• 대한화학회지
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• 제60권4호
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• pp.257-260
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• 2016

A new perfluorobutyl substituted cyclic type disodium alkanesulfonate is designed, synthesized and characterized as alternative substance to perfluorooctane sulfonic acid (PFOS, 1), a well-known surfactant. Cylic type sulfonate was accomplished from commercially available 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol in four steps. Bio-degradable perfluorobutyl moiety was introduced from fluorous diol, which is symmetrically substituted amphiphile via installation of an intermediate trifluoromethanesulfonyl ester and easily manipulated by double displacement of triflate using potassium malonate and further reduction followed by nucleophilic ring opening are key reactions to get target disodium alkanesulfonate. The efficiency and simplicity in the synthesis of this material offer a new strategy to design PFOS alternatives.

• Bulletin of the Korean Chemical Society
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• 제20권4호
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• pp.422-426
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• 1999

The Grignard reactions of bis(chloromethyl)dimethylsilane (1) with trimethylchlorosilane (2) in THF give both the intermolecular C-Si coupling and intramolecular C-C coupling products. At beginning stage, 1 reacts with Mg to give the mono-Grignard reagent ClCH2Me2SiCH2MgCl (1) which undergoes the C-Si coupling reaction to give MC2Si(CH2SiMe3)2 3, or C-C coupling to a mixture of formula Me3SiCH2(SiMe2CH2CH2)nR1 (n = 1, 2, 3, ..; 4a, R1I = H: 4b, R1 = SiMe3). In the reaction, two reaction pathways are involved: a) Ⅰ reacts with 2 to give Me3SiCH2SiMe2CH2Cl 6 which further reacts with Mg to afford a Me2SiCH2Mel-SiCH2MgCl (Ⅱ) or b) I cyclizes intramolecularly to a silacyclopropane intermediate A, which undergoes a ring-opening polymerization by the nucleophilic attack of the intermediates I or Ⅱ, followed by the termination reaction with H2O and 2, to give 4a and 4b, respectively. As the mole ratio of 2/1 increased from 2 to 16 folds, the formation of product 3 increased from 16% to 47% while the formation of polymeric products 4 was reduced from 60% to 40%. The intermolecular C-Si coupling reaction of the pathway a becomes more favorable than the intramolecular C-C coupling reaction of the pathways b at the higher mole ratio of 2/1.

• 폴리머
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• 제36권3호
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• pp.262-267
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• 2012

할로겐화알킬($PhCH_2Br$, $PhCH_2Cl$, MeI)과 설폰산에스테르(MeOTf)를 개시제로 사용하여 $100^{\circ}C$, 24시간의 반응조건으로 2-(1,3,3-trimethyl-6-azabicyclo[3,2,1]-oct-6-yl)-4,5-dihydro-1,3-oxazoline(TAO)의 중합을 실시, 개시제에 의한 폴리머구조의 영향을 관찰한 결과, 양쪽 개시제 모두 거의 동일한 연쇄이동에서 나타나는 경향과 비슷한 결과를 얻었다. 그러나 개시제에 의한 폴리머의 구조는 설폰산에스테르계 개시제에서는 거의 100% pendant type 폴리머가 생성되는 반면, 할로겐화알킬계 개시제를 사용한 TAO중합은 pendant type 단위와 main chain type의 단위가 소량 생성됨이 확인되어 이것은 구핵성이 높은 할로겐 음이온에 의한 이중이성화중합이 부분적으로 진행되었음을 확인하였으며, 개시제로 Merrifield수지를 사용한 TAO와의 공중합에서는 다량의 단일중합체가 부생되는 그래프트 공중합체가 생성되었다.