Patent CH-695057-A5 (CH)
Title: New metal-organic monoacyl-alkyl-phosphine compounds are used for production of acyl-phosphine oxide or acyl-phosphine sulfide photoinitiators for use in light-curable compositions, e.g. paint, printing ink, adhesives
Inventor: WOLF JEAN-PIERRE
IPC: C07F9/53
Filed: 2001-06-05
Abstract: New metal-organic monoacyl-alkyl-phosphines are claimed. Metal-organic compounds of formula (I) are new. [Image] Ar : formula (IV), or cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl or an -, S- or N-containing 5- or 6-membered heterocyclic ring (all optionally substituted with halogen, 1-4C alkyl and/or 1-4C alkoxy); [Image] R 1, R 21-20C alkyl, OR 11, CF 3or halogen and R 3-R 5= H, 1-20C alkyl, OR 11or halogen, or any two of these groups (R 1-R 5) may form a 1-20C alkylene bridge, optionally containing -O-, -S- or -NR 14-; R 61-24C alkyl (optionally substituted with cycloalkenyl, phenyl, CN, COR 11, COOR 11, CON(R 14) 2, OCOR 11, OCOOR 11, -N(R 14)CON(R 14)-, OCONR 14, -N(R 14)COOR 11, cycloalkyl, halogen, OR 11, SR 11, NR 12R 13or oxiranyl), 2-24C alkyl with non-adjacent, in-chain O, S and/or NR 14group(s) (optionally substituted with phenyl, OR 11, SR 11, NR 12R 13, CN, COR 11, COOR 11, CON(R 14) 2and/or oxiranyl), 2-24C alkyl with non-adjacent, in-chain O, S or NR 14(optionally substituted with OR 11, SR 11or NR 12R 13), 5-24C cycloalkenyl (optionally with non-adjacent O, S or NR 14and optionally substituted withOR 11, SR 11or NR 12R 13), 1-24C aralkyl (optionally ring-substituted with 1-12C alkyl, 1-12C alkoxy or halogen), 4-24C cycloalkyl (optionally with non-adjacent O, S and/or NR 14and optionally substituted with OR 11, SR 11or NR 12R 13), 8-24C arylcycloalkyl or 8-24C arylcycloalkenyl; R 11H, 1-20C alkyl, 2-20C alkenyl, 3-8C cycloalkyl, phenyl, benzyl, or 2-20C alkyl with in-chain O or S atom(s) and optionally substituted with OH and/or SH; R 12, R 13H, 1-20C alkyl, 3-8C cycloalkyl, phenyl, benzyl or 2-20C alkyl with in-chain O atom(s) and optionally substituted with OH and/or SH, or R 12and R 13together may form a 3-5C alkylene group (optionally with in-chain O, S or NR 14); R 14H, phenyl, 1-12C alkyl, or 2-12C alkyl with in-chain O or S and optionally substituted with OH and/or SH; M : H, lithium, sodium or potassium. Independent claims are also included for: (a) compounds of formula (II) and (III); (b) the selective production of (I) by reaction of an acyl halide of formula Ar-CO-X (IV) with a dimetalated organophosphine R 6-P(M 1) 2(V) in a mol ratio of 1:1, followed by hydrolysis if (I) with M = H is required; (c) the production of (II) by reaction of (IV) with (V) as above, reaction of the product with a different acyl halide (Y 1-CO-X) (IVa) and oxidation or sulfidation of the phosphine (for A = O or S); (d) the production of (II) (with A = O and x = 1) by reaction of (I) with phosgene to give the phosphine chloride, reaction with an alcohol to give Ar-CO-P(R 6)(OR) and reaction with acyl halide (IVa); (e) the production of (III) by reaction of (IV) with (V), reaction of the product with a compound of formula Z 1-X (VI) or Z 1-X' (VI') and oxidation or sulfidation as above; (f) the production of (III) by reaction of (IV) with an asymmetrical phosphine R 6-P(Z 1)-H (VII) in presence of an organolithium compound to give an acylphosphine, followed by oxidation or sulfidation; (g) the production of (III) by reaction of (I) with phosgene, reaction of the phosphine chloride with an alcohol (see above) and reaction with a halide Z 1-X (in methods c-h); (h) photo-hardenable compositions containing photo-polymerizable unsaturated compounds plus compound(s) (II) and/or (III) as photoinitiators; (i) the photopolymerization of non-volatile, mono-, oligo- or poly-meric compounds with ethylenic double bond(s) by irradiating the compositions (i) with light in the 200-600 nm range; (j) substrates coated with the compositions; (k) the photographic production of relief images by exposing the coated substrates to light to form an image and then removing the unexposed parts with a solvent. [Image] A : O or S; x : 0 or 1; Y 11-18C alkyl (optionally substituted with phenyl(s)), 1-18C haloalkyl, 2-18C alkyl with in-chain O or S (optionally substituted with OH and/or SH), 3-18C cycloalkyl (optionally substituted with 1-10C alkyl, OR 11, CF 3or halogen), 2-18C alkenyl, OR 11, NR 12R 13, a group of formula (IV), -Y 2-CO-P(R 6)(A) x-CO-Ar, or cyclopentyl, cyclohexyl, naphthyl etc. (see other groups as listed above for Ar), with the proviso that Y 1and Ar are not identical; Y 2direct bond or various (cyclo)alk(en)ylene or arylene groups; Z 11-24C alkyl (optionally substituted with OR 15, SR 15, NR 16R 17, phenyl, halogen, CN, -NCA, oxiranyl, -C(A)R 18, -C(A)-OR 18and/or -C(A 1)N(R 18) 2), 2-24C alkyl with in-chain O, S or NR 14(optionally substituted as for 1-24C alkyl), 1-24C alkoxy (optionally substituted with phenyl, CN, NCA, oxiranyl etc. (see 1-24C alkyl), -C(A)-OR 11, -C(A 1)-NR 16R 17, -C(A)-OR 11a, -C(A 1)-N(R 18a)(R 18b), 3-24C cycloalkyl (optionally substituted), 2-24C alkenyl (optionally substituted), 3-24C cycloalkenyl, or (all optionally substituted) phenyl, phenyl linked via -Z 3-, pyridyl, pyrimidyl, s-triazinyl, phthalimidyl, anthraquinonyl (or analogous groups with one CO group replaced by S, CH 2, CO, NR 14or a direct bond), benzophenone groups, -Z 2-P(A) x(R 6)-COAr, polysiloxanyl, polysilanyl, arylthio or benzylthio, or 1-24C alkylthio (optionally with in-chain O or S or optionally substituted with OR 15, SR 15or halogen); A 1O, S or NR 18a; Z 21-24C alkylene, 2-24C alkylene or alkenylene, 3-24C cycloalkylene or cycloalkenylene (all optionally with in-chain hetero atoms as above and optionally substituted), phenylene, -Phe-Z 5-Phe-, -Z 6-Phe-Z 7-, or a polysiloxane or polysilane residue; Phe : phenylene; Z 3CH 2, CHOH, CHCH 3or C(CH 3) 2; Z 5S, O, CH 2, CHCH 3, C(CH 3) 2, C(CF 3) 2, SO, SO 2or CO; Z 6, Z 7CH 2, CHCH 3or C(CH 3) 2; R 11aoptionally substituted alkyl, alkoxy, alkenyl, alkynyl, cycloalkenyl, aralkyl or arylcycloalkyl etc.; R 15as for R 11, or -C(A)-R 18, -C(A)-OR 18or -C(A 1)-N(R 18) 2; R 16, R 17as for R 12, or -C(A)-R 18, -C(A)-OR 18or -C(A 1)-N(R 18) 2; R 18, R 18a, R 18bH or various hydrocarbyl groups (optionally modified and/or substituted); X : Cl or Br; M 1Li, Na or K; X' : -NCA, -NCNZ 1, oxiranyl or -CHO.