Methyl acetate cyanide

Acetone with benzene, butyl acetate, butyl alcohol, carbon tetrachloride, chloroform, cyclohexane, ethanol, ethyl acetate, methyl acetate, methyl cyanide, petroleum ether or water. 

Note Highly polar solvent sweet, ethereal odor soluble in water flammable, burns with a luminous flame highly toxic by ingestion, inhalation and skin absorption miscible with water, methanol, methyl acetate, ethyl acetate, acetone, ethers, acetamide solutions, chloroform, carbon tetrachloride, ethylene chloride, and many unsaturated hydrocarbons immiscible with many saturated hydrocarbons (petroleum fractions) dissolves some inorganic salts such as silver nitrate, lithium nitrate, magnesium bromide incompatible with strong oxidants hydrolyzes in the presence of aqueous bases and strong aqueous acids. Synonyms methyl cyanide, acetic acid nitrile, cyanomethane, ethylnitrile. 

Iso-nitriles, Carbylamines.— The alkyl cyanides because of tlieir relations to acids are known as acid nitriles methyl cyanide by hydrolysis yields acetic acid and it is thus known also as acetic nitrile. The iso-cyanides being isomeric with the nitriles are also termed isonitriles. Another name is sometimes used because of. their amine relationship, viz., carbyl-amine methyl iso-cyanide, CH3—NC, being methyl carbylamine. The lower alkyl-iso-cyanides are liquids with a very strong disagreeable odor. They are readily hydrolized by water but form salts with hydrochloric acid and also with silver cyanide. 

Di- to trihydrate, pink to reddish-brown powder or needles- Practically insol in water, acids, methyl acetate so] in alkali cyanide solns. 

Random copolymers based on acrylonitrile and methacrylonitrile with ethyl a-acetoxyacrylate [69] were synthesized by radical copolymerization. The microstructure of the resulting copolymers was characterized by C NMR spectroscopy, and some reactivity ratios could be assessed. In addition, copolymers based on methyl vinylidene cyanide (MVCN) and vinyl acetate [70], styrene [71], or substituted styrene also exhibit interesting dielectric behavior [72]. 

This sort of intermediate is postulated in another system cyanide ion causes cleavage of the Co-CH2C(0)OCH3 bond in [(methoxycar-bonyl)methyl]cobalamin, resulting in the formation of methyl acetate. Analysis of kinetic isotope effects and other rate data indicate that an intermediate is formed, which is suggested to be the tt-bonded enolate, [NCCo 7,"-CH2=CH(0")Me ]. 

The chemical operations described in the literature to introduce or into citric acid molecule are based essentially on the Grimaux and Adam synthesis. Labeled citric acid was prepared by Wilcox et al. [35] in the reaction of Na CN with 3-chloro-2-carboxy-2-hydroxybutyric acid and the formed nitrile was hydrolyzed directly with hydrochloric acid. From this solution, citric acid was isolated in the form of calcium citrate and finally converted to the acid. An alternative procedme was proposed by Rothchild and Fields [36] to obtain trimethyl citrate from labeled sodium cyanide and di-chloromethyl glycolate. A more complex synthesis of C labeled citric acid is described by Winkel et al. [39]. They used labeled methyl acetate and acetyl chloride (in the presence of hthium 1,1,1,3,3,3,-hexamethyldisilazide, [(CH3)2Si]2NLi which was dissolved in tetrahydiofuran) to obtain methyl acetoac-etate. It reacts in the presence of lithium diisopropylamide, [(CH3)2CH]2NLi, also dissolved in tetrahydrofuran, with dimethyl carbonate to give dimethyl 1,3-ace-tonedicaiboxylate. It is dicarboxylated by the action of bisulfite and potassium cyanide is converted to 3-cyano-3-hydroxy-l,5 pentanedioate and finally hydrolyzed by hydrochloric acid to citric acid. 

As part of the Megacity Initiative Local and Global Research Observations (MILAGRO) project, a comprehensive airborne study by Yokelson et al. reported the first detailed field measurements of biomass emissions in the Northern Hemisphere tropics [169]. Volatile emissions were measured from 20 deforestation and crop residue fires on the Yucatan peninsula. This included two trace gases which are often considered to be useful as indicators of biomass burning. One we have discussed before, namely acetonitrile, and the other is hydrogen cyanide. A variety of instrumentation was co-deployed for this investigation (FTIR spectroscopy, GD-FID, a GC-Trace Analytical Reduction Gas Detector, fluorescence and chemiluminescence instruments and various other spectrometers). PTR-MS was used to monitor methanol, acetonitrile, acetaldehyde, acetone, methyl ethyl ketone, methyl propanal, hydroxyacetone plus methyl acetate, benzene and 13 other volatile species. 

The functions of the potassium carbonate are (a) to neutralise the acetic acid arising from the action of the phosphoric acid upon the acetamide, and (6) to salt out the otherwise soluble methyl cyanide as an upper layer. 

Finally a general approach to synthesize A -pyrrolines must be mentioned. This is tl acid-catalyzed (NH4CI or catalytic amounts of HBr) and thermally (150°C) induced tea rangement of cyclopropyl imines. These educts may be obtained from commercial cyan> acetate, cyclopropyl cyanide, or benzyl cyanide derivatives by the routes outlined below. Tl rearrangement is reminiscent of the rearrangement of 1-silyloxy-l-vinylcyclopropancs (p. 7 83) but since it is acid-catalyzed it occurs at much lower temperatures. A -Pyrrolines constitut reactive enamines and may be used in further addition reactions such as the Robinson anei lation with methyl vinyl ketone (R.V. Stevens, 1967, 1968, 1971). 

Dichloroacetic acid is produced in the laboratory by the reaction of chloral hydrate [302-17-0] with sodium cyanide (31). It has been manufactured by the chlorination of acetic and chloroacetic acids (32), reduction of trichloroacetic acid (33), hydrolysis of pentachloroethane [76-01-7] (34), and hydrolysis of dichloroacetyl chloride. Due to similar boiling points, the separation of dichloroacetic acid from chloroacetic acid is not practical by conventional distillation. However, this separation has been accompHshed by the addition of a eotropeforming hydrocarbons such as bromoben2ene (35) or by distillation of the methyl or ethyl ester. 

Synthetic chemical approaches to the preparation of carbon-14 labeled materials iavolve a number of basic building blocks prepared from barium [ CJ-carbonate (2). These are carbon [ C]-dioxide [ CJ-acetjlene [U— C]-ben2ene, where U = uniformly labeled [1- and 2- C]-sodium acetate, [ C]-methyl iodide, [ C]-methanol, sodium [ C]-cyanide, and [ CJ-urea. Many compHcated radiotracers are synthesized from these materials. Some examples are [l- C]-8,ll,14-eicosatrienoic acid [3435-80-1] inoxn. [ CJ-carbon dioxide, [ting-U— C]-phenyhsothiocyanate [77590-93-3] ftom [ " CJ-acetjlene, [7- " C]-norepinephrine [18155-53-8] from [l- " C]-acetic acid, [4- " C]-cholesterol [1976-77-8] from [ " CJ-methyl iodide, [l- " C]-glucose [4005-41-8] from sodium [ " C]-cyanide, and [2- " C]-uracil [626-07-3] [27017-27-2] from [ " C]-urea. All syntheses of the basic radioactive building blocks have been described (4). 

The formation of ethyl cyano(pentafluorophenyl)acetate illustrates the intermolecular nucleophilic displacement of fluoride ion from an aromatic ring by a stabilized carbanion. The reaction proceeds readily as a result of the activation imparted by the electron-withdrawing fluorine atoms. The selective hydrolysis of a cyano ester to a nitrile has been described. (Pentafluorophenyl)acetonitrile has also been prepared by cyanide displacement on (pentafluorophenyl)methyl halides. However, this direct displacement is always aecompanied by an undesirable side reaetion to yield 15-20% of 2,3-bis(pentafluoro-phenyl)propionitrile. 

This method is an adaptation of that of Dengel. -Methoxy-phenylacetonitrile can also be prepared by the metathetical reaction of anisyl chloride with alkali cyanides in a variety of aqueous solvent mixtures by the nitration of phenylaceto-nitrile, followed by reduction, diazotization, hydrolysis, and methylation 1 by the reduction of ct-benzoxy- -methoxy-phenylacetonitrile (prepared from anisaldehyde, sodium cyanide, and benzoyl chloride) and by the reaction of acetic anhydride with the oxime of -methoxyphenylpyruvic acid. ... 

Methoxy-D-Homo-estra-l,3,5(10)-trien-17a-one (96)" (/) Acetic acid (6.4 ml) is added to a stirred solution of estrone methyl ether (93 1.1 g) in ethanol (35 ml) containing potassium cyanide (6 g) at 0°. After being stirred for 1 hr at 0° and 2.5 hr at room temperature, the reactants dissolve and potassium acetate preciptates. Water (65 ml) is added to the reaction mixture and the precipitated solid is collected by filtration. The crude product is dissolved in ethyl acetate and the ethyl acetate solution is washed with water, dried over anhydrous magnesium sulfate and evaporated to dryness under reduced pressure. Recrystallization of a portion of the crude product from cyclohexane-acetone gives 3-methoxy-17a-cyano-estra-l, 3,5(10)-trien-17j5-ol (94a) as needles mp 158.5°. 

Benzyl cyanide is first reacted with 2-butylbromide in the presence of sodium amide to give 2-phenyl-3-methylvaleronitrile which is hydrolyzed by sulfuric acid to give 3-methyl-2-phenyl-pentanoic acid. 24 g of 2-phenyl-3-methyl-pentanoic acid are heated for one hour at 175° to 185°C with 30 g of 2-diethylaminoethanol and 0.5 g of sodium methylate. The excess diethyl-aminoethanol is removed in vacuo, the residue is dissolved in 300 cc of 2 N-acetic acid, the acid solution is shaken with ether and made alkaline with concentrated potassium carbonate solution and ice. The ether solution Is washed with water, dried with sodium sulfate and evaporated. The residue is distilled under high vacuum, yielding 20 to 21 g of the basic ester (60% of the theoretical) is obtained, the ester boiling at 98° to 100°C at a pressure of 0.03 mm. The hydrochloride of the ester melts at 112° to 113°C and the methobromide at 100° to 101°C. 

Acetonitrile (methyl cyanide, cyanomethane) is frequently used with other solvents such as chloroform and phenol, and particularly with acetic acid. It enables very sharp end points to be obtained in the titration of metal acetates6 when titrated with perchloric acid. 

In asymmetric Strecker synthesis ( + )-(45,55 )-5-amino-2,2-dimethyl-4-phenyl-l,3-dioxane has been introduced as an alternative chiral auxiliary47. The compound is readily accessible from (lS,25)-2-amino-l-phcnyl-l,3-propancdioI, an intermediate in the industrial production of chloramphenicol, by acctalization with acetone. This chiral amine reacts smoothly with methyl ketones of the arylalkyl47 or alkyl series48 and sodium cyanide, after addition of acetic acid, to afford a-methyl-a-amino nitriles in high yield and in diastereomerically pure form. 

Phosphoryl chloride [10025-87-3], 4 Phthalamic acid, A V-diethyl-, methyl ester [2659344-2],63 Piperidine [110-894], 86, 118 acetate [4540-334], 118 Piperidine, 1 chloro- [2156-71-0], 118 Potassium cyanide [151-50-8], 20... 

Hexone (methyl isobutyl ketone) sec-Hexyl acetate Hexylene glycol Hyd razine Hydrogen bromide Hydrogen chloride Hydrogen cyanide... 

The wide latitude of structural variation consistent with bioactivity in this series is illustrated by the observation that antiinflammatory activity is maintained even when the second aromatic group is attached directly to the pyrrole nitrogen rather than to the heterocyclic ring via a carbonyl group as in the previous case. Condensation of p-chloroaniline with hexane-2,5-dione (or its dimethoxy-tetrahydrofuran equivalent) affords pyrrole 7. The acetic acid side chain is then elaborated as above. Thus, Mannich reaction leads to the dimethylaminomethyl derivative 8, which is in turn methylated (9) the quaternary nitrogen replaced by cyanide to afford 10. Hydrolysis of the nitrile then gives clopirac (11). 

Gyclocondensation of diazomalonaldehyde 336 with 4-fluoroaniline carried out in methanol-acetic acid provides l-(4-fluorophenyl)-l,2,3-triazole-l-carbaldehyde 337 in 78% yield. Oxidation with MnOz in the presence of sodium cyanide in methanol converts aldehyde 337 into methyl ester 338 with 79% yield. Hydrazide 339 (84% yield) is obtained in a reaction of ester 338 with hydrazine. Product 339 reacts with various aromatic aldehydes to give hydrazones possessing interesting antiplatelet activity (Scheme 53) <2003BMC2051>. 

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