A process for the manufacture of compounds of the formulae IA or IIA,
- wherein
- Y1*, Y2* and Y1′* are, independently of each other, an element of the fifth group of the periodic table of elements as such or in thioxo or oxo form, wherein in formula IA, Y1* is P(═O), P(═S) or phosphorus (P), and in formula IIA Y1* and Y1′* are P(═O), P(═S) or P;
- Z1*, Z2*, Z3*, Z4*, Z1* and Z2′* are, independently of each other, halogen or an unsubstituted
- or substituted moiety selected from the group consisting of aryl, heterocyclyl, cycloalkyl, aryl-lower alkyl, heterocyclyl-lower alkyl, cycloalkyl-lower alkyl, alkyl, aryloxy, heterocyclyloxy, cycloalkyloxy, aryl-lower alkoxy, heterocyclyl-lower alkoxy, cycloalkyl-lower alkoxy and alkoxy;
- or —N(Q)2 wherein Q is unsubstituted or substituted alkyl or wherein N(Q)2 forms an unsubstituted or substituted heterocycle optionally containing heteroatoms in addition to the N atom of N(Q)2;
- or hydrogen;
- or one or all of the pairs (i) Z1*, and Z2*, (ii) Z3*, and Z4*, (iii) Z1′* and Z2′* form bridges, or one or all of the pairs (i) Z1* and (Z3*, (ii) Z2* and Z4*, (iii) Z1* and Z1′* and (iv) Z2* and Z2′* form bridges, while the residues from ZZ2*, Z2′*, Z3*, Z4*, Z1′* and Z2′*, as far as they are not involved in bridge formation, are as defined above;
- X1 is NR,O or S;
- X2 is CHR1 or CR1;
- X3 is CHR2 or NR2 or, if X2 is CR1, X3 is CR2 or N;
- or additionally, for compounds of formula IIA for the ring system attached to Y1*, X3 is NR, O or S and X1 is CHR2 or NR2 or, if X2 is CR1, X1 is CR2 or N;
- R, R1 and R2, independently of each other, are hydrogen or an unsubstituted or substituted moiety selected from the group consisting of alkyl, aryl, cycloalkyl, heterocyclyl, aryl-lower alkyl, cycloalkyl-lower alkyl and heterocyclyl-lower alkyl or R1 and R2 together form an annealed unsubstituted or substituted mono-, bi- or polycyclic ring system;
- wherein, for the manufacture of a compound of the formula IA, a compound of the formula IIIA,
- wherein the moieties have the meanings given above under formulae IA and IIA, is reacted with an organolithium compound to the corresponding ortho-lithiated derivative of the formula IVA,
- wherein M is lithium, and the other moieties are as defined for compounds of the formulae IIIA;
- if desired, trans-metallating the compounds with M ═Li into other metallates wherein M is a different metal or a metal halide;
- and then
- (a) for the preparation of compounds of the formulae IA a compound of the formula IVA is reacted with a compound of the formula V,
- L-Y2*(Z3*)(Z4*) (V)
- wherein Y2*, Z3* and Z4* have the meanings of the corresponding moieties in formulae IA;
- and L is a leaving group, especially halogen;
- to the corresponding compound of formula IA*,
- wherein the moieties have the meanings given for compounds of the formula IA;
- which compounds fall under the definition of formula IA;
- and, if desired, a resulting compound of the formula IA is converted into a different compound of formula IA, and/or a mixture of isomers of a compound of the formula IA is separated into the individual isomers;
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- (b) for the preparation of a compound of the formula IIA, a compound of the formula IVA,
- is oxidatively dimerized to a corresponding compound of the formula IIA*,
- wherein Y1* and Y1′*, independently of each other, are P(═S), P(═O) or P, Q, X1, X2 and X3 have the meanings given for compounds of the formula IIA;
- which compound falls under the definition of formula IIA;
- and, if desired, a resulting compound of the formula IIA is converted into a different compound of formula IIA, and/or a mixture of isomers of a compound of the formula IIA is separated into the individual isomers;
- or
- (c) for the preparation of a compound of the formula IIA, where X3 is NR, O or S and X1 is CHR2 or NR2 or, if X2 is CR1, X1 is CR2 or N for the ring system attached to Y1 *;
- a two-step protocol involving a Suzuki or Negishi type coupling is used where half a mole of a compound of the formula IVA is transformed to a compound of the formula IVA*
- where M* is 1 or Br for a Negishi type coupling or M* is B(R3)2, where R3 is alkyl or OH, for a Suzuki type coupling;
- to give when reacted with half a mole of compound IVA the corresponding compound of formula IIA*;
- which compound falls under the definition of formula IIA;
- and, if desired, a resulting compound of the formula IIA is converted into a different compound of formula IIA, and/or a mixture of isomers of a compound of the formula IIA is separated into the individual isomers.