Compounds for the detection, capture and/or separation of polluting gases

Abstract

A subject of the present invention is the use of a compound having the general formula (I): (I) wherein V, W, X.sub.4, X.sub.5, X.sub.6, X.sub.7, X.sub.4, X.sub.5, X.sub.6, X.sub.7, Y, Y, R.sub.3, R.sub.3, R.sub.4 and R.sub.4 are as defined in any one of claims 1 to 11, for the detection, capture and/or separation of polluting gases, in particular those selected from the group comprising carbon dioxide, methane, sulfur dioxide, nitrogen oxides, carbon monoxide, linear hydrocarbons, linear mono-olefins and their mixtures, and preferably carbon dioxide. Another subject of the invention is a compound of formula (I) wherein V, W, X.sub.4, X.sub.5, X.sub.6, X.sub.7, X.sub.4, X.sub.5, X.sub.6, X.sub.7, Y, Y, R.sub.3, R.sub.3, R.sub.4 and R.sub.4 are as defined in any one of claims 12 to 21. ##STR00001##

Claims

1. A method for the detection, capture and/or separation of polluting gases, comprising capture and/or separation into/by a compound having general formula (I) ##STR00077## wherein V represents: ##STR00078## W has the same meaning as V or W is absent, and when W is absent then R.sub.4 and R.sub.4 are also absent, X.sub.1, X.sub.2, X.sub.3, X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5, X.sub.6, X.sub.7, X.sub.4, X.sub.5, X.sub.6, X.sub.7, X.sub.8 and X.sub.9 are each independently N or a CH group, when W has the same meaning as V, then Y and Y are each a carbon atom, when W is absent, then Y and Y are each independently N or a CR group, with R representing H, R.sub.a, NR.sub.aR.sub.b, OR.sub.a, SR.sub.a, CO.sub.2R.sub.a, COR.sub.a, CONHR.sub.a, CONR.sub.aR.sub.b, NHCOR.sub.a, SO.sub.2R.sub.a, SO.sub.2NHR.sub.a, SO.sub.2NR.sub.aR.sub.b, PR.sub.aR.sub.b, P(O)R.sub.aR.sub.b, P(O)(OR.sub.a)(OR.sub.b), CH.sub.2PO(OR.sub.a)(OR.sub.b), COCH.sub.2COR.sub.a, CSOR.sub.a, CSR.sub.a, CSNHR.sub.a, CSNR.sub.aR.sub.b, NHCSR.sub.a, P(S)R.sub.aR.sub.b, CSCH.sub.2CSR.sub.a, NHCONHR.sub.a, NHCSNHR.sub.a or a five or six-membered aromatic or heteroaromatic compound chosen from benzene, pyridine, diazine, triazine, tetrazine, pyrrole, thiophene, furan, azole, triazole or tetrazole, with R.sub.a and R.sub.b being each independently H, OH; an alkyl radical having from 1 to 10 carbon atoms (alkyl C.sub.1-C.sub.10); a five or six-membered carbocycle chosen from cyclohexane, piperidine, piperazine, tetrahydrothiophene, tetrahydropyrrole or dihydroazole; or an aromatic or heteroaromatic compound chosen from pyridine, diazine, triazine, tetrazine, pyrrole, thiophene, furan, azole, triazole, tetrazole, benzoazole, benzotriazole or indole, R.sub.1 represents O, S, SO.sub.2, SO, CO, a NR.sub.a, SiR.sub.aR.sub.b, SnR.sub.aR.sub.b, BR.sub.a or a PR.sub.a group, R.sub.a and R.sub.b being as defined above, R.sub.2 and R.sub.2 are each independently COOR.sub.a, NO.sub.2, CONR.sub.aR.sub.b, SO.sub.2R.sub.a, SO.sub.3H, OSO.sub.3H, COR.sub.a, PO.sub.3H.sub.2, OPO.sub.3H.sub.2 or CN, R.sub.a and R.sub.b being as defined above, R.sub.3, R.sub.3, R.sub.4 and R.sub.4 are each independently S, NR.sub.a, P, Se or Te, R.sub.a being as defined above.

2. A method according to claim 1, wherein in the compound of formula (I): V represents: ##STR00079## X.sub.4, X.sub.5, X.sub.6, X.sub.7, X.sub.4, X.sub.5, X.sub.6 and X.sub.7 are each independently N or CH, when W has the same meaning as V, then Y and Y are each a carbon atom, when W is absent, then Y and Y are each independently N or a CR group, R being H, NR.sub.aR.sub.b, CO.sub.2R.sub.a, P(O)(OR.sub.a)(OR.sub.b), CH.sub.2PO(OR.sub.a)(OR.sub.b), R.sub.1 represents S, SO.sub.2, NR.sub.a or O, R.sub.2 and R.sub.2 are each independently NO.sub.2, COOR.sub.a, COR.sub.a or CONR.sub.aR.sub.b, R.sub.3, R3, R.sub.4 and R.sub.4 are each independently S or NR.sub.a, with R.sub.a and R.sub.b are each independently H or an alkyl C.sub.1-C.sub.10.

3. A method according to claim 1, wherein in the compound of formula (I): W, R.sub.4 and R.sub.4 are absent, V represents: ##STR00080##

4. A method according to claim 3, wherein compound of formula (I) is selected from the group consisting of: YYCNH.sub.2, R.sub.1SO.sub.2, R.sub.2R.sub.2NO.sub.2 and R.sub.3R.sub.3S (1), YYCNH.sub.2, R.sub.1SO.sub.2, R.sub.2R.sub.2NO.sub.2 and R.sub.3R.sub.3NH (2), YYN, R.sub.1SO.sub.2, R.sub.2R.sub.2NO.sub.2 and R.sub.3R.sub.3S (3), YYN, R.sub.1SO.sub.2, R.sub.2R.sub.2NO.sub.2 and R.sub.3R.sub.3NH (4), YYN, R.sub.1SO.sub.2, R.sub.2R.sub.2COOR.sub.a and R.sub.3R.sub.3NH (5), YYN, R.sub.1SO.sub.2, R.sub.2R.sub.2COOR.sub.a and R.sub.3R.sub.3S (6), YYN, R.sub.15, R.sub.2R.sub.2COOR.sub.a and R.sub.3R.sub.3S (7), YYN, R.sub.15, R.sub.2R.sub.2COOR.sub.a and R.sub.3R.sub.3NH (8), YYCNH.sub.2, R.sub.1S, R.sub.2R.sub.2COOR.sub.a and R.sub.3R.sub.3NH (9), YYCNH.sub.2, R.sub.1S, R.sub.2R.sub.2COOR.sub.a and R.sub.3R.sub.3S (10), YYCNH.sub.2, R.sub.1S, R.sub.2R.sub.2CONR.sub.aR.sub.b and R.sub.3R.sub.3S (11), YYCNH.sub.2, R.sub.1S, R.sub.2R.sub.2CONR.sub.aR.sub.b and R.sub.3R.sub.3NH (12), YYCNH.sub.2, R.sub.1SO.sub.2, R.sub.2R.sub.2CONR.sub.aR.sub.b and R.sub.3R.sub.3NH (13), YYCNH.sub.2, R.sub.1SO.sub.2, R.sub.2R.sub.2CONR.sub.aR.sub.b and R.sub.3R.sub.3S (14), YYN, R.sub.1SO.sub.2, R.sub.2R.sub.2CONR.sub.aR.sub.b and R.sub.3R.sub.3S (15), YYN, R.sub.1SO.sub.2, R.sub.2R.sub.2CONR.sub.aR.sub.b and R.sub.3R.sub.3NH (16), YYCCOOH, R.sub.1SO.sub.2, R.sub.2R.sub.2NO.sub.2 and R.sub.3R.sub.3S (17), YYCCH.sub.2PO(OC.sub.2H.sub.5).sub.2, R.sub.1SO.sub.2, R.sub.2R.sub.2NO.sub.2 and R.sub.3R.sub.3NH (18), and in each compound (1) to (18): X.sub.1 X.sub.2 X.sub.3 X.sub.1X.sub.2 X.sub.3 X.sub.4 X.sub.5 X.sub.6 X.sub.7 X.sub.4 X.sub.5 X.sub.6 X.sub.7 CH, R.sub.a and R.sub.b are each independently H or an alkyl C.sub.1-C.sub.10.

5. A method according to claim 1, wherein in the compound of formula (I): W has the same meaning as V, V represents: ##STR00081##

6. A method according to claim 5, wherein compound of formula (I) is selected from the group consisting of: R.sub.1SO.sub.2, R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.3R.sub.4R.sub.4NH (19), R.sub.1SO.sub.2, R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.4NH, R.sub.3R.sub.4S (20), R.sub.1S, R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.3R.sub.4R.sub.4NH (21), R.sub.1S, R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.4NH, R.sub.311.sub.4S (22), R.sub.1SO.sub.2, R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.3S, R.sub.4R.sub.4NH (23), R.sub.1S, R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.3S, R.sub.4R.sub.4NH (24), and in each compound (19) to (24): X.sub.1 X.sub.2 X.sub.3 XiX.sub.2 X.sub.3 X.sub.4 X.sub.5 X.sub.6 X.sub.7 X.sub.4X.sub.5 X.sub.6 X.sub.7 CH.

7. A method according to claim 1, wherein in the compound of formula (I): W, R.sub.4 and R.sub.4 are absent, V represents: ##STR00082##

8. A method according to claim 7, wherein compound of formula (I) is selected from the group consisting of: YYN, R.sub.2R.sub.2NO.sub.2 and R.sub.3R.sub.3S (25), YYCPO(OH).sub.2, R.sub.2R.sub.2NO.sub.2 and R.sub.3R.sub.3NH (26), YYCCH.sub.2PO(OC.sub.2H.sub.5).sub.2, R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.3NH (27), YYCCOOH, R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.3S (28), YYCNH.sub.2, R.sub.2R.sub.2CO.sub.2Et, R.sub.3R.sub.3S (29), YYCCOOH, R.sub.2R.sub.2CO.sub.2Et, R.sub.3R.sub.3S (30), and in each compound (25) to (30): X.sub.4X.sub.5X.sub.6X.sub.7X.sub.4X.sub.5X.sub.6X.sub.7X.sub.8X.sub.9CH.

9. A method according to claim 1 wherein in the compound of formula (I): W has the same meaning as V, V represents: ##STR00083##

10. A method according to claim 9, wherein compound of formula (I) is selected from the group consisting of: R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.3R.sub.411.sub.4NH (31), R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.3R.sub.4R.sub.4S (32), R.sub.2R.sub.2CO.sub.2Et, R.sub.3R.sub.3R.sub.411.sub.4S (33), R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.3S, R.sub.4R.sub.4NH (34), and in each compound (31) to (34): X.sub.4X.sub.5X.sub.6X.sub.7R.sub.4X.sub.5X.sub.6X.sub.7X.sub.8X.sub.9CH.

11. A method according to claim 1 for the depollution of the air and/or toxic exhaust fumes.

12. Compound having the general formula (I): ##STR00084## wherein V represents: ##STR00085## W has the same meaning as V or W is absent, and when W is absent then R.sub.4 and R.sub.4 are also absent, X.sub.1, X.sub.2, X.sub.3, X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5, X.sub.6, X.sub.7, X.sub.4, X.sub.5, X.sub.6, X.sub.7, X.sub.8 and X.sub.9 are each independently N or a CH group, when W has the same meaning as V, then Y and Y are each a carbon atom, when W is absent, then Y and Y are each independently N or a CR group, with R representing H, R.sub.a, NR.sub.aR.sub.b, OR.sub.a, SR.sub.a, CO.sub.2R.sub.a, COR.sub.a, CONHR.sub.a, CONR.sub.aR.sub.b, NHCOR.sub.a, SO.sub.2R.sub.a, SO.sub.2NHR.sub.a, SO.sub.2NR.sub.aR.sub.b, PR.sub.aR.sub.b, P(O)R.sub.aR.sub.b, P(O)(OR.sub.a)(OR.sub.b), CH.sub.2PO(OR.sub.a)(OR.sub.b), COCH.sub.2COR.sub.a, CSOR.sub.a, CSR.sub.a, CSNHR.sub.a, CSNR.sub.aR.sub.b, NHCSR.sub.a, P(S)R.sub.aR.sub.b, CSCH.sub.2CSR.sub.a, NHCONHR.sub.a, NHCSNHR.sub.a or a five or six-membered aromatic or heteroaromatic compound chosen from benzene, pyridine, diazine, triazine, tetrazine, pyrrole, thiophene, furan, azole, triazole or tetrazole, with R.sub.a and R.sub.b being each independently H, OH; an alkyl radical having from 1 to 10 carbon atoms (alkyl C.sub.1-C.sub.10); a five or six-membered carbocycle chosen from cyclohexane, piperidine, piperazine, tetrahydrothiophene, tetrahydropyrrole or dihydroazole; or an aromatic or heteroaromatic compound chosen from pyridine, diazine, triazine, tetrazine, pyrrole, thiophene, furan, azole, triazole, tetrazole, benzoazole, benzotriazole or indole, R.sub.1 represents O, S, SO.sub.2, SO, CO, a NR.sub.a, SiR.sub.aR.sub.b, SnR.sub.aR.sub.b, BR.sub.a or a PR.sub.a group, R.sub.a and R.sub.b being as defined above, R.sub.2 and R.sub.2 are each independently COOR.sub.a, NO.sub.2, CONR.sub.aR.sub.b, SO.sub.2R.sub.a, SO.sub.3H, OSO.sub.3H, COR.sub.a, PO.sub.3H.sub.2, OPO.sub.3H.sub.2 or CN, R.sub.a and R.sub.b being as defined above, R.sub.3, R.sub.3, R.sub.4 and R.sub.4 are each independently S, NR.sub.a, P, Se or Te, R.sub.a being as defined above, with the proviso that when W, R.sub.4, R.sub.4 are absent, and V represents ##STR00086## then ##STR00087## do not represent: ##STR00088## and with the proviso that the above formula (I) does not represent one of the seven following compounds wherein: W is absent, V represents ##STR00089## X.sub.4X.sub.5X.sub.6X.sub.7X.sub.4X.sub.5X.sub.6X.sub.7CH, and YYCH, R.sub.1SO.sub.2, R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.3NH; W is absent, V represents ##STR00090## X.sub.4X.sub.5X.sub.6X.sub.7X.sub.4X.sub.5X.sub.6X.sub.7CH, and YYCNH.sub.2, R.sub.1SO.sub.2, R.sub.2R.sub.2SO.sub.3H, R.sub.311.sub.3S; W is absent, V represents ##STR00091## X.sub.4X.sub.5X.sub.6X.sub.7X.sub.4X.sub.5X.sub.6X.sub.7CH, and YYCNH.sub.2; R.sub.1CO; R.sub.2R.sub.2SO.sub.3H, R.sub.311.sub.3S; W is absent, V represents ##STR00092## X.sub.4X.sub.5X.sub.6X.sub.7X.sub.4X.sub.5X.sub.6X.sub.7CH, and YYCH, R.sub.1SO.sub.2; R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.3S; ##STR00093## X.sub.4X.sub.5X.sub.6X.sub.7X.sub.4X.sub.5X.sub.6X.sub.7CH, and YYC, R.sub.3R.sub.3R.sub.4R.sub.4S, R.sub.2R.sub.2NO.sub.2, X.sub.8X.sub.9CH; ##STR00094## X.sub.4X.sub.5X.sub.6X.sub.7X.sub.4X.sub.5X.sub.6X.sub.7CH, and YYC, R.sub.3R.sub.3R.sub.4R.sub.4NH, R.sub.2R.sub.2NO.sub.2, X.sub.8X.sub.9CH; ##STR00095## X.sub.4X.sub.5X.sub.6X.sub.7X.sub.4X.sub.5X.sub.6X.sub.7CH, and YYC, R.sub.3R.sub.3R.sub.4R.sub.4NCH.sub.3, R.sub.2R.sub.2NO.sub.2, X.sub.8X.sub.9CH.

13. Compound according to claim 12, wherein in the compound of formula (I): V represents: ##STR00096## X.sub.4, X.sub.5, X.sub.6, X.sub.7, X.sub.4, X.sub.5, X.sub.6 and X.sub.7 are each independently N or CH, when W has the same meaning as V, then Y and Y are each a carbon atom, when W is absent, then Y and Y are each independently N or a CR group, R being H, NR.sub.aR.sub.b, CO.sub.2R.sub.a, P(O)(OR.sub.a)(OR.sub.b), CH.sub.2PO(OR.sub.a)(OR.sub.b), R.sub.1 represents S, SO.sub.2, NR.sub.a or O, R.sub.2 and R.sub.2 are each independently NO.sub.2, COOR.sub.a, COR.sub.a or CONR.sub.aR.sub.b, R.sub.3, R.sub.3, R.sub.4 and R.sub.4 are each independently S or NR.sub.a, with R.sub.a and R.sub.b are each independently H or an alkyl C.sub.1-C.sub.10.

14. Compound of formula (I) according to claim 12, wherein in the compound of formula (I): W, R.sub.4 and R.sub.4 are absent, V represents: ##STR00097##

15. Compound according to claim 14, which is selected from the group consisting of compounds of formula (I) wherein: YYCNH.sub.2, R.sub.1SO.sub.2, R.sub.2R.sub.2NO.sub.2 and R.sub.3R.sub.3S (1), YYCNH.sub.2, R.sub.1SO.sub.2, R.sub.2R.sub.2NO.sub.2 and R.sub.3R.sub.3NH (2), YYN, R.sub.1SO.sub.2, R.sub.2R.sub.2NO.sub.2 and R.sub.3R.sub.3S (3), YYN, R.sub.1SO.sub.2, R.sub.2R.sub.2NO.sub.2 and R.sub.3R.sub.3NH (4), YYN, R.sub.1SO.sub.2, R.sub.2R.sub.2COOR.sub.a and R.sub.3R.sub.3NH (5), YYN, R.sub.1SO.sub.2, R.sub.2R.sub.2COOR.sub.a and R.sub.3R.sub.3S (6), YYN, R.sub.1S, R.sub.2R.sub.2COOR.sub.a and R.sub.3R.sub.3S (7), YYN, R.sub.1S, R.sub.2R.sub.2COOR.sub.a and R.sub.3R3NH (8), YYCNH.sub.2, R.sub.1S, R.sub.2R.sub.2COOR.sub.a and R.sub.3R.sub.3NH (9), YYCNH.sub.2, R.sub.1S, R.sub.2R.sub.2COOR.sub.a and R.sub.3R.sub.3S (10), YYCNH.sub.2, R.sub.1S, R.sub.2R.sub.2CONR.sub.aR.sub.b and R.sub.3R.sub.3S (11), YYCNH.sub.2, R.sub.1S, R.sub.2R.sub.2CONR.sub.aR.sub.b and R.sub.3R.sub.3NH (12), YYCNH.sub.2, R.sub.1SO.sub.2, R.sub.2R.sub.2CONR.sub.aR.sub.b and R.sub.3R.sub.3NH (13), YYCNH.sub.2, R.sub.1SO.sub.2, R.sub.2R.sub.2CONR.sub.aR.sub.b and R.sub.3R.sub.3S (14), YYN, R.sub.1SO.sub.2, R.sub.2R.sub.2CONR.sub.aR.sub.b and R.sub.3R.sub.3S (15), YYN, R.sub.1SO.sub.2, R.sub.2R.sub.2CONR.sub.aR.sub.b and R.sub.3R.sub.3NH (16), YYCCOOH, R.sub.1SO.sub.2, R.sub.2R.sub.2NO.sub.2 and R.sub.3R.sub.3S (17), YYCCH.sub.2PO(OC.sub.2H.sub.5).sub.2, R.sub.1SO.sub.2, R.sub.2R.sub.2NO.sub.2 and R.sub.3R.sub.3NH (18), and in each compound (1) to (18): X.sub.1 X.sub.2 X.sub.3 X.sub.1X.sub.2 X.sub.3 X.sub.4 X.sub.5 X.sub.6 X.sub.7 X.sub.4 X.sub.5 X.sub.6 X.sub.7 CH, R.sub.a and R.sub.b are each independently H or an alkyl C.sub.1-C.sub.10.

16. Compound of formula (I) according to claim 12, wherein: W has the same meaning as V, V represents: ##STR00098##

17. Compound according to claim 16, which is selected from the group consisting of compounds of formula (I) wherein: R.sub.1SO.sub.2, R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.3R.sub.4R.sub.4NH (19), R.sub.1SO.sub.2, R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.4NH, R.sub.3R.sub.4S (20), R.sub.1S, R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.3R.sub.4R.sub.4NH (21), R.sub.1S, R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.4NH, R.sub.311.sub.4S (22), R.sub.1SO.sub.2, R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.3S, R.sub.4R4NH (23), R.sub.1S, R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.3S, R.sub.4R.sub.4NH (24), and in each compound (19) to (24): X.sub.1 X.sub.2 X.sub.3 XiX.sub.2 X.sub.3 X.sub.4 X.sub.5 X.sub.6 X.sub.7 X.sub.4 X.sub.5 X.sub.6 X.sub.7 CH.

18. Compound of formula (I) according to claim 12, wherein: W, R.sub.4 and R.sub.4 are absent, V represents: ##STR00099##

19. Compound according to claim 18, which is selected from the group consisting of compounds of formula (I) wherein: YYN, R.sub.2R.sub.2NO.sub.2 and R.sub.3R.sub.3S (25), YYCPO(OH).sub.2, R.sub.2R.sub.2NO.sub.2 and R.sub.3R.sub.3NH (26), YYCCH.sub.2PO(OC.sub.2H.sub.5).sub.2, R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.3NH (27), YYCCOOH, R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.3S (28), YYCNH.sub.2, R.sub.2R.sub.2CO.sub.2Et, R.sub.3R.sub.3S (29), YYCCOOH, R.sub.2R.sub.2CO.sub.2Et, R.sub.3R.sub.3S (30), and in each compound (25) to (30): X.sub.4X.sub.5X.sub.6X.sub.7X.sub.4X.sub.5X.sub.6X.sub.7X.sub.8X.sub.9CH.

20. Compound of formula (I) according claim 12, wherein: W has the same meaning as V, V represents: ##STR00100##

21. Compound according to claim 20, which is selected from the group consisting of compounds of formula (I) wherein: R.sub.2R.sub.2CO.sub.2Et, R.sub.3R.sub.3R.sub.4R.sub.4S (33), R.sub.2R.sub.2NO.sub.2, R.sub.3R.sub.3S, R.sub.4R.sub.4NH (34), and in each compound (33) to (34): X.sub.4X.sub.5X.sub.6X.sub.7X.sub.4X.sub.5X.sub.6X.sub.7X.sub.8X.sub.9CH.

22. A method according to claim 1, wherein the polluting gases are those selected from the group comprising carbon dioxide, methane, sulfur dioxide, nitrogen oxides, carbon monoxide, linear hydrocarbons, linear mono-olefins and their mixtures.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1: adsorption isotherms of compounds (1) and (2) of general formula (I), and more particularly of formula (I-1), for carbon dioxide at 303 K.

(2) FIG. 2: adsorption isotherms of compounds (1) and (2) of general formula (I), and more particularly of formula (I-1), for methane at 303 K.

(3) FIG. 3: differential enthalpies of adsorption of carbon dioxide for compounds (1) and (2) of general formula (I), and more particularly of formula (I-1), at 303 K.

(4) FIG. 4: adsorption isotherms of compounds (2) (formula (I-1)) and (19) (formula (I-2)) of general formula (I), for carbon dioxide at 303 K.

(5) FIG. 5: adsorption isotherms of compounds (19) (formula (I-2)) and (31) (formula (I-4)) of general formula (I), for carbon dioxide at 303 K.

(6) FIG. 6: adsorption isotherms of compounds (25) and (28) of general formula (I), and more particularly of formula (I-3), for carbon dioxide at 303 K.

EXAMPLES

Example 1: General Synthesis Protocol of Compounds of General Formula (I)

(7) 1. General Synthesis Protocol of Compounds of General Formulae (I-1) and (I-3)

(8) To a solution of a di-halogenated (or an analogous) derivative (1 equiv.) in a polar solvent (or a mixture of polar solvents) was added a thiol or amino derivative (2.6 equiv.) and a base (such as DIPEA (diisopropylethylamine, Hnig base), NaH, Cs.sub.2CO.sub.3, K.sub.2CO.sub.3, NaOH etc. (2.6 equiv.)) or was added to the reaction mixture. The reaction was heated to reflux or stirred at room temperature and then cooled down to room temperature. The obtain precipitate was filtered off and washed successively with ethanol and water. The obtained solid was dried under vacuum affording the cyclic compound as a colored solid.

(9) 1.1. Synthesis of Compound (1) of the Invention (Formula (I-1)):

(10) ##STR00072##

(11) To a solution of 0.80 g (2.30 mmol) of bis-(4-fluoro-3-nitrophenyl) sulfone in 50 mL of a mixture of ethanol/CH.sub.3CN (v:v) was added, at room temperature, 0.760 g (6.00 mmol) of 4-aminothiophenol. To this reaction mixture was added 0.980 mL of DIPEA. Within 2 min an orange precipitate appeared. The reaction was heated to reflux during 3 h then cooled down to room temperature and then filtered off. The obtained solid was washed with ethanol (50 mL), then with hot water (50 mL) and finally with 50 mL of ethanol. After drying under reduced pressure, a yellow solid (1) was obtained in 92% yield. The melting point is 314.20 C. .sup.1H NMR (250 MHz, DMSO d.sub.6) 8.63 (d, J=1.9 Hz, 2H), 8.06 (dd, J=8.7, 1.9 Hz, 2H), 7.18 (d, J=8.4 Hz, 4H), 6.99 (d, J=8.7 Hz, 2H), 6.68 (d, J=8.4 Hz, 4H), 5.82 (s, 4H). .sup.13C NMR (62.50 MHz, DMSO d.sub.6) 151.46, 148.33, 143.51, 137.00, 136.15, 131.61, 128.95, 125.17, 115.26, 110.60. ESI-MS: 555.1 m/z [M+H].sup.+. 577.1 m/z [M+Na].sup.+. EA calculated for C.sub.24H.sub.18N.sub.4O.sub.6S.sub.3: N, 10.10; C, 51.97; H, 3.27; S, 17.34; found: N, 9.89; C, 51.77; H, 3.21; S, 17.98.

(12) 1.2. Synthesis of Compound (2) of the Invention (Formula (I-1):

(13) ##STR00073##

(14) To a solution of 0.69 g (1 mmol) of bis-(4-fluoro-3-nitrophenyl) sulfone in 50 mL of a mixture of ethanol/CH.sub.3CN (20:30) was added simultaneously at 0 C., 1.66 mL (10.00 mmol) of DIPEA and 1.08 g (6.00 mmol) of 1,4-diaminobenzene dihydrochloride. The reaction mixture was warmed up and heated under reflux over 18 hours. During the course of the reaction a dark brown precipitate was formed. The reaction mixture was cooled down to room temperature and then filtered off. The obtained brown precipitate was washed with ethanol (50 mL), then with hot water (50 mL) and finally with 50 mL of ethanol again. The brown solid was dried under reduced pressure, and a brown solid (2) is obtained in 71% yield. The melting point is 285.28 C. .sup.1H NMR (250 MHz, DMSO d.sub.6) 9.74 (s, 2H), 8.51 (d, J=2.3 Hz, 2H), 7.79 (dd, J=9.2, 2.2 Hz, 2H), 6.93 (dd, J=8.9, 2.8 Hz, 6H), 6.61 (d, J=8.6 Hz, 4H), 5.27 (s, 4H). .sup.13C NMR (62.50 MHz, DMSO d.sub.6) 147.57, 146.70, 132.58, 130.05, 126.76, 126.13, 124.81, 117.19, 113.95. ESI-MS: 521.1 m/z [M+H].sup.+. 543.1 m/z [M+Na].sup.+. EA calculated for C.sub.24H.sub.20N.sub.6O.sub.6S: N, 16.15; C, 55.38; H, 3.87; S, 6.16; found: N, 15.70; C, 54.56; H, 3.76; S, 6.23.

(15) 1.3. Synthesis of Compound (25) of the Invention (Formula (I-3):

(16) ##STR00074##

(17) To a solution of 1.500 g of 4-mercaptopyridine (13.5 mmol) in 20 mL of dry THF was slowly added, at 0 C. under an argon atmosphere, 0.346 g of NaH (14.40 mmol, 60% in mineral oil). The reaction mixture was kept 1 hour under stirring then 1.25 g of 1,5-difluoro-2,4-dinitrobenzene (6.14 mmol) in 10 mL of dry THF was added dropwise. The reaction mixture was stirred at room temperature over 18 h. To the dark brown solution was added 50 mL of water and the precipitate obtained was filtered off and washed with ethanol (70 ml). The pale yellow solid was dried affording compound 25 in 68% yield. .sup.1H NMR (250 MHz, DMSO) 9.02 (s, 1H), 8.52 (dd, J=4.6, 1.3 Hz, 4H), 7.39 (dd, J=4.5, 1.4 Hz, 4H), 6.42 (s, 1H). .sup.13C NMR (101 MHz, DMSO d6) 151.02, 141.88, 141.09, 138.16, 128.28, 126.63, 123.68. ESI-MS: 387 m/z [M+H].sup.+. 393 m/z [M+Li].sup.+. EA calculated for C.sub.16H.sub.10N.sub.4O.sub.4S.sub.2: N, 14.50; C, 49.73; H, 2.61; S, 16.60 found: N, 14.78; C, 49.06; H, 2.49; S, 16.46.

(18) 2. General Synthesis Protocol of Compounds of General Formulae (I-2) and (I-4) (Cyclic Compounds)

(19) Iterative Synthesis:

(20) To a solution of compound (formula I-1 or I-3) in a polar solvent was added a di-halogenated (or an analogous) derivative (1 equiv) followed by a base (2.5 equiv). The reaction mixture was stirred at room temperature or under reflux. Solvent was added or not to precipitate the cyclic derivative. The precipitate was filtered off and washed successively with water and a polar solvent such as ethanol. The solid was finally dried under reduce pressure to afford the pure compound.

(21) One-Pot Synthesis:

(22) To a solution of a di-halogenated (or an analogous) derivative (1 equiv.) in a polar solvent (or a mixture of polar solvents) was added an aromatic compound bearing two acidic groups (such as SH, NH.sub.2, OH etc. (1 equiv.) followed by a base (2.5 equiv.). The reaction was heated to reflux or stirred at room temperature and then cooled down to room temperature. The obtain precipitate was filtered off and washed successively with ethanol and water. The obtained solid was dried under vacuum affording the corresponding compound as a solid.

(23) 2.1. Synthesis of Compound (19) of the Invention (Formula (I-2):

(24) ##STR00075##

(25) To a solution of 0.91 mmol of compound 2 in 30 mL of dimethylformamide (DMF) was added, at room temperature, a solution of 1.05 mmol of bis-(4-fluoro-3-nitrophenyl)sulfone) in 5 mL of DMF and 2.91 mmol of diisopropylethylamine (DIPEA). The reaction mixture was heated (90 C.) under magnetic stirring over 5 days. After that, 50 mL of acetonitrile (CH.sub.3CN) were added to precipitate the product and the material was filtered. The obtained solid was carefully washed with 100 mL of CH.sub.3CN. The dark red solid was dried under reduced pressure affording the macrocycle in 51%. .sup.1H NMR (250 MHz, DMSO.sub.d6) (ppm): 9.91 (s, 4H); 8.58 (s, 4H); 7.91 (d, J=7.90 Hz, 4H); 7.41 (s, 8H); 7.19 (d, J=8.80 Hz, 4H). ESI-MS (m/z): 823 [MH].sup.+. EA calculated for C.sub.38H.sub.24N.sub.8O.sub.12S.sub.2: C: 52.43; H: 2.93; N: 13.59; S: 7.77; found: C: 52.53; H: 2.92; N: 12.84; S: 7.52.

(26) 2.2. Synthesis of Compound (31) of the Invention (Formula (I-4):

(27) ##STR00076##

(28) To a solution of N, N-(4,6-dinitro-1,3-phenylene)dibenzene-1,4-diamine in CH.sub.3CN in the presence of DIPEA (5 equiv) was added 1,5-difluoro-2,4-dinitrobenzene (1 equiv.). The reaction mixture was refluxed under reflux to afford a precipitate of 31, which was isolated by filtration in 84% yield. 31 could not be characterized in solution by .sup.1H NMR due its lack of solubility even in DMSO. MS (ESI): 543 [MH]+; EA calculated for C.sub.24H.sub.16N.sub.8O.sub.8: C, 52.95; H, 2.96; N, 20.58; found: C, 52.44; H, 3.07; N, 20.22.

Example 2: Gas Adsorption Measurements of Compounds of General Formula (I)

(29) Method:

(30) Compounds of general formula (I), and more particularly of formula (I-1), (I-2), (I-3) and (I-4) were tested for gas adsorption measurements, for instance CO.sub.2 and CH.sub.4, and results are reported on FIGS. 1 to 6.

(31) 0.40 g of sample was used. Prior to each experiment, samples were outgassed ex situ at 333 K for 16 h under a secondary vacuum of 10.sup.3 mbar. High-pressure gas adsorption measurements were carried out at 303 K (Kelvin) and up to 30 bars with CO.sub.2 and CH.sub.4 using a homemade high-throughput instrument.sup.(5). However, most differences in the data are visible up to 2 bars. The gases were obtained from Air Liquide. Methane (CH.sub.4) was of 99.9995% purity, carbon dioxide (CO.sub.2) was of 99.995% purity.

(32) Gas adsorption is measured via a manometric gas dosing system on six samples in parallel with a point-by-point introduction of gas to the sample. The amounts of gas adsorbed are calculated by an equation of state using the Reference Fluid Thermodynamic and Transport Properties (REFPROP) software package 8.0 of the National Institute of Standards and Technology (NIST).sup.(6). This experimental device is convenient because only 100 mg of sample is used, and each sample can be thermally activated individually in situ under primary vacuum, at a given final temperature overnight (here around 50-60 C.).

(33) Adsorption experiments were combined with microcalorimetry. The adsorption enthalpy was obtained by coupling that kind of system with a Tian-Calvet type microcalorimeter.

(34) In this case, the experimental device allows the determination of the adsorption isotherm and the adsorption enthalpy simultaneously. An exothermic thermal effect accompanied each introduction. This peak in the curve of energy with time has to be integrated to provide an integral (or pseudo-differential) molar enthalpy of adsorption for each dose.

(35) 1. Gas Adsorption Measurements of Compounds (1) and (2) (Formula (I-1))

(36) FIGS. 1 and 2 show respectively the adsorption isotherms of compounds (1) and (2) for carbon dioxide (CO.sub.2) (FIG. 1) and methane (CH.sub.4) (FIG. 2).

(37) These measurements are relevant up to 20 bars approximately. Indeed, above 20 bars we observe a slight increase the amount adsorbed whereas we expect more something like a plateau, according to the global shape of the adsorption isotherm, indicating a kind of saturation of the sample. This behavior is more an artifact of the experimental device, which is more pronounced when the adsorption is weak.

(38) The difference between compounds (1) and (2) provides from the replacement of two sulfurs present in compound (1) by two secondary amine functions in compound (2).

(39) Compound (1) is most efficient for molecule adsorption than compound (2). It could be deduced than sulfur functions accompanied by primary amine function on phenyl groups are more efficient for molecule adsorption than other combinations.

(40) The differential enthalpies of adsorption of carbon dioxide for compounds (1) and (2) are reported on FIG. 3. The enthalpy of adsorption for the samples in the low-pressure region is in the range 30 to 35 kJ.Math.mol.sup.1. The enthalpies of adsorption decrease with increasing loading to reach a value at approximately 10 kJ.Math.mol.sup.1.

(41) This value is not representative of a real adsorption behavior because if adsorption is still occurring in a system the resulting enthalpies must be higher or at least equal to the enthalpy of liquefaction of CO.sub.2 (17.5 kJ.Math.mol.sup.1). When the energetic values measured/calculated drop below the enthalpy of liquefaction of CO.sub.2 it means that the adsorption phenomenon is very poor and these values are a combination of various effects/errors, and couldn't help to the understanding of the system in this domain. These trends (the decreasing energetic profile) suggest that at low pressure, adsorption occurs on specific sites prior to coverage of the remaining surface. According to the literature.sup.(7), this value of 35 kJ mol.sup.1 is in the same order of magnitude than that could be attempt for carbon dioxide adsorption with some metal-organic frameworks materials.

(42) Regenerability of the sample has been evaluated under mild conditions. Indeed for each gas (CO.sub.2 and CH.sub.4) two measurements with the same parameters are performed on the sample. Between the first experiment and the second experiment, the sample is submitted to an evacuation step at 30 C. and under primary vacuum during one hour. By this way, from the second gas adsorption measurement the regenerability/recovery of the sample can be checked under these conditions.

(43) 2. Gas Adsorption Measurements of Compounds (25) and (28) (Formula (I-3))

(44) From FIG. 6 one can deduce that the chemical groups at the periphery affect dramatically the adsorption properties of the acyclic compounds regardless the cavity size. The chemical groups at the periphery will affect both the supramolecular intermolecular interactions and the interaction with the pollutant. Compound (28) is more efficient for CO.sub.2 adsorption than compound (25). The only difference between the two open-chain structures is related to their end-substitution. The latter will modify the porosity of the bulk material through the formation of a possible 3D-supramolecular network, which will affect the adsorption properties in conjunction with its direct interaction with the pollutant.

(45) 3. Gas Adsorption Measurements of Compounds (2) (Formula (I-1)), (19) (Formula (I-2) and (31) (Formula (I-4))

(46) One can deduce from FIG. 4 that compound (19) (cyclic compound) is most efficient for molecule adsorption than compound (2), which represents the open-chain analogue of compound (19). Thus the effect of the macrocyclic structure (compound 19) is to increase the ligand field strength. One can also deduce from FIG. 5 that compound (19) (cyclic compound) is most efficient for molecule adsorption than compound (31). Thus the larger cavity present in compound (19) (compared to the cavity present in compound (31)) led to greater amount of CO.sub.2 adsorbed.

(47) Conclusion on the Adsorption Properties of Compounds of Formula (I)

(48) Compounds of formula (I) have demonstrated efficient adsorption properties toward gaseous pollutant such as CO.sub.2 and CH.sub.4 for instance. Owing their non-planar structures, compounds of formula (I) lead to porous bulk material in which the adsorption efficiency can be governed and modulated by several structural factors. Generally speaking open-chain compounds of formula I-1 and I-3 exhibit a lower efficiency compared to their cyclic counterparts of formula I-2 and 1-4. The peripheral substituents dramatically affect the adsorption properties by varying the bulk material porosity and governing the interactions with the pollutants. In addition, the cavity sizes of the compounds of formula (I) modulate the adsorption efficiency. Thus, compounds having larger cavities in conjunction with the appropriate substituents present the highest adsorption capabilities. Cyclic structures of formula I-2 exhibit higher adsorption efficiencies compared to the cyclic structures of formula I-3 due to larger cavities.

BIBLIOGRAPHY

(49) 1. N. Stem, Stem Review on the Economics of Climatic Change, Cambridge University Press, Cambridge, 2006. 2. B. Metz et al., Intergovernmental Panel on Climate Change, Special Report on Carbon Dioxide Capture and Storage, Cambridge University press, Cambridge, 2005, http://www.ipcc.ch/. 3. M. Z. Jacobson, Energy Environ. Sci. 2009, 2,148. 4. D. M. D'Alessandro et al., Carbon Dioxide Capture, Angew. Chem. Int. Ed., 2010, 49, pp. 6058-6082. 5. Wiersum, A. D.; Giovannangeli, C.; Vincent, D.; Bloch, E.; Reinsch, H.; Stock, N.; Lee, J. S.; Chang, J.-S.; Llewellyn, P. L. ACS Comb. Sci. 2013, 15, 111-119. 6. Lemmon, E. W.; McLinden, H. M. MO Reference Fluid Thermodynamic and Transport Properties; REFPROP 8.0; National Institute of Standards and Technology: Gaithersburg, Md., 2007. 7. X.-J. Hou, P. He, H. Li and X. Wang, J. Phys. Chem. C, 2013, 117, 2824-2834.