Syntheses and uses of isotopically labelled cyanides

Pichat, L.

doi:10.1002/9780470771242.ch13

Cited by 4 publications

(5 citation statements)

References 167 publications

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“…The reaction between cyanide and the keto acids is consistent with cyanide's known tendency to attack to carbonyl compounds as a nucleophile (32). The protection these compounds conferred on NCIMB 11764 against cyanide inhibition finds further analogy with reports describing the ability of Pyr and ␣Kg to act as cyanide antagonists (6,7,9,36).…”

Section: Discussionsupporting

confidence: 72%

“…Identification of cyanohydrin reaction products. Cyanide is known to add readily to carbonyl compounds, including Pyr, for which it was reported over 40 years ago that the cyanohydrin is formed as the corresponding reaction product (14,32). However, the description of cyanohydrins in general has received limited attention.…”

Section: Identification Of ␣-Keto Acids As Cyanide-scavenging Agentsmentioning

confidence: 99%

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Accumulation of α-Keto Acids as Essential Components in Cyanide Assimilation by Pseudomonas fluorescens NCIMB 11764

Kunz

Chen

Pan

1998

Appl Environ Microbiol

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Pyruvate (Pyr) and α-ketoglutarate (αKg) accumulated when cells of Pseudomonas fluorescens NCIMB 11764 were cultivated on growth-limiting amounts of ammonia or cyanide and were shown to be responsible for the nonenzymatic removal of cyanide from culture fluids as previously reported (J.-L. Chen and D. A. Kunz, FEMS Microbiol. Lett. 156:61–67, 1997). The accumulation of keto acids in the medium paralleled the increase in cyanide-removing activity, with maximal activity (760 μmol of cyanide removed min−1 ml of culture fluid−1) being recovered after 72 h of cultivation, at which time the keto acid concentration was 23 mM. The reaction products that formed between the biologically formed keto acids and cyanide were unambiguously identified as the corresponding cyanohydrins by 13C nuclear magnetic resonance spectroscopy. Both the Pyr and α-Kg cyanohydrins were further metabolized by cell extracts and served also as nitrogenous growth substrates. Radiotracer experiments showed that CO2 (and NH3) were formed as enzymatic conversion products, with the keto acid being regenerated as a coproduct. Evidence that the enzyme responsible for cyanohydrin conversion is cyanide oxygenase, which was shown previously to be required for cyanide utilization, is based on results showing that (i) conversion occurred only when extracts were induced for the enzyme, (ii) conversion was oxygen and reduced-pyridine nucleotide dependent, and (iii) a mutant strain defective in the enzyme was unable to grow when it was provided with the cyanohydrins as a growth substrate. Pyr and αKg were further shown to protect cells from cyanide poisoning, and excretion of the two was directly linked to utilization of cyanide as a growth substrate. The results provide the basis for a new mechanism of cyanide detoxification and assimilation in which keto acids play an essential role.

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Section: Discussionsupporting

confidence: 72%

Section: Identification Of ␣-Keto Acids As Cyanide-scavenging Agentsmentioning

confidence: 99%

Accumulation of α-Keto Acids as Essential Components in Cyanide Assimilation by Pseudomonas fluorescens NCIMB 11764

Kunz

Chen

Pan

1998

Appl Environ Microbiol

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“…Cyanohydrins are thermally unstable and decompose to hydrocyanic acid and carbonyl compounds when heated (Pichat, 1970).…”

Section: Introductionmentioning

confidence: 99%

The Effect of Chlorination on Organocyanide Compounds

Theis¹,

Young

2002

Water Environment Research

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Results are presented that explore the possibility of organocyanide compounds in wastewater contributing to elevated cyanide levels in the chlorinated effluents of publicly owned treatment works. Four model compounds, acetonitrile, amygdalin, cyanocobalamin, and 2-acetoxy-3-butenenitrile, were selected and tested with varying chlorine dosages for release of cyanide by total and diffusible cyanide procedures. The coenzyme form of vitamin B 12 , which does not contain cyanide, was also tested. It was found that acetonitrile and amygdalin do not yield cyanide with or without chlorination, cyanocobalamin had increased release with increased chlorine dosages, and 2-acetoxy-3butenenitrile had generally decreased release of cyanide with increased chlorine dosages. Both cyanocobalamin and coenzyme vitamin B 12 gave evidence of the formation of the cobalt-cyanide complex after chlorination, even though the molecular structure of the coenzyme vitamin B 12 contains no cyanide. Water Environ. Res., 74, 51 (2002).

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“…The Bucherer modification of the Strecker reaction involves the reaction of aldehydes or ketones with [ 14 C]cyanide and ammonium carbonate to form a hydantoin, which is then hydrolyzed by acid 62 or base 63 to the amino [1-14 C]acid 62 . To improve on this radiochemically wasteful approach, various stereoselective syntheses using chiral auxiliaries have been developed, as exemplified by the preparation of (S,S)-2,7diamino [1,[8][9][10][11][12][13][14] C 2 ]suberic acid (56) 64 . To improve on this radiochemically wasteful approach, various stereoselective syntheses using chiral auxiliaries have been developed, as exemplified by the preparation of (S,S)-2,7diamino [1,[8][9][10][11][12][13][14] C 2 ]suberic acid (56) 64 .…”

mentioning

confidence: 99%

“…21 Nitrogen nucleophile additions to [ 14 C ]nitriles via iminoester 14 C]Glycine should be mentioned as a building block accessible from [ 14 C]cyanide in good overall yield 83 . It is useful for some reactions in which alkali metal [ 14 C]cyanides normally fail, such as cyanide addition to acetals and aromatic and heteroaromatic aldehydes and ketones1 . In carbon-14 synthesis it is normally generated in situ and used immediately in subsequent Lewis acid catalyzed chemical transformations.…”

mentioning

confidence: 99%