Fragmentierung von α‐Aminoketoximen. IV. Teil Der Einfluss sterischer. Faktoren Fragmentierungsreaktion, 17. Mitteilung

Grob, C. A.; Sieber, Alexander

doi:10.1002/hlca.19670500838

Cited by 13 publications

(3 citation statements)

References 14 publications

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“…The crude product was concentrated by distillation. A fraction with bp 69-78 °C (18 mm) was obtained in a yield of 5.1 g. According to GLC analysis, the fraction consisted of 81% of iV-methyl-2-cyanopyrrolidine (8a) 21…”

Section: A Controlled Potential Electrolysis Of Jv-methylpiperidinementioning

confidence: 99%

Anodic cyanation of tertiary aliphatic and heterocyclic amines

Chiba¹,

Takata²

1977

J. Org. Chem.

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Section: A Controlled Potential Electrolysis Of Jv-methylpiperidinementioning

confidence: 99%

Anodic cyanation of tertiary aliphatic and heterocyclic amines

Chiba¹,

Takata²

1977

J. Org. Chem.

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“…The alkylation of 19 (0.100 g, 0.422 mmol) with NaH (0.030 g, 1.3 mmol) and ethyl bromide (0.20 mL, 2.6 mmol) was conducted as for 6. Chromatography on silica gel with petroleum ether-EtOAc (6:1) as eluent gave 21 (0.068 g, 61%): mp 99-100 °C; IR 2970 (w), 2930 (w), 1715 (s), 1710 (s), 1650 (s), 1615 (m), 1600 (s), 920 (s), 820 (m), 760 (s), 750 (m), 690 cm-1 (s); mass spectrum (84 °C) m/e (rel intensity) 266 (M + 1,14), 265 (M+, 71), 237 (M -C2H4, 5), 223 (M -CH2CO, 100), 208 (M -CH2CO -CH3, 97). Product 22 was similarly obtained from 20 in 52% yield: mp 125-130 °C; IR 1700 (s), 1650 cm-1 (s); mass spectrum (86 °C) m/e (rel intensity) 301 ( + 2,19), 299 (M+, 43), 271 (M -C2H4, 4), 257 (M -CH2CO, 71), 242 (M -CH2CO -CH3, 97).…”

Section: Methodsmentioning

confidence: 99%

The mechanism of indeno[1,2,3-de]quinolin-2-one formation

Meltzer¹,

Staskun²

1977

J. Org. Chem.

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“…Further conExperimental) (40,41). The nmr signals for the firmation of the pyrrolidine ring was obtained olefinic protons were slightly displaced down-by dehydration of a crude oxime mixture, via field (0.1 -0.2 ppm) relative to the parent the tosylates, to give the common nitrile 4 which alkenylamines, likely resulting from a long range is a known compound (45). anisotropic effect of the nitrosamino group.…”

Section: Introductionmentioning

confidence: 95%

Synthesis of azacyclic compounds by an aminium radical route: orbital overlap requirements

Perry¹,

Chen²,

Menon³

et al. 1976

Can. J. Chem.

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Can. J. Chem. 54, 2385 (1976. Model compounds of A4v5-, A5.'j-, and a6.7-alkenylnitrosarnines were synthesized and photolyzed to generate the corresponding alkenylaminium radicals. The A5~6-alkenylan~inium radicals underwent efficient intramolecular addition leading to the exclusive formation of pyrrolidine derivatives, the yield of which was lower if the steric strain and hindrance were severe in the cyclization transition state. The A6s7-alkenylaminium radical cyclized inefficiently to piperidine derivatives and the A4~5-alkenylarninium radicals did not appear to cyclize; in both cases other pathways having lower activation energies, such as elimination and hydrogen abstraction, predominated. Evidence that the direction of cyclization is controlled by the degree of p-orbital overlap, but not by stability of the developing products, in the transition state is presented. The stereochernical factors associated with the overlap determined the yields of the cyclization products. This is in excellent agreement with the fact that the transition state of cyclization is reached at an early stage in the reaction coordinate. Metal ion catalyzed or radical initiated decomposition of some alkenyl chlorarnines were found either to cyclize to a mixture of pyrrolidine and piperidine derivatives or to undergo no cyclization. Chem. 54, 2385Chem. 54, (1976.On a synthetise et photolyse des cornposCs rnodkles de A4n5-, A5s6-et A6r7-alkenylnitrosarnines qui ont conduit aux radicaux alkknylarninium correspondants. Les radicaux A5:6-alkenylaminium subissent des rkactions d'addition intrarnoliculaires efficaces conduisant a la formation exclusive de derives de la pyrolidine; le rendement de ce compose est diminui si l'emp@chernent et la contrainte stCrique sont importants dans l'etat de transition rnenant a la cyclisation. Le radical A6r7-alkknylarniniurn se cyclise d'une fason inefficace pour conduire a des derives de la piperidine et les radicaux A4.5-alkknylarninium ne sernblent pas se cycliser; dans les deux cas d'autres chernins rkactionels ayant des energies d'activation plus basses, tels que les Climinations et les enlkvernents d'hydrogkne, prkdorninent. On prCsente des donnees indiquant que la direction de la cyclisation est contr6lk par le degrC de recouvrement des orbitales p dans 1'Ctat de transition; il ne semble pas que cette direction soit influenck par la stabilitk des produits qui se forrnent. Les facteurs stCrCochimiques associks avec le recouvrement dkterrninent les rendernents des produits de cyclisation. Ceci est en excellent accord avec le fait que, dans les coordonnees de la reaction, 1'Ctat de transition de la cyclisation est atteint t6t. On a trouvC que les dtkornpositions catalyskes par les ions mCtalliques ou initiies par les radicaux de quelques chloramines d'alkknyles conduisent soit une cyclisation fournissant un mClange de dCrives de la pyrolidine et de la pipkridine soit qu'ils ne conduisent pas des cyclisations.[Traduit par le journal]

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Fragmentierung von α‐Aminoketoximen. IV. Teil Der Einfluss sterischer. Faktoren Fragmentierungsreaktion, 17. Mitteilung

Cited by 13 publications

References 14 publications

Anodic cyanation of tertiary aliphatic and heterocyclic amines

Anodic cyanation of tertiary aliphatic and heterocyclic amines

The mechanism of indeno[1,2,3-de]quinolin-2-one formation

Synthesis of azacyclic compounds by an aminium radical route: orbital overlap requirements

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