Oxalyl cyanide

Compound 67 has also been prepared by (1) reaction of DAMN with oxalyl chloride (56LA95) and (2) by reaction of DISN with oxalyl chloride, followed by treatment with ethanethiol (72JOC4136). 

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DAMN and oxalyl cyanide (64) condense to give the pyrazines 59,67, and 68 in 65% overall isolated yield (Scheme 27). 

Synonyms and trade names carbon nitride. Dicyan, Dicyanogen, Ethane-dinitrile Nitriloacetonitrile, Oxalonitrile, Oxalic Acid Dinitrile, oxalyl cyanide... 

SYNS CARBON nitride CYANOGENE (FRENCH) CYANOGEN GAS (DOT) DICYANOGEN ETHANEDINITRILE NITRILOACETONITRILE OXALIC ACID DINITRILE OXALONITRILE OXALYL CYANIDE PRUSSITE RCRA WASTE NUMBER P031... 

Reactions. DISN (I) when heated with water is hydrolyzed to oxalic acid controlled hydrolysis with p-TsOH in THF gives oxalyl cyanide. This substance is highly reactive... 

Oxalic acid, 155,157, 331,480,482 Oxalyl chloride, 361 Oxalyl cyanide, 155-156... 

OXALYL CYANIDE (460-19-5) Flammable gas. Able to form unstable peroxides on prolonged storage in air. Explosive reaction occurs with acids, liquid oxygen, oxidizers. 

Formula C2N2 MW 52.04 CAS [460-19-5] Structure N=C—C=N Synonyms ethanedinitrile oxalic acid dinitrile oxalonitrile oxalyl cyanide carbon nitride dicyan... 

Synonyms Carbon nitride Cyanogene Cyanogen gas Dicyan Dicyanogen Ethane dinitrile Nitriloacetonitrile Oxalic acid dinitrile Oxalonitrile Oxalyl cyanide... 

Controlled hydrolysis of DISN with two equivalents of p-toluenesulphonic acid monohydrate gave the previously unknown oxalyl cyanide. 

The solid-phase synthesis of the 2(lff)-pyrazinone scaffold is based on a Strecker reaction of commercially available Wang amide linker with appropriate aldehyde and tetramethylsilyl (TMS) cyanide, followed by cyclization of a-aminonitrile with oxalyl chloride resulting in the resin linked pyrazinones. This approach allows a wide diversity at the C-6-position of pyrazinone scaffold (Scheme 35, Table 1). As it has been shown for the solution phase, the sensitive imidoyl chloride moiety can easily undergo an addition/elimination reaction with in situ-generated sodium methoxide affording the resin-linked... 

Oxazolidinediones have been prepared by one-pot condensation of benzyl cyanides, isocyanates, and 2-chloro-2-oxoacetate as shown in Scheme 85. The anion derived from BuLi deprotonation of benzyl cyanide attacks the isocyanate to give intermediates 306, which can undergo condensation and cyclization with ethyl oxalyl chloride to give the 4,5-oxazolidinedione products <2004SL1963>. 

Bredereck and Schmotzer (1044), from diaminomaleonitrile (DAMN hydrogen cyanide tetramer) and oxalyl chloride, prepared 2,3-dicyano-5,6-dihydroxy-pyrazine but Stetten and Fox (1049) could not prepare 23-diamino-5-hydroxy-pyrazine from glycine amide and oxamide. Section 11.3 lists preparations from a, -diamino or a, -diimino compounds and reagents other than a,0-dicarbonyl compounds (384) with additional data (1050) and oxidation of 23-dichloro-quinoxaline with hot aqueous potassium permanganate gave 23-dicarboxy-5,6-dihydroxypyrazine (1051). 

Compared to the older procedures the use of acid iodides in acetonitrile or dichloromethane as solvent constituted a remarkable improvement. Aromatic and aliphatic acyl cyanides are accessible by this route. For example acyl cyanides of cinnamic acid and phenylacetic acid could be obtained in 33% and 49% yields. Copper(I) cyanide in diethyl ether in the presence of lithium iodide gave a-cyano ketones in 50-70%. The reaction can be carried out at room temperature in diethyl ether or slightly above or at 80 C in acetonitrile. It is not possible to obtain the acyl cyanide from acryloyl chloride, chloroformate or oxalyl chloride by this approach. 

The 4,10,16-triaza-18-crown-6 macrocycle shown above was first prepared by Lehn and coworkers (Graf and Lehn, 1975 Lehn, 1985) and was an important intermediate for the synthesis of the first macrotetracyclic polyethers (Canceill et al., 1982 Kotzyba-Hibert et al., 1981 Pratt et al., 1988). The key step in this synthesis was conversion of A-tosyldiethanolamine [TsN(CH2CH20H)2] into the diacid dichloride, TsN(CH2CH20CH2C0Cl)2. As shown above, this conversion was accomplished by reaction with chlo-roacetic acid followed by oxalyl chloride (method A) (Miller et al., 1989) or by chloromethylation, sodium cyanide, hydrolysis and conversion of the diacid to the diacid dichloride (method B) (Graf and Lehn, 1981). The third hypothetical method to the diacid dichloride shown above starts with tosylamide and 5-chloro-3-oxa-l-pentanol followed by Jones oxidation and thionyl chloride (method C) (Qian et al., 1990). 

This method is particularly suitable for the synthesis of a-ethylenic and aromatic acyl cyanides but it also provides a valuable method of preparing certain aliphatic acyl cyanides (Table 6.6). The reaction fails with acryloyl chloride, sulphonyl chlorides, ethyl chloroformate and oxalyl chloride. 

Acidic reagents seem to offer milder conditions. Dehydration reactions forming cyanides can be performed with phosgene [1049-1052], diphosgene [1053-1055], triphosgene [1056], phenyl chloroformate [1057], oxalyl chloride [1058, 1059], tri-chloroacetyl chloride [1060-1062], acetic anhydride [1063-1074], TFAA [1075-1082], phosphorus oxides [1083-1088], phosphorus oxychloride [1089-1098], phosphorus pentachloride [1099], triphenylphosphine/haloalkanes [1100-1103], thionyl chloride [1104-1118], p-tosyl chloride [1119-1124], triflic anhydride [1125-1127], chlorosulfonyl isocyanate [1128], the Burgess reagent [1129], phenyl chloro-thionoformate [1130], cyanuric chloride [1131-1134], carbodiimides [1135, 1136], CDC [1137], PyBOP [1138], AlCU/Nal [1139], and acetonitrile/aldehyde [1140], and by pyrolysis [1141]. 

The use of oxalyl chloride as a dehydrating agent has been developed into a general procedure for preparing cyanides from carboxamides under Swem oxidation conditions, affording a great variety of structures such as 1392-1396 in mostly excellent yields [1059]. The proposed mechanism is outlined. 

Reaction schemes 257,258 and 259 gave some examples of some modes of formation of this important class of pyrethroids. The technical processes however, in order to obtain products as pure as possible, consists of the esterification of the acid chloride. Particularly sensible optically active acid chlorides may be obtained by chlorination with the system oxalyl chloride/DMF at lower temperatures [789]. In case of free cyanohydrine an acid scavenger is necessary [789 a], Alternatively, zinc chloride catalyzes the addition of an acid chloride to the aldehyde 280 to give the a-chlorobenzyl esters [790], which easily react with sodium cyanide [791] to give particularly clean products [792]. 

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