Organosilanes and substrates covalently bonded with same and methods for synthesis and use

Abstract

The present invention provides novel silicon compounds, methods for making these novel silicon compounds, compositions comprising these novel silicon compounds attached to substrates, methods for attaching the novel silicon compounds to substrates and methods for using the compositions in a variety of chromatographic applications.

1 . A composition comprising a compound of structural Formula (II): 
     
       
         
         
             
             
         
       
     
     or salts, solvates or hydrates thereof 
     wherein:
 R 1 , R 2  and R 3  are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino, aryl, aryloxycarbonyl, arylsulfonyloxy, halo or hydroxyl, optionally substituted with one or more R 14  groups, provided that at least one of R 1 , R 2  and R 3  are not alkyl, aryl or hydroxyl; 
 L 1  is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl; 
 Y is —C(O)N(R 4 )(R 5 ), —N(R 4 )C(O)R 7 , —N(R 4 )S(O 2 )R 7 , —S(O) 2 N(R 4 )(R 5 ), —OC(O)R 7 , —OC(O)N(R 4 )(R 5 ), —N(R 4 )C(O)OR 7 , —N(R 4 )C(O)N(R 5 )(R 6 ) or —N(R 4 )S(O 2 )N(R 5 )(R 6 ); and 
 R 4 , R 5  and R 6  are independently hydrogen, (C 1 -C 6 )alkyl optionally substituted with one or more hydroxy or cyano groups or (C 5 -C 7 )aryl optionally substituted with one or more hydroxy or cyano groups; 
 R 7  is (C 1 -C 6 )alkyl optionally substituted with one or more hydroxy or cyano groups or (C 5 -C 7 )aryl optionally substituted with one or more hydroxy or cyano groups and 
 R 14  is (C 1 -C 6 )alkyl; provided that one of R 4 , R 5  or R 6  is not hydrogen; 
 
     wherein said compound is covalently bonded to a substrate. 
   
   
       2 . The composition of  claim 1  in which said compound of structural Formula (II) is selected from the group consisting of: 
     
       
         
         
             
             
         
       
     
   
   
       3 . The composition of  claim 1  in which the compound is covalently bonded to the substrate by reaction of one or more of R 1 , R 2  and R 3  with reactive groups on the substrate selected from the group consisting of silanol, alkoxysilane, halosilane or aminosilane. 
   
   
       4 . The composition of  claim 1  in which —SiR 1 (R 2 )(R 3 ) is covalently bonded to another compound of  claim 1  by reaction with reactive groups selected from the group consisting of silanol, alkoxysilane or halosilane on the other compound. 
   
   
       5 . The composition of  claim 4  of structural Formula (III): 
     
       
         
         
             
             
         
       
     
   
   
       6 . The composition of  claim 5  having a structure selected from the group consisting of: 
     
       
         
         
             
             
         
       
     
   
   
       7 . A chromatographic method comprising flowing an aqueous liquid through a bed of separation medium comprising a compound of structural Formula (II): 
     
       
         
         
             
             
         
       
     
     or salts, solvates or hydrates thereof 
     wherein:
 R 1 , R 2  and R 3  are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino, aryl, aryloxycarbonyl, arylsulfonyloxy, halo or hydroxyl, optionally substituted with one or more R 14  groups, provided that at least one of R 1 , R 2  and R 3  are not alkyl, aryl or hydroxyl; 
 L 1  is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl; 
 Y is —C(O)N(R 4 )(R 5 ), —N(R 4 )C(O)R 7 , —N(R 4 )S(O 2 )R 7 , —S(O) 2 N(R 4 )(R 5 ), —OC(O)R 7 , —OC(O)N(R 4 )(R 5 ), —N(R 4 )C(O)OR 7 , —N(R 4 )C(O)N(R 5 )(R 6 ) or —N(R 4 )S(O 2 )N(R 5 )(R 6 ); and 
 R 4 , R 5  and R 6  are independently hydrogen, (C 1 -C 6 )alkyl optionally substituted with one or more hydroxy or cyano groups or (C 5 -C 7 )aryl optionally substituted with one or more hydroxy or cyano groups; 
 R 7  is (C 1 -C 6 )alkyl optionally substituted with one or more hydroxy or cyano groups or (C 5 -C 7 )aryl optionally substituted with one or more hydroxy or cyano groups and 
 R 14  is (C 1 -C 6 )alkyl; provided that one of R 4 , R 5  or R 6  is not hydrogen; 
 
     wherein said compound is covalently bonded to a substrate. 
   
   
       8 . A chromatographic method comprising flowing an aqueous liquid through a bed of separation medium comprising a compound of structural Formula (II): 
     
       
         
         
             
             
         
       
     
     or salts, solvates or hydrates thereof, 
     wherein
 R 1 , R 2  and R 3  are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino, aryl, aryloxycarbonyl, arylsulfonyloxy, halo or hydroxyl, optionally substituted with one or more (C 1 -C 6 )alkyl groups, provided that at least one of R 1 , R 2  and R 3  is not alkyl, aryl or hydroxyl; 
 L 1  is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl; and 
 Y is —C(O)N(R 4 )(R 5 ), —N(R 4 )C(O)R 7 , —N(R 4 )S(O 2 )R 7 , —S(O) 2 N(R 4 )(R 5 ), —OC(O)R 7 , —OC(O)N(R 4 )(R 5 ), —N(R 4 )C(O)OR 7 , —N(R 4 )C(O)N(R 5 )(R 6 ) or —N(R 4 )S(O 2 )N(R 5 )(R 6 ), 
 
     wherein
 R 4 , R 5  and R 6  are independently hydrogen, (C 1 -C 6 )alkyl optionally substituted with one or more hydroxy or cyano groups or (C 5 -C 7 )aryl optionally substituted with one or more hydroxy or cyano groups, provided that at least one of R 4 , R 5  and R 6  is not hydrogen; and 
 R 7  is (C 1 -C 6 )alkyl optionally substituted with one or more hydroxy or cyano groups or (C 5 -C 7 )aryl optionally substituted with one or more hydroxy or cyano groups; 
 
     wherein said compound is covalently bonded to a substrate, 
     said composition further comprising a compound of structural Formula (IV) covalently bonded to said substrate: 
     
       
         
         
             
             
         
       
     
     wherein
 R 8 , R 9 , and R 10  are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino aryl, aryloxycarbonyl, aryloxy, arylsulfonyloxy, halo or hydroxyl optionally substituted with one or more independently selected (C 1 -C 6 )alkyl groups, provided that at least one of R 1 , R 2  and R 3  is not alkyl, aryl or hydroxyl; 
 L 2  is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl; and 
 W is an ionizable group and different than Y. 
 
   
   
       9 . A method for the chromatographic separation of analytes in a liquid sample comprising flowing the liquid sample through medium comprising a compound of structural Formula (II): 
     
       
         
         
             
             
         
       
     
     or salts, solvates or hydrates thereof 
     wherein:
 R 1 , R 2  and R 3  are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino, aryl, aryloxycarbonyl, arylsulfonyloxy, halo or hydroxyl, optionally substituted with one or more R 14  groups, provided that at least one of R 1 , R 2  and R 3  are not alkyl, aryl or hydroxyl; 
 L 1  is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl; 
 Y is —C(O)N(R 4 )(R 5 ), —N(R 4 )C(O)R 7 , —N(R 4 )S(O 2 )R 7 , —S(O) 2 N(R 4 )(R 5 ), —OC(O)R 7 , —OC(O)N(R 4 )(R 5 ), —N(R 4 )C(O)OR 7 , —N(R 4 )C(O)N(R 5 )(R 6 ) or —N(R 4 )S(O 2 )N(R 5 )(R 6 ); and 
 R 4 , R 5  and R 6  are independently hydrogen, (C 1 -C 6 )alkyl optionally substituted with one or more hydroxy or cyano groups or (C 5 -C 7 )aryl optionally substituted with one or more hydroxy or cyano groups; 
 R 7  is (C 1 -C 6 )alkyl optionally substituted with one or more hydroxy or cyano groups or (C 5 -C 7 )aryl optionally substituted with one or more hydroxy or cyano groups and 
 R 14  is (C 1 -C 6 )alkyl; provided that one of R 4 , R 5  or R 6  is not hydrogen; 
 
     wherein said compound is covalently bonded to a substrate. 
   
   
       10 . A method for the chromatographic separation of analytes in a liquid sample comprising flowing the liquid sample through medium comprising a compound of structural Formula (II): 
     
       
         
         
             
             
         
       
     
     or salts, solvates or hydrates thereof, 
     wherein
 R 1 , R 2  and R 3  are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino, aryl, aryloxycarbonyl, arylsulfonyloxy, halo or hydroxyl, optionally substituted with one or more (C 1 -C 6 )alkyl groups, provided that at least one of R 1 , R 2  and R 3  is not alkyl, aryl or hydroxyl; 
 L 1  is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl; and 
 Y is —C(O)N(R 4 )(R 5 ), —N(R 4 )C(O)R 7 , —N(R 4 )S(O 2 )R 7 , —S(O) 2 N(R 4 )(R 5 ), —OC(O)R 7 , —OC(O)N(R 4 )(R 5 ), —N(R 4 )C(O)OR 7 , —N(R 4 )C(O)N(R 5 )(R 6 ) or —N(R 4 )S(O 2 )N(R 5 )(R 6 ), 
 
     wherein
 R 4 , R 5  and R 6  are independently hydrogen, (C 1 -C 6 )alkyl optionally substituted with one or more hydroxy or cyano groups or (C 5 -C 7 )aryl optionally substituted with one or more hydroxy or cyano groups, provided that at least one of R 4 , R 5  and R 6  is not hydrogen; and 
 R 7  is (C 1 -C 6 )alkyl optionally substituted with one or more hydroxy or cyano groups or (C 5 -C 7 )aryl optionally substituted with one or more hydroxy or cyano groups; 
 
     wherein said compound is covalently bonded to a substrate, 
     said composition further comprising a compound of structural Formula (IV) covalently bonded to said substrate: 
     
       
         
         
             
             
         
       
     
     wherein
 R 8 , R 9 , and R 10  are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino aryl, aryloxycarbonyl, aryloxy, arylsulfonyloxy, halo or hydroxyl optionally substituted with one or more independently selected (C 1 -C 6 )alkyl groups, provided that at least one of R 1 , R 2  and R 3  is not alkyl, aryl or hydroxyl; 
 L 2  is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl; and 
 W is an ionizable group and different than Y. 
 
   
   
       11 . A method for simultaneous analysis of cationic, neutral and anionic surfactants in a liquid sample comprising flowing the liquid sample through medium comprising the composition of a compound of structural Formula (II): 
     
       
         
         
             
             
         
       
     
     or salts, solvates or hydrates thereof, 
     wherein
 R 1 , R 2  and R 3  are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino, aryl, aryloxycarbonyl, arylsulfonyloxy, halo or hydroxyl, optionally substituted with one or more (C 1 -C 6 )alkyl groups, provided that at least one of R 1 , R 2  and R 3  is not alkyl, aryl or hydroxyl; 
 L 1  is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl; and 
 Y is —C(O)N(R 4 )(R 5 ), —N(R 4 )C(O)R 7 , —N(R 4 )S(O 2 )R 7 , —S(O) 2 N(R 4 )(R 5 ), —OC(O)R 7 , —OC(O)N(R 4 )(R 5 ), —N(R 4 )C(O)OR 7 , —N(R 4 )C(O)N(R 5 )(R 6 ) or —N(R 4 )S(O 2 )N(R 5 )(R 6 ), 
 
     wherein
 R 4 , R 5  and R 6  are independently hydrogen, (C 1 -C 6 )alkyl optionally substituted with one or more hydroxy or cyano groups or (C 5 -C 7 )aryl optionally substituted with one or more hydroxy or cyano groups, provided that at least one of R 4 , R 5  and R 6  is not hydrogen; and 
 R 7  is (C 1 -C 6 )alkyl optionally substituted with one or more hydroxy or cyano groups or (C 5 -C 7 )aryl optionally substituted with one or more hydroxy or cyano groups; 
 
     wherein said compound is covalently bonded to a substrate, 
     said composition further comprising a compound of structural Formula (IV) covalently bonded to said substrate: 
     
       
         
         
             
             
         
       
     
     wherein
 R 8 , R 9 , and R 10  are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino aryl, aryloxycarbonyl, aryloxy, arylsulfonyloxy, halo or hydroxyl optionally substituted with one or more independently selected (C 1 -C 6 )alkyl groups, provided that at least one of R 1 , R 2  and R 3  is not alkyl, aryl or hydroxyl; 
 L 2  is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl; and 
 W is an ionizable group and different than Y. 
 
   
   
       12 . A chromatography column comprising the composition of  claim 1  packed in a suitable housing. 
   
   
       13 . A packing comprising the compound of  claim 1  covalently bonded to a first substrate and a compound of structural Formula (IV) bonded to a second substrate wherein Formula (IV) is: 
     
       
         
         
             
             
         
       
       R 8 , R 9 , and R 10  are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino aryl, aryloxycarbonyl, aryloxy, arylsulfonyloxy, halo or hydroxyl, optionally substituted with one or more of the same or different R 13  groups, provided that at least one of R 1 , R 2  and R 3  are not alkyl, aryl or hydroxyl; 
       R 13  is (C 1 -C 6 )alkyl; 
       L 2  is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl; and 
       W is an ionizable group. 
     
   
   
       14 . The compound of  claim 13 , in which the first substrate and the second substrate are a silica substrate.