2-bromo-3,3,3-propionitrile

Zenitz obtained the analogous compounds 237 and 238 by the action of the corresponding a-cyano-w-bromo-w-alkanes on 2-methylindolyl magnesium bromide in ether. Eiter and Svierak prepared a-(3-indolyl)propionitrile (239) by the action of a-bromopropionitrile on indole magnesium iodide in anisole. ... 

Propargyl bromide Propyne, 3-bromo- (8) 1-Propyne, 3-bromo- (9) (106-96-7) Tributyltin hydride Stannane, tributyl- (8,9) (688-73-3) Azobisisobutyronitrile Propionitrile, 2,2 -azobis[2-methyl- (8) Propanenitrile, 2,2 -azobis[2-methyl- (9) (78-67-1)... 

The photostimulated reaction of propionitrile anions with haloarenes in liquid ammonia has been studied as a synthetic route to a-arylpropionic acids32. Thus, 2-bromonaphthalene gave 76% yield of the product, whereas 2-bromo-6-methoxynaphtha-lene, p-bromobiphenyl and l-chloro-2-metoxynaphthalene yielded 81%, 52% and 52% of the substitution products, respectively. 

This CAB has also been applied to the enantioselective Diels-Alder reaction of a-bromo-a,/3-enals with dienes [10]. a-Bromo-a,/3-enals are useful dienophiles in the Diels-Alder process because of the exceptional synthetic versatility of the resulting adducts e.g., an important intermediate for prostaglandin synthesis [17a]. In the presence of 10 mol % 2, R = H, a-bromoacrolein and cyclopentadiene in dichloro-methane undergo a smooth Diels-Alder reaction to give the (5)-bromo aldehyde in quantitative yield, 95 % ee and 94 6 exolendo CHO) diastereoselectivity (Eq. 11). Similar results are obtained for the catalyst 2, R = o-PhOCgHj, in propionitrile quantitative yield, 98 % ee ((5) enantiomer major), 94 6 exolendo CHO) diastereoselectivity (Eq. 11). Other examples are listed below. 

Fig. 2. Relative scale of the Tc of the main HTSC groups and solidification points of different mixed solvents chloroethane + butyronitrile (I), n-pentane + methylcyclohexane + n-propanol (II), bromo-ethane + butyronitrile + isopentane + methylcyclopentane (III), chloromethane + dimethyl ether (IV), bromoethane + butyronitrile (V), propionitrile + butyronitrile (VI), methanol + dichloromethane (VII), ammonia + isopropanol + dimethylformamide (VIII). Data are taken from [28, 152].

Following their work on the synthesis of the parent compound 2,6-naphthyridine (105) (105). Taurins and Li reported their work in full (107) and at the same time reported a synthesis of the 4-methyl derivative 104, isolated by Harkiss and Swift (62). 4-Cyano-3-pyridyl-acetonitrile (275) was methylated (CFLI-NaOQHs) in the side chain to afford 2-(4-cyano-3-pyridyl)propionitrile (276), which was treated with hydrogen bromide in ether to afford 3-amino-l-bromo-4-methyl-2,6-naphthyridine (277). Diazo-tization/bromination and replacement of the bromine groups with hydrazine gave 278, and reaction with CuS04 in acetic acid afforded 4-methyl-2,6-naphthyridine (98) (Scheme 23) (107), whose spectroscopic properties were identical with those reported previously (62,63). 

Nitriles condense with malonyl chloride to give 2-chloro4,6-dihydroxypyii-dines (MI-174) in 23 to 63% yield and/or the pyrimidones (XII-17S) or chloropyranooxazines (Section I.5.C.) depending on conditions. 5-Bromo-3-carbethoxy-2-chloro-4,6-dihydroxypyridine (XII-176, R = CO2C2H5) is prepared either by bromination of MI-174 (R = C02Et) or by cyclization of bromomalonyl chloride and ethyl cyanoacetate. Methylmalonyl chloride did not react with propionitrile. The product from acetonitrile and malonyl chloride, first described as 2-chloro-4,6-dihydroxypyridine (MI-174,R = H), is6-chloro-2-methyl-4-pyrimidone (XI-175, R = H). ... 

It has also been shown that phase transfer conditions are effective for promoting carbanion arylation by nucleophilic aromatic substitution. 2-Phenylpropionitrile reacts with 4-nitrochlorobenzene to give 2-phenyl-2-(4-nitrophenyl)-propionitrile in 82% yield (see Eq. 10.23) [33]. Similar results were observed for several other chlorinated nitroaromatics, but two cases deserve special attention. First, the reaction of 2-phenylpropionitrile with 4-bromo-4-nitrobenzophenone affords the aromatic substitution product, but the leaving group in this reaction is nitrite, not bromide (see Eq. 10.24) [34]. Nitrite is known to be a good leaving group in nucleophilic aromatic... 

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