Patent EP-2332944-A2 (EP)
Inventor: PAULUTH DETLEF DR
IPC: C09K19/16
Filed: 2003-02-20
Abstract: Preparing cyclic compounds (I)-(IV), comprises carrying out: (a) Suzuki coupling of substituted phenyl derivative (V), substituted phenanthrene derivative (VI), substituted 9,10-dihydro-phenanthrene derivative (VII) and substituted 9H-fluorene derivative (VIII) with a substituted boronic acid- or a substituted boronic acid ester compound (X); (b) subsequent halo-demetallation, preferably iododesilylation; and (c) Suzuki coupling with a substituted boronic acid- or a substituted boronic acid ester compound (XI), by combinatorial synthesis, in a matrix like arrangement of reaction vessels. Preparing cyclic compounds of formulae (I)-(IV), comprises carrying out: (a) Suzuki coupling of substituted phenyl derivative of formula (V), substituted phenanthrene derivative of formula (VI), substituted 9,10-dihydro-phenanthrene derivative of formula (VII) and substituted 9H-fluorene derivative of formula (VIII) with a substituted boronic acid- or a substituted boronic acid ester compound of formula (X); (b) subsequent halo-demetallation, preferably iododesilylation; and (c) Suzuki coupling with a substituted boronic acid- or a substituted boronic acid ester compound of formula (XI), by combinatorial synthesis, in a matrix like arrangement of reaction vessels. either m, n : 0 or 1; or m+n : 1 or 2; X : single bond, -CH 2-CH 2-, -CH=CH-, -CC- or substituted phenyl moiety of formula (IX); L : R, F, Cl, Br, I, OH, OR, SH, SR, CN, NO 2, NO, CHO, COOH, COOR, CONH 2, CONHR, CONR 2, CF 3, NH 2, NHR, NR 2; R : 6C aryl (optionally further substituted by 1-12C alkyl), 1-12C alkyl, 1-12C alkenyl or 1-12C acyl; either a-f : 0-2 (denotes the number of substituents on the aromatic ring); or a+b+c+d+e+f : 3-8; R 1>, R 2> : 1-12C alkyl, 1-12C alkoxy (both optionally branched and optionally chiral), H, F, Cl, CN, NCS, 2-8C alkenyl or 2-8C alkynyl, where one CH 2may be replaced by -O-, -CO-, -O-CO- or -COO, the heteroatoms are not directly linked with each other, and/or at least one H may be replaced by halo, preferably F, and one or two CH groups in (I)-(IV) may be substituted by N; Z : l, Cl, Br or triflate; M : Si, Ge or Sn; R 3>-R 5> : H, 1-12C alkyl or 1-12C alkoxy; and either R 6>, R 7> : H, 1-12C alkyl, 2-12C alkenyl or aryl; or R 6>, R 7> : bridged cyclically, where one or two CH groups in (V)-(VIII) and in (X) and (XI), may be replaced by N. Provided that if m is 0 in R 1>or n is 0 in R 2>, one CH 2group in R 1>or R 2>may be replaced by (i) trans-1,4-cyclohexylene (in which at least one nonadjacent CH 2group may be replaced by oxygen and/or sulfur), (ii) residue comprising 1,4-bicyclo(2,2,2)octylene, piperidin-1,4-diyl, naphthalen-2,6-diyl, decahydronaphthalen-2,6-diyl or 1,2,3,4-tetrahydronaphthalen-2,6-diyl or (iii) 1,4-cyclohexenylene (all residues may be substituted by cyano group and/or halo. Independent claims are also included for: (1) a cyclic compound of formula (XIII) and (XVIII); and (2) a substituted boronic acid- or substituted boronic acid ester compound of formula (XIX) and (XXI), where one or two CH group in the aromatic ring of (XIX) and (XXI) may be replaced by N. Y1 : substituted phenyl moiety of formula (XIV), substituted phenanthrene moiety of formula (XV), substituted 9,10-dihydro-phenanthrene moiety of formula (XVI) or substituted 9H-fluorene moiety of formula (XVII); o, p : 1; R 11>, R 21> : 1-7C alkyl; r : m or n; and either R 31> : R 1>(when r = m); or R 31> : R 2>(when r = n). [Image] [Image] [Image] [Image] [Image] [Image] [Image] [Image] [Image] [Image] [Image].