Dicarboxylic acid monomers and methods of making and using the same
View Patent ↗Disclosed herein are phenylindane dicarboxylic acid (PIDA) monomers, polymer compositions comprising the PIDA monomers, and methods of preparing PIDA monomers. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present disclosure.
1. A method for preparing a phenylindane dicarboxylic acid monomer, the method comprising:
a) reacting an alkylstyrene under acid catalyzed conditions effective to provide a first reaction product comprising at least one C20 to C32 phenylindane; and
b) reacting the first reaction product under a metal catalyzed oxidation conditions effective to provide a second reaction product comprising a racemic mixture including a phenylindane dicarboxylic acid monomer.
2. The method of claim 1 , wherein the phenylindane dicarboxylic acid monomer does not exhibit a half maximal inhibitory concentration (IC 50 ) less than 0.00025M for alpha or beta in vitro estradiol receptors.
3. The method of claim 1 , wherein the alkylstyrene has a structure represented by the formula:
wherein each of R1 and R2 is each independently selected from hydrogen and C1-C3 alkyl.
4. The method of claim 1 , wherein the alkylstyrene is alpha-methylstyrene.
5. The method of claim 1 , wherein the alkylstyrene is α-p-dimethylstyrene.
6. The method of claim 1 , wherein the phenylindane is trimethyl phenylindane.
7. The method of claim 1 , wherein the phenylindane is tetramethyl phenylindane.
8. The method of claim 1 , further comprising the step of reacting limonene to provide the the alkylstyrene.
9. The method of claim 1 , further comprising the step of reacting an alkylbenzene to provide the alkylstyrene.
10. The method of claim 9 , wherein the alkylbenzene is p-cymene or p-bromo toluene, or a combination thereof.
11. The method of claim 1 , further comprising the step of reacting an acetophenone to provide the alkylstyrene.
12. The method of claim 11 , wherein the acetophenone is reacted in the presence of a Grignard reagent.
13. The method of claim 12 , wherein the Grignard reagant is methyl magnesium bromide.
14. The method of claim 1 , wherein the phenylindane dicarboxylic acid monomer has a structure represented by the formula:
wherein R 1 , R 2 , R 3 , and R 5 are each independently a C1-C3 alkyl group, a is 0-1, b is 0-4, c is 0-4 and d is 0-3, and each R 4 is independently a hydrogen or a C1-C3 alkyl group.
15. The method of claim 1 , wherein the phenylindane dicarboxylic acid monomer has a structure represented by the formula
wherein each R 4 is independently hydrogen or a C1-C3 alkyl group.
16. The method of claim 1 , wherein the phenylindane dicarboxylic acid monomer has a structure represented by the formula:
wherein wherein each R 4 is independently hydrogen or a C1-C3 alkyl group.
17. The method of claim 1 , wherein the phenylindane dicarboxylic acid monomer is 3-(4-carboxyphenyl)-1,1,3-trimethyl-5-indan carboxylic acid, 3-(4-carboxyphenyl)-1,3-diethyl-1-methyl-5-indan carboxylic acid, or 3-(4-carboxyphenyl)-1,3-dipropyl-1-methyl-5-indan carboxylic acid.
18. The method of claim 1 , wherein the phenylindane dicarboxylic acid monomer is this monomer is as 1,3,3-trimethyl-1-phenylindan-4′,5-dicarboxylic acid.
19. The method of claim 1 , wherein the acid catalyzed conditions comprise reacting the alkylstyrene in the presence of hydrochloric acid, sulfuric acid or nitric acid, or a combination thereof.
20. The method of claim 1 , wherein the acid catalyzed conditions or the metal catalyzed oxidation conditions comprise adjusting the temperature to at least about 40° C.
21. The method of claim 1 , wherein the the acid catalyzed conditions or the metal catalyzed oxidation conditions comprise adjusting the temperature in the range of from about 40° C. to about 250° C.
22. The method of claim 1 , wherein the acid catalyzed conditions or the metal catalyzed oxidation conditions comprise maintaining the reaction for at least about 1 hours.
23. The method of claim 1 , further comprising reacting the first reaction product to provide a reaction product comprising at least one acetylated phenylindane.
24. The method of claim 23 , wherein reacting is acetylating with an acetylating agent in the presence of a Friedel-Crafts catalyst to provide reaction product comprising an isomer mixture.
25. The method of claim 24 , wherein the acetylating agent is acetyl chloride, chloroacetyl chloride or acetic anhydride, or a combination thereof.
26. The method of claim 24 , wherein the Friedel-Crafts catalyst comprises aluminum chloride, zinc chloride, or iron(III) chloride, or a combination thereof.
27. The method of claim 23 , wherein the acetylated phenylindane is diacetyl phenylindane.
28. The method of claim 1 , wherein the metal catalyzed oxidation conditions comprise reacting the first reaction product in the presence of an oxidizing agent.
29. The method of claim 28 , wherein the oxidizing agent comprises: chromic anhydride(CrO3); oxygen containing heavy metals comprising one or more of manganese, cobalt, lead, iron, nickel, copper, and vanadium; or oxides of one or more of manganese, cobalt, lead, iron, nickel, copper, and vanadium; or a combination thereof.
30. The method of claim 1 , wherein the metal catalyzed oxidation conditions comprise reacting the first reaction product in the presence of KMnO 4 and pyridine.
31. The method of claim 1 , wherein the first reaction product comprises at least about 50 wt % of phenylindane.
32. The method of claim 1 , wherein the second reaction product comprises at least about 50 wt % of phenylindane dicarboxylic acid.
33. The method of claim 1 , wherein the method provides a final yield of phenylindane dicarboxylic acid of at least about 60%.
34. The method of claim 1 , further comprising purifying the second reaction product under conditions effective to provide a reaction product comprising at least 90 wt % phenylindane dicarboxylic acid.
35. The method of claim 34 , further comprising the step of filtering, separating, washing, or drying, or a combination thereof.
36. The method of claim 34 , wherein purifying comprises dissolving the reaction product using aqueous NaHCO3 solution or glacial acetic acid, or a combination thereof.
37. The method of claim 34 , wherein purifying comprises adjusting the pH of reaction product to a pH effective to provide a solid reaction product.
38. The method of claim 1 , further comprising separating of the second reaction product.
39. The method of claim 38 , wherein the separating comprises chiral separation of the racemic mixture using high pressure liquid chromatography.
40. A method for preparing a phenylindane dicarboxylic acid monomer, the method comprising:
a) reacting alphamethylstyrene under first reaction conditions effective to provide a first reaction product comprising at least one phenylindane;
b) acetylating the first reaction product in the presence of a Friedel-Crafts catalyst to provide second reaction product comprising an acetylated phenylindane; and
c) reacting the second reaction product under second reaction conditions effective to provide a second reaction product comprising at least one phenylindane dicarboxylic acid monomer.
41. A method for preparing a phenylindane dicarboxylic acid monomer, the method comprising:
a) reacting a alkylbenzene to provide a first reaction product comprising at least one alkylstyrene;
b) reacting the first reaction product under first reaction conditions effective to provide a second reaction product comprising at least one phenylindane; and
c) reacting the second reaction product under second reaction conditions effective to provide a second reaction product comprising at least one phenylindane dicarboxylic acid monomer.