Cycloalkylnorbornene monomers, polymers derived therefrom and their use in pervaporation

1. A compound of formula (I):

wherein:

each occurrence of X independently represents —CH 2 —or —CH 2 —CH 2 —;

m is an integer from 0 to 5 inclusive;

at least one of R 1 , R 2 , R 3 and R 4 independently represents -L-(C 7 -C 14 )tricycloalkyl or a group of formula (A):

 wherein:

each occurrence of Y independently represents —CH 2 —or —CH 2 —CH 2 —;

n is 1; and

R 5 , R 6 , R 7 and R 8 independently represents hydrogen, methyl, ethyl, linear or branched (C 3 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryl, (C 5 -C 10 )heteroaryl(C 1 -C 1 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 1 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, (C 1 -C 6 )acyloxy, or halogen;

L represents a bond; or

R 1 and R 3 taken together with the carbon atom to which they are attached form a substituted or unsubstituted (C 5 -C 7 )cycloalkyl or (C 6 -C 12 )bicycloalkyl ring;

remaining one or more of R 1 , R 2 , R 3 and R 4 independently represents hydrogen, methyl, ethyl, linear or branched (C 3 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryl, (C 5 -C 10 )heteroaryl(C 1 -C 3 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 ))aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, (C 1 -C 6 )acyloxy, or halogen;

wherein each of aforementioned groups, where valence is permissible, is optionally substituted with one or more groups selected from (C 1 -C 6 )alkyl, (C 3 -C 7 )cycloalkyl, (C 1 -C 6 )perfluoroalkyl, halogen, hydroxy, acetoxy, phenyl, hydroxyphenyl, acetoxyphenyl and a group of formula (B):

wherein:

D is (CH 2 ) r where r is an integer from 1to 5 inclusive, phenylene,

C 6 H 4 (CH 2 ) s where s is an integer from 1to 3 inclusive, or ((CH 2 ) t —O) u where t and u independently are integers from 1to 4 inclusive;

E is methyl, ethyl, CF 3 or C 2 F 5 ; and

R 13 is hydrogen or (C 1 -C 5 )alkyl.

2. The compound according to claim 1 , wherein X is CH 2 , m is 0;

each of R 2 , R 3 and R 4 is hydrogen, R 1 being a group of formula (A),

wherein Y is CH 2 , n is 1, and is represented by formula (II):

wherein:

each occurrence of R 5 , R 6 , R 7 and R 8 independently represents hydrogen, methyl, ethyl, -n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CF 3 , phenyl, benzyl, hydroxy, acetoxy, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, tert-butoxy, PhOH, PhOAc, C(CF 3 ) 2 OH , CH 2 C(CF 3 ) 2 OH, (CH 2 ) 2 C(CF 3 ) 2 OH, (CH 2 ) 3 C(CF 3 ) 2 OH, or PhC(CF 3 ) 2 OH.

3. The compound according to claim 1 , which is selected from the group consisting of:

2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane;

2-(bicyclo[2.2.1]hept-5-en-2-yl)-5-phenyl-bicyclo[2.2.1]heptane;

2-(bicyclo[2.2.1]hept-5-en-2-yl)decahydro-1,4:5,8-dimethanonaphthalene;

2-(bicyclo[2.2.1]heptenyl)-6-bicyclo[2.2.1]heptylbicyclo[2.2.1]heptane;

3-(bicyclo[2.2.1]hept-5-en-2-yl)tricyclo[2.2.1.0 2,6 ]heptane; and

1-(bicyclo[2.2.1]hept-5-en-2-yl)adamantane.

4. A compound of formula (III):

wherein:

each occurrence of R 5 , R 6 , R 7 and R 8 independently represents hydrogen, methyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CF 3 , bicycloheptyl, or phenyl.

5. The compound according to claim 4 , which is selected from the group consisting of:

2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane;

2-(bicyclo[2.2.1]hept-5-en-2-yl)-5-phenyl-bicyclo[2.2.1]heptane; and

2-(bicyclo[2.2.1]heptenyl)-6-bicyclo[2.2.1]heptylbicyclo[2.2.1]heptane.

6. A polymer comprising a first repeating unit represented by formula (IA), said repeating unit is derived from a monomer of formula (I):

wherein:

each occurrence of X independently represents —CH 2 —or —CH 2 —CH 2 —;

m is an integer from 0 to 5 inclusive;

at least one of R 1 , R 2 , R 3 and R 4 independently represents a group of formula (A):

wherein:

each occurrence of Y independently represents —CH 2 —or —CH 2 —CH 2 —;

n is 0 or 1; and

R 5 , R 6 , R 7 and R 8 independently represents hydrogen, methyl, ethyl, linear or branched (C 3 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl,(C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryl, (C 5 -C 10 )heteroaryl(C 1 -C 3 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, (C 1 -C 6 )acyloxy, or halogen;

L represents a bond; or

R 1 and R 3 taken together with the carbon atom to which they are attached form a substituted or unsubstituted (C 5 -C 7 )cycloalkyl or (C 6 -C 12 )bicycloalkyl ring;

remaining one or more of R 1 , R 2 , R 3 and R 4 independently represents hydrogen, methyl, ethyl, linear or branched (C 3 -C 3 - 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryl, (C 5 -C 10 )heteroaryl(C 1 -C 3 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, (C 1 -C 6 )acyloxy, or halogen;

wherein each of aforementioned groups, where valence is permissible, is optionally substituted with one or more groups selected from (C 1 -C 6 )alkyl, (C 3 -C 7 )cycloalkyl, (C 1 -C 6 )perfluoroalkyl, halogen, hydroxy, acetoxy, phenyl, hydroxyphenyl, acetoxyphenyl and a group of formula (B):

wherein:

D is (CH 2 ) r where r is an integer from 1to 5 inclusive, phenylene, C 6 H 4 (CH 2 ) s where s is an integer from 1to 3 inclusive, or ((CH 2 ) t —O) u where t and u independently are integers from 1to 4 inclusive;

E is methyl, ethyl, CF 3 or C 2 F 5 ; and

R 13 is hydrogen or (C 1 -C 5 )alkyl.

7. The polymer according to claim 6 , wherein R 1 is a group of formula (A), R 5 is hydrogen or phenyl, X and Y are CH 2 , m is 0, n is 0 or 1, L is a bond, and R 2 , R 3 , R 4 , R 6 , R 7 and R 8 are each hydrogen.

8. The polymer according to claim 6 further comprising a second repeating unit represented by formula (VA), said second repeat unit is derived from the monomer of formula (V):

wherein:

each occurrence of Z independently represents —CH 2 —or —CH 2 —CH 2 —;

v is an integer from 0 to 5 inclusive;

R 9 , R 10 , R 11 and R 12 independently represents hydrogen, methyl, ethyl, linear or branched (C 3 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 5 -C 10 )heteroaryl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, (C 1 -C 6 )acyloxy, halogen, or a group of formula (B):

 wherein:

D is (CH 2 ) r where r is an integer from 1to 5 inclusive, phenylene, C 6 H 4 (CH 2 ) s where s is an integer from 1to 3 inclusive, or ((CH 2 ) t —O) u where t and u independently are integers from 1to 4 inclusive;

E is methyl, ethyl, CF 3 or C 2 F 5 ; and

R 13 is hydrogen or (C 1 - 5 )alkyl; and

wherein each of aforementioned groups, where valence is permissible, is optionally substituted with a group selected from (C 1 -C 6 )alkyl, (C 3 -C 7 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 1 -C 6 )perfluoroalkyl, halogen, hydroxy, acetoxy, phenyl, hydroxyphenyl, acetoxyphenyl and a group of formula (B):

wherein D, E and R 13 are as defined above.

9. The polymer according to claim 8 , wherein Z is —CH 2 —, v is 0, each of R 10 , R 11 and R 12 is hydrogen and R 9 is —CH 2 C(CF 3 ) 2 OH, R 1 is a group of formula (A), X and Y are —CH 2 —, m is 0, n is 0 or 1, R 5 is hydrogen or phenyl, each of R 2 , R 3 , R 4 , R 6 , R 7 and R 8 is hydrogen.

10. The polymer according to claim 6 , which is a homopolymer of 2-(bicyclo [2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]-heptane.

11. The polymer according to claim 8 which is selected from:

a copolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane and hydroxyhexafluoroisopropylmethylnorbornene;

a copolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane and norbornene; and

a copolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane and 5-n-butylbicyclo[2.2.1]hept-2-ene.

12. A compound of formula (I):

wherein:

each occurrence of X independently represents —CH 2 —or —CH 2 —CH 2 —;

m is an integer from 0 to 5 inclusive;

at least one of R 1 , R 2 , R 3 and R 4 independently a group of formula (A):

 wherein:

each occurrence of Y independently represents —CH 2 —or —CH 2 —CH 2 —;

n is 0; and

R 5 , R 6 , R 7 and R 8 independently represents hydrogen, methyl, linear or branched (C 3 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryl, (C 5 -C 10 )heteroaryl(C 1 -C 3 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, (C 1 -C 6 )acyloxy, or halogen;

L represents a bond; or

R 1 and R 3 taken together with the carbon atom to which they are attached form a substituted or unsubstituted (C 5 -C 7 )cycloalkyl or (C 6 -C 12 )bicycloalkyl ring;

remaining one or more of R 1 , R 2 , R 3 and R 4 independently represents hydrogen, methyl, ethyl, linear or branched (C 3 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryl, (C 5 -C 10 )heteroaryl(C 1 -C 3 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, (C 1 -C 6 )acyloxy, or halogen;

wherein each of aforementioned groups, where valence is permissible, is optionally substituted with one or more groups selected from (C 1 -C 6 )alkyl, (C 3 -C 7 )cycloalkyl, (C 1 -C 6 )perfluoroalkyl, halogen, hydroxy, acetoxy, phenyl, hydroxyphenyl, acetoxyphenyl and a group of formula (B):

wherein:

D is (CH 2 ) r where r is an integer from 1to 5 inclusive, phenylene,

C 6 H 4 (CH 2 ) s where s is an integer from 1to 3 inclusive, or ((CH 2 ) t —O) u where t and u independently are integers from 1to 4 inclusive;

E is methyl, ethyl, CF 3 or C 2 F 5 ; and

R 13 is hydrogen or (C 1 -C 5 )alkyl.

13. The compound according to claim 12 , wherein X is CH 2 , m is 0; each of R 2 , R 3 and R 4 is hydrogen, R 1 being a group of formula (A), wherein Y is CH 2 , n is 0, L is a bond, and is represented by formula (III):

wherein:

each occurrence of R 5 , R 6 , R 7 and R 8 independently represents hydrogen, methyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, CF 3 , bicycloheptyl, phenyl, benzyl, hydroxy, acetoxy, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, tert-butoxy, PhOH, PhOAc, C(CF 3 ) 2 OH, CH 2 C(CF 3 ) 2 OH, (CH 2 ) 2 C(CF 3 ) 2 OH (CH 2 ) 3 C(CF 3 ) 2 OH, or PhC(CF 3 ) 2 OH.