1. A polymer-supported metal cluster composition comprising a transition metal and a cross-linked polymer, wherein the transition metal is supported by the cross-linked polymer and the cross-linked polymer is obtained by cross-linking a cross-linkable polymer wherein the cross-linkable polymer contains at least one hydrophobic side chain and at least one hydrophilic side chain, wherein at least one hydrophilic side chain has a cross-linkable functional group, and wherein each hydrophobic side chain is free of hydrophilic substituents and cross-linkable functional groups, and wherein the composition is prepared, in a solution, by forming a micelle wherein clusters of the metal are supported by the cross-linkable polymer and then cross-linking the cross-linkable polymer.
2. The composition as in claim 1, wherein the cross-linkable polymer contains a hydrophobic side chain containing an aromatic group, and the micelle is formed by supporting a transition metal by the cross-linkable polymer using a ligand exchange reaction between a transition metal chelate and the aromatic group of the cross-linkable polymer.
3. The composition as in claim 1, wherein the metal clusters are 20 nm or smaller in diameter.
4. The composition as in claim 1, wherein the transition metal is at least one selected from the group consisting of palladium, cobalt, nickel, rhodium, ruthenium, iridium, gold and platinum.
5. The composition as in claim 1, wherein the transition metal is at least one selected from the group consisting of palladium, ruthenium, iridium, gold and platinum.
6. The composition as in claim 1, wherein the transition metal has zero valence.
7. The composition as in claim 1, wherein the cross-linkable polymer contains a hydrophilic side chain having an epoxy group, a carboxyl group, an isocyanate group or a thioisocyanate group.
8. The composition as in claim 7, wherein the cross-linkable polymer further contains at least one type of a hydrophilic side chain having a hydroxyl group, a primary or secondary amino group, or a thiol group.
9. The composition as in claim 1, wherein the cross-linkable polymer is: (i) a polymer or a copolymer obtained by polymerizing or copolymerizing at least one type of A1) monomer having an aromatic group as a hydrophobic side chain, a hydrophilic side chain having a cross-linkable functional group and a polymerizable double bond; or (ii) a copolymer obtained by copolymerizing at least two types of monomers selected from the group consisting of B1) monomer, B2) monomer, and B3) monomer, wherein the B1) monomer is a monomer having an aromatic group as a hydrophobic side chain, a hydrophilic side chain having a cross-linkable functional group and a polymerizable double bond, the B2) monomer is a monomer having an aromatic group as a hydrophobic side chain and a polymerizable double bond, and the B3) monomer is a monomer containing a hydrophilic side chain having a cross-linkable functional group and a polymerizable double bond.
10. The composition as in claim 9, wherein the cross-linkable polymer is a copolymer obtained by copolymerizing at least two types of monomers selected from B1) monomer, B2) monomer, and B3) monomer, wherein the B1) monomer is a monomer represented by chemical formula 1:
wherein R1 is a hydrogen atom or an alkyl group having 1-6 carbon atom(s), R2 is an aryl group having 6-14 carbon atoms, R3 is a covalent bond, an alkylene group having 1-6 carbon atom(s), \u2014R9(OR10)m\u2014, \u2014R9(COOR10)n\u2014 or R9(COOR10)o(OR10)p\u2014,
wherein R9 is independently a covalent bond or an alkylene group having 1-6 carbon atom(s), R10 is independently an alkylene group having 2-4 carbon atoms, m, n and p are integers of 1-10 and o is 1 or 2,
R4 is a carboxyl group, an isocyanate group, an isothiocyanate group, a hydroxyl group, a primary or secondary amino group, a thiol group or a group represented by chemical formula 2:
or chemical formula 3:
wherein R5 is independently an alkylene group having 1-6 carbon atom(s), R6 and R7 are each independently a hydrogen atom or an alkyl group having 1-6 carbon atom(s),
and R6 may form a 3-6 membered ring with R5 or R7,
the B2) monomer is a monomer represented by chemical formula 4:
wherein R1 and R2 are independently as defined above, R11 is a hydrogen atom or an alkyl group having 1-6 carbon atom(s),
and the B3) monomer is a monomer represented by chemical formula 5:
wherein R1, R3, R4 and R11 are independently as defined above.
11. A method for performing a hydrogenation reaction, a dehydrogenation reaction, an oxidation reaction, an allylic substitution reaction, a coupling reaction or a carbonylation reaction, wherein the method comprises catalyzing the reaction with a composition of claim 1.
12. The composition as in claim 9, wherein the cross-linkable polymer is a polymer obtained by polymerizing one type of A1) monomer represented by chemical formula 1:
wherein R1 is a hydrogen atom or an alkyl group having 1-6 carbon atom(s), R2 is an aryl group having 6-14 carbon atoms, R3 is a covalent bond, an alkylene group having 1-6 carbon atom(s), \u2014R9(OR10)m\u2014, \u2014R9(COOR10)n\u2014 or R9(COOR10)o(OR10)p\u2014,
wherein R9 is independently a covalent bond or an alkylene group having 1-6 carbon atom(s), R10 is independently an alkylene group having 2-4 carbon atoms, m, n and p are integers of 1-10 and o is 1or 2,
R4 is a carboxyl group, an isocyanate group, an isothiocyanate group, a hydroxyl group, a primary or secondary amino group, a thiol group or a group represented by chemical formula 2:
or chemical formula 3:
wherein R5 is independently an alkylene group having 1-6 carbon atom(s), R6 and R7 are each independently a hydrogen atom or an alkyl group having 1-6 carbon atom(s),
and R6 may form a 3-6 membered ring with R5 or R7.
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
1. A compound of formula I
in which
R1 is Hal, NO2, CF3, COOH, COOR or H,
R2 is R, Hal, CN, NO2, NHR, NRR, NHCOR, NHSO2R, OR, CO\u2014R, CO\u2014NHR, CF3, OCF3, SCF3, SO3R, SO2R, SO2NR, SR, COOH or COOR,
R3 is Hal or CO\u2014NHR,
R is H or unsubstituted or mono-, di-, tri- or tetra-R4-substituted A, Ar, Het, (CH2)qHet or (CH2)qAr,
A is unbranched, branched or cyclic alkyl having 1-14 C atoms, in which one or two CH2 groups are each optionally replaced by O, S, or \u2014CH\u2550CH\u2014 andor 1-7 H atoms are each optionally replaced by F or Cl,
Ar is phenyl, naphthyl or biphenyl, each of which is unsubstituted or mono-, di- or trisubstituted by A, Hal, OH, OA, CN, NO2, NH2, NHA, NA2, NHCOA, SCF3, SO2A, COOH, COOA, CONH2, CONHA, CONA2, NHSO2A, SO2NH2, SO2NHA, SO2NA2, CHO or COA,
Het is a mono- or bicyclic saturated, unsaturated or aromatic heterocycle having 1 to 4 N, O andor S atoms, which may be unsubstituted or mono-, di- or trisubstituted by carbonyl oxygen, Hal, A,\u2014(CH2)b\u2014Ar, \u2014(CH2)b-cycloalkyl, OH, OA, NH2, NHA, NA2, NO2, CN, COOH, COOA, CONH2, CONHA, CONA2, NHCOA, NHCONH2, NHSO2A, CHO, COA, SO2NH2 andor S(O)gA,
Hal is F, Cl, Br or I,
R4 is Hal, OH, CN, NO2, CF3, OCF3, SCF3, SO2A or OA,
X is O, S, or NH,
{circle around (Y)} is phenyl or a monocyclic aromatic heterocycle having 1 to 4 N, O andor S atoms,
b is 0, 1, 2, 3 or 4,
g is 0, 1 or 2,
n, m, p, q are each, independently of one another, 1, 2, 3, or 4,
or a pharmaceutically acceptable salt, or stereoisomer thereof, including mixtures of stereoisomers in all ratios.
2. A compound according to claim 1, in which R2 is H.
3. A compound according to claim 1, in which {circle around (Y)} is phenyl, furyl, thienyl, pyrrolyl, imidazolyl, pyridyl or pyrimidinyl.
4. A compound according to claim 1, in which
R2 is H,
{circle around (Y)} is phenyl, furyl, thienyl, pyrrolyl, imidazolyl, pyridyl or pyrimidinyl,
X is O, S, or NH,
n, p, are each, independently of one another, 1, 2, 3 or 4,
m is 1.
5. A compound according to claim 1, wherein A is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-, 2- or 3-methylbutyl, 1,1-, 1,2- or 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-, 2-, 3- or 4-methylpentyl, 1,1-, 1,2-, 1,3-, 2,2-, 2,3- or 3,3-dimethylbutyl, 1- or 2-ethylbutyl, 1-ethyl-l-methylpropyl, 1-ethyl-2-methylpropyl, 1,1,2- or 1,2,2-trimethylpropyl, linear or branched heptyl, octyl, nonyl, decyl, trifluoromethyl, pentafluoroethyl, 1,1,1-trifluoroethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or cycloheptyl.
6. A compound according to claim 5, wherein A is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, or tert-butyl.
7. A compound according to claim 5, wherein A is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, trifluoromethyl, pentafluoroethyl, or 1,1,1-trifluoroethyl.
8. A compound according to claim 1, wherein A is alkyl having 1, 2, 3, 4, 5 or 6 C atoms, in which one or two CH2 groups are each optionally replaced by O, S, or by \u2014CH\u2550CH\u2014, and 1-7 H are each optionally replaced by F or Cl.
9. A compound according to claim 1, wherein Ar is phenyl, naphthyl or biphenyl, which in each case is mono-, di- or trisubstituted by substituents selected from A, fluorine, chlorine, bromine, iodine, hydroxyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, nitro, cyano, formyl, acetyl, propionyl, tri-fluoromethyl, amino, methylamino, ethylamino, dimethylamino, diethylamino, benzyloxy, sulfonamido, methylsulfonamido, ethylsulfonamido, propylsulfonamido, butylsulfonamido, dimethylsulfonamido, phenylsulfonamido, carboxyl, methoxycarbonyl, ethoxycarbonyl, and aminocarbonyl.
10. A compound according to claim 1, wherein Het is 2- or 3-furyl, 2- or 3-thienyl, 1-, 2- or 3-pyrrolyl, 1-, 2, 4- or 5-imidazolyl, 1-, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5-oxazolyl, 3-, 4- or 5-isoxazolyl, 2-, 4- or 5-thiazolyl, 3-, 4- or 5-iso-thiazolyl, 2-, 3- or 4-pyridyl, 2-, 4-, 5- or 6-pyrimidinyl, furthermore preferably 1,2,3-triazol-1-, -4- or -5-yl, 1,2,4-triazol-1-, -3- or 5-yl, 1- or 5-tetrazolyl, 1,2,3-oxadiazol-4- or -5-yl, 1,2,4-oxadiazol-3- or -5-yl, 1,3,4-thiadiazol-2- or -5-yl, 1,2,4-thiadiazol-3- or -5-yl, 1,2,3-thiadiazol-4- or -5-yl, 3- or 4-pyridazinyl, pyrazinyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-indolyl, 4- or 5-isoindolyl, 1-, 2-, 4- or 5-benzimidazolyl, 1-, 3-, 4-, 5-, 6- or 7-benzopyrazolyl, 2-, 4-, 5-, 6- or 7-benzoxazolyl, 3-, 4-, 5-, 6- or 7- benzisoxazolyl, 2-, 4-, 5-, 6- or 7-benzothiazolyl, 2-, 4-, 5-, 6- or 7-benzisothiazolyl, 4-, 5-, 6- or 7-benz-2,1,3-oxadiazolyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-quinolyl, 1-, 3-, 4-, 5-, 6-, 7- or 8-isoquinolyl, 3-, 4-, 5-, 6-, 7- or 8-cinnolinyl, 2-, 4-, 5-, 6-, 7- or 8-quinazolinyl, 5- or 6-quinoxalinyl, 2-, 3-, 5-, 6-, 7- or 8-2H-benzo-1,4-oxazinyl, furthermore preferably 1,3-benzodioxo1-5-yl, 1,4-benzodioxan-6-yl, 2,1,3-benzothiadiazol-4-or -5-yl, or 2,1,3-benzoxadiazol-5-yl, which in each case is unsubstituted or mono-, di- or trisubstituted by substituents selected from carbonyl oxygen, F, Cl, Br, methyl, ethyl, propyl, phenyl, benzyl, -CH2-cyclohexyl, hydroxyl, methoxy, ethoxy, amino, methylamino, dimethylamino, nitro, cyano, carboxyl, methoxycarbonyl, aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, acetamino, ureido, methylsulfonylamino, formyl, acetyl, aminosulfonyl, and methylsulfonyl, or
Het is 2,3-dihydro-2-, -3-, -4- or -5-furyl, 2,5-dihydro-2-, -3-, -4- or 5-furyl, tetrahydro-2- or -3-furyl, 1,3-dioxolan-4-yl, tetrahydro-2- or -3-thienyl, 2,3-dihydro-1-, -2-, -3-, -4- or -5-pyrrolyl, 2,5-dihydro-1-, -2-, -3-, -4- or -5-pyrrolyl, 1-, 2- or 3-pyrrolidinyl, tetrahydro-1-, -2- or -4-imidazolyl, 2,3-dihydro-1-, -2-, -3-, -4- or -5-pyrazolyl, tetrahydro-1-, -3- or -4-pyrazolyl, 1,4-dihydro-1-, -2-, -3- or -4-pyridyl, 1,2,3,4-tetrahydro-1-, -2-, -3-, -4-, -5- or -6-pyridyl, 1-, 2-, 3- or 4-piperidinyl, 2-, 3- or 4-morpholinyl, tetrahydro-2-, -3- or -4-pyranyl, 1,4-dioxanyl, 1,3-dioxan-2-, -4- or -5-yl, hexahydro-1-, -3- or -4-pyridazinyl, hexahydro-1-, -2-, -4- or -5-pyrimidinyl, 1-, 2- or 3-piperazinyl, 1,2,3,4-tetrahydro-1-, -2-, -3-, -4-, -5-, -6-, -7- or -8-quinolyl, 1,2,3,4-tetrahydro-1-,-2-,-3-, -4-, -5-, -6-, -7- or -8-isoquinolyl, 2-, 3-, 5-, 6-, 7- or 8- 3,4-dihydro-2H-benzo-1,4-oxazinyl, furthermore preferably 2,3-methylenedioxyphenyl, 3,4-methylenedioxyphenyl, 2,3-ethylenedioxyphenyl, 3,4-ethylenedioxyphenyl, 3,4-(difluoromethylenedioxy)phenyl, 2,3-dihydrobenzofuran-5- or 6-yl, 2,3-(2-oxomethylenedioxy)phenyl, 3,4-dihydro-2H-1,5-benzodioxepin-6- or -7-yl, 2,3-dihydrobenzofuranyl, 2,3-dihydro-2-oxofuranyl, 2-oxopiperidin-l-yl, 2-oxopyrrolidin-l-yl, 2-oxo-1H-pyridin-l-yl, 3-oxomorpholin-4-yl, 4-oxo-1H-pyridin-l-yl, 2,6-dioxopiperidinl-yl, 2-oxopiperazin-l-yl, 2,6-dioxopiperazin-l-yl, 2,5-dioxopyrrolidin-l-yl, 2-oxo-1,3-oxazolidin-3-yl, 3-oxo-2H-pyridazin-2-yl, 2-caprolactam-l-yl, 2-hydroxy-6-oxopiperazin-l-yl, 2-methoxy-6-oxopiperazin-l-yl, or 2-azabicyclo2.2.2octan-3-on-2-yl.
11. A compound according to claim 10, wherein
A is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-, 2- or 3-methylbutyl, 1,1-, 1,2- or 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-, 2-, 3- or 4-methylpentyl, 1,1-, 1,2-, 1,3-, 2,2-, 2,3- or 3,3-dimethylbutyl, 1- or 2-ethylbutyl, 1-ethyl-l-methylpropyl, 1-ethyl-2-methylpropyl, 1,1,2- or 1,2,2-trimethylpropyl, linear or branched heptyl, octyl, nonyl, decyl, trifluoromethyl, pentafluoroethyl, 1,1,1-trifluoroethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or cycloheptyl; and
Ar is phenyl, naphthyl or biphenyl, which in each case is mono-, di- or trisubstituted by substituents selected from A, fluorine, chlorine, bromine, iodine, hydroxyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, nitro, cyano, formyl, acetyl, propionyl, tri-fluoromethyl, amino, methylamino, ethylamino, dimethylamino, diethylamino, benzyloxy, sulfonamido, methylsulfonamido, ethylsulfonamido, propylsulfonamido, butylsulfonamido, dimethylsulfonamido, phenylsulfonamido, carboxyl, methoxycarbonyl, ethoxycarbonyl, and aminocarbonyl.
12. A compound according to claim 1, wherein {circle around (Y)} is phenyl, pyridyl or pyrimidinyl.
13. A compound according to claim 1, in which
R1 is Hal, NO2, CF3, COOH, COOR or H,
R2 is H,
Y is phenyl, furyl, thienyl, pyrrolyl, imidazolyl, pyridyl or pyrimidinyl, and
X is O, S, or NH.
14. A compound selected from:
benzoxazol-2-yl-4-(pyridin-4-yloxy)phenyllamine,
benzoxazol-2-yl-4-(pyridin-4-ylsulfanyl)phenyllamine,
N-benzoxazol-2-yl-N\u2032-pyridin-4-ylbenzene- 1,4-diamine,
2-4-(pyridin-4-ylsulfanyl)phenylaminobenzoxazole-5-carboxylic acid,
2-4-(pyridin-4-yloxy)phenylaminobenzoxazole-6-carboxylic acid,
2-4-(pyridin-4-ylsulfanyl)phenylaminobenzoxazole-6-carboxylic acid,
methyl 2-4-(pyridin-4-ylamino)phenylaminobenzoxazole-6-carboxylate,
(5-nitrobenzoxazol-2-yl)-4-(pyridin-4-ylsulfanyl)phenylamine,
(5-nitrobenzoxazol-2-yl)-4-(pyridin-4-yloxy)phenylamine,
N-(5-nitrobenzoxazol-2-yl)-N\u2032-pyridin-4-ylbenzene-1,4-diamine,
(6-nitrobenzoxazol-2-yl)-4-(pyridin-4-yloxy)phenylamine,
(6-nitrobenzoxazol-2-yl)-4-(pyridin-4-ylsulfanyl)phenylamine,
N-(6-nitrobenzoxazol-2-yl)-N\u2032-pyridin-4-ylbenzene-1,4-diamine,
(5-chloro-7-nitrobenzoxazol-2-yl)-4-(pyridin-4-yloxy)phenylamine,
(5-chloro-7-nitrobenzoxazol-2-yl)-4-(pyridin-4-ylsulfanyl)phenyl-amine,
N-(5-chloro-7-nitrobenzoxazol-2-yl)-N\u2032-pyridin-4-ylbenzene-1,4-diamine,
(7-bromo-5-trifluoromethylbenzoxazol-2-yl)-4-(pyridin-4-yloxy)phenyl-amine,
(7-bromo-5-trifluoromethylbenzoxazol-2-yl)-4-(pyridin-4-ylsulfanyl)phenyl-amine,
(7-bromo-5-trifluoromethylbenzoxazol-2-yl)-4-(4-fluorophenylsulfanyl)-phenylamine,
N-4-(bromotrifluoromethylbenzoxazol-2-ylamino)phenyl-4-fluoro-benzenesulfonamide, 4-(2-amino-6-methylpyrimidin-4-yloxy)phenyl-(7-bromo-5- trifluoro-methylbenzoxazol-2-yl)amine,
N-methyl-4-4-(bromotrifluoromethylbenzoxazol-2-ylamino)phenoxyl-pyridine-2-carboxamide,
N-methyl-4-4-(bromotrifluoromethylbenzoxazol-2-ylamino)phenylsulfanyl-pyridine-2-carboxamide, and
(7-bromo-5-trifluoromethylbenzoxazol-2-yl)-4-(2,4-difluorophenylsulfanyl)-phenylamine,
and pharmaceutically acceptable salts, and stereoisomers thereof, including mixtures of stereoisomers in all ratios.
15. A pharmaceutical composition comprising at least one compound according to claim 1 and one or more excipients andor adjuvants.
16. A pharmaceutical composition comprising at least one compound according to claim 1, and at least one active ingredient in addition to said one compound according to claim 1.
17. A kit consisting of separate packs of a) an effective amount of a compound according to claim 1, and b) an effective amount of an active ingredient in addition to said compound according to claim 1.
18. A process for preparation of a compound according to claim 1, said process comprising:
reacting a compound of formula II
with a compound of formula III