• 대한화학회지
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• 제42권2호
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• pp.228-231
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• 1998

• Bulletin of the Korean Chemical Society
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• 제20권4호
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• pp.441-444
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• 1999

The alkyl Grignard addition reaction on 1-benzyltetrazolylimine proceeds to give N-alkylated products (azophilic addition) and, in contrast, the same reaction on 2-benzyltetrazolylimine produced predominantly C-alkylated products (carbophilic addition). In this report we described theoretical explanations for this experimental finding on the basis of the frontier molecular orbitals and the electrostatic nature of the reactants and the reaction intermediates.

• 대한화학회지
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• 제23권6호
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• pp.392-395
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• 1979

몇가지 유기할로겐화물, 즉 브롬화에틸, 염화부틸, 브롬화페닐 및 염화벤질등을 탄화수소중에서 그리냐르법으로 무수사염화주석과 반응시켰다. 이때 소량의 에테르를 그리냐르반응단계에서 계내에 투입하엿을 때 보다 용이하게 반응이 진행되어 좋은 수율로 유기주석화합물들을 얻을 수 있었다.

• 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.

• 대한화학회지
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• 제62권4호
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• pp.314-318
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• 2018

• Bulletin of the Korean Chemical Society
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• 제20권4호
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• pp.427-430
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• 1999

The Grignard coupling reaction of bis(chloromethyl)diorganosilanes [(ClCH2)2SiR1R2: R1 = R2 = Me, la; R1 = Me, R2 = Ph, lb; R1 = R2 = Ph, lc] with diorganodichlorosilanes [(Cl2SiR3R4: R3 = R4 = Me, 2a; R3 = Me, R4 = Ph, 2b; R3 = R4 = Ph, 2c] at THE reflux temperature gave the intermolecular C-Si coupling product of 1,1,3,3-tetraorgano-1,3-disilacyclobutanes 3a-f in poor to moderate yields ranging from 7% to 50% along with polydiorganosilapropanes. The cyclization reaction of la-c with methyl-substituted dichlorosilanes 2a, b gave 1,3-disilacyclobutanes 3a-c, e, d in moderate yields (42-50%), while the same reaction with dichlorodiphenylsilane (2c) to 1,3-disilacyclobutanes 3d, f resulted in low yield (7-18%) probably due to the steric hindrance of two-phenyl groups on the silicon of 2c.

• Bulletin of the Korean Chemical Society
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• 제20권1호
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• pp.122-124
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• 1999

• Bulletin of the Korean Chemical Society
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• 제28권2호
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• pp.281-284
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• 2007

Neopentyl arenesulfonates react with secondary alkylmagnesium chlorides in the presence of dppfNiCl2 to produce the corresponding arenes via the reductive cleavage of carbon-sulfur bond. Highest yield is obtained by using three equivalents of Grignard reagent to a mixture of arenesulfonate and dppfNiCl2 in Et2O at room temperature. This reaction represents a novel method allowing the efficient hydrogenolysis of sulfur-containing groups in aromatic compounds.

• Bulletin of the Korean Chemical Society
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• 제26권9호
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• pp.1410-1414
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• 2005

Neopentyl arenesulfonates reacted with primary alkylmagnesium halides in the presence of $(PPh_3)_2NiCl_2$ to produce the corresponding alkylarenes. The efficiency of this coupling reaction considerably depends on the nature of catalyst and solvent. Highest yield was obtained by using three equivalents of Grignard reagent to a mixture of $(PPh_3)_2NiCl_2$ and arenesulfonate in refluxing $Et_2O$. This reaction represents a novel method allowing the efficient and creative substitution of sulfur-containing groups in aromatic compounds. It also shows that the alkyloxysulfonyl group might be a suitable alternative to halides and triflate in some circumstances.

• Journal of Photoscience
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• 제8권2호
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• pp.75-77
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• 2001

The Grignard reaction of methyl pyropheophorbide-a (MPP-a) was performed to introduce lengthy alkyl chain for improving lipophilicity. After the introduction of alkyl chain to the both of carbonyls, peripheral aldehyde and cyclopentanone, the obtained diol 3 was subjected to dehydration to give monodehydrate product 4 selectively. The Qy band of prepared compounds were affected by the substituents on the Qy axis (N$\sub$21/-N$\sub$23/).