Transesterification catalysts fixed on solid support materials

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.

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 
 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; and  
 n is 1, 2, 3 or 4; where,  
 when n=1,  
 A is —OR 104 ; and  
 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; where  
 R 106  is  
                     
 H, alkyl having from 1 to 24 C atoms, phenyl, cycloalkyl having from 5 to 12 C atoms or  
                     
 and  
 R 110  is H or —CH 3 ;  
 R 111  is H or alkyl having from 1 to 24 C atoms; and  
 R 112  is H or —CH 3 , with the proviso that R 110  and R 112  are not simultaneously —CH 3 ;  
 or, when n=2,  
 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; and  
 x is from 2 to 20;  
 or, when n=3,  
 A is  
                     
 in which  
 R 107  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; 
 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;  
 or n is 2;  
 R 101  is tert-butyl or  
                     
 R 102  is CH 3 ;  
 R 103  is H;  
 m is 2;  
 A is —O—(CH 2 CH 2 O) a CH 2 CH 2 O—; and  
 a is from 1 to 30;  
 or n is 3;  
 R 101  and R 102  are tert-butyl;  
 R 103  is H;  
 m is 2; and  
 A is —O—CH 2 —CH(O—)—CH 2 —O—;  
 or n is 4;  
 R 101  and R 102  are tert-butyl;  
 R 103  is H;  
 m is 2; and  
 A is C(CH 2 —O—) 4 .  
 
     
     
         4 . Process according to  claim 1  for preparing compounds of the formula (XX)  
       
         
           
           
               
               
           
         
       
       in which 
 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;  
 A 200  is, when p=1, C 1 -C 12 alkyl, C 1 -C 12 alkyl substituted by —C(O)OH or C 2 -C 5 alkenyl; or, when p=2, C 1 -C 12 alkylene; 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 
 R 210  and R 211  are, independently of one another, C 1 -C 4 alkyl; and  
 x is from 1 to 12;  
 with a compound of the formula  
 R 212 OC(O)—A 210 —(O)COR 213   (XXXI) 
 in which  
 R 212  and R 213  are, independently of one another, C 1 -C 4 alkyl; and  
 A 210  is C 1 -C 12 alkylene.  
 
     
     
         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 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; and  
 Y are, independently of one another, C 1 -C 18 alkyl, phenyl or C 1 -C 18 alkyl/phenyl;  
 with a compound of the formula  
 Sn[R 2 ] 4   (IIb), 
 in which  
 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, OH, —OC 1 -C 18 alkyl, —OC 6 -C 16 aryl, —OOC—C 1 -C 18 alkyl, —OOC-phenyl, SH, —N(Si(CH 3 ) 3 ) 2 , SC 1 -C 18 alkyl, —SC 6 -C 16 aryl, —SC(O)—C 1 -C 18 alkyl, —SC(O)-phenyl, —SC(S)—C 1 -C 18 alkyl, —SC(S)-phenyl, H or an oxygen bridge to a further Sn atom;  
 or two radicals R 2  are together ═S or ═O,  
 with the proviso that at least one R 2  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 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; and  
 Y are, independently of one another, C 1 -C 18 alkyl, phenyl or C 1 -C 18 alkyl/phenyl;  
 with a compound of the formula  
 Sn[R 2 ] 4   (IIb), 
 in which  
 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, OH, —OC 1 -C 18 alkyl, —OC 6 -C 16 aryl, —OOC—C 1 -C 18 alkyl, —OOC-phenyl, SH, —N(Si(CH 3 ) 3 ) 2 , SC 1 -C 18 alkyl, —SC 6 -C 16 aryl, —SC(O)—C 1 -C 18 alkyl, —SC(O)-phenyl, —SC(S)—C 1 -C 18 alkyl, —SC(S)-phenyl, H or an oxygen bridge to a further Sn atom;  
 or two radicals R 2  together are ═S or ═O,  
 with the proviso that at least one R 2  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 SiO 2 , TiO 2 , ZrO 2 , MgO, NiO, WO 3 , Al 2 O 3 , La 2 O 3 , 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 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; and  
 Y are, independently of one another, C 1 -C 18 alkyl, phenyl or C 1 -C 18 alkyl/phenyl; is reacted with a compound of the formula  
 Sn[R 2 ] 4   (IIb), 
 in which  
 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, OH, —OC 1 -C 18 alkyl, —OC 6 -C 16 aryl, —OOC—C 1 -C 18 alkyl, —OOC-phenyl, SH, —N(Si(CH 3 ) 3 ) 2 , SC 1 -C 18 alkyl, —SC 6 -C 16 aryl, —SC(O)—C 1 -C 18 alkyl, —SC(O)-phenyl, —SC(S)—C 1 -C 18 alkyl, —SC(S)-phenyl, H or an oxygen bridge to a further Sn atom;  
 or two radicals R 2  are together ═S or ═O,  
 with the proviso that at least one R 2  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(R 2 ) 4  to form an immobilizable Sn—S compound and this compound is immobilized on an inorganic support,  
       where 
 (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; 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 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; and  
 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; and  
 M is H or an alkali metal.  
 
     
     
         12 . Use of 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, as catalyst in the transesterification of carboxylic esters.