Bromide Bromobenzoate

Brom-. of or combined with bromine bromo- (as Brombenzoeadure, bromobenzoic acid) bromide of (as Brombaryum, barium bromide). -ammoD, tn., ammonium, n. ammonium bromide, -antimon, n. antimony bromide, -arsen, n., -arsem k, tn. arsem c bromide. ather, tn. ethyl bromide, -athyl, n. ethyl bromide. athylen, n. ethylene bromide, athyiformin, n. Pharm.) bromalin. -atom, n. bromine atom, -baryum, n. barium bromide. beere, /. blackberry, brombeerrot, a. blackberry ed. 

A mixture consisting of 22.7 g potassium o-bromobenzoate, 16.6 g 2,6-dichloro-3-methvlani-line, 12 ml N-ethylmorpholine, 60 ml diethylene glycol dimethyl ether, and 1.0 g anhydrous cupric bromide is heated in a nitrogen atmosphere at 145 C to 155°C for 2 hours. The reaction mixture is diluted with 60 ml diethylene glycol dimethyl ether and acidified with 25 ml concentrated hydrochloric acid. The acidic mixture is diluted with 100 ml of water and the liquid phase decanted from the insoluble oil. The insoluble oil is stirred with methanol and the crystalline N-(2,6-dichloro-3-methylphenyl)anthranilic acid which separates is collected and washed with methanol. The product, after recrystallization from acetone-water mixture melts at 248 C to 250°C. 

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... 

Meclofenamic acid Meclofenamic acid, iV-(2,6-dichloro-m-tolyl)anthranylic acid (3.2.20), is synthesized analogous to flufenamic acid, by the reaction of potassium salt of 2-bromobenzoic acid with 2,6-dichloro-3-methylaniline in the presence of copper (11) bromide in a mixture of iV-ethylmorpholine and diglyme [82,83]. 

The addition of hydrogen bromide and sulfur dioxide to phenylpropiolic acid (210) in diethyl ether at -50 °C is reported to give 3-bromobenzo[6]thiophene-2-carboxylic acid (211) (75ZOR1776). If hydrogen bromide and sulfur dioxide can react under these conditions to give thionyl bromide, the reaction is similar to the reaction of thionyl chloride with unsaturated acids, reported in the previous section. 

A systematic investigation of the copper-catalyzed reaction between 2-bromobenzoic acid and the anions of 1,3-dicarbonyl compounds has established the optimum conditions for the direct arylation of the /3-dicarbonyl moiety (75T2607). The use of sodium hydride as the base and copper(I) bromide as catalyst is recommended. The absence of a protic solvent ensures that competitive attack on the bromobenzoic acid by a solvent-derived base leading to a salicylic acid is eliminated. For larger scale reactions the addition of toluene offers some practical advantages. 

Esters of 2-acetonylbenzoic acid are formed when methyl 2-bromobenzoates are treated with 7r-(2-methoxyallyl)nickel bromide (77JOC1329). Cyclization to the isocoumarin occurs on treatment with sodium hydride in benzene with a trace of t-butanol (Scheme 183). A... 

When 2-bromobenzoic esters are treated with ir-(2-methoxyallyl)nickel bromide, the acetonyl group is introduced. Reductive cyclization of the methyl 2-acetonylbenzoates yielded isochroman-l-ones (77JOC1329). 

It was not until thirty-eight years later that this method of synthesis was applied to the aromatic series. Rosenmund,8 in 1921, prepared phenyl-arsonic acid (in low yield) and o-carboxyphenylarsonic acid (44% yield) from tripotassium arsenite and bromobenzene and o-bromobenzoic acid, respectively. Since that time only one other arsonic acid, o-phenylene-diarsonic acid,29 82 has been obtained in good yields by Rosenmund s method. From two other aromatic bromides, p-bromobenzoic add and... 

The four related compounds oxalomycin (157), neooxalomycin (158), cur-romycin A (159), and curromycin B (160) were reported in 1985 157 and 158 were isolated from a yet to be identified Streptomyces species (79, 80) and 159 and 160 from an ethidium bromide-treated strain of S. hygroscopicus (81, 82). The absolute configuration of oxalomycin (157) and neooxalomycin (158) has been determined by application of a combination of X-ray crystallography and chemical correlation to degradation products, the important derivatives being the p-bromobenzoate 161, obtained from 157 by ozonolysis-reduction, acetylation, partial hydrolysis, and reacylation with p-bromobenzoyl chloride, and the erythro acetate 162 which was obtained along with the threo compound 163 after acetylation of the ozonolysis products of 157 (79, 80). No stereochemical infor-... 

In a similar manner the reaction of sodium 2-bromobenzoate with the carbanion derived from pentane-2,4-dione initially yields the dioxo acid (490). In ethanol, a retro-Claisen deacylation leads to 2-acetonylbenzoic acid (491), but at higher temperatures 3-methyI-isocoumarin is formed (Scheme 177) (75JCS(P1)1267). Copper(I) bromide may be used as a catalyst, although this is only necessary for the initial step. The cyclization process is considered to involve reaction between the carboxylate group and an enolate ion arising from loss of one of the acyl groups. A similar reaction occurs with l-bromo-2-naphthoic and 3-bromo-2-naphthoic acids giving the naphtho[2,l-c]pyran-4-one (492) and naphtho[2,3-c]pyran-l-one (493), respectively. 

A mixture of 35 g. of copper sulfate, 100 g. of sodium bromide, 30 g, of copper turnings, 33 g. of concentrated sulfuric acid, and 300 ml. of water is heated to boiling. After the color is gone from the solution, 40 g. (0.29 mole) of anthranilic acid is added and the mixture cooled to below 10°. An aqueous solution containing 22 g. (0.32 mole) of sodium nitrite is added dropwise, the temperature of the reaction mixture being held below 10°, and the mixture allowed to stand at room temperature for several hours. Filtration of the mixture gives a 90 yield of crude o-bromobenzoic acid. The pure acid, m.p. 150°, is obtained in 82% yield by recrystallization from hot water. 

In the case of bromo-compounds, studies, mostly with Co y-radiation, have been reported on methyl bromide - , ethyl bromide , 1-bromobutane , other linear bromoalkanes , and bromobenzene . Behaviour under neutron-irradiation has been described for bromobenzenes - and bromobenzoic acids . 

Miyadera also studied borohydride reduction of benzo[b]quinolizinium salts (cf. 3) obtaining the hexahydro derivatives 121 and 122, and the octa-hydro derivative 123.129 It has been shown that bromine adds to benzo[b]-quinolizinium bromide (3) to give a tetrabromo derivative (124), from which 10-bromobenzo[b]quinolizinium bromide (125) was obtained after treatment with sodium acetate.71... 

Attempts to brominate benzo[h]quinolizinium bromide (3) with liquid bromine gave an addition product (Section II,B). Bromination with bromine and aluminum bromide in dimethylformamide gave 1 l-bromobenzo[b]-quinolizinium bromide (137).71 Sulfuryl chloride and aluminum chloride under similar reaction conditions gave the chlorobenzquinolizinone (139), presumably from the 6,11-dichlorobenzquinolizinium salt (138).71 Without... 

Kirsch and coworkers extended this methodology to include benzo[Z)]thiophenes [187], They presented examples where 6-aminobenzo[Z)]thiophenes were coupled with aryl bromides as well as the converse between 6-bromobenzo[Z)]thiophenes and anilines. For example, benzothiophene 290 and 3,4-dimethoxyaniline in the presence of Pd(OAc)2, and racemic-BlNAP to deliver 291 in 70% yield. In addition, the 6-aminobenzothiophene 292 reacted with 4-fluoro-1-bromobenzene using the same catalytic system to furnish the 6-ammobenzothiophene 293 in excellent yield [187a]. 

Condensation of enolates derived from 3-dlcarbonyl compounds with o-bromobenzoic acid in the presence of cuprous bromide affords the displacement product directly. 

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