| 主权项 |
1. A process for the preparation of compounds of formula (I): wherein, n is an integer from 1 to 6 m is 1 or 2, R1, if n is 1, is a substituent of formula (IIa)
—C(1)R62—C(2)H(Z)(R7) (IIa)wherein,(1) and (2) indicate the numeration of the carbon atom, wherein C(1) is bound to the central phosphorous atom depicted in formula (I), andZ is a substituent selected from the group consisting of —CN, —NO2, —(CO)H, —(CO)R8, —(CO)OH, —(CO)OR8, —(CO)NH2, —(CO)NH(R8), —(CO)N(R8)2, —(SO2)R8, —(PO)(R8)2, —(PO)(OR8)2, —(PO)(OR8)(R8) or heteroarylR6 and R7 each substituent independently is hydrogen, Z or R8 andR8 independently of further substituents R8 which may be present in the substituent of formula (IIa) is alkyl, alkenyl or aryl or two substituents R8 irrespective of whether they are both part of a substituent Z or belong to different substituents selected from Z, R6 and R7 together are alkanediyl or alkenediyl or alternatively, where two substituents —(CO)R8 are present within the substituent of formulae (IIa) are together —O— or —NR4—,wherein, whereby the alkyl, alkenyl, aryl, alkanediyl and alkenediyl substituents areeither not, once, twice or more than twice interrupted by non-successive functional groups selected from the group consisting of:
—O—, —S—, —SO2—, —SO—, —SO2NR4—, NR4SO2—, —NR4—, —CO—, —O(CO)—, (CO)O—, —O(CO)O—, —NR4(CO)NR4—, NR4(CO)—, —(CO)NR4—, —NR4(CO)O—, —O(CO)NR4—, —Si(R5)2—, —OSi(R5)2—, —OSi(R5)2O—, —Si(R5)2O—,and,either not, additionally or alternatively either once, twice or more than twice interrupted by bivalent residues selected from the group consisting of heterocyclo-diyl, and aryldiyl,
and,either not, additionally or alternatively either once, twice or more than twice substituted by substituents selected from the group consisting of:
oxo, hydroxy, halogen, cyano, azido, C6-C14-aryl, C1-C8-alkoxy, C1-C8-alkylthio, —SO3M, —COOM, PO3M2, —PO(N(R5)2)2, PO(OR5)2, —SO2N(R4)2, —N(R4)2, —N(R4)3+An−, —CO2N(R5)2, —COR4, —OCOR4, —NR4(CO)R5, —(CO)OR4,—NR4(CO)N(R4)2, —Si(OR5)y(R5)3-y, —OSi(OR5)y(R5)3-y with y=1, 2 or 3, or or R1, if n is 1, is a substituent of formulae (IIb), (IIc) or (IId)
—C(1)R62—N(R8)2 (IIb)—C(1)R62—NH(R8) (IIc)—(C(1)═O)—NHR8 (IId),wherein,(1) indicates the carbon atom bound to the central phosphorous atom depicted in formula (I), and R1, if n is >1,
is a substituent of formula (IIe) or (IIf)
R*[C(2)HR9—C(1)(R9)2—]n (IIe)R**[NH—(C(1)═O)—]n (IIf),wherein, in formula (IIe), R* is either
a divalent substituent selected from the group consisting of —CO— and —SO2— (for n=2), ora n-valent substituent selected from the group consisting of heteroaryl-n-yl and R10(-Het-(C═O)—)n, wherein Het independently is either O or NR4 and R10 is alkane-n-yl, alkene-n-yl or aryl-n-yl and wherein the carbonyl carbons are bound to the C(2) carbon atoms,wherein, the aforementioned alkane-n-yl and alkene-n-yl substituents of R10 areeither not, once, twice or more than twice interrupted by non-successive functional groups selected from the group consisting of:
—O—, —NR4—, —CO—, —O(CO)—, —(CO)O—, NR4(CO)—, —(CO)NR4—,and,either not, additionally or alternatively either once, twice or more than twice interrupted by aryldiyl,and,either not, additionally or alternatively either once, twice or more than twice substituted by substituents selected from the group consisting of:
hydroxy, C1-C8-alkoxy, —COOM, —N(R4)2, —CO2N(R5)2, —COR4, —OCOR4, —NR4(CO)R5, —(CO)OR4, (1) and (2) indicate the numeration of the carbon atom, wherein each of the n C(1) carbon atoms is bonded to the central phosphorous atom depicted in formula (I) via the bond “—” shown on the right side of the bracket, andR9 independently of each other are hydrogen, alkyl, alkenyl or aryl or two substituents R9 irrespective of whether they are both bound to C(2) or not are together alkanediyl or alkenediyl,wherein, the aforementioned alkyl, alkenyl, alkane-n-yl and alkene-n-yl substituents of R9 areeither not, once, twice or more than twice interrupted by non-successive functional groups selected from the group consisting of:
—O—, —S—, —SO—, —SO2NR4—, NR4SO2—, —CO—, —O(CO)—, (CO)O—, —O(CO)O—, —NR4(CO)NR4—, NR4(CO)—, —(CO)NR4—, —NR4(CO)O—, —O(CO)NR4—, —Si(R5)2—, —OSi(R5)2—, —OSi(R5)2O—, —Si(R5)2O—,and,either not, additionally or alternatively either once, twice or more than twice interrupted by bivalent residues selected from the group consisting of heterocyclo-diyl, and aryldiyl,
andeither not, additionally or alternatively either once, twice or more than twice substituted by substituents selected from the group consisting of:
oxo, hydroxy, halogen, cyano, azido, C6-C14-aryl, C1-C8-alkoxy, C1-C8-alkylthio, —SO3M, —COOM, PO3M2, —PO(N(R5)2)2, PO(OR5)2, —SO2N(R4)2, —N(R4)2, —N(R4)3+An−, —CO2N(R5)2, —COR4, —OCOR4, —NR4(CO)R5, —(CO)OR4,—NR4(CO)N(R4)2, —Si(OR5)y(R5)3-y, —OSi(OR5)y(R5)3-y with y=1, 2 or 3, and wherein in formula (IIf), R** is a n-valent substituent selected from the group consisting of alkane-n-yl, alkene-n-yl and aryl-n-yl wherby R** is bound to the nitrogen atoms,
wherein, whereby the aforementioned alkane-n-yl and alkene-n-yl substituents areeither not, once, twice or more than twice interrupted by non-successive functional groups selected from the group consisting of:
—O—, —CO—, —O(CO)—, —(CO)O—, —NR4(CO)—, —NR4(CO)O—, —NR4(CO) NR4—, —(CO)NR4— or isocyanurate, oxadiazintrione, uretdione, biuret or allophanate groups,and,either not, additionally or alternatively either once, twice or more than twice interrupted by aryldiyl,
andeither not, additionally or alternatively either once, twice or more than twice substituted by substituents selected from the group consisting of:
hydroxy, —NCO, C1-C8-alkoxy, —N(R4)2, —CO2N(R5)2, —COR4, —OCOR4, —NR4(CO)R5, —(CO)OR4,(1) indicates the numeration of the carbon atom, wherein whereby each of the n C(1) carbon atoms is bonded to the central phosphorous atom depicted in formula (I) via the bond “—” shown on the right side of the bracket, and R2 and R3 are independently of each other aryl or heterocyclyl, alkyl or alkenyl,
wherein, the aforementioned alkyl and alkenyl substituents of R2 and R3 areeither not, once, twice or more than twice interrupted by non-successive functional groups selected from the group consisting of:
—O—, —NR4—, —CO—, —OCO—, —O(CO)O—, NR4(CO)—, —NR4(CO)O—, O(CO)NR4—, —NR4(CO)NR4—,and,either not, additionally or alternatively either once, twice or more than twice interrupted by bivalent residues selected from the group consisting of heterocyclo-diyl, and aryldiyl,
andeither not, additionally or alternatively either once, twice or more than twice substituted by substituents selected from the group consisting of:
oxo, hydroxyl, halogen, cyano, C6-C14-aryl; heterocyclyl, C1-C8-alkoxy, C1-C8-alkylthio, —COOM, —SO3M, —PO3M2, —SO2N(R4)2, —NR4SO2R5, —N(R4)2—, —N+(R4)3An−, —CO2N(R4)2, —COR4—, —OCOR5, —O(CO)OR5, NR4(CO)R4, —NR4(CO)OR4, O(CO)N(R4)2, —NR4(CO)N(R4)2,wherein whereby in all formulae where usedR4 is independently selected from the group consisting of hydrogen, C1-C8-alkyl, C6-C14-aryl, and heterocyclyl or N(R4)2 as a whole is a N-containing heterocycle,R5 is independently selected from the group consisting of C1-C8-alkyl, C6-C14-aryl, and heterocyclyl or N(R5)2 as a whole is a N-containing heterocycle,M is hydrogen, or 1/q equivalent of an q-valent metal ion or is an ammonium ion or a guanidinium ion or a primary, secondary, tertiary or quarternary organic ammonium ion, andAn− is 1/p equivalent of a p-valent anion,the process comprising at least the step of reacting compounds of formula (III) if n is 1, with compounds of formulae (IVa), (IVb),(IVc) or (IVd),
R62C(1)═C(2)(Z)(R7) (IVa),R62C(1)═N+(R8)2An− (IVb),R62C(1)═NR8 (IVc),R8—NCO (IVd), if n is >1, with compounds of formulae (IVe) or (IVf),
R*[R9C(2)═C(1)(R9)2]n— (IVe),R**[NCO]n (IVf), wherein, in formulae (III) and (IVa) to (IVf), (1), (2), R2, R3, R6, R7, R8, R9, R*, R**, n, m, An− and Z have the same meaning as described for formulae (I) and (IIa) to (IVf) above, and wherein, in formula (II), M2 is hydrogen, or 1/q equivalent of an q-valent metal ion or is an ammonium ion or a heterocycylium cation, a guanidinium ion or a primary, secondary, tertiary or quarternary organic ammonium ion, and wherein the reaction if M2 is hydrogen is carried out in the presence of a base. |
