US20020022731A1 - Transesterification catalysts fixed on solid support materials - Google Patents
Transesterification catalysts fixed on solid support materials Download PDFInfo
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- US20020022731A1 US20020022731A1 US09/819,453 US81945301A US2002022731A1 US 20020022731 A1 US20020022731 A1 US 20020022731A1 US 81945301 A US81945301 A US 81945301A US 2002022731 A1 US2002022731 A1 US 2002022731A1
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- alkylene
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- 0 C[Si](C)(C)*S[Sn](C)(C)C Chemical compound C[Si](C)(C)*S[Sn](C)(C)C 0.000 description 36
- FBJSQPBKKOJOEM-UHFFFAOYSA-N C#C#C#C#CC.CN1N=C2C=CC=CC2=N1 Chemical compound C#C#C#C#CC.CN1N=C2C=CC=CC2=N1 FBJSQPBKKOJOEM-UHFFFAOYSA-N 0.000 description 3
- OJYHCRARAPEIRI-UHFFFAOYSA-N CC.CN1N=C2C=CC=CC2=N1 Chemical compound CC.CN1N=C2C=CC=CC2=N1 OJYHCRARAPEIRI-UHFFFAOYSA-N 0.000 description 3
- HRKVJWNVXRNCID-UHFFFAOYSA-N C#CC(C)C(C)C(C)=O.CCC1=CC(C)=C(C)C(C)=C1 Chemical compound C#CC(C)C(C)C(C)=O.CCC1=CC(C)=C(C)C(C)=C1 HRKVJWNVXRNCID-UHFFFAOYSA-N 0.000 description 2
- IPCLALPYYBNLPP-UHFFFAOYSA-N C.C.C.CC(=O)OC1CC(C)N(C)C(C)C1 Chemical compound C.C.C.CC(=O)OC1CC(C)N(C)C(C)C1 IPCLALPYYBNLPP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N CC(C)=O Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HLVBHUJZBNZCQC-UHFFFAOYSA-N *.CC(=O)CC1=CC(C)=C(O)C(C)=C1C Chemical compound *.CC(=O)CC1=CC(C)=C(O)C(C)=C1C HLVBHUJZBNZCQC-UHFFFAOYSA-N 0.000 description 1
- CRAYBSCXEWNIMA-UHFFFAOYSA-K C.C.CO[Si](CCS[Sn](C)(C)Cl)(OC)O[Y].[H][Sn](C)(C)SCC[Si](OC)(OC)O[Y] Chemical compound C.C.CO[Si](CCS[Sn](C)(C)Cl)(OC)O[Y].[H][Sn](C)(C)SCC[Si](OC)(OC)O[Y] CRAYBSCXEWNIMA-UHFFFAOYSA-K 0.000 description 1
- HSCSAHCBNFLEAS-UHFFFAOYSA-N C.COCC(C)(COC)COC Chemical compound C.COCC(C)(COC)COC HSCSAHCBNFLEAS-UHFFFAOYSA-N 0.000 description 1
- PDBZWCSOHUBFTI-UHFFFAOYSA-N C.COCC(COC)(COC)COC Chemical compound C.COCC(COC)(COC)COC PDBZWCSOHUBFTI-UHFFFAOYSA-N 0.000 description 1
- LVNXRZRMTDEUSV-UHFFFAOYSA-N CC.CO.COC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1.COC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1.O Chemical compound CC.CO.COC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1.COC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1.O LVNXRZRMTDEUSV-UHFFFAOYSA-N 0.000 description 1
- ATEBBJDINOPJHX-UHFFFAOYSA-N CCC(CC)CC.CCC(CC)CC.CCC(CC)CC.CCC(CC)CC Chemical compound CCC(CC)CC.CCC(CC)CC.CCC(CC)CC.CCC(CC)CC ATEBBJDINOPJHX-UHFFFAOYSA-N 0.000 description 1
- FVCNQFWNIPNDTH-UHFFFAOYSA-N CCCCCCCCOC(=O)CCc1cc(N2N=C3C=CC=CC3=N2)c(O)c(C(C)(C)C)c1.CO.COC(=O)CCc1cc(N2N=C3C=CC=CC3=N2)c(O)c(C(C)(C)C)c1 Chemical compound CCCCCCCCOC(=O)CCc1cc(N2N=C3C=CC=CC3=N2)c(O)c(C(C)(C)C)c1.CO.COC(=O)CCc1cc(N2N=C3C=CC=CC3=N2)c(O)c(C(C)(C)C)c1 FVCNQFWNIPNDTH-UHFFFAOYSA-N 0.000 description 1
- SMMZUXIKTNGOMT-UHFFFAOYSA-N CCCCSSCCCC.CCO[Si](CCCSSCCC[Si](OC)(OCC)OC1CCCCCCCCC1)(OC)OC.CO.CO.CO.O.O.OC1CCCCCCCCC1 Chemical compound CCCCSSCCCC.CCO[Si](CCCSSCCC[Si](OC)(OCC)OC1CCCCCCCCC1)(OC)OC.CO.CO.CO.O.O.OC1CCCCCCCCC1 SMMZUXIKTNGOMT-UHFFFAOYSA-N 0.000 description 1
- AAQLGPFQNCSUJC-UHFFFAOYSA-N CCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1.COC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1.OCC(CO)(CO)CO Chemical compound CCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1.COC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1.OCC(CO)(CO)CO AAQLGPFQNCSUJC-UHFFFAOYSA-N 0.000 description 1
- KYVLNIHEEDPWSG-UHFFFAOYSA-N CO.CO.CO.CO[Si](C)(C)C.CO[Si](C)(C)OC.CO[Si](C)(OC)OC Chemical compound CO.CO.CO.CO[Si](C)(C)C.CO[Si](C)(C)OC.CO[Si](C)(OC)OC KYVLNIHEEDPWSG-UHFFFAOYSA-N 0.000 description 1
- KUBAQMLTGUGYGD-UHFFFAOYSA-N CO.CO.CO.CO[Si](CCCS)(OC)OC.CO[Si](CCCS)(OC)OC1CCCCCCCCC1.C[Si](C)(C)CCCS.O.O.O.O.O.OC1CCCCCCCCC1 Chemical compound CO.CO.CO.CO[Si](CCCS)(OC)OC.CO[Si](CCCS)(OC)OC1CCCCCCCCC1.C[Si](C)(C)CCCS.O.O.O.O.O.OC1CCCCCCCCC1 KUBAQMLTGUGYGD-UHFFFAOYSA-N 0.000 description 1
- PTOOVEFBMMTMJP-UHFFFAOYSA-N COCC(C)(COC)COC Chemical compound COCC(C)(COC)COC PTOOVEFBMMTMJP-UHFFFAOYSA-N 0.000 description 1
- MBXZBSXAFUVONM-UHFFFAOYSA-N COCC(COC)(COC)COC Chemical compound COCC(COC)(COC)COC MBXZBSXAFUVONM-UHFFFAOYSA-N 0.000 description 1
- KZEPDJYHIMGAPP-UHFFFAOYSA-N C[N](C)(C)N[IH][N](C)(C)C Chemical compound C[N](C)(C)N[IH][N](C)(C)C KZEPDJYHIMGAPP-UHFFFAOYSA-N 0.000 description 1
- PWORFEDVDWBHSJ-UHFFFAOYSA-N C[n]1nc(cccc2)c2n1 Chemical compound C[n]1nc(cccc2)c2n1 PWORFEDVDWBHSJ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/122—Metal aryl or alkyl compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0228—Sulfur-containing compounds with a metal-sulfur link, e.g. mercaptides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
- C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
Definitions
- the present invention relates to immobilized tin-sulfur catalysts, their preparation and their use in transesterification reactions of carboxylic esters.
- R is usually a C 1 -C 4 alkyl radical and R′ and Z are each an organic radical.
- the reaction is an equilibrium reaction. In general, the (lower-boiling) alcohol liberated is distilled off during the reaction.
- a series of different catalysts for this reaction are known (Junzo Otera, Chem. Rev., 93 (1993) 1449-1470), e.g. acids, bases, amines, metal alkoxides and also, inter alia, organotin compounds. Many of these esterification reactions are carried out at temperatures in the range from 80° C. to above 200° C.
- Organotin compounds are known and very mild catalysts for transesterifications of carboxylic esters with alcohols.
- a problem associated with conventional tin catalysts is achieving an economical separation of the tin from the reaction product.
- a possible solution is the use of immobilized tin catalysts which can be separated off.
- the present invention provides a process for the transesterification of carboxylic esters, characterized in that the catalyst used is a tin(IV) compound comprising a radical of the formula
- L is an at least divalent radical and at least one of the free valences of the Si in formula (I) is bound to the inorganic support.
- R 101 and R 102 are identical or different and are H, alkyl having from 1 to 18 C atoms, phenyl, C 1 -C 4 alkyl-substituted phenyl, phenylalkyl having from 7 to 9 C atoms, C 5 -C 12 cycloalkyl, C 1 -C 4 alkyl-substituted C 5 -C 12 cycloalkyl or a radical
- R 103 is H or CH 3 ;
- R 105 is H, Cl, —SO 3 H or C 1 -C 4 alkyl
- m is 0, 1, 2 or 3;
- n 1, 2, 3 or 4;
- A is —OR 104 ;
- R 104 is alkyl having from 2 to 45 C atoms, C 2 -C 45 alkyl interrupted by one or more oxygen, cycloalkyl having from 5 to 12 C atoms, alkenyl having from 2 to 18 C atoms, —CH 2 CHOHCH 2 OC(O)R 109 or —CH 2 CH 2 —OR 106 ; and
- R 109 is H, alkyl having from 1 to 8 C atoms, alkenyl having from 3 to 5 C atoms or benzyl;
- R 112 is
- H alkyl having from 1 to 24 C atoms, phenyl, cycloalkyl having from 5 to 12 C atoms or
- R 110 is H or —CH 3 ;
- R 111 is H or alkyl having from 1 to 24 C atoms.
- R 112 is H or —CH 3 , with the proviso that R 110 and R 112 are not simultaneously —CH 3 ;
- A is —O—C x H 2x —O—, —O—(CH 2 CH 2 O) a CH 2 CH 2 O— or —O—CH 2 CH ⁇ CHCH 2 —O—; in which
- a is from 1 to 30;
- x is from 2 to 20;
- R 107 is alkyl having from 1 to 24 C atoms or phenyl
- R 101 is tert-butyl or
- R 102 is tert-butyl
- R 103 and R 105 are H;
- m is 2; A is OR 104 ;
- R 104 is (CH 2 ) 17 CH 3 , C 8 H 17 (isomer mixture), C 2 -C 45 alkyl interrupted by one or more oxygen, —CH 2 CHOHCH 2 OC(O)R 109 ; and
- R 109 is alkenyl having from 3 to 5 C atoms
- n 2;
- R 101 is tert-butyl or
- R 102 is CH 3 ;
- R 103 is H
- m 2;
- A is —O—(CH 2 CH 2 O) a CH 2 CH 2 O—;
- a is from 1 to 30;
- n 3;
- R 101 and R 102 are tert-butyl
- R 103 is H
- m 2;
- A is —O—CH 2 —CH(O—)—CH 2 —O—;
- n 4;
- R 101 and R 102 are tert-butyl
- R 103 is H
- m 2;
- A is C(CH 2 —O—) 4 .
- R 200 and R 201 are, independently of one another, C 1 -C 4 alkyl
- R 202 is H, C 1 -C 18 alkyl, O or C 1 -C 18 alkoxy;
- p is 1 or 2.
- R 210 and R 211 are, independently of one another, C 1 -C 4 alkyl
- x is from 1 to 12;
- R 212 and R 213 are, independently of one another, C 1 -C 4 alkyl
- a 210 is C 1 -C 12 alkylene.
- the compounds obtainable by reaction of the compounds (XXX) with (XXXI) are, in general, oligomeric or polymeric compounds or mixtures of such compounds.
- the stoichiometric ratios and reaction parameters make it possible to influence the formation of the compounds or mixtures of compounds.
- Alkyl having up to 45 C atoms can be a linear or branched alkyl group and can be, for example: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, 3-heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, 2-ethylbutyl, 1-methylpentyl, 1,3-dimethylbutyl, 1,1,3,3-tetramethylbutyl, 1-methylhexyl, isoheptyl, 1-methylheptyl, 1,1,3-trifluoride
- R 101 and R 102 are the t-butyl group. Preference is also given to R 101 ⁇ —CH 3 and R 102 ⁇ t-butyl or R 101 ⁇ isopropyl and R 102 ⁇ t-butyl. As R 103 , preference is given to —H. Preferred R 111 , R 107 and R 106 are alkyl groups having from 1 to 18 C atoms.
- cycloalkyl substituents having from 5 to 12 C atoms are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl and cyclododecyl. Preference is given to cyclohexyl.
- Examples of C 1 -C 4 alkyl-substituted cycloalkyl having from 5 to 12 C atoms are 2- or 4-methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl and t-butylcyclohexyl.
- C 1 -C 4 alkyl-substituted phenyl substituents are methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl and 6-butylphenyl.
- phenylalkyl having from 7 to 9 C atoms are benzyl, phenethyl, ⁇ -methylbenzyl and ⁇ , ⁇ -dimethylbenzyl. Preference is given to benzyl.
- Alkenyl having up to 18 C atoms is, for example, vinyl, propenyl, allyl, butenyl, methallyl, hexenyl, decenyl or heptadecenyl.
- tin(IV) compounds which can be used as catalysts in the process of the invention are, in general, mixtures of compounds of various compositions. Preference is given to compounds or mixtures of compounds obtainable by reaction of a compound of the formula:
- t is 1, 2 or 3;
- u is 0, 1 or 2;
- v is 1, 2, 3, 4, 5, 6, 7, 8 or 9;
- w is 1, 2 or 3
- L is an at least divalent C 1 -C 18 alkylene, C 2 -C 18 alkenylene, phenylene, C 1 -C 18 alkylene/phenylene radical or C 2 -C 18 alkylene or C 1 -C 18 alkylene/phenylene radical interrupted by one or more O, C(O), S, C(S), N(Y), C(O)—N(Y), N(Y)—C(O)—N(Y) and/or N(Y)—C(O)—O;
- Support is an inorganic support material
- R 1 are, independently of one another, C 1 -C 4 alkoxy, phenoxy, C 1 -C 4 alkyl, phenyl or halogen;
- Y are, independently of one another, C 1 -C 18 alkyl, phenyl or C 1 -C 18 alkyl/phenyl;
- R 2 are, independently of one another, C 1 -C 18 alkyl, substituted C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 1 -C 18 haloalkyl, C 6 -C 16 haloaryl, C 3 -C 16 haloheteroaryl, C 1 -C 4 alkylphenyl, C 1 -C 4 alkoxyphenyl, halo-C 1 -C 4 alkylphenyl, halo-C 1 -C 4 alkoxyphenyl, C 1 -C 12 hydroxyalkyl, C 3 -C 8 cycloalkyl, C 6 -C 16 aryl, substituted C 6 -C 16 aryl, C 7 -C 16 aralkyl, C 3 -C 6 heterocycloalkyl, C 3 -C 16 heteroaryl, C 4 -C 16 heteroaralkyl, —Cl, —Br, —I,
- L is preferably C 1 -C 18 alkylene, C 2 -C 18 alkenylene, phenylene or C 1 -C 18 alkylene/phenylene, particularly preferably C 1 -C 18 alkylene, very particularly preferably C 2 -C 6 alkylene.
- R 1 is preferably C 1 -C 4 alkoxy, particularly preferably methoxy or ethoxy.
- R 2 is preferably halogen, OH or ⁇ O, particularly preferably chlorine.
- Examples of an at least divalent C 1 -C 18 alkylene radical are linear or branched C 1 -C 18 alkylene radicals of the type mentioned further below in which at least one further H atom is replaced by a direct bond, for example —CH 2 —, —CH 2 CH 2 —, —C(CH 3 ) 2 —, —CH 2 C(CH 3 )CH 2 —, ⁇ CH— or —CH 2 CHCH 2 —.
- At least divalent C 2 -C 18 alkenylene radicals are analogous to the at least divalent alkylene radicals described; they have one or more C—C double bonds.
- Examples of at least divalent phenylene radicals are o-phenylene or p-phenylene.
- At least divalent C 1 -C 18 alkylene/phenylene radicals are derived from the at least divalent alkylene radicals described by the alkylene chain being interrupted by phenylene, where phenylene can also form the beginning and/or the end of the chain.
- At least divalent C 2 -C 18 alkylene or C 2 -C 18 alkylene/phenylene radicals interrupted by one or more O, C(O), S, C(S), N(Y), C(O)—N(Y), N(Y)—C(O)—N(Y) and/or N(Y)—C(O)—O are derived from the analogous at least divalent radicals described; in the case of a plurality of interrupting radicals, these are generally not directly adjacent.
- radicals of this type in which the interrupting radicals can also form the beginning and/or the end of the chain are: —CH 2 CH 2 —O—CH 2 —CH 2 —, —CH 2 —C 6 H 4 —CH 2 —O—CH 2 —, —CH 2 —CH 2 —C(O)—CH 2 , —CH 2 —CH 2 —C(O), —CH 2 —CH—CH 2 —CH 2 —N(C 2 H 5 )—CH 2 —CH 2 —O— or —CH 2 —CH 2 —CH—CH 2 —O—CH 2 —CH 2 —O—.
- Trivalent alkylene radicals L are, for example,
- halogen is to be understood as being fluorine, chlorine, bromine or iodine. In the case of a plurality of halogen substituents, these can be of the same type or mixed (for example Cl and F).
- Alkyl is methyl, ethyl, isopropyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl or the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl radicals.
- Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl or 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, trifluoromethyl or dichlorofluoromethyl.
- Alkoxy is, for example, methoxy, ethoxy, propyloxy, i-propyloxy, n-butyloxy, i-butyloxy, s-butyloxy or t-butyloxy; preferably methoxy or ethoxy.
- Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy or 2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy or trifluoromethoxy.
- Cycloalkyl is, for example, cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl or cycloheptyl, preferably cyclopropyl, cyclopentyl or cyclohexyl.
- Alkoxyalkyl is, for example: methoxymethyl, ethoxymethyl, propyloxymethyl, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxypropyl, ethoxypropyl or propyloxypropyl.
- Phenyl including phenyl as part of a substituent such as phenoxy, phenylthio, phenoxycarbonyl, phenylaminocarbonyl, benzyl or benzoyl, can in general be present in unsubstituted form or be substituted by further substituents.
- the substituents can then be in the ortho, meta and/or para positions.
- Preferred substituent positions are the ortho and para positions relative to the ring linkage point.
- Preferred substituents are halogen atoms.
- Aralkyl is, for example, benzyl, phenylethyl, 3-phenylpropyl, ⁇ -methylbenzyl, phenylbutyl or ⁇ , ⁇ -dimethylbenzyl.
- Aryl and analogously haloaryl are, for example, phenyl, tetralin, indene, naphthalene, azulene or anthracene.
- Heteroaryl and analogously haloheteroaryl are, for example, pyrrole, furan, thiophene, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, purine, quinoline or isoquinoline.
- Heterocycloalkyl is, for example, oxirane, oxetane, azetidine, azirine, 1,2-oxathiolane, pyrazoline, pyrrolidine, piperidine, piperazine, morpholine, dioxolane, tetrahydropyran, tetrahydrofuran or tetrahydrothiophene.
- the inorganic support materials are preferably glass, silicates, semimetal oxides and metal oxides which are particularly preferably in the form of powder having a mean particle diameter of from 10 nm to 5 mm.
- the particles can be compact or porous. Porous particles preferably have a high internal surface area, for example 1-1200 m 2 /g.
- Further preferred support materials are inorganic support materials containing OH groups. Examples of oxides and silicates are SiO 2 , TiO 2 , ZrO 2 , MgO, NiO, WO 3 , Al 2 O 3 , La 2 O 3 , silica gels, clays and zeolites. Particularly preferred support materials are silica gels, aerosils, aluminum oxide, titanium oxide and mixtures thereof.
- An example of glass as support material is “controlled pore glass”, which is commercially available.
- a further aspect of the present invention is a tin(IV) compound comprising a radical of the formula
- L is an at least divalent radical and at least one of the free valences of the Si in formula (I) is bound to the inorganic support, with the exception of tin(IV) compounds which have two or three hydrocarbon radicals on the Sn and only one tin-sulfur bond and the Si is bound via the three free valences to an OH-containing inorganic support.
- Preferred immobilized tin(IV) compounds comprise a radical of the formula (Ia)
- L is a divalent radical and at least one of the free valences of each Si in formula (Ia) is bound to the inorganic support.
- immobilized tin(IV) compounds are those which comprise a radical of the formula (Ib)
- L is a trivalent radical and at least one of the free valences of Si in formula (Ib) is bound to the inorganic support.
- the meanings of L, including the preferences, are indicated above.
- t is 1, 2 or 3;
- u is 0, 1 or 2;
- v is 1, 2, 3, 4, 5, 6, 7, 8 or 9;
- w is 1, 2 or 3
- L is an at least divalent C 1 -C 18 alkylene, C 2 -C 18 alkenylene, phenylene, C 1 -C 18 alkylene/phenylene radical or C 2 -C 18 alkylene or C 1 -C 18 alkylene/phenylene radical interrupted by one or more O, C(O), S, C(S), N(Y), C(O)—N(Y), N(Y)—C(O)—N(Y) and/or N(Y)—C(O)—O;
- Support is an inorganic support material:
- R 1 are, independently of one another, C 1 -C 4 alkoxy, phenoxy, C 1 -C 4 alkyl, phenyl or halogen;
- Y are, independently of one another, C 1 -C 18 alkyl, phenyl or C 1 -C 18 alkyl/phenyl;
- R 2 are, independently of one another, C 1 -C 18 alkyl, substituted C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 1 -C 18 haloalkyl, C 6 -C 16 haloaryl, C 3 -C 16 haloheteroaryl, C 1 -C 4 alkylphenyl, C 1 -C 4 alkoxyphenyl, halo-C 1 -C 4 alkylphenyl, halo-C 1 -C 4 alkoxyphenyl, C 1 -C 12 hydroxyalkyl, C 3 -C 8 cycloalkyl, C 6 -C 16 aryl, substituted C 6 -C 16 aryl, C 7 -C 16 aralkyl, C 3 -C 6 heterocycloalkyl, C 3 -C 16 heteroaryl, C 4 -C 16 heteroaralkyl, —Cl, —Br, —I,
- t is 2 or 3
- u is 0 or 1
- v is 1 or 2
- w is 1 or 2.
- Examples of compounds comprising a radical of the formula (I) or of compounds obtainable by reaction of compounds of the formulae (IIa) and (IIb) are:
- Support Si can be illustrated by
- a further aspect of the present invention is the preparation of the tin(IV) compounds bound to (immobilized on) an inorganic support which are according to the invention or can be used according to the invention. This can be carried out in various ways which are known in principle. In the following, two basic methods of preparation are described by way of example.
- Method 1 A thiol is first immobilized and the immobilized thiol is subsequently reacted with a tin(IV) compound.
- L, v and w are as defined above, including the preferences;
- R 1 ′ is C 1 -C 4 alkyl or phenyl
- R 1 ′′ are, independently of one another, C 1 -C 4 alkoxy, phenoxy or halogen
- i 0, 1 or 2, with the proviso that w+i is less than 4.
- the immobilization of alkoxy silanes and halosilanes on an inorganic support has been comprehensively described in the literature (for example by: K. K. Unger, Porous Silica, in Journal of Chromatography Library, Vol 16, Elsevier Scientific Publishing Company (1979)).
- the loading density (mmol of thiol/g of support) of the Si thiol can be controlled within a wide range by means of the amount of Si thiol used relative to the amount of support used and by means of the immobilization conditions.
- the Si thiol compound is usually dissolved in a solvent (e.g. xylene, toluene, benzene, THF, methylene chloride, ethyl acetate or ether).
- nonpolar and high-boiling solvents Preference is given to nonpolar and high-boiling solvents.
- This solution is then added to the support (or vice versa) and the mixture is typically stirred gently for 3-50 hours, preferably for about 10-20 hours, at temperatures of from 50° C. to the reflux temperature.
- the water formed or the alcohol formed is distilled off.
- the product is then filtered off and washed with a suitable solvent (e.g. alcohol) to remove any excess thiol.
- the product can subsequently be dried at elevated temperature, preferably under reduced pressure, or it can be directly, without drying, slurried in a solvent suitable for the reaction with Sn(IV) compounds.
- the procedure can be carried out under inert gas (e.g. nitrogen, argon) if necessary.
- Sn(IV) The immobilized thiols are subsequently reacted with Sn(IV).
- Sn compounds having Sn—S bonds Gmelin, 8th edition, tin.
- These can be either pure Sn(R 2 ) 4 compounds or mixtures of various Sn(R 2 ) 4 compounds.
- the 4 radicals R 2 can be identical or different.
- At least one R 2 has to be a radical which can react with a thiol group to form an S—Sn bond.
- Compounds having a radical R 2 of this type are preferably halides, alkoxides, carbonates or Sn compounds having OH or Sn ⁇ O groups.
- Sn(alkyl) 4 compounds can react with thiols to form an Sn—S bond.
- the Sn(IV) compound is generally dissolved in a suitable solvent (e.g. linear and cyclic alkanes, aromatics such as benzene or toluene, halogenated hydrocarbons, nitromethane, DMSO, alcohols, acetone, carboxylic acids such as acetic acid, esters, DMF, nitrites and also water) and the solution is added to the Si thiol fixed on the support, or vice versa.
- a suitable solvent e.g. linear and cyclic alkanes, aromatics such as benzene or toluene, halogenated hydrocarbons, nitromethane, DMSO, alcohols, acetone, carboxylic acids such as acetic acid, esters, DMF, nitrites and also water
- the addition can be carried out at temperatures of from ⁇ 78° C. to 100°
- the reaction with the Si thiol can result in liberation of hydrohalic acid. This can be neutralized by means of bases (for example alkalis, carbonates, ammonia, amines).
- bases for example alkalis, carbonates, ammonia, amines.
- the reaction mixture is stirred slowly at temperatures of from 20° C. to the boiling point of the solvent. The reaction time is typically from 1 hour to a number of days.
- the product is then filtered off, washed with solvents such as alcohols, water, and, if necessary, after-treated with a slightly basic aqueous solution or a solution which modifies the ligand or ligands.
- the ratio of S to Sn can be controlled via the amount of Sn(IV) which is added relative to the amount of thiol immobilized on the support. The ratio of S/Sn can vary in the range from 1:1 to 10:1.
- the ratio of S/Sn can also be changed afterwards by coproportionation with an Sn(IV) compound.
- the immobilized catalysts can be used without drying or they can be dried at elevated temperature (preferably under reduced pressure) before use and, if necessary, also be thermally treated before use, for example at a temperature in the range 100° C.-300° C.
- Such disulfides are known or can be prepared in a simple way by known methods (W. Buder, Z. Naturforsch., 34b (1979) 790-793). Some of them are commercially available and are described, for example, in the company document “Chemieutz im Degussa Klastechniktechnisch”, Volume 1, pages 94-99, 1988.
- the immobilized disulfides can subsequently be either
- thiols or thiolates e.g. using Na 2 S, K 2 S, glucose, sodium dithionite, phosphine
- Sn(IV) compounds as described for the thiols.
- the invention therefore also provides a process for preparing compounds of the formula (I) according to claim 1 immobilized on inorganic supports by reacting a compound of the formula:
- t is 1, 2 or 3;
- u is 0, 1 or 2;
- v is 1, 2, 3, 4, 5, 6, 7, 8 or 9;
- w is 1, 2 or 3
- L is an at least divalent C 1 -C 18 alkylene, C 2 -C 18 alkenylene, phenylene, C 1 -C 18 alkylene/phenylene radical or a C 2 -C 18 alkylene or C 1 -C 18 alkylene/phenylene radical interrupted by one or more O, C(O), S, C(S), N(Y), C(O)—N(Y), N(Y)—C(O)—N(Y) and/or N(Y)—C(O)—O;
- Support is an inorganic support material
- R 1 are, independently of one another, C 1 -C 4 alkoxy, phenoxy, C 1 -C 4 alkyl, phenyl or halogen;
- Y are, independently of one another, C 1 -C 18 alkyl, phenyl or C 1 -C 18 alkylphenyl;
- R 2 are, independently of one another, C 1 -C 18 alkyl, substituted C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 1 -C 18 haloalkyl, C 6 -C 16 haloaryl, C 3 -C 16 haloheteroaryl, C 1 -C 4 alkylphenyl, C 1 -C 4 alkoxyphenyl, halo-C 1 -C 4 alkylphenyl, halo-C 1 -C 4 alkoxyphenyl, C 1 -C 12 hydroxyalkyl, C 3 -C 8 cycloalkyl, C 6 -C 16 aryl, substituted C 6 -C 16 aryl, C 7 -C 16 aralkyl, C 3 -C 6 heterocycloalkyl, C 3 -C 16 heteroaryl, C 4 -C 16 heteroaralkyl, —Cl, —Br, —I,
- Method 2 Firstly preparation of an, if desired isolated, immobilized Sn—S compound and then immobilization of this compound.
- General literature on the preparation of Sn compounds having Sn—S bonds Gmelin, 8th edition, tin.
- Pure immobilized Sn—S compounds or mixtures thereof are obtained by reacting n o compounds of the type Si—SM having n o .v.w SM groups either partially or completely with compounds Sn(R 2 ) 4 so as to form at least one Sn—S bond.
- M is H or an alkali metal, preferably Na, K or Li, and n o is 1-4, preferably 1-3.
- the immobilizable Sn—S compounds are prepared by reaction of the thiol or a thiolate with Sn(R 2 ) 4 .
- the hydrohalic acid formed can be neutralized by means of a base (e.g. alkalis, carbonates, ammonia, amines).
- the immobilizable Sn—S compounds are prepared by reaction of the thiol with Sn(R 2 ) 4 . If necessary, the HO-alkyl, HO-aryl, H 2 O or amine formed during the reaction can be distilled off.
- the preferred stoichiometry on the Sn can be set by selection of the thiol/Sn ratio.
- the immobilizable Sn—S compounds can be immobilized on a support or polycondensed in a manner analogous to that for the thiol compounds (see Method 1).
- the invention therefore likewise provides a further process for preparing a tin(IV) compound bound to an inorganic support, characterized in that a compound of the formula
- (R 1 )′ is C 1 -C 4 alkyl or phenyl
- (R 1 )′′ are, independently of one another, C 1 -C 4 alkoxy, phenoxy or halogen;
- i is 0, 1 or 2, with the proviso that w+i is less than or equal to 4;
- v is 1, 2, 3 or 4;
- w is 1, 2 or 3;
- L is an at least divalent C 1 -C 18 alkylene, C 2 -C 18 alkenylene, phenylene, C 1 -C 18 alkylene/phenylene radical or a C 2 -C 18 alkylene or C 1 -C 18 alkylene/phenylene radical interrupted by one or more O, C(O), S, C(S), N(Y), C(O)—N(Y), N(Y)—C(O)—N(Y) and/or N(Y)—C(O)—O;
- Support is an inorganic support material
- R 2 are, independently of one another, C 1 -C 4 alkoxy, phenoxy, C 1 -C 4 alkyl, phenyl or halogen;
- Y are, independently of one another, C 1 -C 18 alkyl, phenyl or C 1 -C 18 alkyl/phenyl;
- n o is 1, 2, 3 or 4;
- M is H or an alkali metal.
- the immobilized catalysts can be used without drying or can be dried at elevated temperature (preferably under reduced pressure) before use and can, if necessary, also be thermally treated before use (at temperatures in the range 100° C.-300° C.).
- the catalyst can be present in dispersed form in the reactants and is filtered off after the reaction is complete.
- the catalyst which has become exhausted by use can be regenerated and reused or else can be discarded. It is also possible to arrange the catalyst in a fixed bed and to carry out the reaction in, for example, a flow reactor (continuous process).
- the transesterification is advantageously carried out by reacting the starting materials either in the form of a solution in a solvent or, if they are not liquid, in the form of a melt produced by increasing the temperature.
- Solvents employed are the compounds and mixtures which are customary per se, for example aromatic hydrocarbons such as benzene and alkyl-substituted or halogenated benzenes, in particular toluene, xylene or dichlorobenzene, high-boiling aliphatic hydrocarbons such as high-boiling paraffins, aprotic solvents such as dimethylformamide or dimethylaniline.
- aromatic hydrocarbons such as benzene and alkyl-substituted or halogenated benzenes, in particular toluene, xylene or dichlorobenzene
- high-boiling aliphatic hydrocarbons such as high-boiling paraffins
- aprotic solvents such as dimethylformamide or dimethylaniline.
- the catalyst is added to the reaction mixture in amounts of, for example, from 0.001 to 10 mol %, advantageously from 0.01 to 1 mol %, of active material, based on the compounds comprising a radical of the formula (I).
- the ratio of carboxylic ester and alcohol in the reaction mixture is not critical and can be, for example, from 0.8 to 1.3 mol of the carboxylic ester per equivalent of the alcohol.
- the reaction temperature can be, for example, from 110 to 250° C., preferably from 130 to 210° C.
- the transesterification of the carboxylic esters generally takes from 1 to 10 hours, advantageously from 1 to 5 hours and preferably from 1 to 3 hours, to achieve optimum yields.
- the catalyst can, for example, be present as a suspension in the reaction mixture in the form of powder through to broken pieces. Use of the catalyst in a fixed bed is a further possible way of carrying out the process.
- the catalyst can, if it was present in suspension, be separated off, for example filtered off, and the end product can be isolated by methods known per se, for example crystallization from a solvent such as methanol, isopropanol, methanol/water mixture, etc.
- reaction mixture and/or the end product can be neutralized using an acid, e.g. formic acid, acetic acid, sulfuric acid, hydrochloric acid, etc.
- an acid e.g. formic acid, acetic acid, sulfuric acid, hydrochloric acid, etc.
- carboxylic esters and alcohols used in the process of the invention are known or can be obtained by methods known per se.
- the invention further provides for the use of a tin(IV) compound comprising a radical of the formula
- L is an at least divalent radical and at least one of the free valences of the Si in formula (I) is bound to the inorganic support, as catalyst in the transesterification of carboxylic esters.
- the carboxylic esters prepared according to the invention are, for example, valuable antioxidants against oxidative, thermal or actinic degradation of sensitive organic materials.
- Such materials are, for example, synthetic polymers of functional liquids such as lubricants, hydraulic fluids or metalworking fluids, etc.
- Examples A2-A9 are carried out according to the above-described general procedure, giving the results shown in Table 1 for the corresponding variations. TABLE 1 Preparation, deviation from the procedure Analysis of Loading Ex. No. Support described S content mmol S/g A2 Silica gel Batch using only 20 g of support, drying of 2.85% 0.89 Merck 100 the silica gel not by azeotropic distillation in toluene but under reduced pressure (5 mbar) at 120° C. for 2 hours. Immobilization in 80 ml of toluene and 0.05 mol of 3-mercaptopropyltrimethoxy- silane. Washing only with methanol.
- A4 Silica gel As in procedure described 1.65% 0.52 Grace 332 A5 Silica gel, Drying of the silica gel not by azeotropic 0.75% 0.234 Grace 332 distillation in toluene but in high vacuum (0.1 mbar) at 140° C. for 4 hours.
- A6 and Silica gel After addition of 3-mercaptopropyltri- 2.98% 0.93
- A7 Grace 332 methoxysilane 0.5 ml of methanesulfonic acid added.
- A8 and Silica gel 0.269 mol of 3-mercaptopropyltrimethoxy- 2.73% 0.85 A9 Merck 100 silane added. Washing only with methanol.
- the bis(3-triethoxysilylpropyl) disulfide is prepared by a method analogous to that described by W. Buder, Z. Naturforsch., 34b (1979) 790-793.
- silica gel Merck 100 50 g are stirred in 250 ml of toluene in an inert gas atmosphere and dried by distilling off about 50 ml of toluene. After cooling to about 40° C., 23.7 g (0.05 mol) of bis(3-triethoxysilylpropyl) disulfide are added, the mixture is again distilled briefly and subsequently stirred at 100°-110° C. for 20 hours, ensuring that the ethanol formed can distill off. After cooling, the support is filtered off, washed with 2 ⁇ 100 ml of each of ethyl acetate, methanol and hexane and finally dried under reduced pressure (1 mbar) at 70° C. for 15 hours. This gives white material having an S content of 1.83%. This corresponds to a loading density of 0.29 mmol of disulfide per g.
- Half of the methanol-moist material (30 mmol of S) is slurried in 150 ml of toluene and slowly treated while stirring at room temperature with 3.9 g (15 mmol) of SnCl 4 and subsequently with a freshly prepared sodium methoxide solution in methanol (30 mmol of sodium in 35 ml of methanol).
- the mixture is stirred for 4 hours at room temperature, #then filtered, washed (2 ⁇ 100 ml each of methanol, NaHCO 3 2M, water, methanol) and the product is dried under reduced pressure (5 mbar) at 80° C. for 15 hours.
- #The tin content of the product is 30% higher than that of Example B5.
- the white prodct is dried under reduced pressure (5 mbar) at 50° C. for 15 hours. e 95 mbar to 50° C. for 15 hours. bar at 60° C. for 15 hours. , 2 ⁇ hexane) and the white product is dried under reduced pressure (5 mbar) at 70° C. for 15 hours. educed pressure (5 mbar) at 70° C. for 15 hours.
- a suspension of 40 g of silica gel Merck 100 in 300 ml of toluene is first dried by azeotropic distillation of 100 ml of toluene. After cooling to room temperature, 31.2 g of the tin compound 1412/21 are added, the mixture is briefly distilled and stirred for 18 hours at 100° C., ensuring that the alcohol formed can distill off. After cooling, the product is filtered off, washed (100 ml each: 3 ⁇ methanol, 3 ⁇ ethyl acetate, 3 ⁇ hexane) and dried under reduced pressure (5 mbar) at 70° C. for 15 hours.
- B36 Immobilization of the Compound from Example B32 (Ph) 2 Sn[S(CH 2 ) 3 Si(OCH 3 ) 3 ] 2
- B37 Immobilization of the compound from Example B31 (Bu) 2 SnCl[S(CH 2 ) 3 Si(OCH 3 ) 3 ]
- Example B35 Prepared the same way as in Example B35, except that the reaction is carried out using 23.1 g of the Sn compound from Example B31 and that washing is carried out as follows: 100 ml each; 3 ⁇ methanol, 1 ⁇ NaHCO 3 1M, 3 ⁇ water, 3 ⁇ methanol, 2 ⁇ ethyl acetate, 2 ⁇ hexane.
- the resulting clear solution is allowed to stand for 6 days in an open vessel, resulting in evaporation of the acetone and formation of a yellowish-white mass. This is partially dried overnight at 70° C. under reduced pressure (5 mbar), washed (50 ml each: 3 ⁇ methanol, 1 ⁇ NaHCO 3 2M, 3 ⁇ water, 3 ⁇ methanol, 2 ⁇ ethyl acetate, 2 ⁇ hexane) and dried under reduced pressure (5 mbar) at 70° C. for 15 hours.
- the catalyst is still active even after the 5th reuse.
- the selectivity is greater than 99%.
- the transmission at 425 nm is above 99% in all reuses.
- the catalyst is still active even after the 5th reuse.
- the selectivity is greater than 99%.
- the transmission at 425 nm is above 99% in the reuse.
- the selectivity is greater than 99%.
- the transmission at 425 nm is above 99% in the reuse.
- the selectivity is greater than 99%.
- the transmission at 425 nm is above 99% in the reuse.
- the catalyst is still active even after the 1st reuse.
- the selectivity is greater than 99%.
- the transmission at 425 nm is above 99% in the reuse.
- the catalyst is still active even after the 1st reuse.
- the selectivity is greater than 99%.
- the transmission at 425 nm is above 99% in the reuse.
- the catalyst is still active even after the 1st reuse.
- the selectivity is greater than 99%.
- the transmission at 425 nm is above 98%.
- the catalyst is still active even after the 1st reuse.
- Example B3 The catalyst described in Example B3 is used for the above transesterification.
- 4.0 g of catalyst, 100 g of compound (103) and 73.7 g of isooctanol isomer mixture are placed in a stirred glass reactor provided with a reflux condenser heated to 80° C. and a vacuum pump.
- the reactor is subsequently evacuated to 400 mbar and the reaction mixture is heated to reflux temperature while stirring.
- the methanol formed in the reaction is distilled off through the reflux condenser heated to 80° C. and is condensed in a downstream cold trap. After about 4 hours, a boiling temperature of the reaction mixture of 180-185° C. is reached.
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Abstract
A description is given of a process for the transesterification of carboxylic esters, characterized in that the catalyst used is a tin(IV) compound comprising a radical of the formula
bound to an inorganic support, where L is an at least divalent radical and at least one of the free valences of the Si in formula (I) is bound to the inorganic support, novel tin(IV) compounds and their preparation.
Description
- The present invention relates to immobilized tin-sulfur catalysts, their preparation and their use in transesterification reactions of carboxylic esters.
-
- in which R is usually a C1-C4alkyl radical and R′ and Z are each an organic radical. The reaction is an equilibrium reaction. In general, the (lower-boiling) alcohol liberated is distilled off during the reaction. A series of different catalysts for this reaction are known (Junzo Otera, Chem. Rev., 93 (1993) 1449-1470), e.g. acids, bases, amines, metal alkoxides and also, inter alia, organotin compounds. Many of these esterification reactions are carried out at temperatures in the range from 80° C. to above 200° C.
- It is economically advantageous if the reactions can be carried out in the melt without solvents. A further advantage is gained if the product does not have to be purified by distillation or extraction after the reaction. For this reason, a catalyst should be able to be used at high temperatures (reaction in the melt) and the catalyzed reaction must not lead to discolored products.
- Organotin compounds are known and very mild catalysts for transesterifications of carboxylic esters with alcohols. A problem associated with conventional tin catalysts is achieving an economical separation of the tin from the reaction product. A possible solution is the use of immobilized tin catalysts which can be separated off.
-
- These compounds are proposed as catalysts for transesterifications in a temperature range of 50-150° C. They can be decanted or filtered off and reused a number of times. In most cases, reuse is associated with a drop in activity. No information is given about Sn leaching, for example as residual tin content of the product.
-
-
- Essentially the same compounds as in the abovementioned publications are described in DE 31 19 643.
-
- bound to an inorganic support, where L is an at least divalent radical and at least one of the free valences of the Si in formula (I) is bound to the inorganic support.
- These immobilized tin-sulfur catalysts can be used in a wide temperature range and, after the reaction, can be separated from the reaction product simply and completely by solid/liquid separation operations, for example filtration, centrifugation and decantation. The catalysts which have been filtered off continue to be catalytically active and can be reused a number of times.
-
- in which
-
- R103 is H or CH3;
- R105 is H, Cl, —SO3H or C1-C4alkyl;
- m is 0, 1, 2 or 3; and
- n is 1, 2, 3 or 4; where,
- when n=1,
- A is —OR104; and
- R104 is alkyl having from 2 to 45 C atoms, C2-C45alkyl interrupted by one or more oxygen, cycloalkyl having from 5 to 12 C atoms, alkenyl having from 2 to 18 C atoms, —CH2CHOHCH2OC(O)R109 or —CH2CH2—OR106; and
- R109 is H, alkyl having from 1 to 8 C atoms, alkenyl having from 3 to 5 C atoms or benzyl; where
-
-
- and
- R110 is H or —CH3;
- R111 is H or alkyl having from 1 to 24 C atoms; and
- R112 is H or —CH3, with the proviso that R110 and R112 are not simultaneously —CH3;
- or, when n=2,
- A is —O—CxH2x—O—, —O—(CH2CH2O)aCH2CH2O— or —O—CH2CH═CHCH2—O—; in which
- a is from 1 to 30; and
- x is from 2 to 20;
- or, when n=3,
-
- R107 is alkyl having from 1 to 24 C atoms or phenyl,
- or, when n=4,
-
- The process is particularly preferred for preparing compounds of the formula (X) in which n is one;
-
- R102 is tert-butyl;
- R103 and R105 are H;
- m is 2; A is OR104;
- R104 is (CH2)17CH3, C8H17 (isomer mixture), C2-C45alkyl interrupted by one or more oxygen, —CH2CHOHCH2OC(O)R109; and
- R109 is alkenyl having from 3 to 5 C atoms;
- or n is 2;
-
- R102 is CH3;
- R103 is H;
- m is 2;
- A is —O—(CH2CH2O)aCH2CH2O—; and
- a is from 1 to 30;
- or n is 3;
- R101 and R102 are tert-butyl;
- R103 is H;
- m is 2; and
- A is —O—CH2—CH(O—)—CH2—O—;
- or n is 4;
- R101 and R102 are tert-butyl;
- R103 is H;
- m is 2; and
- A is C(CH2—O—)4.
-
- in which
- R200 and R201 are, independently of one another, C1-C4alkyl;
- R202 is H, C1-C18alkyl, O or C1-C18alkoxy;
- A200 is, when p=1, C1-C12alkyl, C1-C12alkyl substituted by —C(O)OH or C2-C5alkenyl; or, when p=2, C1-C12alkylene; and
- p is 1 or 2.
-
- in which
- R210 and R211 are, independently of one another, C1-C4alkyl; and
- x is from 1 to 12;
- with a compound of the formula
- R212OC(O)—A210—(O)COR213 (XXXI)
- in which
- R212 and R213 are, independently of one another, C1-C4alkyl; and
- A210 is C1-C12alkylene.
- The compounds obtainable by reaction of the compounds (XXX) with (XXXI) are, in general, oligomeric or polymeric compounds or mixtures of such compounds. The stoichiometric ratios and reaction parameters make it possible to influence the formation of the compounds or mixtures of compounds.
- Examples of the substituents in the formulae (X), (XX), (XXX) and (XXXI) are given below.
- Alkyl having up to 45 C atoms can be a linear or branched alkyl group and can be, for example: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, 3-heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, 2-ethylbutyl, 1-methylpentyl, 1,3-dimethylbutyl, 1,1,3,3-tetramethylbutyl, 1-methylhexyl, isoheptyl, 1-methylheptyl, 1,1,3-trimethylhexyl, 1-methylundecyl, eicosyl, henicosyl, docosyl, triacontyl and others. Preference is given to alkyl having 1-12 C atoms and particular preference is given to alkyl having 1-8 C atoms. When mention is made of i-C8H17, this is to be understood as including a mixture of isomers.
- A very particularly preferred example of R101 and R102 is the t-butyl group. Preference is also given to R101═—CH3 and R102═t-butyl or R101═isopropyl and R102═t-butyl. As R103, preference is given to —H. Preferred R111, R107 and R106 are alkyl groups having from 1 to 18 C atoms.
- Examples of cycloalkyl substituents having from 5 to 12 C atoms are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl and cyclododecyl. Preference is given to cyclohexyl.
- Examples of C1-C4alkyl-substituted cycloalkyl having from 5 to 12 C atoms are 2- or 4-methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl and t-butylcyclohexyl.
- Examples of C1-C4alkyl-substituted phenyl substituents are methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl and 6-butylphenyl.
- Examples of phenylalkyl having from 7 to 9 C atoms are benzyl, phenethyl, α-methylbenzyl and α,α-dimethylbenzyl. Preference is given to benzyl.
- Alkenyl having up to 18 C atoms is, for example, vinyl, propenyl, allyl, butenyl, methallyl, hexenyl, decenyl or heptadecenyl.
- When m=2, the group described is, for example, —CH2—CH2—; when m=3, the group described is, for example, —CH2—CH2—CH2— or —CH2—CH(CH3)—.
-
- in which
- t is 1, 2 or 3;
- u is 0, 1 or 2;
- v is 1, 2, 3, 4, 5, 6, 7, 8 or 9; and
- w is 1, 2 or 3,
- with the proviso that t+u+w=4;
- L is an at least divalent C1-C18alkylene, C2-C18alkenylene, phenylene, C1-C18alkylene/phenylene radical or C2-C18alkylene or C1-C18alkylene/phenylene radical interrupted by one or more O, C(O), S, C(S), N(Y), C(O)—N(Y), N(Y)—C(O)—N(Y) and/or N(Y)—C(O)—O;
- Support is an inorganic support material;
- R1 are, independently of one another, C1-C4alkoxy, phenoxy, C1-C4alkyl, phenyl or halogen; and
- Y are, independently of one another, C1-C18alkyl, phenyl or C1-C18alkyl/phenyl;
- with a compound of the formula
- Sn[R2]4 (IIb),
- in which
- R2 are, independently of one another, C1-C18alkyl, substituted C1-C18alkyl, C2-C18alkenyl, C1-C18haloalkyl, C6-C16haloaryl, C3-C16haloheteroaryl, C1-C4alkylphenyl, C1-C4alkoxyphenyl, halo-C1-C4alkylphenyl, halo-C1-C4alkoxyphenyl, C1-C12hydroxyalkyl, C3-C8cycloalkyl, C6-C16aryl, substituted C6-C16aryl, C7-C16aralkyl, C3-C6heterocycloalkyl, C3-C16heteroaryl, C4-C16heteroaralkyl, —Cl, —Br, —I, OH, —OC1—C18alkyl, —OC6—C16aryl, —OOC—C1-C18alkyl, —OOC-phenyl, SH, —N(Si(CH3)3)2, SC1-C18alkyl, —SC6-C16aryl, —SC(O)—C1-C18alkyl, —SC(O)-phenyl, —SC(S)—C1-C18alkyl, —SC(S)-phenyl, H or an oxygen bridge to a further Sn atom;
- or two radicals R2 are together ═S or ═O,
- with the proviso that at least one R2 radical which can react with an SH group to form an S—Sn bond is present.
- L is preferably C1-C18alkylene, C2-C18alkenylene, phenylene or C1-C18alkylene/phenylene, particularly preferably C1-C18alkylene, very particularly preferably C2-C6alkylene.
- R1 is preferably C1-C4alkoxy, particularly preferably methoxy or ethoxy.
- R2 is preferably halogen, OH or ═O, particularly preferably chlorine.
- Examples of an at least divalent C1-C18alkylene radical are linear or branched C1-C18alkylene radicals of the type mentioned further below in which at least one further H atom is replaced by a direct bond, for example —CH2—, —CH2CH2—, —C(CH3)2—, —CH2C(CH3)CH2—, ═CH— or —CH2CHCH2—.
- At least divalent C2-C18alkenylene radicals are analogous to the at least divalent alkylene radicals described; they have one or more C—C double bonds.
- Examples of at least divalent phenylene radicals are o-phenylene or p-phenylene.
- At least divalent C1-C18alkylene/phenylene radicals are derived from the at least divalent alkylene radicals described by the alkylene chain being interrupted by phenylene, where phenylene can also form the beginning and/or the end of the chain.
- At least divalent C2-C18alkylene or C2-C18alkylene/phenylene radicals interrupted by one or more O, C(O), S, C(S), N(Y), C(O)—N(Y), N(Y)—C(O)—N(Y) and/or N(Y)—C(O)—O are derived from the analogous at least divalent radicals described; in the case of a plurality of interrupting radicals, these are generally not directly adjacent. Examples of radicals of this type in which the interrupting radicals can also form the beginning and/or the end of the chain are: —CH2CH2—O—CH2—CH2—, —CH2—C6H4—CH2—O—CH2—, —CH2—CH2—C(O)—CH2, —CH2—CH2—C(O), —CH2—CH—CH2—CH2—N(C2H5)—CH2—CH2—O— or —CH2—CH2—CH—CH2—O—CH2—CH2—O—.
-
- with the proviso that the sum of the C atoms is not more than 18.
- In the above definitions, halogen is to be understood as being fluorine, chlorine, bromine or iodine. In the case of a plurality of halogen substituents, these can be of the same type or mixed (for example Cl and F).
- Alkyl is methyl, ethyl, isopropyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl or the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl radicals. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl or 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, trifluoromethyl or dichlorofluoromethyl.
- Alkoxy is, for example, methoxy, ethoxy, propyloxy, i-propyloxy, n-butyloxy, i-butyloxy, s-butyloxy or t-butyloxy; preferably methoxy or ethoxy.
- Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy or 2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy or trifluoromethoxy.
- Cycloalkyl is, for example, cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl or cycloheptyl, preferably cyclopropyl, cyclopentyl or cyclohexyl.
- Alkoxyalkyl is, for example: methoxymethyl, ethoxymethyl, propyloxymethyl, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxypropyl, ethoxypropyl or propyloxypropyl.
- Phenyl, including phenyl as part of a substituent such as phenoxy, phenylthio, phenoxycarbonyl, phenylaminocarbonyl, benzyl or benzoyl, can in general be present in unsubstituted form or be substituted by further substituents. The substituents can then be in the ortho, meta and/or para positions. Preferred substituent positions are the ortho and para positions relative to the ring linkage point. Preferred substituents are halogen atoms.
- Aralkyl is, for example, benzyl, phenylethyl, 3-phenylpropyl, α-methylbenzyl, phenylbutyl or α,α-dimethylbenzyl.
- Aryl and analogously haloaryl are, for example, phenyl, tetralin, indene, naphthalene, azulene or anthracene.
- Heteroaryl and analogously haloheteroaryl are, for example, pyrrole, furan, thiophene, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, purine, quinoline or isoquinoline.
- Heterocycloalkyl is, for example, oxirane, oxetane, azetidine, azirine, 1,2-oxathiolane, pyrazoline, pyrrolidine, piperidine, piperazine, morpholine, dioxolane, tetrahydropyran, tetrahydrofuran or tetrahydrothiophene.
- The inorganic support materials are preferably glass, silicates, semimetal oxides and metal oxides which are particularly preferably in the form of powder having a mean particle diameter of from 10 nm to 5 mm. The particles can be compact or porous. Porous particles preferably have a high internal surface area, for example 1-1200 m2/g. Further preferred support materials are inorganic support materials containing OH groups. Examples of oxides and silicates are SiO2, TiO2, ZrO2, MgO, NiO, WO3, Al2O3, La2O3, silica gels, clays and zeolites. Particularly preferred support materials are silica gels, aerosils, aluminum oxide, titanium oxide and mixtures thereof. An example of glass as support material is “controlled pore glass”, which is commercially available.
-
- bound to an inorganic support, where L is an at least divalent radical and at least one of the free valences of the Si in formula (I) is bound to the inorganic support, with the exception of tin(IV) compounds which have two or three hydrocarbon radicals on the Sn and only one tin-sulfur bond and the Si is bound via the three free valences to an OH-containing inorganic support.
-
- in which L is a divalent radical and at least one of the free valences of each Si in formula (Ia) is bound to the inorganic support.
-
- in which L is a trivalent radical and at least one of the free valences of Si in formula (Ib) is bound to the inorganic support. The meanings of L, including the preferences, are indicated above.
-
- in which
- t is 1, 2 or 3;
- u is 0, 1 or 2;
- v is 1, 2, 3, 4, 5, 6, 7, 8 or 9; and
- w is 1, 2 or 3,
- with the proviso that t+u+w=4;
- L is an at least divalent C1-C18alkylene, C2-C18alkenylene, phenylene, C1-C18alkylene/phenylene radical or C2-C18alkylene or C1-C18alkylene/phenylene radical interrupted by one or more O, C(O), S, C(S), N(Y), C(O)—N(Y), N(Y)—C(O)—N(Y) and/or N(Y)—C(O)—O;
- Support is an inorganic support material:
- R1 are, independently of one another, C1-C4alkoxy, phenoxy, C1-C4alkyl, phenyl or halogen; and
- Y are, independently of one another, C1-C18alkyl, phenyl or C1-C18alkyl/phenyl;
- with a compound of the formula
- Sn[R2]4 (IIb),
- in which
- R2 are, independently of one another, C1-C18alkyl, substituted C1-C18alkyl, C2-C18alkenyl, C1-C18haloalkyl, C6-C16haloaryl, C3-C16haloheteroaryl, C1-C4alkylphenyl, C1-C4alkoxyphenyl, halo-C1-C4alkylphenyl, halo-C1-C4alkoxyphenyl, C1-C12hydroxyalkyl, C3-C8cycloalkyl, C6-C16aryl, substituted C6-C16aryl, C7-C16aralkyl, C3-C6heterocycloalkyl, C3-C16heteroaryl, C4-C16heteroaralkyl, —Cl, —Br, —I, OH, —OC1-C18alkyl, —OC6-C16aryl, —OOC—C1-C18alkyl, —OOC-phenyl, SH, —N(Si(CH3)3)2, SC1-C18alkyl, —SC6-C16aryl, —SC(O)—C1-C18alkyl, —SC(O)-phenyl, —SC(S)—C1-C18alkyl, —SC(S)-phenyl, H or an oxygen bridge to a further Sn atom;
- or two radicals R2 together are ═S or ═O,
- with the proviso that at least one R2 radical which can react with an SH group to form an S—Sn bond is present.
- Preferably, t is 2 or 3, u is 0 or 1, v is 1 or 2 and w is 1 or 2.
-
-
-
- In general, no uniform bond is obtained.
- A further aspect of the present invention is the preparation of the tin(IV) compounds bound to (immobilized on) an inorganic support which are according to the invention or can be used according to the invention. This can be carried out in various ways which are known in principle. In the following, two basic methods of preparation are described by way of example.
- Method 1: A thiol is first immobilized and the immobilized thiol is subsequently reacted with a tin(IV) compound.
-
- in which
- L, v and w are as defined above, including the preferences;
- R1′ is C1-C4alkyl or phenyl;
- R1″ are, independently of one another, C1-C4alkoxy, phenoxy or halogen; and
- i is 0, 1 or 2, with the proviso that w+i is less than 4.
- The immobilization of alkoxy silanes and halosilanes on an inorganic support has been comprehensively described in the literature (for example by: K. K. Unger, Porous Silica, in Journal of Chromatography Library, Vol 16, Elsevier Scientific Publishing Company (1979)). The loading density (mmol of thiol/g of support) of the Si thiol can be controlled within a wide range by means of the amount of Si thiol used relative to the amount of support used and by means of the immobilization conditions. The Si thiol compound is usually dissolved in a solvent (e.g. xylene, toluene, benzene, THF, methylene chloride, ethyl acetate or ether). Preference is given to nonpolar and high-boiling solvents. This solution is then added to the support (or vice versa) and the mixture is typically stirred gently for 3-50 hours, preferably for about 10-20 hours, at temperatures of from 50° C. to the reflux temperature. The water formed or the alcohol formed is distilled off. The product is then filtered off and washed with a suitable solvent (e.g. alcohol) to remove any excess thiol. The product can subsequently be dried at elevated temperature, preferably under reduced pressure, or it can be directly, without drying, slurried in a solvent suitable for the reaction with Sn(IV) compounds. To prevent possible oxidation of the thiol to corresponding disulfides, the procedure can be carried out under inert gas (e.g. nitrogen, argon) if necessary.
- It is also possible to obtain thiol-containing solids (polysiloxanes) by condensation of “Si thiol” compounds either alone or together with alkoxysilanes. Examples are given in DE 30 29 599 (crosslinking of metal-phosphine-Si(OR)3 complexes with H2O to give polysiloxanes and also crosslinking of phosphine-Si(OR)3 to give polysiloxanes and subsequent formation of metal complexes). A review may be found, for example, in C. J. Brinker, G. W. Scherrer, Buch: Sol Gel Science, Academic Press (1990).
- The immobilized thiols are subsequently reacted with Sn(IV). (General literature on the preparation of Sn compounds having Sn—S bonds: Gmelin, 8th edition, tin). These can be either pure Sn(R2)4 compounds or mixtures of various Sn(R2)4 compounds. The 4 radicals R2 can be identical or different. At least one R2 has to be a radical which can react with a thiol group to form an S—Sn bond. Compounds having a radical R2 of this type are preferably halides, alkoxides, carbonates or Sn compounds having OH or Sn═O groups. It is also known that Sn(alkyl)4 compounds can react with thiols to form an Sn—S bond. The Sn(IV) compound is generally dissolved in a suitable solvent (e.g. linear and cyclic alkanes, aromatics such as benzene or toluene, halogenated hydrocarbons, nitromethane, DMSO, alcohols, acetone, carboxylic acids such as acetic acid, esters, DMF, nitrites and also water) and the solution is added to the Si thiol fixed on the support, or vice versa. The addition can be carried out at temperatures of from −78° C. to 100° C. In the case of Sn-halogen compounds, the reaction with the Si thiol can result in liberation of hydrohalic acid. This can be neutralized by means of bases (for example alkalis, carbonates, ammonia, amines). After the Sn(IV) compound(s) and the Si thiol have been combined, the reaction mixture is stirred slowly at temperatures of from 20° C. to the boiling point of the solvent. The reaction time is typically from 1 hour to a number of days. The product is then filtered off, washed with solvents such as alcohols, water, and, if necessary, after-treated with a slightly basic aqueous solution or a solution which modifies the ligand or ligands. The ratio of S to Sn can be controlled via the amount of Sn(IV) which is added relative to the amount of thiol immobilized on the support. The ratio of S/Sn can vary in the range from 1:1 to 10:1.
- The ratio of S/Sn can also be changed afterwards by coproportionation with an Sn(IV) compound.
- The immobilized catalysts can be used without drying or they can be dried at elevated temperature (preferably under reduced pressure) before use and, if necessary, also be thermally treated before use, for example at a temperature in the range 100° C.-300° C.
-
- in which the substituents are as defined above, including their preferences, and i is 1-3.
- Such disulfides are known or can be prepared in a simple way by known methods (W. Buder, Z. Naturforsch., 34b (1979) 790-793). Some of them are commercially available and are described, for example, in the company document “Chemieforschung im Degussa Forschungszentrum Wolfgang”, Volume 1, pages 94-99, 1988.
- The immobilized disulfides can subsequently be either
-
- or
- b) first reduced to thiols or thiolates (e.g. using Na2S, K2S, glucose, sodium dithionite, phosphine) and subsequently reacted with Sn(IV) compounds as described for the thiols.
-
- in which
- t is 1, 2 or 3;
- u is 0, 1 or 2;
- v is 1, 2, 3, 4, 5, 6, 7, 8 or 9; and
- w is 1, 2 or 3,
- with the proviso that t+u+w=4;
- L is an at least divalent C1-C18alkylene, C2-C18alkenylene, phenylene, C1-C18alkylene/phenylene radical or a C2-C18alkylene or C1-C18alkylene/phenylene radical interrupted by one or more O, C(O), S, C(S), N(Y), C(O)—N(Y), N(Y)—C(O)—N(Y) and/or N(Y)—C(O)—O;
- Support is an inorganic support material;
- R1 are, independently of one another, C1-C4alkoxy, phenoxy, C1-C4alkyl, phenyl or halogen; and
- Y are, independently of one another, C1-C18alkyl, phenyl or C1-C18alkylphenyl;
- with a compound of the formula
- Sn[R2]4 (IIb),
- in which
- R2 are, independently of one another, C1-C18alkyl, substituted C1-C18alkyl, C2-C18alkenyl, C1-C18haloalkyl, C6-C16haloaryl, C3-C16haloheteroaryl, C1-C4alkylphenyl, C1-C4alkoxyphenyl, halo-C1-C4alkylphenyl, halo-C1-C4alkoxyphenyl, C1-C12hydroxyalkyl, C3-C8cycloalkyl, C6-C16aryl, substituted C6-C16aryl, C7-C16aralkyl, C3-C6heterocycloalkyl, C3-C16heteroaryl, C4-C16heteroaralkyl, —Cl, —Br, —I, OH, —OC1-C18alkyl, —OC6-C16aryl, —OOC—C1-C18alkyl, —OOC-phenyl, SH, —N(Si(CH3)3)2, SC1-C18alkyl, —SC6-C16aryl, —SC(O)—C1-C18alkyl, —SC(O)-phenyl, —SC(S)—C1-C18alkyl, —SC(S)-phenyl, H or an oxygen bridge to a further Sn atom;
- or two radicals R2 are together ═S or ═O,
- with the proviso that at least one R2 radical which can react with an SH group to form an S—Sn bond is present.
- Method 2: Firstly preparation of an, if desired isolated, immobilized Sn—S compound and then immobilization of this compound. (General literature on the preparation of Sn compounds having Sn—S bonds: Gmelin, 8th edition, tin). Pure immobilized Sn—S compounds or mixtures thereof are obtained by reacting no compounds of the type Si—SM having no.v.w SM groups either partially or completely with compounds Sn(R2)4 so as to form at least one Sn—S bond.
- The substituents and the indices i, v and w are as defined above, including their preferences, M is H or an alkali metal, preferably Na, K or Li, and no is 1-4, preferably 1-3.
-
- If at least one R2 is halogen, the immobilizable Sn—S compounds are prepared by reaction of the thiol or a thiolate with Sn(R2)4. In the reaction with the thiol, the hydrohalic acid formed can be neutralized by means of a base (e.g. alkalis, carbonates, ammonia, amines).
- If at least one R2 is O-alkyl, O-aryl, OH or N(alkyl)2 or two R2 are together a double bond to oxygen, the immobilizable Sn—S compounds are prepared by reaction of the thiol with Sn(R2)4. If necessary, the HO-alkyl, HO-aryl, H2O or amine formed during the reaction can be distilled off.
- It is also known that Sn(alkyl)4 compounds can react with thiols to form an Sn—S bond (Gmelin).
- Where a plurality of R2 can react with the thiol/thiolate, the preferred stoichiometry on the Sn can be set by selection of the thiol/Sn ratio.
- The immobilizable Sn—S compounds can be immobilized on a support or polycondensed in a manner analogous to that for the thiol compounds (see Method 1).
-
- is reacted with a compound of the formula Sn(R2)4 to form an immobilizable Sn—S compound and this compound is immobilized on an inorganic support,
- where
- (R1)′ is C1-C4alkyl or phenyl;
- (R1)″ are, independently of one another, C1-C4alkoxy, phenoxy or halogen; and
- i is 0, 1 or 2, with the proviso that w+i is less than or equal to 4;
- v is 1, 2, 3 or 4; and
- w is 1, 2 or 3;
- L is an at least divalent C1-C18alkylene, C2-C18alkenylene, phenylene, C1-C18alkylene/phenylene radical or a C2-C18alkylene or C1-C18alkylene/phenylene radical interrupted by one or more O, C(O), S, C(S), N(Y), C(O)—N(Y), N(Y)—C(O)—N(Y) and/or N(Y)—C(O)—O;
- Support is an inorganic support material;
- R2 are, independently of one another, C1-C4alkoxy, phenoxy, C1-C4alkyl, phenyl or halogen; and
- Y are, independently of one another, C1-C18alkyl, phenyl or C1-C18alkyl/phenyl;
- no is 1, 2, 3 or 4; and
- M is H or an alkali metal.
- After the immobilization, the immobilized catalysts can be used without drying or can be dried at elevated temperature (preferably under reduced pressure) before use and can, if necessary, also be thermally treated before use (at temperatures in the range 100° C.-300° C.).
- The catalyst can be present in dispersed form in the reactants and is filtered off after the reaction is complete. The catalyst which has become exhausted by use can be regenerated and reused or else can be discarded. It is also possible to arrange the catalyst in a fixed bed and to carry out the reaction in, for example, a flow reactor (continuous process).
- The transesterification is advantageously carried out by reacting the starting materials either in the form of a solution in a solvent or, if they are not liquid, in the form of a melt produced by increasing the temperature.
- Solvents employed are the compounds and mixtures which are customary per se, for example aromatic hydrocarbons such as benzene and alkyl-substituted or halogenated benzenes, in particular toluene, xylene or dichlorobenzene, high-boiling aliphatic hydrocarbons such as high-boiling paraffins, aprotic solvents such as dimethylformamide or dimethylaniline.
- The catalyst is added to the reaction mixture in amounts of, for example, from 0.001 to 10 mol %, advantageously from 0.01 to 1 mol %, of active material, based on the compounds comprising a radical of the formula (I).
- The ratio of carboxylic ester and alcohol in the reaction mixture is not critical and can be, for example, from 0.8 to 1.3 mol of the carboxylic ester per equivalent of the alcohol.
- The reaction temperature can be, for example, from 110 to 250° C., preferably from 130 to 210° C.
- The transesterification of the carboxylic esters generally takes from 1 to 10 hours, advantageously from 1 to 5 hours and preferably from 1 to 3 hours, to achieve optimum yields.
- The catalyst can, for example, be present as a suspension in the reaction mixture in the form of powder through to broken pieces. Use of the catalyst in a fixed bed is a further possible way of carrying out the process.
- After the reaction has ended, the catalyst can, if it was present in suspension, be separated off, for example filtered off, and the end product can be isolated by methods known per se, for example crystallization from a solvent such as methanol, isopropanol, methanol/water mixture, etc.
- If necessary, the reaction mixture and/or the end product can be neutralized using an acid, e.g. formic acid, acetic acid, sulfuric acid, hydrochloric acid, etc.
- The carboxylic esters and alcohols used in the process of the invention are known or can be obtained by methods known per se.
-
- bound to an inorganic support, where L is an at least divalent radical and at least one of the free valences of the Si in formula (I) is bound to the inorganic support, as catalyst in the transesterification of carboxylic esters.
- The carboxylic esters prepared according to the invention are, for example, valuable antioxidants against oxidative, thermal or actinic degradation of sensitive organic materials. Such materials are, for example, synthetic polymers of functional liquids such as lubricants, hydraulic fluids or metalworking fluids, etc.
-
- General Procedure for Immobilizing 3-mercaptopropyltrimethoxysilane
- 100 g of support are stirred in 700 ml of toluene in an inert gas atmosphere and dried by distilling off 200-300 ml of toluene. After cooling to about 40° C., 40 ml (0.215 mol) of 3-mercaptopropyltrimethoxysilane are added, the mixture is again distilled briefly and subsequently stirred for 20 hours at 100°-110° C., ensuring that the methanol formed can distill off. After cooling, the support is filtered off, washed with 2×200 ml of each of ethyl acetate, methanol and hexane and finally dried under reduced pressure (1 mbar) at 70° C. for 15 hours.
- 20 g of dried silica gel (Merck 100) (2 hours at 110° C. in a vacuum oven) are suspended in 80 ml of dried toluene in a flask fitted with a stirrer and treated with 10 g (51 mmol) of 3-mercaptopropyltrimethoxysilane (Fluka, purum). The mixture is stirred for 12 hours at 100° C. and the methanol formed is distilled off. The solid is then filtered off and washed 4 times with 100 ml of methanol. Finally, the functionalized silica gel is dried under reduced pressure at 70-100° C. This gives 22.4 g of product having an S content of 2.85%. This corresponds to a loading density of 0.89 mmol of thio compound per g of material.
- Examples A2-A9 are carried out according to the above-described general procedure, giving the results shown in Table 1 for the corresponding variations.
TABLE 1 Preparation, deviation from the procedure Analysis of Loading Ex. No. Support described S content mmol S/g A2 Silica gel Batch using only 20 g of support, drying of 2.85% 0.89 Merck 100 the silica gel not by azeotropic distillation in toluene but under reduced pressure (5 mbar) at 120° C. for 2 hours. Immobilization in 80 ml of toluene and 0.05 mol of 3-mercaptopropyltrimethoxy- silane. Washing only with methanol. A3 Silica gel 0.260 mol of 3-mercaptopropyltrimethoxy- 2.33% 0.73 Merck 100 silane added. Washing only with methanol. A4 Silica gel, As in procedure described 1.65% 0.52 Grace 332 A5 Silica gel, Drying of the silica gel not by azeotropic 0.75% 0.234 Grace 332 distillation in toluene but in high vacuum (0.1 mbar) at 140° C. for 4 hours. A6 and Silica gel, After addition of 3-mercaptopropyltri- 2.98% 0.93 A7 Grace 332 methoxysilane, 0.5 ml of methanesulfonic acid added. A8 and Silica gel 0.269 mol of 3-mercaptopropyltrimethoxy- 2.73% 0.85 A9 Merck 100 silane added. Washing only with methanol. - Immobilization of bis(3-triethoxysilylpropyl) disulfide
-
- 50 g of silica gel Merck 100 are stirred in 250 ml of toluene in an inert gas atmosphere and dried by distilling off about 50 ml of toluene. After cooling to about 40° C., 23.7 g (0.05 mol) of bis(3-triethoxysilylpropyl) disulfide are added, the mixture is again distilled briefly and subsequently stirred at 100°-110° C. for 20 hours, ensuring that the ethanol formed can distill off. After cooling, the support is filtered off, washed with 2×100 ml of each of ethyl acetate, methanol and hexane and finally dried under reduced pressure (1 mbar) at 70° C. for 15 hours. This gives white material having an S content of 1.83%. This corresponds to a loading density of 0.29 mmol of disulfide per g.
- All reactions are carried out under inert gas.
- 8 g of the thio compound fixed to silica gel from Example A1 are suspended in 60 ml of hexane, cooled to 0° C. and slowly treated with 5.12 g of an 18.1% solution of SnCl4 in hexane. After 15 minutes, 0.8 g of triethylamine is added and the mixture is stirred for 2 hours at room temperature. Finally, the product is filtered off, washed first with hexane, then with a sodium carbonate solution and with water and then dried overnight under reduced pressure at 80° C. This gives 8.1 g of product having an S content of 2.7% and an Sn content of 2.46%. This corresponds to an Sn loading density of 0.201 mmol/g and a ratio of Sn to S of about 1:4.
- The results of the reaction of immobilized sulfur compounds with SnCl4 and the variations of the experimental parameters are summarized in Table 2. (MW in kg means weight of product in kg per mol of Sn)
TABLE 2 Summary of the SnCl4 —S catalysts Analy- Analy- Cat. Support- sis sis MW No. SH Support Remarks 5% Sn % S/Sn kg B2 A2 Merck 2.7 2.46 4.1 4.8 100 B3 A3 Merck 2.24 3.25 2.55 3.64 100 B4 A6 Grace 2.75 3.34 3.1 3.57 332 B5 A6 Grace 2.8 3.28 3.2 3.63 332 B6 A6 Grace 2.83 3.1 3.4 3.84 332 B7 A6 Grace 2.71 2.57 3.9 4.63 332 B8 A6 Grace 2.84 2.01 5.3 5.96 332 B9 A6 Grace 2.74 3.88 2.63 3.07 332 B10 A6 Grace 2.78 3.44 3 3.46 332 B11 A5 Grace 0.72 1.06 2.53 11.2 332 B12 A8 Merck 2.42 3.8 2.37 3.13 100 B13 Integrated Merck 1.89 2.22 3.2 5.34 100 B14 A7 Grace 2.8 5.13 2.03 2.33 332 B15 A7 Grace 2.8 4.86 2.15 2.45 332 B16 A6 Grace Copropor- 2.85 4.26 2.5 2.8 332 tionation #reduced pressure (5 mbar) at 80° C. for 15 hours. #the white product is dried under reduced pressure (5 mbar) at 80° C. for 15 hours. #2 × hexane), the white product is dried under reduced pressure (5 mbar) at 80° C. for 15 hours. #the white product is dried under reduced pressure (5 mbar) at 80° C. for 15 hours. #After cooling, the support is filtered off and washed with 2 × 200 ml of methanol. (A small sample is dried and analyzed → S content: 1.93%). Half of the methanol-moist material (30 mmol of S) is slurried in 150 ml of toluene and slowly treated while stirring at room temperature with 3.9 g (15 mmol) of SnCl4 and subsequently with a freshly prepared sodium methoxide solution in methanol (30 mmol of sodium in 35 ml of methanol). The mixture is stirred for 4 hours at room temperature, #then filtered, washed (2 × 100 ml each of methanol, NaHCO3 2M, water, methanol) and the product is dried under reduced pressure (5 mbar) at 80° C. for 15 hours. #The tin content of the product is 30% higher than that of Example B5. - The results of the reaction of immobilized alkyl thiols with various Sn(IV) compounds and the various experimental conditions are summarized in Table 3.
TABLE 3 Summary of various Sn(IV) compounds. Examples B17-29 Cat. Support- Sn Analysis Analysis MW No. SH compound S % Sn % S/Sn kg B17 A4 Bu2SnO 1.51 4.11 1.36 2.9 B18 A4 Ph2SnO 1.48 3.35 1.65 3.57 B19 A4 BuSnCl3 1.53 3.14 1.81 3.79 B20 A4 BuSnCl3 1.51 2.68 2.01 4.44 B21 A4 BuSnCl3 1.63 2.01 3.02 5.92 B22 A4 PhSnCl3 1.46 2.62 2.1 4.55 B23 A4 Bu3SnCl 1.49 3.94 1.41 3.02 B24 A4 Ph3SnOH 1.41 4.46 1.18 2.57 B25 A4 BuSnO)OH 1.6 2.77 2.15 4.3 B26 A4 ‘Sn(OEt)4’ 1.6 3.44 1.72 3.0 B27 A6 Bu2SnOAc 2.72 4.26 2.37 2.8 B28 A6 BuSn(OH)2Cl 2.42 3.8 2.37 3.14 B29 A9 BuSn(OH)2Cl 2.54 4.36 2.17 2.75 ar) at 50° C. for 15 hours. . for 15 hours. exane) the white prodct is dried under reduced pressure (5 mbar) at 50° C. for 15 hours. e 95 mbar to 50° C. for 15 hours. bar at 60° C. for 15 hours. , 2 × hexane) and the white product is dried under reduced pressure (5 mbar) at 70° C. for 15 hours. educed pressure (5 mbar) at 70° C. for 15 hours. - Immobilization of Sn(IV)—S Compounds Having Trialkoxysilane Radicals
- Preparation of the Sn(IV)—S Compounds Having Trialkoxysilane Radicals
- B30 Preparation of (Bu)2Sn[S(CH2)3Si(OCH3)3]2
- 2 HS(CH2)3Si(OCH3)3+(Bu)2SnCl2+2 (C2H5)3N→(Bu)2Sn[S(CH2)3Si(OCH3)3]2+2 (C2H5)3N*HCl
- 98.2 g (0.50 mol) of 3-mercaptopropyltrimethoxysilane and 52.6 g (0.52 mol) of triethylamine together with 200 ml of n-hexane are placed in a reaction vessel. Subsequently, a solution of 76.0 g (0.25 mol) of dibutyltin dichloride in 300 ml of n-hexane is metered in over a period of about 20 minutes and the reservoir is rinsed with 200 ml of n-hexane. The internal temperature rises from 20 to 35° C. during this step. A white solid starts to precipitate right at the beginning of the metered addition. After stirring for 24 hours at about 20° C., the precipitate is filtered off, the filtrate and the residues are washed with 200 ml of n-hexane. The still slightly turbid filtrates are combined and evaporated in a double-wall reactor to a temperature of about 61° C. and 1 hPa, which results in disappearance of the turbidity. At 20° C., about 143 g of a slighty yellowish, liquid product are drained off (91.8% of theory). Microanalysis: S 10.44%, Sn 19.2%.
- B31 Preparation of (Bu)2SnCl[S(CH2)3Si(OCH3)3]
- (Bu)2Sn[S(CH2)3Si(OCH3)3]2+(Bu)2SnCl2→2 (Bu)2SnCl[S(CH2)3Si(OCH3)3]
- In a test tube, 24.3 g (0.080 mol) of tributyltin dichloride are dissolved in 49.9 g (0.080 mol) of the compound from Example B30 while warming gently (about 50° C.) and allowed to stand for 2 days at room temperature. Microanalysis: S 6.29%, Sn 26.5%
- B32 Preparation of (Ph)2Sn[S(CH2)3Si(OCH3)3]2
- 2 HS(CH2)3Si(OCH3)3+(Ph)2SnCl2+2 (C2H5)3N→(Ph)2Sn[S(CH2)3Si(OCH3)3]2+2 (C2H5)3N*HCl
- Method of preparation analogous to Example B30 except that 86 g (0.25 mol) of diphenyltin dichloride are used in place of dibutyltin dichloride. The liquid product is obtained in a yield of 87.5%. Microanalysis: S 10.12%, Sn 17.1%
- B33 Preparation of Sn[S(CH2)3Si(OCH3)3]4
- 4 HS(CH2)3Si(OCH3)3+SnCl4+4 (C2H5)3N→Sn[S(CH2)3Si(OCH3)3]4+4 (C2H5)3N*HCl
- 98.2 g (0.50 mol) of 3-mercaptopropyltrimethoxysilane and 50.6 g (0.50 mol) of triethylamine together with 200 ml of n-hexane are placed in a reaction vessel. Subseuquently, a solution of 32.6 g (0.125 mol) of tin tetrachloride in 250 ml of n-hexane is metered in over a period of about 45 minutes. The further procedure is the same as in Example B30. The liquid product is obtained in a yield of 85.1%. Microanalysis: S 12.2%, Sn 14.5%
- B34 Preparation of SnCl4−n[S(CH2)3Si(OCH3)3]n
- Sn[S(CH2)3Si(OCH3)3]4+SnCl4→2 SnCl4−n[S(CH2)3Si(OCH3)3]n
-
- B35: Immobilization of the Compound from Example B30 1412/21
- (Bu)2Sn[S(CH2)3Si(OCH3)3]2
- A suspension of 40 g of silica gel Merck 100 in 300 ml of toluene is first dried by azeotropic distillation of 100 ml of toluene. After cooling to room temperature, 31.2 g of the tin compound 1412/21 are added, the mixture is briefly distilled and stirred for 18 hours at 100° C., ensuring that the alcohol formed can distill off. After cooling, the product is filtered off, washed (100 ml each: 3×methanol, 3×ethyl acetate, 3×hexane) and dried under reduced pressure (5 mbar) at 70° C. for 15 hours.
- B36: Immobilization of the Compound from Example B32 (Ph)2Sn[S(CH2)3Si(OCH3)3]2
- Prepared the same way as in Example B35, except that the reaction is carried out using 33.7 g of the Sn compound from Example B32.
- B37: Immobilization of the compound from Example B31 (Bu)2SnCl[S(CH2)3Si(OCH3)3]
- Prepared the same way as in Example B35, except that the reaction is carried out using 23.1 g of the Sn compound from Example B31 and that washing is carried out as follows: 100 ml each; 3×methanol, 1×NaHCO3 1M, 3×water, 3×methanol, 2×ethyl acetate, 2×hexane.
- B38: Immobilization of the Compound from Example B34 SnCl4−n[S(CH2)3Si(OCH3)3]n
- Prepared the same way as in Example B35, except that the reaction is carried out using 29 g of the Sn compound B34 and that washing is carried out as follows: 100 ml each: 3×methanol, 1×NaHCO3 1M, 3×water, 3×methanol, 2×ethyl acetate, 2×hexane.
- The results are summarized in Table 4.
TABLE 4 Immobilization of Sn(IV)-S compounds having trialkoxysilane radicals Sn Cat. compound Analysis Analysis MW No. Support No. Sn compound S % Sn % S/Sn kg B35 Merck B30 ((MeO)3Si-C3H6- 1.94 4.2 1.72 2.84 100 S)2SnBu2 B36 Merck B32 ((MeO)3Si-C3H6- 2.36 3.86 2.28 3.01 100 S)2SnPh2 B37 Merck B31 ((MeO)3Si-C3H6- 2.16 4.4 1.82 2.71 100 S)Sn(Bu)2Cl B38 Merck B34 ((MeO)3Si-C3H6- 4.58 3.48 4.9 3.35 100 B S)nSnCl4-n - Preparation of Sn—S Compounds by Sol-Gel Processes
- Sol-gel processes are described, for example, in the following publications:
- C. J. Brinker, G. W. Scherrer, book: Sol Gel Science, Academic Press (1990).
- L. L. Hench and J. K. West, Chem. Rev., 90 (1990) 33-72.
- U. Schubert et al., J. Non Cryst. Solids, 105 (1988) 165-170.
- P. Panster, CLB Chemie in Labor und Biotechnik, 43 (1992) 16-21.
- These processes can be used in an analogous way for the immobilization of the catalysts of the invention. Examples B39 and 40 illustrate this.
- B39
- 5.42 g (6 mmol) of ((CH3O)3Si—C3H6—S)4Sn (compound from Example B33), 7.3 g (48 mmol) of tetramethoxysilane, 1.56 g (6 mmol) of tin tetrachloride and 100 ml of acetone are combined while stirring in a flask. 34 ml of a 2.8N phosphoric acid solution are added dropwise to the above solution over a period of 30 minutes. The resulting solution is allowed to stand for 4 days in an open vessel, resulting in evaporation of the acetone and formation of a yellowish-white mass. This is stirred for 14 hours in 200 ml of water, filtered off, washed (30 ml each: 3×methanol, 1×NaHCO3 2M, 3×water, 3×methanol, 2×ethyl acetate, 2×hexane) and dried under reduced pressure (5 mbar) at 70° C. for 15 hours.
- B40
- 2.83 g of triethylamine are added to a solution of 7.92 g (52 mmol) of tetramethoxysilane, 0.94 g (4 mmol) of n-octyltrimethoxysilane, 2.75 g (14 mmol) of 3-mercaptopropyltrimethoxysilane, 100 ml of acetone and 1.82 g (7 mmol) of tin tetrachloride, resulting in formation of a white precipitate. 35 ml of a 2.8N phosphoric acid solution are added dropwise to this mixture over a period of 30 minutes. The resulting clear solution is allowed to stand for 6 days in an open vessel, resulting in evaporation of the acetone and formation of a yellowish-white mass. This is partially dried overnight at 70° C. under reduced pressure (5 mbar), washed (50 ml each: 3×methanol, 1×NaHCO3 2M, 3×water, 3×methanol, 2×ethyl acetate, 2×hexane) and dried under reduced pressure (5 mbar) at 70° C. for 15 hours.
- The results are summarized in Table 5.
TABLE 5 Sn catalysts prepared by sol-gel processes: Analysis Analysis MW Cat. No. Composition S % Sn % S/Sn kg B39 ((MeO)3Si-C3H6-S)4Sn, SnCl4, (MeO)4Si 6.62 10.4 2.64 1.28 B40 (MeO)3Si-C3H6-SH, SnCl4, (MeO)4Si, n-Octyl- 5.1 7.45 2.55 1.6 Si(OMe)3 - Immobilization of Sn—S Compounds on Disulfides Bound to Supports
- B41
- 8 g of a material (Deloxan® DSP from Degussa) prepared as described in the literature (U. Deschler et al., Angew. Chemie., 98 (1986) 237-53; P. Panster, CLB Chemie in Labor und Biotechnik, 43 (1992) 16-21) by copolycondensation of bis(3-trialkoxysilylpropyl) disulfide and having a sulfur content of 19.7% are dried in 50 ml of toluene by azeotropic distillation of 20 ml of toluene. After cooling, a solution of 1.68 g (3.69 mmol) of Sn(N(SiCH3)2)2 in 15 ml of toluene is added dropwise at room temperature. The mixture is then stirred for 15 hours at 70° C. and for another 2 hours at 120° C. After cooling to room temperature, it is filtered, washed (30 ml each: 3×methanol, 1×NaHCO3 2M, 3×water, 3×methanol, 2×ethyl acetate, 2×hexane) and dried under reduced pressure (5 mbar) at 70° C. for 15 hours.
- B42
- 10 g of the disulfide bound to silica gel from Example A10 in 70 ml of toluene are dried by azeotropic distillation of 40 ml of toluene. After cooling, a solution of 1.26 g (2.85 mmol) of Sn(N(SiCH3)2)2 in 10 ml of toluene is added dropwise at room temperature. The further procedure is analogous to Example B41.
- B43
- Reduction of the disulfide to thiol: 90 ml of methanol, 10 ml of 1,4-dioxane, 10 ml of water, 5 g of triphenylphosphine and 1 ml of methanesulfonic acid are added to 16 g of the disulfide described in PU732.1 and the mixture is stirred at 70° C. for 17 hours. Subsequently, the product is filtered off and washed with 700 ml of methanol/toluene. Reaction with SnCl4: 0.74 g of sodium acetate is added while stirring to half of the moist product in 30 ml of methanol and, subsequently, 1.04 g of tin tetrachloride are slowly added. After 2 hours, the mixture is filtered and washed (40 ml each: 1×MeOH, 1×H2O, 2×NaHCO3 2M, 3×water, 3×MeOH) and dried under reduced pressure (5 mbar) at 70° C. for 15 hours.
TABLE 6 Sn catalysts based on immobilized dialkyl disulfides: Im- mob. Anal- di- y- Analy- Cat. sul- sis sis MW No. Support fide Sn compound S % Sn % S/Sn kg B41 Deloxan DSP Sn(N(SiCH3)2)2 18.39 4.28 16 2.8 B42 Merck A10 Sn(N(SiCH3)2)2 1.64 2.86 2.14 4.17 100 B43 Deloxan DSP SnCl4 17.93 5.34 12.5 2.23 reduced -
- 17.5 g of compound (101) (60 mmol) and 13.5 g of stearyl alcohol (50 mmol) are melted at 120° C. in a rotary evaporator. 2 g of the catalyst from Example B1 are then added and, under reduced pressure (100 mbar), the temperature is increased to 190° C. over a period of 30 minutes. The vacuum is then improved to 8 mbar over a period of 1 hour 20 minutes. After a further 30 minutes, the melt is then filtered and the catalyst is reused. In 4 reuses of the catalyst, a conversion of 85-90% according to GC is obtained in each case and the product in each case contains less than 1 ppm of Sn.
- 142.6 g (0.489 mol) of compound (101) and 120.35 g (0.445 mol) of stearyl alcohol are placed in a sulfation flask and heated to 180° C. under inert gas. 15.39 g of catalyst from Example B3 are added to this melt. The apparatus is evacuated to 3 mbar, the contents are stirred at 180° C. for 4 hours and the methanol formed is continuously distilled off. Subsequently, the mixture is cooled to 150° C. and filtered. Reuse: The unwashed catalyst can be reused as described above.
- Results
Results: Conversion based on stearyl alcohol used ppm of tin in crude Catalyst use (GC) product Fresh cat. 76.8% 2 1st reuse 95.8% <1 2nd reuse 98.2% 1 3rd reuse 99.6% <1 4th reuse 99.9% <1 5th reuse 99.5% <1 - In all cases the selectivity is greater than 99%. The transmission at 425 nm is over 99% in all reuses.
- The catalyst is still active even after the 5th reuse.
- The procedure is the same as described in Example C2. Batch size: 30.2 g (0.111 mol) of compound (101), 25.6 g (0.101 mol) of stearyl alcohol, 2.79 g of catalyst from Example B12.
- Results
Results: Conversion based on stearyl alcohol used ppm of tin in crude Catalyst use (GC) product Fresh cat. 61.4% 2 1st reuse 89.9% 1 2nd reuse 98.6% <1 3rd reuse 95.6% 1 4th reuse 97.5% 2 5th reuse 97.5% <1 - In all cases, the selectivity is greater than 99%. The transmission at 425 nm is above 99% in all reuses.
- The catalyst is still active even after the 5th reuse.
- The procedure is the same as for Mü19. Batch size: 30.2 g (0.111 mol) of compound (101), 25.6 g (0.101 mol) of stearyl alcohol, 1.28 g of catalyst from Example B17.
- Results
Results: Conversion based on stearyl alcohol used ppm of tin in crude Catalyst use (GC) product Fresh catalyst 75.5% 8 1st reuse 91.1% 5 - In all cases, the selectivity is greater than 99%. The transmission at 425 nm is above 99% in the reuse.
- The catalyst is still active even after the 1st reuse.
- The procedure is the same as that described in Example C2. Batch size: 33 g (0.12 mol) of compound (1019), 25.5 g (0.101 mol) of stearyl alcohol, 2.18 g of catalyst from Example B20.
- Results
Results: Conversion based on stearyl alcohol used ppm of tin in crude Catalyst use (GC) product Fresh catalyst 87.5% 8 1st reuse 78.5% 10 - In all cases, the selectivity is greater than 99%. The transmission at 425 [lacuna] is above 96%.
- The procedure is the same as that described in Example C2. Batch size: 30.2 g (0.111 mol) of compound (101), 25.6 g (0.101 mol) of stearyl alcohol, 1.26 g of catalyst from Example B28.
- Results
Results: Conversion based on stearyl alcohol used ppm of tin in crude Catalyst use (GC) product Fresh catalyst 98.7% 4 1st reuse 99.4% <2 - In all cases, the selectivity is greater than 99%. The transmission at 425 nm is above 99% in the reuse.
- The catalyst is still active even after the 1st reuse.
- The procedure is the same as that described in Example C2. Batch size: 30.2 g (0.111 mol) of compound (101), 25.6 g (0.101 mol) of stearyl alcohol, 1.1 g of catalyst from Example B25.
- Results
Results: Conversion based on stearyl alcohol used ppm of tin in crude Catalyst use (GC) product Fresh catalyst 62.8% 2 1st reuse 82.1% 1 - In all cases, the selectivity is greater than 99%. The transmission at 425 nm is above 99% in the reuse.
- The catalyst is still active even after the 1st reuse.
- The procedure is the same as that described in Example C2. Batch size: 129.7 g (0.445 mol) of compound (101), 120.4 g (0.445 mol) of stearyl alcohol, 2.974 g of catalyst from Example B35.
- Results
Results: Conversion based on stearyl alcohol used ppm of tin in crude Catalyst use (GC) product Fresh catalyst 92.9% 28 1st reuse 96% 17 - In all cases, the selectivity is greater than 99%. The transmission at 425 nm is above 99% in the reuse.
- The catalyst is still active even after the 1st reuse.
- The procedure is the same as that described in Example C2. Batch size: 30.2 g (0.111 mol) of compound (101), 25.6 g (0.101 mol) of stearyl alcohol, 1.24 g of catalyst from Example B41.
- Results
Results: Conversion based on stearyl alcohol used ppm of tin in crude Catalyst use (GC) product Fresh catalyst 99.77% <1 1st reuse 98.5% 1 - In all cases, the selectivity is greater than 99%. The transmission at 425 nm is above 99% in the reuse.
- The catalyst is still active even after the 1st reuse.
- The procedure is the same as that described in Example C2. Batch size: 30.2 g (0.111 mol) of compound (101), 25.6 g (0.101 mol) of stearyl alcohol, 3.72 g of catalyst from Example B42.
- Results
Results: Conversion based on stearyl alcohol used ppm of tin in crude Catalyst use (GC) product Fresh catalyst 85.2% 5 1st reuse 86.7% 5 - In all cases, the selectivity is greater than 99%. The transmission at 425 nm is above 98%.
- The catalyst is still active even after the 1st reuse.
-
- The catalyst described in Example B3 is used for the above transesterification. 4.0 g of catalyst, 100 g of compound (103) and 73.7 g of isooctanol isomer mixture are placed in a stirred glass reactor provided with a reflux condenser heated to 80° C. and a vacuum pump. The reactor is subsequently evacuated to 400 mbar and the reaction mixture is heated to reflux temperature while stirring. The methanol formed in the reaction is distilled off through the reflux condenser heated to 80° C. and is condensed in a downstream cold trap. After about 4 hours, a boiling temperature of the reaction mixture of 180-185° C. is reached. After further reaction for 3 hours, a conversion of 99.8% at a selectivity of almost 100% in respect of the initially charged methyl ester is achieved. After cooling the reaction mixture to 120° C., the catalyst is filtered off and reused in the next 2 reaction batches. Here, the filtered-off, unwashed catalyst is again mixed with 100 g of methyl ester, compound (103) and 73.7 g of isooctanol and the reaction is carried out using the above procedure. A conversion of 99.6% is achieved after only 5 hours. The selectivity is likewise almost 100%. The residual tin content of the product is 30 ppm both in the first test and also in the 2 recycling tests.
-
- 250.0 g (0.856 mol) of methyl 3,5-bis(1,1-dimethyl)-4-hydroxyphenylpropionate [sic] (101), 23.3 g (0.171 mol) and 5.12 g of catalyst from Example B29 are heated to 180° C. and held at this temperature for 6.5 hours. During this time, the pressure is gradually reduced to 3 mbar. 15.2 g (0.47 mol, 70% of theory) of the reaction product (105) are obtained. The catalyst is recovered by filtration. A clear, colorless product is obtained.
- Transesterification of a Glyceride Mixture with Methyl 3,5-bis(1,1-dimethyl)-4-hydroxyphenyl-propionate [sic] (101)
- 65.0 g of coconut oil (about 0.096 mol), 50.9 g of glycerol 86.6% (0.48 mol), 292.4 g of methyl 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionate (101) (1.00 mol) and 8.0 g of catalyst from Example B29 are slowly heated while stirring to 200° C. in a 1 liter flask provided with a dephlegmator at 60° C., a condenser at 15-20° C. and a cold trap at −80° C., with a pressure of 200 mbar being set. The temperature is held at 200° C. for two hours and the pressure is reduced from 200 mbar to 20 mbar over a period of one hour. 6.6 g of water and 30.0 g of methanol are taken off. The catalyst is recovered by filtration. 343.4 g of product are obtained as a clear, yellowish resin.
Claims (12)
1. Process for the transesterification of carboxylic esters, characterized in that the catalyst used is a tin(IV) compound comprising a radical of the formula
bound to an inorganic support, where L is an at least divalent radical and at least one of the free valences of the Si in formula (I) is bound to the inorganic support.
2. Process according to claim 1 for preparing compounds of the formula (X)
in which
R101 and R102 are identical or different and are H, alkyl having from 1 to 18 C atoms, phenyl, C1-C4alkyl-substituted phenyl, phenylalkyl having from 7 to 9 C atoms, C5-C12cycloalkyl, C1-C4alkyl-substituted C5-C12cycloalkyl or a radical
R103 is H or CH3;
R105 is H, Cl, —SO3H or C1-C4alkyl;
m is 0, 1, 2 or 3; and
n is 1, 2, 3 or 4; where,
when n=1,
A is —OR104; and
R104 is alkyl having from 2 to 45 C atoms, C2-C45alkyl interrupted by one or more oxygen, cycloalkyl having from 5 to 12 C atoms, alkenyl having from 2 to 18 C atoms, —CH2CHOHCH2OC(O)R109 or —CH2CH2—OR106; and
R109 is H, alkyl having from 1 to 8 C atoms, alkenyl having from 3 to 5 C atoms or benzyl; where
R106 is
H, alkyl having from 1 to 24 C atoms, phenyl, cycloalkyl having from 5 to 12 C atoms or
and
R110 is H or —CH3;
R111 is H or alkyl having from 1 to 24 C atoms; and
R112 is H or —CH3, with the proviso that R110 and R112 are not simultaneously —CH3;
or, when n=2,
A is —O—CxH2x—O—, —O—(CH2CH2O)aCH2CH2O— or —O—CH2CH═CHCH2—O—; in which
a is from 1 to 30; and
x is from 2 to 20;
or, when n=3,
A is
in which
R107 is alkyl having from 1 to 24 C atoms or phenyl,
or, when n=4,
A is
3. Process according to claim 2 for preparing compounds of the formula (X) in which n is one;
R101 is tert-butyl or
R102 is tert-butyl;
R103 and R105 are H;
m is 2; A is OR104;
R104 is (CH2)17CH3, C8H17 (isomer mixture), C2-C45alkyl interrupted by one or more oxygen, —CH2CHOHCH2OC(O)R109; and
R109 is alkenyl having from 3 to 5 C atoms;
or n is 2;
R101 is tert-butyl or
R102 is CH3;
R103 is H;
m is 2;
A is —O—(CH2CH2O)aCH2CH2O—; and
a is from 1 to 30;
or n is 3;
R101 and R102 are tert-butyl;
R103 is H;
m is 2; and
A is —O—CH2—CH(O—)—CH2—O—;
or n is 4;
R101 and R102 are tert-butyl;
R103 is H;
m is 2; and
A is C(CH2—O—)4.
4. Process according to claim 1 for preparing compounds of the formula (XX)
in which
R200 and R201 are, independently of one another, C1-C4alkyl;
R202 is H, C1-C18alkyl, O or C1-C18alkoxy;
A200 is, when p=1, C1-C12alkyl, C1-C12alkyl substituted by —C(O)OH or C2-C5alkenyl; or, when p=2, C1-C12alkylene; and
p is 1 or 2.
5. Process according to claim 1 for preparing carboxylic esters by reaction of a compound of the formula (XXX)
in which
R210 and R211 are, independently of one another, C1-C4alkyl; and
x is from 1 to 12;
with a compound of the formula
R212OC(O)—A210—(O)COR213 (XXXI)
in which
R212 and R213 are, independently of one another, C1-C4alkyl; and
A210 is C1-C12alkylene.
6. Process according to claim 1 , wherein the catalyst is a compound or a mixture of compounds obtainable by reaction of a compound of the formula (IIa)
in which
t is 1, 2 or 3;
u is 0, 1 or 2;
v is 1, 2, 3, 4, 5, 6, 7, 8 or 9; and
w is 1, 2 or 3,
with the proviso that t+u+w=4;
L is an at least divalent C1-C18alkylene, C2-C18alkenylene, phenylene, C1-C18alkylene/phenylene radical or C2-C18alkylene or C1-C18alkylene/phenylene radical interrupted by one or more O, C(O), S, C(S), N(Y), C(O)—N(Y), N(Y)—C(O)—N(Y) and/or N(Y)—C(O)—O;
Support is an inorganic support material;
R1 are, independently of one another, C1-C4alkoxy, phenoxy, C1-C4alkyl, phenyl or halogen; and
Y are, independently of one another, C1-C18alkyl, phenyl or C1-C18alkyl/phenyl;
with a compound of the formula
Sn[R2]4 (IIb),
in which
R2 are, independently of one another, C1-C18alkyl, substituted C1-C18alkyl, C2-C18alkenyl, C1-C18haloalkyl, C6-C16haloaryl, C3-C16haloheteroaryl, C1-C4alkylphenyl, C1-C4alkoxyphenyl, halo-C1-C4alkylphenyl, halo-C1-C4alkoxyphenyl, C1-C12hydroxyalkyl, C3-C8cycloalkyl, C6-C16aryl, substituted C6-C16aryl, C7-C16aralkyl, C3-C6heterocycloalkyl, C3-C16heteroaryl, C4-C16heteroaralkyl, —Cl, —Br, —I, OH, —OC1-C18alkyl, —OC6-C16aryl, —OOC—C1-C18alkyl, —OOC-phenyl, SH, —N(Si(CH3)3)2, SC1-C18alkyl, —SC6-C16aryl, —SC(O)—C1-C18alkyl, —SC(O)-phenyl, —SC(S)—C1-C18alkyl, —SC(S)-phenyl, H or an oxygen bridge to a further Sn atom;
or two radicals R2 are together ═S or ═O,
with the proviso that at least one R2 radical which can react with an SH group to form an S—Sn bond is present.
7. Tin(IV) compound comprising a radical of the formula
bound to an inorganic support, where L is an at least divalent radical and at least one of the free valences of the Si in formula (I) is bound to the inorganic support, with the exception of tin(IV) compounds which have two or three hydrocarbon radicals on the Sn and only one tin-sulfur bond and the Si is bound via the three free valences to an OH-containing inorganic support.
8. Immobilized tin(IV) compounds or mixtures of compounds according to claim 7 , obtainable by reaction of a compound of the formula (IIa)
in which
t is 1, 2 or 3;
u is 0, 1 or 2;
v is 1, 2, 3, 4, 5, 6, 7, 8 or 9; and
w is 1, 2 or 3,
with the proviso that t+u+w=4;
L is an at least divalent C1-C18alkylene, C2-C18alkenylene, phenylene, C1—C18alkylene/phenylene radical or C2-C18alkylene or C1-C18alkylene/phenylene radical interrupted by one or more O, C(O), S, C(S), N(Y), C(O)—N(Y), N(Y)—C(O)—N(Y) and/or N(Y)—C(O)—O;
Support is an inorganic support material:
R1 are, independently of one another, C1-C4alkoxy, phenoxy, C1-C4alkyl, phenyl or halogen; and
Y are, independently of one another, C1-C18alkyl, phenyl or C1-C18alkyl/phenyl;
with a compound of the formula
Sn[R2]4 (IIb),
in which
R2 are, independently of one another, C1-C18alkyl, substituted C1-C18alkyl, C2-C18alkenyl, C1-C18haloalkyl, C6-C16haloaryl, C3-C16haloheteroaryl, C1-C4alkylphenyl, C1-C4alkoxyphenyl, halo-C1-C4alkylphenyl, halo-C1-C4alkoxyphenyl, C1-C12hydroxyalkyl, C3-C8cycloalkyl, C6-C16aryl, substituted C6-C16aryl, C7-C16aralkyl, C3-C6heterocycloalkyl, C3-C16heteroaryl, C4-C16heteroaralkyl, —Cl, —Br, —I, OH, —OC1-C18alkyl, —OC6-C16aryl, —OOC—C1-C18alkyl, —OOC-phenyl, SH, —N(Si(CH3)3)2, SC1-C18alkyl, —SC6-C16aryl, —SC(O)—C1-C18alkyl, —SC(O)-phenyl, —SC(S)—C1-C18alkyl, —SC(S)-phenyl, H or an oxygen bridge to a further Sn atom;
or two radicals R2 together are ═S or ═O,
with the proviso that at least one R2 one [sic] radical which can react with an SH group to form an S—Sn bond is present.
9. Compound according to claim 7 , wherein the inorganic support material is a material selected from the group consisting of SiO2, TiO2, ZrO2, MgO, NiO, WO3, Al2O3, La2O3, silica gels, clays and zeolite.
10. Process for preparing compounds of the formula (I) according to claim 1 immobilized on inorganic supports, characterized in that a compound of the formula:
in which
t is 1, 2 or 3;
u is 0, 1 or 2;
v is 1, 2, 3, 4, 5, 6, 7, 8 or 9; and
w is 1, 2 or 3,
with the proviso that t+u+w=4;
L is an at least divalent C1-C18alkylene, C2-C18alkenylene, phenylene, C1-C18alkylene/phenylene radical or a C2-C18alkylene or C1-C18alkylene/phenylene radical interrupted by one or more O, C(O), S, C(S), N(Y), C(O)—N(Y), N(Y)—C(O)—N(Y) and/or N(Y)—C(O)—O;
Support is an inorganic support material;
R1 are, independently of one another, C1-C4alkoxy, phenoxy, C1-C4alkyl, phenyl or halogen; and
Y are, independently of one another, C1-C18alkyl, phenyl or C1-C18alkyl/phenyl; is reacted with a compound of the formula
Sn[R2]4 (IIb),
in which
R2 are, independently of one another, C1-C18alkyl, substituted C1-C18alkyl, C2-C18alkenyl, C1-C18haloalkyl, C6-C16haloaryl, C3-C16haloheteroaryl, C1-C4alkylphenyl, C1-C4alkoxyphenyl, halo-C1-C4alkylphenyl, halo-C1-C4alkoxyphenyl, C1-C12hydroxyalkyl, C3-C8cycloalkyl, C6-C16aryl, substituted C6-C16aryl, C7-C16aralkyl, C3-C6heterocycloalkyl, C3-C16heteroaryl, C4-C16heteroaralkyl, —Cl, —Br, —I, OH, —OC1-C18alkyl, —OC6-C16aryl, —OOC—C1-C18alkyl, —OOC-phenyl, SH, —N(Si(CH3)3)2, SC1-C18alkyl, —SC6-C16aryl, —SC(O)—C1-C18alkyl, —SC(O)-phenyl, —SC(S)—C1-C18alkyl, —SC(S)-phenyl, H or an oxygen bridge to a further Sn atom;
or two radicals R2 are together ═S or ═O,
with the proviso that at least one R2 radical which can react with an SH group to form an S—Sn bond is present.
11. Process for preparing a tin(IV) compound bound to an inorganic support, characterized in that a compound of the formula
is reacted with a compound of the formula Sn(R2)4 to form an immobilizable Sn—S compound and this compound is immobilized on an inorganic support,
where
(R1)′ is C1-C4alkyl or phenyl;
(R1)″ are, independently of one another, C1-C4alkoxy, phenoxy or halogen; and
i is 0, 1 or 2, with the proviso that w+i is less than or equal to 4;
v is 1, 2, 3 or 4; and
w is 1, 2 or 3;
L is an at least divalent C1-C18alkylene, C2-C18alkenylene, phenylene, C1-C18alkylene/phenylene radical or a C2-C18alkylene or C1-C18alkylene/phenylene radical interrupted by one or more O, C(O), S, C(S), N(Y), C(O)—N(Y), N(Y)—C(O)—N(Y) and/or N(Y)—C(O)—O;
Support is an inorganic support material;
R2 are, independently of one another, C1-C4alkoxy, phenoxy, C1-C4alkyl, phenyl or halogen; and
Y are, independently of one another, C1-C18alkyl, phenyl or C1-C18alkyl/phenyl;
no is 1, 2, 3 or 4; and
M is H or an alkali metal.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/819,453 US20020022731A1 (en) | 1996-12-20 | 2001-03-29 | Transesterification catalysts fixed on solid support materials |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH3157/96 | 1996-12-20 | ||
CH315796 | 1996-12-20 | ||
DE19700534A DE19700534A1 (en) | 1997-01-10 | 1997-01-10 | Cell cover for electrolytic cells |
DE19700534.9 | 1997-01-10 | ||
US09/331,286 US6248899B1 (en) | 1996-12-20 | 1997-12-12 | Transesterification catalysts fixed to solid support materials |
PCT/EP1997/006978 WO1998028256A1 (en) | 1996-12-20 | 1997-12-12 | Transesterification catalysts fixed to solid support materials |
EPPCT/EP97/06978 | 1997-12-12 | ||
US09/819,453 US20020022731A1 (en) | 1996-12-20 | 2001-03-29 | Transesterification catalysts fixed on solid support materials |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/331,286 Division US6248899B1 (en) | 1996-12-20 | 1997-12-12 | Transesterification catalysts fixed to solid support materials |
Publications (1)
Publication Number | Publication Date |
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US20020022731A1 true US20020022731A1 (en) | 2002-02-21 |
Family
ID=4249853
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/331,286 Expired - Fee Related US6248899B1 (en) | 1996-12-20 | 1997-12-12 | Transesterification catalysts fixed to solid support materials |
US09/819,453 Abandoned US20020022731A1 (en) | 1996-12-20 | 2001-03-29 | Transesterification catalysts fixed on solid support materials |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/331,286 Expired - Fee Related US6248899B1 (en) | 1996-12-20 | 1997-12-12 | Transesterification catalysts fixed to solid support materials |
Country Status (10)
Country | Link |
---|---|
US (2) | US6248899B1 (en) |
EP (2) | EP0946487B1 (en) |
JP (1) | JP2001506661A (en) |
KR (1) | KR20000069479A (en) |
AU (1) | AU5757098A (en) |
BR (1) | BR9714168A (en) |
DE (1) | DE59707938D1 (en) |
ES (1) | ES2180077T3 (en) |
TW (1) | TW429247B (en) |
WO (1) | WO1998028256A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6878843B2 (en) | 2000-06-23 | 2005-04-12 | Ciba Specialty Chemicals Corp. | Method for preparing hydroxyphenyl carboxylic acid esters |
KR101058446B1 (en) * | 2002-10-10 | 2011-08-24 | 시바 홀딩 인코포레이티드 | Method for preparing phenolic carboxylic acid derivative by enzymatic catalysis |
CN114539175A (en) * | 2022-01-19 | 2022-05-27 | 江苏富比亚化学品有限公司 | Synthetic method of ultraviolet absorbent UV-384-2 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19924101A1 (en) | 1999-05-26 | 2000-11-30 | Witco Gmbh | Process for the preparation of water-soluble catalysts |
CA2484512C (en) | 2002-05-17 | 2013-04-16 | Othera Pharmaceuticals, Inc. | Treatment of cataracts and other ophthalmic diseases |
US7825134B2 (en) | 2003-05-19 | 2010-11-02 | Othera Holding, Inc. | Amelioration of cataracts, macular degeneration and other ophthalmic diseases |
GB201119871D0 (en) | 2011-11-17 | 2011-12-28 | Davy Process Techn Ltd | Process |
RU2617403C2 (en) * | 2012-09-14 | 2017-04-25 | ТРИНСЕО ЮРОП ГмбХ | Silane-sulfide modified elastomeric polymers |
GB201218078D0 (en) | 2012-10-09 | 2012-11-21 | Davy Process Techn Ltd | Process |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3119643A1 (en) | 1981-05-16 | 1982-12-02 | Paul Rauschert Gmbh & Co Kg, 8644 Pressig | Organotin compounds, process for their preparation, and their use |
DE4317428C1 (en) * | 1993-05-26 | 1994-06-16 | Goldschmidt Ag Th | Mixt. of organo-tin cpds. as catalyst - used for transesterification of (meth)acrylic acid ester monomer or polymer with cpd. contg. hydroxy gps., avoiding discolouration of prod. |
US5498751A (en) | 1993-09-03 | 1996-03-12 | Cps Chemical Company, Inc. | Organotin catalyzed transesterification |
US5436357A (en) | 1994-06-06 | 1995-07-25 | Rohm And Haas Company | Polymer supported organotin catalyst |
-
1997
- 1997-12-12 EP EP97953796A patent/EP0946487B1/en not_active Expired - Lifetime
- 1997-12-12 KR KR1019997005323A patent/KR20000069479A/en not_active Application Discontinuation
- 1997-12-12 BR BR9714168-2A patent/BR9714168A/en not_active IP Right Cessation
- 1997-12-12 EP EP02001188A patent/EP1209144A1/en not_active Withdrawn
- 1997-12-12 DE DE59707938T patent/DE59707938D1/en not_active Expired - Fee Related
- 1997-12-12 AU AU57570/98A patent/AU5757098A/en not_active Abandoned
- 1997-12-12 JP JP52831898A patent/JP2001506661A/en active Pending
- 1997-12-12 US US09/331,286 patent/US6248899B1/en not_active Expired - Fee Related
- 1997-12-12 ES ES97953796T patent/ES2180077T3/en not_active Expired - Lifetime
- 1997-12-12 WO PCT/EP1997/006978 patent/WO1998028256A1/en not_active Application Discontinuation
- 1997-12-18 TW TW086119159A patent/TW429247B/en active
-
2001
- 2001-03-29 US US09/819,453 patent/US20020022731A1/en not_active Abandoned
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6878843B2 (en) | 2000-06-23 | 2005-04-12 | Ciba Specialty Chemicals Corp. | Method for preparing hydroxyphenyl carboxylic acid esters |
KR101058446B1 (en) * | 2002-10-10 | 2011-08-24 | 시바 홀딩 인코포레이티드 | Method for preparing phenolic carboxylic acid derivative by enzymatic catalysis |
CN114539175A (en) * | 2022-01-19 | 2022-05-27 | 江苏富比亚化学品有限公司 | Synthetic method of ultraviolet absorbent UV-384-2 |
Also Published As
Publication number | Publication date |
---|---|
DE59707938D1 (en) | 2002-09-12 |
EP1209144A1 (en) | 2002-05-29 |
EP0946487A1 (en) | 1999-10-06 |
AU5757098A (en) | 1998-07-17 |
TW429247B (en) | 2001-04-11 |
EP0946487B1 (en) | 2002-08-07 |
US6248899B1 (en) | 2001-06-19 |
BR9714168A (en) | 2000-04-25 |
JP2001506661A (en) | 2001-05-22 |
WO1998028256A1 (en) | 1998-07-02 |
KR20000069479A (en) | 2000-11-25 |
ES2180077T3 (en) | 2003-02-01 |
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