with the great surface actually exposed in a large quantity of coffee beans. In opposition to this view our data on the lower iodine value and the high peroxide value of the f a t kept five and one-half months after extraction would indicate that decomposition took place more rapidly when the fat is in compact form than when it is dispersed. This difference is probably due to action of light in one case and inaccessibility of fat in the bean to atmospheric oxygen in the other. During a n aging period of five and one-half months only the acid and peroxide values changed sufficiently to give any promise as a means of measurement of staleness or rancidity. Peroxide contents have been used by Greenbank and Holm (1934), Wheeler (1932), Lea (1931), and others to detect rancidity in fats and oils. Although Coe and LeClerc (1934) have recently cast some doubts upon the value of such determinations as a measure of rancidity, peroxide content is still considered the most reliable test for rancidity of fats. For this reason i t seemed desirable to measure the peroxide contents of the same coffee at different degrees of staleness to see if any relation existed between this constant and the degree of deterioration. After considerable experimentation with various solvents and methods of extraction the following procedure was found quite satisfactory. Ten grams of ground coffee were placed in a ground glass-stoppered Erlenmeyer flask with 50 C.C. of carbon tetrachloride which had previously been shaken with a little mercury to remove traces of chlorine. The mixture was shaken in a shaking machine for three hours. A t the end of that time 25 C.C. of the solvent were filtered off and placed in another ground glass-stoppered flask; 1 C.C. of a saturated solution of potassium iodide in water and 25 C.C.of glacial acetic acid were added. After the mixture had stood for 20 minutes in the dark, 100 C.C. of water and a little starch indicator solution were added. The mixture was then titrated with 0.002 N sodinm thiosulfate until the water layer became colorless. The peroxide content in millimoles of peroxide per kilogram of coffee was computed a s follows :
2X

C.C. of 0.002 N thiosulfate = l L peroxide content 10

The value may be somewhat in error, as the 25 C.C. of solvent filtered off probably does not contain exactly one-half of the peroxides

THE STALING O F COFFEE

in the 10 grams of coffee. However, the error is probably fairly con-

stant and the values obtained comparable. The time of decomposition of the peroxides before titration was varied with the following results :
Length of time Peroxide value

15 min.

20 min. 25 min. 30 min.

0.47 0.47 0.51 0.54

The higher values obtained on 25 and 30 minutes standing are probably due to oxidation of the hydrogen iodide by atmospheric oxygen. The differences are slight, and 20 minutes was chosen as the best time. The amount of iodine adsorbed by the coffee fa t was estimated by extracting a sample of freshly roasted coffee containing no peroxides, exactly as in the determination above, and then adding a known
TABLE 2

Effect of Aging o n Coffee

Description of coffee Peroxide content Acid value Taste test

Coffee 7 mo. old kept in the bean, freshly ground just previous to testing................ Same as above, but kept 7 mo. in the ground state ........................................... Coffee 2% mo. old, kept in the bean and freshly ground before testing.................... Same as above, but kept 294 mo. i n the ground state .......................................... Coffee 1 mo. old, kept in the ground state ..........................................
~

6.4

Tasteless but not rancid Slightly rancid Stale but not rancid

0.501
0.65

5.5

0
Trace

3.4

4.0

Rancid

4.6

Stale but not rancid

I Different

parts of the same bag.

amount of iodine (equivalent to 7.65 C.C.of 0.002 N thiosulfate), the acetic acid, and saturated potassium iodide solution; allowing it t o remain 20 minutes and completing the analysis as usual. An amount of iodine equivalent to 0.07 C.C. of 0.002 normal thiosulfate was adsorbed. This would lower the peroxide value by only 0.014 which is outside the limit of accuracy of the determination. That neither peroxide content nor acid value is a reliable measure of the staleness of coffee is quite evident from the summary of results of the application of this determination to various samples of coffee (Table 2). One cause of the low peroxide values of some stale coffees

S. C. PRESCOTT, R. L. EMERSON A N D L. V. PEAKES, J R .

might be the decomposition of the peroxides to give products of unpleasant taste and smell. It seemed advisable, therefore, to study the effect of moisture on the taste, odor, peroxide content, and acid value of the coffee.
W F E C T OF MOISTURE ON COFFEE

The effect of moisture during the storing of coffee was determined by keeping one lot of coffee in a very dry atmosphere and another batch in contact with air with a relative humidity of 75 per cent. The acid values, moisture, and peroxide values were determined a t intervals. Taste tests were run at the same time. The humidity was controlled by placing small crystallizing dishes containing the ground coffee in desiccators, one of which contained anhydrous calcium chloride, and the other a saturated sodium chloride solution. The salt solution gave a relative humidity of approximately 75 per cent over the range of temperatures existing in the laboratory. The dishes
TABLE 3

E f f e c t of Moisture o n Boastea Coffee

Sample kept over anhydrous calcium chloride Acid value

Peroxide content

Yoisture pet.

Weeks in storage

Sample kept over a saturated sodium chloride solution Acid value

Peroxide content

Moisture
pet.

3.8 3.9 3.9 4.0

0 0
Trace

.....
1 . 4

.....

2.38

0
3

6
9

3.8 4.2 4.3 4.2

0 0
0

..... .....
9.1

2.38

were placed so that free circulation of air within the desiccators was possible. The coffee was frequently stirred and positions of the dishes changed so as to obtain uniform aging. The desiccators were placed in a dark closet to eliminate any effect of light. The first test was made after three weeks. It disclosed that the coffee kept in a moist atmosphere was absolutely lacking in coffee flavor. The sample kept in a dry atmosphere was but little weaker than fresh coffee and could not be classed as stale even after six weeks had elapsed. The moisture contents, peroxide values, and acid values are shown (Table 3 ) . The acid value is that of the extracted f a t and does not depend on the moisture content of the coffee. While this experiment shows the importance of moisture in the deterioration of coffee, it does not substantiate the hypothesis that peroxides are intermediates in this degradation, for no peroxides could be detected in the sample kept in the moisture-free atmosphere. I n all this work no convincing evidence has been obtained t o show that f a t in coffee becomes rancid in the relatively short time that

THE STALING O F COFFEE

it takes coffee to become stale. F o r this reason it seemed wise t o t u r n attention to other constituents of coffee, especially to the aromatic oils which give it taste and odor. Another indication that such an investigation might be advisable was that the salt solution in the desiccator used in the experiment just described contained small amounts of furfuraldehyde; and the volatile oils of coffee have been found to contain furan derivatives.
STUDY O F VOLATILE CONSTITUENTS OF COFFEE

A number of investigators have analyzed the volatile oils from coffee. There is considerable divergence in their results. A part of this is probably due to the use of different types of coffee. Other differences may be due to variation in method of isolation of the oils. Still others must be attributed to misinterpretation of experimental results.

Summary of Previous Work The first systematic study of the aromatic oils of coffee was undertaken by Oscar Bernheimer (1880). H e obtained oils by condensing coffee-roaster gases. From these he isolated a material which he believed to be a methyl derivative of saligenin. The material which he obtained distilled from 195 to 198C. (383 to 388.4"F.). It was the principal constituent of the liquid portion of his product. The other components found which might affect aroma were acetic acid, methylamine, pyrrol, and acetone. If the material obtained by Bernheimer was a methyl derivative of saligenin it would havd had one of the following formulas:

o-methoxybenzyl alcohol

o-hydroxybenzylmethyl ether

The first of these compounds had been prepared by Cannizzarro and Korner (1872). Bijtsch (1880) pointed out that this could not be the same compound that Bernheimer had, for its physical properties were quite different. There is, for example, a difference of over 50 degrees in boiling points. H e believed that it was probably the compound represented by Formula 11. This was shown not to be the case, however, by Thiele and Dimroth (1889) who synthesized it. This compound certainly could not be that isolated by Bernheimer, as it could not be distilled a t atmospheric pressure without almost complete resinification, while that obtained from coffee distilled a t almost 200C. (392F.) under normal pressure. Neither of the two ethers of saligenin which were prepared synthetically resembled coffee in

S. C. PRESCOTT, R. L. EMERSON A N D L. V. PEAKES, JR.

odor, although Botsch thought that his crude methoxybenzyl alcohol had coffee-like odor which disappeared on purification. Although this work would seem to prove rather definitely that Bernheimer could not have had a methyl ether of saligenin, a number of years later Sethness (1924) published a paper in which he speaks of methyl ether of saligenin being the chief constituent of the aromatic oils of coffee. He steam-distilled coffee on a large scale and obtained a product of like boiling point. Apparently he ran no chemical tests on the material. Sethness states that Lehmann and Wilhelm steamdistilled coffee and also found caffeol, or chemically speaking, the methyl ether of saligenin to be the principal ingredient of the fraction possessing the powerful coffee aroma. The only paper that we have been able to find by Lehmann and Wilhelm (1898) contained no statement o r experimental evidence as t o the chemical nature of steam distillate of coffee. Bernheimer seems to have been the only investigator to present chemical evidence that the material boiling at 195 to 198C. (383 to 388.4F.) was a derivative of saligenin. That it was a methyl ether of this compound seems impossible. It seems probable that Sethness and Bernheimer both obtained the same material, yet no other investigator has obtained any material resembling this product as the main constituent of the volatile oils of coffee. Other investigators have obtained quite different results. A fern years after Bernheimer, Jaeckle (1898) also analyzed the condensate from coffee-roaster gases. He identified acetone, furfuraldehyde, formic and acetic acids, pyridine, ammonia, and trimethylamine. This paper was soon followed by a report of the excellent work by Erdmann (1902). Erdmann steam-distilled large amounts of coffee and analyzed the steam distillate. He used a total of 225 kilograms of coffee in his experiments. He was the first to use the coEee itself as a starting material rather than the condensate from the roaster gases. Erdmann found about 42 per cent of his product t o be acidic. This was mostly valeric acid but contained some acetic acid. The neutral portion (58 per cent) was largely furfuryl alcohol but also contained some phenols and an extremely small amount of a compound boiling at 93C. (199.4F.) under 12 mm. pressure. This fraction contained nitrogen. Some years later Bertrand and Weisweiller (1913) analyzed a similar fraction and reported that the nitrogen content is due t o the presence of pyridine. Grafe (1912) also analyzed the oils in coffee which were volatile with steam. He also reports valeric and acetic acids, furfuryl alcohol, phenols, furfuran derivatives, and a pyridine derivative which gives coffee its aroma. Grafe was chiefly interested in a comparison of normal and decaffeinated coffees and his work is

THE STALING O F COFFFEE

on a comparatively small scale. He depended largely on color reactions and odors for his identification. More recently Schmalfuss and Barthmeyer (1929) have shown the presence of diacetyl in coffee. A chronological tabulation of the findings from previous work on the volatile oils of coffee is included here (Table 4).
TABLE
4

Bindings from Previous Work on Volatile Oils of Coffee

Investigator
ComDounds identified

0. Bernheimer' (1880) ......... A methyl derivative of saligenin, caffeine, higher

f a t t y acids, acetic acid, hydroquinone, methylamine, pyrrol, acetone. A. Monari and L. Scoeciantil (1895)

..........

Pyridine. Furfural, caffeine, pyridine, ammonia, trimethylamine, acetic and formic acids, and acetone. A valeric acid in large amounts, a little acetic acid, phenols, furfuryl alcohol, a fraction boiling 93" C. (199.4' F.) a t 13 mm., containing nitrogen and having the odor of coffee. This last material in extremely small amounts. Acetic and valeric acids, furfuryl alcohol, furfuran compounds, phenols, and a pyridine derivative.

H. Jaeckle'

(1898) ...............

E. Erdmann (1902) .............

V. Grafe (1912) ...................

G. Bertrand and

G. Weisweiller (1913) .........

R. E. Sethness (1924) .........
H. Schmalfuss and H. Barthmeyer (1929) ........

Pyridine. Methyl ether of saligenin claimed t o be the principal constituent of coffee oils.

Diacetyl.

Analyzed Condensate from coffee-roaster gases.

INVESTIGATION OF VOLATILE OILS IN COFFEE

a. Extractiort of Coffee by M e t h o l The problem of separation of volatile constituents from the remainder of the roasted coffee is almost as d%cult and important as identification of these compounds. The percentage of volatile oil in roasted coffee is always very small, e.g., Erdmann obtained 83.3 grams of volatile oils from 150 kilograms of roasted coffee. This corresponds t o about 0.05 per cent. Three methods of isolation have been used:

10

S . C. PR.ESCOTT, R. L. EMERSON AND L. V. PEAKES, JR.

(1) condensation of liquids and solids in the roaster gases, ( 2 ) steam distillation of roasted coffee, and ( 3 ) extraction of roasted coffee with ether. The first of these methods does not necessarily give the same products as occur in the roasted coffee. The use of steam distillation is more reliable, but alteration of oils may occur owing to the action of the water. As has been previously shown coffee aroma is greatly affected by action of water vapor. The last method, extraction by a solvent, seemed the most promising and was tried in this laboratory, but it also had some disadvantages. A series of preliminary tests indicated that methyl alcohol gave an extract having a very pleasant and distinct coffee odor, and this alcohol was used as a solvent. It soon became evident that extraction with this solvent gave an extract which upon distillation of the solvent left a residue which was too viscous to allow the removal of any volatile components by vacuum distillation. It mas found possible to precipitate a part of this viscous material by addition of ethyl ether. Taking advantage of this fact the procedure indicated (Table 5 ) was developed. It was necessary to carry out the last precipitation with petroleum ether as ethyl ether was no longer effective. From the yields of volatile oils at the end of this procedure it is quite evident that some of the desired volatile components were occluded in the precipitates thrown down by the ether. The ether precipitate was semicrystalline but very difEcult to purify. All attempts t o filter it failed. Decantation of the supernatant liquid was resorted to. The volatile oil was shown to consist of furfuryl alcohol with a little furfuraldehyde, acetic acid, and some water-insoluble liquid which may have been an ester or esters of furfuryl alcohol. This method was finally abandoned because of the length of procedure and small yields of the desired product.

A variation of the above scheme was to add basic lead acetate to the methanol extract. Much of the viscous material in the extract will precipitate with basic lead acetate and may be separated in this manner. However, much of the volatile constituents must also be occluded in some manner, for the yields of these compounds were practically nil. Nor did this method serve as a method of purification of the non-volatile materials precipitated by the lead acetate, for upon regeneration by hydrogen sulfide they were more tarry than before. A description of the four volatile fractions is given below.
Description o f Volatile M a t t e r Extracted from Coffee by Methanol Fraction boiling from 77C. (170.6"F.) at 40 mm. pressure. About 0.15 C.C. Partly miscible with water. Refractive index 1.4480 a t 25.5"C. (77.2"F.).

THE STALING O F COFFEE

1 1

(attempts a t purification futile)

Concentrate in an atm. of COz

Solid, m.p. 232-236' C. on a n immersion thermometer (probably caffeine)

Concentrate in an atm. of coz Thick concentrate Add ether Solution (no separation) Add petroleum ether

Tarry material

Petroloum ether

+ ether I+ methanol

Solution Concentrate Concentrated extract Vacuum distil Residue (discarded)

(Mineral oil added t o reduce frothing)

Four fractions

12

S. C. PRESCOTT, R. L. EMERSON AND L. V. PEAKES, JR.

Gave a strong fuchsin aldehyde test. Vapors colored aniline acetate paper red. Formed a dimethon whose crystalline structure resembled that from furfuraldehyde when viewed under a microscope. It was mixed mith small droplets of oil. From the above data it was concluded that this fraction mas largely furfuraldehyde. The boiling point of furfuraldehyde is 77 to 78C. (170.6 to 172.4'F.) a t 40 mm. pressure. Fraction boiling from 88 to 94C. (190.4 to 201.2"F.) a t 40 mm. pressure. About 0.3 C.C. About one-half soluble in water. A s m a l l amount treated with a naphthylisocynate gave a urethane melting a t 127 to 128C. (260.6 to 262.4"F.). The urethane from fqrfuryl alcohol melts a t 129C. After extracting with water this fraction had a refractive index of 1.4628 at 25.5"C. (77.2"F.). The refractive index of furfuryl formate is 1.4672; that of furfuryl acetate, 1.4604; both at 25.5"C. (77.2"F.). This may be one or a mixture of these esters. Fraction boiling 92 to 100C. (197.6 t o 212F.) a t 4.5 mm. pressure. About 0.1 C.C. Saponification value 47. Fraction boiling a t 109C. (228.2"F.) a t atmospheric pressure. About 1 drop. Identified as acetic acid by the p-nitrobenzyl ester, m.p. 78C. (172.4"F.F.).

b. Extraction of the Coffee Brew From experience with extracting coffee with methanol we felt quite certain some method of separation of volatile constituents from other extractible material must be devised. A change in solvent was also considered, but even with a solvent like petroleum ether, which extracts a comparatively small amount of material, the ratio of nonvolatile to volatile constituents i n the extract is very high. One simple method of separating the desired volatile oils from other materials extracted by organic solvents is to make first a coffee brew (water extract) and then extract it with a n organic solvent. A n extraction apparatus was devised in which the coffee brew was dropped in a fine spray through columns of organic solvent five feet long. A t first three solvents were used in succession, ethyl ether, chloroform, and ethyl acetate. Chloroform was then eliminated because it extracted the same compounds as ethyl ether and necessitated a bothersome type of apparatus in which the brew passed up through the solvent rather than being dropped down through it as in the case of the lighter solvents. A test was also run to determine the number of five-foot tubes of ether necessary f o r complete extraction of the coffee. Practically nothing could be extracted after the brew had passed through 27 tubes and the amount of volatile material obtained from the nineteenth to twenty-seventh tube was hardly sufficient to warrant the in-

THE STALING O F COFFEE

13

crease in time necessary f o r their use. The nature of the extracted oil seemed the same as in the previous tubes. The scheme followed consists of making 10.5 kilograms of Xantos coffee into 45 liters of brew. The coffee is roasted in the laboratory within a few hours of the time it is used. A medium roast is employed. The coffee brew is then passed through 20 tubes of ethyl ether, five feet long and about two centimeters in diameter. After passing through the ether, the coffee is then dropped down 10 tubes of ethyl acetate. Impurities in the ethyl acetate interfered with identification of any compounds extracted from the coffee brew, so it is uncertain at present if this extraction is worth while. The ether in the tubes was changed after nine liters of brew had passed through. The ether extract was dried over anhydrous sodium sulfate and then anhydrous calcium sulfate (Drierite). TLe extract was concentrated by distilling off the ether in an atmosphere of carbon dioxide gas. Usually the concentration was interrupted when the volume of the solution had reached about 200 C.C. and this was then combined with other similar batches. After again drying over anhydrous calcium sulfate the greater part of the ether was removed from the combined extracts by distillation on a water bath. Carbon dioxide gas was passed through the apparatus to reduce the amount of oxidation. The final stages of the distillation were carried out under reduced pressure. The receiver was covered with dry ice so as to condense all the distillate. The pressure was reduced as low as possible so as to reduce the temperature of distillation. Usually two to four millimeters were obtained. No attempt was made to determine the boiling points, as superheating always occurred. The distillate was carefully redistilled fractionally later. The temperature of the oil bath used for heating was never over 160C. (320F.). c. Analysis of Ether Extract of Coffee Brew The distillate from the ether extract was separated into the following fractions : A . That distilling at room temperature under 5 mm. pressure. About 1.2 C.C. B. That distilling u p t o 70C. (158F.) at 40 mm. About 2 C.C. C. That distilling from 70 t o 100C. (158 to 212F.) at 40 mm. About 4 C.C. D. That distilling from 100C. (212F.) at 40 mm. to 120C. (248F.) a.t 3 to 4 mm. About 1.5 C.C. These fractions were treated as follows:
Fraction A. Redistilled, this fraction boiled from 70 t o 78"O. (158 to 172.4"F.) at atmospheric pressure. It was almost completely water soluble. It was identified a s ethyl alcohol by the a-naphthylcarbamate, m.p. 77 to 78C. (170.6 to 172.4"F.).

14

S. C. PRESCOTT, R.. L. EMERSON AND L. V. PEAKES, J R .

Fraction B. On redistillation nearly all of this fraction boiled at 110 t o 118C. (230 t o 244.4"F.). A little resinified material was left i n the bottom of the distilling flask. It had a n acid value of 124. Acetic acid has a theoretical value at 167. It was identitied a s acetic acid by the p-bromophenacyl ester, m.p. 85 to 86C. (185 t o 1 8 6 3 F . ) . The acetic ester of p-bromophenacyl alcohol melts a t 86C. (18623F.). A mixed melting point with the derivative prepared from acetic showed no depression. This fraction is evidently essentially acetic acid. Fraction C.
An acid value showed t h a t this fraction still contained considerable acid. The fraction gave about 0.5 C.C. of liquid distilling below 70C. (158F.) a t 40 mm. The remainder distilled from 77 to 100C. (170.6 to 212F.) under 40 mm. pressure. The last fraction was largely soluble in water. After shaking with several times its volume all b u t 0.5 C.C. dissolved. The water-insoluble portion was dried over anhydrous sodium sulfate and then over anhydrous calcium sulfate and distilled. A few drops distilled a t 77 t o 85C. (170.6 to 212F.) a t 40 mm. This gave a strong aniline acetate reaction. This is probably largely furfuraldehyde. The remainder of the water-insoluble portion distilled at 95 to 98C. (203 to 208.4"F.) a t 40 mm. A saponification value corresponded to about 50 per cent ester calculated as furfuryl acetate. B.P. of furfuryl acetate 95 t o 97C. (203 to 206.6"F.) a t 40 mm. The water solution of the soluble components was saturated with salt and extracted several times with ether. These ether extracts mere combined and d-ried over anhydrous calcium sulfate. After the ether was removed by distillation the residue distilled a t 9 1 t o 94C. (195.8 to 201.29F.) at 40 mm. Furfuryl alcohol boils at 92 to 94C. (197.6 to 201.2"F.) a t 40 mm. This material was identified a s furfuryl alcohol by its a-naphthylcarbamate, m.p. 127 to 128C. (260.6 to 262.4"F.). The melting point of the a-naphthylcarbamate from furfuryl alcohol is given as 129C. (264.2"F.). A mixed m.p. with the urethane prepared from furfuryl showed no depression. The residue in t h e flask (1 t o 2 drops), after the distillation of the material shown t o be furfuryl alcohol, smelled like phenol or the cresols. The flask was washed out with water and a drop of very dilute ferric chloride solution added. A deep violet color appeared. To another portion of the water solution bromine water was added. A white turbidity appeared. However, practically no precipitate settled out on standing.
The one-half cubic centimeter of material distilling below 70C. (168F.) at 40 mm. was redistilled. It distilled a t 115 to 140C. (239 to 284F.) at atmospheric pressure. The greater p a r t of it distilled from 115 t o 120C. (239 to 248F.). There was a little tarry material left in the flask. The distillable material was identified as acetic acid by making the p-bromophenacyl ester, m.p. 85 t o 86C. (185 t o 186.8"F.). From the above we can conclude t h a t this fraction was one-eighth acetic acid. The remainder was nearly all furfuryl alcohol b u t also contained some ester, probably furfuryl formate, and a small amount of a phenol.

Fraction D.
The material in this fraction was very viscous; it was redistilled. Only about 1ex. distilled. Most of this boiled at 95 to 103C. (203 t o 217.4"F.) a t 1to 1.5 mm. There was considerable loss in manipulation owing to the high viscosity of the material. A sodium fusion followed by a cyanide test showed the presence of

THE STALING O F COFFEl3

15

nitrogen. It had a n acid value ,of 34.5 (ex. 0.1 normal alkali per gram). It was shaken with several times its volume of water. The insoluble oil was separated and dried over anhydrous sodium sulfate and then over anhydrous calcium sulfate. This water-insoluble portion still gave a positive but much weaker nitrogen test. It had a n acid value of 34.7. Phenolphthalein was used as the indicator a n d the end point was sharp. The material was very viscous. It gave a light violet color with dilute ferric chloride solution. There was too little left to test further. The water solution of the water soluble components was saturated with salt a n d extracted several times with ethyl ether. These extracts were combined and dried over sodium sulfate and then over calcium sulfate. The ether was removed by distillation. The residue was quite fluid. It had a n acid value of 33.5. The end point was poor and the red color of phenolphthalein kept increasing a s more alkali was added. This residue contained nitrogen. The test was much stronger than i n the case of the water-soluble portion. The color formed by the addition of a few drops of dilute ferric chloride solution to a water solution of the material was a very intense violet. This mas much stronger than in the case of the water-insoluble portion. A water solution reduced Tollen's reagent immediately at room temperature. It did not give Feigl's (1934) test for primary aromatic amines with 4-pyridyl pyridium chloride solution. Apparently it is not positive that the substance is not a primary aromatic amine, as methyl anthranilate did not give the test, although anthranilic acid gave a very fine positive result. From the above data it seems likely that the viscous, water-insoluble materid is an acid. It may b e a f a t t y acid from the coffee fat. Its acid value is aboxt right. The water-soluble portion is probably a phenol. The indistinct end point color with ferric chloride and reduction of Tollen's reagent all point to this.

Redistillation of Last Portions of Ether Which Distilled at Atmospheric Pressure The last few cubic centimeters of ether t o distill a t atmospheric pressure had been saved from several runs. These were combined and distilled through a good column having a water reflux. After a small quantity distilled, the distillate, between 78 and 90" C. (172.4 and 194' F.), became very yellow and smelled of diacetyl. A little of the distillate was extracted with water and treated with nickel sulfate, hydroxylamine sulfate, and ammonia. The bright red nickel dimethylglyosime precipitated. The fraction was nearly all soluble i n water and smelled of alcohol. The extraction of the coffee by ether and the identification of the extracted compounds is summarized in tabular form (Table 6).
DISCUSSION O F PRESENT WORK A N D THAT O F PREVIOUS INVESTIGATORS

The results of the present investigation do not wholly agree with those of any previous investigation. We agree with Grafe (1912) and Erdmann (1902) that furfnryl alcohol is the chief neutral constituent

TABLE
6

Extraction of Coffee Brew with Ether

10.5 kilograms of coffee -k 45 liters of water Passed through ethyl ether Ether extract I

Passed' through ethyl acetate

I

I
Concentrated in an atm. of carbon dioxide gas.

Spent brew

I
I

Redistilled
Of

I
ether
Vacuum distilled

last

.1

Diacetyl: identified by yellow color, odor. Boiling range 78

-i
Fraction C. 4
C.C.

1
Redistilled Fraction B.P. 77 to 100C. (170.6 to 212F.) at 40 mm. Water

.1

Fraction D. 1.5 C.C. Redistilled B.P. 95 to 3.03"C. (203 t o 217.4"F.) a t 1to 1.5 mm. Water

Acetic acid 0.5 C.C.

J. Fraction A. 1 0.e. Boiled at room temp. at 40 mm. Redistilled it boiled a t 70 to 78" C. (158 to 172.4" F.) a t atmospheric pressure. Identified a3 akohol by a-naphthylcarbamate.

Fraction B. 2 C.C. B.P. 110 to 118C. (230 ti0 244.4"F.F.) C. (230 to 244.4" F.) when redistilled. Identified as acetic acid by the p bromophenacyl ester.

C.C.

Water insol. 0.5 B.P. 95 to 98C. (203 to 208.4"P.) at 40 mm. Saponification showed 50% ester as furfuryl acetate.

Water sol., B.P. 91 t o 94C. (195.8 to 201.2"F.) at 40 mm. Identified as furfuryl alcohol by a-naphthylcarbamate. Residue a f t e r redist. smelled of phenol. Color with Feel8 and turbidity with E n

Water insol. Weak N test. Weak color with FeC% sol. A.V. 34.5 Viscous.

Water sol. Strong N test. Intense color with FeCls. Reduced Tollen's reagent A.V. 33.5. End point indistinct. Probably a phenol. Fairly fluid.

T H E STALING O F COFFEE

17

of aromatic oils of coffee. Erdmann found a valeric acid, however, to be the main acid component. Acetic was found to be the principal acid in the present work. There can be little doubt that this was the acid occurring in our products, as both the odor and boiling points of the two acids could not be mistaken. I n addition to this we have the additional evidence of a mixed melting of the p-bromophenacyl ester of the acid from the coffee and that from acetic acid. Santos coffee was used in both researches. The method of isolation of the oils was different and may possibly have something t o do with this divergency. Grafe reports that his acid fraction smelled of acetic acid but calculates it as a valeric acid on titration. H e gives no derivatives. Both Erdmann and Grafe agree that coffee owes its odor to a nitrogen-containing componnd. Sethness (1924) also reports nitrogen in his caffeol fractions. The high-boiling, water-soluble fraction which we found had a fine coffee aroma. It contained nitrogen and may be the compound to which coffee owes its delicate aroma. However, we have found that it is very dangerous to judge by the odor of materials extracted. Extracts having a good coffee aroma may be almost entirely composed of materials of different aromas o r of practically no aroma. Whatever compound gives coffee its pleasant odor must occur in extremely small amounts and be capable of scenting huge amounts of material. As pointed out in the discussion of the previous work, it has been rather well established that Bernheimer (1880) could not have had a methyl derivative of saligenin. However, we examined our extracts for indications of the presence of this compound. It certainly was not a major constituent of our volatile oils. Both ethers of saligenin boil 20 to 40 degrees higher than the materials obtained by us when distilled a t 40 mm. It is hard to believe that a difference in the type of coffee used would make this difference, f o r Grafe gave evidence that the furfuryl alcohol probably comes from decomposition of the hemicellulose of the thick endosperm cells. It seems t h a t this reaction should occur regardless O f the type of coffee used. Of course the amount would vary. It is really difficult to see why Bernheimer and Sethness did not obtain any furfuryl alcohol. -The boiling points of furfuryl alcohol and the caffeol reported by Bernheimer are over 20 degrees apart, and Bernheimer also obtained salicylic acid from his material. Sethness checked his boiling point but gave no derivative.
RELATION OF STALENESS TO CHEMICAL

COMPOSIT~ON

OF VOLATILE OILS I N COFFEE

The mixture of volatile materials extracted from coffee is very unstable. This instability is probably due t o the peculiar composition

18

S. C. PRESCOTT, R. L. EMERSON A N D L.

V .

PEAKES, J R .

of the mixture. It soon became apparent in this work that furfuryl alcohol is unstable in the presence of even very small amounts of acid. If the mixture of volatile ingredients freshly extracted from the coffee be kept for a short time, much darkening and finally resinification takes place. If exposed to air this change is very evident even overnight. Sealed in an evacuated tube the change is much retarded. After the acid is separated from the mixture by distillation, however, a much greater stability is noticed in the furfuryl alcohol fraction. I n order to test whether this decomposition could have anything to do with the unpleasant taste of stale coffee small portions of a freshly distilled and of a dark sample which had been exposed to air for some time following distillation were dissolved in equal amounts of water and tasted. The solution of the old sample left an unpleasant bitter taste i n the mouth. This was entirely absent in the case of solution of the freshly distilled sample. Another test was run on a mixture of furfuryl alcohol and its acetic and formic esters. These had been carefully redistilled and were fairly free from acid. After eight weeks the sample in an unsealed tube had become quite brown, that in a sealed tube under an air pressure of two millimeters was a very pale yellow, while that placed in an atmosphere having a 75 per cent humidity was a dark brown. Only the sample kept in a moist atmosphere had gone off appreciably in taste. It should be noticed that the relative stabilities of the three samples is the same as that of coffee kept under similar conditions. Coffee kept in a vacuum is the best preserved, that in air is not nearly so well preserved, and that in a moist atmosphere deteriorates very fast. If nearly an equal volume of acid had been added to these samples and they had been spread over a large surface, the differences and rate of deterioration would have been much greater. This is the condition in the coffee bean and especially in ground coffee after the carbon dioxide gas has had time to escape. It is the similarity between the instability of impure furfuryl alcohol and of roasted coffee that makes us believe that these mixtures play an important part in the staleness of coffee. It is nearly impossible t o single out one group of compounds in such a complex mixture as coffee and to say that they are responsible f o r its deterioration without first investigating other constituents. Repetition of this work on a somewhat larger scale will probably show up the presence of other easily changed materials. F o r instance the fraction suspected of b e h g a phenol and reducing Tollens reagent is very likely quite unstable in air and may be an important one of the group of compounds giving coffee its odor and taste. Some of the non-volatile constituents may also decompose in air to give products having un-

THE STALING OF COFFEE

19

pleasant tastes and odors. A t present we can say that we have isolated a mixture of compounds which are unstable in air and would seem to be in part responsible for the staleness of coEee, and we wish to point out the possibility of any group of compounds other than the f a t being responsible for the staleness of coffee. This statement is based on experimental observations and not on pure speculation.
REFEIRENCES

BENGIS, R. O., Ah?) ANDERSON, R. J., 1932. The chemistry of the coffee-bean. I. Concerning the unsaponifiable matter of the coffee-bean oil. Preparation and properties of kahweol. J. Biol. Chem. 97, 99. ~, 1934. The chemistry of t h e coffee-bean. 11. The composition of the glycerides of the coffee-bean oil. J. Biol. Ghem. 105, 139. BEENHDIMER, OSCAR, 1880. Zur Eenntniss der Rostproducte des Coffees. Monatsh. f . Chemie 1, 456. Bmmh?), G., AND WEISWELLLER, G., 1913. Sur la Composition de l'essence de Caf6; Presence de la Pyridine. Compt. rend. Acad. d. sc. 157, 212. BOTSCH, K. 1880. Zur Kenntniss der Saligeninderivate. Monatsh. f. Chemie 1, 621. BRFIDT, OUET,1934. Where does the gas in roasted coffee come from? Food Industries 6, 348. CANNIZZARRO AND EORNER, 1872. (Referred to in a communication by H. Schiff.) Ber. d. deutsrh. chem. Gesellsch. 5 , 435. COE, M. R., AND LECLERC,J. A., 1934. Photochemical studies of rancidity. Peroxide values of oils a s affected by selective light. Ind. Eng. Chem. 26, 245. ERDMANN, E. 1902. Beitraz zur Eenntniss des Kaffeeiiles. Ber. d. deutsch. chem. Gesellsch. 35, 1846. F ~ G FRITZ, L, 1934. Z u r Eenntnis der Photopyridinreaktion. J. prakt. Chem. (2) 139, 180. GRAFE, VICTOR,1912. Untersuchungen iiber die Herkunft des Eaffeals. Monatsh. f. Chemie 33, 1389. GREENBANK, G. R., AND HOLM,G. E., 1934. Antioxidants for f a t s and oils. Ind. Eng. Chem. 26, 243. JAECKLE, HERMANN,1898. Studien iiber die Produkte der Eaffeerostung, ein Beitrag zur Keuutniss des sog. Eaffeearomas (Caffeol). Ztschr. f. Untersuch. d. Nahrungs- u. Genussmittel 1, 457. B, LEA,C. H., 1931. The effect of light on the oxidation of fats. Proc. Roy. SOC. 106, 175. LEHMANN, E. B., AND WILHEIL.~, F., 1898. Besitzt das Coffeon und die coffei'nfreien Eaffeesurrogate eiue kaffeeartige Wirknng. Arch. f. Hyg. 32, 310. MON~RI, A., AND SCOCCIANTI, L., 1895. L a piripina nei prodotti della torrefagiolie del caffe. Annali di chimica e di farmacolgia 21, 70. Miner Laboratories, 1934. Acidity in coffee. The National Federation of Coffee Growers of Colombia. New P o r k City, 1 5 pp. SCEMAWUSS, HANS,A N D BARTHYEYER, HELENE, 1929. Deacelyl als Aromabestandteil von Lebens und Gunubmitteln. Biochem. Ztschr. 216, 330. SETENHSS, R. E., 1924. Coffee's aromatic principles. Tea and Coffee Trade J. 46, 570. THIELE, J., A.ND DINROTE, O., 1589. Versuche mit 0- und p- Nitrobenzylchlorid. Ann. d. Chem. 305, 110.

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S. C. PRESCOTT, R. L. EMERSON A N D L. V. PEAKES, J R .

TRIGG, C. W., 1919. Coffee. R. K. D. Bul. 1, No. 3, 14. Ifellon Institute, Pittsburgh, Pa. WENDT, G. L., 1930. New processes f o r liquid coffee. Glass Packer 3, 581, 601.
WEIDLEIN, E. R., 1934. Research a t Mellon Institute during 1933-34. Abstr. Twenty-first Annual Report of the Director, E. R. Weidlein, to the Trustees of the Institution. Ind. Eng. Chem. News Edition 12, 142. WHEELER,D. H., 1932. Peroxide formation a s a measure of autoxidative deterioration. Oil and Soap 9, 89.