Up-Scale Synthesis of p-(CH2=CH)C6H4CH2CH2CH2Cl by CuCN Catalyzed Coupling Reaction of Grignard Reagent with BrCH2CH2CH2Cl
- 주제(키워드) Grignard reagents , CuCN catalyst , coupling reaction , large scale , PhCu(CN)Mg(THF)4Cl crystal
- 주제(DDC) 547
- 발행기관 아주대학교
- 지도교수 이분열
- 발행년도 2023
- 학위수여년월 2023. 2
- 학위명 석사
- 학과 및 전공 일반대학원 분자과학기술학과
- 실제URI http://www.dcollection.net/handler/ajou/000000032595
- 본문언어 한국어
- 저작권 아주대학교 논문은 저작권에 의해 보호받습니다.
초록/요약
Grignard reagents featuring carbanion characteristics are generally unreactive toward alkyl halides and require a catalyst for the coupling reaction. With the need to synthesize p-(CH2=CH)C6H4CH2CH2CH2Cl on a large-scale, the coupling reaction of p-(CH2=CH)C6H4MgCl with BrCH2CH2CH2Cl was attempted to screen the catalysts, and CuCN was finally determined to be the best catalyst affording the desired compound in 80% yield with no generation of Wurtz coupling side product CH2=CHC6H4C6H4CH=CH2. The p-(CH2=CH)C6H4Cu(CN)MgCl species was proposed as an intermediate based on the X-ray structure of PhCu(CN)Mg(THF)4Cl. The structures of p-(CH2=CH)C6H4CH2CH2CH2MgCl and p-ClC6H4MgCl were also elucidated, which existed as an aggregate with MgCl2, proposing that some portion of the Grignard reagents were possibly lost in the coupling reaction owing to co-precipitation with the byproduct MgCl2. Using the developed syntheses, [p-(CH2=CH)C6H4CH2CH2CH2]2Zn which is latently useful compound for the production of PS-block-PO-block-PS, respectively, was successfully synthesized with considerable cost reductions.
more목차
제 1장 Introduction 1
제 2장 Results and Discussion 2
1. Catalyst Screening 2
2. Large-scale synthesis of 1 and 2 5
제 3장 Experimental Section 9
1. General remarks 9
2. Catalyst Screening 9
3. Large-scale synthesis of p-(CH2=CH)C6H4CH2CH2CH2Cl 10
4. Large-scale synthesis of [p-(CH2=CH)C6H4CH2CH2CH2]2Zn 10
5. PhCu(CN)Mg(THF)4Cl 11
6. X-ray crystallography 11
제 4장 Conclusions 12
제 5장 Acknowledgements 13
제 6장 References 13
제 7장 Supporting information 19
