Oxalyl Dichloride

The widely used Moifatt-Pfltzner oxidation works with in situ formed adducts of dimethyl sulfoxide with dehydrating agents, e.g. DCC, AcjO, SO], P4O10, CCXTl] (K.E, Pfitzner, 1965 A.H. Fenselau, 1966 K.T. Joseph, 1967 J.G. Moffatt, 1971 D. Martin, 1971) or oxalyl dichloride (Swem oxidation M. Nakatsuka, 1990). A classical procedure is the Oppenauer oxidation with ketones and aluminum alkoxide catalysts (C. Djerassi, 1951 H. Lehmann, 1975). All of these reagents also oxidize secondary alcohols to ketones but do not attack C = C double bonds or activated C —H bonds. 

Staudinger, H., Z Angew. Chem., 1922, 35, 657 Her., 1913, 46, 1426 In absence of mechanical disturbance, potassium or potassium-sodium alloy appears to be stable in contact with oxalyl dibromide or oxalyl dichloride, but the mixtures are very shock-sensitive and explode very violently. 

The 2,3-dioxo-6-thioxo-2,3,5,6-tetrahydro-l/7-imidazo[l,2-A]pyrazole 393 and 5,6-dioxo-2,3-dihydro-l//-imidazo[l,2- ]-imidazole 395 were synthesized by condensation of the respective 5-amino-3-thioxo-2,3-dihydro-pyrazole 392 and 2-aminoimidazoline 394 compounds with either oxalyl dichloride or diethyl oxalate in moderate to poor yields (Equations 178 and 179) <1995JPR472, 2002EJM845>. These cyclizations can suffer from various side reactions such as expulsion of CO, polymerization, or formation of open-chain products. To solve these problems, reagents such as oxalic acid bis-imidoyl- and bis-hydrazoylchlorides 397 and 400 as well as 2,3-dichloroquinoxalines 403... 

Isophthaloyl chloride, 2888 f Isopropyl chloroformate, 1560 Methanesullinyl chloride, 0435 Methoxyacetyl chloride, 1165 4-Methoxybenzoyl chloride, 2930 f Methyl chloroformate, 0599 Oleoyl chloride, 3772 Oxalyl dibromide, 0583 Oxalyl dichloride, 0605... 

In 1985, Nakonieczna and coworkers observed that Ai,A-dimethylchloromethani-minium chloride 91 formed from iV,iV-dimethylformamide and oxalyl dichloride is an... 

Isophthaloyl chloride, 2883 f Isopropyl chloroformate, 1555 Methanesulfinyl chloride, 0434 Methoxyacetyl chloride, 1161 4-Methoxybenzoyl chloride, 2925 f Methyl chloroformate, 0732 Oleoyl chloride, 3766 Oxalyl dibromide, 0580 Oxalyl dichloride, 0602... 

Chen C, XI C, Jiang Y, Hong X (2005) 1,1-cycloaddition of oxalyl dichloride with dialkenylmetal compounds formation of cyclopentadienone derivatives by the reaction of 1,4,-dilithio-l,3-dienes or zirconacyclopentadienes with oxalyl chloride in the presence of CuCl. J Am Chem Soc 127 8024-8025... 

Oxalyl dichloride in benzene converts an imino-amine (51.3) into a fused tri-azinedione ring. 

Heating a thiophenol with oxalyl dichloride in diethyl ether gives a good yield of a benzo[6]thiophene-2,3 dione its chemistry has been reviewed [3514]. 

Oxalyl dichloride has been used to prepare a tetrathiadiaza macrocycle. A tetrathiadiamine was reacted with oxalyl dichloride to give the macrocyclic diamide in an 80% yield (method Z-7) (Voronkov et al., 1979). 

Typical procedure. 4-Fluorobenzoyl isocyanate and 4-methoxybenzoyl isocyanate [333] Oxalyl dichloride (1.25 molar equiv.) was quickly added to a suspension of 4-fluorobenzamide or 4-methoxybenzamide in dichloromethane (ca. 2.2 m) at 20 °C. The resulting clear solution was refluxed for 12-20 h, and then the solvent was evaporated. The crude acyl isocyanates were purified by distillation. 

Similar transformations using oxalyl dichloride were applied to obtain dialkox-yphosphono-acetylisocyanates 4S3 [329, 337, 338]. 

Tris(trijluoromed4ylsulfatiyl)acetyl isocyanate 485 was prepared in 70% yield from the corresponding amide 484 and oxalyl dichloride at 150 °C [339]. 

Tab. 4.20. Acyl isocyanates 481 prepared with oxalyl dichloride. ...

Several oxoacetyl isocyanates (Table 4.21) have been prepared with oxalyl dichloride starting from the corresponding oxalamic acid esters. 

Phosphoramidic or thiophosphoramidic add dialkyl esters (Et, tPr) read with oxalyl dichloride to give the corresponding isocyanates [348, 349] under mild conditions, i.e. 1 h, 50 °C in tetradiloromethane 64% yield [350]. 

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