3508-99-4Relevant academic research and scientific papers
Hydrodecyanation of Secondary Alkyl Nitriles and Malononitriles to Alkanes using DiMeImd-BH3
Kawamoto, Takuji,Oritani, Kyohei,Kawabata, Atsushi,Morioka, Tsubasa,Matsubara, Hiroshi,Kamimura, Akio
, p. 6137 - 6142 (2020/05/22)
The decyanation of secondary aliphatic nitriles and the 2-fold decyanation of malononitriles leading to alkanes in the presence of 1,3-dimethylimidazol-2-ylidene borane (diMeImd-BH3) are reported. These reactions proceed via a radical mechanism that involves the addition of a borane radical to the nitrile to form an iminyl radical, followed by cleavage of a carbon-carbon bond. Theoretical calculations suggest that the β-cleavage of these iminyl radicals, which affords NHC-BH2CN and the corresponding alkyl radicals, is the rate-determining step in this reaction.
Lithium naphthalenide-induced reductive alkylation and addition of aryl-and heteroaryl-substituted dialkylacetonitriles
Tsao, Jing-Po,Tsai, Ting-Yueh,Chen, I-Chia,Liu, Hsing-Jang,Zhu, Jia-Liang,Tsao, Sheng-Wei
scheme or table, p. 4242 - 4250 (2011/02/25)
Lithium naphthalenide (LN)-induced reductive alkylation/addition reactions of aryl-, pyridyl-, and 2-thienyl-substituted dialkylacetonitriles have been investigated. Upon treatment with LN in THF at -40°C, both aryl and pyridyl precursors could undergo the reductive decyanation smoothly, and the in situ generated carbanions could be readily trapped by alkyl halides, ketones, aldehydes, or even oxygen to afford a wide range of functionalized aromatic derivatives bearing a newly established quaternary carbon. To effect the desired reductive alkylation of 2-thienyldialkylacetonitriles, a much lower temperature such as -100°C was required. Also with these substrates, an interesting ring-opening/S-alkylation process was observed when the reductive alkylation were performed at -78°C to give 1-alkylsulfanyl-1,3,4-trienes. A mechanistic discussion is given for this observation.
Organic catalyst with enhanced enzyme compatibility
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, (2008/06/13)
This invention relates to cleaning compositions comprising organic catalysts having enhanced enzyme compatibility and processes for making and using such cleaning compositions.
Inhibitors of Acyl-CoA:Cholesterol Acyltransferase. 4. A Novel Series of Urea ACAT Inhibitors as Potential Hypocholesterolemic Agents
Trivedi, Bharat K.,Holmes, Ann,Stoeber, Terri L.,Blankley, C. John,Roark, W. Howard,et al.
, p. 3300 - 3307 (2007/10/02)
We have synthesized a series of N-phenyl-N'-aralkyl and N-phenyl-N'-(1-phenylcycloalkyl)ureas as inhibitors of acyl-CoA:cholesterol acyltransferase (ACAT).This intracellular enzyme is thought to be responsible for the esterification of dietary cholesterol; hence inhibition of this enzyme could reduce diet-induced hypercholesterolemia.For this series of compounds, the in vitro ACAT inhibitory activity was improved by increasing the bulk of the 2,6-substituents on the phenyl ring.Additionally, we found that spacing of the aromatic rings was critical for ACAT inhibitory activity.A phenyl ring five atoms away from the requiste 2,6-diisopropylphenyl moiety was optimal for in vitro activity.Substitution α to the N'-phenyl moiety enhanced in vitro potency.In the case of phenylcycloalkyl ureas, ACAT inhibitory activity was independent of the size of the cycloalkyl ring.From this series of analogs, compound 25, which had excellent in vitro potency for inhibiting ACAT, was found to lower plasma cholesterol by 73percent in vivo when administrated in the diet at 50 mg/kg in an animal model of hypercholesterolemia.In this model, compound 25 lowered plasma cholesterol dose dependently and was as efficacious as the Lederle ACAT inhibitor CL 277082.
The efficiency of diphenylalkylsulfonium salts as alkylating agents
Badet, Bernard,Julia, Marc,Lefebvre, Christian
, p. 431 - 434 (2007/10/02)
A series of the title reagents have been used for the alkylation of a number of nucleophiles including iodide, cyanide, thiocyanate and fluoride ions as well as ethyl acetoacetate, phenylacetonitrile and a variety of nitrogen heterocyclic compounds.The results compared favorably with literature methods.
THE EFFECT OF POLYMER SWELLING ON ALKYLATION OF PHENYLACETONITRILE BY POLYMER-SUPPORTED PHASE TRANSFER CATALYSIS
Balakrishnan, Thayikkannu,Ford, Warren T.
, p. 4377 - 4380 (2007/10/02)
Alkylation of phenylacetonitrile by 1-bromobutane with 50percent sodium hydroxide and a polymer-supported phase transfer catalyst proceeds fastest when the phenylacetonitrile is added to the mixture before the 1-bromobutane.
Wanderungstendenzen cyclischer, polycyclischer und methylverzweigter Alkylreste bei der Beckmann-Umlagerung
Langhals, Heinz,Ruechardt, Christoph
, p. 3831 - 3854 (2007/10/02)
The migration aptitudes of polycyclic bridgehead groups, cycloalkyl groups as well as of β-, γ- and δ-branched alkyl groups in the Chapman variant of the Beckmann rearrangement were determined.From these data it is concluded that at transition state 2 the migrating group is not resembling a planarised carbenium ion R+, but rather a pentacoordinated carbonium ion structure.Because only small geometrical changes occur in the migrating group vertical stabilisation of charge at transition state is believed to have significant influence on the migration aptitudes.
