IP Library Granted Patent US 11,492,356
Granted Patent B2
US 11,492,356 · App. 16/565,981 · Granted Nov 8, 2022

Cavitand compositions and methods of use thereof

Inventors: Kevin Travis Holman (McLean, VA); Christopher Kane (Arlington, VA)
Assignee: Georgetown University
C07D493/22B01D53/02B01J20/22B01J20/226B01J20/28095C01B23/0089C07C7/20C07C17/389C07C41/36C07F7/1804C10L3/10B01D2253/20B01D2253/204B01D2256/18B01D2257/11B01D2257/2062B01D2257/2064B01D2257/2066B01D2257/504B01D2257/704B01D2257/7022B01D2257/7025Y02P20/151
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Quick Facts
Patent No.
US 11,492,356
App. No.
16/565,981
Granted
Nov 8, 2022
Kind
B2
Abstract

Cavitand compositions that comprise void spaces are disclosed. The void spaces may be empty, which means that voids are free of guest molecules or atoms, or the void spaces may comprise guest molecules or atoms that are normally in their gas phase at standard temperature and pressure. These cavitands may be useful for industrial applications, such as the separation or storage of gasses. Novel cavitand compounds are also disclosed.

Claims (46)

1. A composition comprising a compound of formula (I):

and/or a stereoisomer thereof; wherein

R is H, C 1 -C 6 alkyl, halo, or NO 2 ;

R 1 is H, C 1 -C 6 alkyl, Ph, (C 1 -C 6 alkyl) x Ph, (C(halo) 3 ) x Ph, or (halo) x Ph;

Y is —Si(C 1 -C 6 alkyl) 2 -; and

x is an integer from 1-3, and

wherein the composition is in a crystalline form that comprises void spaces of at least 15 Å 3 ; and wherein the void spaces are free of other atoms and molecules.

2. The composition of claim 1 ; wherein for the compound of formula (I):

R is H, CH 3 , Br, or NO 2 ;

R 1 is H, CH 3 , CH 2 CH 3 , i-Bu, Ph, 4-CH 3 Ph, 4-CF 3 Ph, 3,5-(CF 3 ) 2 Ph, or 3,5-F 2 Ph; and

Y is —Si(CH 3 ) 2 —,—Si(CH 3 CH 2 ) 2 —, or —Si(i-Pr) 2 —.

3. The composition of claim 1 ; wherein for the compound of formula (I):

R is H;

R 1 is H, CH 3 , i-Bu, Ph, 4-CF 3 Ph, 3,5-(CF 3 ) 2 Ph, or 3,5-F 2 Ph; and

Y is —Si(CH 3 ) 2 —, —Si(CH 3 CH 2 ) 2 —, or —Si(i-Pr) 2 —.

4. The composition of claim 1 ; wherein for the compound of formula (I):

R is H, CH 3 , or Br;

R 1 is H, CH 3 , CH 2 CH 3 , Ph, or 4-CH 3 Ph; and

Y is —Si(CH 3 ) 2 —, or Si(CH 2 CH 3 ) 2 .

5. The composition of claim 1 ; wherein the compound of formula (I) is the rccc or the rctt stereoisomer.

6. A composition comprising a compound of formula (I):

and/or a stereoisomer thereof; wherein the compound of formula (I) is selected from the following (R, R 1 , Y):

(H, H, Si(CH 3 ) 2 ); (H, i-Bu, Si(CH 3 ) 2 ); (CH 3 , CH 3 , Si(CH 3 ) 2 ); (CH 3 , CH 3 CH 2 , Si(CH 3 ) 2 ); (CH 3 , H, Si(CH 3 CH 2 ) 2 ); (CH 3 , CH 3 , Si(CH 3 CH 2 ) 2 ); (H, H, Si(i-Pr) 2 ); (H, CH 3 , Si(i-Pr) 2 ); (CH 3 , H, Si(i-Pr) 2 ); and (CH 3 , CH 3 , Si(i-Pr) 2 ).

7. The composition of claim 1 ; wherein the compound of formula (I) comprises void spaces of 20 Å 3 to 300 Å 3 .

8. The composition of claim 1 ; wherein thermogravimetric analysis (TGA) of the composition reveals no more than 1% mass loss up to the temperature of sublimation of the composition.

9. A composition comprising a compound of formula (I)

and/or a stereoisomer thereof;

wherein the composition is a host-guest complex, where at least some void spaces of the composition comprise one or more guest gas molecules or atoms, and

wherein the compound of formula (I) is selected from the following (R, R 1 , Y):

(H, H, Si(CH 3 ) 2 ); (H, i-Bu, Si(CH 3 ) 2 ); (CH 3 , CH 3 , Si(CH 3 ) 2 ); (CH 3 , CH 3 CH 2 , Si(CH 3 ) 2 ); (CH 3 , H, Si(CH 3 CH 2 ) 2 ); (CH 3 , CH 3 , Si(CH 3 CH 2 ) 2 ); (H, H, Si(i-Pr) 2 ); (H, CH 3 , Si(i-Pr) 2 ); (CH 3 , H, Si(i-Pr) 2 ); and (CH 3 , CH 3 , Si(i-Pr) 2 ).

10. The composition of claim 9 ; wherein the guest gas is selected from one or more of acetylene, argon, krypton, xenon, carbon dioxide, methane, ethylene, ethane, propyne, propene, propane, fluoromethane, chloromethane, chloroethane, dimethylether, freons, gaseous fluorocarbons, methanethiol, oxygen, nitrogen, and bromomethane.

11. A chemical compound of formula (IIa);

and/or a stereoisomer thereof; wherein

R 4 is H, CH 3 , i-Bu, Ph, 4-CF 3 Ph, 3,5-(CF 3 ) 2 Ph, or 3,5-F 2 Ph; and

Z is —Si(CH 3 ) 2 —, —Si(CH 3 CH 2 ) 2 —, or —Si(i-Pr) 2 —;

wherein R 4 is not CH 3 when Z is —Si(CH 3 ) 2 —, or Si(CH 3 CH 2 ) 2 .

12. The chemical compound of claim 11 ; wherein the compound of formula (IIa) is selected from the following (R 4 , Z):

(H, Si(CH 3 ) 2 ); (i-Bu, Si(CH 3 ) 2 ); (H, Si(i-Pr) 2 ); and (CH 3 , Si(i-Pr) 2 ).

13. The composition of claim 1 , wherein (R, R 1 , Y) is (H, H, Si(CH 3 ) 2 ).

14. The composition of claim 9 , wherein (R, R 1 , Y) is (H, H, Si(CH 3 ) 2 ).

15. A composition comprising a compound of formula (I):

and/or a stereoisomer thereof; wherein

R is H, C 1 -C 6 alkyl, halo, or NO 2 ;

R 1 is H, C 1 -C 6 alkyl, Ph, (C 1 -C 6 alkyl) x Ph, (C(halo) 3 ) x Ph, or (halo) x Ph;

Y is Si(C 1 -C 6 alkyl) 2 ; and

x is an integer from 1-3, provided that when Y is —Si(CH 3 ) 2 — then R is not CH 3 and R 1 is not H, wherein the composition is in a crystalline form that comprises void spaces of at least 15 Å 3 ; and wherein the void spaces are free of other atoms and molecules.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 5, 2021
From: HOLMAN, KEVIN TRAVIS; KANE, CHRISTOPHER
To: GEORGETOWN UNIVERSITY
Reel/Frame 055821/0834 →
Continuity (5)
Division 14387317
Provisional Application 61799037 · Mar 15, 2013
Provisional Application 61765600 · Feb 15, 2013
Provisional Application 61614967 · Mar 23, 2012
Related Publication 20200071338A1 · Mar 5, 2020