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    • 37. 发明授权
    • Synthesis of olefinic oxides from olefin and oxygen
    • 从烯烃和氧气合成烯属氧化物
    • US4256649A
    • 1981-03-17
    • US923280
    • 1978-07-10
    • Paul N. Dyer
    • Paul N. Dyer
    • B01J31/24C07D301/06C07D303/04
    • B01J31/2404C07D301/06C07D303/04B01J2231/72B01J2531/824B01J2540/22
    • Propylene oxide and other olefinic oxides are synthesized by reacting an olefin and oxygen in the presence of a catalytic amount of a complex. The complex is of the type L.sub.2 MX.sub.2, L.sub.2 M or L.sub.2 MR where M is palladium, X is an acidic anion (preferably chloride); R is an olefinic group (preferably a propylene group) and L.sub.2 consists of two monodentate ligands or a single bidentate ligand.L.sub.2 :(a) is resistant to oxidation under the conditions of the process;(b) is of the type AR.sub.1 R.sub.2 R.sub.3 or R.sub.4 R.sub.5 AR.sub.6 AR.sub.7 R.sub.8 where A is phosphorous or arsenic and R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.8 are as defined herein;(c) (in the case of a monodentate ligand) has a cone angle not less than 170.degree. when A is phosphorous and has a cone angle not less than 142.degree. when A is arsenic; or(d) in the case of a bidentate ligand) the monodentate equivalent of each part of the bidentate ligand has a cone angle of not less than 170.degree. when A is phosphorous and of not less than 142.degree. when A is arsenic.Increased yields of olefinic oxide may be obtained by the introduction of hydrogen.
    • 环氧丙烷和其它烯烃氧化物是通过烯烃和氧在催化量的络合物存在下反应合成的。 络合物是类型L2MX2,L2M或L2MR,其中M是钯,X是酸性阴离子(优选氯化物); R是烯基(优选丙烯基),L2由两个单齿配体或单个二齿配体组成。 L2:(a)在工艺条件下耐氧化; (b)为AR1R2R3或R4R5AR6AR7R8,其中A为磷或砷,R1,R2,R3,R4,R5,R6,R7和R8如本文所定义; (c)(在单齿配体的情况下)当A为磷时具有不小于170°的锥角,并且当A为砷时具有不小于142°的锥角; 或(d)在二齿配体的情况下),当A为磷时,双齿配体的每一部分的单齿当量具有不小于170°的锥角,并且当A为砷时,其角度不小于142°。 通过引入氢可以获得增加的氧化烯的产率。