• Title/Summary/Keyword: Alkylation reaction

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Photochemical Synthesis of Aspartylphenylalanyl Methyl Ester (광 알킬화 반응에 의한 Aspartylphenylalanyl Methyl Ester의 합성)

  • Sang Chul Shim;Kyu Ho Chae
    • Journal of the Korean Chemical Society
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    • v.19 no.5
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    • pp.367-374
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    • 1975
  • Glycine residue in N-X-glycylphenylalanine methyl ester(X = trifluoroacetyl or acetyl) was converted into aspartic acid derivative by a photoalkylation reaction. The reaction was induced with 350 nm lamp using a combination of diacetyl/di-t-butyl peroxide (DBP) as the photoinitiator, and acetic anhydride as the alkylating agent. In the thermal reaction with DBP and acetic anhydride, the same alkylation reaction of the dipeptide was observed. From this thermal alkylation reaction the photoalkylation reaction is also thought to undergo via free radical mechanism.

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Synthesis of 4-Phenyltetralone Derivatives and Reaction Mechanism

  • Kwon, Soon-Kyoung;Park, Young-Nam
    • Archives of Pharmacal Research
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    • v.23 no.4
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    • pp.329-331
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    • 2000
  • 4-(p-Chlorophenyl)tetralone (6) and 7-chloro-5-(p-chlorophenyl)tetralone (9) are key intermediates for the development of benzazepinone derivative haftens. These compounds could be synthesized from 4-phenyltetralone derivatives by triflic acid catalyzed Friedel-Crafts reaction. The reaction mechanism of Friedel-Crafts alkylation/acylation with lactones in triflic acid is presented. According to our tentative research, ring opening of protonated lactone (2) occurs in alkyl cleavage and the rate of the reaction is not dependent on concentration of triflic acid. So, alkylation of lactone in Friedel-Crafts reaction is presumed to be $A_{AL}$ 1. In second step, intramolecular acylation of the intermediates 4 to 6, 4 can be transformed to a triflic acid-carboxylic anhydride and then the cyclization is undergone after leaving of the triflate anion.

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Solvent Free N-Heterocyclization of Primary Amines to N-Substituted Azacyclopentanes Using Hydrotalcite as Solid Base Catalyst

  • Dixit, Manish;Mishra, Manish;Joshi, P.A.;Shah, D.O.
    • Bulletin of the Korean Chemical Society
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    • v.33 no.5
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    • pp.1457-1464
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    • 2012
  • An ecofriendly catalytic route for selective synthesis of $N$-substituted azacyclopentanes, nitrogen-containing heterocyclic intermediates for many bioactive compounds, was established by carrying out $N$-heterocyclization (di $N$-alkylation) of primary amines with 1,4-dichloro butane (as dialkylating agent) using catalytic amount of hydrotalcite as solid base catalyst. The hydrotalcite was found to be efficient solid base catalyst for di $N$-alkylation of different primary amines (aniline, benzyl amine, cyclohexyl amine and n-butyl amine) giving 82 to 96% conversion (at optimized reaction condition) of 1,4-dichloro butane and > 99% selectivity of respective $N$-substituted azacyclopentanes within 30 min. under solvent free condition. The reaction parameters significantly influence the conversion of 1,4-dichloro butane to $N$-substituted azacyclopentanes. The nature of substituent present on amino group affects the reactivity of amine substrates for di $N$-alkylation reaction with 1,4-dichloro butane. The 1,4-dichloro butane was found to be highly reactive alkylating agent for di $N$-alkylation of amines as compared to 1,4-dihydroxy butane. The reusability of the catalyst and its chemical stability in the reaction was demonstrated.

Gasoline Desulfurization by Catalytic Alkylation over Methanesulfonic Acid

  • Wu, Xiaolin;Bai, Yunpeng;Tian, Ying;Meng, Xuan;Shi, Li
    • Bulletin of the Korean Chemical Society
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    • v.34 no.10
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    • pp.3055-3058
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    • 2013
  • Methanesulfonic acid (MSA) was used as catalyst to remove trace organic sulfur (thiophene) from Fluid Catalytic Cracking gasoline (FCC) via alkylation with olefins. The reactions were conducted in Erlenmeyer flask equipped with a water-bath under atmospheric pressure. The influence of the temperature, the reaction time, and the mass ration of MSA were investigated. After a 60 min reaction time at 343 K, the thiophene conversion of 98.7% was obtained with a mass ration of MSA to oil of 10%. The catalyst was reused without a reactivation treatment, and the thiophene conversion reached 92.9% at the third time. The method represents an environmentally benign route to desulfur, because MSA could easily be separated from the reaction mixture via decantation and it could be reused.

Single-molecule Alkylation of Isoparaffin Using Peroxide Initiator for Making Synthetic Lubricant (합성 윤활유 제조를 위한 퍼옥사이드계 개시제를 이용한 이소파라핀의 단독 알킬레이션)

  • Khadka, Roshan;Lee, Sang-Woo;Kim, Yong-Woon;Ryu, Jae-Wook;Yim, Jin-Heong
    • Polymer(Korea)
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    • v.38 no.4
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    • pp.496-501
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    • 2014
  • Polyalphaolefin (PAO) is a synthetic lubricant that is superior to mineral-based lubricants in terms of physical and chemical characteristics such as low pour point (PP), and high viscosity index (VI). This paper first reports a novel preparation route for a synthetic lubricant via alkylation of isoparaffins using a peroxide initiator without olefin. Alkylation of three kinds of isoparaffins such as i-$C_{16}$, i-$C_{18}$, and i-$C_{23}$ as well as alkylation of i-$C_{18}$ with 2-pentene using di-tert butyl peroxide initiator were conducted under various conditions to confirm alkylation reaction from isoparaffins themselves i.e; Single-molecule alkylation. Various properties of each alkylates (VI and PP) were investigated as a synthetic lubricant. Single-molecule alkylation made from i-$C_{16}$ a,nd i-$C_{18}$ showed ultra high VI (>140) and low PP (< $-30^{\circ}C$).

Friedel-Crafts Type alkylation of 1,2,3,4,5,6,7,8,-Octahydroanthracene with Vinylchlorosilanes:Synthesis of Mono,Bis[2-(chlorosilyl)ethyl]-1,2,3,4,5,6,7,8,-Octahydroanthracenes

  • Gong, Seong-Deok;Lee, Chang-Yeob;Yoo, Bok-Ryul;Lee, Myong-Euy;Jung, Il-Nam
    • Bulletin of the Korean Chemical Society
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    • v.23 no.9
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    • pp.1213-1221
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    • 2002
  • Friedel-Crafts alkylation reaction of an isomeric mixture of 1,2,3,4,5,6,7,8- (2) and 1,2,3,4,5,6,7,8-octahydrophenanthrene (2') with excess vinylchlorosilanes such as vinyl(methyl)dichlorosilane (1a) and vinyltrichlorosilane (1b) in the presence of aluminum chloride catalyst at 80 $^{\circ}C$ gives only one dialkylated products, 9,10-bis[2-(chlorosilyl)ethyl]-1,2,3,4,5,6,7,8-octahydroanthrenes [(Cl2XSiCH2CH2)2C14H16: X = Me (4a), Cl (4b)] in good yields, but 9,10-bis[2-(chlorosilyl)ethyl]-1,2,3,4,5,6,7,8-octahydrophenanthrenes are not obtained. However, monoalkylation of 2 with 1 affords a mixture of both isomeric compounds, 9-[2-(chlorosilyl)ethyl]-1,2,3,4,5,6,7,8-octahydroanthracenes 3 and -phenanthrenes 3'. The yield of product 3' is always higher than that of 3. When a mixture of 3 and 3' is alkylated again with 1, only product 4 without phenanthrene type compounds is obtained, indicating that the isomerizations between 2 and 2', or 3 and 3'occur under the alkylation condition. The alkylation with dimethylvinylchlorosilane or trimethylvinylsilane did not proceed. The structure of 4a is determined by X-ray single crystal diffraction analysis.

Synthesis of an Intermediate for Carbaprostacyclin: Stereoselective Synthesis of 1-Alkoxy-3-benzenesulfonyl-3-cyano-4-ethenyl cyclopentane (카바프로스타싸이클린 중간체의 합성 : 1-Alkoxy-3-benzenesulfonyl-3-cyano-4-ethenyl cyclopentane의 입체선택적 합성)

  • 서영거;정재경;구본암;최영기;조윤상
    • YAKHAK HOEJI
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    • v.39 no.1
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    • pp.41-47
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    • 1995
  • An efficient and stereoselective synthetic route to the trisubstituted hydroxy cyclopentane as an useful synthetic intermediate for carbaprostacyclin is described. Pd(0)-mediated intramolecular alkylation of allylic carbonate has been employed as a key reaction.

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Alkylation and Allylation of Lithium Arylborates Factors Affecting the Di/Mono Substitution Ratio$^\dag$

  • Lee, Ho-Seong;Song, Yang-Sup;Lee, Dong-Doo
    • Bulletin of the Korean Chemical Society
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    • v.8 no.5
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    • pp.424-425
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    • 1987
  • Alkylation and allylation of arylborates give mono(ipso) and/or di(ortho and ipso) substitution products. Those factors which promote polarization or ionization of alkylating agents favor di substitution. The ${\sigma}$-type(ipso) substitution reaction of arylborates involves direct interaction of the carbon-boron bonds rather than predissociation of arylborates into aryllithiums and boranes.