IP Library › Granted Patent US 9,433,895

Granted Patent B2

US 9,433,895 · App. 14/072,439 · Granted Sep 6, 2016

Reversible room-temperature ionic liquids

Inventors: Tao Yu (Arlington, VA); Richard G. Weiss (Bethesda, MD); Taisuke Yamada (Arlington, VA); Mathew George (Newark, DE)

Assignee: Georgetown University

B01D53/62 B01D53/1493 C07C213/08 C07C257/14 C07C271/02 C07C319/20 C07C323/43 C07D487/04

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Quick Facts

Patent No.: US 9,433,895
App. No.: 14/072,439
Granted: Sep 6, 2016
Kind: B2

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USPTO Patent Center↗ Full Patent PDF↗

Abstract

One aspect of the present invention relates to salts that are room-temperature ionic liquids (RTILs), methods of making them, and methods of using them in connection with temporary or permanent gas sequestration. Another aspect of the present invention relates to a class of solvents which can be transformed into RTILs by exposure to a gas, and methods of using them in connection with temporary or permanent gas sequestration.

Claims (85)

1. A salt represented by:

wherein

R 9 is absent or represents one or more substituents attached to the ring, each of which is independently selected from the group consisting of H, halogen, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —(CH 2 ) n —R 8 , —OR 8 , —N(R 8 ) 2 , —SR 8 , —C(═O)OR 8 , —OC(═O)R 8 , —NR 8 C(═O)R 8 , —C(═O)N(R 8 ) 2 , —C(═O)SR 8 , —SC(═O)R 8 , —S(═O)R 8 , —S(═O) 2 R 8 , —S(═O) 2 OR 8 , —C(═O)R 8 , —C(═NR 8 )R 8 , —C(═S)R 8 , —C(R 8 )═C(R 8 ) 2 , —C≡CR 8 , —CH(R 8 ) 2 , —C(R 8 ) 3 , and —(CH 2 ) n —NH 2 ;

z is zero or an integer in the range of 1 to 3;

R 5 represents H, halogen, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —(CH 2 ) n —R 8 , —OR 8 , —N(R 8 ) 2 , —SR 8 , —C(═O)OR 8 , —OC(═O)R 8 , —NR 8 C(═O)R 8 , —C(═O)N(R 8 ) 2 , —C(═O)SR 8 , —SC(═O)R 8 , —S(═O)R 8 , —S(═O) 2 R 8 , —S(═O) 2 OR 8 , —C(═O)R 8 , —C(═NR 8 )R 8 , —C(═S)R 8 , —C(R 8 )═C(R 8 ) 2 , —C≡CR 8 , —CH(R 8 ) 2 , —C(R 8 ) 3 , or —(CH 2 ) n —NH 2 ;

R 6 represents H, halogen, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —(CH 2 ) n —R 8 , —OR 8 , —N(R 8 ) 2 , —SR 8 , —C(═O)OR 8 , —OC(═O)R 8 , —NR 8 C(═O)R 8 , —C(═O)N(R 8 ) 2 , —C(═O)SR 8 , —SC(═O)R 8 , —S(═O)R 8 , —S(═O) 2 R 8 , —S(═O) 2 OR 8 , —C(═O)R 8 , —C(═NR 8 )R 8 , —C(═S)R 8 , —C(R 8 )═C(R 8 ) 2 , —C≡R 8 , —CH(R 8 ) 2 , —C(R 8 ) 3 , or —(CH 2 ) n —NH 2 ;

Y represents independently for each occurrence O or S;

R 8 represents independently for each occurrence —(CH 2 ) n —CH 3 , cycloalkyl, aryl, or heteroaryl; and

n represents independently for each occurrence an integer in the range 1-10 inclusive.

2. The salt of claim 1 , wherein

R 9 represents H, halogen, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —(CH 2 ) n —R 8 , —C(R 8 )═C(R 8 ) 2 , —C≡CR 8 , —CH(R 8 ) 2 , or —C(R 8 ) 3 ;

3. The salt of claim 1 , wherein

R 9 represents H, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, —(CH 2 ) n —R 8 , —CH(R 8 ) 2 , or —C(R 8 ) 3 ;

R 5 represents H, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, —(CH 2 ) n —R 8 , —CH(R 8 ) 2 , or —C(R 8 ) 3 ; and

R 6 represents H, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, —(CH 2 ) n —R 8 , —CH(R 8 ) 2 , or —C(R 8 ) 3 .

4. The salt of claim 1 , wherein

R 9 represents H, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, —(CH 2 ) n —R 8 , —CH(R 8 ) 2 , or —C(R 8 ) 3 ;

R 5 represents H, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, —(CH 2 ) n —R 8 , —CH(R 8 ) 2 , or —C(R 8 ) 3 ;

R 6 represents H, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, —(CH 2 ) n —R 8 , —CH(R 8 ) 2 , or —C(R 8 ) 3 ; and

Y is O.

5. A salt represented by:

wherein

R 5 represents H, halogen, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —(CH 2 ) n —R 8 , —OR 8 , —N(R 8 ) 2 , —SR 8 , —C(═O)OR 8 , —OC(═O)R 8 , —NR 8 C(═O)R 8 , —C(═O)N(R 8 ) 2 , —C(═O)SR 8 , —S C(═O)R 8 , —S(═O)R 8 , —S(═O) 2 R 8 , —S(═O) 2 OR 8 , —C(═O)R 8 , —C(═NR 8 )R 8 , —C(═S)R 8 , —C(R 8 )═C(R 8 ) 2 , —C≡CR 8 , —CH(R 8 ) 2 , —C(R 8 ) 3 , or —(CH 2 ) n —NH 2 ;

R 6 represents H, halogen, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —(CH 2 ) n —R 8 , —OR 8 , —N(R 8 ) 2 , —SR 8 , —C(═O)OR 8 , —OC(═O)R 8 , —NR 8 C(═O)R 8 , —C(═O)N(R 8 ) 2 , —C(═O)SR 8 , —S C(═O)R 8 , —S(═O)R 8 , —S(═O) 2 R 8 , —S(═O) 2 OR 8 , —C(═O)R 8 , —C(═NR 8 )R 8 , —C(═S)R 8 , —C(R 8 )═C(R 8 ) 2 , —C≡CR 8 , —CH(R 8 ) 2 , —C(R 8 ) 3 , or —(CH 2 ) n —NH 2 ;

Y represents independently for each occurrence O or S;

R 8 represents independently for each occurrence —(CH 2 ) n —CH 3 , cycloalkyl, aryl, or heteroaryl; and

n represents independently for each occurrence an integer in the range 1-10 inclusive.

6. The salt of claim 5 , wherein

7. The salt of claim 5 , wherein

R 5 represents H, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, —(CH 2 ) n —R 8 , —CH(R 8 ) 2 , or —C(R 8 ) 3 ; and

R 6 represents H, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, —(CH 2 ) n —R 8 , —CH(R 8 ) 2 , or —C(R 8 ) 3 .

8. The salt of claim 5 , wherein

R 5 represents H, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, —(CH 2 ) n —R 8 , —CH(R 8 ) 2 , or —C(R 8 ) 3 ;

R 6 represents H, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, —(CH 2 ) n —R 8 , —CH(R 8 ) 2 , or —C(R 8 ) 3 ; and

Y is O.

9. A method of preparing a salt, comprising the step of contacting a gas with a first compound and a second compound, wherein said first compound is represented by

wherein

R 9 is absent or represents one or more substituents attached to the ring, each of which is independently selected from the group consisting of H, halogen, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —(CH 2 ) n —R 8 , —OR 8 , —N(R 8 ) 2 , —SR 8 , —C(═O)OR 8 , —OC(═O)R 8 , —NR 8 C(═O)R 8 , —C(═O)N(R 8 ) 2 , —C(═O)SR 8 , —S C(═O)R 8 , —S(═O)R 8 , —S(═O) 2 R 8 , —S(═O) 2 OR 8 , —C(═O)R 8 , —C(═NR 8 )R 8 , —C(═S)R 8 , —C(R 8 )═C(R 8 ) 2 , —C≡CR 8 , —CH(R 8 ) 2 , —C(R 8 ) 3 , and —(CH 2 ) n —NH 2 ;

R 8 represents independently for each occurrence —(CH 2 ) n —CH 3 , cycloalkyl, aryl, or heteroaryl;

n represents independently for each occurrence an integer in the range 1-10 inclusive;

z is zero or an integer in the range of 1 to 3; and

said second compound is represented by

wherein

R 5 represents H, halogen, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —(CH 2 ) n —R 8 , —OR 8 , —N(R 8 ) 2 , —SR 8 , —C(═O)OR 8 , —OC(═O)R 8 , —NR 8 C(═O)R 8 , —C(═O)N(R 8 ) 2 , —C(═O)SR 8 , —S C(═O)R 8 , —S(═O)R 8 , —S(═O) 2 R 8 , —S(═O) 2 OR 8 , —C(═O)R 8 , —C(═NR 8 )R 8 , —C(═S)R 8 , —C(R 8 )═C(R 8 ) 2 , —C≡CR 8 , —CH(R 8 ) 2 , —C(R 8 ) 3 , or —(CH 2 ) n —NH 2 ;

R 6 represents H, halogen, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —(CH 2 ) n —R 8 , —OR 8 , —N(R 8 ) 2 , —SR 8 , —C(═O)OR 8 , —OC(═O)R 8 , —NR 8 C(═O)R 8 , —C(═O)N(R 8 ) 2 , —C(═O)SR 8 , —S C(═O)R 8 , —S(═O)R 8 , —S(═O) 2 R 8 , —S(═O) 2 OR 8 , —C(═O)R 8 , —C(═NR 8 )R 8 , —C(═S)R 8 , —C(R 8 )═C(R 8 ) 2 , —C≡CR 8 , —CH(R 8 ) 2 , —C(R 8 ) 3 , or —(CH 2 ) n —NH 2 ;

R 8 represents independently for each occurrence —(CH 2 ) n —CH 3 , cycloalkyl, aryl, or heteroaryl;

n represents independently for each occurrence an integer in the range 1-10 inclusive; and

said gas is represented by:

Y═X═Y

wherein

X represents C or N; and

Y represents independently for each occurrence O or S.

10. A method comprising the step of contacting a first gas with an ionic liquid, thereby generating a second gas; wherein said ionic liquid is represented by:

wherein

said first gas is an inert gas;

said second gas is CO 2 or CS 2 ;

R 5 represents H, halogen, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —(CH 2 ) n —R 8 , —OR 8 , —N(R 8 ) 2 , —SR 8 , —C(═O)OR 8 , —OC(═O)R 8 , —NR 8 C(═O)R 8 , —C(═O)N(R 8 ) 2 , —C(═O)SR 8 , —S C(═O)R 8 , —S(═O)R 8 , —S(═O) 2 R 8 , —S(═O) 2 OR 8 , —C(═O)R 8 , —C(═NR 8 )R 8 , —C(═S)R 8 , —C(R 8 )═C(R 8 ) 2 , —C≡CR 8 , —CH(R 8 ) 2 , —C(R 8 ) 3 , or —(CH 2 ) n —NH 2 ;

R 6 represents H, halogen, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —(CH 2 ) n —R 8 , —OR 8 , —N(R 8 ) 2 , —SR 8 , —C(═O)OR 8 , —OC(═O)R 8 , —NR 8 C(═O)R 8 , —C(═O)N(R 8 ) 2 , —C(═O)SR 8 , —S C(═O)R 8 , —S(═O)R 8 , —S(═O) 2 R 8 , —S(═O) 2 OR 8 , —C(═O)R 8 , —C(═NR 8 )R 8 , —C(═S)R 8 , —C(R 8 )═C(R 8 ) 2 , —C≡CR 8 , —CH(R 8 ) 2 , —C(R 8 ) 3 , or —(CH 2 ) n —NH 2 ;

X represents C;

Y represents independently for each occurrence O or S;

R 8 represents independently for each occurrence —(CH 2 ) n —CH 3 , cycloalkyl, aryl, or heteroaryl;

R 9 is absent or represents one or more substituents attached to the ring, each of which is independently selected from the group consisting of H, halogen, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —(CH 2 ) n —R 8 , —OR 8 , —N(R 8 ) 2 , —SR 8 , —C(═O)OR 8 , —OC(═O)R 8 , —NR 8 C(═O)R 8 , —C(═O)N(R 8 ) 2 , —C(═O)SR 8 , —S C(═O)R 8 , —S(═O)R 8 , —S(═O) 2 R 8 , —S(═O) 2 OR 8 , —C(═O)R 8 , —C(═NR 8 )R 8 , —C(═S)R 8 , —C(R 8 )═C(R 8 ) 2 , —C≡CR 8 , —CH(R 8 ) 2 , —C(R 8 ) 3 , and —(CH 2 ) n —NH 2 ;

z is zero or an integer in the range of 1 to 3; and

n represents independently for each occurrence an integer in the range 1-10 inclusive.

11. A method of removing a gas from a mixture, comprising the step of contacting said mixture with a first compound and a second compound, wherein said first compound is represented by

wherein

R 9 is absent or represents one or more substituents attached to the ring, each of which is independently selected from the group consisting of H, halogen, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —(CH 2 ) n —R 8 , —OR 8 , —N(R 8 ) 2 , —SR 8 , —C(═O)OR 8 , —OC(═O)R 8 , —NR 8 C(═O)R 8 , —C(═O)N(R 8 ) 2 , —C(═O)SR 8 , —S C(═O)R 8 , —S(═O)R 8 , —S(═O) 2 R 8 , —S(═O) 2 OR 8 , —C(═O)R 8 , —C(═NR 8 )R 8 , —C(═S)R 8 , —C(R 8 )═C(R 8 ) 2 , —C≡CR 8 , —CH(R 8 ) 2 , —C(R 8 ) 3 , or —(CH 2 ) n —NH 2 ;

R 8 represents independently for each occurrence —(CH 2 ) n —CH 3 , cycloalkyl, aryl, or heteroaryl;

n represents independently for each occurrence an integer in the range 1-10 inclusive;

z is zero or an integer in the range of 1 to 3; and

said second compound is represented by

wherein

R 5 represents H, halogen, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —(CH 2 ) n —R 8 , —OR 8 , —N(R 8 ) 2 , —SR 8 , —C(═O)OR 8 , —OC(═O)R 8 , —NR 8 C(═O)R 8 , —C(═O)N(R 8 ) 2 , —C(═O)SR 8 , —S C(═O)R 8 , —S(═O)R 8 , —S(═O) 2 R 8 , —S(═O) 2 OR 8 , —C(═O)R 8 , —C(═NR 8 )R 8 , —C(═S)R 8 , —C(R 8 )═C(R 8 ) 2 , —C≡CR 8 , —CH(R 8 ) 2 , —C(R 8 ) 3 , or —(CH 2 ) n —NH 2 ;

R 6 represents H, halogen, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —(CH 2 ) n —R 8 , —OR 8 , —N(R 8 ) 2 , —SR 8 , —C(═O)OR 8 , —OC(═O)R 8 , —NR 8 C(═O)R 8 , —C(═O)N(R 8 ) 2 , —C(═O)SR 8 , —S C(═O)R 8 , —S(═O)R 8 , —S(═O) 2 R 8 , —S(═O) 2 OR 8 , —C(═O)R 8 , —C(═NR 8 )R 8 , —C(═S)R 8 , —C(R 8 )═C(R 8 ) 2 , —C≡CR 8 , —CH(R 8 ) 2 , —C(R 8 ) 3 , or —(CH 2 ) n —NH 2 ;

R 8 represents independently for each occurrence cycloalkyl, aryl, or heteroaryl;

n represents independently for each occurrence an integer in the range 1-10 inclusive; and

said gas is represented by:

Y═X═Y

wherein

X represents C or N; and

Y represents independently for each occurrence O or S.

Assignments (2)

CONFIRMATORY LICENSE Recorded May 21, 2025

From: GEORGETOWN UNIVERSITY

To: NATIONAL SCIENCE FOUNDATION

Reel/Frame 071340/0158 →

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 3, 2014

From: YU, TAO; WEISS, RICHARD G.; YAMADA, TAISUKE; GEORGE, MATHEW

To: GEORGETOWN UNIVERSITY

Reel/Frame 032119/0920 →

Continuity (3)

Continuation 12524639

Provisional Application 60898116 · Jan 29, 2007

Related Publication 20140120013A1 · May 1, 2014