14368-40-2

Basic information

• Product Name: (2E)-3-phenylbut-2-enenitrile
• CAS NO: 14368-40-2
• Molecular Formula: C₁₀H₉N
• Molecular Weight: 143.1852
• Mol File: 14368-40-2.mol

Chemical Properties

• Boiling Point: 251.5°C at 760 mmHg
• Flash Point: 105.9°C
• Density: 0.996g/cm³
• Vapor Pressure: 0.0204mmHg at 25°C
• Refractive Index: 1.543
• CAS DataBase Reference: (2E)-3-phenylbut-2-enenitrile(CAS DataBase Reference)
• NIST Chemistry Reference: (2E)-3-phenylbut-2-enenitrile(14368-40-2)
• EPA Substance Registry System: (2E)-3-phenylbut-2-enenitrile(14368-40-2)

Safety Data

• Hazardous Substances Data: 14368-40-2(Hazardous Substances Data)

Usage

Uses

Used in Fragrance and Flavoring Industry:
(2E)-3-phenylbut-2-enenitrile is used as a key ingredient in the creation of fragrances and flavorings due to its distinctive almond-like scent and flavor profile. It contributes to the development of a wide range of products, including perfumes, colognes, and food additives, enhancing their sensory appeal.
Used in Pharmaceutical Synthesis:
In the pharmaceutical industry, (2E)-3-phenylbut-2-enenitrile serves as a precursor in the synthesis of various medicinal compounds. Its unique chemical structure allows for the development of new drugs with potential therapeutic applications, making it an important component in drug discovery and medicinal chemistry.
Used in Organic Chemistry as a Building Block:
(2E)-3-phenylbut-2-enenitrile is utilized in organic chemistry as a versatile building block for the synthesis of a variety of organic compounds. Its carbon-nitrogen triple bond can be manipulated through various chemical reactions, enabling the creation of new molecules with diverse properties and applications.

Upstream product

• 107-14-2 chloroacetonitrile 
• 98-86-2 acetophenone 
• 372-09-8 cyanoacetic acid 
• 4786-20-3 but-2-enenitrile 
• 16978-76-0 1-phenyl-2-(piperidin-1-yl)diazene 
• 1021149-42-7 C₁₅H₁₉NO 
• 16917-35-4 (E)-(1-bromoprop-1-en-2-yl)benzene 
• 120695-48-9 3-cyano-2-phenyl-1-N,N-dimethylamino-1-propene 
• 71-43-2 benzene 
• 75-77-4 chloro-trimethyl-silane 
• 18881-60-2 bis-trimethylsilanyl-acetonitrile 
• 934-10-1 3-phenylbut-1-ene 
• 18293-53-3 2-trimethylsilylacetonitrile 
• 935-02-4 3-Phenyl-2-propynonitrile 

Downstream Products

• 129906-63-4 3-phenyl-2-buten-1-amine 
• 77434-51-6 (Z)-4-Bromo-3-phenyl-but-2-enenitrile 
• 77434-70-9 methyl 4-benzyl-2-(4-chlorophenyl)-3,4-dihydro-2H-1,4-dioxazine-2-acetate 
• 120284-57-3 6-Methyl-4-oxo-6-phenyl-2-thioxohexahydropyrimidine 
• 20132-76-7 3-phenyl-butyronitrile 
• 54518-43-3 3-methyl-3-phenylglutaronitrile 
• 82946-76-7 1-amino-2-cyano-3,4-dimethyl-3,4-diphenylcyclopent-1-ene 
• 72157-10-9 2-(2-Phenyl-1-propenyl)-2-imidazoline 
• 1263066-86-9 (S)-3-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butanenitrile 
• 14368-40-2 (Z)-3-phenylbut-2-enenitrile 
• 77434-68-5 (4-Benzyl-2-phenyl-3,4-dihydro-2H-benzo[1,4]oxazin-2-yl)-acetonitrile 
• 7386-65-4 (2E)-3-phenylbut-2-enamide 
• 1196-67-4 (E)-β-methylcinnamaldehyde 
• 2031-46-1 (R)-3-phenylbutanol 

Relevant articles and documents

Wadsworth-Emmons reaction: The unique catalytic reaction by a solid base

The near-stoichiometric amount of bases is used both in laboratory and industry in Wadsworth-Emmons (WE) reactions, since the by-product, (EtO) 2P(O)OH, formed in the reaction neutralizes the base into an inert salt. A strategy to design, develop, and evolve the recyclable Mg-Al-hydrotalcite-OtBu (HT-OtBu) by the interaction of KOtBu with the calcined hydrotalcite that transforms a well-defined stoichiometric WE reaction into a catalytic one in an effort to minimize the quantum of effluents released and reduce the cost of the process is described here. HT-OtBu is found to be an efficient solid base for WE reactions for the simple synthesis of α,β-unsaturated esters and nitriles for the first time. The HT-OtBu, composed of various ratios of Mg/Al (i.e., 2, 2.5, and 3) and different contents of tBuO - (Mg/Al:3), and their precursors were prepared and well characterized to draw a correlation between structure and reactivity of the hydrotalcites in WE reactions.

Palladium-catalyzed synthesis of nitriles from N-phthaloyl hydrazones

The Pd-catalyzed transformation of N-phthaloyl hydrazones into nitriles involving the cleavage of an N-N bond is reported. The use of N-heterocyclic carbene as a ligand is essential for the success of the reaction. N-Phthaloyl hydrazones prepared from aromatic aldehydes or cyclobutanones are applicable to this transformation, which gives aryl or alkenyl nitriles, respectively.

Sulfur-controlled and rhodium-catalyzed formal (3 + 3) transannulation of thioacyl carbenes with alk-2-enals and mechanistic insights

A rhodium-catalyzed denitrogenative formal (3 + 3) transannulation of 1,2,3-thiadiazoles with alk-2-enals is achieved, producing 2,3-dihydrothiopyran-4-ones in moderate to excellent yields. An inverse KIE of 0.49 is obtained, suggesting the reversibility of the oxidative addition of thioacyl Rh(i) carbenes to alk-2-enals. The late-stage structural modifications of steroid compounds are realized. Moreover, our studies show that thioacyl carbenes have different reactivities to those of α-oxo and α-imino carbenes, and highlight the importance of heteroatoms in deciding the reactivities of heterovinyl carbenes.

Heteroleptic Copper-Based Complexes for Energy-Transfer Processes: E → Z Isomerization and Tandem Photocatalytic Sequences

Energy-transfer processes involving copper complexes are rare. Using an optimized heteroleptic copper complex, Cu(bphen)(XantPhos)BF4, photosensitized E → Z isomerization of olefins is demonstrated. The XantPhos ligand afforded sensitizers with improved catalyst stability, while the bphen ligand lengthened the excited-state lifetime. A series of 25 di- and trisubstituted alkenes underwent photoisomerization, including macrocycles and 1,3-enynes. Cu(bphen)(XantPhos)BF4 could also be employed in a tandem ATRA/photoisomerization process employing arylsulfonyl chlorides, an example of photoisomerization with halide-substituted olefins.

Copper-Photocatalyzed Contra-Thermodynamic Isomerization of Polarized Alkenes

The contra-thermodynamic isomerization of α- and β-substituted cinnamate derivatives catalyzed by the Cu(OAc)2/rac-BINAP complex under blue light irradiation is reported. The use of an oxazolidinone template, which favored the complexation of the copper catalyst to the substrate, allowed the E → Z isomerization of the catalytically formed chromophore under simple and robust reaction conditions in good to excellent ratios. The mechanism of this process based on the transient formation of a chromophore was also studied.

Amination of Carbenium Ions Generated by Directed Protonolysis of Cyclopropane

Directed intramolecular protonolyis of the cyclopropane C-C bond is demonstrated as a strategy to generate carbenium ions. This intermediate can be subjected to amination with nitriles under Ritter reaction conditions. Directing groups such as carbamate, carboxamide, urea, ester, and ketone were found to be efficient for regioselective anti-Markovnikov cleavage of cyclopropane. Depending on the directing group, the amination provided orthogonally protected 1,4-diamine, ?-amino carboxylic, and ?-amino ketone derivatives.

Covalent Immobilization of (?)-Riboflavin on Polymer Functionalized Silica Particles: Application in the Photocatalytic E→Z Isomerization of Polarized Alkenes

The covalent immobilization of the biomimetic, photo-organocatalyst (?)-riboflavin on silica micro- and nanoparticles via atom transfer radical polymerization (ATRP) is disclosed. Given the effectiveness of (?)-riboflavin as a versatile, environmentally benign photocatalyst, an immobilization strategy based on acrylate-linker modification of the catalyst core and controlled polymerization on initiator pre-functionalized silica particles has been developed. Validation of this approach is demonstrated in the E→Z isomerization of a benchmark cinnamonitrile (Z/E up to 88:12) with 0.97 mol % catalyst loading. Characterization of the immobilized photocatalyst supports covalent embedding of the catalyst in the polymeric brushes on the silica particle surface.

Cyclization of Ketones with Nitriles under Base: A General and Economical Synthesis of Pyrimidines

A facile, general, and economical synthesis of diversely functionalized pyrimidines has been realized under basic conditions via the copper-catalyzed cyclization of ketones with nitriles. The reaction proceeds via a novel pathway involving the nitriles ac

Metal-Free Direct C?H Cyanation of Alkenes

A metal-free and direct alkene C?H cyanation is described. Directing groups are not required and the mechanism involves electrophilic activation of the alkene by a cyano iodine(III) species generated in situ from a [bis(trifluoroacetoxy)iodo]arene and tri

Photocatalytic E → Z isomerization of polarized alkenes inspired by the visual cycle: Mechanistic dichotomy and origin of selectivity

Iteratively executed with exquisite spatial and temporal control, the selective isomerization of polarized alkenes underpins a plethora of complex biological processes ranging from natural product biosynthesis through to the mammalian visual cycle. However, nature's proficiency conceals the inherent difficulties in replicating this contrathermodynamic transformation in the laboratory. Recently, we disclosed the first highly Z-selective isomerization of polarized alkenes, employing the cinnamoyl chromophore as a retinal surrogate under UV-irradiation (402 nm) with (-)-riboflavin (Vitamin B2) as an inexpensive, organic photocatalyst (J. Am. Chem. Soc. 2015, 137, 11254-11257). This study was inspired by the propensity of crystalline (-)-riboflavin in the eyes of vertebrates to invert the intrinsic directionality of retinal isomerization. Herein, we extend this methodology to include a bioinspired, catalytic E → Z isomerization of α,β-unsaturated nitriles, thereby mimicking the intermediate Opsin-derived, protonated Schiff base in the visual cycle with simple polarized alkenes. Replacement of the iminium motif by a cyano group is well tolerated and gives an additional degree of versatility for postisomerization functionalization. Broad substrate scope is demonstrated (up to 99:1 Z:E) together with evidence of mechanistic dichotomy via both singlet and triplet energy transfer mechanisms. Kinetic studies, temperature dependent photostationary state correlations and investigation of substituent-based electronic perturbation of the alkene identified polarization combined with increased Z-isomer activation barriers as the selectivity governing factors in catalysis. This investigation demonstrates the importance of internal structural preorganization on photostationary composition and explicates the augmented Z-selectivity upon hydrogen-alkyl exchange at the β-position of the alkene.