Derivatives of a- and b-naphthoic acids.
Wahl, Andre; Goedkoop, Martinus L.; Heberlein, Edouard.
Bull. Soc. Chim., 6 (1939) 533-548.
Abstract: A review and reinvestigation of methods for the prepn. of naphthoic acids (34 references) led to the selection of three:
(1) C10H7MgBr + CO2 (Gilman, et al., C. A. 25, 2146), (2) sapon. of C10H7CN and (3) sapon. and oxidation of C10H7CH2Cl. The nitriles were best prepd.
by strongly heating 400 g. of C10H7SO3Na and 300 g. of K4Fe(CN)6 with 100 g. of Fe2O3 and 100 g. of Fe turnings (to give better heat distribution).
Although the yields were only 30 and 22% for the a- and b-nitriles, resp., this method is preferred to the Sandmeyer, which involves large vols. of
soln. The nitriles were sapond. at 140° for 2 hrs. with 63 g. of NaOH and 460 cc. of EtOH per 100 g. a-C10H7CH2Cl (I) was best prepd. from C10H8,
(CH2O)3, and HCl, following Darzens and Levy (C. A. 30, 2561.8). b-C10H7CH2Cl (II) was prepd. by passing dry Cl into b-C10H7Me and a little PCl3 at
230-50° until 60% of the theoretical Cl had reacted. I and II were changed to the corresponding aldehydes by hexamethylenetetramine (Mayer, et al.,
C. A. 17, 100) which were then oxidized to the corresponding acids by Na2Cr2O7 in boiling AcOH. See C. A. 32, 2930.3 for the conversion of the
aldehydes into a- and b-C10H7COCH2CO2Et (III) and (IV), resp. In addn. to the derivs. described therein, the following are now reported:
a-naphthylisoxazolone, m. 193° (by using NH2OH); oxime of a-C10H7Ac, m. 142° (by using NH2OH.HCl); a-C10H7COCH2CONHPh, m. 119-20°;
a-C10H7COCH2CONHC6H4OMe-o, m. 124°; phenylazo deriv. of enolic III; p-nitrophenylazo deriv. of enolic III, m. 137°; and b-naphthylisoxazolone, m.
159°. This last gave b-naphthylisoxazoloneindoleindigo, b-C10H7C:N.O.CO.C:C.CO.C6H4.NH, deep red needles, m. 250°,
b-naphthylisoxazole-2-(7-chloroindole)indigo, violet, m. 214-26°, and b-naphthylisoxazole-2-(5,7-dimethylindole)indigo, violet, m. 190-1°, when
boiled in benzene with the appropriate isatin chloride. b-C10H7CHO gave 2,7-dimethyl-3,6-diamino-b-naphthylacridine, a brown basic dye, by
condensation with m-tolylenediamine, cyclization, and oxidation.
When the pyrazolones of III and IV made with NH2NH2, PhNHNH2, and p-NO2C6H4NHNH2 were coupled in alk. soln. with diazotized sulfanilic and
naphthionic acids, the resulting dyes gave very fast yellow shades on wool. |