I972
CHARLESD. HURDAND WILLIAM A. BONNER
Anal. Calcd. for C13H12N20a: K, 10.77. Found: N, 10.64. I-Methy14-carbostyriacetonitrile (VI).-Fourteen grams (0,054 mole) of V was warmed with 100 ml. of acetic anhydride in a 500-ml. round-bottomed flask. Evolution of c a r p n dioxide started a t 30-35" and had ceased a t 75-80 . After removal of the acetic anhydride in vacuum, the residual solid was crystallized as fine white needles from a solution of 100 ml. of acetone in 200 ml. of benzene; yield 7.2 g. (67.370),m. p. 186.5-187.5'. .Anal. Calcd. for Cl2Hl0N20: 3,14.14. Found: E, 14.66. I-Methyl4carboStyrilacetic Acid (VII).-Five grams (0.025 mole) of VI was refluxed with a mixture of 95% ethyl alcohol (45 ml.) and concentrated hydrochloric acid (45 ml.) for eight hours. After removal of most of the alcohol by evaporation on a steam-bath and cooling the residual solution in ice, a white granular solid separated. The solid was dissolved in 10% sodium carbonate solution and reprecipitated by neutralization with 6 N hydrochloric acid; yield 4.2 g. (79y0). The acid (VII) was recrystallized from a benzene-ether (3:2) solution; m. p, 185.5186.5' (dec.). Anal. Calcd. for C12HllN03: N, 6.45. Found: N, 6.35. Ethyl 1-Methyl4carbostyriacetate (MI).-A solution of 2 g. (0.01 mole) of VI in 50 ml. of absolute ethyl alcohol was heated to reflux temperature and dry hydrogen chloride passed into the solution for three hours. The alcohol was removed by evaporation on a steam-bath then the solid residue was treated with 100 ml. of water, neutralized with sodium carbonate and extracted with ether. After drying, the ether was evaporated and the residue extracted with 100 ml. of a boiling mixture (1: 1) of benzene and ligroin (b. p. 70-80'). The insoluble portion (1.2 g.) proved to be VI. Concentration of the solution gave a 0.6 g . yield of the ester (VIII); white needles, m. p . 94-95". Anal, Calcd. for C14HJ5NO3: N, 5.71. Found: N, 6.26. l-Methyl-4-(~t-cyanostyryl)-carbostyril (IX).-A mixture of 1 g. (0.005 mole) of VI, 1 g. (0.01 mole) of benzddehyde and 5 ml. of acetic anhydride was heated in an oilbath at 140-150' for twelve hours. The solution was poured into 50 ml. of water, neutralized with sodium hydroxide and the solid which precipitated was crystallized from 10 ml. of 95% ethyl alcohol giving a white ffocculent solid; yield 0.2 g. (14%).. Two recrystallizations from alcohol gave a product which melted at 231.5-232.5'. Anal. Calcd. for C ~ Q H ~ , NN, ~ O9.79. : Found: N, 9.70.
Vol. 67
Nitration of 1,4-Dhethylcarbostyril (I).-Fifteen grams (0.087 mole) of I was dissolved in 36 ml. of concentrated sulfuric acid contained in a 500-ml. three-necked roundbottomed flask fitted with a mechanical stirrer and a dropping funnel. The solution was cooled t o '5 and 15 g. (0.23 mole) of fuming nitric acid (sp. gr. 1.5) in 10 g. of concentrated sulfuric acid added dropwise while the solution was stirred. The temperature was maintained at 5-10'. After addition of the mixed acids, the solution was allowed to stand for two hours a t 10' and finally a t room temperature for twelve hours. The nitration mixture was poured onto 300 g. of chipped ice; yield 13g. (a) Isolation of the Mononitro Derivative.-Nine and one-half grams of the crude nitro compound was extracted with 150 ml. of a hot benzeneacetone solution (l:l), filtered and the filtrate cooled in an ice-bath; yield 3.7 g. (39%), m. p. 218-220'. Pale yellow needles were obtained after two recrystallizations of the nitro compound from the benzene-acetone solution; m. p. 228.5-229'. Anal. Calcd. for C11HloN20a: N, 12.84. Found: N, 13.1, 12.94. (b) Isolation of the Trinitro Derivative.-The benzeneacetone filtrate from (a) was evaporated to dryness, then the residue extracted with 100 ml. of boiling 95% ethyl alcohol and filtered. The alcohsl-insoluble solid (2.5 g.) was crystallized from 100 ml. of boiling xylene as a finely divided yellow solid; m. p. 204-205'. Recrystallization from 20 ml. of an acetone-ethyl alcohol (1 : 1)solution gave bright yellow platelets; m. p. 207-208.5'. .4nd Calcd. for CllHsN&: C, 42.86; H,2.6; N, 18.18. Found: C, 430, 43.0; H,2.87, 3.24; N, 18.3
summary 1. Satisfactory methods have been described for the use of diketene and a secondary alkyl aromatic amine in the preparation of N-alkylacetoacetanilides and conversion of the latter substances to 1-alkyl-4-methylcarbostyrils. 2. The condensation of 1,4-dimethylcarbostyril with ethyl oxalate has been described and the synthesis of several compounds from ethyl 1-methyl-4-carbostyrilppvate has been given. 3. The nitration of 1,4-dimethyIcarbosty1il has been described. BLOOMINGTON, INDIANA
RECEIVED AUGUST 23, 1945
[CONTRIBUTIONFROM THE CHEMICAL LABORKTORY O F NORTHWESTERN UNIVERSITY]
The Glycosylation of Hydrocarbons by Means of the Grignard Reagent BY CHARLESD. HURDAND WILLIAMA. BONNER~ In previous communications2 it has been demonstrated that reaction may be brought about between sugar derivatives and aromatic hydrocarbons in the presence of aluminum chloride. Reaction of benzene, for example, with either glucose pentaacetate or tetraacetylglucosyl chloride gives rise to tetraacetylglucosylbenzene and 1,ldiphenyl-1-desoxyglucitol. It was assumed that the glucose type of configuration was retained in the reaction products. Proof of this assutnption is now presented by synthesizing one of these same compounds by means of the Grignard reagent (1) Corn Products Co Research Fellow, 1941-1944. (2) Hurd and Bonner, Tms J O U R N A L . 67, 1864, 1759 (1915).
under such conditions that isomerization could not occur. As a matter of fact, it would not have been unreasonable to assume that inversion might have occurred in the presence of aluminum chloride in view of the results of Hudson and collaborators3 on the synthesis of heptaacetylneolactosyl chloride from lactose octaacetate and a mixture of aluminum chloride and phosphorus pentachloride. The glucose portion of lactose rearranges to an altrose unit during this process. The basis for assuming that tetraacetylglucosyl (3) Hudson, r b t d . , 48, 2002 (1926); Runz and Hudson, ibie, 48, 1978. 2435 (1926), Richtmyer and Hudson, ibrd , 67, 1716 (1935); Hockett and Chandler, ;bid., 66, 627 (1944).
GLYCOSYLATION OF HYDROCARBONS BY THE GRIGNARD REAGENT
Nov., 1945
1973
to form diisopropylidene derivatives of D-rhamnito1 and 6-desoxy-~-gulitol. After finding that aldosyl halides or acetates yielded nothing of promise with Grignard reagents, Paal and co-workers10turned their attenc1 R' + MgXCl tion to the behavior of Grignard reagents toward R'MgX --+ RCH< RcH
