Granted Patent B2

US 12,329,158 · App. 18/373,376 · Granted Jun 17, 2025

Inventors: Daniel MacLean (Woodland, CA); Richard M. Jacobson (Chalfont, PA); Timothy Malefyt (Stroudsburg, PA)

Assignee: AGROFRESH INC.

A01N55/08A01N25/18A01N55/00A23B2/721A23B4/16A23B4/20A23B7/152A23B7/154A61K9/0034A61K9/70A61K31/69

Abstract

Claims (92)

1. A method of treating a food packaging material with an antimicrobial agent, the method comprising:

administering a benzoxaborole treatment to one or more surfaces of the food packaging material, wherein the benzoxaborole treatment comprises one or more benzoxaborole compounds,

drying the one or more surfaces of the food packaging material,

placing a food product inside of the food packaging material,

wherein the one or more benzoxaborole compounds are:

i) of formula (IV), or a salt thereof:

wherein A and D together with the carbon atoms to which they are attached form a 5-, 6-, or 7-membered fused ring which may be substituted by C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, hydroxy, halogen, nitro, nitrile, amino, amino substituted by one or more C 1 -C 6 -alkyl groups, carboxy, acyl, aryloxy, carbonamido, carbonamido substituted by C 1 -C 6 -alkyl, sulfonamido or trifluoromethyl or the fused ring may link two oxaborole rings;

X is a group —CR 7 R 8 wherein R 7 and R 8 are each independently hydrogen, C 1 -C 6 -alkyl, nitrile, nitro, aryl, arylalkyl or R 7 and R 8 together with the carbon atom to which they are attached form an alicyclic ring; and

R 6 is hydrogen, C 1 -C 18 -alkyl, C 1 -C 18 -alkyl substituted by C 1 -C 6 -alkoxy, C 1 -C 6 -alkylthio, hydroxy, amino, amino substituted by C 1 -C 18 -alkyl, carboxy, aryl, aryloxy, carbonamido, carbonamido substituted by C 1 -C 6 -alkyl, aryl or arylalkyl, arylalkyl, aryl, heteroaryl, cycloalkyl, C 1 -C 18 -alkyleneamino, C 1 -C 18 -alkyleneamino substituted by phenyl, C 1 -C 6 -alkoxy or C 1 -C 6 -alkylthio, carbonyl alkyleneamino or a radical of formula (V):

wherein A, D and X are as defined herein before, or

ii) formula (A):

R A -L A -G-L B -R B   (A),

wherein

each of R A and R B is independently a of R A and R B is of formula (E):

wherein each R 6 is independently hydrogen, alkyl, alkene, alkyne, haloalkyl, haloalkene, haloalkyne, alkoxy, alkeneoxy, haloalkoxy, aryl, heteroaryl, arylalkyl, arylalkene, arylalkyne, heteroarylalkyl, heteroarylalkene, heteroarylalkyne, halogen, hydroxyl, nitrile, amine, ester, carboxylic acid, ketone, alcohol, sulfide, sulfoxide, sulfone, sulfoximine, sulfilimine, sulfonamide, sulfate, sulfonate, nitroalkyl, amide, oxime, imine, hydroxylamine, hydrazine, hydrazone, carbamate, thiocarbamate, urea, thiourea, carbonate, aryloxy, or heteroaryloxy;

n=1, 2, 3, or 4;

B is boron;

X 2 =(CR 6 2 ) m where m=1 or 2;

each of L A and L B is independently —O— or

each of R and R′ is independently hydrogen, unsubstituted or substituted C 1-18 -alkyl, arylalkyl, aryl, or heterocyclic moiety; and

G is a substituted or unsubstituted C 1-18 -alkylene, arylalkylene, arylene, or heterocyclic moiety; and acceptable salts thereof.

2. The method of claim 1 , wherein the food product is selected from the group consisting of a strawberry, a raspberry, a blackberry, and a blueberry.

3. The method of claim 1 , wherein the benzoxaborole is of formula (IV), or a salt thereof:

wherein A and D together with the carbon atoms to which they are attached form a 5-, 6-, or 7-membered fused ring which may be substituted by C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, hydroxy, halogen, nitro, nitrile, amino, amino substituted by one or more C 1 -C 6 -alkyl groups, carboxy, acyl, aryloxy, carbonamido, carbonamido substituted by C 1 -C 6 -alkyl, sulfonamido or trifluoromethyl or the fused ring may link two oxaborole rings;

X is a group —CR 7 R 8 wherein R 7 and R 8 are each independently hydrogen, C 1 -C 6 -alkyl, nitrile, nitro, aryl, arylalkyl or R 7 and R 8 together with the carbon atom to which they are attached form an alicyclic ring; and

R 6 is hydrogen, C 1 -C 18 -alkyl, C 1 -C 18 -alkyl substituted by C 1 -C 6 -alkoxy, C 1 -C 6 -alkylthio, hydroxy, amino, amino substituted by C 1 -C 18 -alkyl, carboxy, aryl, aryloxy, carbonamido, carbonamido substituted by C 1 -C 6 -alkyl, aryl or arylalkyl, arylalkyl, aryl, heteroaryl, cycloalkyl, C 1 -C 18 -alkyleneamino, C 1 -C 18 -alkyleneamino substituted by phenyl, C 1 -C 6 -alkoxy or C 1 -C 6 -alkylthio, carbonyl alkyleneamino or a radical of formula (V):

wherein A, D and X are as defined herein before.

4. The method of claim 3 , wherein the benzoxaborole compound is has the structure

or a salt thereof.

5. The method of claim 1 , wherein the benzoxaborole has the structure formula (A):

R A -L A -G-L B -R B   (A),

wherein

each of R A and R B is independently a of R A and R B is of formula (E):

wherein each R 6 is independently hydrogen, alkyl, alkene, alkyne, haloalkyl, haloalkene, haloalkyne, alkoxy, alkeneoxy, haloalkoxy, aryl, heteroaryl, arylalkyl, arylalkene, arylalkyne, heteroarylalkyl, heteroarylalkene, heteroarylalkyne, halogen, hydroxyl, nitrile, amine, ester, carboxylic acid, ketone, alcohol, sulfide, sulfoxide, sulfone, sulfoximine, sulfilimine, sulfonamide, sulfate, sulfonate, nitroalkyl, amide, oxime, imine, hydroxylamine, hydrazine, hydrazone, carbamate, thiocarbamate, urea, thiourea, carbonate, aryloxy, or heteroaryloxy;

n=1, 2, 3, or 4;

B is boron;

X 2 =(CR 6 2 ) m where m=1 or 2;

each of L A and L B is independently —O— or

each of R and R′ is independently hydrogen, unsubstituted or substituted C 1-18 -alkyl, arylalkyl, aryl, or heterocyclic moiety; and

G is a substituted or unsubstituted C 1-18 -alkylene, arylalkylene, arylene, or heterocyclic moiety; and acceptable salts thereof.

6. The method of claim 3 , wherein the benzoxaborole has the structure

or a salt thereof.

7. The method of claim 1 , wherein administering the benzoxaborole treatment to food packaging material comprises embedding the benzoxaborole compound into the food packaging material, impregnating the food packaging material with the benzoxaborole compound, or coating the food packaging material with the benzoxaborole compound.

8. The method of claim 1 , wherein the food packaging material is a chamber.

9. The method of claim 8 , wherein the chamber is a clamshell.

10. The method of claim 9 , wherein the clamshell comprises polyethylene terephthalate.

11. A large-scale method of treating a plurality of chambers with an antimicrobial agent, the method comprising:

placing a plurality of chambers in a position to be treated wherein each of the chambers comprise one or more surfaces,

administering the antimicrobial treatment to one or more surfaces of the plurality of chambers during preformation, formation, or postformation of the plurality of chambers, wherein the antimicrobial treatment comprises one or more benzoxaborole compounds,

drying the one or more surfaces of the plurality of chambers, and affixing the benzoxaborole compound to the one or more surfaces of the plurality of chambers,

wherein the one or more benzoxaborole compounds are:

i) of formula (IV), or a salt thereof:

wherein A and D together with the carbon atoms to which they are attached form a 5-, 6-, or 7-membered fused ring which may be substituted by C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, hydroxy, halogen, nitro, nitrile, amino, amino substituted by one or more C 1 -C 6 -alkyl groups, carboxy, acyl, aryloxy, carbonamido, carbonamido substituted by C 1 -C 6 -alkyl, sulfonamido or trifluoromethyl or the fused ring may link two oxaborole rings;

X is a group —CR 7 R 8 wherein R 7 and R 8 are each independently hydrogen, C 1 -C 6 -alkyl, nitrile, nitro, aryl, arylalkyl or R 7 and R 8 together with the carbon atom to which they are attached form an alicyclic ring; and

R 6 is hydrogen, C 1 -C 18 -alkyl, C 1 -C 18 -alkyl substituted by C 1 -C 6 -alkoxy, C 1 -C 6 -alkylthio, hydroxy, amino, amino substituted by C 1 -C 18 -alkyl, carboxy, aryl, aryloxy, carbonamido, carbonamido substituted by C 1 -C 6 -alkyl, aryl or arylalkyl, arylalkyl, aryl, heteroaryl, cycloalkyl, C 1 -C 18 -alkyleneamino, C 1 -C 18 -alkyleneamino substituted by phenyl, C 1 -C 6 -alkoxy or C 1 -C 6 -alkylthio, carbonyl alkyleneamino or a radical of formula (V):

wherein A, D and X are as defined herein before, or

ii) formula (A):

R A -L A -G-L B -R B   (A),

wherein

each of R A and R B is independently a of R A and R B is of formula (E):

wherein each R 6 is independently hydrogen, alkyl, alkene, alkyne, haloalkyl, haloalkene, haloalkyne, alkoxy, alkeneoxy, haloalkoxy, aryl, heteroaryl, arylalkyl, arylalkene, arylalkyne, heteroarylalkyl, heteroarylalkene, heteroarylalkyne, halogen, hydroxyl, nitrile, amine, ester, carboxylic acid, ketone, alcohol, sulfide, sulfoxide, sulfone, sulfoximine, sulfilimine, sulfonamide, sulfate, sulfonate, nitroalkyl, amide, oxime, imine, hydroxylamine, hydrazine, hydrazone, carbamate, thiocarbamate, urea, thiourea, carbonate, aryloxy, or heteroaryloxy;

n=1, 2, 3, or 4;

B is boron;

X 2 =(CR 6 2 ) m where m=1 or 2;

each of L A and L B is independently —O— or

each of R and R′ is independently hydrogen, unsubstituted or substituted C 1-18 -alkyl, arylalkyl, aryl, or heterocyclic moiety; and

G is a substituted or unsubstituted C 1-18 -alkylene, arylalkylene, arylene, or heterocyclic moiety; and acceptable salts thereof.

12. The method of claim 11 , wherein the benzoxaborole is of formula (IV), or a salt thereof:

wherein A and D together with the carbon atoms to which they are attached form a 5-, 6-, or 7-membered fused ring which may be substituted by C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, hydroxy, halogen, nitro, nitrile, amino, amino substituted by one or more C 1 -C 6 -alkyl groups, carboxy, acyl, aryloxy, carbonamido, carbonamido substituted by C 1 -C 6 -alkyl, sulfonamido or trifluoromethyl or the fused ring may link two oxaborole rings;

X is a group —CR 7 R 8 wherein R 7 and R 8 are each independently hydrogen, C 1 -C 6 -alkyl, nitrile, nitro, aryl, arylalkyl or R 7 and R 8 together with the carbon atom to which they are attached form an alicyclic ring; and

R 6 is hydrogen, C 1 -C 18 -alkyl, C 1 -C 18 -alkyl substituted by C 1 -C 6 -alkoxy, C 1 -C 6 -alkylthio, hydroxy, amino, amino substituted by C 1 -C 18 -alkyl, carboxy, aryl, aryloxy, carbonamido, carbonamido substituted by C 1 -C 6 -alkyl, aryl or arylalkyl, arylalkyl, aryl, heteroaryl, cycloalkyl, C 1 -C 18 -alkyleneamino, C 1 -C 18 -alkyleneamino substituted by phenyl, C 1 -C 6 -alkoxy or C 1 -C 6 -alkylthio, carbonyl alkyleneamino or a radical of formula (V):

wherein A, D and X are as defined herein before.

13. The method of claim 12 , wherein the benzoxaborole compound is has the structure

or a salt thereof.

14. The method of claim 11 , wherein the benzoxaborole has the structure formula (A):

R A -L A -G-L B -R B   (A),

wherein

each of R A and R B is independently a of R A and R B is of formula (E):

wherein each R 6 is independently hydrogen, alkyl, alkene, alkyne, haloalkyl, haloalkene, haloalkyne, alkoxy, alkeneoxy, haloalkoxy, aryl, heteroaryl, arylalkyl, arylalkene, arylalkyne, heteroarylalkyl, heteroarylalkene, heteroarylalkyne, halogen, hydroxyl, nitrile, amine, ester, carboxylic acid, ketone, alcohol, sulfide, sulfoxide, sulfone, sulfoximine, sulfilimine, sulfonamide, sulfate, sulfonate, nitroalkyl, amide, oxime, imine, hydroxylamine, hydrazine, hydrazone, carbamate, thiocarbamate, urea, thiourea, carbonate, aryloxy, or heteroaryloxy;

n=1, 2, 3, or 4;

B is boron;

X 2 =(CR 6 2 ) m where m=1, 2, 3, or 4;

each of L A and L B is independently —O— or

each of R and R′ is independently hydrogen, unsubstituted or substituted C 1-18 -alkyl, arylalkyl, aryl, or heterocyclic moiety; and

G is a substituted or unsubstituted C 1-18 -alkylene, arylalkylene, arylene, or heterocyclic moiety; and acceptable salts thereof.

15. The method of claim 14 , wherein the benzoxaborole has the structure

or a salt thereof.

16. The method of claim 11 , wherein administering the benzoxaborole treatment to the one or more surfaces of the plurality of chambers during preformation, formation, or postformation of the plurality of chambers further comprises embedding the benzoxaborole compound into the food packaging material, impregnating the food packaging material with the benzoxaborole compound, or coating the food packaging material with the benzoxaborole compound.

17. The method of claim 11 , wherein the one or more surfaces of the plurality of chambers further comprise a liquid-absorbing material.

18. The method of claim 17 , wherein the liquid-absorbing material provides for quick-release or slow-release of the benzoxaborole treatment over a time period.

19. The method of claim 11 , wherein the plurality of chambers are a plurality of clamshells.

20. The method of claim 19 , wherein the plurality of clamshells comprise polyethylene terephthalate.

Continuity (15)

References Cited (292)