Salts cyanide

Historically these compounds have been made in two-step processes. Eor smaller volumes, reaction of an appropriate ketone or aldehyde with a cyanide salt followed by treatment with an ammonium salt proves satisfactory (Strecker synthesis). Eor larger volumes, treatment of the ketone or aldehyde with HCN to produce a cyanohydrin, followed by treatment with ammonia has been practiced. However, in 1990, DuPont began practicing a new one-step... 

Cyanides. Salts of the complex ion, [Au(CN)2] , can be formed directiy from gold, ie, gold dissolves ia dilute solutions of potassium cyanide ia the presence of air. Additionally, a gold anode dissolves ia a solution of potassium cyanide. The potassium salt can be isolated by evaporation of the solution and purified by recrystallization from water (177). Boiling of the complex cyanide ia hydrochloric acid results ia formation of AuCN [506-65-01]. Halogens add oxidatively to [Au(CN)2] to yield salts of [Au(CN)2X2] which are converted to the tetracyanoaurates usiag excess cyanide (178). These last can also be prepared directiy from the tetrahaloaurates. 

Liquid Nitriding. As in gas nitriding, the process is carried out below the austenite region, and hardening is associated with the formation of hard nitrides in the ferrite. Liquid cyanide salts are used with others to provide the source of nitrogen. 

The cleavage products of several sulfonates are utilized on an industrial scale (Fig. 3). The fusion of aromatic sulfonates with sodium hydroxide [1310-73-2J and other caustic alkalies produces phenohc salts (see Alkylphenols Phenol). Chlorinated aromatics are produced by treatment of an aromatic sulfonate with hydrochloric acid and sodium chlorate [7775-09-9J. Nitriles (qv) (see Supplement) can be produced by reaction of a sulfonate with a cyanide salt. Arenesulfonates can be converted to amines with the use of ammonia. This transformation is also rather facile using mono- and dialkylamines. 

GATTERMAN - KOCH Cartionylation Synthesis of aromatic aldehydes or ketones using cyanide salts or CO - HCI and Lewis adds. 

Hydrogen bromide Hydrogen chloride Hydrogen cyanide and cyanide salts (excluding cyanogen and cyanogen chloride)... 

Caution This reaction involves highly toxic cyanide salts. It may be carried out safely, however, if prudent laboratory procedures are practiced. In particular, cyanide residues should be collected and disposed of separately (Note 1), and the entire sequence should be perform,ed in an efficient hood. 

When mixed with Na thiosulfate or cyanide salts and heated, violent explns occur. A similar reaction occurs if an ammonium salt is melted with a nitrite salt. NaN02 at 460°F in contact with the fiber drums in which it is shipped undergoes a vigorous decompn reaction producing a proplnt-type burning until the carton is consumed (Ref 6)... 

An analogous regioselective effect of silver ions on an addition reaction of arene-diazonium ions was found by Ignasiak et al. (1975) with cyanide salts. Potassium cyanide yields diazocyanides (Ar— N2 — C = N see Sec. 6.6), i.e., C-coupling products, but with silver cyanide - albeit in low yield (7-9%) - diazoisocyanides (Ar—N2 — N = C) are formed (a better synthesis of diazoisocyanides is described in Sec. 6.4). 

The replacement of a halide or sulfonate by cyanide ion, extending the carbon chain by one atom and providing an entry to carboxylic acid derivatives, has been a reaction of synthetic importance since the early days of organic chemistry. The classical conditions for preparing nitriles involve heating a halide with a cyanide salt... 

Wear chemical safety goggles if dust or solutions of cyanide salts may come into contact with the eye wear full-length face shields with forehead protection if dusts, molten salts, or solutions of cyanide salts contact the lace. 

HCN is the most preferred cyanide source in cyanohydrin synthesis. Besides HCN, several different cyanide sources, like potassium cyanide, are being used in biotransformation. Alternative methods for the safe handling of cyanides on a laboratory scale are, for instance, to use cyanide salts in solution. These solutions can be acidified and used as the aqueous layer in two-phase systems or the HCN can be extracted into the organic layer with the desired solvent for reactions in an organic phase. After the reaction, excess cyanide can readily be destroyed with iron(II) sulfate, or iron(III) chloride or bleach. Cyanide can also be presented in the form of organic cyano, such as acetone cyanohydrin [46] or cyanoformates. However, as claimed by Effenberger, some results could not be reproduced [47]. 

Simple cyanides typically refer to alkali water-soluble salts, such as NaCN, KCN, Ca(CN)2, and Hg(CN)2, but also include several cyanide salts of alkali, alkaline earth, or heavy metals, that is, Zn(CN)2, Cd(CN)2, Ni(CN)2, and AgCN, of varying degrees of solubility. In water, NaCN and KCN will completely dissociate to give free cyanide. All simple cyanides ionize in water to release cyanide ion which, depending on pH, will form hydrocyanic acid. For sodium cyanide, the reaction proceeds as follows ... 

Cyanates contain the OCN group. Inorganic cyanates that are formed industrially by the oxidation of cyanide salts hydrolyze in water to form ammonia and bicarbonate ion. Alkyl cyanates are insoluble in water and form cyanurates. Alkyl isocyanates contain the OCN radical, are formed from cyanates, and, like cyanates, are readily hydrolyzed. Thiocyanates (SCN group) are formed from cyanides and sulfur-containing materials and are relatively stable. 

Hydrogen cyanide (HCN) is a colorless, highly poisonous gas or liquid (below 26.7 °C) having an odor of bitter almonds (Hartung 1994 Pesce 1994). It is a weak acid. Exposures may occur in industrial situations as well as from cigarette smoke and combustion products and from naturally occurring cyanide compounds in foods. There is a potential for exposure when any acid is mixed with a cyanide salt. Intravenously administered sodium nitroprusside (Na2[Fe(CN)5N0]-2H20) has been used clinically to lower blood pressure (Schulz et al. 1982). Chemical and physical properties are listed in Table 5-2. 

It should be noted that HCN can be absorbed through the skin. For this reason, ACGIH (1996) and NIOSH (1997) guidelines carry a skin notation. Drinker (1931) cites the case of three men protected with gas masks in an atmosphere of 2% (20,000 ppm) HCN. After 8 or 10 min the men felt symptoms of marked dizziness, weakness, and throbbing pulse. They left the chamber just before collapse. For several hours after the exposure they experienced weakness, high pulse rate, and headache. They were incapacitated for several days, followed by complete recovery. Based on exposure to several cyanide salts, the dermal LD50 in rabbits was calculated to be 6.7 mg CN/kg (Ballantyne 1983). 

Leeser, J.E., J.A.Tomenson, and D.D.Bryson. 1990. A cross-sectional study of the health of cyanide salt production workers. Report No. OHS/R/2, ICI Central Toxicology Laboratory, Alderley Park, Maccles field, Cheshire, U.K. 

NIOSH (National Institute for Occupational Safety and Health). 1976. Criteria for a Recommended Standard. Occupational Exposure to Hydrogen Cyanide and Cyanide Salts (NaCN, KCN, and Ca(CN)2). PB 266 230, DHEW (NIOSH) Pub. No. 77-108, U.S. Department of Health, Education, and Welfare U.S. Government Printing Office, Washington, DC. 

OSHA sets levels of cyanide that are allowable in workplace air. The permissible exposure limit (PEL) for cyanide salts is 5 milligrams of cyanide per cubic meter of air (mg/m3) averaged over an 8-hour workday and 40-hour workweek. NIOSH sets guidelines for chemicals in workplace air. Their recommended exposure limit (REL) for workers for 10 minutes is 5 mg/m3 for calcium cyanide, hydrogen cyanide, potassium cyanide, and sodium cyanide. 

Oral exposure to cyanide usually results from accidental, homicidal, or suicidal ingestion of cyanide salts. Sodium cyanide and potassium cyanide are the most frequently studied cyanide compounds. Copper cyanide, potassium silver cyanide, silver cyanide, and calcium cyanide are other compounds that humans could encounter through oral or dermal exposure. Cassava roots and certain fruit pits contain compounds that can be broken down to form cyanide. Cassava roots form the staple diet of some populations in Africa, Central and South America, and Asia. However, it must be noted that cassava roots are notoriously deficient in protein and other nutrients and contain many other compounds, in addition to cyanide, that could be responsible for some of the observed toxic effects. Thiocyanate is a metabolite of cyanide that is formed in the body after exposure to cyanide compounds. When possible, all oral exposures are expressed as mg CN/kg/day. 

Gastrointestinal effects can be caused by central nervous system stimulation (nausea) or by direct contact (necrosis) with cyanide salts. 

Hydrogen cyanide and cyanide salts are important environmental contaminants, and there are numerous reports dealing with the identification and quantitation of cyanide in air, water, and other environmental media. Representative examples of monitoring methods for cyanide are included in Table 6-2. 

Occupational air (NIOSH Method 7904) Filtered air collected in midget impinger containing NaOH extraction of filter with NaOH sulfide removed. Specific ion electrode (HCN cyanide salts) 2.5 pg CNa 96.7 at 5-21 mg/m3 NIOSH 1989a... 

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