Preparation of aromatic aldehydes by the "nitroso" method.Eliseeva, V. N.; Devitskaya, T. A.
Zhur. Priklad. Khim. (1956), 29 1894-6.
CAN 51:39146 AN 1957:39146
Abstract
Stirring p-ONC6H4NMe2 (from 50 g. amine), 212 g. com. HCl, 25 g. MeOPh, and 10 g. urotropine(aka hexamine) in 20 ml. H2O 8 hrs. at 50° followed by steam distn. gave 44% anisaldehyde. Similarly, 35 g. p-ONC6H4NMe2, 242 g. com. HCl, 0.4 g. ZnCl2, 25 g. MeOPh, and 10 g. urotropine in 20 g. H2O gave 56% anisaldehyde. ONC6H4NMe2 (from 50 g. amine), 121 g. com. HCl, 0.4 g. ZnCl2, 25 g. o-CH2O2C6H4, and 7 g. urotropine stirred 8 hrs. at 50° and steam distd. gave 40% heliotropine; similarly, 35 g. p-ONC6H4NMe2, 121 g. com. HCl, 0.4 g. Al shavings, 25 g. o-CH2O2C6H4, and 7 g. urotropine stirred 8 hrs. at 50°, treated with 500 ml. H2O, heated 6 hrs. at 50°, extd. with C6H6, and the ext. distd. gave 42% heliotropin; the pure product, m. 36.5-7° (from EtOH).
Preparation of aromatic aldehydes by the "nitroso" method.Eliseeva, V. N.; Devitskaya, T. A.
J. Appl. Chem. U.S.S.R. (1956), 29 2043-5.
Journal written in English. CAN 52:40390 AN 1958:40390
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Preparation of aromatic aldehydes by the nitroso method. II.Eliseeva, V. N.; Devitskaya, T. A.; Laskina, E. D.
Tr. Vses. Nauchn.-Issled. Inst. Sintetich. i Natural'n.
Dushistykk Veshchestv (1961), (No. 5), 18-21.
CAN 57:55948 AN 1962:455948
Abstract
cf. CA 51, 7326c. The title compds. were prepd, by method described (lot. cit.) from phenols and their 0-derivs. by action of p-nitrosodimethylaniline and urotropine in the presence of A1 or a mixt. of CuSO4, MnSO4, and ZnCl2 and isolated either by steam distn. or (after hydrolysis) by extn. with org. solvents. The phenol (O-alkylating group) and aldehydes prepd. from it, its % yield (% purity), b.p., m.p., n20D, d20, m.p. of corresponding oxime, and odor were given: o-cresol (Me), 4-methoxy-3-methylbenzaldehyde, 44 (99.26), b5-7 125-7°, -, 1.5698, 1.0337, 68-9.5°, like acetophenone; o-cresol (Et), 4-ethoxy-3-methylbenzaldehyde, 61)(100), b4-5 120-7°, 27-30°, -, -, 92.5-3.0°, like mixt. of heliotropin and obepin; o-cresol (Me), 6-methoxy-3-methylbenzaldehyde, 54(100), b3 104°, -, 1.5522, 1.0056, 143-4° like methyl salicylate; tert-butyl m-cresol (Me), methoxymetbyl-tert-butylbenzaldehyde (indeterminate structure), 54-68(99.6), b5 135-7°, 78-84°, -, -, 122-3°, disagreeable. Similarly, methylguaiacol gave in poor yield 4-hydroxy-5-methoxy-2-methylbenzaldehyde (proposed structure), m. 172-3°. Product of alkylation of optol (mixt. of pyrocatechol and its homologs) with CH2Cl2 gave 3,4-methylendioxy-6-methylbenzaldehyde (proposed structure), m. 86-7° (oxime, m. 89°), odor like heliotropin, p-Cresol yielded 6-hydroxy-3-methylbenzaldehyde in 24% yield, m. 53% oxime m. 103-4°. 1,2-Ethylenedioxybenzene gave 3,4-ethylendioxybenzaldehyde in 60% yield, m. 52.5°, with heliotropin-like odor. An attempt to prep. by this method aldehydes from heliotropin, cumene, triisopropylbenzene, benzyl ale., and dibenzylformal was unsuccessful.
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