4-cyano-1 -methyl

A solution of 4% aq. H2SO4, (301) was heated to 50"C over 30-60 min. Nitrogen was bubbled through the solution during this time. 4-(Cyano-methyl)phenylhydrazine hydrochloride (1080g, 4.77 mol) was added as a solid to the heated mixture. After it had dissolved, A,A-dimethyl-4,4-dimethoxy-butanamine (965 g, 5.98 mol) was added over a period of 30 min. The mixture was then heated at reflux for 2 h. The reaction mixture was cooled and diluted with portions of 30%o aq. NH4OH (21 total) over 0.5 h at a rate to maintain the temperature at 25-30°C. The product was then extracted into isopropyl acetate (3 x 101). The solution was concentrated to 31 which led to a precipitate which was isolated by filtration and washed with cold isopropyl acetate to give 827.4 g (76%) of product. 

Acetic acid, (4-chloro-2-oxobenzothiazolin-3-yl)- — see Benazolin Acetic acid, cyano-methyl ester... 

Whereas the pyrrolo[l,2-a]azepinium cation, a 107t-aromatic system, is unknown, 5-(cyano-methyl)pyrrolo[1,2-a]azepinium perchlorate (7) is available by protonation of the cyanomethy-lene derivative 6 in perchloric acid.7 H NMR studies reveal that the cation has a completely delocalized -electron system. 

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... 

A similar reaction the with rran.v-isomer 3b gave c -3,5-dimethylcyclohexene (4) with very high diastereoselectivity. Accordingly, the stereochemistry of this substitution is anti. Deuterium labeling experiments using the 1-deuterio or 3-deuterio derivative of 3 a showed that the ratio of SN2 /SN2 with lithium dimethylcuprate was about 50 50, while the ratio with lithium cyano(methyl)cupratc was >96 4. 

Reaction of (2S)-(/T)-5-Benzyloxy-1,2-cpnxy-3-pentonc (3) with Lithium Cyano(methyl)cuprate55 ... 

Abietylamine, dehydro-, A tnfluoro- [Acetamide, 2,2,2-trifluoro-/V-[ [1,2,3,4,4a, 9,10,1 Oa-octahydro-l, 4a-dtmethyl-7-(l-methylethyl)-l -phenanthrenyl ] -methyl]-, [17 (la,4ad,10aa))-, 125 Acetamides, A-arylalkyl-, 7 Acetanilide, 2,2,2-tnfluoro- [Acetamide, 2,2,2-tnfluoroTV-phenyl-], 122 Acetic acid, cyano-, methyl ester, 63 Acetic acid, methoxy-, 70 Acetic acid, phenoxy-, 68 Acetic acid, phenyl- [Benzeneacetic acid],... 

In order to find out whether captodative substitution of a methyl radical can lead to persistency, the rate of disappearance by bimolecular selfreaction was measured for typical sterically unhindered captodative radicals (Korth et al., 1983). The t-butoxy(cyano)methyl radical, t-butylthio(cyano)-methyl radical and methoxy(methoxycarbonyl)methyl radical have rate constants for bimolecular self-reactions between 1.0 x 10 and 1.5 X 10 1 mol s Mn the temperature range —60 to - -60°C. The dilTusion-controlled nature of these dimerizations is supported by the Arrhenius activation parameters. Thus, it has to be concluded that there is no kinetic stabilization for captodative-substituted methyl radicals. On the other hand, if captodative-substituted radicals are encountered which are kinetically stabilized (persistent) or which exist in equilibrium with their dimers, then other influences than the captodative substitution pattern alone must be added to account for this phenomenon. 

MCR also tolerates the aliphatic isocyanide functionality [150], thus allowing the union with various IMCRs. Finally, we developed the first example of a triple MCR process (SCR toward 83) based on our 2//-2-imidazoline (65) and W-(cyano-methyl)amide (32) MCRs united with the Ugi-4CR (Fig. 25). 

Acetic acid, chloro, tert butyl ester, 55, 94 Acetic acid, cyano-, ethyl ester, 55, 58, 60 Acetic acid, cyano-, methyl ester, 56, 63 Acetic acid, 3,4-dimethoxy-phenyl-, 55,45, 46... 

A summary of the in situ use of the azobenzene probases is given in Table 2. Apart from the generation of ylid, referred to above, the main applications have been for N- and C-alkylation of weak nitrogen and carbon acids, for the promotion of condensation and substitution reactions involving carbanions such as the cyano-methyl anion, for an interesting carboxylation reaction (entries 4 and 17), and for base-promoted cyclisations (entries 5 and 6). 

METHYL oi-CYANOPELARGONATE (Pelargonic acid, 0-cyano-, methyl ester)... 

The sodium compound is condensed with a-brom-propionic ester to form cyano-methyl succiuic ester ... 

The instability of 1-azabuta-1,3-dienes arising from the imine moiety and the low reactivity as dienes in the Diels-Alder reaction are sometimes problems. Benzylidene(cyano)methyl-l,3-benzothia/oxazoles, featuring a stabilized imine moiety in the form of a heteroaromatic ring... 

A group of l,3,4-oxadiazolin-5-ones and l,3,4-oxadiazoline-5-thiones show antitubercular activity.18,43a 76,84 86,181, 132,157 160 They have been investigated with regard to their mode of action. 2-(4 -Pyridyl)-l,3,4-oxadiazolin-5-one (S 57) has shown itself active against Mycobacterium tuberculosis and Mycobacterium leprae.86-158 It possesses some advantages compared with isonicotinic acid hydrazide. Derivatives of S 57 also have some tuberculostatic activity.159, lfl1,162 Further tuberculostatic compounds are derived from p-aminosalicylic acid, for example WS 127 [2-(4 -amino-2 -hydroxyphenyl)-l,3,4-oxadiazoline-5-thione] and WS 174 [2-(4 -acetamido-2 -hydroxyphenyl)-l,3,4-oxadiazolin-5-one].85 2-Cyano-methyl-l,3,4-oxadiazolin-5-one shows a tuberculostatic activity comparable with that of Reazid. 18 Oxadiazolin-5-ones and oxa-... 

Further SRR could be achieved by replacing carbonyl 6 to imine 61, which resulted in the formation of bis-amino oxazoles 65 (catalyzed by a Brpnsted acid). Finally, our research group serendipitously discovered the formation of M-(cyano-methyl)amides 70 when primary a-isocyanoamide 67 was used as an input (Scheme 7, SRR, Brpnsted acid was applied only with primary amines) [60]. The mechanism of this reaction will be discussed further in Sect. 3.3. 

ETHANENITRILE ETHYL NITRILE METHANECARBONITRILE METHANE, CYANO- METHYL CYANIDE METHYLKYANID NCI-050822... 

Brandt, H., Hbrnle, R. and Leverenz, K. (1982). Color stable modification of monoazo dyestuff—viz butyl cyano methyl nitrophenyl azo pyridone, used for dyeing polyester fibers. Bayer AG Patent DE 3 046 587. [274]... 

The anthranilic acid may also be converted into phenyl glycine ortho-carboxylic acid by the action of formaldehyde and potassium cyanide, yielding first cyano-methyl anthranilic acid which on hydrolysis is converted into the phenyl glycine compound. 

A synthetically very useful reaction sequence would be the anodic oxidation of I via the iminium ion V to the substitution product VIII. The addition of nucleophiles to V in the case of purely aliphatic amines has, however, only found limited application. For example, the cyanide ion may be used as a nucleophile, giving a-cyanation products or a-amino acids after hydrolysis. Thus, anodic oxidation of methyl-diisopropylamine in methanol/water (1 1) in the presence of sodium cyanide leads to the formation of cyano-methyl-diisopropylamine in 55% yield, and 2-cyano-A- -propylpyrrolidine is formed from A- -propylpyrrolidine in 59% yield [16] ... 

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