Cyano-benzoic acid

The regioselectivity of a Rhodococcus rhodochrous nitrilase has been demonstrated for the conversion of 5-fluoro-l,3-dicyanobenzene to 5-fluoro-3-cyano-benzoic acid [62]. The nitrilase was expressed in an Escherichia coli transformant, and a cell-free extract was employed as catalyst (0.14wt% cell-free extract) in 0.1m sodium phosphate buffer (pH 7.2) at 25 °C containing 0.18 m 5-fluoro-l,3-dicyanobenzene. After 72 h, the conversion was >98% and the reaction was stopped by addition of phosphoric acid (pH 2.4) to yield 5-fluoro-3-cyano-benzoic acid as a crystalline product (97% isolated yield). 

Stark, G A (1977) Cleavage at cysteine by nitro-thio-cyano-benzoic acid Methods Enzymol 47, 129-132. 

Mono-Substituted Benzoic Compounds. Of the numerous mono-substituted benzoic acids tested, four were found to have much higher activity than the rest. These have been selected for advanced field testing and include 2-chlorobenzoic acid, 3-hydroxybenzoic acid, 3-cyano-benzoic acid, and 4-methoxybenzoic acid. (Although numerous di-substi-tuted benzoic acid compounds have been screened, none has been outstanding. )... 

This apparently simple synthetic route has some hidden pitfalls. Already in the first step, decarboxylative metallation of 2-cyano benzoic acid (3), an extremely resistant substrate due to competing co-ordination of cyano group to copper, has the required catalytic system consisting of Cu(II)0 and 1,10-phenantroIine as bidentate N,N-ligand for Cu(II) ions. This catalytic system proved particularly effective in the specific solvent mixture NMP/quinoline (2 1). Yields of 4 up to 80% were... 

Because cyano groups may be hydrolyzed to carboxylic acids (Section 20 19) the Sand meyer preparation of aryl nitriles is a key step m the conversion of arylammes to sub stituted benzoic acids In the example just cited the o methylbenzomtnle that was formed was subsequently subiected to acid catalyzed hydrolysis and gave o methylbenzoic acid in 80-89% yield... 

A one-pot preparation of pyrrolo[l,2-a]quinazoline libraries with three points of diversification by condensation of a-cyano-ketones and 2-hydrazino-benzoic acids has been developed by Hulme and coworkers (Scheme 6.252) [439]. The protocol simply involved heating a solution of equimolar amounts of the two building blocks in acetic acid at 150 °C for 5 min. In many cases, the final products precipitated directly from the reaction mixture. In such cases, simple washing with diethyl ether yielded the products in >95% purity. A 63-member library was prepared by employing seven a-cyano-ketones and nine 2-hydrazino-benzoic acids. 

Plant. In plants, the cyano group is hydrolyzed to an amido group which is subsequently oxidized to a carboxylic acid. Hydrolyzes to hydroxybenzoic acid (Hartley and Kidd, 1987). In plants, bromoxynil may hydrolyze to a benzoic acid (Humburg et al., 1989). Bromoxynil-resistant cotton was recently developed by inserting a bxn gene cloned from the soil bacterium Klebsiella ozaenae. This gene, which encodes a specific nitrolase, converted bromoxynil to its primary metabolite 3,5-dibromo-4-hydroxybenzoic acid (Stalker et al, 1988). 

Figure 14.6 Structures of some commonly used MALDI matrices (a) 2,5-dihydroxy benzoic acid (DHB), (b) a-cyano-4-hydroxy-cinnamic acid, and (c) sinapinic acid (SA). Combination of these acidic MALDI matrices with organic bases leads to the formation of ionic liquid matrices.

Most commonly used matrix systems are derivatives of benzoic acid (e.g., 2,5-dihydroxybenzoic acid (DHB), derivatives of cinnamic acid (e.g., a-cyano-4-hydroxycinnamic acid (CHCA) or sinapinic acid (SA) (Figure 14.6) as well as heteroaromatic compounds containing nitrogen but numberless other substances and substance classes have been applied as matrices [36]. 

Here the five atoms to add to the carbon C-2 may be furnished by /J-mercaptoacrylamides or isothiazoles (Scheme 24). Condensation of 2-cyano-3-mercapto-3-methylthioacrylamide with benzoic acid in the... 

The kinetics and mechanism of the phosphorus-catalysed dimerization of acrylonitrile to give 1,4-dicyanobut-l-ene and 2,4-dicyanobut-l-ene have been studied.114 The reactions of aryhminodimagnesium (138) with //-substituted p-cyanobenzophenones, l-cyano-9-fluorenenone, o-, m-, and p-dicyanobcnzcnes, and o-, m-, and p-nitrobenzonitriles have been examined.115 The effect of pressure on the reaction of 3 -methyl- l-(4-tolyl)triazene (139) and benzoic acid in chloroform and acetonitrile has been studied.116 The effect of acids on the rate of urethane formation from alcohols and isocyanates in the presence of alkyltin carboxylates has been examined.117 A Hammett a value has been reported for the amidine group N=CHNMe2 and used for the prediction of the basicity of sites in bifunctional amidines.118... 

Coupling, of benzenediazonium chloride with acetoacetic acid, 32, 84 of diazotized 3,5-dichloro-2-amino-benzoic acid to give 4,4, 6,6 -tetra-chlorodiphenic acid, 31, 96 of diphenyldichloromethane to tetra-phenylethylene, 31, 104 Crotonaldehyde, diethyl acetal, 32, 5 Cyanoacetamide, 32, 34 Cyanoacetic acid, 31, 25 -Cyanobenzaldehyde, 30, 100 3-Cyano-5,6-dimethyl-2(l)-pyridone,... 

Dichloro-phenyl)-ethoxy]-4-methoxy-benzoic acid (0.29 mmol) dissolved in 2 ml DMF was treated with A-ethylmorpholine (1.16 mmol), 1 -pyridin-4-ylmethyl-piperazine (0.29 mmol), and 0-((cyano(ethoxycarbonyl)methylene)amino)-l, 1,3,3-tetramethyluronium tetrafluoroborate (0.3 mmol), then stirred 60 minutes at ambient temperature. The mixture was concentrated, then dissolved in CH2C12, washed three times with saturated NaHC03 solution, dried with Na2S04, and reconcentrated. The residue was purified by chromatography with silica gel using n-heptane/EtOAc, 1 1, then EtOAc, and finally EtOAc/methyl alcohol, 10 1, and 102 mg product isolated. MS ES+, m/z = 500 (M+)... 

Benzoic acids substituted with alkyl, halo, hydroxyl, alkoxyl, cyano, or nitro groups react to give the corresponding substituted anilines in 41-80% yields. The carboxyl group in an a-amino acid does not react with hydrazoic acid the reaction proceeds, however, if the amino group is further removed. This difference in reactivity is shown by the conversion of a-aminoadipic acid to i(-ornithlne (75%). ... 

The chemical information available through LFER is primarily the reaction constant p, but this value depends upon the substituent constants selected for the construction of the LFER. The u values available are ct, ct", ct" or and Ui, these quantities are listed, for many substituents, in Tables 7-1, 7-3, 7-4, 7-6, and 7-7. A reasonable approach is to plot log k against the substituent constant defined by a standard reaction that is expected to be most like the reaction under study. It is also reasonable to plot log k against several of the ct quantities, seeking the best correlation. [In choosing between two types of substituent constants, it is necessary to make use of substituents for which the two scales (say ct and rr, for example) are not themselves correlated, for otherwise both LFERs will be acceptable. ] The ct or o constants should be applicable to reactions that do not combine reaction sites and para substituents of the + and — type (push-pull systems capable of through resonance) for example, one would not expect ct" or o to provide good correlations for reactions of phenols or anilines substituted with nitro or cyano or for reactions of benzoic acids substituted with amino or methoxy. 

Cl3H11N02 2-(phenylamino)benzoic acid 91-40-7 25.00 1.2003 2 25863 C13H13NO 4-cyano-4-phenylcyclohexanone 25115-74-6 25.00 1.1006 2... 

By fusion of naphthalene sulphonic acids with potassium cyanide the corresponding cyano naphthalenes are obtained. These compounds are nitriles of naphthalene acids. The mono-carboxyl acids are known as naphthoic acids while the di-carboxyl acids are termed naphthalic acids. The naphthoic acids are similar to benzoic acid and the naphthalic acids are like the phthalic acids. The naphthalic acid... 

Anodic acetoxylation of furan can be done in acetic acid containing acetate [173, 174] and benzoyloxylation in DMF containing benzoic acid and lithium chloride [175]. A mixture of cis- and ra 5-benzoyloxylated product is formed. Cyanomethoxylation of 2,5-dimethylfuran gives a mixture of cis- and rmn5-2-cyano-5-methoxy-2,5-dimethyldihydro-furan [176-178]. 

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