15673-05-9

Usage

Synthesis Reference(s)

Canadian Journal of Chemistry, 54, p. 1345, 1976 DOI: 10.1139/v76-191

Upstream product

• 558-37-2 tert-butylethylene 
• 74-90-8 hydrogen cyanide 
• 7677-24-9 trimethylsilyl cyanide 
• 119072-55-8 tert-butylisonitrile 
• 150464-47-4 copper(I) cyanide 
• 64-17-5 ethanol 
• 89379-02-2 tert-butylmercury iodide 
• 107-13-1 acrylonitrile 
• 3531-47-3 (t-butyl)trimethylstannane 
• 917-92-0 3,3-Dimethylbut-1-yne 
• 598-98-1 Methyl pivalate 
• 773837-37-9 sodium cyanide 
• 15672-88-5 neohexyliodide 
• 625-28-5 Isovaleronitrile 

Downstream Products

• 10228-99-6 ethyl 4,4-dimethylpentanoate 
• 18925-44-5 4,4-dimethyl-pentan-1-amine 
• 153187-02-1 4,4-dimethylpentanoyl m-chlorobenzoyl peroxide 
• 84784-45-2 N-(4,4-dimethylpentyl)-N'-phenylthiourea 
• 53561-63-0 diethyl (2,2-dimethylpropyl)malonate 
• 561-83-1 5-allyl-5-(2,2-dimethyl-propyl)-pyrimidine-2,4,6-trione 
• 55809-36-4 3-amino-5-tert-butylisoxazole 

Relevant academic research and scientific papers

Pd-Catalyzed intermolecular C-H bond arylation reactions: Effect of bulkiness of carboxylate ligands

A bulky carboxylic acid bearing one 1-adamantylmethyl and two methyl substituents at the α-position is demonstrated to work as an efficient carboxylate ligand source in Pd-catalyzed intermolecular C(sp2)-H bond arylation reactions. The reactions proceeded smoothly under mild conditions, taking advantage of the steric bulk of the carboxylate ligands.

Process for the Catalytic Reversible Alkene-Nitrile Interconversion

The present invention refers to processes for catalytic reversible alkene-nitrile interconversion through controllable HCN-free transfer hydrocyanation.

Efficient nickel-catalyzed hydrocyanation of alkenes using acetone cyanohydrin as a safer cyano source

An active nickel catalyst prepared in situ from a Ni(II) compound, phosphine ligand, and zinc powder was found to be an efficient catalyst system for the hydrocyanation of various alkenes using acetone cyanohydrin as a safer cyano source. The combination of NiCl2·6H2O and 1,3-bis(diphenylphosphino)propane was the most efficient catalyst precursor in DMF. Under the optimized conditions, various styrenes, heterocyclic alkenes, and aliphatic alkenes were converted to their corresponding nitriles in excellent yields.

Influence of bulky substituents on histamine H3 receptor agonist/antagonist properties

Novel derivatives of 3-(1H-imidazol-4-yl)propanol were designed on the basis of lead compounds belonging to the carbamate or ether series possessing (partial) agonist properties on screening assays of the histamine H3 receptor. One pair of enantiomers in the series of α-methyl-branched chiral carbamates was stereoselectively prepared in high optical yields. Enantiomeric purity was checked by Mosher amide derivatives of precursors and capillary electrophoresis of the final compounds with trimethyl-β-cyclodextrin as chiral selector, and was determined to be ≥95%. The novel compounds were investigated in various histamine H3 receptor assays in vitro and in vivo. Some compounds displayed partial agonist activity on synaptosomes of rat brain cortex, whereas others exhibited antagonist properties only. Selected compounds were investigated in [125I]iodoproxyfan binding studies on the human histamine H3 receptor and showed high affinity in the nanomolar concentration range. Under in vivo conditions after oral administration to mice, some of the compounds exhibited partial or full agonist activity in the brain at low dosages. The (S)-enantiomer of one pair of chiral carbamates (9) proved to be the eutomer; thus, the (S)-enantiomer was selected for further pharmacological studies. In a peripheral in vivo test model in rats, measuring the level of inhibition of capsaicin-induced plasma extravasation, (S)-9 again proved its high oral agonist potency with full intrinsic activity (ED50 values of 0.07-0.1 mg/kg depending on tissue).

Electron-Transfer-Photosensitized Conjugate Alkylation

Photoinduced electron transfer (PET) from an aliphatic donor to a sensitizer and fragmentation of the radical cation leads to alkyl radicals. Radical alkylation of electron-withdrawing substituted alkenes and alkynes has been obtained in this way, and its scope has been explored. Effective sensitizers are tetramethyl pyromellitate (TMPM), 1,4-dicyanonaphthalene (in combination with biphenyl, DCN/BP), and 1,2,4,5-tetracyanobenzene. Radical precursors are tetraalkylstannanes, 2,2-dialkyldioxolanes, and, less efficiently, carboxylic acids. Steady-state and flash photolysis experiments show that escape out of cage of radical ions is the main factor determining the yield of radical formation. This is efficient with triplet sensitizers such as TMPM, while with singlet sensitizers, the use of a "cosensitizer" is required, as in the DCN/BP system. Radical cations containing primary alkyl radicals escape and fragment more efficiently than those containing tertiary radicals. The thus-formed radicals are trapped by electron-withdrawing substituted alkenes, and the relative efficiency is determined by the rate of radical addition, in accord with the proposed mechanism. Among the alkynes tested, only dimethyl acetylenedicarboxylate reacts, and the order of radical reactivity is different. It is suggested that a different mechanism operates in this case and involves assistance by the alkyne to the radical cation fragmentation.

tert-Butylation of α,β-unsaturated nitriles by tert-butylmercury halides in the presence of iodide ion

Iodide ion promotes the free radical addition of t-BuHgI to acrylonitrile to form t-BuCH2CH(CN)HgI. A facile reaction of the adduct 1-cyanoalkyl radical with t-BuHgI2- is indicated. Further promotion is observed in the pre

Radical addition to alkenes via electron transfer photosensitization

A method for radical addition to alkenes is reported which is based on the photosensitized oxidation of a tetraalkylstannane by an excited acceptor (A*), fragmentation of the radical cation, and addition of the thus formed radical to an electron-withdrawing substituted alkene (acrylonitrile and dimethyl maleate). Aromatic nitriles and esters can be used as the electron acceptors, and they are chosen in such a way that their radical anion (A?-) reduces the adduct (and not the educt) radical. In this way the adduct radical is reduced and protonated to yield the end product, and the acceptor functions as a nonconsumed electron transfer sensitizer. In several cases the alkylation occurs more efficiently in the presence of a secondary donor (phenanthrene or biphenyl). However, when the acceptor is too easily reduced in the ground state (as with 1,2,4,5-benzenetetracarbonitrile), coupling of the adduct radical with A?- competes with its reduction.

Reductive alkylation of electronegatively-substituted alkenes by alkylmercury halides

Photolysis of alkylmercury halides in the presence of electronegatively-substituted 1-alkenes yields adduct radicals [RCH2CH(EWG).] that in some cases react with RHgX to form RCH2CH(HgX)(EWG), e.g., EWG = (EtO)2PO or PhSO2. When the EWG is carbonyl or cyano, the resonance stabilized adduct radicals fail to react with the alkyl mercury halide. In these cases photolysis with RHgCl/KI in Me2SO leads to the adduct mercurial via reaction of the adduct radicals with RHgI2-. The reactions of tertiary-enolyl adduct radicals are inefficient with RHgX/KI, and disproportionation of the adduct radicals is the major reaction pathway. For secondary- or tertiary-adduct radicals the reductive alkylation products are formed in excellent yield by reaction with RHgCl and silyl hydrides in Me2SO solution in a process postulated to involve RHgH as an intermediate. The relative reactivities of a number of α,β-unsaturated systems toward t-Bu. have been measured by competitive techniques. The results demonstrate a high reactivity of s-cis enones relative to the s-trans conformers.

PHOSPHINE NICKEL COMPLEX AS CATALYST IN REACTIONS OF ORGANIC BROMIDES RBr WITH α,β-UNSATURATED KETONES, NITRILES, AND ESTERS. CONJUGATE ADDITION OF R GROUP AND H ATOM ACROSS THE C=C BOND

Reactions of organic bromides, particularly of secondary and tertiary alkyl bromides, with α,β - unsaturated carbonyl compounds and acrylonitryle in the presence of the catalytic system nickel complex-zinc result in formation of products of conjugate addition of the organic moiety of the bromide and a hydrogen atom across the C=C double bond of the unsaturated substrate.

Radical-chain Decomposition of Cyclohexa-1,4-diene-3-carboxylates and 2,5-Dihydrofuran-2-carboxylates

3-Methylcyclohexa-1,4-diene-3-carboxylates and 2-methyl-2,5-dihydrofuran-2-carboxylates decompose to generate free alkyl radicals which have been incorporated into chain reactions producing alkyl bromides, alkene adducts and ring-closure products.