Benzoyl Cyanide Research Articles

Benzoyl cyanide, a general radical acylating reagent for photoredox-catalyzed benzylic site-selective acylation reactions

Benzoyl cyanide, a general radical acylating reagent for photoredox-catalyzed benzylic site-selective acylation reactions

Chemistry of (E)‐2‐(2,4‐Dioxochroman‐3‐ylidene)‐2‐phenylacetonitrile: Access to Biscoumarin‐Fused Trioxabicycles

AbstractA series of biscoumarin‐fused 2,6,9‐trioxabicyclo[3.3.1]nona‐3,7‐dienes were synthesized from base‐mediated coupling of 4‐hydroxycoumarins with benzoyl cyanides and followed by treating with pyridine and thionyl chloride. The mechanism of this reaction was proposed to involve the formation of (E)‐2‐(2,4‐dioxochroman‐3‐ylidene)‐2‐phenylacetonitrile as a key intermediate, which could further react with 2‐(2,4‐dioxochroman‐3‐yl)‐2‐hydroxy‐2‐phenylacetonitrile to yield biscoumarin‐fused trioxabicycles.

A Convenient Esterification of N‐Heteroarene Methanols via C–CN Bond Cleavage of Benzoyl Cyanides as Acylating Sources

AbstractAn efficient and straightforward methodology for the esterification of various N‐heteroarene methanols using benzoyl cyanides as acylating sources through a simply mixing conditions has been reported. The acyl groups were in‐situ generated via chemoselective C–CN bond cleavage to give the N‐heteroarenemethyl esters. This process features in readily accessible starting materials and offers an easy operational procedure, and broad substrate scope with excellent selectivity.

An NHC-catalyzed [3+2] cyclization of β-disubstituted enals with benzoyl cyanides.

The NHC-catalyzed asymmetric [3+2] cyclization of benzoyl cyanides to homoenolate generated in situ from enals was reported. This methodology leads to the efficient construction of a series of chiral cyclic compounds bearing vicinal quaternary stereocenters under mild reaction conditions. Additionally, the representative large-scale and derivatization reactions of the chiral cyclic products reveal the potential synthetic utility of this protocol.

Headspace Volatiles and Endogenous Extracts of Prunus mume Cultivars with Different Aroma Types.

Prunus mume is a traditional ornamental plant, which owed a unique floral scent. However, the diversity of the floral scent in P. mume cultivars with different aroma types was not identified. In this study, the floral scent of eight P. mume cultivars was studied using headspace solid-phase microextraction (HS-SPME) and organic solvent extraction (OSE), combined with gas chromatography-mass spectrometry (GC-MS). In total, 66 headspace volatiles and 74 endogenous extracts were putatively identified, of which phenylpropanoids/benzenoids were the main volatile organic compounds categories. As a result of GC-MS analysis, benzyl acetate (1.55–61.26%), eugenol (0.87–6.03%), benzaldehyde (5.34–46.46%), benzyl alcohol (5.13–57.13%), chavicol (0–5.46%), and cinnamyl alcohol (0–6.49%) were considered to be the main components in most varieties. However, the volatilization rate of these main components was different. Based on the variable importance in projection (VIP) values in the orthogonal partial least-squares discriminate analysis (OPLS-DA), differential components of four aroma types were identified as biomarkers, and 10 volatile and 12 endogenous biomarkers were screened out, respectively. The odor activity value (OAV) revealed that several biomarkers, including (Z)-2-hexen-1-ol, pentyl acetate, (E)-cinnamaldehyde, methyl salicylate, cinnamyl alcohol, and benzoyl cyanide, contributed greatly to the strong-scented, fresh-scented, sweet-scented, and light-scented types of P. mume cultivars. This study provided a theoretical basis for the floral scent evaluation and breeding of P. mume cultivars.

Regioselective benzoylation of unprotected β-glycopyranosides with benzoyl cyanide and an amine catalyst – application to saponin synthesis

Regioselective protection of trans-trans triol and tetrol moieties in carbohydrates was achieved with BzCN as the benzoylating agent and amine catalysts. The protocols are useful for the chemical synthesis of oligosaccharides and saponins.

Catalytic Regioselective Benzoylation of 1,2-trans-Diols in Carbohydrates with Benzoyl Cyanide: The Axial Oxy Group Effect and the Action of Achiral and Chiral Amine Catalysts

Regioselective protection of the polyfunctional carbohydrates with acyl groups under catalytic conditions is a prerequisite for efficient structural modification and chain extension via glycosidati...

Catalyst‐free straightforward synthesis of 3‐cyano‐3‐arylamino‐2‐oxindoles through hydrocyanation with benzoyl cyanide

AbstractThe effective hydrocyanation of 3‐(arylimino)indolin‐2‐ones with benzoyl cyanide under catalyst‐free condition at room temperature to synthesize 3‐cyano‐3‐arylamino‐2‐oxindoles is described. This protocol benefits from low toxicity, inexpensive, and easy‐to‐handle cyanating agent, no catalysts, no additives, mild conditions, good substrate tolerance, and simple work‐up procedure. This reaction successfully offers an alternative to structurally diverse 3,3‐disubstituted oxindoles.

Copper-catalyzed direct cyanation of terminal alkynes with benzoyl cyanide

Copper-catalyzed direct cyanation of terminal alkynes is achieved using less toxic, stable and easy to handle benzoyl cyanide as a cyanide source and air as an oxidant. This protocol provides a good alternative to the preparation of 3-arylpropiolonitriles under mild condition.

An efficient green synthesis of novel 1H-imidazo[1,2-a]imidazole-3-amine and imidazo[2,1-c][1,2,4]triazole-5-amine derivatives via Strecker reaction under controlled microwave heating

Abstract A highly efficient multi-component one-pot synthesis of novel 1H-imidazo[1,2-a]imidazole-3-amine and imidazo[2,1-c][1,2,4]triazole-5-amine derivatives has been developed through the reaction of easily available aromatic aldehydes, benzoyl cyanide and either 2-aminoimidazole-4,5-dicarbonitrile or 3-amino-1,2,4-triazole in pyridine under controlled microwave heating. The process is environmentally friendly, is operationally simple, with short reaction time and with high yields.

Identification of saturated and unsaturated 1-methoxyalkanes from the Thai millipede Orthomorpha communis as potential \u201cRaincoat Compounds\u201d

Mixtures of saturated and unsaturated 1-methoxyalkanes (alkyl methyl ethers, representing more than 45.4% of the millipede hexane extracts) were newly identified from the Thai polydesmid millipede, Orthomorpha communis, in addition to well-known polydesmid defense allomones (benzaldehyde, benzoyl cyanide, benzoic acid, mandelonitrile, and mandelonitrile benzoate) and phenolics (phenol, o- and p-cresol, 2-methoxyphenol, 2-methoxy-5-methylphenol and 3-methoxy-4-methylphenol). The major compound was 1-methoxy-n-hexadecane (32.9%), and the mixture might function as “raincoat compounds” for the species to keep off water penetration and also to prevent desiccation.

Synthesis of 2-(2-oxoindolin-3-ylidene)-2-arylacetonitriles through transition metal-free C(sp2)[sbnd]CN bond construction

An efficient method for the construction of C(sp2)CN bonds directly from C(sp2-H) cyanation of 3-arylideneindolin-2-ones with benzoyl cyanide under transition metal-free condition is described. Various 2-(2-oxoindolin-3-ylidene)-2-arylacetonitriles were efficiently synthesized using air as an oxidant under mild conditions. This protocol has excellent functional group tolerance and can be easily scaled up with good efficiency. This reaction successfully offers an alternative to structurally diverse alkenyl nitriles.

Catalyst Free Selective Monobenzoylation of Diols with Benzoyl Cyanide: A Robust and Regioselective Strategy

AbstractA general and robust strategy for regio‐ and chemoselective benzoylation of diols and polyols was developed under catalyst‐free reaction conditions. This approach is highly flexible in generating a diverse range of 1,2‐, 1,3‐, and 1,4‐monobenzoylated‐adducts in excellent yields without the involvement of expensive catalysts. Collectively, these results have implications in reducing the burden of cost and toxicity associated with the catalysts used in earlier methods.

Cu(TFA)2‐Catalyzed Picolinamido‐Directed C(sp2)−H Cyanation of Naphthalenes by Using Benzoyl Cyanide as a Cyano Source

AbstractA protocol for the Cu(TFA)2‐catalyzed (TFA=trifluoroacetic acid) picolinamido‐directed C8−H cyanation of naphthalene derivatives with benzoyl cyanide as the cyano source has been developed. A series of 8‐cyano‐1‐(picolinamido)naphthalene derivatives were efficiently obtained in moderate to good yields by using this method. We prepared a total of 22 products, 10 of which have not previously been reported. Benzoyl cyanide was originally employed for the C(sp2)−H cyanation of arenes. The picolinamide moiety served a critical role as the directing group in this cyanation reaction of naphthalenes.

Generation of hazardous methyl azide and its application to synthesis of a key-intermediate of picarbutrazox, a new potent pesticide in flow

Generation and reactions of methyl azide (MeN3) were successfully performed by using a flow reactor system, demonstrating that the flow method serves as a safe method for handling hazardous explosive methyl azide. The reaction of NaN3 and Me2SO4 in a flow reactor gave a MeN3 solution, which was used for Huisgen reaction with benzoyl cyanide in a flow reactor after minimal washing. The resulting 1-methyl-5-benzoyltetrazole serves as a key intermediate of picarbutrazox (IX), a new potent pesticide.

1-Phenyl-2-pentanone and methyl salicylate: new defense allomone components and their content shift during ontogenetic development of the millipede Nedyopus tambanus mangaesinus (Polydesmida: Paradoxosomatidae)

Twelve components were identified in hexane extracts of the polydesmid millipede Nedyopus tambanus mangaesinus (Attems, 1909) and their contents were examined at all stadia of ontogenetic development including two adult conditions (before and after hibernation). Two compounds, 1-phenyl-2-pentanone and methyl salicylate, were newly identified as components of the millipede together with six well-known polydesmoid compounds (benzaldehyde, benzyl alcohol, benzoic acid, benzoyl cyanide, mandelonitrile, and mandelonitrile benzoate) and four phenols (phenol, p-cresol, 2-methoxyphenol, and 2-methoxy-4-methylphenol). Benzaldehyde and benzoyl cyanide were distributed from nymphs at stadium I, and other components started to become detectable at more advanced stadia. The largest content (35.1%) of methyl salicylate was detected in nymphs at stadium I, together with benzaldehyde and benzoyl cyanide, implying the reinforcement of defensive functions during or after egg emergence. The content (18.8%) of 1-phenyl-2-pentanone reached a maximum in hibernated females among all stadia and conditions. Its female-biased distribution at the mating season (ca. 5.7-fold more than in males) implies its sexually related functions.

2+2+2] cycloaddition reactions of α,β-unsaturated N-arylaldimines, acetylenedicarboxylates and 2-arylidene-1,3-indanediones

The domino [2+2+2] cycloaddition reaction of α,β-unsaturated N-arylaldimines, dialkyl acetylenedicarboxylates and 2-arylidene-1,3-indanediones in dry methylene dichloride at room temperature afforded isomeric 2′-styryl-1,2′,3,4′-tetrahydro-1′H-spiro[indene-2,3′-pyridines] in good yields. Under similar conditions, the reaction of α,β-unsaturated N-arylaldimines with two molecules of dialkyl acetylenedicarboxylates resulted in 1-aryl-6-styryl-1,6-dihydropyridine-2,3,4,5-tetracarboxylates. Additionally, the three-component reaction of α,β-unsaturated N-arylaldimines, dimethylacetylenedicarboxylate and benzoyl cyanide also gave isomeric 1,3-oxazine-4,5-dicarboxylates.

Hydrogen peroxide as a new defensive compound in "benzoyl cyanide" producing polydesmid millipedes.

Hydrogen peroxide was newly and simultaneously demonstrated with well-known hydrogen cyanide as a component of defensive secretions of "benzoyl cyanide" producing polydesmid millipedes. Presence of hydrogen peroxide was successively evidenced by Trinder reagent's spray with colorless as well as oily smears of defensive secretions containing benzoyl cyanide and hydrogen cyanide by alkaline picrate paper treatment. Linear correlation was demonstrated between quantities of hydrogen peroxide and benzoyl cyanide. By qualitative assay, seven benzoyl cyanide containing polydesmidans (six species of adults and one species of a nymph at stadium I) tested positive to Trinder reagent, indicative of the presence of hydrogen peroxide (together with hydrogen cyanide), while two cyanogenic species without benzoyl cyanide exhibited negative responses to the reagent. Two types of millipedes were elucidated as species of cyanogenic Polydesmida.

An efficient and catalyst-free synthesis of N-arylidene-2-arylimidazo[1,2-a]pyridine-3-ylamine derivatives via Strecker reaction under controlled microwave heating

AbstractAn efficient one-pot multicomponent reaction of 2-aminopyridine with aromatic aldehydes and either benzoyl cyanide or cyanamide in pyridine under controlled microwave heating afforded N-aryldene-2-arylimidazo[1,2-a]-pyridine-3-ylamine derivatives. The reaction is catalyst free and is of high atom economy.

ChemInform Abstract: Regioselective Acylation of Diols and Triols: The Cyanide Effect.

Central topics of carbohydrate chemistry embrace structural modifications of carbohydrates and oligosaccharide synthesis. Both require regioselectively protected building blocks that are mainly available via indirect multistep procedures. Hence, direct protection methods targeting a specific hydroxy group are demanded. Dual hydrogen bonding will eventually differentiate between differently positioned hydroxy groups. As cyanide is capable of various kinds of hydrogen bonding and as it is a quite strong sterically nondemanding base, regioselective O-acylations should be possible at low temperatures even at sterically congested positions, thus permitting formation and also isolation of the kinetic product. Indeed, 1,2-cis-diols, having an equatorial and an axial hydroxy group, benzoyl cyanide or acetyl cyanide as an acylating agent, and DMAP as a catalyst yield at −78 °C the thermodynamically unfavorable axial O-acylation product; acyl migration is not observed under these conditions. This phenomenon was sub...