INDUSTRIAL AND ENGINEERING CHEMISTRY
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Vol. 23, No. 10
pharmacologist, apply the knowledge gained from the study of barbituric acids to the development of the ideal hypnotic and anesthetic. Acknowledgment
The author wishes to express his appreciation to G. H. A. Clowes for his suggestions, and to E. E. Swanson for his pharmacological evaluations of the barbituric acids. The compounds listed in Table I and the hydantoins used were prepared in T. B. Johnson's laboratory by Robert Herbst, and tested by C. L. Rose of the Lilly Research Laboratories.
cc. M A 0
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Literature Cited
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Graph V
ture of naturally occurring alkaloids, having sedative effect, has not contributed much to the development of hypnotics. Work must still be done in a rather empirical fashion. If there is any special group that can be called the hypnophore or pharmacophor group in hypnotics, it is the alkyl group, the hypnotic effect of which can be varied by attachment to different polar groups. Many hundred variations of barbituric acids are possible through changes of the two aliphatic substituents. Although less than 10 per cent of these have been made, this field can be considered as quite thoroughly explored. The synthetic chemist must now, in cooperation with the
(11) (12) (13) (14)
(15) (16) (17)
(18) (19) (20) (21)
(1) Bancroft. \\'. D . , and Richter, G . H . , Colloid Symposium Monograph, p. 215, Chemical Catalog, 1931; J. Phys. Chem., 36, 215 (1931). (2) Bousquet, E. W., and Adams, R . , J. A m . Chem. Soc., 62, 224 (1930). (3) Carnot, P . , and Tiffeneau, M., Compl. rend., 176, 242 (1922). (4) Dox, A. W., and Hjort, A. M., J. A m . Chem. Soc., 46,-252 (1924). (5) Dox, A. Itr.,and Hjort, J . Pharmacol., 31, 455 (1927). (6) Dox, A. W., and Yoder, L.,J. A m . Chem. Soc., 45, 1757 (1923). (7) Eddy, S . B . , J. Pharmacol., 33, 43 (1928). (8) Henderson, V. E . , Physiol. Re%, 10, 171 (1930). (9) Hill, A. J., and Keach, D. T., J. A m . Chem. SOC.,48, 257 (1926). (10) Hseuh, C. M . , and Marvel, C. S., Ibid., 50, 855 (192s). Koppanyi, T., and Lieberson, A,, J. Pharmacol., 39, 177 (1930). Munch, J . C., and Schwartze, E. W., Jr., J. Lab. Clin. Med., 10, 985 (1925). Nielson, C., Higgens, J. A . , and Spruth, H . C., J. Pharm. Erpll. Med., 26, 371 (1926). Norris, J. F., "Contemporary Developments in Chemistry," Colorado Univ. Press, 1927. Norris, J. F., and Young, R . C., J. A m . Chem. Soc., 62, 5066 (1930). Richardson, B. W.. Med. Times and GQZ.,18, 703-6 (1869). Shonle, H . A , , Keltch, A. K . , and Swanson, E. E., J. A m Chem Soc. 52, 2440 (1930). Shonle. H . A , , and Moment, A., Ibid.,45, 243 (1923). Vogt, M., Arch. e x p f l . Pafh. Pharmakot., 152, 341 (1930). Volwiler, E. H., J . Am. Chem. Soc., 47, 2236 (1925). Volwiler, E . H., and Tabern, D . L , Ibid.,62, 1676 (1930)
Preparation of Vinegar from Coffee Fruit Pulp' F. W. Freise VILLAN. S.
DA
POMPEIA, 3
6 SIR., ~ ~No. 15. RIC. DE ALBUQUERQVE, FED. DIST..BRAZIL
T
HE raw material is the pulp which covers the two
seeds or beans of the cherry-like coffee fruit and which is freed from the seeds in the so-called "wet process of coffee preparation." The ripe pulp is of a bright scarlet color and amounts to 40 per cent of the weight of the entire berry. The average composition of the pulp may be figured as follows: %
Moisture. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42.660 Volatile o i l s . .. . . . . . . . . . . . . . . . . . . . . . . . . . . 0 . 1 1 2 Waxes, fats, resins.. . . . . . . . . . . . . . . . . . . . 1 . 1 8 4 Tannins., . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.557 Raw fiber.. . . . . . . . . . . . . . . . . . . . . . . . . . . 2 7 . 4 4 5 Sugars.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 . 4 5 5 Mineral substances. . . . . . . . . . . . . . . . . . . . . . 3 . 7 7 2 6.815 Notspedfied . . . . . . . . . . . . . . . . . . . . . . . . . . .
The maximum amount of sugar, 12.553 per cent, was found in a sample of Botucatu coffee in complete state of ripeness. Among the sugars, glucose and sucrose may be identified; the highest amount of the latter was found to be 1.25 per cent. 1
Received April 28, 1931.
To secure a rapid and uniform fermentation, the pulp must be reduced to a mash. When this mash is pasteurized a t 75" C. during 45-55 minutes and then inoculated with a culture-e. g., of Saccharomyces octoporus, a good fennentation sets in within 24 hours (temperature being held a t 23-25' C.) and reaches its climax on the fourth day. After 12 days the fermentation is complete and clarification must follow. Calculated on 100 grams of sugar, an average of 43.5 grams of alcohol is present. The specific gravity of the liquid is about 1.006, and the acetic acid contents, 0.25 gram per 100 cc. When this liquid is acidified in barrels filled with wood chips slaked in previously prepared strong vinegar, the temperature of the acidification room being held a t 35" C., the vinegar which results is of a clear Rhine-wine color, has a smell like pear oil and a taste resembling old whisky. The taste disappears within 3 or 4 weeks of storage and the color clears up somewhat. The vinegar has a specific gravity of 1.0154, a total acid
October, 1931
I N D U S T R I A L A N D ENGINEERING C H E M I S T R Y
content, as acetic acid, of 4.60 per cent, traces of ethyl alcohol, 3.67 grams of solids and 1.29 grams of ash in 100 cc., 0.97 gram or 75.2 per cent of this ash being soluble. hlash which is not completely ripe admixed to ripe mash causes the fermentation process to come to a standstill after some hours of slow fermentation. The motive is the presence of great amounts of salicylic acid in the pulp. Methanol
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derived from the pectin in the fruit is present in overripe mash. Unpasteurized mash always shows amyl alcohol in the fermented liquid, and during fermentation a strong ammoniacal odor denoting the bacterial activity on amino acids is experienced. The vinegar output is on an average about 74 per cent of the theoretical.
Quick-Freezing Citrus Fruit Juices and Other Fruit A Preliminary Report E. :M. Chace and H. D. Poore L.ABOKATORY OF F R Y I T 4 S D v I . . G E T I B L E
CIIEXISTRY,
B u R E ; , ~O F CHEMISTRY A S D SOILS, E. ROAD,Los ANGELES, C.ALIF.
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DEPARTXEXT OF
.kGKICULTURE,
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SUl'TH
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HE greatest progresh Kearly a thousand packages of fruit juices and other apple juice by sloiv freezing in p r e s e r v i n g food* fruit products have been frozen at temperatures well and separating the colicend u r i n g t h e past fenbelow -10" F. (-23.3" C.). Glasses and glass jars, trate f r o m t h e ice crystals decades has been in the fields with and without vacuum closure, cr0wn-P bottles, by means of c e n t r i f u g a l s . of canning and of cold storfricti0n-W tins, tightly sealed, and open tins have Cans containing 300 pounds been used. The air has been washed from some of of orange juice were frozen in age. u p to this time, the canned product has gone to the juices with carbon dioxide, and carbon dioxide has the ordinary comlnercial ice machines, 24 hours being albeen used to fill the head space of other packages. the consumer in the original container, in which it can be Samples have been s t ~ m dat 7 " F. ( - 13.9" c.)for nearly lowed for congealing. The kept f o r a n y r e a s o n a b l e 300 days, and then for 75 days a t 45' F. (7.2" C.) withcakes were broken downin an l e n g t h of t i m e . On t h e out spoilage and, in most cases, without seriously ice c r u s h e r a n d s p u n as other hand, cold storage has affecting the flavor. rapidly as possible in a centrifugal of the s u g a r - h o u s e usua'ly been used with food in bulk, which, after removal from cold storage, has been type. By tnice r e t r e e h g the concentrate obtained, asirup conplaced in the hands of the consumer as rapidly as possible taining as high as 60 per cent solids could be produced. Howfor immediate consumption. The improvements in refrigera- ever, the concentrate when diluted had neither the flavor nor tion, both in commercial establishments and in the home, the aroma of the original juice. After considering the cost have now made it possible for the retailer and the housewife of the operation and the quality of the product, the investigato maintain a temperature sufficiently low to keep many food tion was abandoned. Over more than a year ago, however, experiments in quick products over long periods of time. Some twenty years ago, the coldpack industry was started freezing a t from -10" to -50' F. (-23.3' to -45.6' C.) by the berry growers of the Korthwest, and it has developed were undertaken with citrus and other fruit products. The into a large and profitable business. After many attempts results obtained by packing the containers in Dry-Ice (solid to preserve berries in cold storage, methods have been de- carbon dioxide) were so satisfactory that a small freezer was veloped which place in the hands of the manufacturers of built in which a current of 30 per cent calcium chloride brine jams, jellies, and ice creams a superior frozen raw product was cooled by passing it over Dry-Ice bunkers. While a t a reasonable cost. When a few years ago the fish dealers theoretically solid carbon dioxide should produce a temof the Atlantic seaboard began placing frozen fish fillets on perature below -110" F. (-78.9' C.), the lower limit of the market the berry packers began experimenting with small temperature in this apparatus was controlled by the freezing packages of frozen berries for home consumption, and in 1929 point of the calcium chloride, which was around -54" F. 1,200,000 one-pound cartons of frozen berries were packed; (-47.8' C.). Recently a larger freezer has been constructed in 1930 the pack was increased to 1,900,000 carLons. The which is completely surrounded by solid carbon dioxide bunksuccess of these products has encouraged investigation in ers in such a way that the alcohol used in place of the calcium freezing other fruits and vegetables. Naturally the attention chloride brine can be maintained a t a temperature below of investigators has been drawn especially to those fruits and -80' F. (-62.2' C.). juices which could not be satisfactorily pasteurized by heat. Fruit juices (including orange, grapefruit, lemon, tangelo, Diehl (2, 3 ) , Birdseye ( I ) , Woodroof (9, IO), Telson and apple, pomegranate, and pineapple) have been frozen in Lang ( 7 ) , Joslyn and Marsh ( 5 ) , McConkie (6),Reynolds crown-cap bottles, in vacuum-closure glasses and glass (8), and others have reported their results in both scientific jars, and in tin cans. Grapefruit hearts, orange slices, pineand trade journals, as well as in official publications. Pack- apple slices, etc., have been frozen both in glass and in apes ranging in size from l / 4 Dound to 10 pounds have been tin. used, a n i temperatures ranging from 10" F. (-12.2' C.) to Preliminary Experhents -80' F. (-62.2' C.) have been tried. The interest of this laboratory in freezing citrus juices Preliminary experiments were carried out in which orange followed the work of Gore (4) in his attempts to concentrate juice was frozen in 8-ounce open Cans a t -500 F. (-45.60 c.). The juice was satisfactorily frozen in less than 30 minutes, IReceived M a y 14, 1931. * Food Research Division Contribution No. 108. a smooth-grained, uniformly frozen cake being obtained
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