I. Preparation and reactions of 2-chloroperfulorocycloalkenyl $(C_6, C_3)$ Metal (Cu, Zn) reagents : 1-chloro-2-iodooctafluoro-cyclohexene reacted with activated zinc powder in DMF solvent at room temperature to give 2-chlorooctafluorocyclohex-1-enyl zine iodide. Treatment of this organozinc reagent with CuBr at room temperature for 1 hr provided a simple route to the 2-chlorooctafluorocyclohex-1-enyl copper reagent in excellent yield. This copper reagent exhibited excellent thermal stability at room temperature in the absence of oxygen and/or moisture.
Alkylation reaction of this organocopper reagent were performed, and the reaction of this copper reagent with acyl haides gave acylated polyflourocyclohexenes, which have not been reported in the literature.
2-Chloro-3,3-difluorocycloprop-1-enylzinc iodide was also prepared from 1-chloro-3,3-difluoro-2-iodocyclopropene with acid washed zinc powder in good yield in DMF/HMPA cosolvent. This zinc reagent exhibited excellent stability at room temperature in the absence of oxygen and/or moisture. The reaction of this zinc reagent with a various of acyl and alkyl halides was found to be catalyzed by CuBr and represents a convenient root to the synthesis of vinylic substituted 3,3-difluorocyclopropene derivatives. In this reaction, HMPA was a useful cosolvent. A mechanistic interpretation may be explained by oxidative addition and reductive elimination. Oxidative addition of an alkyl halide to the copper(I) reagent yield a plannar copper(III) intermediate. Reductive elimination of two organic ligands from the copper(III) intermediate lead to a coupled product and Cu(I) species.
II. 1-Chloroperfluorocycloalkene derivatives with nucleophiles:
1-Acetyl-2-chloroperfluorocycloalkenes and 1-benzoyl-2-ch-loroperfluorocycloalkenes were prepared by the coupling reaction of 2-chloroperfluorocycloalkenyl copper reagent with acetyl chloride and benzoyl chlorode. Similarly, 1-chloro-2{p-nitro-phenyl)perfluorocyclopentene and cyclohexene were prepared by the reaction of 2-chloroperfluorocyclopentenyl and hexenyl copper reagent with p-nitroiodobezene. These compounds contain not only highly activated double bonds but also charge stabilizing groups in vinylic position. We have studied on the reaction of these compounds with various uncleophiles. They were very susceptable to the uncleophilic attack at the trigonal carbon bearing chlorin. The strong polarization effect of generated carbanion intermediate by the acyl group or p-nitrophenyl group undoubtedly dictate selectivity. Cyclobutene and cyclopentene derivatives undergo interestion nucleophlic displacement reaction of vinylic chlorin with alkoxide, amine and triethylphosphite without alllylic rearrangement under mild condition. However, we have found that additional factors must be considered in cyclohexene derivatives in which both "inward" and " outward" elimination occur from methoxide ion sttack on perfluorocyclohexene derivatives. Also we have found that the order of activating power of double is benzoyl group>acetyl group>>p-nitrophenyl group and 1-chloro-tetrafluorocyclobutene derivatives were more reactive than 1-chloro-hexafluorocyclopentene derivatives to the various nucleophiles.
1-아세틸-2-클로로퍼플루오로시클로 알켄 유도체들과 1-벤조일-2-클로로퍼플르오로시클로 알켄 유도체들이 2-클로로퍼플루오로시클로알케닐 구리시약과 아세틸 클로라이드와 벤조일 클로라이드와의 커플링 반응으로부터 합성되었다. 또한 1-클로로-2-(p-니트로페닐)퍼프루오로시클로펜텐과 헥산은 2-클로로퍼플루오로시클로펜테닐 그리고 헥세닐 구리시약과 p-니트로이오도벤젠의 반응으로부터 합성하였다. 이들 화합물들은 활성화된 이중 결합과 비닐릭 위치의 하전을 안정화시킬 수 있는 기들을 갖고 있다. 시클로부텐과 시클로펜텐 유도체들은 알콕시드, 아민 그리고 트리에틸포스파이트와 쉽게 반응하여 알릴릭 재배열이 일어나지 않고 비닐 클로린만이 치환된 화합물이 얻어졌다. 그러나, 시클로헥센 유도체들과 메톡사이드 이온과의 반응에는 "인워드" 그리고 "아웃워드" 엘리미네이션을 고려하여야한다는 것을 알았다.
또한 이중결합의 반응활성화 정도는 벤조일그룹 $>$ 아세틸그룹 $>>$ p-니트로페닐 그룹순 이었고, 1-클로로테트라플루오로시클로부텐 유도체들이 1-클로로헥사플루오로시클로펜텐 유도체들보다 여러 가지 친핵체들에 대해 반응성이 컸다.
