Propionic 2-nitroso

The oxidation of A-acyl-A-arylhydroxylamines with lead tetraacetate is very rapid even at very low temperatures. The product obtained is the corresponding aromatic nitroso compound. The most favorable reaction conditions involve propionic acid or ethanol-acetic acid as a solvent and reaction times of less than 10 sec at temperatures of —20°C or lower [87]. The use of ethanol-acetic acid is particularly recommended for several reasons. First, since the product is best isolated by steam distillation, the solvent assists in steamdistilling rapidly. The ethanol in the distillate helps minimize clogging of the condenser and also solubilizes small quantities of impurities that may be entrained. 

Nitrosodiphenylmetbanol (called 4-Nitroso-a-phenylbenzyl Alcohol in CA), ON.C H4.CH(OH).C6H5 mw 213-23, N 6.57% yel ndls, mp 114—17° was obtd with 4,4J-dibenzoylazoxybenzene when j6-(p-nitrodi-phenylmethylthio) propionic acid was boiled with 5%NaOH for 1 min only, cooling on ice, diluting with ice-water, and separating the two fractions (Ref 2)... 

This prompted us to develop a novel regioselective nitrosation procedure for resorcinol monoethers, e.g. for monobenzyl resorcinol, as starting material (Fig. (11)). Solid sodium nitrite in anhydrous propionic acid as solvent was an effective system for the completely regioselective nitrosation of the subject compounds. High yields of pure 2-nitroso products were obtained. Attack at the 4-position becomes only competitive in the presence of water in the solvent. Absence of water was ensured by addition of one percent of propionic anhydride. The excellent regioselectivity observed is obviously related to the presence of nitrosyl... 

Cyclization of a,j8-unsaturated acid hydrazides319 or /3-hydroxy-propionic acid hydrazides1177-1327 forms 3-pyrazolidinones. The /9-hydroxy acid derivatives have usually been cyclized with acid at elevated temperatures. If the hydrazides of aryl hydrazines are used, N-l substitution occurs. It has been reported that a,/9-unsaturated acid hydrazines cyclize by treatment of the hydrazide with nitrous acid (eq. 245),335,479,1028,1029 leading to formation of l-nitroso-... 

L Alanosine, 3-(,Mydroxyrtitmftoam no)-v-alan ne L-2-amino-3-(hydroxynitrosoaminfnpropano tc acid L-2-amino-3-[(N-nitroso)hydroxylaimno]propionic acid. CjH7-N304 mol wt 149.11- C 24-16%, H 4.73%, N 28.18%, O 42 92%. Antibiotic substance from ihe fermentation of Streptomyces alanosinicus n. sp. Prepn Neth. pat, Appl. 

Amido-propionic acids — Alanins — CiHiNOi — 89.— Two are known, isomeric with sarcosin and with lactamid. One, a Alanin,. CH,-CH (NH,)-COOH, is formed by the reduction of a nitroso-propionic acid by Sn-j-HCl. The other, j3 Alanin, CHiNHi—CH> —COOH, whose constitution is similar to that of glycocol, is formed either by the reduction of /J nitrosopropionic acid, or by the action of 13 iodopropionic acid on ammonia. either exists, so far as known at present, in nature. 

A soln. of 5.0 g. ethyl a-oximinopropionate in methylene chloride immersed in an ice bath, treated with a slow stream of nitrosyl chloride until the weight increase is 4.0 g., then allowed to stand 45 hrs. at 0 ethyl a-chloro-a-nitroso-propionate. Y 89%. F. e. s. L. W. Kissinger and H. E. Ungnade, J. Org. Chem. 23, 1517 (1958). 

---