Thies, Heinrich and Schönenberger, Helmut and Qasba, P. K. (1969) Reactions of alpha -aminonitriles. III. Reactions of alpha -aminonitriles and Grignard reagents. Effect of the degree of branching and chain length on the course of the reactions. Archiv der Pharmazie und Berichte der Deutschen Pharmazeutischen Gesellschaft 302 (1), pp. 30-42.
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The reactions of the 4 isomeric butylmagnesium chlorides with alpha -piperidinoacetonitrile (I) and 4 of its alpha -substituted derivs. of general formula II were studied. I underwent adduct formation and dimerization, to give isomeric butyl piperidinomethyl ketones (III) and the dimer 3-amino-2,3-dipiperidinocrotononitrile (IV). The other compds. underwent Grignard exchange to give V (R2 = isomeric Bu), dimer exchange, VI, or H exchange to give VII. Reaction was incomplete in some cases. These results show the effect of branching in the nitrile and in the Grignard. The b.p. of the products are given (product and b.p./mm. given): III (R = Bu), 120 Deg/15; III (R = iso-Bu), 110-13 Deg/15; III (R = sec-Bu), 116-18 Deg/15; IV, 167-9 Deg/0.3; V (R = H, R1 = Me, R2 = Bu), 92-3 Deg/13; V (R = H, R1 = Me, R2 = iso-Bu), 88 Deg/13; V (R = H, R1 = Me, R2 = tert-Bu), 82 Deg/13; VI (R = H, R1 = Me), 148 Deg/15 and 295-8 Deg/715; VII (R = H, R1 = Me), 130-2 Deg/720; V (R = H, R1 = Pr, R2 = Bu), 105 Deg/13; V (R = H, R1 = Pr, R2 = iso-Bu), 104 Deg/13; VII (R = H, R1 = Pr), 171-3 Deg/725; V (R = R1 = Me, R2 = Bu), 94 Deg/13; V (R = R1 = Me, R2 = iso-Bu), 94 Deg/13; VII (R = R1 = Me), 145-8 Deg/720; V (R = Me, R1 = Et, R2 = Bu), 110-12 Deg/-13; V (R = Me, R1 = Et, R2 = iso-Bu), 110-11 Deg/13; VII (R = Me, R1 = Et), 173-5 Deg/715. The reactions mechanisms and the effects of chain branching on the reactions are discussed.
|Additional information (public):||CAN 70:96567 27 Heterocyclic Compounds (One Hetero Atom) 21901-13-3P; 21901-14-4P; 21901-15-5P; 21901-95-1P; 21901-96-2P; 21901-97-3P; 21901-98-4P; 21901-99-5P; 21902-00-1P; 21902-01-2P; 21902-02-3P; 21902-03-4P; 21902-04-5P; 21902-05-6P; 21902-06-7P; 21902-07-8P; 21902-08-9P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of)|
|Institutions:||Chemistry and Pharmacy > Institute of Pharmacy > Retired Professors > Prof. Schönenberger|
|Keywords:||Nitriles Role: RCT (Reactant), RACT (Reactant or reagent) (amino, Grignard reactions of, chain branching in relation to) Chains (branching of, Grignard reactions of amino nitriles in relation to) Grignard reaction (of amino nitriles, chain length in relation to) aminonitriles Grignards reaction Grignards aminonitriles reaction nitriles amino Grignards reaction piperidine nitriles Grignards|
|Subjects:||500 Science > 540 Chemistry & allied sciences|
|Refereed:||Yes, this version has been refereed|
|Created at the University of Regensburg:||Unknown|
|Deposited On:||19 Nov 2010 06:17|
|Last Modified:||19 Nov 2010 06:17|