Methyl 2,5-dichlorobenzoate

The photostimulated reaction of o-, m-, and p-C6H4Cl2 with Mc3Sn ions gives disubstitution in 58%, 90%, and 88% yield, respectively [39] in addition, methyl 2,5-dichlorobenzoate and methyl 3,6-dichloro-2-methoxybenzoate afford bistannylated aromatic compounds in 99% and 64% yields, respectively [40]. Disubstitution products are also obtained by the reaction of 2,6-and 3,5-dichloropyridine under photoinitiation in about 80% yield (Scheme 10.26). Even trisubstitution is possible by the photoinduced reaction of 1,3,5-C6H3C13 with Me3Sn ions in liquid ammonia, in 71% yield [39]. 

In a recent application, it was found that methyl 2,5-dichlorobenzoate 46 reacted with Me Sn" ions in liquid ammonia under irradiation to afford disubstitution product 47 in 99% (Eq. 10.16) [42] ... 

In a recent investigation, the photostimulated reaction of methyl 2,5-dichlorobenzoate 46 (R=H) or methyl 3,6-dichloro-2-methoxybenzoate 71 (R = OMe) with PhS ions in excess in liquid ammonia was studied (Eq. 10.27). Compound 46 afforded mainly the product 72 (R=H, 88%) with retention of the chlorine, whereas 71 yielded the disubstitution product 73 (R=OMe) with 80% yield. The different reactivity observed was explained on the basis of the activation energy necessary for the from the tr to the a of the C—Cl bond and the fragmentation of the radical anion intermediates [65] ... 

Methamidophos, see Acephate Methane, see Acetaldehyde, Benzoic acid, 7 Bromobenzoic acid. 3-Bromobenzoic acid. 4-Bromobenzoic acid. Bromoform, Carbatyl, Catechol, 2-Chlorobenzoic acid. 3-Chlorobenzoic acid. Chloroform, Dibromochloromethane, 2,5-Dichlorobenzoic acid. 1,2-Dichloroethane, Ethylamine, Ethyl bromide. Ethylene dibromide, Ethylenimine, Formic acid, Hydroqninone, 4 Hvdroxvbenzoic acid. Indole, 2-Iodobenzoic acid. 3 lodobenzoic acid. Methyl bromide, 4-Iodobenzoic acid. 2-Methylphenol, 4-Methylphenol, Phenol, Prorocatechuic acid. Svringic acid. Svringaldehvde. TCDD, Tetrachloroethylene, Toluene, Trichloroethylene, Vanillin. Vanillic acid. Vinyl chloride... 

Plimmer, J.R. Photolysis of TCDD andtrifltrralin on silica and soil. BuU. Environ. Contam. Toxico ., 20(l) 87-92, 1978. Plimmer, J.R. and Hummer. B.E. Photolysis of amiben (3-amino-2.5-dichlorobenzoic acid) and its methyl ester. J. Agric. Food Chem., 17(l) 83-85, 1969. 

A somewhat similar isomerization was observed with the sultam 5-methylimino-4-phenyl-l,3,4-dithiazolidine 1-dioxide (17 i = H). On heating at 60°C in the presence of benzoyl chloride, rearrangement into the isomeric 5-phenylimino-4-methyl-l,3,4-dithiazolidine 1-dioxide (19, 1 = H) was found (Scheme IV.ll). As intermediate can be proposed the amidinium salt 18 (78JOC4951). Furthermore, NMR-controlled test tube experiments revealed that this rearrangement also occurs under influence of aluminum trichloride and methanesulfonyl chloride. Also, the 2-phenyl derivative 17 (R = CeHs) could be isomerized it required heating in acetone with m-dichlorobenzoic acid as catalyst (Scheme IV.ll). 

The sulfones of 3-methyl-, 3-methoxy-, 3-dimethylamino-, and 3-piperidinobenzo[6]thiophene yield only sulfur dioxide and intractable tars on being heated in inert solvents, whereas 2-bromo- and 2,3-dichlorobenzo[6]thiophene-l,1-dioxide are extremely stable to... 

Tropine (34.24 g) is treated with anhydrous diethyl ether and ethereal hydrogen chloride and the precipitated hydrochloride is isolated by evaporation of the solvent. 3,5-Dichlorobenzoylchloride (51.7 g) is added and the mixture stirred at 140°C for 15 minutes during which time the mixture liquifies, evolves hydrogen chloride gas and resolidifies. After heating for a further 15 minutes the cooled solid is dissolved in water, an excess of an aqueous solution of potassium carbonate is added, and the base is extracted with ethyl acetate. Evaporation of the dried ethyl acetate solution yields a solid, which is recrystallized from aqueous methanol to yield 3,5-dichlorobenzoic acid 8-methyl-8-aza-bicyclo[3.2.1]oct-l-yl ester (endo). MP 95°C (51.8 g). 

Gordon WP, Cheng H, Larsen DL, Ragner JA, Landmesser NG (1992) identification of urinary metabolites of 8-methyl-8-azabicyclo-[3,2,l] octan-3-yl 3,5-dichlorobenzoate (MDL 72,222) in the dog and monkey. Drug Metab Dispos 20 596-602... 

Dichlorobenzoic acid [50-45-3] M 191.0, m 168.3, 169-170, pK s 2.67. Aromatic acid impurities (to <0.05%) can be removed via the ( )-a-methylbenzylamine salt as described for 2,4-dichlorobenzoic acid [Ley Yates Organic Process Research Development 12 120 2008.] Crystallise the acid fromH20, aqueous EtOH, or 30% aqueous AcOH and several times from C6Hg, then dry it in vacuo at 40° overnight. The methyl ester has m 35-39. [Hope Riley J Chem Soc 123 2478 1923, Lock Monatsh Chem 90 687 1959, Shorter Mather J Chem Soc 4744 1961, Beilstein 9II 228, 9 IV 998.]... 

Methylpiperidino)propyl 3,4-dichlorobenzoate. See Piperalin Methylpirimiphos. See Pirimiphos-methyl Methyl pivalate... 

Synonyms endo-8-Methyl-8-azabicyclo[3.2.1]octan-3-ol-3,5-dichlorobenzoate Trade Names ... 

Preparation by Fries rearrangement of 4-chloro-3-methyl-phenyl 2,5-dichlorobenzoate with aluntin-ium chloride for 30 min at 150-160° [458]. 

Preparation by Fries rearrangement of 4-methyl-phenyl 2,6-dichlorobenzoate with aluminium chloride in refluxing ethylene dichloride for 3 h (68%) [1080],... 

Preparation by Fries rearrangement of the intermediate 5-methyl-2-isopropy-Iphenyl 2,4-dichlorobenzoate formed in sim by reaction of 2,4-dichlorobenzoyl chloride with thymol in the presence of aluminium chloride in nitrobenzene at r.t. for24h(70%)[1166]. 

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