I. Synthesis and Reactions of 2-Chlorohexafluorocyclopentenyl Zinc and Copper Reagent
1-Chloro-2-iodohexafluorocyclopentene reacted with activated zinc powder in DMF solvent at room temperature to give 2-chloro-hexafluorocyclopentenyl zinc reagent in 96% yield.
Treatment of this organozinc reagent with cuprous bromide at room temperature for one hour provided a simple route to the 2-chlorohexafluorocyclopentenyl copper reagent in quantitative yield. 2-Chlorohexafluorocyclopentenyl copper reagent exhibited good thermal stability at room temperature in the absence of oxygen and/or moisture and formed a wide variety of new carbon-carbon and carbon-heteroatom bonds via reactions with alkyl halides, vinyl halides, acyl halides, and heteroatomic halides.
Alkylation and coupling reactions of this organocopper reagent were performed, and the reaction of this organocopper reagent with acyl halides and heteroatomic halides gave the previously inaccessible substituted polyfluorocyclopentene derivatives.
II. Reaction of 1-Chlorohexafluorocyclopentene Derivatives with Various Nucleophiles
1-Acetyl-2-chloro-, 1-benzoyl-2-chloro-, and 1-chloro-2-p-nitrophenylhexafluorocyclopentene were prepared by the reaction of 2-chlorohexafluorocyclopentenyl copper reagent with acetyl chloride, benzoyl chloride, and p-nitroiodobenzene, respectively.
These compounds contain not only highly activated double bonds but also charge stabilizing groups in vinylic position.
These compounds reacted readily with alkoxide, amine, and phosphite to undergo interesting nucleophilic displacement reactions of vinylic chlorine without allylic rearrangement.
In reaction of 1-acetyl-and 1-benzoyl-2-chlorohexafluorocyclopentene with Grignard reagent, nucleophilic attack occurred at the carbonyl carbon rather than at the beta-carbon to give tertiary alcohol product.
1 - 아세틸 - 2 - 클로로 -, 1 - 벤조일 - 2 - 클로로 - 그리고 1 - 클로로 - 2 - 파라 - 니트로페닐헥사플루오로시클로펜텐을 2 - 클로로헥사플루 오로시클로펜텐일 구리시약과 아세틸 클로라이트, 벤조일 클로라이드 그리고 파라 - 니트로요오드벤젠과 각각 반응시켜 제조하였다. 이러한 화합물들은 활성화된 이중 결합을 갖고 있을 뿐만 아니라 비닐닉 위치에 하전을 안정화 시킬 수 있는 기들을 갖고 있다. 이러한 화합물들은 알콕사이드, 아민 그리고 포스파이드와 쉽게 반응하여 알릴릭 재배열이 일어나지 않고 비닐 클로린만이 친핵치환 반응이 일어난 화합물이 생성되었다.
1 - 아세틸과 1 - 벤조일 - 2 - 클로로헥사플루오로시클로펜텐과 그리그나드 시약과 반응에서는 친핵성 공격이 베타 탄소보다 오히려 카보닐 탄소에 일어나서 3차 알코올이 생성되었다.
