December, 1934
I N D U ST R I A L A N D E N G IN E E R I N G C H E M I STR Y
until the samples became sticky. Very little caking was noted in any case, the mixtures remaining free-flowing until the sticky point was reached. S o loss of water of crystallization was noted in any case. The results are collected in Table VII. TABLE VII. HYGROSCOPICITY O F MIXTURES O F IJRE.4 WITH T W O SdMPLES O F TRICALCIUM PHOSPHATE ( A , B ) A S D WITH ANHYDROUS TRICALCIUM PHOSPHATE (C) PHOSPHATE IN
MIXTURE
% 90 80 60 50 40 30
RELATIVEHUMIDITY WHEN MIXTURE BECAME STICKY % A B C 96:3 77.2 77.2 77 2 77.2
96.3 85.2 75.2 75.2 75.2 75.2
96.3 85.2 77.2 77.2 77.2 77.2
TOTAL GAINIK W E I G H T WHEN MIXTUREBECAME STICKY
urea and hydrated tricalcium phosphate do not lose water of crystallization under any of the conditions tried is partial evidence that no compound exists.
ACKNOWLEDGMENT The writers wish to thank S. B. Hendricks and M. E. Jefferson for making the microscopic and x-ray determinations. Thanks are due also to various members of the staff for valuable suggestions and the loan of analyzed materials.
% A 75 89 27 28 24 26
B
C
52 29 24 22 19 16
55 33 19 18 13 12
When the proportion of tricalcium phosphate is below 80 per cent, all mixtures become sticky a t a relative humidity slightly above that a t which urea itself becomes sticky (72.4 per cent), but, when more than 80 per cent tricalcium phoqphate is present, the mixture is very nonhygroscopic and is able to withstand relative humiditieq of 85 per cent or higher. No attempt has been made to prepare a compound between urea and tricalciurn phosphate. The fact that mixtures of
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LITERATURE CITED Adams and Mera, IND.ENG.CHmf., 21, 305 (1929). Assoc. Official Agr. Chem., Methods of Analysis, p. 16 (1925). 4 Ibid., p. 20. Clark, J . Phys. Chem., 35, 1232 (1931). Keenan, ISD. ENG.CHEM.,22, 1378 (1930). Matignon, Dode, and Langlade, Compt. rend., 194, 1289 (1932). Mom, Schilb, and Warning, IND.ESG. CHEM.,25, 142 (1933). (7) Ross, Jacob, and Beeson, J . Assoc. Oficial *4gr. Chem., 15, 227 (1) (2) (2 (3) (4) (5) (6)
(1932). (8) Whittaker, Lundstrom, and Hendricks, IXD.ENG. CHEV.,25, 1280 (1933). (9) Wiley, “Principles and Practice of Agricultural Analysis,” p. 162, Chemical Publishing Co., Easton, Pa., 1931.
RECEIVED September 22, 1934.
Effect of Malvaceous Seeds on Stored-Egg Quality F. W. LORENZAKD H. J . ALMQUIST, University of California, Berkeley, Calif.
A
T Y P E of deterioration Crude kapok oil, the seeds of cheeseweed of yolk deterloration similar t o of the the effects of cottonseed oil. in stored eggs, known in (buttonwuredor mallow) and other t h e trade as “pink Schaible, Moore, and RIoore (’7) f a m i l y .I falcaceae, as well a s cottonseed meal after feeding cottonseed meal, white>,” has caused occasional severe l o s s e s . Characteristic and crude Or Partially refined cottonseed oil, crude or treated in a number of ways, have concluded that yolk symptoms of this form of decause the “pink-white” storage deterioration in discoloration is due to gossypol, terioration are: eggs. T h e inclusion of these materials in the feed of whicht”aspresentin thoseprod(a) The albumen 19 ucts found to discolor yolks. t o reddish in color but normal in laying h m s can be detected by applying the Sher.il.ood (9) has reported other respects. Halphen test to the feed and to the yolk f a t Of chemical analyses of yolks from ( b ) The yolk color varies from normal t o a salmon or near red. fresh or stored eggs produced by these hens. hens fed cottonseed meal and (c) The yolks are noticeably has pointed out that not only Cheeseweed is common in m a n y poultry dislarger than normal. water but protein may be ( d ) The yolkmaterialiswatery tricts, and is more often available to poultry taken up by the yolks during at room temperatures but usually than Other members Of Ihe plant family* cold storage. claylike in consistency at cold storage temperatures. This weed is probably ihe p r i m a r y cause of p i n k EXPERIRIEKTS TO CORRELATE ( e ) The cooked yolks are rubwhites where cottonseed meal is not fed. bery in consistency PINK-WHITE DEVELOPMEKT ( j ) The yolks tend to acquire WITH FEEDING a normal color, rind the pink tinge of the albumen tends to disappear when the eggs are cooked. In the supply of pink-white eggs submitted to this labora( 9 ) Bacteriological examination shows that pink-white eggs tory, several normal eggs were found which had received the may be free from d&ructive microorganisms. same storage treatment as the others, hence it waq possible ( h ) The eggs have no abnormal odor. to make a comparison of the chemical analyses of yolks from This list includes many of the effects of cottonseed meal the two kinds of eggs. Composite samples of yolk from the feeding, as described by Sherwood (8,g), Sipe ( I o ) , Thomp- two sources were dried to practically constant meight. The son ( 1 1 ) and ~ KemPster (6). The whites are often Pink and crude fat was determined by thorough extraction with ethyl the Yolk color may often be red, olive, brown, Or black. The alcohol, and the crude protein was determined by the usual loss of quality in storage eggs appears to increase with the Kjeldahl procedure, The results are as follows: cottonseed meal content of the ration. Except when large CRUDE CRUDE amounts of cottonseed meal have been fed, the fresh eggs FAT PROTEIN PROTEIN appear to be normal. TOTAL ( O N DRY (Ov DRY FAT Heller, Searcy, and Thompson ( 3 ) have reported that S O U R c E O F yoLK BASIS) BASIS) RATIO % % % gossypol, present in cottonseed oil, does not discolor egg Normal stored eggs 68.4 31 9 0 47 47.8 yolks when fed in a purified form but does cause other forms Pink-white eggs 39.7 63.3 36.5 0.58
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INDUSTRIAL AND ENGlNEERING
The data are in accord wit’h the observations of Sherwood (9) on yolks from eggs produced on cottonseed meal rations.
The yolks are more watery, the relative fat content of the solids is lower than normal, and the relative protein content is correspondingly higher. The ratio of protein to fat obtained from the normal stored eggs is practically the same as the ratio of 0.46 found in fresh eggs. It is evident that the storage changes in pink-white egg yolks closely resemble those reported in yolks of eggs produced on cottonseed meal. I n the search for further direct evidence to correlate the deveIopment of pink whites with feeding, it was found that a specific chemical test for cottonseed fat, the Halphen test (2), would give a positive result when applied to the extracted yolk fat from pink-white eggs: The fat was extracted from the wet yolk by allowing it to stand with several volumes of ethyl ether for 24 hours or more. The ether layer was then decanted off, and most of the ether evaporated with the aid of a fan. The remaining fatty material was taken up in 5 cc. of isoamyl alcohol t o which 5 cc. of carbon disulfide containing 1 per cent of sulfur were added. The mixture was heated in a calcium chloride bath, st first carefully until the carbon disulfide and ether were evaporated, and then vigorously for an hour or more. A positive test was indicated by a slowly developing pink or reddish color. The t,est was applied in the same way t,o mixed feed and feed materials. Green pigments which were also extracted from certain feed ingredients interfered with the Halphen test. It was found that these pigments could be removed without impairing the Halphen test by filtering the ext’ract several times through bone black.
It is well known that the feeding of cottonseed meal will cause the body fat of hogs, cattle, etc,, to respond to the Halphen test. I n an experiment to ascertain whether the same is true for hens, cottonseed oil was fed to a group of hens a t a level of 2 per cent of t,he total ration. The cottonseed oil used was designated as “prime summer yellow” and had been given a preliminary refining treatment consisting of neutralization and removal of free fatty acids, a process which also removes much color from the oil. Soon after the feeding started, it was found that the depot fat of the birds and the extracted yolk fat of the fresh eggs would give a positive Halphen test. After 3 months of storage the eggs produced from the cottonseed oil ration developed all the characteristics of pink-white eggs. Olive and black yolks, such as those resulting from the feeding of cottonseed meal, were not observed. Eggs produced on a control ration did not respond to the Halphen test and did not derelop pink whites during storage. Similar experiments made with coconut, peanut, sesame, linseed, and soy-bean oil failed to show any deteriorative effects on stored eggs. Many examples of pink-white eggs have come from flocks to which Cottonseed meal had not been fed. A surrey was made of the members of the cotton plant family (Nalvaceae) with the View of detecting other plants with similar effects on eggs, to which poultry might have ready access. A preliminary report on this phase of the problem has been given by Lorenz, Almquist, and Hendry (6). The plant Malvu par~$lora (commonly known as cheeseweed, buttonweed, or mal!ow) is often found growing in poultry yards or a t their boundaries and might easily be available to poultry. Lavetera ussurgenti,iiora (commonly known as California windbreak), Althea rosm (common hollyhock), and Sida hederacea (alkali mallow), are other me11 known relatives of the cotton plant. The fat extracted from the seeds of these plants gave, in every case, a positive reaction to the Halphen test. It has been shoxm by Ivanov (4) that the Halphen test is characterist,ic of all plants of the family Malvaceae, as well as of the Tiliaceae and Rombacaceae. Cheeseweed and California windbreak seeds were collected in quantity and fed to hens a t a level of 1 to 5 per cent of the ration. The eggs produced by these hens gave positive re-
CHEMISTRY
Vol. 26, No. 12
sults with the Halphen test but were normal in appearance a-hen fresh. After one month of storage the eggs began to show the characteristics of pink-white eggs when candled and when opened. These characteristics became more and more prominent with longer storage periods and heavier doses of seed. I n storage, eggs from cheeseweed seed rations seemed to develop pink whites and the associated characteristics sooner and to a greater degree than did other eggs. The fat of the kapok plant, a member of the Bombacaceae family, is also known to respond to the Halphen test. Kapok meal has occasionally been used in poultry feeds The effect of crude kapok oil on the quality of eggs was next investigated. The oil and the feeds in which it was mixed a t a level of 1 per cent gave strong Halphen tests by the procedure described. Fresh eggs produced on this feed were found to give positive Halphen tests but to show no visible abnormalities. After 2 months of cold storage, however, the eggs developed all the symptoms of pink-white deterioration to a marked degree.
DISCUSSION OF RESULTS In no case throughout this work were olive yolks produced. This suggests that there exists another substance in cottonseed meal, or in crude cottonseed oil, which causes the olive color of yolks either by acting as a simple pigment or by Causing color changes which are different from those resulting in red or salmon colored yolks. The olive to black discoloration might easily obscure the salmon discoloration if both occurred simultaneously. The former discoloration appears to be peculiar to crude cottonseed products since it was not found in feeding other malvaceous materials. The ammonia yolk-darkening test described by Schaible, Moore, and Moore (7‘) was invariably negative, indicating from a different standpoint that substances present in cottonseed meal or crude cottonseed oil, and not present in partially refined cottonseed oil or in seeds of plants related to the cotton plant, may be incorporated in egg yolks. While the Halphen test may be employed to advantage on feeds, it cannot be used to test all eggs intended for storage. It may be useful as a confirmatory test in special cases where the feeding of cottonseed meal or the avaiIability of cheeseweed, etc., to poultry is suspected. Cheeseweed is found in practically all regions of the United States and foreign countries, except a t high altitudes. Therefore, the farm flock, which is allon-ed to run freely on range and to pick up much of its feed there, often has access to cheeseweed. It is important to exercise care in selecting alfalfa or alfalfa products for poultry rations since old stands of alfalfa often become heavily infested with cheeseweed. A laying hen forms a number of yolks simultaneously. It is possible, therefore, that a number of yolks may be simultaneously contaminated as a result of a single ingestion of material containing a deteriorative constituent. In this manner pink-vhite eggs may be produced for several weeks after malvaceous materials are no longer available to hens. Almquist, Lorenz, and Burrnester (1) have shown, however, that malvaceous fat which has been deposited in the body fat of laying liens is not later redeposited in yolk fat; hence it is not capable of causing pink-white deterioration. To guard against the production of eggs which may develop pink whites, it will be necessary to make certain that cottonseed meal, kapok meal, cottonseed oil, cheeseweed, etc,, have not been available to the hens for a period of several weeks in advance of and during the storage season. ACKKOVLEDGZIENT The authors gratefully acknowledge the valuable assistance received from G. W. Hendry, asswiate agronomist in the Experiment Station, and from Mrs. PIT. P. Bellue, senior
I N D U S T R I A L A 3 D E K G I I% E E R I N G C H E hl I S T R Y
December, 1934
seed analyst in the Bureau of Field Crops, in the study and identification of plants concerned in this investigation.
LITERATURE CITED (1) Alniquist, H. J., Lorenz, F. W., and Burmester, B. R., J . B i d . Chem., 106, 365-71 (1934). (2) Assoc. Official h g r . Chem., Methods of Analysis, p. 330 (1931). (3) Heller, V. C., Searcy, V., and Thompson, R. B., Proc. Okla. A c a d . S c i . , 12, 45-52 (1932). (4) Ivanov, S., Rer. deut. botan. Ges., 45, 588-91 (1927).
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( 5 ) Kempster, H. L., Mo. Agr. Expt. Sta., Bull. 285, 93-9 (1930). (6) Lorenz, F. W., Slmquist, H. J., and Hendry, G. W., Science, 77, 606 (1933). ( 7 ) Schaible, P. J., Moore, L. A., and Moore, J. M., Poultru Sci., 12, 334 (1933). ( 8 ) Sherwood, R. M., Texas Agr. Expt. Sta., Bull. 376, 1-12 (1928). (9) Ibid., 429, 5-19 (1931). (10) Sipe, G. R., M i s s . Sta. Rept., 1930, 31-5. (11) Thompson, R. B., Okla. A g r . E.rpt. Sta. R e p t . , 1930, 87-94. RECEIVED September 11, 1934.
Studies in the Friedel and Crafts Reaction Preparation of Ketones and Keto Acids P. H. GROGGINSAKD R. H.
%GEL
Color and Farm Waste Division, Bureau of Chemistry and Soils, Washington, D. C. I n the Friedel and Crafts reaction the introduction of halogen carriers-e. g., particles of metallic iron and alum inum-exert no marked effect, either in the preparation of alkyl aryl ketones or keto acids. T h e addition of easily decomposed oxyhalogen compounds-e. g., thionyl chloride and potass i u m chlorate-to the reaction mass is deleterious in the preparation of acetophenone from acetic anhydride and benzene, and in some keto acids. I n the synthesis of alkyl aryl ketones f r o m acid anhydrides and aromatic compounds, it is possible to cause both trcyl groups to become reactive by employing at least three molecular proportions qf alumi-
T
H I S investigation deals with the influence of the following factors on the preparation of ketones and keto acids according to the Friedel and Crafts reaction:' ( a ) the aluminum chloride ratio (in the qynthesis of ketones) ; ( b ) the halogen carriers, metallic iron and aluminum; and (c) the oxylialogen compound?, thionyl chloride and potassium chlorate. Further interest lies in determining the practicability of employing iron reactors in liquid-phase reaction.. It is of fundamental interest to know the influence of these metals, since the condensing agents employed in this synthesis are the correqponding halides. In Friedel and Crafts condensations iiivolving carboxylic acid anhydrides, there is a partial degradation of the metal halides because of their activity as halogenating agents ( 2 , I ? ) , and in the cace of phthalic anhydride tautomeric changes may also occur because of the migration of chlorine atoms (6, 6 , l a ) . Other relationships are indicated by a consideration of tlie following two reactions, each leading to tlie formation of acetophenone : u
.41c13
1 U. S. P a t e n t 1,966,797, issued t o Groggins and Nags1 in 1934, and four applications for other patents resulting from this research have been aEsigned t o the Secretary of Agriculture, from whom license to ure may be obtained. All foreign rights reserved.
num chloride per mole of anhydride. A theory is adcanced and ecidence is adduced indicating why 3 moles of aluminurn chloride are required. Preliminary results also suggest the practicability of treating aliphatic acid anhydrides with a l u m i n u m chloride as a technical procedure for the manufacture of acid chlorides when the residual a l u m i n u m chloride salt of the carboxylic acid can be used profitably in the Friedel and Crafts condensations. Experiments in cast-iron reactors suggest the feasibility of employing suitably designed certical iron reactors jor carrying out such liquid-phase reactions. ., 0
O
C
O CH3 AIC13
+ CH3 COAlC13 + HC1
(2)
'I
0
The liberation of hydrogen chloride plays an important part in the progress of these reactions, yet the acid anhydride contains no halogen atom initially. If, in tlie reaction according to Equation 1, a premature labilization of chlorine should take place because of the action of aluminum cliloride on acetyl chloride ( d ) , it would lead to side reactions and thus presumably minimize ,the formation of the addition compound from Jvhich the deiired ketone and hydrogen chloride are liberated. Reaction 2 , however, appears t o depend on the preliminary transfer of a chlorine atom, resulting in the formation of the acid chloride derivative which is known to react with the liberation of hydrogen chloride. The formation of an addition compound of aluminum chloride and the least saturated of the organic reactants is generally postulated as a preliminary step in the Friedel and Crafts reaction. Some of these complexes hare been i3olated ( I O , 13, 14), and in many instances their presence has been confirnied by conductivity measurements (13, 18, 19). Little is known as to whether the formation and decomposition of such addition compounds are affected by the presence
