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    • 7. 发明授权
    • Process for preparing aryl- or heteroarylhexadienoic acids
    • 制备芳基或杂芳基己二烯酸的方法
    • US4355168A
    • 1982-10-19
    • US212238
    • 1980-12-02
    • Gian P. ChiusoliWilliam GiroldiniLuciano PalliniGiuseppe Salerno
    • Gian P. ChiusoliWilliam GiroldiniLuciano PalliniGiuseppe Salerno
    • B01J31/00C07B31/00C07B37/02C07B61/00C07C51/00C07C51/353C07C57/42C07C59/64C07C67/00C07D333/24C07D213/55C07C51/347
    • C07D333/24C07C51/353
    • There is disclosed and claimed a process for preparing aryl- and heteroarylhexadienoic acids which is characterized in that an aryl- or heteroarylacetylene having the formula: R--C.tbd.CH, wherein R is an aryl or heteroaryl group, optionally substituted and having in the aggregate up to 20 carbon atoms, is reacted with 3-butenoic acid CH.sub.2 .dbd.CH--CH.sub.2 --COOH, in an alcoholic medium, at temperatures maintained between 50.degree. C. and 120.degree. C., approximately, in the presence of a catalyst selected from among the phosphinic complexes of rhodium having the formulas: III, Rh(PR'.sub.3).sub.n L.sub.m X associated with alkaline salts of carboxylic acids having up to 4 carbon atoms, and IV, Rh(PR'.sub.3).sub.n L.sub.p.sup.+ Y.sup.-, wherein R' is a hydrocarbyl group having up to 12 carbon atoms; "L" is a linear or cyclic olefin selected from among the olefins having from 2 to 10 carbon atoms and the chelating olefins having from 6 to 8 carbon atoms, n is an integer from 1 to 3, m is an integer from 0 to 2 and such that n+m=2 or 3, and p is an integer from 0 to 3 and such that n+p=3 or 4; X is an anion selected from among the haloid anions, preferably the hydrochloric anion, and the anions of carboxylic acids having up to 4 carbon atoms and Y is a sparingly coordinating anion, preferably selected from PF.sub.6.sup.- and BF.sub.4.sup.-.The compounds obtained are used as intermediates for organic syntheses, with particular regard to the so-called "fine chemicals" such as, for example, additives for polymers and paints, plasticizers, and the like.
    • 公开并要求了一种制备芳基 - 和杂芳基己二烯酸的方法,其特征在于具有下式的芳基 - 或杂芳基乙炔:其中R是芳基或杂芳基,其中R是芳基或杂芳基, 20个碳原子与3-丁烯酸CH 2 = CH-CH 2 -COOH在醇的介质中在保持在50℃和120℃之间的温度下反应,大约在存在催化剂的情况下,选自 具有以下结构式的铑的次膦酸络合物:III,Rh(PR'3)nLmX与具有至多4个碳原子的羧酸的碱金属盐,以及IV,Rh(PR'3)nLp + Y-,其中R'为 具有至多12个碳原子的烃基; “L”是选自具有2至10个碳原子的烯烃和具有6至8个碳原子的螯合烯烃,n为1至3的整数的直链或环状烯烃,m为0至2的整数 并且使得n + m = 2或3,并且p是0至3的整数,并且使得n + p = 3或4; X是选自卤素阴离子,优选盐酸阴离子的阴离子和具有至多4个碳原子的羧酸阴离子,Y是一种微量配位阴离子,优选选自PF6-和BF4-。 所得化合物用作有机合成的中间体,特别涉及所谓的“精细化学品”,例如聚合物和油漆的添加剂,增塑剂等。