42867-40-3

Usage

Uses

Used in the Chemical Industry:
Pivaloyl Cyanide is used as a reagent for the deoxygenation of aromatic ketones. This application is significant because it allows for the conversion of aromatic ketones into their corresponding hydrocarbons, which are important intermediates in the synthesis of various organic compounds.
Additionally, Pivaloyl Cyanide is used as a reagent for the selective synthesis of secondary alcohols. This selective synthesis is crucial in the production of specific alcohols that are required as building blocks for more complex organic molecules, such as pharmaceuticals, agrochemicals, and other specialty chemicals.

Synthesis Reference(s)

Journal of the American Chemical Society, 72, p. 2792, 1950 DOI: 10.1021/ja01162a531

InChI:InChI=1/C6H9NO/c1-6(2,3)5(8)4-7/h1-3H3

Upstream product

• 27644-18-4 pivaloyl bromide 
• 544-92-3 copper(I) cyanide 
• 21864-77-7 2-tert.-Butylimino-3.3-dimethyl-butyronitril 
• 7677-24-9 trimethylsilyl cyanide 
• 3282-30-2 pivaloyl chloride 
• 34836-17-4 (3,3-Dimethyl-1-nitroso-2-oxo-butyl)-triphenyl-phosphonium; chloride 
• 2179-92-2 tri-n-butyltin cyanide 
• 87988-96-3 4-azido-5-(tert-butyl)isoxazole 
• 22767-90-4 1,1,1-Trifluoro-5,5-dimethyl-2,4-hexanedione 

Downstream Products

• 114838-64-1 O-pivaloyl-N-phenylhydroxilamine 
• 132540-70-6 C₁₂H₁₇NO₂ 
• 120345-61-1 O-2,2-dimethylbutyryl-2-hydroxy-2-phenylacetonitrile 
• 944576-49-2 C₁₈H₂₀N₄O₂ 
• 116278-66-1 N-(4-chloro-2-hydroxyphenyl)-2,2-dimethylpropanamide 
• 33509-43-2 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one 
• 1006610-14-5 rac-2-tert-butyl-2-hydroxy-4-oxo-4-phenyl-butyronitrile 
• 912650-29-4 (S)-3-[N-(O-trimethylacetyl)-N-(1-phenyl-ethyl)-amino]-propionic acid tert-butyl ester 
• 912650-30-7 C₁₈H₂₇NO₄ 
• 912650-31-8 (S)-N-(2-benzenesulfonyl-ethyl)-N-(1-phenyl-ethyl)-O-trimethylacetylhydroxylamine 
• 912650-32-9 C₁₆H₂₂N₂O₂ 

Relevant academic research and scientific papers

Acyl Cyanides as Bifunctional Reagent: Application in Copper-Catalyzed Cyanoamidation and Cyanoesterification Reaction

Cu-catalyzed domino decyanation and cyanation reaction of acyl cyanides with amines or alcohols have been developed. The cyano sources were generated in situ via C-CN cleavage yielding the corresponding cyano substituted amides or esters in moderate to excellent yields. This approach features a cheap copper catalyst, domino decyanation and cyanation reaction, readily available starting materials, broad substrate scope, operational simplicity, and the potential for further transformation of the cyano group.

Synthesis of a Bolm's 2,2′-Bipyridine Ligand Analogue and Its Applications

A new method of synthesis of an analogue of Bolm's 2,2′-bipyridine ligand based on the catalytic [2+2+2] cyclotrimerization of 1-halodiynes with nitriles was developed. Crucial step of the whole synthesis turned out to be homodimerization of a substituted 2-bromopyridine to the corresponding bipyridine, that was studied and optimized. The newly prepared bipyridine (S,S)-2 was then tested as a chiral ligand in metal-catalyzed enantioselective reactions. Out of the studied reactions the most promising results were obtained in epoxide ring opening (82% yield, 98% ee) and Mukaiyama aldol reaction (>96% yield, 99/1 dr, 92% ee). In the case of Mukaiyama-aldol reaction as well as in the Michael addition, novel ligand 2 proved its robustness compared to Bolm's ligand as it was less sensitive to the purity of used reagents. (Figure presented.).

Detrifluoroacetylation of 4,4,4-trifluoro-3,3-dihydroxy-2-(hydroxyimino)butan-1-ones as a convenient synthetic strategy for acyl cyanides Dedicated to Academician Valery N. Charushin on his 65th birthday.

A reaction reinvestigation of fluorinated 1,3-dicarbonyl compounds with NaNO2 in acidic conditions revealed the formation of corresponding 1,1,1-trifluoro-3-hydroxyimino-butan-2,4-diones which predominantly isolated as hydrates. A novel synthesis of ethoxy-, alkyl-, (het)aryl substituted carbonylcyanides via acid-catalyzed detrifluoroacetylation of obtained 2-hydroxyimino derivatives of 1,3-dicarbonyl compounds was described.

A Ruthenium Complex-Catalyzed Cyclotrimerization of Halodiynes with Nitriles. Synthesis of 2- and 3-Halopyridines

Monohalo- and dihalodiynes efficiently undergo [2+2+2] cyclotrimerization with nitriles in the presence of a catalytic amount of the ruthenium complex Cp*RuCl(cod) (10 mol%) to afford the corresponding halopyridines under ambient conditions in good isolated yields (up to 90%). The halopyridines are formed as two separable regioisomers. This is the first example of a direct synthesis of halopyridines from haloalkynes and nitriles. (Figure presented.) .

Lewis acid-lewis base-catalysed enantioselective addition of α-ketonitriles to aldehydes

Additions of structurally diverse α-ketonitriles to aromatic and aliphatic prochiral aldehydes yielding highly enantioenriched acylated cyanohydrins were achieved using a combination of a titanium salen dimer and an achiral or chiral Lewis base. In most cases high yields and high enantioselectivities were observed. The ee was moderate in the initial part of the reaction but increased over time. This could be avoided, and higher ees obtained, by keeping the titanium complex, in the presence or absence of aldehyde and ketonitrile, at -40°C prior to the addition of the Lewis base. A mechanism initiated by nucleophilic attack of the tertiary amine at the carbonyl carbon atom of the ketonitile is supported by 13C labelling experiments.

SYNTHESIS AND THERMAL DECOMPOSITION OF 4-AZIDOISOXAZOLES

The diazonium salts derived from 1a,b decompose at 0 deg C to give α-cyanodiazoketones 3a,b and, in the case of 1b, also the N-hydroxytriazole 4.The azides 2a,b were prepared from the diazonium salts at -15 deg C.The diazonium salt from 1c is more stable and can be converted into the azide 2c at 0 deg C, along with formation of 5 as a side product.Kinetic measurements have been carried out for the thermal fragmentation of 2a - c which indicated that the reactions occur by a concerted mechanism.

Process for the preparation of acyl cyanides

A novel process for the preparation of acyl cyanides of the general formula wherein R represents an optionally substituted alkyl radical with 1 to 8 carbon atoms, an optionally substituted cycloalkyl radical with 3 to 12 carbon atoms, an optionally substituted aryl radical or an optionally substituted 5-membered or 6-membered heterocyclic radical, which can additionally be fused to a benzene ring, in which a carboxylic acid fluoride or the general formula in which R has the abovementioned meaning is reacted with an alkali metal cyanide, optionally in the presence of a diluent, at a temperature between 10° and 200° C. The acylcyanides (I) can be used as intermediates in the synthesis of known herbicides.

Preparation of acyl cyanides

Acyl cyanides of the formula STR1 in which R represents an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms or an optionally substituted aryl group, or an optionally substituted 5-membered or 6-membered heterocyclic radical which additionally can be fused to a benzene ring, are obtained in high yields by reacting carboxylic acid anhydrides of the formula R--CO--O--CO--R (II) with trimethylsilyl cyanide, (CH3)3 Si--CN (III), if appropriate in the presence of a catalyst and, if appropriate, in the presence of a diluent, at a temperature between 50° and 250° C. The acyl cyanides can be used as intermediate products, for example, for the preparation of certain herbicidally active compounds of the triazinone series.

Preparation of pivaloyl cyanide

In the preparation of pivaloyl cyanide of the formula by reaction of pivalic acid anhydride with anhydrous hydrocyanic acid, the improvement which comprises carrying out the reaction continuously in the presence of a catalyst comprising an alkali metal/copper cyanide complex, an alkaline earth metal/copper cyanide complex or an alkali metal salt, or an alkaline earth metal salt, of an aliphatic, cycloalkphatic or aromatic, carboxylic acid, or a precursor of such a salt, in either case optionally in admixture with a Lewis acid, and in the presence of an inert, aprotic organic diluent, which boils above about 210° C., at a temperature between about 180° and 240° C., by simultaneously and continuously dropping the pivalic acid anhydride and introducing the hydrocyanic acid in gaseous form into a stirred suspension of the catalyst in the diluent, and continuously distilling the crude product mixture consisting essentially of pivaloyl cyanide, pivalic acid and unreacted hydrocyanic acid, the unreacted hydrocyanic acid being separated off by evaporation and being recycled to the reaction vessel, and the pivaloyl cyanide being separated from the precipitated crude product mixture by fractional distillation in vacuo. Advantageously the reaction is carried out at a temperature between about 195° and 225° C., the complex cyanide of the formula Na3 [Cu(CN)4 ], K3 [Cu(CN)4 ], Ca3 [Cu(CN)4 ]2 or Ba3 [Cu(CN)4 ]2 is employed as the catalyst, diphenyl ether is employed as the diluent, and about 1 to 2 moles of pivalic acid anhydride and about 5 to 8 moles of hydrocyanic acid are introduced into the suspension of catalyst per hour.

Process for the preparation of acyl cyanide compounds

This invention relates to a new process for the preparation of acyl cyanides of the general formula wherein R1 is an optionally substituted alkyl radical up to 18 carbon atoms, an optionally substituted cycloalkyl radical with 3 to 12 carbon atoms, an optionally substituted aryl radical or an optionally substituted 5- or 6-membered heterocyclic radical, which can additionally also be fused with a benzene ring, which process comprises reacting a carboxylic acid anhydride of the formula with an alpha-hydroxynitrile of the formula STR1 in which R2 and R3 are identical or different and represent a hydrogen atom, an optionally substituted alkyl radical with 1 to 18 carbon atoms, an optionally substituted cycloalkyl radical with 3 to 12 carbon atoms, an optionally substituted aryl radical or an optionally substituted 5- or 6-membered heterocyclic radical, which can additionally also be fused with a benzene ring. The acyl cyanides (I) are known compounds and can be used as starting material for the synthesis of herbicides.