On the Structure of Hydrogen Cyanide

McCrosky, C. R.; Bergstrom, F. W.; Waitkins, G. R.

doi:10.1021/ja01255a508

Cited by 12 publications

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“…Notably, this process affords the hydrogen isocyanide (HNC) instead of HCN (Δ G ≠ TS0 = 11.1 versus Δ G ≠ TS0′ = 38.4 kcal mol −1 (ref. 39 ) (Fig. 4a and Fig.…”

Section: Mainmentioning

confidence: 98%

Organocatalytic stereoselective cyanosilylation of small ketones

Zhou

Bae

et al. 2022

Nature

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Enzymatic stereoselectivity has typically been unrivalled by most chemical catalysts, especially in the conversion of small substrates. According to the ‘lock-and-key theory’1,2, enzymes have confined active sites to accommodate their specific reacting substrates, a feature that is typically absent from chemical catalysts. An interesting case in this context is the formation of cyanohydrins from ketones and HCN, as this reaction can be catalysed by various classes of catalysts, including biological, inorganic and organic ones3–7. We now report the development of broadly applicable confined organocatalysts for the highly enantioselective cyanosilylation of aromatic and aliphatic ketones, including the challenging 2-butanone. The selectivity (98:2 enantiomeric ratio (e.r.)) obtained towards its pharmaceutically relevant product is unmatched by any other catalyst class, including engineered biocatalysts. Our results indicate that confined chemical catalysts can be designed that are as selective as enzymes in converting small, unbiased substrates, while still providing a broad scope.

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“…Notably, this process affords the hydrogen isocyanide (HNC) instead of HCN (Δ G ≠ TS0 = 11.1 versus Δ G ≠ TS0′ = 38.4 kcal mol −1 (ref. 39 ) (Fig. 4a and Fig.…”

Section: Mainmentioning

confidence: 98%

Organocatalytic stereoselective cyanosilylation of small ketones

Zhou

Bae

et al. 2022

Nature

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“…Other workers have noted the effectiveness of pyridine in promoting the reaction of hydrogen cyanide with acyl chlorides ( 5 ) and with sulfur or selenium (6). Small amounts of pyridine (1 or 2%) were not effective.…”

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confidence: 97%

“…Replacement of pyridine by ethylamine in the solution of acetone oxime in hydrogen cyanide produced a rapid formation of red oil from which no -hydroxylaminoisobutyronitrile was recovered. Other workers have noted the effectiveness of pyridine in promoting the reaction of hydrogen cyanide with acyl chlorides (5) and with sulfur or selenium (6). Hydrolysis of the nitriles, von Miller and Ploechl hydrolyzed a-hydroxylamino nitriles to the corresponding acids (lb) by the use of concentrated hydrochloric acid for several hours at 25°.…”

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confidence: 99%

PREPARATION AND REACTIONS OF Α-Hydroxylamino NITRILES

Hurd¹,

Longfellow²

1951

J. Org. Chem.

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In 1892-1894 von Miller, Ploechl, and their coworkers (1) reported the addition of hydrogen cyanide to aliphatic oximes and the hydrolysis of the a-hydroxylamino nitriles thus obtained to a-hydroxylamino acids. A few subsequent papers (a, 3) have appeared but work in this field has been largely neglected except for a-hydroxylaminoisobutyronitrile. The last compound has been investigated by several workers (4) because it is the starting point of Piloty's synthesis of porphyrexide. In these studies 20-29% yields were obtained using acetone oxime and a diluted hydrogen cyanide, about three-fifths of the oxime being recovered. If absolute hydrogen cyanide was used, as recommended by von Miller and Ploechl, an oil was formed from which practically no hydroxylaminoisobutyronitrile was obtained.In the present investigations the reactions of butyraldehyde oxime and heptanal oxime with absolute hydrogen cyanide yielded up to 75% and 37% of the expected nitriles, respectively; but the nitriles were seldom obtained in satisfactory purity by this reaction. The best yields were obtained if the operation was interrupted when it changed in color from golden yellon-to orange. At later changes of color from orange to red no nitrile could be isolated. Continued reaction gave rise to black viscous oils and, ultimately, black, coke-like solids. Xeactions in these later stages were quite vigorous. Confirming von Miller and Ploechl (la), we found that neither of the benzaldoximes reacted to form an adduct with hydrogen cyanide, even under a variety of conditions. Also, P-2-furaldosime forms no adduct. Propionaldehyde 2 ! 4dinitrophenylhydrazone was insoluble in hydrogen cyanide and did not react.Butyraldehyde oxime, in contrast, was found to add hydrogen cyanide even from a solution in acetic acid. Furthermore, 2-hydroxylaminovaleronitrile was prepared conveniently and in excellent yield by the reaction of butyraldehyde, hydroxylammonium chloride, sodium cyanide, and potassium dihydrogen phosphate in aqueous solution. Vnfortunately, this last procedure is not general. Although propionaldehyde reacted under these conditions to give 2-hydroxylaminobutyronitrile, heptanal gave only its oxime and none of the nitrile. Formaldehyde reacted under these conditions to give a liquid product which decomposed vigorously at room temperature. Acetone gave only a tar.The yield of 2-hydroxylaminooctanenitrile from heptanal oxime mas increased to 55% by the use of an equivalent of pyridine and an excess of hydrogen cyanide. Small amounts of pyridine (1 or 2%) were not effective. Similarly, pyridine promoted reaction of acetone oxime and hydrogen cyanide to give a 38% yield of a-hydroxylaminoisobutyronitrile, a significant increase over the

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Polymere Blausäure

Völker¹

1960

Angewandte Chemie

129

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Die aminosaure-fr'eien D-Wachse boviner Stamme sind inaktiv. AuBerdem konnen die D-Wachse zur Erzeugung von allergischer Enzephalomyelitis beim Yaninchen verwendet werden (Arbeiten von Waksmang9), Colover loo) und White lol)). lmmunisierung In der Literatur findet man mehrere Hinweise, da8 aich durch Injektion bestimmter Lipoid-Fraktionen, Immunisierungen erreichen lassen, die denen von BCG verursachten vergleichbar sind. Hier waren vor allem die Arbeiten von Boquef und Nkgre102) uber das ,,Methyl-Antigen"103) und die von Choucroun93) iiber das , , P~K O "~~) zu erwahnen. Die Versuche von Boquet und N$grelo2) wurden kiirzlich von Weiss und DubosloP) wiederholt und abgeandert. Weiss und Dubos zeigten, daR man unter bestimmten Um-9 9 ) B . H . Waksman u. R. D. Adams, J. Infect. Diseases 93, 21 [1953]. loo) J. Colover, Brain 77, 435 119541; J . Colover u. R. Consden, Nature [London] 777, 749 [1956]; J. Cotover, ebenda 782, 104 [1958]. lol) R. G. White u. A. H . E. Marshall, Immunology; 7, 1 1 1 [1958]. IU2) A. Boquet u. L. N i g r e , C. R. Seances Soc. Biol. Filiales 86, 581 [1922]; L. Negre: Les lipoides dans le bacille tuberculeux et la tuberculose. Masson, Paris 1950; Prevention e t traitement specifique de la tuberculose par le B. C. 0. e t l'antigkne methylique, Masson, Paris 1956. Io3) ,,Methyl-Antigen" ist ein methylalkoholischer Extrakt aus zuvor entfetteten Tuberkel-Bakterien.Polymere standen rnit Methanol Fraktionen extrahieren kann, die immunisierende Eigenschaften haben. Vor kurzem fand D u~o s~~~) , daR Lipo-polysaccharide (Endotoxine) gramnegativer Bakterien diese Immunitat, die allerdings nicht sehr spezifisch zu sein scheint, betrachtlich erhohen. Lipopolysaccharide allein zeigen die gleiche Wirkung. Die immunisierende Wirkung des ,,PmKo" scheint von anderen Autoren nicht bestatigt worden zu sein. Nach unveroffentlichten Untersuchungen von H . Bloch und Rnffet immunisieren D-Wachse, die dem ,,PmKo" chemisch ahnlich sind, nicht. Wahrscheinlich mu13 ein Lipoid und eine bis jetzt noch unbekannte Substanz gleichzeitig anwesend sein, wenn eine Immunitat auftreten soil, die sich mit jener vom BCG hervorgerufenen vergleichen la13t. Die Arbeiten unseres Laboratoriums, iiber die hier berichtet wurde, erhielfen die gropzugige Unterstiifzung der ,, Fondation Waksman pour le Diveloppemenf des Recherches Microbiologiques en France". Fur die Herstellung groper Mengen Bakferienkulturen danken wir vor allem Prof. J . Forschunyslaboratoriurn dcr Firma Rohm Q Haas G . m. b. H., Darmstadt Polymerer Cyanwasserstoff, ublicherweise als polymere Blausaure oder Azulrninsaure bezeichnet, entsteht durch anionische Polymerisation von HCN in waOriger Losung. Die Reaktion verlauft iiber dimere Blausaure (Iminoacetonitril). Gleichzeitig findet zwischen y-standigen Nitril-Gruppen Ring-schluR statt, wodurch das kettenformige Polymer stabilisiert wird. Die Bruttozusammensetzung der polymeren Blausaure weicht von der Formel (HCN), durch einen mehr oder rninder groBen Sauerstoff-Gehalt ab. Der Sauerstoff starnrnt aus Reaktionen rni...

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On the Structure of Hydrogen Cyanide

Cited by 12 publications

References 0 publications

Organocatalytic stereoselective cyanosilylation of small ketones

Organocatalytic stereoselective cyanosilylation of small ketones

PREPARATION AND REACTIONS OF Α-Hydroxylamino NITRILES

Polymere Blausäure

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