PORPHYRAZINES AS EFFICIENT, CATALYTIC AND SCALABLE METHOD TO PRODUCE CHLORINE DIOXIDE

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Patent No.: US None
App. No.: 18/405,407

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Abstract

Methods, kits, cartridges, and compounds related to generating chlorine dioxide by exposing ClO 2 − to at least one of an iron porphyrin catalyst or an iron porphyrazine catalyst are described.

Claims (40)

1 . A composition comprising a compound selected from Fe III TDMImP, the ferric form thereof, Fe III TM-2,3-PyPz, or the ferrous form thereof, Fe II TM-2,3-PyPz, an isomeric form of Fe III TM-2,3-PyPz, an isomeric form of Fe II TM-2,3-PyPz, an iron porphyrin catalyst, and an iron porphyrazine catalyst.

2 . The composition of claim 1 comprising the Fe III TDMImP.

3 . The composition of claim 1 comprising the Fe III TM-2,3-PyPz.

4 . The composition of claim 1 comprising the isomeric form of Fe III TM-2,3-PyPz.

5 . The composition of claim 1 comprising the isomeric form of Fe III TM-2,3-PyPz.

6 . The composition of claim 1 comprising the iron porphyrin catalys, wherein the iron porphyrin catalyst has the structure of formula I:

wherein the a is the oxidation state II, III or IV of the Fe and R 1 , R 2 , R 3 , and R 4 are independently selected from the group consisting of TM2PyP, TM4PyP, TDMImP, and TDMBImp, which have a structure of formulas II, III, IV and V, respectively:

and at least one of R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are independently selected from the group consisting of H; methyl; ethyl; propyl; isopropyl; n-butyl; sec-butyl; isobutyl; CH 2 —(CH 2 ) n1 —CH 3 where n1=5-20; CH 2 —(CH 2 ) n2 —CH 2 —X where n2=0-20; —CH 2 (CO)—(CH 2 ) n3 —CH 2 —X where n3=0-20; —CH 2 —Ar—X; (CH 2 ) n —X; (CH 2 ) m Ar—X; (CH 2 ) m Ar—Y; (CH 2 ) n —Y; CH 2 CONH—Y; CH 2 COO—Y; CH 2 CO(CH 2 ) P —Y; (OCH 2 CH 2 ) m —Y; (OCH 2 CH 2 ) m —X; Y 2 —X; CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 3 , —CH 2 CO 2 CH 2 CH 3 ·alkyl, CH 2 CH 2 OCH 3 , CH 2 CH 2 OCH 2 CH 2 OCH 3 , (CH 2 ) n —X, (CH 2 ) n —Y, (CH 2 ) n Ar—X, (CH 2 ) n Ar—Y, CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 3 , CH 2 CO 2 CH 2 CH 3 , (OCH 2 CH 2 ) m —X, (OCH 2 CH 2 ) m —Y, Y 2 —X, or Y 2 C(Z 1 ) 3 ; where Z 1 is CH 2 OCH 2 (CH 2 ) n X, CH 2 OCH 2 (CH 2 ) n Y, or (CH 2 ) n C(O)Y 2 C(Z 2 ) 3 ; Z 2 is CH 2 OCH 2 CH 2 C(O)Y 2 C(Z 4 ) 3 ; Z 4 is CH 2 OCH 2 CH 2 X or (CH 2 ) n C(O)—Y 2 —C(Z 5 ) 3 ; Z 5 is CH 2 OCH 2 CH 2 C(O)Y 2 C(Z 6 ) 3 ; Z 6 is CH 2 OCH 2 CH 2 C(O)O(CH 2 CH 2 O) m CH 2 CH 2 O, (CH 2 ) n OCH 2 C(CH 2 OH) 3 , (CH 2 ) n OCH 2 CH(CH 2 OH) 2 , (CH) n OCH 2 C(CH 2 OH) 2 (CH 3 ), (CH 2 ) n OCH 2 C[CH 2 OCH 2 C(CH 2 OH) 3 ] 3 , (CH 2 ) n OCH 2 C[CH 2 OCH 2 C(CH 2 O[CH 2 CH 2 O] m CH 2 CH 2 OX) 3 , CH 2 CONH—Y, CH 2 CO—Y, or CH 2 CO(CH 2 ) P —Y; Y is OH, (O—CH 2 CH 2 ) m —W 1 or (CH 2 CH 2 ) m —W 2 ; W 1 is OH, or (O—(CH 2 CH 2 ) m OH); W 2 is OR 16 and R 16 is alkyl; and Y 2 is —(CH 2 ) n O—, —(CH 2 ) n NH—, —(CH) n S—; CH 2 CONH—, CH 2 COO—, or CH 2 CO(CH 2 ) p —; where

Ar is substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, or substituted or unsubstituted naphthyl and when Ar is the phenyl in —CH 2 —Ar—X, (CH 2 ) m Ar—X, or (CH 2 ) m Ar—Y, the X or Y is attached ortho- meta- or para to the —CH 2 — attached to pyridoporphyrazine;

n is 1 to 10; m is 1 to 200; p is 1 or 2; X is COOH, COO(alkyl 1 ), CONH 2 , CONH(alkyl 1 ), CON(alkyl 1 ) 2 , CO(CH 2 ) p alkyl 1 , OPO 3 H 2 , PO 3 H 2 , SO 3 H, NH 2 , N(alkyl 1 ) 2 , or N(alkyl 1 ) 3 +, where alkyl 1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl; Y is OH or (O—CH 2 CH 2 ) m —W 1 or (CH 2 CH 2 ) m —W 2 , where W 1 is OH, or (O—(CH 2 CH 2 ) m OH) and W 2 is O-alkyl; m is 1 to 200, Y 2 is —(CH 2 ) n O—, —(CH 2 ) n NH—, —(CH) n S—; CH 2 CONH—, CH 2 COO—, or CH 2 CO(CH 2 ) p —, where p is 1 or 2, and n is 1 to 10; and

L 1 and L 2 are, independently absent, halide, oxo, aquo, hydroxo, CN, OPO 3 H, or alcohol.

7 . The composition of claim 6 , wherein R 1 , R 2 , R 3 , and R 4 are TDMBImp.

8 . The composition of claim 6 , wherein R 1 , R 2 , R 3 , and R 4 are TM2PyP or TM4PyP.

9 . The composition of claim 1 comprising the iron porphyrazine catalyst, wherein the iron porphyrazine catalyst has the structure of formula VI:

wherein a is the oxidation state II, III or IV of the Mn and each of A 1 , A 2 , A 3 , A 4 , B 1 , B 2 , B 3 , B 4 , C 1 , C 2 , C 3 , C 4 , D 1 , D 2 , D 3 and D 4 are independently selected from N+-R n , N, C—H, C—X, and C—R n ;

when N+-R n is selected, only one in each set of A 1 , B 1 , C 1 , and D 1 ; A 2 , B 2 , C 2 , and D 2 ; A 3 , B 3 , C 3 , and D 3 ; or A 4 , B 4 , C 4 , and D 4 is N+-R n ;

when N is selected, only one in each set of A 1 , B 1 , C 1 , and D 1 ; A 2 , B 2 , C 2 , and D 2 ; A 3 , B 3 , C 3 , and D 3 ; or A 4 , B 4 , C 4 , and D 4 is N;

each R n is independently selected from the group consisting of H; methyl; ethyl; propyl; isopropyl; n-butyl; sec-butyl; isobutyl; CH 2 —(CH 2 ) n1 —CH 3 where n1=5-20; CH 2 —(CH 2 ) n2 —CH 2 —X where n2=0-20; CH 2 (CO)—(CH 2 ) n3 —CH 2 —X where n3=0-20; CH 2 —Ar—X; (CH 2 ) n —X; (CH 2 ) m Ar—X; (CH 2 ) m Ar—Y; (CH 2 ) n —Y; CH 2 CONH—Y; CH 2 COO—Y; CH 2 CO—Y; CH 2 CO(CH 2 ) P —Y; (OCH 2 CH 2 ) m —Y; (OCH 2 CH 2 ) m —X; Y 2 —X; CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 3 ; CH 2 CO 2 CH 2 CH 3 ; CH 2 CH 2 OCH 3 ; CH 2 CH 2 OCH 2 CH 2 OCH 3 ; (CH 2 ) n —Y; (CH 2 ) n Ar—X; (CH 2 ) n Ar—Y; and Y 2 C(Z 1 ) 3 ; Z 1 is CH 2 OCH 2 (CH 2 ) n X, CH 2 OCH 2 (CH 2 ) n Y, or (CH 2 ) n C(O)Y 2 C(Z 2 ) 3 ; Z 2 is CH 2 OCH 2 CH 2 C(O)Y 2 C(Z 3 ) 3 ; Z 3 is CH 2 OCH 2 CH 2 X or (CH 2 ) n C(O)—Y 2 —C(Z 4 ) 3 ; Z 4 is CH 2 OCH 2 CH 2 C(O)Y 2 C(Z 5 ) 3 ; and Z 5 is CH 2 OCH 2 CH 2 C(O)O(CH 2 CH 2 O) m CH 2 CH 2 O, (CH 2 ) n OCH 2 C(CH 2 OH) 3 , (CH 2 ) n OCH 2 CH(CH 2 OH) 2 , (CH 2 ) n OCH 2 C(CH 2 OH) 2 (CH 3 ), (CH 2 ) n OCH 2 C[CH 2 OCH 2 C(CH 2 OH) 3 ] 3 , (CH 2 ) n OCH 2 C[CH 2 OCH 2 C(CH 2 O[CH 2 CH 2 O] m CH 2 CH 2 OX) 3 , CH 2 CONH—Y, CH 2 CO—Y, or CH 2 CO(CH 2 ) P —Y; where

n is 1 to 10; m is 1 to 200; p is 1 or 2; X is COOH, COO(alkyl 1 ), CONH 2 , CONH(alkyl 1 ), CON(alkyl 1 ) 2 , CO(CH 2 ) p alkyl 1 , OPO 3 H 2 , PO 3 H 2 , SO 3 H, NH 2 , N(alkyl 1 ) 2 , or N(alkyl 1 ) 3 +, where alkyl 1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl; Y is OH, (O—CH 2 CH 2 ) m —W 1 or (CH 2 CH 2 ) m —W 2 ; W 1 is OH, or (O—(CH 2 CH 2 ) m OH); W 2 is O-alkyl; and Y 2 is —(CH 2 ) n O—, —(CH 2 ) n NH—, —(CH 2 ) n S—; CH 2 CONH—, CH 2 COO—, or CH 2 CO(CH 2 ) p —; and

L 1 and L 2 are independently absent, halide, oxo, aquo, hydroxo, CN, OPO 3 H, or alcohol.

10 . The composition of claim 9 , wherein Rn is TDMBImp, TM2PyP, or TM4PyP.

11 . A composition comprising a compound selected a manganese porphyrin catalyst, and a manganese porphyrazine catalyst.

12 . The composition of claim 11 comprising the manganese phorphyrin catalyst, wherein the manganese porphyrin catalyst has the structure of formula I:

wherein a is the oxidation state II, III or IV of the Mn and R 1 , R 2 , R 3 and R 4 are independently selected from the group consisting of TM2PyP, TM4PyP, TDMImP, and TDMBImp, which have a structure of formulas II, III, IV and V, respectively:

and at least one of R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are independently selected from the group consisting of H; methyl; ethyl; propyl; isopropyl; n-butyl; sec-butyl; isobutyl; CH 2 —(CH 2 ) n1 —CH 3 where n1=5-20; CH 2 —(CH 2 ) n2 —CH 2 —X where n2=0-20; —CH 2 (CO)—(CH 2 ) n3 —CH 2 —X where n3=0-20; —CH 2 —Ar—X; (CH 2 ) n —X; (CH 2 ) m Ar—X; (CH 2 ) m Ar—Y; (CH 2 ) n —Y; CH 2 CONH—Y; CH 2 COO—Y; CH 2 CO(CH 2 ) P —Y; (OCH 2 CH 2 ) m —Y; (OCH 2 CH 2 ) m —X; Y 2 —X; CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 3 ; —CH 2 CO 2 CH 2 CH 3 ; alkyl; CH 2 CH 2 OCH 3 ; CH 2 CH 2 OCH 2 CH 2 OCH 3 ; (CH 2 ) n —X; (CH 2 ) n —Y; (CH 2 ) n Ar—X; (CH 2 ) n Ar—Y; CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 3 ; CH 2 CO 2 CH 2 CH 3 ; (OCH 2 CH 2 ) m —X; (OCH 2 CH 2 ) m —Y; Y 2 —X; or Y 2 C(Z 1 ) 3 ; Z 1 is CH 2 OCH 2 (CH 2 ) n X, CH 2 OCH 2 (CH 2 ) n Y, or (CH 2 ) n C(O)Y 2 C(Z 2 ) 3 ; Z 2 is CH 2 OCH 2 CH 2 C(O)Y 2 C(Z 4 ) 3 ; Z 4 is CH 2 OCH 2 CH 2 X or (CH 2 ) n C(O)—Y 2 —C(Z 5 ) 3 ; Z 5 is CH 2 OCH 2 CH 2 C(O)Y 2 C(Z 6 ) 3 ; Z 6 is CH 2 OCH 2 CH 2 C(O)O(CH 2 CH 2 O) m CH 2 CH 2 O, (CH 2 ) n OCH 2 C(CH 2 OH) 3 , (CH 2 ) n OCH 2 CH(CH 2 OH) 2 , (CH) n OCH 2 C(CH 2 OH) 2 (CH 3 ), (CH 2 ) n OCH 2 C[CH 2 OCH 2 C(CH 2 OH) 3 ] 3 , (CH 2 ) n OCH 2 C[CH 2 OCH 2 C(CH 2 O[CH 2 CH 2 O] m CH 2 CH 2 OX) 3 , CH 2 CONH—Y, CH 2 CO—Y, or CH 2 CO(CH 2 ) P —Y; Y is OH, (O—CH 2 CH 2 ) m —W 1 or (CH 2 CH 2 ) m —W 2 ; W 1 is OH, or (O—(CH 2 CH 2 ) m OH); W 2 is OR 16 and R 16 is alkyl; and Y 2 is —(CH 2 ) n O—, —(CH 2 ) n NH—, —(CH) n S—; CH 2 CONH—, CH 2 COO—, or CH 2 CO(CH 2 ) p — where

L 1 and L 2 are, independently absent, halide, oxo, aquo, hydroxo, CN, OPO 3 H, or alcohol.

13 . The composition of claim 12 , wherein R 1 , R 2 , R 3 and R 4 are TDMBImp.

14 . The composition of claim 12 , wherein R 1 , R 2 , R 3 and R 4 are TM2PyP or TM4PyP.

15 . The composition of claim 11 comprising the manganese porphyrazine catalyst, wherein the manganese porphyrazine catalyst has the structure of formula VI:

wherein a is the oxidation state II, III or IV of the Mn and each of A 1 , A 2 , A 3 , A 4 , B 1 , B 2 , B 3 , B 4 , C 1 , C 2 , C 3 , C 4 , D 1 , D 2 , D 3 and D 4 are independently selected from N+-R n , C—H, C—X, and C—R n ;

when N+-R n is selected, only one in each set of A 1 , B 1 , C 1 , and D i ; A 2 , B 2 , C 2 , and D 2 ; A 3 , B 3 , C 3 , and D 3 ; or A 4 , B 4 , C 4 , and D 4 is N+-R n ;

when N is selected, only one in each set of A 1 , B 1 , C 1 , and D 1 ; A 2 , B 2 , C 2 , and D 2 ; A 3 , B 3 , C 3 , and D 3 ; or A 4 , B 4 , C 4 , or D 4 is N;

each R n is independently selected from the group consisting of H; methyl; ethyl; propyl; isopropyl; n-butyl; sec-butyl; isobutyl; CH 2 —(CH 2 ) n1 —CH 3 where n1=5-20; CH 2 —(CH 2 ) n2 —CH 2 —X where n2=0-20; —CH 2 (CO)—(CH 2 ) n3 —CH 2 —X where n3=0-20; —CH 2 —Ar—X; (CH 2 ) n —X; (CH 2 ) m Ar—X; (CH 2 ) m Ar—Y; (CH 2 ) n —Y; CH 2 CONH—Y; CH 2 COO—Y; CH 2 CO(CH 2 ) P —Y; (OCH 2 CH 2 ) m —Y; (OCH 2 CH 2 ) m —X; Y 2 —X; CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 3 and —CH 2 CO 2 CH 2 CH 3 ; alkyl; CH 2 CH 2 OCH 3 ; CH 2 CH 2 OCH 2 CH 2 OCH 3 ; (CH 2 ) n —X; (CH 2 ) n —Y; (CH 2 ) n Ar—X; (CH 2 ) n Ar—Y; CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 3 ; CH 2 CO 2 CH 2 CH 3 ; (OCH 2 CH 2 ) m —X; (OCH 2 CH 2 ) m —Y; Y 2 —X; o Y 2 C(Z 1 ) 3 ; Z 1 is CH 2 OCH 2 (CH 2 ) n X, CH 2 OCH 2 (CH 2 ) n Y, or (CH 2 ) n C(O)Y 2 C(Z 2 ) 3 ; Z 2 is CH 2 OCH 2 CH 2 C(O)Y 2 C(Z 4 ) 3 ; Z 4 is CH 2 OCH 2 CH 2 X or (CH 2 ) n C(O)—Y 2 —C(Z 5 ) 3 ; Z 5 is CH 2 OCH 2 CH 2 C(O)Y 2 C(Z 6 ) 3 ; Z 6 is CH 2 OCH 2 CH 2 C(O)O(CH 2 CH 2 O) m CH 2 CH 2 O, (CH 2 ) n OCH 2 C(CH 2 OH) 3 , (CH 2 ) n OCH 2 CH(CH 2 OH) 2 , (CH) n OCH 2 C(CH 2 OH) 2 (CH 3 ), (CH 2 ) n OCH 2 C[CH 2 OCH 2 C(CH 2 OH) 3 ] 3 , (CH 2 ) n OCH 2 C[CH 2 OCH 2 C(CH 2 O[CH 2 CH 2 O] m CH 2 CH 2 OX) 3 , CH 2 CONH—Y, CH 2 CO—Y, or CH 2 CO(CH 2 ) P —Y; Y is OH, (O—CH 2 CH 2 ) m —W 1 or (CH 2 CH 2 ) m —W 2 ; W 1 is OH, or (O—(CH 2 CH 2 ) m OH); W 2 is OR 16 and R 16 is alkyl; and Y 2 is —(CH 2 ) n O—, —(CH 2 ) n NH—, —(CH) n S—; CH 2 CONH—, CH 2 COO—, or CH 2 CO(CH 2 ) p —; and where

L 1 and L 2 are, independently absent, halide, oxo, aquo, hydroxo, CN, OPO 3 H, or alcohol.

16 . The composition of claim 15 , wherein R n is TDMBImp, TM2PyP, or TM4PyP.