Copper(I) cyanide

• Catalog No.: 12135
• CAS Number: 544-92-3
• M. F.: CCuN
• M. W.: 89.5634

SYNONYMS

• Title: 氰化亚铜(I)
• IUPAC name: λ^1-copper(1+) ion iminomethanide
• IUPAC Traditional name: λ^1-copper(1+) ion cyanide

DATABASE IDS

• CAS Number: 544-92-3
• EC Number: 208-883-6
• MDL Number: MFCD00010975
• Beilstein Number: 3587244
• Merck Index: 142661

PROPERTIES

• Apperance: Powder
• Density: 2.92
• Melting Point: 473°C
• Solubility: Practically insoluble in water, alcohol. Soluble in NH4OH
• GHS Hazard statements: H300-H310-H330-H400-H410
• European Hazard Symbols: Highly toxic (T+)
• European Hazard Symbols: Nature polluting (N)
• GHS Precautionary statements: P260-P301+P310-P304+P340-P320-P330-P361-P405-P501A
• Risk Statements: 26/27/28-32-50/53
• RTECS: GL7150000
• Safety Statements: 7-28-29-45-60-61
• TSCA Listed: 是
• Hazard Class: 6.1
• UN Number: UN1587
• Packing Group: II

REFERENCES

• For reviews, see: Org. React., 22, 253 (1975); 41, 135 (1992); Synthesis, 63 (1972); Tetrahedron, 45, 349 (1989).
• Details and safety evaluation have been reported for the scale-up of the classical Sandmeyer procedure for the conversion of arylamines to nitriles: Org. Process Res. Dev., 6, 1059 (2004). For a non-aqueous alternative to the Sandmeyer reaction, using alkyl nitrite and CuCN in DMSO, see: Tetrahedron, 52, 7137 (1996).
• In the presence of TMS chloride and NaI, terminal alkynes are converted to cyanoalkynes: Tetrahedron Lett., 34, 5911 (1993).
• Aryl bromides and iodides are converted to nitriles by heating with CuCN (the Rosenmund-von Braun reaction). Early procedures were carried out neat at temperatures in excess of 250^o; but much better results are usually obtained in refluxing DMF at about 160-170^o: J. Org. Chem., 26, 2522 (1961). The product is often obtained as a Cu(I) complex. Alternative methods of decomplexation are described (same ref.) using excess NaCN, or, more conveniently, either oxidation to Cu(II) with FeCl₃, chelation with ethylenediamine. For a review, see: Chem. Rev., 87, 779 (1987). For alternative methods for conversion of aryl halides and triflates to nitriles, see Tetrakis(triphenylphosphine)palladium(0), 10548 and L15836. For a review of palladium- and copper-catalyzed cyanation reactions, see: Eur. J. Inorg. Chem., 3513 (2004).
• Reacts with alkyllithiums to give either "lower order" organocuprates RCu(CN)Li, or, more usefully, the "higher order" reagents R₂Cu(CN)Li₂. For studies of the structure of higher order cuprates, see: J. Org. Chem., 60, 4310, 4312 (1995). These can undergo coupling reactions with primary or secondary alkyl halides: J. Am. Chem. Soc., 103, 7672 (1981); J. Org. Chem., 48, 3334 (1983); 1,4-addition to ɑ?-unsaturated carbonyl groups: Tetrahedron Lett., 23, 3755 (1982); J. Org. Chem., 49, 3938 (1984); Org. Synth. Coll., 8, 112 (1993); and attack epoxides at the less hindered position: J. Am. Chem. Soc., 104, 2305 (1982); J. Org. Chem., 49, 3938 (1984); Org. Synth. Coll., 8, 33 (1993).