Phenacylamine

Photolysis of phenacylamines (32) gives azetidin-3-ols (33) as minor products (66CC289). Higher and more consistent yields are obtained from photolyses of a-N-alkylamidoaceto-phenones (34), which gives N-tosylazetidines (35) in 74-95% yield (71JA2793). The key step... 

Alternatively, imidazotriazine 491 was prepared [89JCR(S)206] by the thermal cyclization of carbethoxy hydrazone 490, which was prepared from carbaldehyde acetal 489. The latter was prepared by cyclocondensation of the respective phenacylamine hydrochloride with diethoxy acetonitrile in the presence of sodium methoxide. 

Peroxides, test for, 41, 92 Peroxy acids from carboxylic acids and 70% hydrogen peroxide, 43, 96 Peroxybenzoic acid, 43,93 iodometric analysis of, 43, 94 Peroxystearic acid, 43,96 Phenacylamine hydrochloride, 41, 82... 

C],jH2(iN20 65514-97-8) see Nomifensine At-methyl-N-(2-aminobenzyl)phenacylamine (CitHisNjO 119810-30-9) see Nomifensine 4-(methylamino)butanoic acid hydrochloride (C5H,2C1N02 6976-17-6) see Azelastine methyl 3-amino-2-butenoate... 

C H,, N203 85660-33-9) see Nomifensine 7V-methyl-lV-(2-nitrobenzyl)phenacylamine (C (,H 9N203 102436-67-9) see Nomifensine 2-methyl-5-nitro-4,6-dihydroxypyrimidine (C5H5N3O4 53925-27-2) see Moxonidine 2-methyl-5-nitroimidazole... 

The submitters did not redistil the feri-butyl hypochlorite. If it is desired to avoid the use of feri-butyl hypochlorite, an equivalent quantity of dichloramine (N,N-dichlorobenzene-sulfonamide, Arapahoe Chemical Co., Boulder, Colorado) may be substituted. This material is soluble in benzene but the benzene-sulfonamide is not therefore the reaction mixture must be filtered just before the addition of the sodium methoxide solution. Using this technique, the submitters obtained 44-52% of phenacylamine hydrochloride. 

Phenacylamine hydrochloride has been prepared by (1) the hydrolysis of the quaternary salt obtained from phenacyl bromide and hexamethylenetetramine (the Delepine reaction),6-11 (2) the hydrolysis of N-phenacylphthalimide (the Gabriel reaction),12-14... 

Of the procedures cited in Section 3, procedures (1), (3), and (4) have been examined by the submitters for comparison with the present procedure. Of these, the present procedure and that based on the Delepine reaction (1) appeared to be the most satisfactory for preparative purposes. Yields by the two procedures were comparable however, the Delepine reaction could be run somewhat more conveniently on a larger scale (provided that one was willing to accept a tedious extraction of the product from the copious quantity of ammonium salts with which it is mixed). The Delepine reaction also makes a lesser demand on the skill and technique of the operator. On the other hand, attempts in the submitters laboratory to extend the Delepine reaction to sec-bromides have been unsuccessful therefore the Delepine reaction appears to lack the generality of the present procedure, which shares such generality, apparently, with procedures (2), (3), (7). and (8). Furthermore, the Delepine reaction gives a mixture of phenacylamine hydrochloride and hydrobromide M0 (although the submitters have found that by careful fractional crystallization from isopropyl alcohol-hydrochloric acid solution about 50% of the pure hydrochloride can be obtained). 

---