104-61-0Relevant articles and documents
O-H hydrogen bonding promotes H-atom transfer from α C-H bonds for C-alkylation of alcohols
Jeffrey, Jenna L.,Terrett, Jack A.,MacMillant, David W.C.
, p. 1532 - 1536 (2015)
The efficiency and selectivity of hydrogen atom transfer from organic molecules are often difficult to control in the presence of multiple potential hydrogen atom donors and acceptors. Here, we describe the mechanistic evaluation of a mode of catalytic activation that accomplishes the highly selective photoredox a-alkylation/lactonization of alcohols with methyl acrylate via a hydrogen atom transfer mechanism. Our studies indicate a particular role of tetra-n-butylammonium phosphate in enhancing the selectivity for α C-H bonds in alcohols in the presence of allylic, benzylic, α-C=O, and α-ether C-H bonds.
Mercapturic Acid Conjugates as Urinary End Metabolites of the Lipid Peroxidation Product 4-Hydroxy-2-nonenal in the Rat
Alary, Jacques,Bravais, Fabienne,Cravedi, Jean-Pierre,Debrauwer, Laurent,Rao, Dinesh,Bories, Georges
, p. 34 - 39 (1995)
4-Hydroxy-2-nonenal (HNE), an aldehyde end product of lipid peroxidation in biological systems, is capable of producing a range of powerful biological effects. Despite its biological relevance, the metabolic fate of this aldehyde is unknown in vivo. This study examines the urinary excretion of HNE in the rat and the nature of metabolites formed. Following iv administration of HNE, the majority of the dose appeared in urine (67.1 percent after 48 h). The radio-HPLC metabolic profile showed that no unchanged parent compound was detected in urine whereas at least four metabolites were present, most of them corresponding to mercapturic acid conjugates. Two major pathways were involved in the biotransformation of HNE in vivo: (i) reduction/oxidation of the aldehyde group, and (ii) conjugation to endogenous glutathione leading to mercapturic acid conjugates in urine. These end products were isolated by HPLC and identified by mass spectrometry as HNE mercapturic acid, 1,4-dihydroxynonene mercapturic acid, 4-hydroxynonenoic mercapturic acid, and the corresponding lactone.
Conjugate Addition of gem-Borazirconocene Alkenes to Michael Acceptors
Pereira, Schubert,Srebnik, Morris
, p. 1805 - 1808 (1995)
gem-Borazirconocenes, 1, readily add across Michael acceptors in the presence of Cu(I)Br*SMe2, to afford 1,4-addition products in good to excellent yilds.In the case of cycloalkenones diastereomers are produced, with the anti product favored.The selectivity with cyclopentenone is high (9:1), while with cyclohexenone it is less (3:1).In the present context, gem-borazirconocene alkanes can be regarded as α-hydroxyl anion equivalents.
Efficient and convenient preparation of γ-nonalactone, with use of a Dean-Stark trap to remove methanol
Tu, Song,Shen, Youyu,Dong, Wan,Yang, Jing,Zhang, Chen,Ye, Liyi
, p. 1613 - 1618 (2014)
We describe the development of an efficient and convenient process for preparation of γ-nonalactone. The synthesis was accomplished by free-radical addition of methyl acrylate and n-hexanol. A Dean-Stark trap filled with water and n-hexanol was used to remove the methanol generated during the process. Orthogonal experiments were performed to optimize the reaction conditions, and the desired product, γ-nonalactone, was produced in better than 70 % yield.
A new coupling reaction between β-lactones and electrophiles mediated by a SmI2/(NiI2 catalytic) system
Machrouhi, Fouzia,Namy, Jean-Louis
, p. 11111 - 11122 (1998)
β-lactones react with ketones aldehydes and imines in the presence of a SmI2/(NiI2 catalytic) system to afford substituted tetrahydrofuranones and pyrrolidinones.
Carbon-Carbon Bond Formation by the Use of Chloroiodomethane as a C1 Unit. II. The Preparation and Synthetic Application of 1-Chloro-3-iodoheptane
Miyano, Sotaro,Hokari, Hiroshi,Umeda, Yoshiharu,Hashimoto, Harukichi
, p. 770 - 774 (1980)
Terminal alkenes, R-CH=CH2 (R=Et, n-Pr, n-Bu, N-Hex), were readily transformed into 1-chloro-3-iodoalkanes by the AIBN-induced free radical addition of chloroiodomethane.Thus, 1-chloro-3-iodoheptane was obtained from 1-hexene in an 88percent yield; this in turn was allowed to react with dialkyl malonates in the presence of alkoxides in alcohols to give dialkyl 2-butylcyclobutane-1,1-dicarboxylates and dialkyl (E)-3-octene-1,1-dicarboxylates (7), either of which could be obtained preferentially by the choice of the experimental parameters.The olefinic product, 7, was further utilized for the synthesis of (E)-5-decenyl acetate and/or 1,4-nonanolide.
Characterisation of a by-product formed in the industrial production of γ-nonalactone
Chen, Haitao,Wang, Dan,Liu, Yongguo,Zhang, Guoying,Wang, Tianyi,Wang, Yang,Yang, Shaoxiang,Sun, Baoguo,Tian, Hongyu
, p. 141 - 143 (2016)
Distillation residues from the industrial production of γ-nonalactone, which is accomplished by reaction of hexanol with methyl acrylate initiated by t-butyl peroxide, yielded a by-product which we deduced to be 4-(methoxycarbonylethyl)-γ-nonalactone. The possible pathway of formation of this by-product is discussed.
Synthesis of (±)-4-alkanolides from pent-4-enoic acid
Ugurchieva,Lozanova,Zlokazov,Veselovsky
, p. 657 - 659 (2008)
Synthesis of (±)-4-hexanolide, (±)-4-nonanolide, and (±)-4-dodecanolide, racemic forms of the insect signal substances, has been accomplished by cationic cyclization of pent-4-enoic acid and its amide in the key step.
Preparation method of coconut aldehyde
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Paragraph 0017-0022, (2021/02/10)
The invention discloses a preparation method of coconut aldehyde. The method comprises the following steps: step 1, mixing n-hexanol, acrylic acid and di-tert-butyl peroxide with uniform stirring, andcarrying out heat insulation on an obtained mixed solution; step 2, mixing n-hexanol with a beta molecular sieve catalyst, performing stirring, heating and heat preservation in a nitrogen environment, dropwise adding the mixed solution obtained in the step 1 at a constant speed during the heat preservation, continuously separating out byproducts including water, tert-butyl alcohol and methanol inthe reaction process, and continuously performing reacting for 1-2 hours after dropwise adding is finished; and step 3, after the reaction is finished, performing cooling, recovering low-boiling-point substances and n-hexanol in the reaction solution in vacuum, performing cooling after the recovery is finished to obtain a crude product, and carrying out reduced pressure distillation on the crudeproduct to obtain a coconut aldehyde product. The novel environment-friendly high-efficiency beta molecular sieve catalyst adopted by the invention shows good catalytic activity and selectivity in coconut aldehyde synthesis, can be repeatedly used, can be cyclically regenerated in manners of high-temperature roasting and the like, and is high in reaction yield, and the technological process is easy to control, and is beneficial to forming industrial large-scale production.
Identification of Bond-Weakening Spirosilane Catalyst for Photoredox α-C?H Alkylation of Alcohols
Sakai, Kentaro,Oisaki, Kounosuke,Kanai, Motomu
supporting information, p. 337 - 343 (2019/12/24)
The development of catalyst-controlled site-selective C(sp3)?H functionalization is a current major challenge in organic synthesis. This paper describes DFT-guided identification of pentavalent silicate species as a novel bond-weakening catalyst for the α-C?H bonds of alcohols together with a photoredox catalyst and a hydrogen atom transfer catalyst. Specifically, Martin's spirosilane accelerated α-C?H alkylation of alcohols. (Figure presented.).
