22031-56-7

Upstream product

• 22629-43-2 1-Cyan-1-hydroxy-hexylphosphonsaeure-diaethylester 
• 74-90-8 hydrogen cyanide 
• 693-02-7 hex-1-yne 
• 544-92-3 copper(I) cyanide 
• 110-62-3 pentanal 
• 372-09-8 cyanoacetic acid 
• 16640-68-9 cyanomethylene triphenylphosphorane 
• 592-41-6 1-hexene 
• 107-13-1 acrylonitrile 
• 142-61-0 Hexanoyl chloride 
• 6281-07-8 hexanoyl-phosphonic acid diethyl ester 
• 16486-84-3 2-bromoheptanal 
• 104413-32-3 7-bromo-2-heptenenitrile 
• 143546-36-5 1-<<(6-cyano-5-hexenyl)carbonyl>oxy>-2-(1H)-pyridinethione 

Relevant academic research and scientific papers

Acceptor, Donor, and Captodative Stabilization in Transition States of 5-hexen-1-yl Radical Cyclizations

Rate constants and activation parameters for cyclization of the 6-substituted hex-5-en-1-yl radicals (6-cyano (1b), 6-methoxy (1c), and 6-cyano-6-methoxy (1d)) have been determined.At 50 deg C, the rate constants for cyclization to the corresponding cyclopentylmethyl radicals are 1.65 x 10E8, 1.45 x 10E6, and 2.49 x 10E8 s-1, respectively.The rate accelerations for the cyclizations of 1b-d relative to that of the parent radical, hex-5-en-1-yl (1a), are discussed in terms of the substituents' perturbations of the highest occupied (HOMO) and lowest unoccuped molecular orbital (LUMO) of the alkene moiety.The large rate accelerations of 1b and 1d (275-fold and 415-fold, respectively, at 50 deg C) result primarily from increased interaction of the semioccupied molecular orbital (SOMO) with the alkene LUMO, whereas the small rate acceleration of 1c results from increased SOMO-HOMO interaction.Radicals 1b and 1d were found to have looser, hence earlier, transition states for cyclization than do 1a and 1c.Comparison of the Ea's for 1b-d relative to that for 1a indicates that there is a slight extra stabilization (captodative effect) in the transition state for cyclization of 1d.

Synthesis of α,β-unsaturated aldehydes and nitriles via cross-metathesis reactions using Grubbs' catalysts

A series of α,β-unsaturated aldehydes and nitriles of significant interest in the fragrance industry have been prepared using Grubbs' catalysts in cross-metathesis reactions of electron-deficient olefins (i.e., acrolein, crotonaldehyde, methacrolein, and acrylonitrile) with various 1-alkenes, including 1-decene, 1-octene, 1-hexene and 2-allyloxy-6-methylheptane. The latter is of particular interest, as it has not previously being used as a substrate in cross-metathesis reactions and allows access to valuable intermediates for the synthesis of new fragrances. Most reactions gave good selectivity of the desired CM product (≥90%). Detailed optimisation and mechanistic studies have been performed on the cross-metathesis of acrolein with 1-decene. Recycling of the catalyst has been attempted using ionic liquids.

3-[4-(7H-PYRROLO[2,3-D]PYRIMIDIN-4-YL)-1H-PYRAZOL-1-YL]OCTANE- OR HEPTANE-NITRILE AS JAK INHIBITORS

The present invention relates to the Janus kinase (JAK) inhibitors 3-[4-(7H-pyrrolo[2,3- d]pyrimidin-4-yl)-1H-pyrazol-l-yl]octanenitrile or 3-[4-(7H-pyrrolo[2,3-d]pyrimidin-4-y1)-1H- pyrazol-l-yl]heptanenitrile, as well as its compositions and methods of use, which is useful in the treatment of JAK-associated diseases including, for example, inflammatory and autoimmune disorders, skin disorders, cancer, and other diseases.

ALPHA, BETA, UNSATURATED NITRILES AS FRAGRANCES

The use of short chain α,β-unsaturated nitriles as flavour and fragrance ingredient and flavour and fragrance applications comprising them.

Highly active phosphine-free carbene ruthenium catalyst for cross-metathesis of acrylonitrile with functionalized olefins

The carbene ruthenium complex [1,3-bis(2,6-dimethylphenyl)-4,5- dihydroimidazol-2-ylidene](C5H5N)2(Cl) 2RuCHPh (8) was prepared by the reaction of [1,3-bis (2,6-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene](PPh3)(Cl) 2RuCHPh (7) with pyridine and used as a highly effective catalyst for the cross-metathesis of acrylonitrile with various functionalized olefins.

The Cyanation of Vinyl Halides with Alkali Cyanides Catalyzed by Nickel(0)-Phosphine Complexes Generated In Situ: Synthetic and Stereochemical Aspects

The cyanation of β-bromostyrenes catalyzed by Ni(PPh3)n, which was generated in situ from NiBr2(PPh3)2-Zn-PPh3 (Ni:Zn:P=1:3:2 molar ratio), was at first examined with various MCN (M=K, Na)-dipolar aprotic solvent systems by several procedures.The presence of excess cyanide ion inhibited the reaction.However, when the KCN-DMF system with some intermediate cyanide solubility was used, the nitriles were obtained in high yields and high stereoselectivity at 50 deg C by almost all of the procedures attempted.On the contrary, the KCN-HMPA and KCN-MeCN systems with cyanide solubilities accelerated the coupling of the halides to inhibit the cyanation, and in general the NaCN-DMF and NaCN-HMPA systems with high cyanide solubilities needed to reduce Ni(II) before adding MCN in order to make the catalytic reaction start.Vinyl halides such as 1- and 2-halo (Cl, Br)-1-alkenes, 2-bromo-2-butenes, 3-bromo-3-hexenes, and 1-chlorocyclohexene were also cyanated using suitable procedures and MCN-solvent systems to give the corresponding nitriles in high yields and fair-to-good stereoselectivities.However, with (Z)-2-ethoxy-1-bromoethene the (E)-nitrile, though its selectivity markedly varied with the reaction temperature, was obtained as the main product.The cyanation of ethyl (Z)-β-bromoacrylate and ethyl α-bromoacrylate was unsuccessful due to polymerization.

Picosecond radical kinetics. Rate constants for reaction of benzeneselenol with primary alkyl radicals and calibration of the 6-cyano-5-hexenyl radical cyclization

The cyclopropylcarbinyl radical ring opening was used as a radical clock to determine rate constants for benzeneselenol trapping in THF and in toluene. Hydrogen atom transfer trapping from PhSeH appeared to be partially diffusion controlled. An operational Arrhenius function for trapping in THF is log (kT·M s) = 11.03 - 2.21/2.3RT. The recommended function for PhSeH trapping in other low-viscosity organic solvents is log (kT·M s) = 10.87 - 2.10/2.3RT. The rate constant for trapping at 25°C is 2.1 × 109 M-1 s-1. The kinetic values are expected to apply for PhSeH trapping of simple primary alkyl radicals. As a check on this assumption, cyclization of the 6-cyano-5-hexenyl radical (9), produced from the corresponding PTOC ester radical precursor, was calibrated with PhSH and PhSeH trapping. The two trapping agents gave essentially equivalent results. The cyclizations of both (E)- and (Z)-9 are described by log (kr·s) = 11.0 - 3.8/2.3RT. This fast rearrangement (kr = 1.6 × 108 s-1 at 25°C) could prove to be useful as a radical clock for timing fast second-order processes.

A New Simple Synthesis of Isomerically Pure α,β-Unsaturated Nitriles via Hydroboration of Alkynes

Terminal alkynes are converted into (E)-1-cyanoalk-1-enes in good yields via hydroboration followed by reaction with copper(I) cyanide and copper(II) acetate in the presence of a small amount of water, in hexamethylphosphoric triamide.

Therapeutically active 3-amino-1-halogenated phenyl-2-pyrazolines and their C4 and C5 analogs

A method of meliorating the inflammation and/or the progressive joint deterioration characteristic of arthritic disease, preventing the onset of asthmatic symptoms and allergic diseases, treating pain or treating bacterial and fungal infections in mammals using 3-amino-1-halogenated phenyl-2-pyrazolines and their C4 and C5 analogs.

The Stereochemistry of Organometallic Compounds. XXIV. Nickel(0)-Catalysed Additions of Hydrogen Cyanide to Alkynes

Hydrogen cyanide will add to alkynes bearing a wide range of substituents with cis stereospecificity, high regioselectivity, and in moderate-to-good yields, when the reaction is catalysed by tetrakis-(triphenyl phosphite)nickel(0).