A Practical Photochemically Induced Method for N-N Bond Cleavage of N,N-Disubstituted Hydrazides

Abstract

The development of an unprecedented methodology based upon direct photolysis of N,N-disubstituted hydrazides to secure N-N bond cleavage and to trigger the formation of NH-free lactams has been disclosed.

Key words

cleavage - photochemistry - synthetic methods - hydrazides - lactams

References and Notes

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24

2-Diphenylamino-3-[1-phenylmeth-(E)-ylidene]-2,3-dihydroisoindol-1-one (1g) was prepared from 2-diphenyl-amino-isoindole-1,3-dione^²5 and benzylmagnesium bromide following a reported procedure.^¹9
Analytical Data
Mp 225-226 ˚C. ^¹H NMR (300 MHz, CDCl₃): δ = 6.93 (s, 1 H, CH=), 7.05 (t, J = 7.0 Hz, 2 H, H_arom), 7.20-7.51 (m, 15 H, H_arom), 7.55 (d, J = 7.6 Hz, 1 H, H_arom), 7.91 (d, J = 7.5 Hz, 1 H, H_arom) ppm. ^¹³C NMR (75 MHz, CDCl₃): δ = 111.7, 119.5 (4 × CH), 123.3, 123.5 (2 × CH), 124.0, 128.0, 128.5, 128.7 (2 × CH), 129.4 (4 × CH), 129.5 (2 × CH), 129.7, 133.1, 132.5, 133.7, 134.6, 144.6 (2 × C), 164.5 (CO) ppm. Anal. Calcd for C₂₇H₂₀N₂O: C, 83.48; H, 5.19; N, 7.21. Found: C, 83.62; H, 5.12; N, 7.00.

27

1-Dimethylamino-6-phenylpiperidin-2-one (1h) was prepared from benzaldehyde hydrazone [N,N-dimethyl-N′-(1-phenylmethylidene)hydrazine] following a previously described synthetic sequence:^²¹ addition of allyllithium, amidation with acryloyl chloride, RCM, hydrogenation
(Pd/C).
Analytical Data
Colorless oil. ^¹H NMR (300 MHz, CDCl₃): δ = 1.54-1.88 (m, 3 H), 2.04-2.11 (m, 1 H), 2.47-2.55 (m, 1 H), 2.75 (s, 6 H, 2 × CH₃), 4.65 (t, J = 5.4 Hz, 1 H), 7.25-7.31 (m, 5 H, H_arom) ppm. ^¹³C NMR (75 MHz, CDCl₃): δ = 16.9, 32.8, 34.0, 64.8, 126.9, 127.3, 128.3, 142.4, 170.7 (CO) ppm. Anal. Calcd for C₁₃H₁₈N₂O: C, 71.53; H, 8.31; N, 12.83. Found: C, 71.71; H, 8.49; N, 13.09.