Notes- The Hydrogenation of Nitriles to Primary Amines

Gould, Francis E.; Johnson, Grannis S.; Ferris, Arthur F.

doi:10.1021/jo01079a600

Cited by 69 publications

(37 citation statements)

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“…In triflouroacetic acid this reaction takes place quite rapidly. Similar selectivities a r e also observed in the hydrogenation of phenylpyridines, isoquinoline (73), and polycyclic compounds [87]. The complete hydrogenation of isoquinoline in acetic acid, however, gives predominantly the cis isomer, 74 [87].…”

Section: Heterocvclic Comdoundssupporting

confidence: 62%

“…If a Raney cobalt catalyst is not available, other techniques can be used for the preparation of primary amines. When the reaction is run in the presence of sodium acetate and acetic anhydride, the product primary amine (55) is trapped a s the amide (60) [73] and cannot react with the imine. If an ammoniacal alcohol solution is used (usually with Raney nickel), the imine reacts preferentially with the ammonia to give the 1,l-diamine compound 61 which is then hydrogenolyzed to the primary amine "741.…”

Section: H Nitriles and Iminesmentioning

confidence: 99%

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Organic Functional Group Hydrogenation

Augustine

1976

Catalysis Reviews

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Section: Heterocvclic Comdoundssupporting

confidence: 62%

Section: H Nitriles and Iminesmentioning

confidence: 99%

Organic Functional Group Hydrogenation

Augustine

1976

Catalysis Reviews

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“…Employing the aforementioned premise, the products of base-induced decomposition of 5f are thought to be nine parts of the fused ring compound cis-l-carbethoxybicyclo- [5.3.0]decan-6-one (13), one part of its corresponding trans isomer (14), and one part of the bridged ring ketone l-carbethoxybicyclo[4.3.1]decan-l-one (15). The structure of 13 is based on its C13H2003 molecular formula, the presence of infrared stretching bands at 1725 and 1705 cm-1 for ester and cycloheptanone carbonyl functions, and the presence of a one-hydrogen triplet in the nmr at d 3.83 for a bridgehead hydrogen proximate to the keto function; the characteristics of 14 are very similar to those of 13.…”

Section: Scheme Imentioning

confidence: 99%

Ring enlargements. XIII. Intramolecular diazoalkane-carbonyl reactions

Gutsche¹,

ZANDSTRA²

1974

J. Org. Chem.

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The scope of the intramolecular diazoalkane-carbonyl reaction, described in earlier papers in this series, has been extended by application to (a) 2-carbethoxycycloalkanones carrying acyclic side chains at the 2 position containing potential diazoalkyl moieties and (b) cycloalkanones carrying cyclic side chains at the 2 position containing potential diazoalkyl moieties. Of the several compounds studied, the three most synthetically useful ones are 2-carbethoxycyclopentanone carrying a three-carbon acyclic side chain (forming the bridged ring ketone 6 as the major product), 2-carbethoxycyclohexanone carrying a three-carbon acyclic side chain (forming the bridged ring ketone 9 as the major product), and cyclohexanone carrying an N-nitrosopyrrolidone-containing side chain (forming the bridged ring ketones 25 and 26 as the major products).Earlier papers in this series have described diazoalkanecarbonyl reactions that are (a) intermolecular and involve cycloalkanones and N-nitrosolactamsl and (b) intramolecular and involve cycloalkanones carrying potential diazoalkyl moieties.2 9 3 The present paper is concerned with both of these aspects of the diazoalkane-carbonyl reaction, extending the scope of its application.Reactions of 2-Carbethoxycycloalkanones Carrying Acyclic Side Chains at the C-2 Position Which Contain Potential Diazoalkyl Moieties (5). Following the general procedures that have been previously described,2 *3 2-carbethoxycyclopentanone (la) and 2-carbethoxycyclohexanone (lb) were converted to N-acetyl-( l'-carbethoxy-2'-ketocycloalky1)alkylamines containing cyclopentanone and cyclohexanone rings carrying two-carbon, three-carbon, and four-carbon side chains (4), .as illustrated in Scheme I. Nitrosation with dinitrogen tetroxide yields the corresponding N-nitroso compounds (5). Scheme IPreparation of N-Nitroso-N-acetyl-( 1'-carbethoxy-2'-ketocycloalky1)alkylamines ( 5 ) 0 9 no -q: -0 3 CHJ, CO,Et (CH, 1a.m = O R = (CH,),, CN R = (CHJ, CN b , m = l 3a,m = 0;n = 1 b,m = 1;n =1 c, m = O;n = 2 d, m = l;n = 2 K = CH,CH=CHCN Za, m = 0:n = 1 b, rn = 1; n =1 c , m = O ; n = 2 d. m = 1: n = 2 R = CH,CH=CHCN e.m=O e,m=O f , m = l f , m = l sa, m = 0; n = I b, m = 1; n = 1 c: m = 0; n 2 d, m =1; n = 2 e, m = 0; n 3 f, nz = 1; n = 3 4 a , m = O n = 1 b, m = 1; n = 1 c, m = 0; n = 2 d, m =l; n 3 2 e , m = O ; n = 3 f, m = l ; n = 3Base-induced decomposition of the compounds carrying two-carbon side chains (5a and 5b) results in the formation of complex mixtures which were not investigated further, Base-induced decompositions of the compounds carrying three-carbon side chains (5c and 5d), on the other hand, proceed smoothly and yield more' tractable reaction mixtures. Thus, potassium carbonate induced decomposition of 5c at 25" gives a mixture containing l-carbethoxybicyclo[3.2.1]octan-8-one (6) and 1,4-dicarbethoxycycloheptanone (7), the alcoholysis product from 6. The structure of 6 is commensurate with a CllH1603 molecular formula, infrared stretching bands at 1760 and 1730 cm-l for cyclopentanone and ester carbonyl ...

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“…Otherwise, a further transformation to release the primary amine is required, as for example in the synthesis of benzylamine hydrochloride (50) (Scheme 12). [46,77] Scheme 12 Selective Synthesis of a Primary Amine by Trapping with Acetic Anhydride [ The addition of an alkali metal hydroxide (e.g., potassium hydroxide), an alkaline earth metal hydroxide (e.g., calcium hydroxide), or a quaternary ammonium hydroxide (e.g., tetrabutylammonium hydroxide) to the reaction mixture also favors the formation of the primary amine as, for example, in the synthesis of 2-(aminomethyl)phenol (51) (Scheme 13). [78] The complicated theory underlying this effect of an alkali is thoroughly discussed in the literature.…”

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confidence: 99%