• Title/Summary/Keyword: Acetals

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Theoretical Studies on the Cationic Polymerization Mechanism of Cyclic Acetals (산 촉매하의 Cyclic Acetals 공중합반응에 관한 분자궤도론적 연구)

  • Young-Gu Cheun;Jae-Kyung Kim
    • Journal of the Korean Chemical Society
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    • v.36 no.2
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    • pp.197-204
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    • 1992
  • The cationic polymerization of cyclic acetals are investigated theoretically using the semiempirical MINDO/3, MNDO, and $AM_1$, methods. The nucleophilicity and basicity of cyclic acetals can be explained by the negative charge on oxygen atom of cyclic acetals. The reactivity of propagation in the polymerization of cyclic acetals can be represented by the positive charge on $C_2$ atom and the low LUMO energy of active species of cyclic acetals. The reactivity of 2-buthyl-1,3-dioxepane(2-Bu-DOP) of cyclic oxonium and opening carbenium ion form is expected computational stability of the oxonium ion by 5${\sim}$7kcal/mole favoring the carbenium ion. Owing to the rapid equilibrium of these cation forms and the reaction coordinate based on calculation that the reaction coordinate based on calculation that the chain growth $S_N1$ mechanism will be at least as fast as that for $S_N2$ mechanism.

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Photoaddition Reactions of Silyl Ketene Acetals with Aromatic Carbonyl Compounds: A New Procedure for β-Hydroxyester Synthesis

  • Yoon, Ung-Chan;Kim, Moon-Jung;Moon, Jae-Joon;Oh, Sun-Wha;Kim, Hyun-Jin;Mariano, Patrick S.
    • Bulletin of the Korean Chemical Society
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    • v.23 no.9
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    • pp.1218-1242
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    • 2002
  • Photochemical reactions of aromatic carbonyl compounds with silyl ketene acetals have been explored. Irradiation of acetonitrile or benzene solutions containing aryl aldehydes or ketones in the presence of silyl ketene acetals is observed to promo te formation of ${\beta}-hydroxyester$, 2,2-dioxyoxetane and 3,3-dioxyoxetane products. The ratios of these photoproducts, which arise by competitive single electron transfer (SET) and classical Paterno-Buchi mechanistic pathways, is found to be dependent on the degree of methyl-substitution on the vinyl moieties of the ketene acetals in a manner which reflects expected alkyl substituent effects on the oxidation potentials of these electron rich donors. An analysis of the product distribution arising by irradiation of a solution containing butyrophenone (6) and the silyl ketene acetal 9, derived from methyl isobutyrate, provides an estimate of the rate constants for the competitive Norrish type Ⅱ, SET and Paterno-Buchi processes occuring. Finally, sequences involving silyl ketene acetal-aryl aldehyde or ketone photoaddition followed by 2,2-dioxyoxetane hydrolysis represent useful procedures for Claisen-condensation type, ${\beta}-hydroxyester$ synthesis.

Synthesis of N,N-Dimethylurea Derivative By Use of Dimethylformamide Dialkyl Acetals (디메틸포름아미드 디알킬 아세탈을 이용한 우레아 유도체의 합성)

  • Soon-Yung Hong
    • Journal of the Korean Chemical Society
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    • v.26 no.6
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    • pp.403-406
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    • 1982
  • Reactions of N-acyl-1,4-dimethoxy-2-naphthylamines with N,N-dimethylformamide dialkyl acetals afforded, in all cases, the same product, N,N-dimethyl-N'-2-(1,4-dimethoxy)naphthylurea. In these reactions, it was observed that N,N-dimethylformamide dialkyl acetals act as a dimethylamination agent when electron-deficient cites are present in the substrates.

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Regioselective Synthesis of Heterocyclic Ketene N,N-, N,O- and N,S-acetals in Aqueous Medium

  • Chanu, Langpoklakpam Gellina;Singh, Okram Mukherjee;Jang, Sang-Hun;Lee, Sang-Gyeong
    • Bulletin of the Korean Chemical Society
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    • v.31 no.4
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    • pp.859-862
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    • 2010
  • The reactions of ketene dithioacetals with ethane-1,2-diamine, propane-1,3-diamine, 2-aminoethanol, 3-aminopropanol, and 2-aminoethanethiol in ordinary water in the absence of any acid/base catalyst afforded the heterocyclic ketene N,N-, N,O- and N,S-acetals in good yields.

Silica Sulfuric Acid/Wet $SIO_2$as a Novel System for the Deprotection of Acetals by Using Microwave Irradiation under Solvent Free Conditions (무용매 조건하에서 황산/젖은 $SIO_2$와 마이크로웨이브를 이용한 아세탈의 새로운 탈보호기 방)

  • BiBi Fathemeh, Mirjalili; Mohammad Ali, Zolfigol;Abdolhamid, Bamoniri
    • Journal of the Korean Chemical Society
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    • v.45 no.6
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    • pp.546-548
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    • 2001
  • Neat chlorosulfonic acid reacts with silica gel to give silica sulfuric acid in which sulfuric acid is immobilized on the surface of silica gel via covalent bond. A combination of silica sulfuric acid and wet SiO$_2$ was used as an effective deacetalizating agent for the conversion of acetals to their corresponding carbonyl derivatives by using microwave irradiation under solvent free conditions.

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