Aminimides. III. A convenient synthesis of isopropenyl isocyanate

Slagel, R. C.; Bloomquist, Arnold E.

doi:10.1139/v67-426

Cited by 23 publications

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“…Aminimides can be obtained by the thermal reaction of sulfonyl azides with pyridines and amines (Scheme a), by sulfonylation of N -amino pyridium salts (Scheme b), , as well as by quaternization of hydrazine derivatives (Scheme c) . However, many of these synthetic protocols exhibit low selectivity and therefore show a narrow substrate scope or give aminimides in low yields with the concomitant formation of side products from competing reactions …”

Section: Introductionmentioning

confidence: 99%

Functional-Group-Tolerant, Silver-Catalyzed N–N Bond Formation by Nitrene Transfer to Amines

et al. 2017

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Silver(I) promotes the highly chemoselective N-amidation of tertiary amines under catalytic conditions to form aminimides by nitrene transfer from PhI═NTs. Remarkably, this transformation proceeds in a selective manner in the presence of olefins and other functional groups without formation of the commonly observed aziridines or C-H insertion products. The methodology can be applied not only to rather simple tertiary amines but also to complex natural molecules such as brucine or quinine, where the products derived from N-N bond formation were exclusively formed. Theoretical mechanistic studies have shown that this selective N-amidation reaction proceeds through triplet silver nitrenes.

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Section: Introductionmentioning

confidence: 99%

Functional-Group-Tolerant, Silver-Catalyzed N–N Bond Formation by Nitrene Transfer to Amines

et al. 2017

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“…Aminimides have been successfully tested as carrier molecules for uphill transport through liquid membranes, as a model for assisted transport across the cell membrane. 14 Additionally, aminimides have become of interest to polymer chemists [15][16][17][18][19][20][21][22][23][24] as monomer or as isocyanate precursors.…”

Section: Introductionmentioning

confidence: 99%

Electronic and Molecular Structure of Aminimides (1-Acyl-2,2,2-trimethyldiazan-2-ium-1-ide). 1. Formaminimide (HCON^-N⁺Me₃)

2006

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The electronic structure and geometries of (Z)- and (E)-H-CON- N+(CH3)3 have been examined at two levels of theory: B3LYP (basis sets 6-311+G(d,p), 6-311++G(d,p), and 6-311G(3df,3pd)) and MP2(full)/6-311++G(d,p). The (Z) conformation about the C(O)-N(-) bond is thermodynamically preferred over the (E) configuration. Natural bond orbital calculation locates one lone pair of the N- in the HOMO, which is the p(z) natural hybrid orbital (perpendicular to the O=CN- N+ plane). The second lone pair (of lower energy) of N- occupies the HOMO-3, which is the natural hybrid orbital sp(1.12) (sp(1.01) for the (E) conformation, sp(1.74) in the rotational transition state). The carbonyl pi bond is the HOMO-2. The charge-transfer ability of the negative nitrogen in H-CON- N+ (CH3)3 is more powerful than that of the neutral amidic nitrogen in dimethylformamide. The following facts convincingly sustain this view: (1) the higher rotational barrier (stronger C-N(-) bond) in the case of H-CON- N+ (CH3)3, (2) natural resonance theory analysis predicts almost equal weights for the (Z)-H-C(=O)N- N+ (CH3)3 and the (Z)-H-C(O-)=NN+ (CH3)3 canonical resonance structures whereas the weight of the HCON(CH3)2 structure is almost twice as large as that of HC(O-)=N+ (CH3)2, and (3) the second-order perturbation stabilization, as a result of the donor (N-)/acceptor (carbonyl) interaction, is 101.3 kcal/mol for H-CON- N+ (CH3)3 and only 64.4 kcal/mol for dimethylformamide.

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“…In addition These compounds can be copolymerized with other vinyl monomers to form acrylic polymers. When either the aminimide monomer or acrylic polymer containing aminimide groups is heated, isocyanate groups are generated as follows (37,38,181) 0…”

Section: Introductionmentioning

confidence: 99%

Advances in Polyurethane Coatings (1969 to Early 1972)

Chang¹,

Scriven²,

Peffer³

et al. 1973

Product R&D

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Aminimides. III. A convenient synthesis of isopropenyl isocyanate

Cited by 23 publications

References 0 publications

Functional-Group-Tolerant, Silver-Catalyzed N–N Bond Formation by Nitrene Transfer to Amines

Functional-Group-Tolerant, Silver-Catalyzed N–N Bond Formation by Nitrene Transfer to Amines

Electronic and Molecular Structure of Aminimides (1-Acyl-2,2,2-trimethyldiazan-2-ium-1-ide). 1. Formaminimide (HCON^-N⁺Me₃)

Advances in Polyurethane Coatings (1969 to Early 1972)

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Aminimides. III. A convenient synthesis of isopropenyl isocyanate

Cited by 23 publications

References 0 publications

Functional-Group-Tolerant, Silver-Catalyzed N–N Bond Formation by Nitrene Transfer to Amines

Functional-Group-Tolerant, Silver-Catalyzed N–N Bond Formation by Nitrene Transfer to Amines

Electronic and Molecular Structure of Aminimides (1-Acyl-2,2,2-trimethyldiazan-2-ium-1-ide). 1. Formaminimide (HCON-N+Me3)

Advances in Polyurethane Coatings (1969 to Early 1972)

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Electronic and Molecular Structure of Aminimides (1-Acyl-2,2,2-trimethyldiazan-2-ium-1-ide). 1. Formaminimide (HCON^-N⁺Me₃)