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Braverman, S.; Cherkinsky, M.; Birsa, M. L., Science of Synthesis, (2005) 18, 150.
Usually, reactions of isocyanates with carbon nucleophiles follow the general route presented in Scheme 135, and amide derivatives are formed when isocyanates are allowed to react with active methyl and methylene compounds, Grignard reagents, or lithiated compounds. A large number of such reactions have been carried out on compounds having a R1CH2CO group in which R1 is preferentially, but not necessarily, an electron-withdrawing substituent. Thus, dialkyl malonates react with phenyl and methyl isocyanate at room temperature in the presence of triethylamine or alkali to give dialkyl carbamoylmalonates 244 (Scheme 136). Heating the reaction mixture leads to consumption of two moles of isocyanate and formation of 1,3-disubstituted barbituric acid 5-carboxylates 245.[552] With 1-naphthyl isocyanate, the cyclization occurs without heating.
Meeeee 888 Meeeeeee ee Meeeeeeeeee eeee Meeeeee Meeeeeeee[888]
M eeee-eeeeeeeee eeeeeeee ee eeeee 8-eeeeeeeeeeeeeeeeee (888) eeee ee eeeeeeeeeeeee eeeeeeeeeee eeeee-eeeeeeeeeeeeeeeee eeeeeeeeee 888 eeeeeee ee eee eeeeeeeee ee eee eeeeeeeeeeeee 8,8-eeeeeeeeeeee-8-eeeeeeeeeeee 888 (Meeeee 888).[888] Mee eeeeeeee eeeeeeee eeeeeee eee eeeeeeeeeeee ee eee eeeeee M-eeeeee 888, eeeeeeee ee M—M eeeeeeeee ee eeee eee eeee.
Meeeee 888 Meeeeeee ee Meeeeeeeeee eeee Meeee 8-Meeeeeeeeeeeeeeeee[888]
Mee eeee eeeeeeee eee eeee eeeeeee ee eee eeeeeeeeeee ee β-eeeee eeeeeeeeee 888, eee eeeeeeeeeeeee ee eee eeeeeeeee ee eeeeeeeee eeee eeeeeeeeeee.[888] Meeeeeeee ee eeee-eeeee eeeeeeeeeeeeeeee (888) eeee eeeeee eeeeeee eee ee eeeee ee eeee eeeeeeeeee ee eee eeeeeeeeeeeeeee eeeeeee eee eeeeeeeeee 888 ee eee eeee eee ee 88–88% eeeeee (Meeeee 888). Meeeeeee eee eeeeeeeeeeee eeeeeeeeeee eeeeeeeeeee 888 eeeee ee eeeeeeee ee eee eeeee eeeeeeee eeeeeeee, eeee eeee eeeeeeeeeeee eeeeee eeeeee eee eeeeeeeeeeee, e eeeeeee eeee eee eeeeeeeeeee ee eee eeeeeeee ee eeeeee eee.
Meeeee 888 Meeeeeee ee Meeeeeeeeee eeee eeee-Meeee Meeeeeeeeeeeeeee[888]
Meee eee eeeeee eeeeeeeeeee eeeee eeee eeeeeeeeeeeeeee 888 ee eeeeeeeeeeee ee eeee eeeeeeeeeee eeee eee eeeeeeeee ee eeeeee eee M-eeeeee ee e eeeeeee ee M- eee M-eeeeeee (eeeeeeeee ee eee eeeeeeeeeeee ee 888) (Meeeee 888).[888] Mee eeeeeee, eeeeeeeee ee eeeeee eeeeeeeeee eeee eeeeeeeeee- eee 8-eeeeeeeeeeeeeeee-eeeeeeeeeee 888 eeee eeee ee eee M-eeeeeee 888, eeeee eeeeeeeeeee-, eeeeeeeeee-, eee 8-eeeeeeeeeeeeeeeeeeeeeeee-eeeeeeeeeee eeeeeeeeeeeeeee eeee ee e eeeeeee ee eee eeeeeeeeeeeee M-eeeeeee 888 eee M-eeeeeee 888.
Meeeee 888 Meeeeeee ee Meeeeeeeeee eeee Meeeeeeeeeeeeee[888]
Meeeeeeeeeeee eeeeeeeee eeeee eeeeeee eeee eeeeeeeeeee. Meeeeeee ee eeeeeeeee eeeeee 888, eeeeee eeeeeeee eeee eeeeeee eeeeeeeeeeeee eee eeeeee eeeeeeee, eeee eeee eee eeeee eeeeeeeeeee ee e eeeeeeeeee eeeeee eee eee eeeeeeeee eeeeeeeee ee eeeeeeeeeeeee eeeeeee eeeeeeeeeee 888 (Meeeee 888).[888] Meee eeeeeeee 888 eee eeeeeeeeeeee eeeeeeee ee eeee eeeeee, eeee ee eee eeee eeeeeeeee e eeeee eeee-eeeee eeeeeeeeee ee e eeeeeeee eeeee. Meeeeeeee, eeeeeeeeeeeeeeeeeeeeee 888 eeee eeee eeeeeeee ee eee eeeeeeee ee eeee eeeeeeeeeee eeee eee eeeeeeeee eeeeeeeeeeeeeeee 888.[888] Meeeeee eee eeeeeeee eeeeeeeee ee eeeee 888, eee eeeeeeee ee eeeeeeeeeeeeee eee eeee α-eeeeeee 888 eee eeeeee ee eeeeeeee eeeeee.
Meeeee 888 Meeeeeeee ee Meeeeeeeeee eeee Meeeeeeeeeeee Meeeeeee[888,888]
Mee eeeeeeee ee eeeeeeeeeee eeee eeeeeeeee eeeeeee eee eeee eeeeeee ee eee eeeeeeeeeeee ee eeeeeee eeeeeeeeeeee eeeeeee. Meee, eeeeee eee eeeeeeeee eeeeeeeeeee eeeee eeee eeeeeeee ee −88°M eeee eeeeeeeee eeeeeeeeeeeee eee 8-eeeeeeeeee-8,8-eeeee ee eeeeee M-eeeeeeeeeeeeeee eeeeeee eeeeeeeeeeee 888 (Meeeee 888). Meeeeeeeeeee 888, eeeeeee eeee eeeeeeeeeeeee, eeeeeee e eeeeee eeeeeeeeeee ee eee eeeeeeee ee eeeeee(M) eeeeeee ee eeeeeee ee eeee eee M-[8-eeeeeee-8(8M)-eeeeeeeeeeee]eeeeee 888. Meeeeeeeeee ee eeeeeeeeeeee 888, eeeeeee eeee 8-eeeeeeeeee-8,8-eeeee, eeeeeeee eeee eeeeeeeeee eee eeeeeeee e eeeeeee ee eeeeeeeeeeee eeeeeeeeeee 888 eee eeeeeeeeeeeeeee 888.[888] 8,8-Meeeeeeeeeeee eeeeeeeeee eee ee eeeeee eeeeeeee ee eeee eeeee ee eee eeeeeeeeeee ee eeeeeeeeeee eeee eeeeeeeee eeeeeee eee eeeeeee ee e eee-eee eeeeeeeee. Meee, 8-(eeeeeeeeeeeeeee)-8-eeeeeeeeeeeeeeeeee (888) eee eeee eeeeeeeeeee ee 88% eeeee ee eee eeeeeeee ee eeeeeeeee eeee-eeeeeeeeeee ee eeeeee eeeeeeeeee ee e eeeeeeeeeeeeeee/eeeeee eeeeeeee eeeeeeee ee eeeeeeeeeeeeeeeeeee ee eeeeeeeeeeee 888 eee eeeeeeeeeeeeee eeeeeeeeeee ee eeeeeeeee 888.[888]
Meeeee 888 Meeeeeeee ee Meeeeeeeeee eeee Meeeeeeee Meeeeee[888,888]
Meeeeeee ee eeeeeeeeeee eeee eeeeeeeee, eeeeeeee, eee eeeeeee Meeeeeee eeeeeeee ee e eeeeeeeeee eeeee eee eee eeeeeeeeeee ee eeeeeeeee eeeeee. Me eee eeeeeeeeee eeeeeeeeeee M8 ee eeeeee eeeeeee eeee eee eeeeeeeee eeeee 888, eeeeeee eeeeee 888 eee eeee ee eeeeeeee ee eeee eeeeeeee. Meeeeeeeeeeeee eeeeeeeeee eee eeeeeeeeeeee eeeeeeeeee eee eeeeeeeeeeee eeeeeeee ee eeee eeeeeeee (Meeeee 888).[888] Meee, eeeeeeee ee eeeeeeeeeeeeee eeeeeeeeee ee e eeeeeeee ee eee Meeeeeee eeeeeee, eeeeeeee ee eeeeeee eeeeee, eeeeeee eee eeeeeeeeeeeee eeeee 888 eeeee eeee eeeeeee eeeeeee ee eee eeeeeeeeeee eeeeee. Me eee eeee ee eee eeeeeeee ee e Meeeeeee eeeeeee eeee eeeeeeeeeeee eeeeeeeeee, eee eeeeeeeee eeeeeeee eeeeeee ee eee eeeee 888. Meeeeeeeee ee eeeeeeeee eeeeeee ee eee eeeeeeeeeeee eeeee eeeeeee eee eeeeeeeeeeeee eeeee 888.
Meeeee 888 Meeeeeeee ee Meeeeeeeeee eeee Meeeeeee Meeeeeee[888]
Meeeeeeeeeee Meeeeeeee
M-(eeee-Meeee)-8-(Meeeeeeeeeeeeee)-8-eeeeeeeeeeeeeeeee (888, M8 = Me); Meeeeee Meeeeeeee:[888]
Me e eeeeee ee eeeeeeeee eeeee eeeeee (8 × 88 eM) MeM (8.88 e ee e 88% eeeeeeeeee ee eeeeeee eee, 8.88 eeee, 8.88 eeeee) ee eee MMM (88 eM) eeeee ee eeeee eeeeeeeeee ee −88°M eee eeeee eeeeeeee, eee eeeeeee, e eeee ee M-(eeee-eeeee)-8-eeeeeeeeeeeeeeee (8.8 e, 8.88 eee) ee eee MMM (88 eM). Mee eeee eee eeee ee eeee ee 8°M eee 8–88 eee, eee eeeeeee eeeeeeeee eeeeeeeeee eeeeeeeeee (8.88 e, 8.88 eeee) eee eeeee. Meeee 88 e ee ee, eee eeeeeee eee eeeeeeee eeee eee. ee MM8Me (88 eM), eeeeeeeee eeee Me8M (8 × 888 eM), eeeeee eeeee eeee ee MM8Me (88 eM) eee eeeee (8 × 88 eM), eeeee (Me8MM8), eee eeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee ee eeeeee eee. Meeeeeeeeeeeee (eeeeee eee, eeeeeeeee eeeee/MM8Me8 8:8 ee 8:8) eeeeeee eee eeeeeee ee eeeee eeeeeee; eeeee: 8.88 e (88%); ee 88–88°M; MM (MMe) ν̃eee: 8888 (MM), 8888 (e-MeM—M=M), 8888 ee−8 (MM—M=M).
References
| [552] | Meeeeee, M.; Meeeeee, M.; Meeee, M. M.; Meeeeee, M., Meee. Mee., (8888) 888, 888. |
| [553] | Meeeeeee, M. Me.; Meee, M. M.; Meeeeeeeee, M. M., Meeeeeeeeeee, (8888) 88, 8888. |
| [554] | Meeee-Meeeeeee, M.; Meeeeeee, M.; Meeeeeee, M. M., Meeeeeeeeee Meee., (8888) 88, 8888. |
| [555] | Meeee, M. M.; Meeeee, M.; Meeeeeee, M.; Meeee, M., M. Meeeeeeeee. Meee., (8888) 88, 888. |
| [556] | Meeeee, M.; Meeeeeeee, M.; Meeeeeeeee, M.; Meeeeeeee, M., Meeee. Meeeee., (8888) 88, 8888. |
| [557] | M'Meeee, M. M.; Meee, M. M., M. Mee. Meee., (8888) 88, 8888. |
| [558] | Meeeeee, M. M.; Meeeeeeeeeee, M. M.; Meeee'eee, M. M.; Meeeeee, M. M.; Meeeeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
| [559] | Meeeeee, M. M.; Meeeeeee, M.; Meeeeeee, M. M., Meeeeeeee Meeeee., (8888), 88. |
| [560] | Meeeee, M. M.; Meeeeee, M. M., Meeeeeeeeee Meee., (8888), 888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 8, 888.
- 8.Meeeee-Meee, (8888) M 8, 888.
- 8.Meeeee-Meee, (8888) M 8-8, 8888.
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