IP Library › Granted Patent US 8,574,453

Granted Patent B2

US 8,574,453 · App. 12/524,639 · Granted Nov 5, 2013

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

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Quick Facts

Patent No.: US 8,574,453
App. No.: 12/524,639
Granted: Nov 5, 2013
Kind: B2

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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 (110)

1. A salt represented by:

wherein

R 1 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 , or —C(R 8 ) 3 ;

R 2 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 , or —C(R 8 ) 3 ;

R 3 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 , or —C(R 8 ) 3 ;

R 4 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 , or —C(R 8 ) 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 , —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.

2. The salt of claim 1 , wherein

3. The salt of claim 1 , wherein

R 1 represents H, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, —(CH 2 ) n —R 8 , —CH(R 8 ) 2 , or —C(R 8 ) 3 ;

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

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

R 4 represents H, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, —(CH 2 ), —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 ), —R 8 , —CH(R 8 ) 2 , or —C(R 8 ) 3 .

4. The salt of claim 1 , wherein

R 1 represents H, alkyl, fluoroalkyl, cycloalkyl, heterocycloalkyl, —(CH 2 ) n —R 8 , —CH(R 8 ) 2 , or —C(R 8 ) 3 ;

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

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

R 4 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. The salt of claim 1 , wherein Y is O.

6. The salt of claim 1 , wherein

Y is O; and

R 1 , R 3 , and R 4 are methyl.

7. The salt of claim 1 , wherein

Y is O;

R 1 , R 3 , and R 4 are methyl; and

R 2 represents n-C 4 H 9 , n-C 5 H 11 , n-C 6 H 13 , n-C 7 H is , or n-C 8 H 17 .

8. The salt of claim 1 , wherein

Y is O;

R 1 , R 3 , and R 4 are methyl;

R 2 represents n-C 4 H 9 , n-C 5 H 11 , n-C 6 H 13 , n-C 7 H 15 , or n-C 8 H 17 ; and

R 5 is H.

9. The salt of claim 1 , wherein R 1 , R 3 , and R 4 are methyl;

R 2 represents n-C 4 H 9 , n-C 5 H 11 , n-C 6 H 13 , n-C 7 H 15 , or n-C 8 H 17 ;

Y is O;

R 5 is H; and

R 6 represents n-C 4 H 9 , sec-C 4 H 9 , t-C 4 H 9 , cyclohexyl, n-C 6 H 13 , n-C 8 H 17 , —C 2 H 4 NH 2 , or —C 6 H 12 NH 2 .

10. The salt of claim 1 , wherein

R 1 , R 3 , and R 4 are methyl;

R 2 is n-C 8 H 17 ;

Y is O;

R 5 is H; and

R 6 represents n-C 4 H 9 or n-C 8 H 17 .

11. 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

wherein

R 3 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 , or —C(R 8 ) 3 ;

R 4 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 , or —C(R 8 ) 3 ;

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;

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 , —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 , —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 , —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;

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.

12. 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 1 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 , or —C(R 8 ) 3 ;

R 3 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 , or —C(R 8 ) 3 ;

R 4 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 , or —C(R 8 ) 3 ;

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 , —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.

13. 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

wherein

R 3 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 , —CH(R 8 ) 2 , or —C(R 8 ) 3 ;

R 4 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 , —CH(R 8 ) 2 , or —C(R 8 ) 3 ;

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;

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 , —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 , —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 071337/0852 →

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 10, 2011

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

To: GEORGETOWN UNIVERSITY

Reel/Frame 025606/0230 →

Continuity (2)

Provisional Application 60898116 · Jan 29, 2007

Related Publication 20110076214A1 · Mar 31, 2011