| 摘要 |
Production of compounds with 3 or 4 linked benzene rings from silyl- and halogen-terminated compounds with 2 benzene rings by combinatorial synthesis, involving Suzuki coupling with a boronic acid or ester, halo-demetallation (preferably iodo-desilylation) and Suzuki coupling with another boronic acid or ester. A method for the production of ring compounds of formula (I)-(IV) (in which the aromatic rings may contain 1 or 2 nitrogen atoms instead of CH) from compounds of formula (V) and corresponding compounds (VI-VIII) involves a combinatorial synthesis in which the following steps are carried out in a matrix of reaction vessels: (A) Suzuki coupling with a boronic acid or boronate ester of formula (X), (B) halo-demetallation, preferably iodo-desilylation and (C) Suzuki coupling with a boronic acid or boronate ester of formula (XI). m, n = 0 or 1; (m+n) = 1 or 2; X = a single bond, -CH2CH2-, -CH=CH- or a 1,4-phenylene group substituted with Lf; L = R, F, Cl, Br, I, OH, OR, SH, SR, CN, NO2, NO, CHO, COOH, COOR, CONH2, CONHR, CONR2, CF3, NH2, NHR or NR2; R = 1-12C alkyl, alkenyl or acyl, or 6C aryl (optionally substituted with 1-12C alkyl); a-f = 0, 1 or 2; (a+b+c+d+e+f) = 1-8, preferably 3-8; R1, R2 = H, F, Cl, CN, NCS, optionally chiral 1-12C alkyl or alkoxy or 2-8C alkenyl or alkynyl (all optionally with a CH2 group replaced by O, CO, OCO or COO and/or with one or more H replaced by halogen, preferably F, and (if m = 0 in R1 or n = 0 in R2) by (a) trans-1,4-cyclohexylene (optionally with one or more non-adjacent CH2 groups replaced by O and/or S), (b) 1,4-bicyclo(2.2.2)-octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl or its decahydro or 1,2,3,4-tetrahydro-derivatives, or (c) 1,4-cyclohexenylene, all types (a, b, c) being optionally substituted with CN and/or halogen); Z = I, Cl, Br or OTf; M = Si, Ge or Sn; R3-R5 = H, 1-12C alkyl or 1-12C alkoxy; R6, R7 = H, 1-12C alkyl or alkenyl, or aryl, or R6 and R7 may be bridged to form a ring. Independent claims are also included for (1) ring compounds (I-IV) as above (2) boronic acids and boronate esters(X, XI) as above. |
