Chemistry Reference
In-Depth Information
Tab. 4.20.
Acyl isocyanates 481 prepared with oxalyl dichloride.
R (481)
Reaction conditions
References
Pivaloyl
Solv.: 1,2-DCE
325
Propionyl, Isovaleryl, Isobutyryl, Butyryl
Solv.: 1,2-DCE
326
Propionyl
Solv.: dichloromethane
325
Trifluoroacetyl
Solv.: 1,2-DCE
327, 328
Chloroacetyl
Solv.: 1,2-DCE, 5 h, heating, 71%
Solv.: benzene, 5 h, heating
Solv.: 1,2-DCE, 64%
329, 330
331
332
Dichloroacetyl
Solv.: 1,2-DCE, 68%
331
2,2-Dichloropropionyl
Solv.: 1,2-DCE
325
Trichloroacetyl
Solv.: 1,2-DCE, 60%
326, 331, 333
3-Bromo-2,2-dimethylpropanoyl
Solv.: 1,2-DCE, 24 h, heating, 81%
334
Phenyl-acetyl
Solv.: 1,2-DCE, 24 h, heating, 36%
331
Diphenyl-acetyl
Solv.: 1,2-DCE, 24 h, heating, 37%
331
3,4-Dichlorophenyl-acetyl
Solv.: 1,2-DCE, 24 h, heating, 97%
331
Benzoyl
Solv.: 1,2-DCE, 24 h, heating, 75%
Solv.: dichloromethane, 80%
331
333
Bromoacetyl
Solv.: 1,2-DCE
335
4-Fluorobenzoyl
Solv.: dichloromethane, 95%
333
4-Methoxybenzoyl
Solv.: dichloromethane, 90%
333
The acylation of diethyl
iminocarbonate,
(EtO)
2
C
b
NH, with oxalyl chloride
or phosgene, gave (EtO)
2
C
b
NC(OEt)
b
NCO
2
Et, EtO
2
CNCO,
(EtO
2
CNH)
2
CO,
[CON
C(OEt)
2
]
2
, and (CONHCO
2
Et)
2
. The primary intermediates in the reactions
were (EtO)
2
C
b
NCOCOCl [341].
Several oxoacetyl isocyanates (Table 4.21) have been prepared with oxalyl di-
chloride starting from the corresponding oxalamic acid esters.
b
NCOCl and (EtO)
2
C
b
O
O
(COCl)
2
O
O
H
2
N
R
OCN
R
chlorinated solvents
O
O
486
487
Tab. 4.21.
Oxoacetyl isocyanates prepared with oxalyl dichloride.
R (487)
Reaction conditions
References
Me
Dichloromethane, 15 h, heating
Dichloromethane
Chloroform, 55%
342
325
343
Et
Chloroform
1,2-DCE, 5 h, 0
C and then heating at reflux for 5 h, 82%
344
345, 346
Pr
342
