49748-63-2

Upstream product

• 873-73-4 4-n-chlorophenylacetylene 
• 13472-08-7 azobis(2-cyanobutane) 
• 105-56-6 ethyl 2-cyanoacetate 
• 105-34-0 methyl 2-cyanoacetate 
• 4553-07-5 ethyl phenylcyanoacetate 
• 42122-34-9 3-(4-chlorophenyl)propioloyl chloride 
• 42122-09-8 3-(4-chlorophenyl)-2-propynamide 
• 613-90-1 benzoyl cyanide 
• 773837-37-9 sodium cyanide 
• 4640-66-8 p-chlorobenzoylacetonitrile 
• 73789-56-7 N-isocyaniminotriphenylphosphorane 
• 1867-38-5 4-chlorobenzylidenemalonodinitrile 
• 4334-74-1 (2E)-2-[(4-methoxyphenyl)methylidene]hydrazine-1-carbothioamide 
• 94794-26-0 (2E)-2-benzylidenehydrazinecarbothioamide 

Downstream Products

• 51791-16-3 3-amino-5-(4-chlorophenyl)isoxazole 
• 127956-39-2 1-<2-cyano-1-(4-chlorophenyl)-ethenyl>-2(1H)-pyridinone 
• 127956-40-5 1-<2-cyano-1-(4-chlorophenyl)-ethenyl>4-phenyl-2(1H)-pyridinone 
• 1174272-07-1 (Z)-3-(4-chlorophenyl)ethynyl-2-propylhex-2-enenitrile 
• 198996-08-6 (Z)-3-(4-chlorophenyl)-3-phenyl-2-propenenitrile 
• 943252-38-8 (Z)-3-chloro-3-(4-chlorophenyl)-2-propenenitrile 
• 127956-41-6 1-<2-cyano-1-(4-chlorophenyl)-ethenyl>-6-methyl-4-phenyl-2(1H)-pyridinone 
• 1395087-83-8 2-(4-chlorophenyl)-5-methylbenzofuran-3-carbonitrile 
• 1395087-46-3 (Z)-3-(4-chlorophenyl)-3-(p-tolyloxy)acrylonitrile 
• 1395087-65-6 (E)-3-(4-chlorophenyl)-3-(p-tolyloxy)acrylonitrile 

Relevant academic research and scientific papers

AlBr3-Promoted stereoselective anti-hydroarylation of the acetylene bond in 3-arylpropynenitriles by electron-rich arenes: Synthesis of 3,3-diarylpropenenitriles

Reactions of 3-arylpropynenitriles (ArC≡CCN) with electron-rich arenes (Ar'H, benzene and its polymethylated derivatives) under the action of aluminum bromide (AlBr3, 6 equiv) at room temperature for 0.5-2 h result in the stereoselective formation of 3,3-

An aerobic and green C-H cyanation of terminal alkynes

This study describes a benign C-H cyanation of terminal alkynes with α-cyanoesters serving as a nontoxic cyanide source. In situ generation of the key copper cyanide intermediate is proposed by a sequence of α-C-H oxidation and copper-mediated β-carbon elimination of α-cyanoesters, releasing the α-ketoester byproduct observed experimentally. The ensuing reaction of copper cyanide with terminal alkynes delivers preferentially cyanoalkynes and surpasses the possible Glaser type dimerization of terminal alkynes or the undesired accumulation of HCN under protic conditions. The presence of the co-oxidant K2S2O8 is crucial to this selectivity, probably by promoting oxidative transmetalation and the resulting formation of the Cu(iii)(acetylide)(CN) intermediate. All the reagents and salts used are commercially available, cheap and nontoxic, avoiding the use of highly toxic cyanide salts typically required in cyanation studies. The scope of this reaction is demonstrated with a set of alkynes and α-cyanoesters. The application of this method to late-stage functionalization of the terminal alkyne group in an estrone derivative is also feasible, showing its practical value for drug design.

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

Synthesis of 1-Cyanoalkynes and Their Ruthenium(II)-Catalyzed Cycloaddition with Organic Azides to Afford 4-Cyano-1,2,3-triazoles

A new method to convert terminal alkynes under relatively mild conditions to 1-cyanoalkynes using in situ formed cyanogen is described. 1-Cyanoalkynes have a higher reactivity than terminal alkynes in the ruthenium(II)-catalyzed regiospecific azide-alkyne cycloaddition to afford 4-cyano-1,2,3-triazoles. A mechanistic proposal different from the one that terminal alkynes adopt under the same reaction conditions is proposed. This work provides a new and convenient two-step sequence to prepare 4-cyano-1,2,3-triazoles from terminal alkynes and organic azides.

One-pot synthesis of propynoates and propynenitriles

An efficient transformation towards propynoates and propynenitriles is herein described. The practical methodology was conducted at low temperature (-78 or -60 °C) in a one-pot manner with the assistance of base rather than any transition metal catalysts. The base-induced protocol exhibits good functional group tolerance (up to 28 examples) and high efficiency (up to 92% yields) towards substituted acetylenes of great synthetic significance, which was also well demonstrated by the gram-scale reactions.

Silver-Mediated Direct C-H Cyanation of Terminal Alkynes with N-Isocyanoiminotriphenylphosphorane

A direct cyanation of terminal alkynes for the synthesis of propionitrile derivatives, with the aid of silver salt using water additive, has been achieved. The cyano source used is N-isocyanoiminotriphenylphosphorane, which is nontoxic, safe, and easy to handle. This protocol is characterized by its operational simplicity, high efficiency with excellent yields, broad substrate scope, and greater functional group tolerance.

Cu-Catalyzed direct cyanation of terminal alkynes with AMBN or AIBN as the cyanation reagent

A Cu-catalyzed direct cyanation of terminal alkynes was reported with broad substrate generality in moderate to high yield, and AMBN (azobisisoamylonitrile)/AIBN (azobisisobutyronitrile) were used as less toxic and effective cyanating sources in open air. Interestingly, addition products were selectively achieved as the major product under the same conditions in argon.

Reaction of arylidenehydrazono-4-aryl-2,3-dihydrothiazole-5-carbonitriles with diethyl acetylenedicarboxylate. Synthesis of (Z)-ethyl 2-[((Z)-2-(E)- arylidenehydrazono)-4-oxo-thiazolidine-5-ylidene]acetates. NMR investigation

(Z)-Ethyl 2-[((Z)-2-(E)-arylidenehydrazono)-4-oxo-thiazolidine-5-ylidene] acetates were synthesized by three different methods: (a) reaction of arylidenehydrazono-4-aryl-2,3-dihydrothiazole-5-carbonitriles with diethyl acetylenedicarboxylate (DEAD) in acetic acid with prolonged reflux, (b) reaction between thiosemicarbazones, 2-arylidenemalononitriles and DEAD under conventional conditions or microwave irradiation, (c) one-pot three-component reaction of thiosemicarbazone derivatives, ylidene and DEAD. The thiazolinone adducts were obtained in good to excellent yields. NMR of the obtained products was investigated.

Copper-catalyzed oxidative transformation of aryl propargylic azides to aryl propiolonitriles

A concise copper(I)-catalyzed oxidative transformation of aryl propargyl azides to aryl propiolonitriles has been developed. Aryl propiolonitrile derivatives can be obtained in moderate to good yields by this strategy. An oxidative Schmidt rearrangement is involved in this transformation. Copyright

Alkynylcyanation of alkynes and dienes catalyzed by nickel

Alkynyl cyanides are found to add across alkynes and 1,2-dienes in the presence of a catalyst prepared in situ from Ni(cod)2, xantphos, and BPh3. A range of functionalized conjugated cis-enynes are obtained with high regioselectivity. The addition reaction across norbornadiene proceeds in the absence of BPh3 to give exo-cis adduct exclusively. A stoichiometric reaction of an alkynyl cyanide, Ni(cod)2, xantphos, and BPh3 gives trans-(xantphos)Ni(CNBPh3)(C{triple bond, long}CSiMe2t-Bu), which is suggested to be a plausible reaction intermediate of the alkynylcyanation reaction.