May, 1941 ium nitrate was added and the solution gently refluxed. The color of the solution changed quickly from pale yellow to orange, at the end of one minute. The solution was refluxed thirty minutes longer and diluted with cold water. The red precipitate was collected and recrystallized from 80% acetic acid; yield, 0.35 g. of isatin, melting a t 199”. A mixed melting point with pure synthetic isatin’ showed no depression.
NOTES
1475
(X
I ; CHrOSOiO-)
Experimental
Nitration.-Fifty grams of the methyl ether (I) was dissolved in 300 cc. of a mixture of equal parts of acetic acid and acetic acid anhydride. The mixture was then placed in an ice-bath, and 50 cc. of concentrated nitric acid (sp. gr. TABLE I 1.42) was then added cautiously in small amounts, while Substance Used, g. Product M. p., OC. Yield, g. the reaction mixture was kept a t a temperature not ex95- 96 2.04 Benzil 2.12 Benzoin ceeding 10’. After the completion of the addition, the re132-133 0.8 Anisil Anisoins 1.2 action mixture was allowed to come t o room tempera102 .9 p-Tolil p-Toluoin 1.9 ture gradually and to stand for thirty minutes; 500 cc. of 160 .5 Furil 1.1 Furoin water was added to hydrolyze the acetic anhydride and 199 .35 0.5 Isatin Dioxindole6 the nitrated ether (11) precipitated a t the same time. I t I am deeply indebted to Prof. David Davidson, was crystallized from methyl alcohol, in large, yellow of Brooklyn College, for his interest and sugges- plates, possessing a faint floral odor. The same product may also be obtained by nitrating first tions and to Dr. M. Jacobi, Director of Labora- the phenol and methylating the mononitrodiisobutylphenol tories, Beth-El Hospital. afterward. (7) “Organic Syntheses,” Coll. Vol. I , p. 321. Reduction.-Thirteen grams of the above nitro com(8) Bosler, Ber., 14, 423 (1881). pound (11) was dissolved in 50 cc. of ethyl alcohol. To this CHEMICAL LABORATORIES solution were added 15 g. of tin and 27 cc. of hydrochloric AND BETH-ELHOSPITAL acid over a period of two hours. During this period the BROOKLYN COLLEGE mixture was refluxed. Complete reduction was indicated RECEIVED MARCH14, 1940 BROOKLYN, N. Y. when all color had disappeared, and when a small sample withdrawn from the reaction mixture dissolved completely Invert Soaps. Quaternary Ammonium Salts of in water. The mixture was then cooled, and 50% sodium hydroxide solution was added until the precipitated tin Derivatives of Long Chain Phenols hydroxide had dissolved. From this the amine (111) was BY JOSEPH B. NIEDEFU AND MARTINI. DEXTER’ extracted with ether, and the ether extract dried over anhydrous sodium sulfate. The ether was then distilled off Some of the previously reported “invert soaps” and the amino compound redistilled in vacuo under reduced involve long chain ethers of 0-,m- and p-amino- pressure. phenoL2 It has now been found that invert soaps The hydrochloride of the amine (IIIa) was prepared by can also be obtained by using short chain ethers passing dry hydrogen chloride gas through a solution of the of the long chain substituted phenols as follows: amine in petroleum ether. The benzoate (IIIb) was prepared by employing the usual Schotten-Baumann proceda,a,y,y-tetrametho-butylphenol (“diisobutyl- ure, using 0.5 cc. of the amine, 2 cc. of benzoyl chloride, and phenol”), prepared by condensing diisobutylene 5 cc. of 20% sodium hydroxide solution. with phen01,~was methylated and the resulting Methylation.-Eight grams of the above primary amine methyl ether (I) was subsequently nitrated to (III), and 8.5 g. of the dimethyl sulfate contained in a yield the mono nitro derivative of p-(ct,a,y,y- stoppered Erlenmeyer flask, were heated in a steam-bath for two hours. The reaction mixture was then cooled and tetrametho)-butyl-anisole (11). This compound treated with 50 cc. of 2 N sodium hydroxide solution. in turn was reduced to the respective amine (111), The mixture was then extracted with ether and the ether which was then converted into the tertiary di- dried over sodium sulfate. The ether was then distilled methylamine (IV), from which, then, water off and the tertiary amine (IV) redistilled a t reduced pressoluble “invert soaps” were prepared by con- sure. Methiodide.-Two cc. of the above tertiary amine (IV) verting this tertiary amine into the respective was dissolved in 20 cc. of methyl iodide and, after a short ammonium salts, the 2-trimethylammonium-4- period of warming, the excess methyl iodide was distilled (a,a, y,y-tetrametho)-butylphenol methyl ether off. The residue (V) was recrystallized from ethyl acetate. iodide (V) and methosulfate (VI), using methyl The compound is soluble in water. Methosulfate.-To 5.3 g. of the tertiary amine (IV) were iodide and dimethyl sulfate, respectively. added 2.6 g. of freshly distilled dimethyl sulfate and 4 cc. The structure of these salts is of dry benzene. The mixture was refluxed a t 120’ for (1) Abstracted from the thesis presented by M. I. Dexter to the two hours. After this time, the benzene was distilled off a t Graduate School of New York University in partial fulfillment of the reduced pressure. The residue was then dissolved in 20 requirements for the degree of Master of Science, May, 1941. cc. of methanol, treated with a little barium carbonate, and (2) R. Kuhn and D . Jerchel, Ber., 13, 1100 (1940). with charcoal. It was filtered and the .methyl alcohol (3) J. B. Niederl, Znd. Eng. Chem., 30, 1269 (1938).
1476
NOTES
Vol. 63
TABLE I Compounds
Formulas
1M.p . ,
OC. (uncor.)
I 4-(cu,cr,y,y-Tetrametho)-butylphenol-methyl ether3 CHIOCBH&~BHIT 46 I1 2-NitroC1aHzsN03 58 I11 2-AminoCidIzsNO (a) Hydrochloride Ci6IzeNOC1 75-77 (b) Benzoyl deriv. CzzHioN02 111 IV 2-DimethylaminoCii"oN0 V Methiodide CisHszNOI 172 VI Methosulfate CioHarNSOa 154 distilled off under reduced pressure. The residue, the methosulfate (VI), was recrystallized from ethyl acetate. The methosulfate dissolves in water instantaneously. CONTRIBUTION FROM THE CHEMICAL LABORATORIES OF NEWYo= UNIVERSITY WASHINGTON SQUARECOLLEGE RECEIVED JANUARY 21, 1941 NEWYORK,N. Y.
B. P.,
'C.(uncor.) 272 (760 mm.) 151 (3 mm.)
160 (8 mm.)
163-165 (8 mm.)
Analyses, % N Calcd. Found
5.28 5.94 5.49 4.13 5.32 3.46 3.61
5.12 5.86 5.36 4.03 5.21 3.61 3.57
cipitated out. The wax-like precipitate was washed with ether and purified by precipitation with anhydrous ether from a concentrated absolute ethyl alcohol solution. THE CHEMICAL LABORATORIES OF ST.JOHN'S UNIVERSITY AND OF NEWYORKUNIVERSITY RECEIVED JANUARY 22, 1941 WASHINGTON SQUARE COLLEGE, NEWYo=, N. Y.
Quaternary Morpholonium Salts1 The Estimation of Primary Carbinol Groups in Carbohydrates BY MARTINE. MCGREAL AND JOSEPH B. NIEDERL
Invert Soaps.
Since none of the previously reported2 "invert soaps" contain a mixed heterocyclic radical i t was thought desirable to prepare and study invert soaps containing a sulfur-nitrogen (long chain ethers of thiazoline phenols),Sor an oxygen-nitrogen heterocyclic ring. For the latter purpose N-tertiary morpholines were chosen as starting materials. N-Ethyl- and N-ethylol-morpholine were converted into N-long chain substituted quaternary morpholonium salts upon treatment with lauryl, myristyl and cetyl bromide, respectively. All the resulting quaternary ammonium salts, which possess the structure as given below, proved to be soluble in water. CHLCH'
/R+
O
