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US4864041A
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Transition metal-substituted polyoxometalates as catalysts for homogenous liquid-phase organic oxidation processes
Assignee: Emory University
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Filing: 1987-02-04
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Granted: 1989-09-05
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Expires: 2007-02-04
Abstract
Abstract A novel process for the homogenous oxidation of organic substrates is disclosed. This process uses a transition metal-substituted polyoxometalate catalyst, which in the presence of an oxygen donor, catalyses the carbon-hydrogen bond (e.g., alkane) hydroxylation reaction and/or epoxidation reaction of the organic substrate.
Inventors
- 👤 Craig L. Hill
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 04:45
CPC Classifications
B; B01; B01J; B01J27/00; B01J27/14; B01J27/186; B01J27/188; C; C07; C07C; C07C29/00; C07C29/48; C07C45/00; C07C45/27; C07C45/28; C07C45/30; C07D; C07D301/00; C07D301/02; C07D303/00; C07D303/02; C07D303/04; B01J2231/00; B01J2231/70; B01J2231/72; B01J2531/00; B01J2531/02; B01J2531/0238; B01J2531/0241; B01J2531/025; B01J2531/80; B01J2531/84; B01J2531/842; C07C2601/00; C07C2601/12; C07C2601/16
Claims Analysis
Total Claims: 25
Claim 1
Independent Claim
189 words
A process for the catalytic oxidation of an organic substrate, comprising: (1) combining the said organic substrate, a transition metal-substituted polyoxometalate and an oxygen donor to obtain a reaction medium; (2) allowing the said transition metal-substituted polyoxometalate to catalyze homogeneously the oxidation of the substrate; and (3) obtaining an oxidized form of the said organic substrate; wherein the said oxidation is a carbon-hydrogen bond hydroxylation reaction or an epoxidation reaction; wherein the said organic substrate is an organic compound containing from 1 to 100 carbon atoms and at least one carbon-hydrogen bond or wherein the said organic substrate is an organic compound containing from 2 to 100 carbon atoms and at least one olefinic functionality; wherein the said transition metal-substituted polyoxometalate is a polyoxometalate derivative having a transition metal ligated by several oxygen atoms of the metal oxide framework of the polyoxometalate and wherein the said transition metal has at least one coordination site available for coordination with either the oxygen donor or the organic substrate or both; and wherein the said transition metal is chromium, manganese, iron, cobalt, nickel, copper, technetium, rubidium, rhodium, palladium, silver, rhenium, or iridium.
Claim 2
Dependent Claim
189 words
A process for the catalytic oxidation of an organic substrate, comprising: (1) combining the said organic substrate, a transition metal-substituted polyoxometalate and an oxygen donor to obtain a reaction medium; (2) allowing the said transition metal-substituted polyoxometalate to catalyze homogeneously the oxidation of the substrate; and (3) obtaining an oxidized form of the said organic substrate; wherein the said oxidation is a carbon-hydrogen bond hydroxylation reaction or an epoxidation reaction; wherein the said organic substrate is an organic compound containing from 1 to 100 carbon atoms and at least one carbon-hydrogen bond or wherein the said organic substrate is an organic compound containing from 2 to 100 carbon atoms and at least one olefinic functionality; wherein the said transition metal-substituted polyoxometalate is a polyoxometalate derivative having a transition metal ligated by several oxygen atoms of the metal oxide framework of the polyoxometalate and wherein the said transition metal has at least one coordination site available for coordination with either the oxygen donor or the organic substrate or both; and wherein the said transition metal is chromium, manganese, iron, cobalt, nickel, copper, technetium, rubidium, rhodium, palladium, silver, rhenium, or iridium.
Claim 3
Dependent Claim
24 words
The process of claim 1, comprising using a transition metal-substituted polyoxometalate in which the transition metal is chromium, manganese, iron, cobalt, nickel, or copper.
Claim 4
Dependent Claim
22 words
The process of claim 1, comprising using a transition metal-substituted polyoxometalate in which the transition metal is chromium, manganese, cobalt, or copper.
Claim 5
Dependent Claim
171 words
The process of claim 1, comprising using a transition metal-substituted polyoxometalate having one of the following formulae: [(M)XW.sub.x Mo.sub.y V.sub.z O.sub.39 Q.sub.a H.sub.b Li.sub.c ;(i) wherein x+y+z=12; [(M)X.sub.2 W.sub.1 Mo.sub.m V.sub.n O.sub.61 ]Q.sub.d H.sub.e Li.sub.c ;(ii) wherein 1+m+=18; [(M)X.sub.5 W.sub.p Mo.sub.q V.sub.r O.sub.109 ]Q.sub.g H.sub.h Li.sub.i ;(iii) where p+q+r=29; wherein: the values of (a+b+c) or of (d+e+f) or of (g+h+i) add up to the charge on the transition metal-substituted polyoxometalate, (M) is the said transition metal which is chromium, manganese, iron, cobalt, nickel, copper, technetium, rubidium, rhodium, palladium, silver, rhenium or iridium; X is phosphorus, arsenic, silicon, germanium, boron, aluminum, cobalt, zinc, or iron; Q is, independent of any other Q in any one transition metal-substituted polyoxometalate molecule, a group R 4 2 N+, R 4 2 P+, or R 4 2 As + , wherein R 2 is independently a C 1-30 alkyl group which is straight, branched, cyclic, or a combination thereof; a C 6-30 aryl group, a C 6-30 aralkyl group, or a C 3-30 aromatic heterocyclic group.
Claim 6
Dependent Claim
15 words
The process of claim 4, wherein (M) comprises chromium, manganese, iron, cobalt, nickel or copper.
Claim 7
Dependent Claim
13 words
The process of claim 4, wherein (M) comprises chromium, manganese, cobalt, or copper.
Claim 8
Dependent Claim
64 words
The process of claim 1, wherein the said oxygen donor comprises a C 1-30 alkyl hydroperoxide, a substituted C 1-30 alkylhydroperoxide, hydrogen peroxide, a C 6-30 iodosylarene, a substituted C 6-30 iodosylarene, a C 1-30 amine-N-oxide, a substituted C 1-30 amine-N-oxide, a C 1-30 peracid, a substituted C 1-30 peracid, a hypochlorite, a halogen oxyanion, an oxaziridine, chromate, dichromate, permanganate, ruthenium or osmium tetroxide.
Claim 9
Dependent Claim
15 words
The process of claim 4, wherein Q is a tetra (C 1-30 ) alkyl ammonium.
Claim 10
Dependent Claim
22 words
The process of claim 4, comprising combining the organic substrate, the transition metal-substituted polyoxometalate, and the oxygen donor together with a solvent.
Claim 11
Dependent Claim
19 words
The process of claim 9, wherein the solvent comprises water, acetonitrile, hexamethylphosphoramide, dichloroethane, dichloromethane, benzene, or a mixture thereof.
Claim 12
Dependent Claim
14 words
The process of claim 4, wherein the said oxidation reaction is an epoxidation reaction.
Claim 13
Dependent Claim
16 words
The process of claim 4, wherein the said oxidation reaction is a carbon-hydrogen bond hydroxylation reaction.
Claim 14
Dependent Claim
32 words
The process of claim 4, comprising using a transition metal-substituted polyoxometalate of the formula [(M)XW 11 O 39 ]QaH b Li c , wherein (M) is Co, Mn, Cu, Fe, or Cr.
Claim 15
Dependent Claim
34 words
The process of claim 4, comprising using a transition metal-substituted polyoxometalate of the formula [(M)X 2 W 17 O 61 ]QdH e Li c , where (M) is Co, Mn, Cu, Fe or Cr.
Claim 16
Dependent Claim
34 words
The process of claim 4, comprising using a transition metal-substituted polyoxometalate of the formula [(M)X 5 W 29 O 109 ]QgH h Li i , wherein (M) is Co, Mn, Cu, Fe or Cr.
Claim 17
Dependent Claim
167 words
The process of claim 4, wherein the said organic substrate comprises a straight C 1-100 alkane, a branched C 4-100 alkane, a cyclic C 3-100 alkane, a C 1-100 haloalkane, a C 4-100 branched haloalkane, a C 3-100 halocyclic alkane, a linear C 2-100 alkene, a branched C 4-100 alkene, a cyclic C 4-100 alkene, a C 6-100 arene, C 7-100 aralkane, a C 3-100 heterocyclic compound containing at least one oxygen atom or at least one sulfur atom or at least one nitrogen atom or at least one phosphorus atom, a C 2-100 ester, a C 2-100 ether, a C 3-100 ketone, C 1-100 aldehyde, C 2-100 nitrile, a C 1-100 carboxylic acid, a C 1-100 nitro compound, a C 1-100 ammonium salt, a C 1-100 thiol, a C 2-100 sulfide, a C 2-100 disulfide, a C 1-100 phosphine, a C 1-100 phosphine oxide, a C 3-100 phosphite, a C 3-100 phosphate or an arsenic or antimony analog of the said phosphine, phosphite or their oxide.
Claim 18
Dependent Claim
181 words
A polyoxometalate of one of the formulae: Q w 1 H 10-w [Co 4 P 2 W 18 O 68 ]·μH 2 O; Q w 1 H 10-w [Cu 4 P 2 W 18 O 68 ]·μH 2 O; Q w 1 H 10-w [Mn 4 P 2 W 18 O 68 ]·μH 2 O; or Q w 1 H 10-w [Fe 4 P 2 W 18 O 68 ]·μH 2 O; wherein: Q 1 is a quaternary salt, R 4 3 N + , R 4 3 P + , or R 4 3 As + , R 3 is independently a C 1-30 alkyl, C 6-30 aryl, or C 7-30 aralkyl, and wherein at least one R 3 is a C 8-30 alkyl when all R 3 in a molecule Q 1 are C 1-30 alkyl and Q 1 is R 3 N+; w is an integer of from 0 to 10; and μ is an integer of from 0 to 50; or wherein at least one group Q.sup.(1)+ or H + is exchanged for a Li + ion.
Claim 19
Dependent Claim
181 words
A polyoxometalate of one of the formulae: Q w 1 H 10-w [Co 4 P 2 W 18 O 68 ]·μH 2 O; Q w 1 H 10-w [Cu 4 P 2 W 18 O 68 ]·μH 2 O; Q w 1 H 10-w [Mn 4 P 2 W 18 O 68 ]·μH 2 O; or Q w 1 H 10-w [Fe 4 P 2 W 18 O 68 ]·μH 2 O; wherein: Q 1 is a quaternary salt, R 4 3 N + , R 4 3 P + , or R 4 3 As + , R 3 is independently a C 1-30 alkyl, C 6-30 aryl, or C 7-30 aralkyl, and wherein at least one R 3 is a C 8-30 alkyl when all R 3 in a molecule Q 1 are C 1-30 alkyl and Q 1 is R 3 N+; w is an integer of from 0 to 10; and μ is an integer of from 0 to 50; or wherein at least one group Q.sup.(1)+ or H + is exchanged for a Li + ion.
Claim 20
Dependent Claim
153 words
A polyoxometalate of one of the formulae: Q.sub.w.sup.2 H.sub.16-w [Co.sub.4 P.sub.4 W.sub.30 O.sub.112 ]·μH.sub.2 O; Q.sub.w.sup.2 H.sub.16-w [Cu.sub.4 P.sub.4 W.sub.30 O.sub.112 ]·μH.sub.2 O; Q.sub.w.sup.2 H.sub.16-w [Mn.sub.4 P.sub.4 W.sub.30 O.sub.112 ]·μH.sub.2 O; or Q.sub.w.sup.2 H.sub.16-w [Fe.sub.4 P.sub.4 W.sub.30 O.sub.112 ]·μH.sub.2 O; wherein: Q 2 is a quaternary salt, or R 4 4 N 30 , R 4 4 P + , or R 4 4 As + , and wherein R 4 is independently a C 1-30 alkyl, C 6-30 aryl, or a C 7-30 aralkyl, and wherein at least one R 4 is a C 8-30 alkyl when all groups R 4 are C 1-30 alkyl in a molecule Q 2 and Q 2 is R 4 4 N + ; w is an integer from 0 to 10; and μ is an integer from 0 to 50; or wherein at least one group Q(.sup.(2)+ or H+is exchanged for a Li + ion.
Claim 21
Dependent Claim
153 words
A polyoxometalate of one of the formulae: Q.sub.w.sup.2 H.sub.16-w [Co.sub.4 P.sub.4 W.sub.30 O.sub.112 ]·μH.sub.2 O; Q.sub.w.sup.2 H.sub.16-w [Cu.sub.4 P.sub.4 W.sub.30 O.sub.112 ]·μH.sub.2 O; Q.sub.w.sup.2 H.sub.16-w [Mn.sub.4 P.sub.4 W.sub.30 O.sub.112 ]·μH.sub.2 O; or Q.sub.w.sup.2 H.sub.16-w [Fe.sub.4 P.sub.4 W.sub.30 O.sub.112 ]·μH.sub.2 O; wherein: Q 2 is a quaternary salt, or R 4 4 N 30 , R 4 4 P + , or R 4 4 As + , and wherein R 4 is independently a C 1-30 alkyl, C 6-30 aryl, or a C 7-30 aralkyl, and wherein at least one R 4 is a C 8-30 alkyl when all groups R 4 are C 1-30 alkyl in a molecule Q 2 and Q 2 is R 4 4 N + ; w is an integer from 0 to 10; and μ is an integer from 0 to 50; or wherein at least one group Q(.sup.(2)+ or H+is exchanged for a Li + ion.
Claim 22
Dependent Claim
134 words
A polyoxometalate of one of the formula: Q.sub.w.sup.3 H.sub.8-w [S.sub.2 Nb.sub.6 W.sub.18 O.sub.77 ]·μH.sub.2 O wherein: Q 3 is a quaternary salt, R 4 5 N + , R 4 5 P + , or R 4 5 As + , and wherein R 5 is a C 1-30 alkyl group, a C 6-30 aryl, or a C 7-30 aralkane group, and wherein at least one R 5 is a C 8-30 alkyl when all groups R 5 in a molecule Q 3 are C 1-30 alkyl and Q 3 is R 4 5 N + ; w is an integer of from 0 to 8; and μ is an integer of from 0 to 50; or wherein at least one group Q.sup.( 3)+ or H + is exchanged for a Li + ion.
Claim 23
Dependent Claim
134 words
A polyoxometalate of one of the formula: Q.sub.w.sup.3 H.sub.8-w [S.sub.2 Nb.sub.6 W.sub.18 O.sub.77 ]·μH.sub.2 O wherein: Q 3 is a quaternary salt, R 4 5 N + , R 4 5 P + , or R 4 5 As + , and wherein R 5 is a C 1-30 alkyl group, a C 6-30 aryl, or a C 7-30 aralkane group, and wherein at least one R 5 is a C 8-30 alkyl when all groups R 5 in a molecule Q 3 are C 1-30 alkyl and Q 3 is R 4 5 N + ; w is an integer of from 0 to 8; and μ is an integer of from 0 to 50; or wherein at least one group Q.sup.( 3)+ or H + is exchanged for a Li + ion.
Claim 24
Dependent Claim
84 words
A polyoxometalate of the formula: Q w 4 H 12-w [(M) 3 P 2 W 18 O 68 ]·μH 2 O wherein: (M) is Co II , Mn II , Cu II , or Fe II ; and Q 4 is a quaternary salt or R 4 6 N + , R 4 6 P + , or R 4 6 As + , where R 6 is a C 1-30 alkyl group, a C 6-30 aryl group, or a C 7-30 aralkyl group.
Claim 25
Dependent Claim
84 words
A polyoxometalate of the formula: Q w 4 H 12-w [(M) 3 P 2 W 18 O 68 ]·μH 2 O wherein: (M) is Co II , Mn II , Cu II , or Fe II ; and Q 4 is a quaternary salt or R 4 6 N + , R 4 6 P + , or R 4 6 As + , where R 6 is a C 1-30 alkyl group, a C 6-30 aryl group, or a C 7-30 aralkyl group.
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