Spirocentric compounds and polymers thereof

Patent metadata

Field	Value
Publication number	US-10953369-B2
Application number	US-201916295910-A
Country	US
Kind code	B2
Filing date	Mar 7, 2019
Priority date	Mar 8, 2018
Publication date	Mar 23, 2021
Grant date	Mar 23, 2021

Abstract

The present invention is directed to novel functionalized spirocentric compounds and polymers thereof that produce hyper-rigid cross-linked membranes.

First claim

What is claimed is:

1. A compound according to Formula I:

wherein:
the carbon indicated by “C” denotes a spiro-carbon;
A 1 and A 2 are each independently selected from:

A 3 is a selected from substituted or unsubstituted C 5 -C 6 aryl, substituted or unsubstituted C 5 -C 6 heteroaryl, substituted or unsubstituted C 5 -C 6 cycloalkyl and substituted or unsubstituted C 5 -C 6 cyclic heterocycloalkyl;
X is —CR 6 , —O—, —S—, NR 6 , —C═O, —C═NR 6 , —C═N—N(R 6 ) 2 , and C═N—OR 6 ;
R 1 , R 2 , R 3 , and R 4 are each independently selected from H and Y—Z, wherein at least one of R 1 , R 2 , R 3 , and R 4 is Y—Z;
R 5 is independently at each occurrence H, Si(OR 6 ) 3 , or Si(R 6 ) 3 ;
R 6 is independently at each occurrence selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl;
Y is independently absent or selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, —NH—(C═O)—; ═NO—C 1-6 alkyl-; and —(C═O)-phenyl-;
Z is independently selected from —N 3 , —C≡CH, C≡C—R′, —C≡N, —(C═O)—H, —SH, —CH═CH 2 , halide, —SO 3 R 6 , —B(OR 6 ) 2 , Sn(R 6 ) 3 , and Zn(R 6 ) 2 ;
R′ is selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, —CN, —CO 2 R 6 , —(C═O)—N(R 6 ) 2 , and —(C═O)—R 6 ; and
R″ is selected from R 3 and R 4 .

2. The compound according to claim 1 , wherein:
A 1 and A 2 are each independently selected from:

X is selected from —CR 6 , —O—, —S—, NR 6 , —C═O, —C═NR 6 , —C═N—N(R 6 ) 2 , and C═N—OR 6 ;
C y is selected from substituted or unsubstituted C 5 -C 6 aryl, substituted or unsubstituted C 5 -C 6 heteroaryl, substituted or unsubstituted C 5 -C 6 cycloalkyl and substituted or unsubstituted C 5 -C 6 cyclic heterocycloalkyl;
Q is selected from —O—, —S—, —N—R 7 , —C═O, —C═NR 7 , —C═N—N(R 7 ) 2 , and —C═N—OR 7 ;
Q′ is independently at each occurrence selected from —O—, —S—, and —N—R 7 ; and
R 7 is independently at each occurrence selected from R 3 and R 4 .

3. The compound according to claim 1 , wherein:
A 1 and A 2 are each independently selected from:

Z is independently selected from —N 3 , —C≡CH, C≡C—R′, —C≡N, —(C═O)—H, —SH, and —CH═CH 2 ;
Q is selected from —O—, —S—, —N—R 7 , —C═O, —C═NR 7 , —C═N—N(R 7 ) 2 , and —C═N—OR 7 ;
R′ is selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, —CN, —CO 2 R 6 , —(C═O)—N(R 6 ) 2 , and —(C═O)—R 6 ;
R 6 is independently at each occurrence selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl, and
R 7 is independently at each occurrence selected from R 3 and R 4 .

4. The compound according to claim 1 , wherein:
A 1 and A 2 are each independently selected from:

Z is independently selected from —N 3 , —C≡CH, C≡C—R′, —C≡N, —(C═O)—H, —SH, and —CH═CH 2 ;
Q′ is independently at each occurrence selected from —O—, —S—, and —N—R 7 ;
R′ is selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, —CN, —CO 2 R 6 , —(C═O)—N(R 6 ) 2 , and —(C═O)—R 6 ;
R 6 is independently at each occurrence selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl, and
R 7 is independently at each occurrence selected from R 3 and R 4 .

5. The compound according to claim 1 , wherein:
A 1 and A 2 are each independently selected from:

Z is independently selected from —N 3 , —C≡CH, C≡C—R′, —C≡N, —(C═O)—H, —SH, and —CH═CH 2 ;
Q is selected from —O—, —S—, —N—R 7 , —C═O, —C═NR 7 , —C═N—N(R 7 ) 2 , and —C═N—OR 7 ;
R′ is selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, —CN, —CO 2 R 6 , —(C═O)—N(R 6 ) 2 , and —(C═O)—R 6 ;
R 6 is independently at each occurrence selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl, and
R 7 is independently at each occurrence selected from R 3 and R 4 .

6. The compound according to claim 1 , wherein:
A 1 and A 2 are each independently selected from:

Z is independently selected from —N 3 , —C≡CH, C≡C—R′, —C≡N, —(C═O)—H, —SH, and —CH═CH 2 ;
Q′ is independently at each occurrence selected from —O—, —S—, and —N—R 7 ;
R′ is selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, —CN, —CO 2 R 6 , —(C═O)—N(R 6 ) 2 , and —(C═O)—R 6 ;
R 6 is independently at each occurrence selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl, and
R 7 is independently at each occurrence selected from R 3 and R 4 .

7. The compound according to claim 1 , wherein:
A 1 and A 2 are each independently selected from:

Z is independently selected from —N 3 , —C≡CH, C≡C—R′, —C≡N, —(C═O)—H, —SH, and —CH═CH 2 ;
Q is selected from —O—, —S—, —N—R 7 , —C═O, —C═NR 7 , —C═N—N(R 7 ) 2 , and —C═N—OR 7 ;
X is selected from —CR 6 , —O—, —S—, NR 6 , —C═O, —C═NR 6 , —C═N—N(R 6 ) 2 , and C═N—OR 6 ;
R′ is selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, —CN, —CO 2 R 6 , —(C═O)—N(R 6 ) 2 , and —(C═O)—R 6 ;
R 6 is independently at each occurrence selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, sub

Assignees

• Georgia Tech Res Inst
• Exxonmobil Res & Eng Co
• Exxonmobil Res & Engineering Company

Inventors

• Finn M G
• Mckay Craig
• Bruno Nicholas
• Thompson Kirstie
• Zhou Huaxing

Classifications

• B01D67/00931

  by introduction of specific groups after membrane formation, e.g. by grafting · CPC title

• B01D2325/0283

  Pore size · CPC title

• B01D69/1251

  by interfacial polymerisation · CPC title

• C07D311/96

  spiro-condensed with carbocyclic rings or ring systems · CPC title

• Y02C20/40

  of CO2 · CPC title