With hydrogen cyanide

It is readily oxidized by air to benzoic acid. With aqueous KOH gives benzyl alcohol and benzoic acid. Gives addition products with hydrogen cyanide and sodium hydrogen sulphite. 

Tertiary amines capable of eliminating a secondary amine to form a conjugated system can react with hydrogen cyanide to form y-keto nitriles by amine replacement. Thus (I) yields p-benzoylpropionitrile (IV) ... 

A few cyanohydrins and ethers of cyanohydrins occur naturally One species of millipede stores benzaldehyde cyanohydrin along with an enzyme that catalyzes its cleavage to benzaldehyde and hydrogen cyanide m separate compartments above its legs When attacked the insect ejects a mixture of the cyanohydrin and the enzyme repelling the invader by spraying it with hydrogen cyanide... 

In the early versions, ethylene cyanohydrin was obtained from ethylene chlorohydrin and sodium cyanide. In later versions, ethylene oxide (from the dkect catalytic oxidation of ethylene) reacted with hydrogen cyanide in the presence of a base catalyst to give ethylene cyanohydrin. This was hydrolyzed and converted to acryhc acid and by-product ammonium acid sulfate by treatment with about 85% sulfuric acid. 

Other methods of production iaclude hydrolysis of glycolonittile [107-16 ] with an acid (eg, H PO or H2SO2) having a piC of about 1.5—2.5 at temperatures between 100—150°C glycolonittile produced by reaction of formaldehyde with hydrogen cyanide recovery from sugar juices and hydrolysis of monohalogenated acetic acid. None of these has been commercially and economically attractive. 

Ritter Reaction (Method 4). A small but important class of amines are manufactured by the Ritter reaction. These are the amines in which the nitrogen atom is adjacent to a tertiary alkyl group. In the Ritter reaction a substituted olefin such as isobutylene reacts with hydrogen cyanide under acidic conditions (12). The resulting formamide is then hydroly2ed to the parent primary amine. Typically sulfuric acid is used in this transformation of an olefin to an amine. Stoichiometric quantities of sulfate salts are produced along with the desired amine. 

Chemical Synthesis. The first synthesis of ascorbic acid was reported ia 1933 by Reichsteia and co-workers (14,39—42) (Fig. 4). Similar, iadependent reports pubHshed by Haworth and co-workers followed shordy after this work (13,43—45). L-Xylose (16) was converted by way of its osazone (17) iato L-xylosone (18), which reacted with hydrogen cyanide forming L-xylonitfile (19). L-Xylonitfile cyclized under mild conditions to the cycloimine of L-ascorbic acid. Hydrolysis of the cycloimine yielded L-ascorbic acid. The yield for the conversion of L-xylosone to L-ascorbic acid was ca 40%. 

Other Processes. Other methods iaclude reaction of lime, (CaO) with hydrogen cyanide (24) and reaction of limestone, (CaCO ), with ammonia (25). 

Cyanohydrins (qv) are formed by the reaction of glucose and similar compounds with hydrogen cyanide. The corresponding aminonitrile from methyl isobutyl ketone can be formed with ammonia and hydrogen cyanide. 

Detection. Many people can detect hydrogen cyanide by odor or taste sensation at the 1 ppm concentration in air, most at 5 ppm, but HCN does not have an offensive odor and a few people cannot smell it even at toxic levels. Anyone planning to work with hydrogen cyanide should be checked with a sniff test employing a known safe concentration. This test should be given periodically. Several chemical detection and warning methods can be employed. The most rehable are modem, electronic monitors based on electrolytes that react with hydrogen cyanide. 

Laboratory work with hydrogen cyanide should be carried out only in a well-ventilated fume hood. Special safety equipment such as air masks, face masks, plastic aprons, and mbber gloves should be used. A chemical proof suit should be available for emergency. Where hydrogen cyanide is handled inside a building, suitable ventilation must be provided. The people involved should be thoroughly trained in first aid. 

The most important rule when working with hydrogen cyanide is never to work alone. This appHes especially to sampling and opening lines and equipment. A second person must be in view at all times about 9 to 10 m away, must be equipped to make a rescue, and must be trained in first aid for hydrogen cyanide exposure. 

Ethylene Cyanohydrin. This cyanohydrin, also known as hydracrylonitnle or glycocyanohydrin [109-78-4] is a straw-colored Hquid miscible with water, acetone, methyl ethyl ketone, and ethanol, and is insoluble in benzene, carbon disulfide, and carbon tetrachloride. Ethylene cyanohydrin differs from the other cyanohydrins discussed here in that it is a P-cyanohydrin. It is formed by the reaction of ethylene oxide with hydrogen cyanide. 

With Hydrogen Cyanide. Ethylene oxide reacts readily with hydrogen cyanide ia the presence of alkaline catalysts, such as diethylamine, to give ethylene cyanohydria. This product is easily dehydrated to give acrylonitrile ia 80—90% yield ... 

Acetone is first reacted with hydrogen cyanide to give acetone cyanohydrin Figure 15.2)... 

Acrylonitrile can be manufactured by reacting acetylene with hydrogen cyanide ... 

The reaction of 17-keto steroids with hydrogen cyanide (or acetone cyanohydrin) to form a mixture of the 17-cyano-17-hydroxy compounds, followed by dehydration and reaction with methyl Grignard reagent, is one of the earliest methods for the conversion of androstanes to pregnanes. 

The enhanced reactivity of fluoroalkyl ketones is also manifested in the failure to stop the reaction with hydrogen cyanide at the stage of cyanohydrins Instead, oxazohdinones or dioxolanones are formed (equation 11) If, however, the reaction IS conducted under basic conditions with sodium bisulfite and sodium cyanide, the desired cyanohydrin can be prepared [ll ... 

Treatment of cotarnine and similar compounds with hydrogen cyanide, alkoxides, mercaptides, hydroxylamine, hydrazine, and amines has been reported to give 1-substituted derivatives of 1,2,3-tetrahydroisoquinoline (171, R = CN, OR, SP, NHOH, NHNH, NHR) (262-265). 

Most reported accidents with hydrogen cyanide involve operators inhaling or being splashed witli liquid hydrogen cyanide. Some of tliese accidents are due to equipment failure (blocked lines, frozen valves, etc.), and some arc due to operator error. 

The preparation of a formyl-substituted aromatic derivative 3 from an aromatic substrate 1 by reaction with hydrogen cyanide and gaseous hydrogen chloride in the presence of a catalyst is called the Gattermann synthesis This reaction can be viewed as a special variant of the Friedel-Crafts acylation reaction. 

A very efficient and universal method has been developed for the production of optically pue L- and D-amino adds. The prindple is based on the enantioselective hydrolysis of D,L-amino add amides. The stable D,L-amino add amides are effidently prepared under mild reaction conditions starting from simple raw materials (Figure A8.2). Thus reaction of an aldehyde with hydrogen cyanide in ammonia (Strecker reaction) gives rise to the formation of the amino nitrile. The aminonitrile is converted in a high yield to the D,L-amino add amide under alkaline conditions in the presence of a catalytic amount of acetone. The resolution step is accomplished with permeabilised whole cells of Pseudomonas putida ATCC 12633. A nearly 100% stereoselectivity in hydrolysing only the L-amino add amide is combined with a very broad substrate spedfidty. 

There are expressions of uncertainty concerning the mechanism of the first step of the Strecker amino acid synthesis13-17. The reaction can proceed via the formation of an imine and subsequent nucleophilic attack of cyanide (path ). Alternatively, it has been speculated that the reaction of the aldehyde with hydrogen cyanide furnishes a cyanohydrin (path ), which then is subjected to a nucleophilic displacement of the hydroxy group by the amino function. 

An efficient stereoselective Strecker synthesis of phenylglycine has been achieved using the tert-butyl ester tm-leucine as the chiral auxiliary. Its benzaldimine reacts with hydrogen cyanide in hexane at — 23 °C to furnish the ( )-diastereomer with the excellent diastereoselectivity of >98 254. 

Until the 1960s, acrylonitrile was, like vinyl acetate, made from acetylene (by reaction with hydrogen cyanide), but research on catalysts in the 1950s led to the much less costly route shown above. 

Hydrogen selenide, a possible by-product, is very toxic, being comparable with hydrogen cyanide. Its accidental inhalation in small amounts may produce a sore throat. 

Huthmacher, K. Krill, S. Reactions with Hydrogen Cyanide (Hydrocyanation). In Applied Homogeneous Catalysis with Organometallic Compounds Cornils, B., Herrmann, W. A., Eds. VCH Weinheim, Germany, 1996 pp 465-486. 

In this reaction the osone (or a-keto aldehyde (VI)) is allowed to react with hydrogen cyanide or preferably with potassium cyanide in aqueous... 

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