EMM-28, a novel synthetic crystalline material, its preparation and use

Patent metadata

Field	Value
Publication number	US-10597300-B2
Application number	US-201916278470-A
Country	US
Kind code	B2
Filing date	Feb 18, 2019
Priority date	Dec 4, 2015
Publication date	Mar 24, 2020
Grant date	Mar 24, 2020

Abstract

A novel synthetic crystalline material, EMM-28, can be synthesized in the presence of an organic structure directing agent (Q) selected from one or more of the following dications:

EMM-28 may be used in organic compound conversion reactions and sorptive processes.

First claim

The invention claimed is:

1. An organic nitrogen compound comprising a dication of formula I, II and III:

2. A method of producing a 1,1′-(1,x-phenylenebis(propane-3,1-diyl))bis(1-methylpyrrolidin-1-ium) compound, where x is 2, 3 or 4, the method comprising:
reacting 1,x-bis(halomethyl)benzene with a dialkyl malonate to produce a tetraalkyl 2,2′-(1,x-phenylenebis(methylene))dimalonate;
converting at least part of the tetraalkyl 2,2′-(1,x-phenylenebis(methylene))dimalonate to 3,3′-(1,x-phenylene)dipropanoic acid;
reducing at least part of the 3,3′-(1,x-phenylene)dipropanoic acid, or an ester thereof, to 3,3′-(1,x-phenylene)bis(propan-1-ol));
reacting at least part of the 3,3′-(1,x-phenylene)bis(propan-1-ol)) with an alkyl- or aryl-sulfonyl halide to produce the corresponding sulfonate diester;
reacting at least part of the sulfonate diester with pyrrolidine to produce 1,x-bis(3-(pyrrolidin-1-yl)propyl)benzene; and
reacting at least part of the 1,x-bis(3-(pyrrolidin-1-yl)propyl)benzene with a methyl halide to produce a 1,1′-(1,x-phenylenebis(propane-3,1-diyl))bis(1-methylpyrrolidin-1-ium) halide.

3. The method of claim 2 wherein at least part of the 3,3′-(1,x-phenylene)bis(propan-1-ol)) is reacted with p-toluenesulfonyl chloride.

4. A method of producing a 1,1′-(1,x-phenylenebis(propane-3,1-diyl))bis(1-methylpyrrolidin-1-ium) compound, where x is 2, 3 or 4, the method comprising:
reacting 1,x-bis(halomethyl)benzene with a dialkyl malonate to produce a tetraalkyl 2,2′-(1,x-phenylenebis(methylene))dimalonate;
converting at least part of the tetraalkyl 2,2′-(1,x-phenylenebis(methylene))dimalonate to 3,3′-(1,x-phenylene)dipropanoic acid;
reducing at least part of the 3,3′-(1,x-phenylene)dipropanoic acid, or an ester thereof, to 3,3′-(1,x-phenylene)bis(propan-1-ol));
reacting at least part of the 3,3′-(1,x-phenylene)bis(propan-1-ol)) with an alkyl- or aryl-sulfonyl halide to produce the corresponding sulfonate diester; and
reacting at least part of the sulfonate diester with 1-methylpyrrolidine to produce a 1,1′-(1,x-phenylenebis(propane-3,1-diyl))bis(1-methylpyrrolidin-1-ium) compound.

5. The method of claim 4 wherein at least part of the 3,3′-(1,x-phenylene)bis(propan-1-ol)) is reacted with p-toluenesulfonyl chloride.

6. A method of producing a 1,1′-(1,x-phenylenebis(propane-3,1-diyl))bis(1-methylpyrrolidin-1-ium) compound, where x is 2, 3 or 4, the method comprising:
reacting 1-(prop-2-yn-1-yl)pyrrolidine with a 1,x-dihalo-substituted benzene to produce a compound of formula (IVA), (IVB) or (IVC):

hydrogenating at least part of the compound of formula (IVA), (IVB) or (IVC) to produce a compound of formula (VA), (VB) or (VC):

 and
reacting at least part of the compound of formula (VA), (VB) or (VC) with a methyl halide to produce a 1,1′-(1,x-phenylenebis(propane-3,1-diyl))bis(1-methylpyrrolidin-1-ium) halide.

7. The method of claim 6 , wherein the 1-(prop-2-yn-1-yl)pyrrolidine is produced by reacting a 3-haloprop-1-yne with pyrrolidine.

8. A method of producing a 1,1′-(1,x-phenylenebis(propane-3,1-diyl))bis(1-methylpyrrolidin-1-ium) compound, where x is 2, 3 or 4, the method comprising:
reacting a compound of formula (VI)

where R 1 is a hydroxyl group or an alkyl- or aryl-sulfonate group, with a 1,x-dihalo-substituted benzene to produce a compound of formula (VIIA), (VIIB) or (VIIC):

9. The method of claim 8 , wherein R 1 is an alkyl- or aryl-sulfonate group and the method further comprises:
hydrogenating at least part of the compound of formula (VIIA), (VIIB) or (VIIC) to produce a compound of formula (VIIIA), (VIIIB) or (VIIIC):

 and
converting at least part of the compound of formula (VIIIA), (VIIIB) or (VIIIC) to a 1,1′-(1,x-phenylenebis(propane-3,1-diyl))bis(1-methylpyrrolidin-1-ium) compound by (i) reaction with 1-methylpyrrolidine or (ii) by reaction with pyrrolidine and then with a methyl halide.

10. The method of claim 9 , wherein R 1 is a 4-methylbenzenesulfonate group.

11. The method of claim 8 , wherein R 1 is an alkyl- or aryl-sulfonate group and the method further comprises:
reacting at least part of the compound of formula (VIIA), (VIIB) or (VIIC) with pyrrolidine to produce a compound of formula (IVA), (IVB) or (IVC):

hydrogenating at least part of the compound of formula (IVA), (IVB) or (IVC) to produce a compound of formula (VA), (VB) or (VC):

 and
reacting at least part of the compound of formula (VA), (VB) or (VC) with a methyl halide to produce a 1,1′-(1,x-phenylenebis(propane-3,1-diyl))bis(1-methylpyrrolidin-1-ium) halide.

12. The method of claim 11 , wherein R 1 is a 4-methylbenzenesulfonate group.

13. The method of claim 8 , wherein R 1 is a hydroxyl group and the method further comprises:
reacting at least part of the compound of formula (VIIA), (VIIIB) or (VIIC) with an alkyl- or aryl-sulfonyl halide such as p-toluenesulfonyl chloride to produce a compound of formula (IXA), (IXB) or (IXC):

14. The method of claim 13 and further comprising:
hydrogenating at least part of the compound of formula (IXA), (IXB) or (IXC) to produce a compound of (XA), (XB) or (XC):

(i4) converting at least part of the compound of formula (XA), (XB) or (XC) into a 3,3-(1,x-phenylene)bis(propane-3,1-diyl)bis(1-methylpyrrolidinium) compound by (i) reaction with 1-methylpyrrolidine or (ii) by reaction with pyrrolidine and then with a methyl halide.

15. The method of claim 13 and further comprising:
reacting at least part of the compound of formula (IXA), (IXB) or (IXC) with pyrrolidine to produce a compound of formula (IVA), (IVB) or (IVC):

hydrogenating at least part of the compound of formula (IVA), (IVB) or (IVC) to produce a compound of formula (VA), (VB) or (VC):

 and
reacting at least part of the compound of formula (VA), (VB) or (VC) with a methyl halide to produce a 1,1′-(1,x-phenylenebis(propane-3,1-diyl))bis(1-methylpyrrolidin-1-ium) halide.

16. A method of producing a 1,1′-(1,x-phenylenebis(propane-3,1-diyl))bis(1-methylpyrrolidin-1-ium) compound, where x is 2, 3 or 4, the method comprising:
reacting a compound of formula (VI)

where R 1 is a hydroxyl group, with 1,x-dihalo-substituted benzene to produce a com

Assignees

• Exxonmobil Res & Eng Co

Inventors

• Schmitt Kirk D
• Vroman Hilda B
• Burton Allen W
• Marella Michael A
• Mabon Ross
• Weston Simon C

Classifications

• C07D207/04

  having no double bonds between ring members or between ring members and non-ring members · CPC title

• C07C303/08

  by reaction with halogenosulfonic acids · CPC title

• C01B39/48 Primary

  using at least one organic template directing agent · CPC title

• B01J37/00

  Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts · CPC title

• B01J29/70

  of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 · CPC title