Polymers of carbon monoxide with olefinically unsaturated compounds
申请人:SHELL INTERNATIONALE RESEARCH
MAATSCHAPPIJ B.V.
公开号:EP0501586A2
公开(公告)日:1992-09-02
Polymers of carbon monoxide with one or more olefinically unsaturated compounds, which
a) can be prepared by polymerization of carbon monoxide with one or more compounds of the general formula CH₂=CH-R⁶-R⁷ in which R⁷ represents an optionally substituted phenyl group which, with one of the carbon atoms of its aromatic ring, is connected to a divalent aliphatic hydrocarbylene bridging group R⁶ containing at least one carbon atom in the bridge, and, optionally, in addition with one or more olefinically unsaturated aliphatic compounds,
b) possess a linear structure, and in which
c) the units from carbon monoxide and the units from the olefinically unsaturated compounds are present in a substantially alternating arrangement.
一氧化碳与一种或多种烯烃不饱和化合物的聚合物,其中
a) 可通过一氧化碳与一种或多种通式为 CH₂=CH-R⁶-R⁷ 的化合物聚合制备,其中 R⁷ 代表任选取代的苯基,该苯基与其芳香环的一个碳原子连接到二价脂肪族烃桥基 R⁶ 上,桥基中至少含有一个碳原子,此外还可任选与一种或多种烯烃不饱和脂肪族化合物聚合、
b) 具有线性结构,其中
c) 来自一氧化碳的单元和来自烯烃不饱和化合物的单元基本上交替排列。
Selective Halogen−Magnesium Exchange Reaction via Organomagnesium Ate Complex
Halogen-magnesium exchange of various aryl halides is achieved with a magnesium ate complex at low temperatures; Tributylmagnesate ((Bu3MgLi)-Bu-n) induces facile iodine-magnesium exchange at -78 degreesC. Dibutylisopropylmagnesate ((PrBu2MgLi)-Pr-i-Bu-n) is more reactive than (Bu3MgLi)-Bu-n, and this reagent accomplishes selective bromine-magnesium exchange at -78 degreesC. This procedure is utilized for the preparation of various polyfunctionalized arylmagnesium species. The exchange of alkenyl halides using this method proceeds with retention of configuration of the double bond.
Catalytic amide base system generated <i>in situ</i> for 1,3-diene formation from allylbenzenes and carbonyls
The amidebasegenerated in situ from tetramethylammonium fluoride and N(TMS)3 catalyzes the synthesis of 1,3-diene from an allylbenzene and carbonyl compound. The system is applicable to the transformations of a variety of allylbenzenes with functional groups (halogen, methyl, phenyl, methoxy, dimethylamino, ester, and amide moieties). Acyclic and cyclic diaryl ketones, pivalophenone, pivalaldehyde