Organo-1-oxa-4-azonium cyclohexane compounds

Abstract

Novel 1-oxa-4-azonium cyclohexane salts are described. These compounds can be used as structure directing agents, and they overcome many of the typical problems associated with OSDA synthesis and subsequent zeolite synthesis. Methods for synthesis of the 1-oxa-4-azonium cyclohexane salts from a variety of starting materials are also described. A substituted hydrocarbon is added to water to form a mixture, and a 1-oxa-4-azacyclohexane derivative is then added. The reaction mixture stirred until a solution containing the 1-oxa-4-azonium cyclohexane salt is obtained.

1 . A morpholinium compound comprising:
 a 1-oxa-4-azonium cyclohexane salt having a structure of:   Formula 1:
   2-R 1 -2-R 2 -3-R 3 -3-R 4 -4-R 9 -4-R 10 -5-R 5 -5-R 6 -6-R 7 -6-R 8 -1-oxa-4- azoniumcyclohexane + -X − , 
   
       wherein R 1 -R 8  are independently selected from H or an alkyl group having the formula C n H 2n+1  where n is in the range from 1 to 4; R 9  and R 10  form a cyclic alkyl group having the formula C m H 2m  forming a heterocycle of ring size q, where m is in the range from 4 to 8, and q is in the range of 5 to m+1; X is a halide or hydroxide; and the total number of C atoms in the molecule is in a range of 8 to 17;
 with the proviso that when R 1 -R 8  are H, and m is 4, X is hydroxide; 
 or Formula 2:
   [bis-N,N′-diR 9 -(2,2′-diR 1 -2,2′-diR 2 -3,3′-diR 3 -3,3′-diR 4 -5,5′-diR 5 -5,5′-diR 6 -6,6-diR 7 -6,6′-diR 8 -1,1′-oxa-4,4′-azonium cyclohexane)-R 10 ] 2+ 2X − ,
 
 
 
       wherein R 1 -R 9  are independently selected from H or an alkyl group having the formula C n H 2n+1 , where n is in the range from 1 to 4, X is halide or hydroxide, the total number of C atoms in the molecule is in the range of 11 to 24, and R 10  is an alkyl group having the formula C m H 2m , where m is in the range from 3 to 8 and is connected to the 4 and 4′ N atoms at positions x and y of the alkyl chain where x and y are independently selected from 1 to m;
 with the proviso that: when R 1 -R 8  are H, R 9  is CH 3 , R 10  is C 4 H 8 , X is 1, and y is 4, X is hydroxide; or when R 1 -R 8  are H, R 9  is CH 3 , R 10  is C 5 H 10,  X is 1, and y is 5, X is hydroxide; or when R 1 -R 8  are H, R 9  is CH 3 , R 10  is C 6 H 12,  X is 1, and y is 6, X is hydroxide; or when R 1 -R 8  are H, R 9  is CH 3 , R 10  is C 7 H 14 , X is 1, and y is 7, X is hydroxide; or when R 1 -R 8  are H, R 9  is C 2 H 5 , R 10  is C 6 H 12 , x is 1, and y is 6, X is hydroxide; 
 or Formula 4:
   2-R 1 -2-R 2 -3-R 3 -3-R 4 -4-R 9 -4-R 10 -5-R 5 -5-R 6 -6-R 7 -6-R 8 -1-oxa-4- azoniumcyclohexane + -X − , 
 
 
       wherein R 1 -R 9  are independently selected from H or an alkyl group having the formula C n H 2n+1 , R 10  is selected from an alkyl group having the formula C n H 2n+1  where n is in the range from 1 to 4, benzyl, 1-methylnaphthalene, 2-methylnaphthalene and a non-olefinic alkyl group having the formula C p H 2p−1  where p is in the range from 4 to 10, X is halide or hydroxide, and the total number of C atoms in the molecule is in the range of 4 to 16;
 or combinations thereof. 
 
     
     
         2 . The morpholinium compound of  claim 1  having the Formula 1, or Formula 2, or Formula 4 wherein X is hydroxide. 
     
     
         3 . The morpholinium compound of  claim 1  having the Formula 1, or Formula 2, or Formula 4 wherein R 1 -R 8  are H. 
     
     
         4 . The morpholinium compound of  claim 3  having the Formula 1 wherein R 9  and R 10  form the cyclic alkyl group, or having the Formula 4 wherein at least one of R 9  and R 10  is the alkyl group having the formula C n H 2n+1 . 
     
     
         5 . The morpholinium compound of  claim 1  having the Formula 1, or Formula 2, or Formula 4 wherein at least one of R 1 -R 8  is the alkyl group. 
     
     
         6 . The morpholinium compound of  claim 5  having the Formula 1 wherein R 9  and R 10  form the cyclic alkyl group, or having the Formula 4 wherein at least one of R 9  and R 10  is the alkyl group having the formula C n H 2n−1 . 
     
     
         7 . The morpholinium compound of  claim 1  having the Formula 1 wherein m is 5, R 1 -R 5  are H, and X is a halide. 
     
     
         8 . The morpholinium compound of  claim 1  having the Formula 2 wherein x is 1, and y is m. 
     
     
         9 . The morpholinium compound of  claim 1  having the Formula 2 wherein when R 9  is the alkyl group, X is hydroxide. 
     
     
         10 . The morpholinium compound of  claim 1  having the Formula 2 wherein R 9  is the alkyl group and n is 1, m is 4, x is 1, and y is 4. 
     
     
         11 . The morpholinium compound of  claim 1  having the Formula 1, or Formula 2, or Formula 4 wherein at least two of R 1 -R 8  are the alkyl group, and wherein the at least two of R 1 -R 8  are R 1  and R 2 , or R 3  and R 4 , or R 5  and R 6 , or R 7  and R 8 . 
     
     
         12 . The morpholinium compound of  claim 1  having the Formula 4 wherein at least two of R 1 -R 8  are the alkyl group, and wherein at least one of R 9  and R 10  is the alkyl group having the formula C n H 2n+1 , or the Formula 1 wherein R 9  and R 10  form the cyclic alkyl group. 
     
     
         13 . The morpholinium compound of  claim 1  having the Formula 1, or Formula 2, or Formula 4 wherein at least two of R 1 -R 8  are the alkyl group, and wherein at least two of R 1 -R 8  are the same alkyl group. 
     
     
         14 . The morpholinium compound of  claim 1  having the Formula 4 wherein R 10  is the alkyl group having the formula C n H 2n−1 . 
     
     
         15 . The morpholinium compound of  claim 1  having the Formula 4 wherein R 10  is benzyl. 
     
     
         16 . The morpholinium compound of  claim 1  having the Formula 4 wherein R 10  is 1-methylnaphthalene or 2-methylnaphthalene. 
     
     
         17 . The morpholinium compound of  claim 1  having the Formula 4 wherein R 10  is the non-olefinic alkyl group having the formula C p H 2p−1  where p is in the range from 4 to 10. 
     
     
         18 . The morpholinium compound of  claim 16  wherein R 10  is selected from the group consisting of cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, dimethylcyclopentyl, cyclooctyl and dimethylcyclohexyl. 
     
     
         19 . The morpholinium compound of  claim 1  having the Formula 2, or Formula 4 wherein the 1-oxa-4-azonium cyclohexane salt comprises at least one of the mono-, di-, or tri-halides or hydroxides of mono-, bis-, or tris-:
 4-butylmorpholine, 4-propylmorpholine, 4-ethylmorpholine, 4-methylmorpholine, morpholine, 2-methylmorpholine, 2,4-dimethylmorpholine, 4-ethyl-2-methylmorpholine, 4-propyl-2-methylmorpholine, 3-methylmorpholine, 3,4-dimethylmorpholine, 4-ethyl-3-methylmorpholine, 4-propyl-3-methylmorpholine, 5-methylmorpholine, 2,5-dimethylmorpholine, 4-ethyl-5-methylmorpholine, 4-propyl-5-methylmorpholine, 5-ethyl-2-methylmorpholine, 6-methylmorpholine, 4,6-dimethylmorpholine, 4-ethyl-6-methylmorpholine, 4-propyl-6-methylmorpholine, 2,6-dimethylmorpholine, 2,4,6-trimethylmorpholine, 4-ethyl-2,6-dimethylmorpholine, 2,3-dimethylmorpholine, 2,3,4-trimethylmorpholine, 4-ethyl-2,3-dimethylmorpholine, 2,5-dimethylmorpholine, 2,4,5-trimethylmorpholine, 4-ethyl-2,5-dimethylmorpholine, 2,2-dimethylmorpholine, 2,2,4-trimethylmorpholine, 4-ethyl-2,2-dimethylmorpholine, 3,3-dimethylmorpholine, 3,3,4-trimethylmorpholine, 4-ethyl-3,3-dimethylmorpholine, 5,5-dimethylmorpholine, 4,5,5-trimethylmorpholine, 4-ethyl-5,5-dimethylmorpholine, 6,6-dimethylmorpholine, 4,6,6-trimethylmorpholine, 4-ethyl-6,6-dimethylmorpholine, 5-ethyl-2-methylmorpholine and combinations thereof. 
 
     
     
         20 . A method for synthesizing a 1-oxa-4-azonium cyclohexane salt, comprising:
 preparing an aqueous mixture comprising water, a substituted hydrocarbon, and a 1-oxa-4-azacyclohexane derivative;   reacting the aqueous mixture;   obtaining a solution comprising the 1-oxa-4-azonium cyclohexane salt,   wherein the mixture and the solution are essentially free of aluminum and silicon.