Nitriles acid methyl esters

The 2-phenyl-2-ethyl-pentane-1,5-diacid-mononitrile-(1) of melting point 72° to 76°C, used as starting material in this process, can be produced for example from o-phenyl-butyric acid nitrile by condensation with acrylic acid methyl ester and subsequent hydrolysis of the thus-obtained 2-phenyl-2-ethyl-pentane-1,5-diacid-monomethyl ester-mononltrile-(l) of boiling point 176° to 185°C under 12 mm pressure. 

The preparation of ester 13 is performed by an acid-mediated hydrolysis of nitrile 12 in methanol. The conditions used are quite vigorous concentrated sulfuric acid, reflux (65 °C), overnight. However, in this reaction the addition of methanol to the protonated nitrile gives the corresponding acetimidic acid methyl ester, and subsequent hydrolysis of this intermediate provides the desired ester 13 in 90 % yield. 

Abramov, V.S., and ITina, N.A., Mechanism of the Arbuzov rearrangement. Part 3. Reaction of the nitrile and methyl ester of a,P-dibromo- and a,P-dichloropropionic acids with phosphites, Zh. Obshch. Khim., 26, 2014, 1956 Chem. Abstr., 51, 1822c, 1957. 

The synthesis is outlined as follows gallic acid3,4,5-tri-methoxybenzoic acid — methyl ester of the 3,4,6-trimethoxybenzoic acid — 3,4,5-trimethoxybenzyl alcohol 3,4,5-trimethoxybenzyl chloride - 3,4,5-trimethoxyphenylacetonitrile — mescaline. The reduction of the methyl ester and of the nitrile has been achieved using lithium aluminum hydride. 

In a model study, Helquist and co-workers described the reaction of dimethyl diazomalonate 128 with benzonitrile to prepare 5-methoxy-2-phenyl-4-oxazolecar-boxylic acid methyl ester 129 nearly quantitatively (Scheme 1.35). Several other 2-aryl-5-methoxy-4-oxazolecarboxylic acid methyl esters were prepared analogously. In addition, 2-aIkyl(aIkenyl)-5-methoxy-4-oxazolecarboxylic acid methyl esters were also prepared, although the yields for aliphatic nitriles were not as good, unless the nitrile was used as solvent. Other metal salts—including Rh2 (NHAc)4, Cu(OTf)2, Cu(C2Hs-acac)2, Rh2(02CC3H7)4, and Rh3(CO)ie— were not as effective as Rh2(OAc)4 in this reaction. 

Synonyms Bismethylisothiocyanatomethane Isothiocyanatomethane Isothiocyanic acid, methyl ester Methane, isothiocyanato Methyl mustard oil MIC MIT MITC Classification Nonaromatic nitrile Empirical CiFIsNS Formula CFijNCS... 

Butyric acid, methyl ester. See Methyl butyrate Butyric acid, 2-methyl-, phenethyl ester. See Phenethyl 2-methyl butyrate Butyric acid nitrile. See Butyronitrile Butyric acid, 1-pentylallyl ester. See 1-Octen-3-yl butyrate... 

The plant Crambe Abyssinica contains about 55% of erucic acid, and brassylic acid monomethyl ester is obtained from erucic acid methyl ester by ozonolysis. Treatment of the brassylic acid monoethyl ester with ammonium hydroxide/sulfuroxydichloride produces the nitrile, and this can be hydrogenated to the amine ... 

Sodium hypochlorite converts the hydroxyl esters 446 and nitriles 447 into the corresponding keto epoxides 449 and 450 and the acetoxy ester 448 into acetoxy epoxide 451, for which the diastereoselectivity was found to be 68% (Ar = Ph) and 48% (Ar = 4-CIC6H4) (Scheme 3.196). The keto-epoxides derived from ester-containing MBH adducts 449 can be further transformed into 2-aroyloxypropenoic acid methyl esters 452 in the presence of tripheny Iphosphine. ... 

The reaction of 3-[(trimethylsilyl)methyl]-3-butenoic acid methyl ester with various simple nitriles in the presence of BCI3 has afforded varying mixtures of pyridones, pyridines, and acylation products (eq 5). 4... 

Hydrogenation is widely used to determine the structure of unsaturated compounds and to determine the olefin content of a wide variety of mixtures. The simplest means of hydrogenating microgram amounts of a sample instantaneously in the chromatographic pathway involves a hydrogenation catalyst and a hydrogen carrier gas. This technique was used for fatty acid methyl esters and a variety of unsaturated compounds (such as alcohols, amides, amines, ketones, esters, ethers, and nitriles) at the microgram level. 

C3H3NO2 oxalic acid methyl ester nitrile 17640-15-2... 

Organic Acids and Their Derivatives (Anhydrides, Nitriles, Ureas). Alkyleneamines react with acids, esters, acid anhydrides or acyl hahdes to form amidoamines and polyamides. Various diamides of EDA are prepared from the appropriate methyl ester or acid at moderate temperatures (25,26). 

Addition of the alcohol 42 to a solution of BF3 Et20/TMSCN in DCM provided the nitrile 43 in 83% yield. Hydrolysis of nitrile 43 then furnished amide 44 in 85% yield. Demethylation of the methoxyindole 44 with BBra in DCM provided the hydroxyindole 45 in 80% yield. This was followed by alkylation of 45 with the bromide 46 under phase transfer conditions to provide the phosphonate ester 47 and subsequent cleavage of the methyl ester by TMS-I furnished trimethylsilyl phosphonic acid 48, which upon alcoholic workup afforded LY311727. 

Although the biosynthetic cascade hypothesis predicts the co-occurrence of endiandric acids D (4) and A (1) in nature, the former compound was not isolated until after its total synthesis was completed in the laboratory (see Scheme 6). Our journey to endiandric acid D (4) commences with the desilylation of key intermediate 22 to give alcohol 31 in 95% yield. The endo side chain is then converted to a methyl ester by hydrolysis of the nitrile to the corresponding acid with basic hydrogen peroxide, followed by esterification with diazomethane to afford intermediate 32 in 92% overall yield. The exo side chain is then constructed by sequential bromination, cyanide displacement, ester hydrolysis (33), reduction, and olefination (4) in a straight-... 

Condensation of phthalaldchydc with iV.yV-bisIcyanomethylJmethylamine furnishes the 3-methyl-3//-3-benzazepine-2,4-dicarbonitrile (66), whereas condensations with A /V-bis(cyano-methyl)arylamines are accompanied by modification of the nitrile group to an amide, acid, or ester function, e.g. 67.100... 

Treatment of the carbanion derived from 94 with nitriles was shown to give enaminesulfoxides 136, which can be converted to a-ketoesters or a-ketoacylamides185, besides the ester of JV-acetylamino acid 137. Using this reaction, the methyl ester of dl-JV-acetyl-5-hydroxytryprophane 138 was synthesized186. 

Tertiary benzylic nitriles are useful synthetic intermediates, and have been used for the preparation of amidines, lactones, primary amines, pyridines, aldehydes, carboxylic acids, and esters. The general synthetic pathway to this class of compounds relies on the displacement of an activated benzylic alcohol or benzylic halide with a cyanide source followed by double alkylation under basic conditions. For instance, 2-(2-methoxyphenyl)-2-methylpropionitrile has been prepared by methylation of (2-methoxyphenyl)acetonitrile using sodium amide and iodomethane. In the course of the preparation of a drug candidate, the submitters discovered that the nucleophilic aromatic substitution of aryl fluorides with the anion of a secondary nitrile is an effective method for the preparation of these compounds. The reaction was studied using isobutyronitrile and 2-fluoroanisole. The submitters first showed that KHMDS was the superior base for the process when carried out in either THF or toluene (Table I). For example, they found that the preparation of 2-(2-methoxyphenyl)-2-methylpropionitrile could be accomplished h... 

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