Potassium 4-chlorobenzoate

Methyl 4-chlorobenzoate (13.65 g, SOmmol) was added in one portion to a stirred slurry of potassium trimethylsilanolate 97 (10.26 g, 80 mmol) in 500 mb dry ether at ambient temperature, under N2. After 4h the white slurry is filtered under N2, washed with ether, and dried under a stream of N2 to afford 13.1 g (84%) analytically pure potassium 4-chlorobenzoate [119] (Scheme 4.62). 

Aromatic aldehydes, formaldehyde, and a-trisubstituted acetaldehydes all undergo the Cannizzaro reaction. In the experiment of this section, 4-chlorobenzaldehyde, an aromatic aldehyde, is converted to 4-chlorobenzyl alcohol and potassium 4-chlorobenzoate, which gives 4-chlorobenzoic acid upon acidification of the reaction mixture (Eq. 16.28). 

N-Phenylanthranilic acid may be prepared by the action of aniline upon c-chlorobenzoic acid in the presence of anhydrous potassium carbonate and a little copper oxide ... 

In a 1 litre round-bottomed flask, equipped with an air condenser, place a mixture of 44 g. of o-chlorobenzoic acid (Section IV,157) (1), 156 g. (153 ml.) of redistilled aniline, 41 g. of anhydrous potassium carbonate and 1 g. of cupric oxide. Reflux the mixture in an oil bath for 2 hours. Allow to cool. Remove the excess of aniline by steam distillation and add 20 g. of decolourising carbon to the brown residual solution. Boil the mixture for 15 minutes, and filter at the pump. Add the filtrate with stirring to a mixture of 30 ml. of concentrated hydrochloric acid and 60 ml. of water, and allow to cool. Filter off the precipitated acid with suction, and dry to constant weight upon filter paper in the air. The yield of iV-phenylanthranilic acid, m.p. 181-182° (capillary tube placed in preheated bath at 170°), is 50 g. This acid is pure enough for most purposes. It may be recrystaUised as follows dissolve 5 g. of the acid in either 25 ml. of alcohol or in 10 ml. of acetic acid, and add 5 ml. of hot water m.p. 182-183°. 

C14H14CI2N2O2 16390-18-4) see Indometacin 4-chlorobenzoic acid methyl ester (C8H7CIO2 1126-46-1) see Moclobemide 2-chlorobenzoic add potassium salt (C7H4CIICO2 16463-38-0) see Thiethylperazine... 

Treatment of methyl p-chlorobenzoate with an equivalent amount of commercial potassium silanolate 97 in abs. diethyl ether affords, after 4h, pure, anhydrous potassium p-chlorobenzoate in 84% yield and methoxytrimethylsilane 13 a. Trimethylsilyl trifluoroacetate reacts hkewise with sodium trimethylsilanolate 96 in THF to give sodium trifluoroacetate, in 98% yield, and hexamethyldisiloxane 7 [119] (Scheme 4.45). 

Diazomethane In a distillation flask equipped with an distillation funnel and a cooler, place a solution of 5 g of potassium hydroxide in 8mL of water and 25 mL of ethanol. Warm the distillation flask to 65 °C in a water-bath. Add a solution of 21.5g (0.1 mol) of A-methyl-lV-nitroso-p-toluenesulfamide in 130 mL of diethyl ether through the instillation funnel in 5 min. If the distillation funnel becomes empty, pour 20 mL of diethyl ether into the funnel, and distill it gradually. Continue distillation until the distilled ether solution becomes colorless. About 3 g of diazomethane is contained in the whole resultant ether distillate. Caution these procedures should be conducted in a laboratory hood Orbencarb, methyl 2-chlorobenzylsulfone (I), 2-chlorobenzoic acid (II), methyl 2-chlorobenzoate analytical standard materials (Ihara Chemical Industries Co., Ltd) Orbencarb and I standard solution for gas chromatography 1.0 qgmL in acetone Methyl 2-chlorobenzoate standard solution for gas chromatography 0.1 qgmL" in n-hexane... 

Flufenamic acid Flufenamic acid, Al-(a, ,a-trifluoro-m-tolyl)anthranylic acid (3.2.18), is synthesized by the reaction of 2-chlorobenzoic acid with 3-trifluoromethylaniline in the presence of potassium carbonate and copper fihngs [78,79]. 

Quinacrine Quinacrine, 6-chloro-9-(4-diethylamino-l-methylbntylamino)-2-methoxy-acridine (37.1.4.3), is synthesized from 6,9-dichloro-2-methoxyacridine (37.1.4.2) and aforementioned 4-diethylamino-l-methylbutylamine (37.1.1.2). The 6,9-dichloro-2-methoxyacridine (37.1.4.2) necessary for the synthesis is made in two stages. The initial reaction of 2,4-dichlorobenzoic acid and p-anizidine in the presence of copper dnst and potassium carbonate gives 2-(4-methoxyanilino)-4-chlorobenzoic acid (37.1.4.1), which upon reaction with phosphorus oxychloride turns into the necessary 6,9-dichloro-2-methoxyacridine (37.1.4.2) [33-38]. 

Synthesis 2-Chlorobenzoic acid is reacted with 3-trifluoromethylaniline in the presence of copper and potassium carbonate (Moffett and Aspergen, 1960 Parke Davis, 1961 Kleemann et al., 1999). 

Acylation of 2-aminopyridine with 2-chlorobenzoylchloride and the subsequent cyclization of 2-(2-chlorobenzamido)pyridine (207) gave 6H-pyrido[l,2,a]quinazolin-6-one (28) (90JHC2005). Cyclocondensation of 2-aminopyridine and 2-chlorobenzoic acid in the presence of potassium carbonate at 190-195°C for 2 h afforded the isomeric ll//-pyrido[2,l-b]-quinazolin-ll-one (27) (24LA(440)311]. 

The cyclodehydration of o-phenoxybenzoic acids has been widely used to synthesize xanthones carrying variety of substituents. An Ullmann reaction provides a useful route to the required acids a 2-chlorobenzoic acid and a phenol react in an inert solvent such as nitrobenzene in the presence of copper bronze and potassium carbonate (53JCS1348). In a modified procedure sodium methoxide is used without solvent at 200 °C (79JA665). Cyclization is accomplished in concentrated sulfuric acid or in acetyl chloride containing a little sulfuric acid (61JCS2312). 

Lithium acetate Sodium p-chlorobenzoate Potassium hydrogen hexanedioate... 

Treatment of the chlorobenzoate 349 with potassium t-butoxide gave the cyclopentane aldehyde 350 (99) while the reduction (LiA1) of chloroketone 351 gave the cyclohexene alcohol 353 via the fragmentation of the intermediate 352 (100). 

Cyclododecanone (2.0 g, 11 mmol) is added to m-chloroperbenzoic acid (4.2 g, 21 mmol) in 25 ml of dry chloroform (CAUTION). The reaction mixture is heated at reflux for 48 hours after which time a starch-iodide test for peroxide is negative. After the mixture is cooled in ice-water, the precipitated m-chlorobenzoic acid is removed by filtration and the chloroform is evaporated to dryness. The residue is taken up in 60 ml of ether, washed three times with 20-ml portions of aqueous potassium carbonate, and once with brine. After drying and removal of solvent there remains crude dodecanolide (1.9 g,... 

Cognate preparations, p-Chlorobenzoic acid. Proceed exactly as for o-chlorobenzoic acid. Use 1250 ml of water, 50 g (0.4 mol) of p-chlorotoluene (Expt 6.71) and 75 g, 37.5 g and 37.5 g (0.95 mol total) of potassium permanganate. When the oxidation is complete, steam distil the mixture to recover any unreacted p-chlorotoluene (3-4 g). Filter the reaction mixture from hydrated manganese dioxide and wash the precipitate with two 100 ml portions of water. Precipitate the p-chlorobenzoic acid in the filtrate (1) by the addition of 75 ml of concentrated hydrochloric acid. Filter the cold solution with suction, wash with cold water and dry in an oven at 100 °C. The yield of p-chlorobenzoic acid, m.p. 234-235 °C, is 55 g (89%). Recrystallisation from hot water raises the m.p. to 238-239 °C. 

N,N -Carbonyldiimidazole (1.65 g, 10 mmol) was added to a solution of o-chlorobenzoic acid (1.57g, lOmmol) in dimethylformamide (10ml) held under nitrogen, and the mixture was stirred for 1 hour at 40 °C. t-Butyl alcohol (1.48 g, 20mmol) and DBU (l,8-diazabicyclo[5.4.0]undec-7-ene, 1.52 g, 10 mmol) were added and the mixture stood for 24 hours at 40 °C. Ether (100 ml) was then added, and the solution was washed with 10 per cent hydrochloric acid (20 ml), water (20 ml), aqueous potassium hydrogen carbonate (20 ml) and dried over anhydrous sodium sulphate. The solvent... 

A mixture of 2-(4-aminophenyl)propionic acid (52.2 g), potassium o-chlorobenzoate (61.5 g), potassium carbonate (43.6 g) and copper powder (0.3 g) in amyl alcohol (620 ml) is heating under reflux for 16 h. The major proportion of the solvent is then removed by steam distillation. The residual aqueous solution is treated with decolorising charcoal (20.0 g) and acidified with 4 N sulfuric acid (220 ml). The cream product which crystallises is dissolved in diethyl ether (500 ml). 

A mixture 31.3 g of o-chlorobenzoic acid, 32.2 g of trifluoromethyl-m-aminobenzene, 3 g of copper powder, 13.8 g of waterless potassium carbonate and 100 ml amyl alcohol was refluxed for 4 hours. To the cooled mixture was added 25 ml of 10 N solution NaOH and the mixture was concentrated and filtrated. Addition to the filtrate hydrochloric acid and water give a sediment of 2-((3-trifluromethyl)phenyl)aminobenzoic acid. After recrystallization from hexane 2-((3-trifluromethyl)phenyl)aminobenzoic acid have melting point 134-136°C. 

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