The stereochemistry of some carboxylic acids derived from 2-norbornene* and bicyclo[2,2,2]oct-2-ene was investigated.The reaction of either 5-e»docyano-2-norbornene (la) or 5-exocyano-2-norbornene (lb) with methyl chloride in the presence of sodamide and liquid ammonia gave 5-eradocyano-5-exomethyl-2-norbornene (III). As a by-product of both reactions, there was obtained an amidine fraction which upon saponification gave 2-norbornene-5-exocarboxamide (II); II also could

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DlBROMO-p-XYLOQUINONE AND SODIOMALONIC ESTER 1739 xanthone, m. p. 249-250 °. Ullmann and Wagner10 report 243°.o-Phenoxy-p-hydroxybenzoic Acid.-Demethylation of o-phenoxy-p-methoxybenzoic acid with aluminum chloride in benzene gave 54% of the hydroxy acid which melted at 163-164°after vacuum sublimation and crystallization from water.Anal. Caled, for C13Hio04 : 0,67.84; H, 4.27. Found: C, 67.64; H, 4.54. p-Phenoxy-o-hydroxybenzoic Acid.-The acid mixture resulting from the oxidation of the 3-methoxy aldehydes was demethylated with aluminum chloride in benzene.The product melted at 162-167°, yield 76%. Vacuum sublimation at 150-170°of 0.126 g. of this product gave 0.122 g. melting at 167-168°. Crystallization from benzene-petroleum ether raised the melting point to 180.8-181.4°. Mixed with an authentic specimen of p-phenoxyo-hydroxybenzoic acid (182.4-183°) the melting point was 180.4-181.2°.Synthesis of p-Phenoxy-o-hydroxybenzoic Acid: 2-Amino-4-chlorotoluene.-2-Nitro-4-chlorotoluene (100 g.) in 100 cc. of methanol was reduced in the presence of 3 g. of Raney nickel at 60°( 2000 lb.). The pure amine boiled at 120-125°(40 mm.), yield 83%.4-Chloro-2-hydroxytoluene.-Diazotization and hydrolysis of the above amine according to the procedure described for 3-bromo-4-hydroxytoluene (above) gave 85% of the chlorocresol melting at 67-68°. Methylation with dimethyl sulfate7 gave 80% of 4-chloro-2-methoxytoluene boiling at 104-106°( 25 mm.).p-Methoxy-o-methoxytoluene.-A mixture of potassium phenoxide (4.3 g.), 5.0 g. of 4-chloro-2-methoxytoluene and 0.1 g. of copper powder was heated for two and one-half hours at 250-270°. The products were taken up in ether and vacuum distilled. The desired diphenyl ether boiled at 275-276°, yield 10%. It was oxidized to the methoxy acid without further purification.p-Phenoxy-o-hydroxybenzoic Acid.-The above compound was oxidized with permanganate in aqueous pyridine. The crude acid melted at 74-75°, yield 31%; it was used without further purification for the preparation of the hydroxy acid, which was obtained by demethylation with hydriodic acid in acetic acid. The pure acid, crystallized from benzene-petroleum ether, melted at 182.4-183.0°.

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