Synthesis of succinimides and quaternary ammonium ions for use in making molecular sieves

Patent metadata

Field	Value
Publication number	US-10035762-B2
Application number	US-201314651918-A
Country	US
Kind code	B2
Filing date	Dec 18, 2013
Priority date	Dec 21, 2012
Publication date	Jul 31, 2018
Grant date	Jul 31, 2018

Abstract

The present invention relates to the synthesis of succinimides, in particular to a method for the synthesis of a succinimide compound, comprising the step of reacting an alkyne, with carbon monoxide and ammonia or an amine, in the presence of an iron catalyst, wherein the reaction is carried out in an amine liquid phase and/or in the absence of an ether solvent. The succinimides may be reduced to quaternary ammonium cations which may be used as structure directing agents in the synthesis of molecular sieves.

First claim

We claim:

1. A method of preparing a quaternary ammonium ion comprising the steps of:
(a) preparing a succinimide compound by reacting (i) an alkyne with (ii) carbon monoxide and (iii) an amine reagent, which is either ammonia or a primary amine, in the presence of (iv) an iron catalyst and, optionally, (v) a tertiary amine solvent, under conditions in which a liquid phase is present, wherein at least one of the following criteria are met: (A) at least 50% by volume of said liquid phase is amines including any primary amine reagent and optional tertiary amine solvent, and (B) the reaction step is carried out in the absence of ether solvents; and
(b) converting said succinimide to a quaternary ammonium ion.

2. The method of claim 1 , wherein said iron catalyst is Fe 3 (CO) 12 or another iron carbonyl catalyst.

3. The method of claim 1 , wherein said amine reagent is a primary amine.

4. The method of claim 1 , wherein the reaction is carried out in the presence of a tertiary amine solvent.

5. The method of claim 1 , wherein the reaction is carried out in a reaction vessel charged with carbon monoxide to at least 310 kPa.

6. The method of claim 1 , wherein said liquid phase is heated to a temperature of from 80° C. to 160° C. during the reaction step.

7. The method of claim 1 , wherein (a) said alkyne is an alkyne other than ethyne.

8. The method of claim 1 , wherein the two acetylenic carbon atoms of (i) said alkyne are bonded to groups independently selected from the group consisting of hydrogen, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 5 -C 16 aryl or aralkyl, and substituted or unsubstituted C 5 -C 16 heteroaryl or heteroaralkyl, with the proviso that both acetylenic carbon atoms are not simultaneously bonded to hydrogen.

9. The method of claim 1 , wherein (iii) said amine reagent is selected from the group consisting of ammonia, a monofunctional primary amine and a bifunctional primary amine, in which the primary amine group(s) in the mono- or bifunctional primary amine are bonded to groups selected from the group consisting of substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 5 -C 16 aryl or aralkyl, and substituted or unsubstituted C 5 -C 16 heteroaryl or heteroaralkyl.

10. The method of claim 1 , wherein said succinimide compound has the formula (I), said (i) alkyne has the formula (II) in which R 1 and R 2 are each independently selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted aryl or aralkyl, and optionally substituted heteroaryl or heteroaralkyl, and said amine (iii) has the formula (III) in which R 3 is selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted aryl or aralkyl, and optionally substituted heteroaryl or heteroaralkyl:

11. The method of claim 10 , in which R 1 and R 2 of the compound of the formula (II) are each independently selected from the group consisting of:
hydrogen, with the proviso that R 1 and R 2 are not both simultaneously hydrogen;
unsubstituted C 1 -C 6 alkyl;
—C 1 -C 6 fluoroalkyl;
C 6 -C 12 mono- or bicyclic aryl or aralkyl optionally substituted with one or two substituents selected from the group consisting of unsubstituted C 1 -C 6 alkyl, C 1 -C 6 fluoroalkyl, unsubstituted C 1 -C 6 alkoxy, halo, phenyl, benzyl, and —NR′R″ wherein R′ and R″ are each independently selected from unsubstituted C 1 -C 4 alkyl; and
C 5 -C 9 mono- or bicyclic heteroaryl or heteroaralkyl, optionally substituted with one or two substituents selected from the group consisting of unsubstituted C 1 -C 6 alkyl, C 1 -C 6 fluoroalkyl, unsubstituted C 1 -C 6 alkoxy, halo, phenyl, benzyl, and 'NR′R″ wherein R′ and R″ are each independently selected from unsubstituted C 1 -C 4 alkyl, and wherein said heteroaryl or heteroaralkyl contains one, two or three ring heteroatoms selected from nitrogen, oxygen and sulfur.

12. The method of claim 10 , in which R 3 of the compound of the formula (III), is selected from the group consisting of:
hydrogen;
unsubstituted C 1- C 6 alkyl;
C 1 -C 6 fluoroalkyl;
C 6 -C 12 mono- or bicyclic aryl or aralkyl optionally, substituted with one or two substituents selected from the group consisting of unsubstituted C 1 -C 6 alkyl, C 1 -C 6 fluoroalkyl, unsubstituted C 1 -C 6 alkoxy, halo, phenyl, benzyl, and —NR′R″ wherein R′ and R″ are each independently selected from unsubstituted C 1 -C 4 alkyl; and
C 5 -C 9 mono- or bicyclic heteroaryl or heteroaralkyl, optionally substituted with one or two substituents independently selected from the group consisting of unsubstituted C 1 -C 6 alkyl, C 1 -C 6 fluoroalkyl, unsubstituted C 1 -C 6 alkoxy, halo, phenyl, benzyl, and —NR′R″ wherein R′ and R″ are each independently unsubstituted C 1 -C 4 alkyl, and wherein said heteroaryl or heteroaralkyl contains one, two or three ring heteroatoms selected from nitrogen, oxygen and sulfur.

13. The method of claim 1 , wherein said quaternary ammonium ion comprises a pyrrolidinium group in which the ring nitrogen is a quaternary ammonium nitrogen and in which at least one, and optionally both, of the 3- and the 4- positions on the pyrrolidinium ring is substituted with a substituent group other than hydrogen.

14. The method of claim 13 , wherein both of said 3- and the 4-positions of the pyrrolidinium group have a substituent.

15. The method of claim 14 , wherein at least one, and optionally both, of said 3- and the 4- positions of the pyrrolidinium ring is substituted with a group comprising from 1 to 20 carbon atoms, and optionally also comprising one or more heteroatoms.

16. The method of claim 13 , wherein the substituents on said 3- and/or the 4-positions are independently selected from the group consisting of substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted heteroaryl and substituted or unsubstituted heteroaralkyl.

17. The method of claim 13 , wherein both of said 3- and the 4-positions on the pyrrolidinium group are substituted by groups which are independently selected from the group consisting of C 1 to C 12 alkyl, cycloalkyl or alkylaromatic groups.

18. The method of claim 13 , wherein said 3- and the 4- positions of the pyrrolidinium group are substituted by groups of identical structure.

19. The method of claim 13 , wherein said substituents on said quaternary ammonium nitrogen of the pyrrolidinium group each comprise from 1 to 20 carbon atoms and optionally, also include one or more heteroatoms, or in which said quaternary ammonium ion comprises two pyrrolidinium groups, said quaternary ammonium nitrogen of each pyrrolidinium group being connected by a bridging group which comprises from 2 to 20 carbon atoms, and optionally includes one or more heteroatoms, and also each having a substituent comprising from 1 to 20 carbon atoms, also optionally including one or more heteroatoms.

20. The method of claim 13 , wherein said substituents on the quaternary ammonium nitrogen of the pyrrolidinium group are independently selected from the group consisting of substituted or unsubstituted alkyl, substituted or unsubstituted aralkyl, and substituted or unsubstituted heteroaralkyl, or in which said quaternary ammonium ion comprises two pyrrolidinium groups, said quaternary ammonium nitrogen of each pyrrolidinium group be

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Schmitt Kirk D
• Zushma Stephen
• Burton Allen W

Classifications

• B01J29/7034

  MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3 · CPC title

• C07D207/408

  Radicals containing only hydrogen and carbon atoms attached to ring carbon atoms · CPC title

• C07D207/48

  Sulfur atoms · CPC title

• C01B39/42

  Type ZSM-12 · CPC title

• C01B39/365

  Type ZSM-8; Type ZSM-11; ZSM 5/11 intermediate · CPC title