The Chlorine Derivatives of Vanillin and Some of Their Reactions

Abstract

The same products were obtained in another experiment in which 0.5 cc. of piperidine was used as a catalyst.Azobenzene and p-Thiocresol.-A solution of 18.2 g. (0.1 mole) of azobenzene and 37.2 g. (0.3 mole) of £-thiocresol in 200 cc. of xylene was refluxed for twenty-five hours. As in all other experiments, a trap2 was used to exclude air. The products obtained were 9.5 g. of aniline, 0.1 g. of benzidine (from a sulfuric acid treatment of the hydrazobenzene present), 5.5 g. of £-thiocresol and 90% of the di-p-tolyl disulfide which should have formed on the basis of the reduction products isolated.Miscellaneous.•-After heating 0.075 mole of benzophenone-anil with four molecular equivalents of ^-thiocresylmagnesium iodide in an ether-xylene solution at 103-107°f or twelve hours, 96% of the anil was recovered. In addition, 0.3 g. of aniline was isolated. Another experiment under corresponding conditions yielded a 95% recovery of the anil, and traces of aniline and di-p-tolyl disulfide.Subsequent to refluxing three equivalents of ^-thiocresylmagnesium iodide with benzalaniline in an ether-xylene solution at 114-124°for forty hours, 96% of the pthiocresol was recovered.The recovery of ^-thiocresol in an experiment in which four molecular equivalents of it were refluxed with benzophenone in xylene for twenty-six hours was 97.8%. A like recovery of ^-thiocresol was had in an experiment wherein eight equivalents were heated with nitrobenzene in xylene for twenty-six hours.

Transformations of chloroguaiacols, chloroveratroles, and chlorocatechols by stable consortia of anaerobic bacteria

“…0.5%) of 4,5,6trichloroguaiacol formed by chlorination of guaiacol existing as a minor impurity in the vanillin. A product completely free of 4,5,6-trichloroguaiacol was obtained by converting the CV to its tri-O-acetate (37), crystallizing this to purity from methanol and hydrolyzing the product with methanolic KOH. The free phenol was liberated by acidification and recrystallized from acetic acid.…”

Conversion of Dichlorovanillins to Trichloroguaiacols - Components of Pulp Bleaching Effluents

“…The formation of a trichloroguaiacol from 2,6-dichlorovanillin (IIc) is unlikely, äs previous studies have shown that chlorination of IIc with sulfuryl Chloride yielded trichloro- vanillin and unreacted starting material (Raiford and Lichty 1930;Hyötyläinen and Knuutinen 1993). Reaction of 5,6-dichlorovanillin (Hd) with l equiv.…”

“…In particular, the aromatic proton signal and the carbon Signals were distinct from those of the 3 known trichloroguaiacols, although both isomers Ic and Id had similar melting points (103-4 °C and 102-4°C respectively). Raiford and Lichty (1930) found that Chlorination of 2-chlorovanillin with chlorine in Chloroform gave, besides 2,5-dichlorovanillin, a red oil which probably contains the crude trichloroguaiacol Ic. The trichloroguaiacol Ic would best be obtained by reaction of 2,5-dichlorovanillin with 0.5 equiv.…”

“…Compound Ha, m. p. 127-9°C, was prepared from vanillin by the procedure of Raiford and Lichty (1930) …”

Aminoalcohols V [1]: A Methodfor the Synthesis of EnantiomericallyPure Ring-Chlorinated Epinephrinesand Norepinephrines

“…2-Chloro-4,5-di(phenylmethoxy)benzaldehyde (1a) [16,36,37], 3-chloro-4,5-di(phenylmethoxy)benzaldehyde (1b) [16,37,38], and 3-chloro-4,5-dihydroxybenzaldehyde (1c) [16,37,38] were prepared according to the literature. A solution of 29.8 g (content of 2a: 84%, 66.5 mmol) of crude 2a, 16.3g (43.51 mmol) of (MBE) 2 O, and 450 mg of triphenylphosphine hydrobromide in 450 ml of CH 2 Cl 2 was stirred for 30 min at room temperature.…”