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    • 4. 发明授权
    • Prescursors for and synthesis of mono- and difunctionalized acetylenes
and difunctional 1,3-diynes
    • 单官能和双功能乙炔和双官能1,3-二炔的前体和合成
    • US5286901A
    • 1994-02-15
    • US732663
    • 1991-07-19
    • Peter J. StangCharles M. CrittellBobby L. WilliamsonViktor Zhdankin
    • Peter J. StangCharles M. CrittellBobby L. WilliamsonViktor Zhdankin
    • C07C23/27C07C25/24C07C45/51C07C49/796C07C203/02C07C319/14C07C321/28C07F9/54C07C309/00
    • C07F9/5449C07C203/02C07C23/27C07C25/24C07C319/14C07C45/511C07C49/796C07F9/5428
    • Precursors and methods for the synthesis of mono- and difunctionalized acetylenes are described. The invention includes novel tricoordinate iodonium transfer reagents and novel alkynyldi(phenyliodonium) salts, both of which are precursors for the functionalized acetylenes. The iodonium transfer reagents take the general form of mixed iodonium sulfonates PhI.sup.+ (X)OSO.sub.2 R.sub.f, where X may be OAc, NHAc, NCO, or CN. These mixed iodonium sulfonates are produced by reaction of iodosobenzene with certain substituted trimethylsilanes.To make the alkynyldi(phenyliodonium) salt PhI.sup.+ C.tbd.CI.sup.+ Ph.cndot.2 R.sub.f SO.sub.3.sup.-,a mixed iodonium sulfonate is reacted with a bistin acetylene of the kind R'.sub.3 SnC.tbd.CSnR".sub.3. Alternatively, the reaction may be performed with disubstituted tin diacetylenes to produce PhI.sup.+ C.tbd.C-C.tbd.CI.sup.+ Ph.cndot.2 R.sub.f SO.sub.3.sup.- to produce a dialkynyldi(phenyliodonium) salt. Subsequent reaction of a nucleophile with the alkynyldi(phenyl-iodonium) salt or dialkynyldi(phenyliodonium) salt produces a difunctional acetylene or a difunctional 1,3-diyne, respectively.
    • 描述了用于合成单官能和二官能乙炔的前体和方法。 本发明包括新型三膦酸碘转移试剂和新型炔基二(苯基碘鎓)盐,它们都是功能化乙炔的前体。 碘转移试剂采用混合碘鎓盐PhI +(X)OSO2Rf的一般形式,其中X可以是OAc,NHAc,NCO或CN。 这些混合的碘磺酸盐是通过碘代苯与某些取代的三甲基硅烷的反应来制备的。 为了制备炔基二(苯基碘鎓盐)PhI + C(三键)Cl + Ph(固点)2 RfSO 3 - ,将混合的碘磺酸盐与R'3SnC(三键)CSnR“3类型的小扁豆乙炔反应。 或者,反应可以用二取代的二乙炔进行,以产生PhI + C(三键)CC(三键)Cl + Ph(固体点)2 RfSO 3 - 以产生二炔基二(苯基碘鎓)盐,随后将亲核试剂与 炔基二(苯基 - 碘鎓)盐或二炔基二(苯基碘鎓)盐分别产生双官能乙炔或二官能1,3-二炔。