Reversible room-temperature ionic liquids

Patent metadata

Field	Value
Publication number	US-9433895-B2
Application number	US-201314072439-A
Country	US
Kind code	B2
Filing date	Nov 5, 2013
Priority date	Jan 29, 2007
Publication date	Sep 6, 2016
Grant date	Sep 6, 2016

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.

First claim

We claim:

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 ;
R 5 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 ; and
R 6 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
R 5 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 ; and
R 6 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 .

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 )

Assignees

• Univ Georgetown

Inventors

• Yu Tao
• Weiss Richard G
• Yamada Taisuke
• George Mathew

Classifications

• C07D487/04

  Ortho-condensed systems · CPC title

• C07C257/14

  having carbon atoms of amidino groups bound to acyclic carbon atoms · CPC title

• B01D53/1493 Primary

  Selection of liquid materials for use as absorbents · CPC title

• C07C319/20

  by reactions not involving the formation of sulfide groups · CPC title

• C07C271/02

  Carbamic acids; Salts of carbamic acids (unsubstituted carbamic acid or salts thereof C01B21/12) · CPC title