Cyanomethylation

The reaction probably proceeds through the S-cyanomethyl isothiouronium (238) salt, which can be isolated when the reaction is carried out in cold acetone. Cyclization takes place upon heating. 

Another naturally occurring nucleoside antibiotic SF-2140 [93207-27-3] C H2qN20, a 3-cyanomethyl-4-methoxyindole nucleoside (55) is found to... 

Cyanopyrazole is obtained from treatment of 4-amino-3-halopyridazines with potassium amide in liquid ammonia, while 4-amino-3,6-dihalopyridazines are rearranged under the same conditions to 3-cyanomethyl-l,2,4-triazole. 

Cyanoacetyl-5-nitro-l,2-benzisothiazole loses carbon dioxide on heating to give the 3-cyanomethyl compound (79JCR(S)395). 3-Hydroxyisothiazole gives 3-chloroisothiazole on... 

Benzylamine, o-chloro-N-(cyanomethyl)-N-methyl-isoindole synthesis from, 4, 323 Benzylisoquinoline alkaloids synthesis, 1, 446 Benzynes... 

Pyridine, 6-cyano-l,2-dihydro-thermal dimerization, 2, 370 Pyridine, 2-cyanomethyl-tautomerism, 2, 159 Pyridine, 4-cyanomethyl-tautomerism, 2, 159 Pyridine, 2-cyano-2,3,4,5-tetrahydro-metallation, 2, 387 Pyridine, 2,5-diacetyl-ipso substitution, 2, 301 Pyridine, 3,5-diacetyl-l,4-dihydro-Hantzsch synthesis, 2, 482 Pyridine, 4-dialkylamino-as acylation catalysts, 2, 34 Pyridine, 2,2-dialkyl-l,2-dihydro-... 

Acetyl-, 5-Carboxy-, and 5-Cyanomethyl, 294 Substituted S-Ethyl Derivatives... 

S-Acetyl-, S-Carboxy-, and 5-Cyanomethyl Thioethers ArSCH2X, X = -COCH3, -CO2H, —CN (Chart 7)... 

Knoevenagel reaction. Addition of the cyanomethyl group has been accom-... 

Table 12.9. Absolute Rates of Addition Reactions of Methyl, Cyanomethyl, and Hydrosymethyl Radicals toward Substituted Aikenes, CHi=CHX...

Methoxymethyl. 257 Benzyloxymethyl, 258 Methoxyethoxymethyl, 258 2-(Trimethylsilyl)ethoxymethyl, 259 Methylthiomethyl, 259 Phenylthiomethyl, 259 Azidomethyl, 260 Cyanomethyl, 260 2,2-Dichloro-1,1-difluoroethyl, 260 2-Chloroethyl, 261 2-Bromoethyl, 261 Tetrahydropyranyl, 261 1-Ethoxyethyl, 261 Phenacyl, 262... 

The cyanomethyl ether, formed from bromoacetonitrile (acetone, K2CO3, 97-100% yield), is cleaved by hydrogenation of the nitrile with Pt02 in EtOH, in 98% yield. The method has also been used for the protection of amines and carbamates. 

Fluorenylmethyl, 387 Methoxymethyl, 388 Methylthiomethyl, 389 Tetrahydropyranyl, 390 Tetrahydrofuranyl, 390 Methoxyethoxymethyl, 390 2-(Trimethylsilyl)ethoxymethyl, 391 Benzyloxymethyl, 391 Pivaloyloxymethyl, 391 Phenylacetoxymethyl, 392 Triisopropylsilylmethyl, 392 Cyanomethyl, 392 Acetol, 393 Phenacyl, 393... 

In addition to thiodiglycolic acid esters, the use of bis(cyanomethyl)sulfide in the Hinsberg reaction has facilitated the preparation of 5-cyano-thiophene-2-carboxamides. Thus, the condensation of biacetyl with bis(cyanomethyl)sulfide resulted in the efficient preparation of 10 (94% yield). 

Heteroaromatic substituents can be incorporated onto the quinoxaline 1,4-dioxide ring system by condensing BFO with the appropriately substituted enamine, cyanomethyl, or 1,3-dicarbonylcompound. 2-Cyanomethyl-l,3-benzothiazole 27 reacted readily with BFO 1 in the presence of potassium carbonate to give the quinoxaline 1,4-dioxide 28 in good yield. 

Dimethylindole magnesium iodide reacts with chloroacetonitrile in ether to give 3-cyanomethyl-2,3-dimethylindolenine (234). Majima and Hoshino obtained 3-(2-cyanoethyl)lndole (235) by the action of -chloropropionitrile on indole magnesium iodide. The reaction was slower with -chloropropionitrilc than with chloro-aoetonitrile. 3-(3-Cyano-w-propyl)indole (236), required as an intermediate in the synthesis of 3-indolyl-y-w-butyric acid, was prepared, but not isolated, by the action of y-chloro-w-butyronitrile on indole magnesium iodide. ... 

When, aiming at its cardiotonic activity (stimulant), the 2,5-dioxo-l,2,5,6,7,8-hexahydro-3-cyano-6-bromoquinoline is made to react with different thioamides, the appropriate 6-substituted 8,9-dihydro- (R = cyanomethyl-, 2-oxopyrrolidinyl-methyl-, 2-oxohexahydroazepinomethyl-, and thioxopyrrolidinylmethyl-) (94KFZ43) or (R = H, Me, NH2, NH/S ) (86JAP(K)1, 89H1517) thiazolo[4,5-/Iquinolines 37 or oxidized products (89H1517) are produced. 

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