US20070197761A1 - 2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidine compounds and methods for making them - Google Patents
2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidine compounds and methods for making them Download PDFInfo
- Publication number
- US20070197761A1 US20070197761A1 US11/740,581 US74058107A US2007197761A1 US 20070197761 A1 US20070197761 A1 US 20070197761A1 US 74058107 A US74058107 A US 74058107A US 2007197761 A1 US2007197761 A1 US 2007197761A1
- Authority
- US
- United States
- Prior art keywords
- radical
- phthalimidine
- group
- aromatic
- aryl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 125000005843 halogen group Chemical group 0.000 claims abstract description 14
- BLNWTAHYTCHDJH-UHFFFAOYSA-O hydroxy(oxo)azanium Chemical compound O[NH+]=O BLNWTAHYTCHDJH-UHFFFAOYSA-O 0.000 claims abstract description 8
- -1 aromatic primary amine Chemical class 0.000 claims description 153
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 claims description 29
- KJFMBFZCATUALV-UHFFFAOYSA-N Phenolphthalein Natural products C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 26
- 230000002378 acidificating effect Effects 0.000 claims description 22
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 6
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical group Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000001448 anilines Chemical class 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- 239000003960 organic solvent Substances 0.000 description 15
- 150000003254 radicals Chemical class 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 125000000524 functional group Chemical group 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- VUPNPTIARVHWSM-UHFFFAOYSA-N CC.CN1C(=O)C2=CC=CC=C2C1(CN)CO Chemical compound CC.CN1C(=O)C2=CC=CC=C2C1(CN)CO VUPNPTIARVHWSM-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 230000001588 bifunctional effect Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 150000003142 primary aromatic amines Chemical class 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 4
- 125000002843 carboxylic acid group Chemical group 0.000 description 4
- 125000001033 ether group Chemical group 0.000 description 4
- 125000001188 haloalkyl group Chemical group 0.000 description 4
- 150000002440 hydroxy compounds Chemical class 0.000 description 4
- 239000008204 material by function Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 150000005840 aryl radicals Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 125000005027 hydroxyaryl group Chemical group 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 125000000468 ketone group Chemical group 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Chemical group 0.000 description 3
- 239000001301 oxygen Chemical group 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Chemical group 0.000 description 3
- 239000010703 silicon Chemical group 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Chemical group 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000008043 acidic salts Chemical class 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000005001 aminoaryl group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000003857 carboxamides Chemical class 0.000 description 2
- 229940023913 cation exchange resins Drugs 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 2
- 125000004092 methylthiomethyl group Chemical group [H]C([H])([H])SC([H])([H])* 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- VTRRCXRVEQTTOE-UHFFFAOYSA-N 1-methylsulfinylethane Chemical compound CCS(C)=O VTRRCXRVEQTTOE-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 description 1
- UERPUZBSSSAZJE-UHFFFAOYSA-N 3-chlorophthalic anhydride Chemical compound ClC1=CC=CC2=C1C(=O)OC2=O UERPUZBSSSAZJE-UHFFFAOYSA-N 0.000 description 1
- BJDDKZDZTHIIJB-UHFFFAOYSA-N 4,5,6,7-tetrafluoro-2-benzofuran-1,3-dione Chemical compound FC1=C(F)C(F)=C2C(=O)OC(=O)C2=C1F BJDDKZDZTHIIJB-UHFFFAOYSA-N 0.000 description 1
- WSKSHHDHKIAMKX-UHFFFAOYSA-N 4,5,6-trichloro-2-benzofuran-1,3-dione Chemical compound ClC1=C(Cl)C(Cl)=CC2=C1C(=O)OC2=O WSKSHHDHKIAMKX-UHFFFAOYSA-N 0.000 description 1
- MCXWABSMXKULCY-UHFFFAOYSA-N 4,5,6-trifluoro-2-benzofuran-1,3-dione Chemical compound FC1=C(F)C(F)=CC2=C1C(=O)OC2=O MCXWABSMXKULCY-UHFFFAOYSA-N 0.000 description 1
- GAIPRQZXSYSCRD-UHFFFAOYSA-N 4,5-dichloro-2-benzofuran-1,3-dione Chemical compound ClC1=CC=C2C(=O)OC(=O)C2=C1Cl GAIPRQZXSYSCRD-UHFFFAOYSA-N 0.000 description 1
- HOLXVIZWJDORKM-UHFFFAOYSA-N 4,5-difluoro-2-benzofuran-1,3-dione Chemical compound FC1=CC=C2C(=O)OC(=O)C2=C1F HOLXVIZWJDORKM-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
- BTTRMCQEPDPCPA-UHFFFAOYSA-N 4-chlorophthalic anhydride Chemical compound ClC1=CC=C2C(=O)OC(=O)C2=C1 BTTRMCQEPDPCPA-UHFFFAOYSA-N 0.000 description 1
- WWJAZKZLSDRAIV-UHFFFAOYSA-N 4-fluoro-2-benzofuran-1,3-dione Chemical compound FC1=CC=CC2=C1C(=O)OC2=O WWJAZKZLSDRAIV-UHFFFAOYSA-N 0.000 description 1
- ROFZMKDROVBLNY-UHFFFAOYSA-N 4-nitro-2-benzofuran-1,3-dione Chemical class [O-][N+](=O)C1=CC=CC2=C1C(=O)OC2=O ROFZMKDROVBLNY-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- HLWYYNFBQUXPLQ-UHFFFAOYSA-N C1CCC(C#N)(C#N)CC1OC(C)(C)OC1CCCCC1 Chemical compound C1CCC(C#N)(C#N)CC1OC(C)(C)OC1CCCCC1 HLWYYNFBQUXPLQ-UHFFFAOYSA-N 0.000 description 1
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- WAGOIGMEGJFOJY-UHFFFAOYSA-N CC.CCC1(CO)C2=CC=CC=C2C(=O)N1C Chemical compound CC.CCC1(CO)C2=CC=CC=C2C(=O)N1C WAGOIGMEGJFOJY-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/46—Iso-indoles; Hydrogenated iso-indoles with an oxygen atom in position 1
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Definitions
- This disclosure relates generally to 2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidine compounds and methods for preparing these compounds. Further, the disclosure relates to polymers including structural units derived from these compounds.
- Polymers are important materials in modern commerce. A variety of polymers having commercial significance, such as polycarbonates, polyamides, polyurethanes, polyesters, and the like have been produced. Many of these polymers have been prepared from monomers that have two chemically identical reactive functional groups (“monofunctional monomers). Polymers prepared from bifunctional monomers, that is monomers having two chemically different reactive functional groups, are also known. Examples of such bifunctional monomers include aminophenols, aminocarboxylic acids, hydroxycarboxylic acids, compounds having an anhydride group and a hydroxy group, and the like. Bifunctional monomers can be useful for preparing polymers that have a combination of some of the desirable properties of the polymers prepared from monofunctional monomers that have only one or the other type of reactive functional groups of the bifunctional monomer.
- bifunctional monomers that can be used for preparing polymers that potentially have a desirable combination of polymer physical properties, such as for example, high temperature stability, resistance to reaction with certain chemicals; high temperature stability and liquid crystalline behavior.
- the present disclosure generally provides for novel 2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidine compounds and methods for preparing them. These novel compounds are useful for preparing monomers and polymers comprising structural units derived from the 2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidine compounds and functional monomers derived therefrom.
- One embodiment is directed to a 2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidine compound having a formula: wherein R 1 is independently selected from a group consisting of a hydrocarbyl radical, a nitro radical, and a halogen atom; “a” is an integer from 0-4; and Ar 1 and Ar 2 are each independently an aromatic radical.
- R 1 is independently selected from a group consisting of a hydrocarbyl radical, a nitro radical, and a halogen atom
- a is an integer from 0-4
- Ar 1 and Ar 2 are each independently an aromatic radical.
- a method for preparing a 2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidine compound comprises reacting a precursor compound with a primary aromatic amine in the presence of an acidic catalyst, wherein the primary aromatic amine has a formula Ar 1 —NH 2 , wherein Ar 1 is an aromatic radical.
- the precursor compound is selected from the group consisting of a phenolphthalein compound, a 2-aryl-3,3-bis(hydroxyaryl)phthalimidine compound, and mixtures thereof.
- a method for preparing a 2-phenyl-3-(aminophenyl)-3-(hydroxyphenyl)phthalimidine compound comprises reacting a precursor compound is selected from the group consisting of phenolphthalein, 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine, and mixtures thereof.
- a polymer comprising structural units derived from at least one 2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidine having a formula, wherein R 1 is independently selected from a group consisting of a hydrocarbyl radical, a nitro radical, and a halogen atom; “a” is an integer from 0-4; and Ar 1 and Ar 2 are each independently an aromatic radical; is provided.
- the FIGURE shows the proton nuclear magnetic resonance spectrum of 2-phenyl-3-(4-aminophenyl)-3-(4-hydroxyphenyl)phthalimidine.
- aliphatic radical refers to an organic radical having s valence of at least one comprising a linear or branched array of atoms which is not cyclic.
- the aliphatic radicals comprise at least one carbon atom.
- the array of atoms forming the aliphatic radical may further include heteroatoms such as nitrogen, sulfur, silicon, selenium and oxygen or may be composed exclusively of carbon and hydrogen.
- the “linear or branched array of atoms which is not cyclic” is intended to include a wide range of functional groups such as alkyl groups, alkenyl groups, alkynyl groups, halo alkyl groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (for example carboxylic acid derivatives such as esters and amides), amine groups, nitro groups and the like.
- a suitable aliphatic radical is the 4-methylpent-1-yl radical, which is a C 6 aliphatic radical comprising a methyl group.
- the4-nitrobut-1-yl group is a C 4 aliphatic radical comprising a nitro functional group.
- suitable aliphatic radicals include a haloalkyl group that comprises one or more halogen atoms which may be the same or different. Suitable halogen atoms include, for example, fluorine, chlorine, bromine, and iodine.
- Aliphatic radicals comprising one or more halogen atoms include the alkyl halides trifluoromethyl, bromodifluoromethyl, chlorodifluoromethyl, hexafluoropropylidene, chloromethyl; difluorovinylidene; trichloromethyl, bromodichloromethyl, bromoethyl, 2-bromotrimethylene (e.g., —CH 2 CHBrCH 2 —), and the like.
- Suitable aliphatic radicals include allyl, aminocarbonyl (—CONH 2 ), carbonyl, dicyanoisopropylidene (—CH 2 C(CN) 2 CH 2 —), methyl (—CH 3 ), methylene (—CH 2 —).
- a C 1 -C 10 aliphatic radical contains at least one but no more than 10 carbon atoms.
- aromatic radical is also sometimes referred herein to as an “aryl radical”.
- the aromatic radical or the aryl radical refers to an array of atoms having a valence of at least one comprising at least one aromatic group.
- the aromatic radical may include heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen, or may be composed exclusively of carbon and hydrogen.
- aromatic radical includes but is not limited to phenyl, pyridyl, furanyl, thienyl, naphthyl, phenylene, and biphenyl radicals.
- the aromatic radical may also include non-aromatic components.
- a benzyl group is an aromatic radical that comprises a phenyl ring (the aromatic group) and a methylene group (the non-aromatic component).
- a tetrahydronaphthyl radical is an aromatic radical comprising an aromatic group (C 6 H 3 ) fused to a non-aromatic component —(CH 2 ) 4 —.
- the “aromatic radical” can encompass a wide range of functional groups such as alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, haloaromatic groups, conjugated dienyl groups, alcohol groups, ether groups, aldehydes groups, ketone groups, carboxylic acid groups, acyl groups (for example carboxylic acid derivatives such as esters and amides), amine groups, nitro groups, and the like.
- the 4-methylphenyl radical is a C 7 aromatic radical comprising a methyl alkyl group.
- the 2-nitrophenyl group is a C 6 aromatic radical comprising a nitro functional group.
- Suitable aromatic radicals may include halogenated aromatic radicals such as trifluoromethylphenyl, hexafluoroisopropylidenebis(4-phen-1-yloxy) (—OPhC(CF 3 ) 2 PhO—), chloromethylphenyl; 3-trifluorovinyl-2-thienyl, 3-trichloromethylphen-1yl (3-CCl 3 Ph—), 4(3-bromoprop-1-yl)phen-1-yl (BrCH 2 CH 2 CH 2 Ph—), and the like.
- aromatic radicals include 4-allyloxyphen-1oxy, 4-aminophen-1yl (H 2 NPh—), 3-aminocarbonylphen-1-yl (NH 2 COPh—), 4-benzoylphen-1yl, dicyanoisopropylidenebis(4-phen-1yloxy) (—OPhC(CN) 2 PhO—), 3-methylphen-1yl, methylenebis(phen-4-yloxy) (—OPhCH 2 PhO—), 2-ethylphen-1-yl, phenylethenyl, 3-formyl-2-thienyl, 2-hexyl-5-furanyl; hexamethylene-1,6-bis(phen-4-yloxy) (—OPh(CH 2 ) 6 PhO—); 4-hydroxymethylphen-1yl (4-HOCH 2 Ph—), 4-mercaptomethylphen-1-yl (4-HSCH 2 Ph—), 4-methylthiophen-1yl (4-CH 3 SPh—), 3-methoxyphen-1yl, 2-
- a C 3 -C 10 aromatic radical includes aromatic radicals containing at least three but no more than 10 carbon atoms.
- the aromatic radical 1-imidazolyl (C 3 H 2 N 2 —) represents a C 3 aromatic radical.
- the benzyl radical (C 7 H 8 —) represents a C 7 aromatic radical.
- cycloaliphatic radical refers to a radical having a valence of at least one and comprising an array of atoms that is cyclic but not aromatic.
- a “cycloaliphatic radical” does not contain an aromatic group and may further include one or more noncyclic components.
- a cyclohexylmethyl group (C 6 H 11 CH 2 —) is a cycloaliphatic radical that comprises a cyclohexyl ring (the array of atoms is cyclic but not aromatic) and a methylene group (the noncyclic component).
- the cycloalophatic radical may further include heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen, or may be composed exclusively of carbon and hydrogen.
- the cycloaliphatic radical can encompass a wide range of functional groups such as alkyl groups, alkenyl groups, alkynyl groups, halo alkyl groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (for example carboxylic acid derivatives such as esters and amides), amine groups, nitro groups and the like.
- the 4-methylcyclopent-1yl radical is a C 6 cycloaliphatic radical comprising a methyl group, the methyl group being a functional group which is an alkyl group.
- the 2-nitrocyclobut-1-yl radical is a C 4 cycloaliphatic radical comprising a nitro group, the nitro group being a functional group.
- a suitable cyclosliphatic radical may also comprise one or more halogen atoms which may be the same or different. Suitable halogen atoms, include, for example, fluorine, chlorine, bromine, and iodine.
- Suitable cycloaliphatic radicals comprising one or more halogen atoms include 2-trifluoromethylcyclohex-1-yl, 4-bromodifluoromethylcyclooct-1-yl, 2-chlorodifluoromethylcyclohex-1-yl, hexafluoroisopropylidene2,2-bis (cyclohex-4-yl) (—C 6 H 10 C(CF 3 ) 2 C 6 H 10 —), 2-chloromethylcyclohex-1-yl; 3-difluoromethylenecylcohex-1-yl; 4-trichloromethylcyclohex-1-yloxy, 4-bromodichloromethylcyclohex-1-ylthio, 2-bromoethylcyclopent-1-yl, 2-bromopropylcyclohex-1-yloxy (e.g.
- cycloaliphatic radicals include 4-allyloxycyclohex-1-yl, 4-aminocyclohex-1-yl (H 2 NC 6 H 10 —), 4-aminocarbonylcyclopent-1-yl (NH 2 COC 5 H 8 —), 4-acetyloxycyclohex-1-yl, 2,2-dicyanoisopropylidenebis(cyclohex-4-yloxy) (—OC 6 H 10 C(CN) 2 C 6 H 10 O—), 3-methylcyclohex-1-yl, methylenebis(cyclohex-4-yloxy) (—OC 6 H 10 CH 2 C 6 H 10 O—), 1-ethylcyclobut-1-yl, cyclopropylethenyl, 3-formyl-2-terahydrofuranyl, 2-hexyl-5-tetrahydrofuranyl; hexamethylene-1,6-bis(cyclo
- the term“2-aryl-3,3-bis(hydroxyaryl)phthalimidine” (AHP) includes the ortho, para and para, para isomers, which generally refers to the placement of the OH functionality within the hydroxyaryl group.
- the term “2-phenyl-3,3-bis(hydroxyphenyl)phthalimidine” (PPPBP) includes the ortho, para and the para, para isomers.
- the term “2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidine” (AAHP) includes the para, para isomer, which refers to the placement of the OH and the NH 2 functional groups, unless otherwise indicated.
- the term “2-phenyl-3-(4-aminophenyl)-3-(4-hydroxyphenyl)phthalimidine” is interchangeable with the abbreviation “AP”.
- the subscript “a” in “(R 1 ) a ” when the subscript “a” in “(R 1 ) a ” is zero, it denotes a structure where all the R 1 substituents are hydrogen atoms. In the case where R 1 is other than a hydrogen atom, the subscript “a” can take values from zero to four, with a value of zero for “a” denoting a structure having only hydrogen atoms as the R 1 substituents.
- AAHP compounds have general formula (I), wherein R 1 is independently selected from a group consisting of a hydrocarbyl radical, a nitro radical, and a halogen atom; “a” is an integer from 0-4; Ar 1 and Ar 2 are each independently an aromatic radical.
- AAHP compounds having formula (I) include those wherein AR 1 and Ar 2 are each independently a monocyclic aromatic radical.
- Ar 1 and Ar 2 are aryl radicals.
- Ar 1 and Ar 2 are each independently a monocyclic aromatic radical, and “a” is zero.
- the 2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidine has a formula (II).
- an exemplary 2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidine has the structure (II), wherein R 1 is a hydrogen atom, and “a” is 4; also called 2-phenyl-3-(4-aminophenyl) -3-(4-hydroxyphenyl)phthalimidine (abbreviated herein as “AP”).
- the 2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidines are prepared by reacting a precursor compound with a primary aromatic amine having a general formula (III), Ar 2 —NH 2 (III) wherein Ar 2 is an aromatic radical.
- Suitable primary aromatic amines include aniline and anilines substituted by one or more C 1 -C 12 aliphatic radicals, one or more C 3 -C 12 cycloaliphatic radicals, or one or more aromatic radicals.
- the precursor compound can comprise a phenolphthalein compound having a formula (IV), wherein Ar 1 , R 1 , and “a” are as described previously for formula (I).
- Phenolphthalein compounds can be prepared by methods, such as for example, by the ring-alkylation reaction of a phthalic anhydride compound of formula (V), wherein R 1 and “a” are as described previously with an aromatic hydroxy compound of formula (VI), Ar 1 —OH (VI) wherein Ar 1 is an aromatic radical.
- a catalyst is generally employed for forming the phenolphthalein compounds.
- the catalyst may be a Lewis acid, such as for example, zinc chloride. aluminum chloride, ferric chloride, boron trifluoride, and the like.
- phthalic anhydrides of formula (V) include phthalic anhydride, halogenated phthalic anhydrides, such as 3-chlorophthalic anhydride, 4-chlorophthalic anhydride, 3,4-dichlorophthalic anhydride, trichlorophthalic anhydride, tetrachlorophthalic anhydride, fluorophthalic anhydride, difluorophthalic anhydride, trifluorophthalic anhydride, tetrafluorophthalic anhydride, and the like; alkoxy-substituted phthalic anhydrides, nitrophthalic anhydrides, and the like.
- Phthalic anhydride is an exemplary phthalic anhydride compound since it is readily available commercially.
- the aromatic hydroxy compound of formula (VI) is exemplified by the parent compound, phenol, as well as any substituted phenol that can undergo the alkylation reaction with the phthalic anhydride compound.
- Some examples of substituted aromatic hydroxy compounds include the cresols (ortho, meta, para isomers), and xylenols (various isomers).
- An exemplary phenolphthalein compound that can be used for preparing the AAHP compounds disclosed herein include the parent phenolphthalein having a formula (VII).
- Suitable precursor compounds for preparing the AAHP compounds can also be 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (VIII), wherein R 1 , “a”, Ar 1 and Ar 2 are as previously described.
- the 2-aryl-3,3-bis (hydroxyaryl)phthalimidine is of formula (IX), wherein R 1 , “a”, and Ar 2 are as previously described.
- the 2-aryl-3,3-bis (hydroxyaryl)phthalimidine precursor includes varying amounts of the corresponding ortho, para-AHP, such as for example, the compound of general formula (X), wherein R 1 , “a”, and Ar 2 are as previously described for formula (IX).
- para, para-PPBP 2-phenyl-3,3-bis(4-hydroxyphenyl) phthalimidine
- the para, para-PPBP may also comprise the corresponding ortho, para-isomer as the precursor compound.
- the reaction of the aromatic primary amine with an AHP compound can be extended to other dihydroxy aromatic compounds that can undergo a similar reaction.
- This reaction can be regarded as a transarylation reaction in which a hydroxyphenyl group in the dihydroxy aromatic compound is exchanged for an aminoaryl group in the presence of an acidic catalyst.
- dihydroxy aromatic compounds that can undergo such a transarylation reaction include compounds of formulas (XI)-(XIII).
- the products produced from the transarylation reaction include structures in which one or both hydroxyphenyl groups have been exchanged for the aminoaryl group, that is —NHAr 2 .
- Suitable acidic catalyst used for forming the AAHP compounds comprise a salt of an organic amine and an acid.
- the acid is selected from the group consisting of an inorganic acid, an organic acid, or combinations of the foregoing acids.
- inorganic acids include hydrochloric acid, sulfuric acid, phosphoric acid, and the like.
- organic acids include sulfonic acids, such as for example, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, and the like; and carboxylic acids, such as formic acid, benzoic acid, and the like.
- Polymeric acidic catalysts, such as those comprising sulfonic acid groups can also be used.
- polymeric acidic catalysts include cation exchange resins comprising sulfonic acid groups. Solid acidic catalysts, such as acidic silica, acidic alumina, and montmorillonite can also be used.
- the organic amine needed to form the acidic catalyst can be a primary amine, a secondary amine, a tertiary amine, or any combination of the foregoing amines.
- Organic amines having one or more basic nitrogen atoms as part of a ring, such as for example, a pyridine compound can also be used.
- Further examples of suitable amines include primary, secondary, and tertiary amines having any combination of aliphatic and aromatic groups bonded to the amine nitrogen.
- Suitable examples of amine salt catalysts include primary, secondary, and tertiary amine hydrochlorides. In one embodiment, hydrochloride salt of the amines of formula (III) above, wherein R 1 is an aromatic radical, can be used.
- acidic salts of primary aromatic amines that also serve as the starting material for preparing the AAHPs of formula (II) above are preferred.
- Aniline is an exemplary organic amine used for preparing an acidic catalyst to form the AAHP compounds.
- the acidic catalyst is introduced as a pre-formed salt into the reactor.
- the catalyst is generated in situ within the reactor by first charging an amine of formula (III) into the reactor, and then adding an appropriate acid to the amine.
- an acid such as an inorganic acid
- Hydrochloric acid is an exemplary inorganic acid.
- Hydrogen chloride gas can also be used.
- about 0.1 part to about 0.3 parts by weight of hydrogen chloride gas is introduced into a reactor charged with the organic amine, such as an aryl amine.
- the thus formed aryl amine hydrochloride can be suitably used as a catalyst in the present disclosure.
- a relatively higher level of the acidic catalyst favors the formation of the AAHP compounds.
- a solvent can optionally be employed to form the acidic catalyst, for example, the aryl amine hydrochloride. The solvent can then be removed (if necessary), and the hydrocarbyl amine of formula (III) can be added, followed by addition of the precursor compound of formula (IV) and/or (VIII).
- the reaction to form the desired products (I) proceeds with an intermediate formation of product having formula (VIII).
- the program of the reaction can be followed by liquid chromatography, wherein the disappearance of the phenolphthalein compound and formation of the intermediate (VIII) and final product (I) can be monitored.
- the reaction temperature and reaction time can be adjusted to facilitate formation of product (I).
- the reaction of the phenolphthalein compound with the hydrocarbyl amine in the presence of the acidic catalyst proceeds by a condensation reaction to form the intermediate products having formula (VIII) and water by-product.
- the water can be removed by simply distilling it out of the reactor. Alternatively, the water can be removed as an azeotrope by using a suitable organic solvent.
- the intermediate product reacts with more hydrocarbyl amine in a second step in the presence of the acidic catalyst to form the desired product having formula (I).
- an aromatic hydroxy compound is produced as a by-product.
- the aromatic hydroxy compound can be removed during the reaction to facilitate the forward reaction.
- the reaction mixture can be refluxed without removing the water or the aromatic hydroxy compound by-products. An excess of the aryl amine over the phenolphthalein may be used to keep the reaction proceeding in the forward direction.
- the temperature can be chosen so as to facilitate formation of the product. Generally, for a given pressure, a relatively higher temperature favors formation of the AAHP compound.
- the reaction can be conducted at a sub-ambient, ambient, or supra-ambient pressure. In an embodiment, a temperature of at least 100° C. can be used to form the AAHP compounds.
- the desired AAHP compounds can then be isolated from the reaction mixture by techniques known in the art for isolating organic amine compounds and/or aromatic hydroxy compounds.
- AHP compounds The para, para-2-aryl-3,3-bis(hydroxyaryl)phthalimidines (AHP compounds), shown in formula (VIII) are produced as intermediates in the preparation of the AAHP compounds, and are themselves valuable as monomers for preparing polymers, such as polycarbonates.
- the reaction conditions to produce a AAHP compound can be modified or optimized to produce both a AHP compound and a AAHP compound as useful products.
- the reaction mixture comprising the AAHP product also comprises the corresponding AHP by-product. Both products can exist as a mixture of para, para and ortho, para isomers. Generally, the para, para isomers of the AAHP and AHP compounds predominate over the corresponding ortho, para isomers.
- the reaction mixture is first quenched with an aqueous mineral acid, such as aqueous hydrochloric acid.
- a solid mixture comprising the AAHP product and the AHP by-product results, which is filtered and dissolved in a mixture of water and an organic solvent, wherein the organic solvent can at least partly dissolve the solid mixture.
- the resulting solution is then contacted with an acidic material, which can bind the AAHP compound through the Nh 2 group.
- Cation exchange resins having sulfonic acid groups can be used to separate the AAHP compound from the AHP compound.
- Any polar solvent that can at least partly dissolve the AAHP can be used. Further, these solvents may be at least partly miscible with water, or fully miscible with water.
- Suitable organic solvents comprise at least one functional group selected from the group consisting of a hydroxy group, a ketone carbonyl group, a carboxylic acid group, an ester group, a sulfoxide group, a nitrile group, an ether group, and a nitro group.
- suitable organic solvents are those that comprise at least member selected from the group consisting of an organic hydroxy compound, an organic ketone, an organic amide, an organic sulfoxide, an organic ether, and an organic nitrile.
- Each of these categories of solvents may comprise more than one functional group, which may be the same or different from the other functional group(s).
- ethanol, ethylene glycol, and 2-ethoxyethanol may be used, either individually, or in any relative proportion as suitable organic solvents.
- aliphatic alcohols having at least one hydroxy group can be used as the organic solvent.
- Suitable organic hydroxy compounds include aliphatic, cycloaliphatic and aromatic hydroxy compounds having at least one hydroxy group.
- the aliphatic hydroxy compounds include linear and branched aliphatic mono-hydroxy compounds, non-limiting examples of which are methanol. ethanol, isopropanol, n-butanol, sec-butanol, iso-butanol, tert-butanol, and the like. Mixtures of these compounds can also be used.
- Aliphatic dihydroxy compounds such as the glycols, exemplified by ethylene glycol, propylene glycol, and the like may also by used.
- Non-limiting examples of aromatic hydroxy compounds include phenol, ortho-cresol, benzyl alcohol, and the like. Some examples of cycloaliphatic hydroxy compounds include cyclopentanol, cyclohexanol, cyclohexanediol, and the like.
- suitable organic hydroxy compounds include methanol, isopropanol, or any combination of methanol and isopropanol. Methanol is an exemplary organic solvent for that can be used isolating the AAHP compound, such a 2-phenyl-3(4-aminophenyl) -3-(4-hydroxyphenyl)phthalimidine (AP).
- Organic ketones suitable for the use as the organic solvent include acetone, 2-butanone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, and the like.
- the organic solvent comprises acetone.
- Suitable organic amides include formamide, acetamide, and the like.
- Organic sulfoxides that may be used as the organic solvent include dimethylsulfoxide, methyl ethyl sulfoxide, diethyl sulfoxide, and the like.
- Non-limiting examples of organic nitriles include the aliphatic nitriles, such as acetonitrile, propionitrile, butyronitrile, and the like.
- Examples of organic nitro compounds that may be used include nitromethane, nitroethane, and the like.
- the organic solvent is methanol, ethanol, isopropanol, sec-butanol, phenol, acetone, butanone, formamide, or dimethylsulfoxide.
- the cation exchange resin having the bound AAHP compound is then treated with a mixture comprising an aqueous acid and an organic solvent that can at least partly dissolve the AAHP compound.
- aqueous include aqueous mineral acids, such as hydrochloric acid, phosphoric acid, and the like.
- the organic solvent include those disclosed above. Aliphatic alcohols, such as methanol, ethanol, isopropanol, and the like are useful organic solvents.
- the acidic mixture liberates the free AAHP compound.
- the para, para isomer of AAHP can then be isolated in a pure form using a technique such as crystallization.
- the AAHP compounds disclosed herein are valuable for making a variety of functional materials by selectively reacting either the Nh 2 group, or the OH group with suitable reactants.
- Selective reaction of the NH 2 group gives rise to functional materials having a free OH group; and selective reaction of the OH group gives rise to functional materials having a free NH 2 group.
- reaction of AP shown below in formula (XIV): with an anhydride, such as phthalic anhydride provides the functional material of formula (XV):
- the functional materials in turn can be used for preparing many different types of polymers.
- the AAHP compounds are also valuable for making a variety of polymers.
- the polymers can be homopolymers, random copolymers, and block copolymers.
- the presence of the NH 2 and the aromatic hydroxy (OH) functional groups makes them suitable as monomers or comonomers for producing a variety of polymers comprising one or more types of structural units derived from these functional groups. Examples of such structural units include formulas (XVI)-(XX),
- Some non-limiting examples of polymers that can be produced using the AAHP compounds disclosed herein include, but not limited to, polyesteramides, polyesterurethanes, polycarbonateamides, and the like.
- This example describes the procedure used for preparing the 2-phenyl-3-(4-hydroxyphenyl)-3-(4-aminophenyl)phthalimidine monomer from phenolphthalein and aniline as starting materials, and aniline hydrochloride as the catalyst.
- the filter cake was washed thoroughly with water(5 ⁇ 100 milliliters) until the water wash was neutral (pH of about 7). Excess water from the filter cake was removed under suction, and the solid was dried at 100-120° C. to constant weight.
- the crude product thus obtained was analyzed by high pressure liquid chromatography (HPLC) and found to contain about 16 weight percent of AP.
- a portion of this material was subjected to preparatory HPLC using a mobile phase consisting of a 86:9:5 volume ratio of solvents (A), (B), and (C); wherein solvent (A) is a 0.02 weight percent solution of phosphoric acid in water, solvent (B) is methanol, and solvent (C) is acetonitrile.
- a column oven temperature of about 40° C., a flow rate of 1 milliliter per minute, and a detector wavelength of 270 nanometers was used for the preparative HPLC.
- the eluate containing the desired AP was collected and evaporated to furnish a pure sample of AP.
- the chemical identity of AP was established by proton nuclear magnetic resonance (NMR) spectroscopy.
- the proton NMR spectrum shows the peaks with assignments to the various types of protons present in AP.
- the assignments are shown as numbers (1 through 10) in the Figures.
- Two-dimensional carbon-proton correlation spectroscopy was used to establish that the NH 2 and the phenolic OH groups were located at the para position of each phenyl ring in AP, thus confirming that the isolated material was the para,para-AP isomer.
- This example describes the procedure used for preparing the monomer 2-phenyl-3-(4-hydroxyphenyl)-3-(4-aminophenyl)phthalimidine (AP) from 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine and aniline as starting materials, and aniline hydrochloride as the catalyst.
- the crude reaction product was obtained as described above in Example 1 by using aniline (83 grams, 0.88 mole), para, para-PPPBP (50 grams, 0.127 mole), and aniline hydrochloride (33 grams; 0.25 mole).
- the crude product contained about 16 weight percent of AP, as determined by HPLC.
- the isolation of pure para, para-AP was achieved by using the same procedure as described for Example 1.
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Abstract
wherein R1 is independently selected from a group consisting of a hydrocarbyl radical, a nitro radical, and a halogen atom; “a” is an integer from 0-4; and Ar1 and Ar2 are each independently an aromatic radical, are disclosed. The 2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidine compounds are useful for preparing other useful monomers and polymers.
Description
- This application is a divisional application of U.S. patent application Ser. No. 11/289,250 filed Nov. 29, 2005, which is incorporated herein in its entirety.
- This disclosure relates generally to 2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidine compounds and methods for preparing these compounds. Further, the disclosure relates to polymers including structural units derived from these compounds.
- Polymers are important materials in modern commerce. A variety of polymers having commercial significance, such as polycarbonates, polyamides, polyurethanes, polyesters, and the like have been produced. Many of these polymers have been prepared from monomers that have two chemically identical reactive functional groups (“monofunctional monomers). Polymers prepared from bifunctional monomers, that is monomers having two chemically different reactive functional groups, are also known. Examples of such bifunctional monomers include aminophenols, aminocarboxylic acids, hydroxycarboxylic acids, compounds having an anhydride group and a hydroxy group, and the like. Bifunctional monomers can be useful for preparing polymers that have a combination of some of the desirable properties of the polymers prepared from monofunctional monomers that have only one or the other type of reactive functional groups of the bifunctional monomer.
- There remains a need for bifunctional monomers that can be used for preparing polymers that potentially have a desirable combination of polymer physical properties, such as for example, high temperature stability, resistance to reaction with certain chemicals; high temperature stability and liquid crystalline behavior.
- The present disclosure, generally provides for novel 2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidine compounds and methods for preparing them. These novel compounds are useful for preparing monomers and polymers comprising structural units derived from the 2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidine compounds and functional monomers derived therefrom.
- One embodiment is directed to a 2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidine compound having a formula:
wherein R1 is independently selected from a group consisting of a hydrocarbyl radical, a nitro radical, and a halogen atom; “a” is an integer from 0-4; and Ar1 and Ar2 are each independently an aromatic radical. To clarify, when “a” is less than 4, each unsubstituted carbon on the aryl ring is bonded to a hydrogen atom as is the accepted chemical shorthand. Further structures presented below are similar. - In another embodiment, a method for preparing a 2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidine compound comprises reacting a precursor compound with a primary aromatic amine in the presence of an acidic catalyst, wherein the primary aromatic amine has a formula Ar1—NH2, wherein Ar1 is an aromatic radical. The precursor compound is selected from the group consisting of a phenolphthalein compound, a 2-aryl-3,3-bis(hydroxyaryl)phthalimidine compound, and mixtures thereof.
- In yet another embodiment, a method for preparing a 2-phenyl-3-(aminophenyl)-3-(hydroxyphenyl)phthalimidine compound comprises reacting a precursor compound is selected from the group consisting of phenolphthalein, 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine, and mixtures thereof.
- In still yet another embodiment, a polymer comprising structural units derived from at least one 2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidine having a formula,
wherein R1 is independently selected from a group consisting of a hydrocarbyl radical, a nitro radical, and a halogen atom; “a” is an integer from 0-4; and Ar1 and Ar2 are each independently an aromatic radical; is provided. - The disclosure may be understood more readily by reference to the following detailed description of the various features of the disclosure and the examples included therein.
- The FIGURE shows the proton nuclear magnetic resonance spectrum of 2-phenyl-3-(4-aminophenyl)-3-(4-hydroxyphenyl)phthalimidine.
- In the following description and claims that follow, reference will be made to a number of terms which shall be defined to have the following meanings: the singular forms “a”, “an” and “the” include plural referents unless the context clearly dictates otherwise. “Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not. The term “hydrocarbyl radical” refers to an aliphatic radical, an aromatic radical, or a cycloaliphatic radical. The terms “formula” and “structure” are used interchangeably herein.
- The term “aliphatic radical” refers to an organic radical having s valence of at least one comprising a linear or branched array of atoms which is not cyclic. The aliphatic radicals comprise at least one carbon atom. The array of atoms forming the aliphatic radical may further include heteroatoms such as nitrogen, sulfur, silicon, selenium and oxygen or may be composed exclusively of carbon and hydrogen. The “linear or branched array of atoms which is not cyclic” is intended to include a wide range of functional groups such as alkyl groups, alkenyl groups, alkynyl groups, halo alkyl groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (for example carboxylic acid derivatives such as esters and amides), amine groups, nitro groups and the like. From example, a suitable aliphatic radical is the 4-methylpent-1-yl radical, which is a C6 aliphatic radical comprising a methyl group. Similarly, the4-nitrobut-1-yl group is a C4 aliphatic radical comprising a nitro functional group. Other suitable aliphatic radicals include a haloalkyl group that comprises one or more halogen atoms which may be the same or different. Suitable halogen atoms include, for example, fluorine, chlorine, bromine, and iodine. Aliphatic radicals comprising one or more halogen atoms include the alkyl halides trifluoromethyl, bromodifluoromethyl, chlorodifluoromethyl, hexafluoropropylidene, chloromethyl; difluorovinylidene; trichloromethyl, bromodichloromethyl, bromoethyl, 2-bromotrimethylene (e.g., —CH2CHBrCH2—), and the like. Further examples of suitable aliphatic radicals include allyl, aminocarbonyl (—CONH2), carbonyl, dicyanoisopropylidene (—CH2C(CN)2CH2—), methyl (—CH3), methylene (—CH2—). ethyl, ethylene, formyl (—CHO), hexyl, hexamethylene, hydroxymethyl (—CH2OH), mercaptomethyl (—CH2SH), methylthio (—SCH3), methylthiomethyl (—CH2SCH3), methoxy, methoxycarbonyl (CH3OCO—), nitromethyl (—CH2NO2), thiocarbonyl, trimethylsilyl ((CH3)3Si—), t-butyldimethylsilyl, trimethyloxysilypropyl ((CH3O)3SiCH2CH2CH2—), vinyl, vinylidene, and the like. By way of further example, a C1-C10 aliphatic radical contains at least one but no more than 10 carbon atoms.
- The term “aromatic radical” is also sometimes referred herein to as an “aryl radical”. The aromatic radical or the aryl radical refers to an array of atoms having a valence of at least one comprising at least one aromatic group. The aromatic radical may include heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen, or may be composed exclusively of carbon and hydrogen. As used herein, the term “aromatic radical”includes but is not limited to phenyl, pyridyl, furanyl, thienyl, naphthyl, phenylene, and biphenyl radicals. The aromatic group is invariably a cyclic structure having 4n+2 “delocalized” electrons where “n” is an integer equal to 1 or greater, as illustrated by phenyl groups (n=1), thienyl groups (n−1), furanyl groups (n=1), naphthyl groups (n=2), azulenyl groups (n=2), anthraceneyl groups (n=3) and the like. The aromatic radical may also include non-aromatic components. For example, a benzyl group is an aromatic radical that comprises a phenyl ring (the aromatic group) and a methylene group (the non-aromatic component). Similarly a tetrahydronaphthyl radical is an aromatic radical comprising an aromatic group (C6H3) fused to a non-aromatic component —(CH2)4—. The “aromatic radical” can encompass a wide range of functional groups such as alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, haloaromatic groups, conjugated dienyl groups, alcohol groups, ether groups, aldehydes groups, ketone groups, carboxylic acid groups, acyl groups (for example carboxylic acid derivatives such as esters and amides), amine groups, nitro groups, and the like. For example, the 4-methylphenyl radical is a C7 aromatic radical comprising a methyl alkyl group. Similarly, the 2-nitrophenyl group is a C6 aromatic radical comprising a nitro functional group. Suitable aromatic radicals may include halogenated aromatic radicals such as trifluoromethylphenyl, hexafluoroisopropylidenebis(4-phen-1-yloxy) (—OPhC(CF3)2PhO—), chloromethylphenyl; 3-trifluorovinyl-2-thienyl, 3-trichloromethylphen-1yl (3-CCl3Ph—), 4(3-bromoprop-1-yl)phen-1-yl (BrCH2CH2CH2Ph—), and the like. Further examples of aromatic radicals include 4-allyloxyphen-1oxy, 4-aminophen-1yl (H2NPh—), 3-aminocarbonylphen-1-yl (NH2COPh—), 4-benzoylphen-1yl, dicyanoisopropylidenebis(4-phen-1yloxy) (—OPhC(CN)2PhO—), 3-methylphen-1yl, methylenebis(phen-4-yloxy) (—OPhCH2PhO—), 2-ethylphen-1-yl, phenylethenyl, 3-formyl-2-thienyl, 2-hexyl-5-furanyl; hexamethylene-1,6-bis(phen-4-yloxy) (—OPh(CH2)6PhO—); 4-hydroxymethylphen-1yl (4-HOCH2Ph—), 4-mercaptomethylphen-1-yl (4-HSCH2Ph—), 4-methylthiophen-1yl (4-CH3SPh—), 3-methoxyphen-1yl, 2-methoxycarbonylphen-1yloxy (methyl salicyl), 2-nitromethylphen-1yl, 3-trimethylsilylphen-1yl, 4-t-butyldimethylsilylphenl-1yl, 4-vinylphen-1yl, vinyldenebis(phenyl, and the like. The term “a C3-C10 aromatic radical” includes aromatic radicals containing at least three but no more than 10 carbon atoms. The aromatic radical 1-imidazolyl (C3H2N2—) represents a C3 aromatic radical. The benzyl radical (C7H8—) represents a C7 aromatic radical.
- The term “cycloaliphatic radical” refers to a radical having a valence of at least one and comprising an array of atoms that is cyclic but not aromatic. As defined herein a “cycloaliphatic radical” does not contain an aromatic group and may further include one or more noncyclic components. For example, a cyclohexylmethyl group (C6H11CH2—) is a cycloaliphatic radical that comprises a cyclohexyl ring (the array of atoms is cyclic but not aromatic) and a methylene group (the noncyclic component). The cycloalophatic radical may further include heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen, or may be composed exclusively of carbon and hydrogen. In addition, the cycloaliphatic radical can encompass a wide range of functional groups such as alkyl groups, alkenyl groups, alkynyl groups, halo alkyl groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (for example carboxylic acid derivatives such as esters and amides), amine groups, nitro groups and the like. For example, the 4-methylcyclopent-1yl radical is a C6 cycloaliphatic radical comprising a methyl group, the methyl group being a functional group which is an alkyl group. Similarly, the 2-nitrocyclobut-1-yl radical is a C4 cycloaliphatic radical comprising a nitro group, the nitro group being a functional group. A suitable cyclosliphatic radical may also comprise one or more halogen atoms which may be the same or different. Suitable halogen atoms, include, for example, fluorine, chlorine, bromine, and iodine. Suitable cycloaliphatic radicals comprising one or more halogen atoms include 2-trifluoromethylcyclohex-1-yl, 4-bromodifluoromethylcyclooct-1-yl, 2-chlorodifluoromethylcyclohex-1-yl, hexafluoroisopropylidene2,2-bis (cyclohex-4-yl) (—C6H10C(CF3)2C6H10—), 2-chloromethylcyclohex-1-yl; 3-difluoromethylenecylcohex-1-yl; 4-trichloromethylcyclohex-1-yloxy, 4-bromodichloromethylcyclohex-1-ylthio, 2-bromoethylcyclopent-1-yl, 2-bromopropylcyclohex-1-yloxy (e.g. CH3CHBrCH2C6H10—), and the like. Further examples of cycloaliphatic radicals include 4-allyloxycyclohex-1-yl, 4-aminocyclohex-1-yl (H2NC6H10—), 4-aminocarbonylcyclopent-1-yl (NH2COC5H8—), 4-acetyloxycyclohex-1-yl, 2,2-dicyanoisopropylidenebis(cyclohex-4-yloxy) (—OC6H10C(CN)2C6H10O—), 3-methylcyclohex-1-yl, methylenebis(cyclohex-4-yloxy) (—OC6H10CH2C6H10O—), 1-ethylcyclobut-1-yl, cyclopropylethenyl, 3-formyl-2-terahydrofuranyl, 2-hexyl-5-tetrahydrofuranyl; hexamethylene-1,6-bis(cycloshex-4-yloxy) (—O C6H10(CH2)6C6H10O—); 4-hydroxymethylcyclohex-1-yl (4-HOCH2C6H10—), 4-mercaptomethylcyclohex-1-yl (4-HSCH2C6H10—), 4-methylthiocyclohex-1-yl (i.e. 4-CH3SC6H10—), 4-methoxycyclohex-1-yl, 2-methoxycarbonylcyclohex-1-yloxy (2-CH3OCOC6H10O—), 4-nitromethylcyclohex-1-yl (NO2CH2C6H10—), 3-trimethylsilylcyclohex-1-yl, 2-t-butyldimethylsilylcycopent-1-yl, 4-trimethoxysilylethylcyclohex-1-yl ((CH3O)3SiCH2CH2C6H10—), 4-vinylcyclohexen-1-yl, vinylidenebis(cyclohexyl), and the like.
- As disclosed herein, unless otherwise stated, the term“2-aryl-3,3-bis(hydroxyaryl)phthalimidine” (AHP) includes the ortho, para and para, para isomers, which generally refers to the placement of the OH functionality within the hydroxyaryl group. As disclosed herein, unless otherwise stated, the term “2-phenyl-3,3-bis(hydroxyphenyl)phthalimidine” (PPPBP) includes the ortho, para and the para, para isomers. As disclosed herein, the term “2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidine” (AAHP) includes the para, para isomer, which refers to the placement of the OH and the NH2 functional groups, unless otherwise indicated. As disclosed herein, the term “2-phenyl-3-(4-aminophenyl)-3-(4-hydroxyphenyl)phthalimidine” is interchangeable with the abbreviation “AP”.
- As disclosed herein, in the structures/formulae for the AAHP's, AHP's, or the phenolphthalein compounds, when the subscript “a” in “(R1)a” is zero, it denotes a structure where all the R1 substituents are hydrogen atoms. In the case where R1 is other than a hydrogen atom, the subscript “a” can take values from zero to four, with a value of zero for “a” denoting a structure having only hydrogen atoms as the R1 substituents.
- The AAHP compounds have general formula (I),
wherein R1 is independently selected from a group consisting of a hydrocarbyl radical, a nitro radical, and a halogen atom; “a” is an integer from 0-4; Ar1 and Ar2 are each independently an aromatic radical. In an embodiment, AAHP compounds having formula (I) include those wherein AR1 and Ar2 are each independently a monocyclic aromatic radical. In another embodiment, Ar1 and Ar2 are aryl radicals. In still another embodiment, Ar1 and Ar2 are each independently a monocyclic aromatic radical, and “a” is zero. In yet another embodiment, the 2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidine has a formula (II).
wherein R1 is independently selected from a group consisting of a hydrocarbyl radical, a nitro radical, and a halogen atom; and “a” is an integer from 0-4. In still another embodiment, an exemplary 2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidine has the structure (II), wherein R1 is a hydrogen atom, and “a” is 4; also called 2-phenyl-3-(4-aminophenyl) -3-(4-hydroxyphenyl)phthalimidine (abbreviated herein as “AP”). - The 2-aryl-3-(aminoaryl)-3-(hydroxyaryl)phthalimidines (AAHPs) are prepared by reacting a precursor compound with a primary aromatic amine having a general formula (III),
Ar2—NH2 (III)
wherein Ar2 is an aromatic radical. Suitable primary aromatic amines include aniline and anilines substituted by one or more C1-C12 aliphatic radicals, one or more C3-C12 cycloaliphatic radicals, or one or more aromatic radicals. - The precursor compound can comprise a phenolphthalein compound having a formula (IV),
wherein Ar1, R1, and “a” are as described previously for formula (I). Phenolphthalein compounds can be prepared by methods, such as for example, by the ring-alkylation reaction of a phthalic anhydride compound of formula (V),
wherein R1 and “a” are as described previously with an aromatic hydroxy compound of formula (VI),
Ar1—OH (VI)
wherein Ar1 is an aromatic radical. - A catalyst is generally employed for forming the phenolphthalein compounds. The catalyst may be a Lewis acid, such as for example, zinc chloride. aluminum chloride, ferric chloride, boron trifluoride, and the like. Non-limiting examples of phthalic anhydrides of formula (V) include phthalic anhydride, halogenated phthalic anhydrides, such as 3-chlorophthalic anhydride, 4-chlorophthalic anhydride, 3,4-dichlorophthalic anhydride, trichlorophthalic anhydride, tetrachlorophthalic anhydride, fluorophthalic anhydride, difluorophthalic anhydride, trifluorophthalic anhydride, tetrafluorophthalic anhydride, and the like; alkoxy-substituted phthalic anhydrides, nitrophthalic anhydrides, and the like. Phthalic anhydride is an exemplary phthalic anhydride compound since it is readily available commercially. The aromatic hydroxy compound of formula (VI) is exemplified by the parent compound, phenol, as well as any substituted phenol that can undergo the alkylation reaction with the phthalic anhydride compound. Some examples of substituted aromatic hydroxy compounds include the cresols (ortho, meta, para isomers), and xylenols (various isomers).
-
- Suitable precursor compounds for preparing the AAHP compounds can also be 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (VIII),
wherein R1, “a”, Ar1 and Ar2 are as previously described. In one embodiment, the 2-aryl-3,3-bis (hydroxyaryl)phthalimidine is of formula (IX),
wherein R1, “a”, and Ar2 are as previously described. In another embodiment, the 2-aryl-3,3-bis (hydroxyaryl)phthalimidine precursor includes varying amounts of the corresponding ortho, para-AHP, such as for example, the compound of general formula (X),
wherein R1, “a”, and Ar2 are as previously described for formula (IX). 2-phenyl-3,3-bis(4-hydroxyphenyl) phthalimidine (para, para-PPBP) is an exemplary 2-aryl-3,3-bis(hydroxyaryl)phthalimidine. The para, para-PPPBP may also comprise the corresponding ortho, para-isomer as the precursor compound. - the reaction of the aromatic primary amine with an AHP compound can be extended to other dihydroxy aromatic compounds that can undergo a similar reaction. This reaction can be regarded as a transarylation reaction in which a hydroxyphenyl group in the dihydroxy aromatic compound is exchanged for an aminoaryl group in the presence of an acidic catalyst. Non-limiting examples of dihydroxy aromatic compounds that can undergo such a transarylation reaction include compounds of formulas (XI)-(XIII).
The products produced from the transarylation reaction include structures in which one or both hydroxyphenyl groups have been exchanged for the aminoaryl group, that is —NHAr2. - Suitable acidic catalyst used for forming the AAHP compounds comprise a salt of an organic amine and an acid. The acid is selected from the group consisting of an inorganic acid, an organic acid, or combinations of the foregoing acids. Some examples of inorganic acids include hydrochloric acid, sulfuric acid, phosphoric acid, and the like. Examples of organic acids include sulfonic acids, such as for example, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, and the like; and carboxylic acids, such as formic acid, benzoic acid, and the like. Polymeric acidic catalysts, such as those comprising sulfonic acid groups can also be used. Examples of polymeric acidic catalysts include cation exchange resins comprising sulfonic acid groups. Solid acidic catalysts, such as acidic silica, acidic alumina, and montmorillonite can also be used.
- The organic amine needed to form the acidic catalyst can be a primary amine, a secondary amine, a tertiary amine, or any combination of the foregoing amines. Organic amines having one or more basic nitrogen atoms as part of a ring, such as for example, a pyridine compound can also be used. Further examples of suitable amines include primary, secondary, and tertiary amines having any combination of aliphatic and aromatic groups bonded to the amine nitrogen. Suitable examples of amine salt catalysts include primary, secondary, and tertiary amine hydrochlorides. In one embodiment, hydrochloride salt of the amines of formula (III) above, wherein R1 is an aromatic radical, can be used. In another embodiment, acidic salts of primary aromatic amines that also serve as the starting material for preparing the AAHPs of formula (II) above are preferred. Aniline is an exemplary organic amine used for preparing an acidic catalyst to form the AAHP compounds.
- In one embodiment, the acidic catalyst is introduced as a pre-formed salt into the reactor. In another embodiment, the catalyst is generated in situ within the reactor by first charging an amine of formula (III) into the reactor, and then adding an appropriate acid to the amine. For example, about ⅓ to about 1 part by weight of an acid, such as an inorganic acid can be added to the amine of formula (III) to generate the acidic salt catalyst. Hydrochloric acid is an exemplary inorganic acid. Hydrogen chloride gas can also be used. In one embodiment, about 0.1 part to about 0.3 parts by weight of hydrogen chloride gas is introduced into a reactor charged with the organic amine, such as an aryl amine. The thus formed aryl amine hydrochloride can be suitably used as a catalyst in the present disclosure. Generally, a relatively higher level of the acidic catalyst favors the formation of the AAHP compounds. A solvent can optionally be employed to form the acidic catalyst, for example, the aryl amine hydrochloride. The solvent can then be removed (if necessary), and the hydrocarbyl amine of formula (III) can be added, followed by addition of the precursor compound of formula (IV) and/or (VIII).
- When the precursor is the phenolphthalein compound, the reaction to form the desired products (I) proceeds with an intermediate formation of product having formula (VIII). The program of the reaction can be followed by liquid chromatography, wherein the disappearance of the phenolphthalein compound and formation of the intermediate (VIII) and final product (I) can be monitored. The reaction temperature and reaction time can be adjusted to facilitate formation of product (I). The reaction of the phenolphthalein compound with the hydrocarbyl amine in the presence of the acidic catalyst proceeds by a condensation reaction to form the intermediate products having formula (VIII) and water by-product. The water can be removed by simply distilling it out of the reactor. Alternatively, the water can be removed as an azeotrope by using a suitable organic solvent. The intermediate product reacts with more hydrocarbyl amine in a second step in the presence of the acidic catalyst to form the desired product having formula (I). In the second step, an aromatic hydroxy compound is produced as a by-product. In an embodiment, the aromatic hydroxy compound can be removed during the reaction to facilitate the forward reaction. In another embodiment, the reaction mixture can be refluxed without removing the water or the aromatic hydroxy compound by-products. An excess of the aryl amine over the phenolphthalein may be used to keep the reaction proceeding in the forward direction. The temperature can be chosen so as to facilitate formation of the product. Generally, for a given pressure, a relatively higher temperature favors formation of the AAHP compound. The reaction can be conducted at a sub-ambient, ambient, or supra-ambient pressure. In an embodiment, a temperature of at least 100° C. can be used to form the AAHP compounds. The desired AAHP compounds can then be isolated from the reaction mixture by techniques known in the art for isolating organic amine compounds and/or aromatic hydroxy compounds.
- The para, para-2-aryl-3,3-bis(hydroxyaryl)phthalimidines (AHP compounds), shown in formula (VIII) are produced as intermediates in the preparation of the AAHP compounds, and are themselves valuable as monomers for preparing polymers, such as polycarbonates. Hence, the reaction conditions to produce a AAHP compound can be modified or optimized to produce both a AHP compound and a AAHP compound as useful products.
- The reaction mixture comprising the AAHP product also comprises the corresponding AHP by-product. Both products can exist as a mixture of para, para and ortho, para isomers. Generally, the para, para isomers of the AAHP and AHP compounds predominate over the corresponding ortho, para isomers.
- In one embodiment, the reaction mixture is first quenched with an aqueous mineral acid, such as aqueous hydrochloric acid. A solid mixture comprising the AAHP product and the AHP by-product results, which is filtered and dissolved in a mixture of water and an organic solvent, wherein the organic solvent can at least partly dissolve the solid mixture. The resulting solution is then contacted with an acidic material, which can bind the AAHP compound through the Nh2 group. Cation exchange resins having sulfonic acid groups can be used to separate the AAHP compound from the AHP compound. Any polar solvent that can at least partly dissolve the AAHP can be used. Further, these solvents may be at least partly miscible with water, or fully miscible with water. Suitable organic solvents comprise at least one functional group selected from the group consisting of a hydroxy group, a ketone carbonyl group, a carboxylic acid group, an ester group, a sulfoxide group, a nitrile group, an ether group, and a nitro group. In one embodiment, suitable organic solvents are those that comprise at least member selected from the group consisting of an organic hydroxy compound, an organic ketone, an organic amide, an organic sulfoxide, an organic ether, and an organic nitrile. Each of these categories of solvents may comprise more than one functional group, which may be the same or different from the other functional group(s). For example ethanol, ethylene glycol, and 2-ethoxyethanol may be used, either individually, or in any relative proportion as suitable organic solvents.
- In one embodiment, aliphatic alcohols having at least one hydroxy group can be used as the organic solvent. Suitable organic hydroxy compounds include aliphatic, cycloaliphatic and aromatic hydroxy compounds having at least one hydroxy group. The aliphatic hydroxy compounds include linear and branched aliphatic mono-hydroxy compounds, non-limiting examples of which are methanol. ethanol, isopropanol, n-butanol, sec-butanol, iso-butanol, tert-butanol, and the like. Mixtures of these compounds can also be used. Aliphatic dihydroxy compounds, such as the glycols, exemplified by ethylene glycol, propylene glycol, and the like may also by used. Non-limiting examples of aromatic hydroxy compounds include phenol, ortho-cresol, benzyl alcohol, and the like. Some examples of cycloaliphatic hydroxy compounds include cyclopentanol, cyclohexanol, cyclohexanediol, and the like. In an embodiment, suitable organic hydroxy compounds include methanol, isopropanol, or any combination of methanol and isopropanol. Methanol is an exemplary organic solvent for that can be used isolating the AAHP compound, such a 2-phenyl-3(4-aminophenyl) -3-(4-hydroxyphenyl)phthalimidine (AP).
- Organic ketones suitable for the use as the organic solvent include acetone, 2-butanone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, and the like. In an embodiment, the organic solvent comprises acetone. Suitable organic amides include formamide, acetamide, and the like. Organic sulfoxides that may be used as the organic solvent include dimethylsulfoxide, methyl ethyl sulfoxide, diethyl sulfoxide, and the like. Non-limiting examples of organic nitriles include the aliphatic nitriles, such as acetonitrile, propionitrile, butyronitrile, and the like. Examples of organic nitro compounds that may be used include nitromethane, nitroethane, and the like.
- In an embodiment, the organic solvent is methanol, ethanol, isopropanol, sec-butanol, phenol, acetone, butanone, formamide, or dimethylsulfoxide.
- The cation exchange resin having the bound AAHP compound is then treated with a mixture comprising an aqueous acid and an organic solvent that can at least partly dissolve the AAHP compound. Examples of aqueous include aqueous mineral acids, such as hydrochloric acid, phosphoric acid, and the like. Examples of the organic solvent include those disclosed above. Aliphatic alcohols, such as methanol, ethanol, isopropanol, and the like are useful organic solvents. The acidic mixture liberates the free AAHP compound. The para, para isomer of AAHP can then be isolated in a pure form using a technique such as crystallization.
- The AAHP compounds disclosed herein are valuable for making a variety of functional materials by selectively reacting either the Nh2 group, or the OH group with suitable reactants. Selective reaction of the NH2 group gives rise to functional materials having a free OH group; and selective reaction of the OH group gives rise to functional materials having a free NH2 group. For example, reaction of AP, shown below in formula (XIV):
with an anhydride, such as phthalic anhydride provides the functional material of formula (XV):
The functional materials in turn can be used for preparing many different types of polymers. - The AAHP compounds are also valuable for making a variety of polymers. The polymers can be homopolymers, random copolymers, and block copolymers. The presence of the NH2 and the aromatic hydroxy (OH) functional groups makes them suitable as monomers or comonomers for producing a variety of polymers comprising one or more types of structural units derived from these functional groups. Examples of such structural units include formulas (XVI)-(XX),
Some non-limiting examples of polymers that can be produced using the AAHP compounds disclosed herein include, but not limited to, polyesteramides, polyesterurethanes, polycarbonateamides, and the like. - The disclosure is explained in more detail with reference to the following non-limiting Examples, which are intended to be illustrative, not limitative.
- This example describes the procedure used for preparing the 2-phenyl-3-(4-hydroxyphenyl)-3-(4-aminophenyl)phthalimidine monomer from phenolphthalein and aniline as starting materials, and aniline hydrochloride as the catalyst.
- A 500 milliliter 4-necked round-bottomed flask with an overhead stirrer, a Dean-Stark apparatus, and a thermometer pocket was charged with aniline 82 grams, 0.88 mole), phenolphthalein (40.5 grams,0.127 mole), and aniline hydrochloride (33 grams, 0.25 mole). The resulting mixture was heated to reflux with stirring (the temperature of the reacting mass was 180-185° C.) for 48 hours under a nitrogen atmosphere. Then, the reaction mass was cooled to 120-125° C. and treated with 5 weight percent aqueous hydrochloric acid. The resulting mixture was stirred for an additional 2 to 3 hours while maintaining the internal temperature at about 50° C. then cooled to ambient temperature, and filtered. The filter cake was washed thoroughly with water(5×100 milliliters) until the water wash was neutral (pH of about 7). Excess water from the filter cake was removed under suction, and the solid was dried at 100-120° C. to constant weight. The crude product thus obtained was analyzed by high pressure liquid chromatography (HPLC) and found to contain about 16 weight percent of AP.
- About 100 grams of the crude product was dissolved in aqueous sodium hydroxide, stirred with 5 grams of activated carbon for about 15 minutes, and filtered. The filtrate was added to aqueous hydrochloric acid (containing 7-10 weight percent of dissolved HCl) with stirring to adjust the pH of the mixture to 3.5-4. After being stirred for another 30 minutes, and ensuring that the pH remained at about 3.5-4, the mixture was filtered and the filter cake was dried to constant weight. The material thus obtained was dissolved in 6 volumes (on a dry basis relative to the volume of the solid material) of a solvent containing 80:20 (volume/volume) of acetone and water, respectively. This solution was heated to a temperature of 40-45° C. and pumped through a column packed with 10 grams (on a dry basis) of a 2 percent crosslinked sulfonated polystyrene-divinylbenzene ion exchange resin at a weighted hourly space velocity of 6-7 (that is about 60-70 grams of the feed solution per hour). The level of AP in the effluent is monitored using HPLC. Generally, the feed solution was pumped through the column till the effluent had approximately 75 parts per million of AP. The pumping was stopped, and the liquid remaining in the column was drained out. Next, a solvent mixture containing 90:10:10 (volume by volume) of acetone, concentrated hydrochloric acid and water, respectively, was prepared and pumped through the column. Then, a solvent mixture containing 80:20 (volume by volume) of acetone and water, respectively, was pumped through the column until the effluent had a neutral pH. The combined effluents was neutralized with an aqueous base containing a basic material, such as sodium hydroxide, sodium carbonate, or sodium bicarbonate. The entire mixture was evaporated to remove the solvents. The solid residue remaining was analyzed by HPLC to contain approximately 50 weight percent of AP. A portion of this material was subjected to preparatory HPLC using a mobile phase consisting of a 86:9:5 volume ratio of solvents (A), (B), and (C); wherein solvent (A) is a 0.02 weight percent solution of phosphoric acid in water, solvent (B) is methanol, and solvent (C) is acetonitrile. A column oven temperature of about 40° C., a flow rate of 1 milliliter per minute, and a detector wavelength of 270 nanometers was used for the preparative HPLC. The eluate containing the desired AP was collected and evaporated to furnish a pure sample of AP. The chemical identity of AP was established by proton nuclear magnetic resonance (NMR) spectroscopy. Referring to the Figure, the proton NMR spectrum shows the peaks with assignments to the various types of protons present in AP. The assignments are shown as numbers (1 through 10) in the Figures. Two-dimensional carbon-proton correlation spectroscopy was used to establish that the NH2 and the phenolic OH groups were located at the para position of each phenyl ring in AP, thus confirming that the isolated material was the para,para-AP isomer.
- This example describes the procedure used for preparing the monomer 2-phenyl-3-(4-hydroxyphenyl)-3-(4-aminophenyl)phthalimidine (AP) from 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine and aniline as starting materials, and aniline hydrochloride as the catalyst.
- The crude reaction product was obtained as described above in Example 1 by using aniline (83 grams, 0.88 mole), para, para-PPPBP (50 grams, 0.127 mole), and aniline hydrochloride (33 grams; 0.25 mole). The crude product contained about 16 weight percent of AP, as determined by HPLC. The isolation of pure para, para-AP was achieved by using the same procedure as described for Example 1.
- This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to make and use the invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
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US7563817B2 (en) * | 2005-12-14 | 2009-07-21 | Sabic Innovative Plastics Ip Bv | Purified 2-aryl-3,3-bis(hydroxyaryl)phthalimidines |
US7514524B2 (en) | 2007-03-30 | 2009-04-07 | Sabic Innovative Plastics Ip B.V. | Methods for producing and purifying 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimidine monomers and polycarbonates derived therefrom |
US7592464B2 (en) | 2007-03-30 | 2009-09-22 | Sabic Innovative Plastics Ip Bv | Methods for producing and purifying 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimidine monomers and polycarbonates derived therefrom |
WO2013173615A1 (en) | 2012-05-16 | 2013-11-21 | Sabic Innovative Plastics Ip B.V. | Compositions and articles of manufacture containing branched polycarbonate |
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US10487077B1 (en) | 2018-06-14 | 2019-11-26 | Sabic Global Technologies B.V. | Bis(benzoxazinyl)phthalimidine and associated curable composition and composite |
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- 2007-04-26 US US11/740,581 patent/US20070197761A1/en not_active Abandoned
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US20030181768A1 (en) * | 2002-03-13 | 2003-09-25 | O' Young Drow Lionel | System and method of producing bisphenol-a (BPA) |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US10273357B2 (en) | 2014-04-15 | 2019-04-30 | Sabic Global Technologies B.V. | High heat polycarbonate compositions |
US10370534B2 (en) | 2014-04-15 | 2019-08-06 | Sabic Global Technologies B.V. | High heat polycarbonate compositions |
Also Published As
Publication number | Publication date |
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WO2007064630A1 (en) | 2007-06-07 |
JP2009517475A (en) | 2009-04-30 |
EP1957456A1 (en) | 2008-08-20 |
US7348439B2 (en) | 2008-03-25 |
US20070123714A1 (en) | 2007-05-31 |
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