WO2022125856A1 - Aromatic enol ethers - Google Patents
Aromatic enol ethers Download PDFInfo
- Publication number
- WO2022125856A1 WO2022125856A1 PCT/US2021/062746 US2021062746W WO2022125856A1 WO 2022125856 A1 WO2022125856 A1 WO 2022125856A1 US 2021062746 W US2021062746 W US 2021062746W WO 2022125856 A1 WO2022125856 A1 WO 2022125856A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acrylate
- benzene
- methacrylate
- prop
- found
- Prior art date
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- -1 Aromatic enol ethers Chemical class 0.000 title claims abstract description 30
- 239000008199 coating composition Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims description 86
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 44
- 125000003342 alkenyl group Chemical group 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 27
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 27
- 239000004816 latex Substances 0.000 claims description 26
- 229920000126 latex Polymers 0.000 claims description 26
- 229920000642 polymer Polymers 0.000 claims description 11
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 10
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 10
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 claims description 4
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 claims description 4
- LPNSCOVIJFIXTJ-UHFFFAOYSA-N 2-methylidenebutanamide Chemical compound CCC(=C)C(N)=O LPNSCOVIJFIXTJ-UHFFFAOYSA-N 0.000 claims description 4
- GASMGDMKGYYAHY-UHFFFAOYSA-N 2-methylidenehexanamide Chemical compound CCCCC(=C)C(N)=O GASMGDMKGYYAHY-UHFFFAOYSA-N 0.000 claims description 4
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 4
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 4
- YHSYGCXKWUUKIK-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C=C YHSYGCXKWUUKIK-UHFFFAOYSA-N 0.000 claims description 4
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 claims description 4
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 4
- 229940065472 octyl acrylate Drugs 0.000 claims description 4
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 4
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 239000002174 Styrene-butadiene Substances 0.000 claims description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011115 styrene butadiene Substances 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000000654 additive Substances 0.000 abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 61
- 150000002084 enol ethers Chemical class 0.000 description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 239000003973 paint Substances 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 239000012855 volatile organic compound Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000003039 volatile agent Substances 0.000 description 6
- SOMMDGRPZCKHBQ-UHFFFAOYSA-N 2-[4-(1-oxopropan-2-yl)phenyl]propanal Chemical compound O=CC(C)C1=CC=C(C(C)C=O)C=C1 SOMMDGRPZCKHBQ-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000000080 wetting agent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 3
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 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 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- WIPHGWMFCZTUIB-UHFFFAOYSA-N C(CC)OCCOCCOCC(=C)C1=CC(=CC=C1)C(=C)COCCOCCOCCC Chemical compound C(CC)OCCOCCOCC(=C)C1=CC(=CC=C1)C(=C)COCCOCCOCCC WIPHGWMFCZTUIB-UHFFFAOYSA-N 0.000 description 2
- SACWOHLCBKEZFL-UHFFFAOYSA-N CC(COC)OCC(OCC(OCC(=C)C1=CC(=CC=C1)C(COC(COC(COC(COC)C)C)C)=C)C)C Chemical compound CC(COC)OCC(OCC(OCC(=C)C1=CC(=CC=C1)C(COC(COC(COC(COC)C)C)C)=C)C)C SACWOHLCBKEZFL-UHFFFAOYSA-N 0.000 description 2
- NTMAMGLYTCGRJB-UHFFFAOYSA-N CC(COC)OCC(OCC(OCC(=C)C1=CC=C(C=C1)C(COC(COC(COC(COC)C)C)C)=C)C)C Chemical compound CC(COC)OCC(OCC(OCC(=C)C1=CC=C(C=C1)C(COC(COC(COC(COC)C)C)C)=C)C)C NTMAMGLYTCGRJB-UHFFFAOYSA-N 0.000 description 2
- IKHKBPFEJVOWJI-UHFFFAOYSA-N COCC(C)OCC(C)OCC(=C)C1=CC=C(C=C1)C(=C)COC(COC(COC)C)C Chemical compound COCC(C)OCC(C)OCC(=C)C1=CC=C(C=C1)C(=C)COC(COC(COC)C)C IKHKBPFEJVOWJI-UHFFFAOYSA-N 0.000 description 2
- OYWNZALRZJDHDZ-UHFFFAOYSA-N COCCOCCOCC(=C)C1=CC=C(C=C1)C(=C)COCCOCCOC Chemical compound COCCOCCOCC(=C)C1=CC=C(C=C1)C(=C)COCCOCCOC OYWNZALRZJDHDZ-UHFFFAOYSA-N 0.000 description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WTBJDTJYLPOHFH-UHFFFAOYSA-N 2-[3-(1-oxopropan-2-yl)phenyl]propanal Chemical compound O=CC(C)C1=CC=CC(C(C)C=O)=C1 WTBJDTJYLPOHFH-UHFFFAOYSA-N 0.000 description 1
- 229920005791 ACRONAL® 296 D na Polymers 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XAAGOZSRLAZVFO-UHFFFAOYSA-N C(C)OCCOCCOCC(=C)C1=CC(=CC=C1)C(=C)COCCOCCOCC Chemical compound C(C)OCCOCCOCC(=C)C1=CC(=CC=C1)C(=C)COCCOCCOCC XAAGOZSRLAZVFO-UHFFFAOYSA-N 0.000 description 1
- HJDZRSKRAJJKAX-UHFFFAOYSA-N C(C)OCCOCCOCC(=C)C1=CC=C(C=C1)C(=C)COCCOCCOCC Chemical compound C(C)OCCOCCOCC(=C)C1=CC=C(C=C1)C(=C)COCCOCCOCC HJDZRSKRAJJKAX-UHFFFAOYSA-N 0.000 description 1
- WUHPBOARHFDCPZ-UHFFFAOYSA-N C(CC)OCCOCCOCC(=C)C1=CC=C(C=C1)C(=C)COCCOCCOCCC Chemical compound C(CC)OCCOCCOCC(=C)C1=CC=C(C=C1)C(=C)COCCOCCOCCC WUHPBOARHFDCPZ-UHFFFAOYSA-N 0.000 description 1
- RPLXIHLWKOHKTH-UHFFFAOYSA-N C(CCC)OCCOCCOCC(=C)C1=CC(=CC=C1)C(=C)COCCOCCOCCCC Chemical compound C(CCC)OCCOCCOCC(=C)C1=CC(=CC=C1)C(=C)COCCOCCOCCCC RPLXIHLWKOHKTH-UHFFFAOYSA-N 0.000 description 1
- CDEZDQBRWHOYBB-UHFFFAOYSA-N C(CCC)OCCOCCOCC(=C)C1=CC=C(C=C1)C(=C)COCCOCCOCCCC Chemical compound C(CCC)OCCOCCOCC(=C)C1=CC=C(C=C1)C(=C)COCCOCCOCCCC CDEZDQBRWHOYBB-UHFFFAOYSA-N 0.000 description 1
- CJSFINJLBWLJDB-UHFFFAOYSA-N CCCOC=C(C)C1=CC=CC(C(C)=COCCCOC)=C1 Chemical compound CCCOC=C(C)C1=CC=CC(C(C)=COCCCOC)=C1 CJSFINJLBWLJDB-UHFFFAOYSA-N 0.000 description 1
- HNLRVVDMPVAHGE-UHFFFAOYSA-N COCC(C)OCC(C)OCC(=C)C1=CC(=CC=C1)C(=C)COC(COC(COC)C)C Chemical compound COCC(C)OCC(C)OCC(=C)C1=CC(=CC=C1)C(=C)COC(COC(COC)C)C HNLRVVDMPVAHGE-UHFFFAOYSA-N 0.000 description 1
- SDFJSAMMAVHPJE-UHFFFAOYSA-N COCCOCCOCC(=C)C1=CC(=CC=C1)C(=C)COCCOCCOC Chemical compound COCCOCCOCC(=C)C1=CC(=CC=C1)C(=C)COCCOCCOC SDFJSAMMAVHPJE-UHFFFAOYSA-N 0.000 description 1
- JRCMHHCEFSABOP-UHFFFAOYSA-N COCCOCCOCCOCC(=C)C1=CC(=CC=C1)C(COCCOCCOCCOC)=C Chemical compound COCCOCCOCCOCC(=C)C1=CC(=CC=C1)C(COCCOCCOCCOC)=C JRCMHHCEFSABOP-UHFFFAOYSA-N 0.000 description 1
- MCBFDZJPINIRSZ-UHFFFAOYSA-N COCCOCCOCCOCC(=C)C1=CC=C(C=C1)C(COCCOCCOCCOC)=C Chemical compound COCCOCCOCCOCC(=C)C1=CC=C(C=C1)C(COCCOCCOCCOC)=C MCBFDZJPINIRSZ-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 239000013058 crude material Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000132 electrospray ionisation Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- JXHZRQHZVYDRGX-UHFFFAOYSA-M sodium;hydrogen sulfate;hydrate Chemical compound [OH-].[Na+].OS(O)(=O)=O JXHZRQHZVYDRGX-UHFFFAOYSA-M 0.000 description 1
- KKVTYAVXTDIPAP-UHFFFAOYSA-M sodium;methanesulfonate Chemical compound [Na+].CS([O-])(=O)=O KKVTYAVXTDIPAP-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/164—Unsaturated ethers containing six-membered aromatic rings
- C07C43/166—Unsaturated ethers containing six-membered aromatic rings having unsaturation outside the aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
Definitions
- AROMATIC ENOL ETHERS FIELD OF THE INVENTION This application relates to chemistry generally. In particular, this application relates to enol ethers and more particularly to aromatic enol ethers. BACKGROUND OF THE INVENTION [0002]
- Enol ethers are useful in a variety of chemical applications such as plasticizers, diluents, wetting agents and paint additives and as intermediates in chemical processes. Plasticizers, diluents, wetting agents and paint additives often are volatile and evaporate into the atmosphere during use. For example, coalescing aids that are added to water-based paints, aid in film formation in latex emulsions.
- the present application relates to an enol ether compound according to Formula I: wherein: A is (C 8-20 ) alkylaryl; R 1a and R 1b are independently (C 1-12 )alkyl, (C 2-12 )alkenyl, (C 3- 8 )cycloalkyl, or 5- to 9-membered aryl or each R 4 is independently (C 1-12 )alkyl, or -C(O)R 5 ; each R 5 is (C 1-12 )alkyl unsubstituted or substituted by R 6 , (C 2-12 )alkenyl unsubstituted or substituted by R 6 , (C 3-8 )cycloalkyl, or 5- to 9- membered aryl; each R 6 is (C 1-4 )alkoxy, or oxo; and each n is independently an integer from 1 to 15 or each R 7 is independently (C 1-12 )alkyl each z is an integer from 1 to 4.
- Alkenyl means an aliphatic hydrocarbon with one or more unsaturated carbon-carbon bonds.
- the alkenyl can specify the number of carbon atoms, for example (C2-12)alkenyl.
- the alkyl group can be unbranched or branched. In some embodiments, the alkyl group is branched. In some embodiments, the alkyl group is unbranched.
- Non-limiting examples of alkanes include ethenyl, propenyl, butenyl, hexa-3,5- dienyl, and the like.
- Alcohol means a chemical containing one or more hydroxyl groups.
- Aldehyde means a chemical containing one or more -C(O)H groups.
- Cycloalkyl means a cyclic hydrocarbon compound. The cycloalkyl can specify the number of carbon atoms in ring system, for example (C3- 8)cycloalkyl. Non-limiting examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclohexyl, and cyclooctyl.
- Aryl means a ring system made up carbon atoms that has at least one ring that is aromatic. The carbon units making up the aryl ring may be specified, for example 5- to 9-membered aryl.
- Non-limiting examples of aryl include phenyl, naphthyl, 2,3-dihydro-1H-indene, and 1,2,3,4- tetrahydronaphthalene.
- Values may be expressed as “about” or “approximately” a given number.
- ranges may be expressed herein as from “about” one particular value and/or to “about” or another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value.
- values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect.
- the terms “a,” “an,” and “the” mean one or more.
- the term “and/or,” when used in a list of two or more items means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed. For example, if a compound is described as containing components A, B, and/or C, the compound can contain A alone; B alone; C alone; A and B in combination; A and C in combination, B and C in combination; or A, B, and C in combination.
- the invention is a compound according to Formula I: wherein: A is (C 8-20 ) alkylaryl; R 1a and R 1b are independently (C 1-12 )alkyl, (C 2-12 )alkenyl, (C 3- 8)cycloalkyl, or 5- to 9-membered aryl or each R 4 is independently (C 1-12 )alkyl, or -C(O)R 5 ; each R 5 is (C 1-12 )alkyl unsubstituted or substituted by R 6 , (C 2-12 )alkenyl unsubstituted or substituted by R 6 , (C 3-8 )cycloalkyl, or 5- to 9- membered aryl; each R 6 is (C 1-4 )alkoxy, or oxo; and each n is independently an integer from 1 to 15 or each R 7 is independently (C 1-12 )alkyl.
- a in Formulas I is 1,2-, 1,3-, or 1,4- disubstituted phenyl.
- each n is an integer from 1 to 3.
- each R 4 is hydrogen.
- each R 4 is (C 1-12 )alkyl.
- each R 4 is independently ethyl.
- each R 4 is (C2-12)alkenyl.
- each R 4 is -C(O)R 5 .
- each R 5 is (C 1-12 )alkyl unsubstituted or substituted by R 6 .
- each R 5 is (C 1- 12 )alkenyl unsubstituted or substituted by R 6 . In some embodiments, each R 5 is (C 3-8 )cycloalkyl. In some embodiments, each R 5 is 5- to 9-membered aryl. [0025] In some embodiments of Formulas I each n is an integer from 1 to 2. In some embodiments, each n is an integer from 1 to 3. In some embodiments, each n is an integer from 1 to 4. In some embodiments, each n is an integer from 1 to 5. In some embodiments, n is an integer from 1 to 6. In some embodiments, n is an integer from 1 to 7. In some embodiments, n is an integer from 1 to 8.
- a in Formulas I is 1,2-, 1,3-, or 1,4- disubstituted phenyl.
- each n is an integer from 1 to 3.
- each R 4 is hydrogen.
- each R 4 is (C 1-12 )alkyl.
- each R 4 is independently ethyl.
- each R 4 is (C2-12)alkenyl.
- each R 4 is -C(O)R 5 .
- each R 5 is (C 1-12 )alkyl unsubstituted or substituted by R 6 .
- Reactive film-hardening compounds react with components in coating compositions to form crosslinks in the films providing improved film properties.
- the enol ether compounds of this invention can be used as reactive film-hardening additives, we mean when added to a coating composition, that a harder film is obtained upon curing the composition than is obtained in the absence of the invention enol ether additives, or that the coating composition exhibits a higher gel fraction than in the absence of the enol ether additive, or that both coating composition hardness and increased gel fraction properties are improved by the addition of the enol ether reactive film-hardening additives.
- the increase in hardness observed in a coating that contains the enol ether additives described herein may be the result of a chemical reaction, so that the additives described herein may be described as “reactive” enol ether film-hardening additives.
- the enol ether materials described herein can also facilitate the individual latex particles coming together to form a continuous film at a given temperature by reducing the minimum film-forming temperature (MFFT) of the latex polymer.
- the enol ethers of the present invention are expected to have particular utility in latex coating compositions such as in acrylic polymer, vinyl acrylic polymer, styrene butadiene polymer and styrene acrylic latex polymer compositions, and mixtures thereof.
- the enol ethers of the present invention are expected to have particular utility in latex coating compositions including, but not limited to styrene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2- ethylhexyl acrylate, isoprene, octyl acrylate, octyl methacrylate, iso-octyl acrylate, iso-octyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, O-methyl styrene, vinyl naphthalene, vinyl toluene, chloromethyl st
- the compounds of Formula I are enol ethers represented by Formulas 20-93: and isomers thereof.
- the enol ethers depicted by Formulas 20-93 are representative of the enol ethers claimed herein. Isomers of the enol ethers depicted by Formulas 20-93 are expected to be produced during synthesis of the enol ethers depicted by Formulas 20-93. All isomers of the enol ethers depicted by Formulas 20-93 and are within the scope of the claims set forth herein.
- the compounds depicted by Formulas I include those having a weight percent volatile content of less than 50%, as measured according to ASTM Method D6886. This test may be conducted generally by heating the sample in a forced air oven at 110°C. for 60 minutes. The weight loss after the test is deemed to result from a loss of volatiles originally present in the sample; the percent volatile present in the original sample may then be calculated. Although the cited test can be conducted on coating compositions containing other components such as latex polymers, the values cited herein may be obtained from a sample of the additive itself.
- the weight percent volatile of a film-hardening aid may be used herein as a yardstick to measure the amount of VOC the additive would contribute to the VOC in a particular end use such as a component of a coating composition.
- EXAMPLES [0040] This invention can be further illustrated by the following examples thereof, although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated. In particular more than one method to make enol ethers is available to the skilled artisan. Methods A, B, and C are described herein.
- mL is milliliter; wt % is weight percent; eq is equivalent(s); hrs or h is hour(s); mm is millimeter; m is meter; GC is gas chromatography;°C is degree Celsius; min is minute; t R is retention time; VOC is volatile organic compound; MeP is methyl palmitate; w/v is weight/volume; ⁇ L is microliter.
- RFHA reactive film-hardening additive.
- Dicarbinol 3 was prepared in a similar manner to di-carbinol 2 using procedure described in Method A. [LC-MS (Column B) tR : 4.55 min, 4.68 min (Exact mass: 254.15 m/z, found 254.2 m/z)]. Di-aldehyde 4 was prepared in a similar manner to di-aldehyde 2 using Method A. GC-MS t R : 14.22 min (Exact mass: 190.10 m/z, found: 190.1 m/z).
- Example 1 Preparation of (E,E/Z,Z) - 1,4-bis(1-(2-butoxyethoxy)prop-1- en-2-yl)benzene [5] GC-MS t R : 22.83 min, 24.34 min, 26.08 min (Exact mass: 390.28 m/z, found 390.3 m/z).
- Example 2 Preparation of (E,E/Z,Z) - 1,4-bis(1-((1-((1-methoxypropan-2- yl)oxy)propan-2-yl)oxy)prop-1-en-2-yl)benzene
- GC-MS t R 25.8 min, 26.2 min, 28.3 min, 28.9 min (Exact mass: 450.30 m/z, found 450 m/z).
- Method B [0046] To a 4-necked round-bottom flask fitted with an overhead stirrer, thermocouple, and nitrogen inlet was added acetic anhydride (5 equiv.) and sodium bisulfate monohydrate (0.025 equiv.).
- the mixture was then heated to 65 °C and held for 30 minutes.
- the dicarbinol was then added dropwise over the course of 4-5 hrs via a pressure-equalizing addition funnel. Once the addition was complete, the reaction was checked by GC. Once complete, the mix was transferred to a 1-neck round-bottom flask and the excess acetic anhydride/acetic acid was removed under reduced pressure using a rotary evaporatory.
- the crude was taken up in toluene.
- the organics were then washed with 10% caustic (x2) solution and then 5% ammonium hydroxide solution.
- the mixture was dried with MgSO 4 and simultaneously treated with activated carbon. After filtration, the volatiles were removed under reduced pressure using a rotary evaporator.
- Example 3 A mixture of (E,E/Z,Z) - 1,4-bis(1-((1-((1-methoxypropan-2- yl)oxy)propan-2-yl)oxy)prop-1-en-2-yl)benzene [6a], (E,Z) - 1-(1-((1-((1- methoxypropan-2-yl)oxy)propan-2-yl)oxy)prop-1-en-2-yl)-4-(3-((1-((1- methoxypropan-2-yl)oxy)propan-2-yl)oxy)prop-1-en-2-yl)benzene [6b], and 1,4-bis(3-((1-((1-methoxypropan-2-yl)oxy)propan-2-yl)
- Example 4 A mixture of (E,E/Z,Z) - 1,4-bis(4,7,10-trimethyl-2,5,8,11- tetraoxatetradec-12-en-13-yl)benzene [7a], (E,Z) - 4,7,10-trimethyl-13-(4- (4,7,10-trimethyl-2,5,8,11-tetraoxatetradec-13-en-13-yl)phenyl)-2,5,8,11- tetraoxatetradec-12-ene [7b], and 1,4-bis(4,7,10-trimethyl-2,5,8,11- tetraoxatetradec-13-en-13-yl)benzene [7c] GC-MS t R : 43.08 (broad peak), 69.53 min (broad peak) (Exact mass: 566.38 m/z, found: 566.5 m/z).
- Example 5 A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- methoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [8a], (E,Z) - 1-(1-(2-(2- methoxyethoxy)ethoxy)prop-1-en-2-yl)-4-(3-(2-(2- methoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [8b], and 1,4-bis(3-(2-(2- methoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [8c] GC-MS t R : 23.9 min, 24.29 min, 24.48 min, 25.64 min, 25.96 min, 27.63 min (Exact mass: 394.24 m/z, found: 394.3 m/z).
- Example 6 a mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- ethoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [9a], (E/Z) - 1-(1-(2-(2- ethoxyethoxy)ethoxy)prop-1-en-2-yl)-4-(3-(2-(2- ethoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [9b], and 1,4-bis(3-(2-(2- ethoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [9c].
- Example 7 A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [10a], (E,Z) - 1-(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)-4-(3-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [10b], 1,4-bis(3-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [10c].
- Example 8 A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [11a], (E,Z) - 1-(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)-4-(3-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [11b], 1,4-bis(3-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [11c].
- Example 9 A mixture of (E,E/Z,Z) - 1,4-di(2,5,8,11-tetraoxatetradec-12- en-13-yl)benzene [12a], (E,Z) - 13-(4-(2,5,8,11-tetraoxatetradec-13-en-13- yl)phenyl)-2,5,8,11-tetraoxatetradec-12-ene [12b], and 1,4-di(2,5,8,11- tetraoxatetradec-13-en-13-yl)benzene [12c].
- Example 10 A mixture of (E,E/Z,Z) - 1,3-bis(1-((1-((1-methoxypropan-2- yl)oxy)propan-2-yl)oxy)prop-1-en-2-yl)benzene [13a], (E/Z) - 1-(1-((1-((1- methoxypropan-2-yl)oxy)propan-2-yl)oxy)prop-1-en-2-yl)-3-(3-((1-((1- methoxypropan-2-yl)oxy)propan-2-yl)oxy)prop-1-en-2-yl)benzene [13b], and 1,3-bis(3-((1-((1-methoxypropan-2-yl)
- Example 11 A mixture of (E,E/Z,Z) - 1,3-bis(4,7,10-trimethyl-2,5,8,11- tetraoxatetradec-12-en-13-yl)benzene [14a], (E/Z) - 4,7,10-trimethyl-13-(3- (4,7,10-trimethyl-2,5,8,11-tetraoxatetradec-13-en-13-yl)phenyl)-2,5,8,11- tetraoxatetradec-12-ene [14b], and 1,3-bis(4,7,10-trimethyl-2,5,8,11- tetraoxatetradec-13-en-13-yl)benzene [14c]
- Example 12 A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- methoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [15a], (E/Z) - 1-(1-(2-(2- methoxyethoxy)ethoxy)prop-1-en-2-yl)-3-(3-(2-(2- methoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [15b], 1,3-bis(3-(2-(2- methoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [15c].
- Example 13-1 and Example 13-2 A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- ethoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [16a], (E/Z) - 1-(1-(2-(2- ethoxyethoxy)ethoxy)prop-1-en-2-yl)-3-(3-(2-(2- ethoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [16b], and 1,3-bis(3-(2-(2- ethoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [16c].
- Example 14 A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [17a], (E/Z) - 1-(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)-3-(3-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [17b], and 1,3-bis(3-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [17c]
- Example 15 A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [18a], (E/Z) - 1-(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)-3-(3-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [18b], and 1,3-bis(3-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [18c].
- Example 16 A mixture of (E,E/Z,Z) - 1,3-di(2,5,8,11-tetraoxatetradec-12- en-13-yl)benzene [19a], (E/Z) - 13-(3-(2,5,8,11-tetraoxatetradec-13-en-13- yl)phenyl)-2,5,8,11-tetraoxatetradec-12-ene [19b], and 1,3-di(2,5,8,11- tetraoxatetradec-13-en-13-yl)benzene [19c].
- the mixture was sparged (sub- surface) with nitrogen at a flow rate of 250 mL/min. The system was then pulled under vacuum. The reaction mixture was heated to 75°C. The lower- boiling alcohol component was continuously removed from the reaction to facilitate water-removal. Over the course of the reaction, fresh lower-boiling alcohol component was added back to the reaction flask such that the liquid volume was maintained up to the marked liquid level on the flask.
- GC and NMR confirmed >99.5% conversion of aldehyde
- the reaction mixture was cooled to ambient temperature and then diluted with a minimal amount of toluene. This mixture was then poured into water containing 1.25 equiv. of NaOH. The layers were separated and the organics were washed with water three times.
- Example 17 A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [10], (E,E/Z,Z) - 1-(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)-4-(1-propoxyprop-1-en-2- yl)benzene [23], and (E,E/Z,Z) - 1,4-bis(1-propoxyprop-1-en-2-yl)benzene [20] GC-MS t R : 29.61 min, 33.23 min, 37.51 min (10, Exact mass: 450.3 m/z, found: 450.4 m/z), 20.85 min, 21.57 min, 21.83 min, 22.75 min (23, Exact mass: 362.2 m/z, found: 362.3 m/z), 17.20 min, 17.52 min, 17.83 min (20, Exact mass: 27
- Example 18 A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [10], (E,E/Z,Z) - 1-(1- butoxyprop-1-en-2-yl)-4-(1-(2-(2-propoxyethoxy)ethoxy)prop-1-en-2- yl)benzene [24], and (E,E/Z,Z) - 1,4-bis(1-butoxyprop-1-en-2-yl)benzene [21]
- Example 19 A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [10], (E,E/Z,Z) - 1-(1- isobutoxyprop-1-en-2-yl)-4-(1-(2-(2-propoxyethoxy)ethoxy)prop-1-en-2- yl)benzene [25], and (E,E/Z,Z) - 1,4-bis(1-isobutoxyprop-1-en-2- yl)benzene [22] GC-MS t R : 29.60 min, 33.18 min, 37.48 min (10, Exact mass: 450.3 m/z, found: 450.4 m/z), 21.17 min, 22.28 min, 23.51 min (25, Exact mass: 376.3 m/z, found: 376.3 m/z), 17.58 min, 18.06 min, 18.55 min (22, Exact mass:
- Example 20 A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- isopropoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [44], (E,E/Z,Z) - 1-(1-(2- (2-isopropoxyethoxy)ethoxy)prop-1-en-2-yl)-4-(1-propoxyprop-1-en-2- yl)benzene [26], and (E,E/Z,Z) - 1,4-bis(1-propoxyprop-1-en-2-yl)benzene [20] GC-MS t R : 27.02 min, 29.68 min, 32.85 min (44, Exact mass: 450.3 m/z, found: 450.4 m/z), 20.32 min, 21.01 min, 21.23 min, 21.98 min (26, Exact mass: 362.2 m/z, found: 362.3 m/z), 17.17 min, 17.55 min, 17.84 min (20,
- Example 21 A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- isopropoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [44], (E,E/Z,Z) - 1-(1- butoxyprop-1-en-2-yl)-4-(1-(2-(2-isopropoxyethoxy)ethoxy)prop-1-en-2- yl)benzene [27], and (E,E/Z,Z) - 1,4-bis(1-butoxyprop-1-en-2-yl)benzene [21] GC-MS t R : 26.94 min, 29.67 min, 32.88 min (44, Exact mass: 450.3 m/z, found: 450.4 m/z), 21.08 min, 22.19 min, 23.43 min (27, Exact mass: 376.3 m/z, found: 376.3 m/z), 18.14 min, 18.68 min, 19.22 min (21, Exact mass:
- Example 22 A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- isopropoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [44], (E,E/Z,Z) - 1-(1- isobutoxyprop-1-en-2-yl)-4-(1-(2-(2-isopropoxyethoxy)ethoxy)prop-1-en- 2-yl)benzene [28], and (E,E/Z,Z) - 1,4-bis(1-isobutoxyprop-1-en-2- yl)benzene [22] GC-MS t R : 27.00 min, 29.67 min, 32.92 min (44, Exact mass: 450.3 m/z, found: 450.4 m/z), 20.59 min, 21.61 min, 21.74 min, 22.71 min (28, Exact mass: 376.3 m/z, found: 376.3 m/z), 17.63 min, 18.06 min, 18.55
- Example 23 A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [11], (E,E/Z,Z) - 1-(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)-4-(1-propoxyprop-1-en-2- yl)benzene [29], and (E,E/Z,Z) - 1,4-bis(1-propoxyprop-1-en-2-yl)benzene [20]
- Example 24 A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [11], (E,E/Z,Z) - 1-(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)-4-(1-butoxyprop-1-en-2-yl)benzene [30], and (E,E/Z,Z) - 1,4-bis(1-butoxyprop-1-en-2-yl)benzene [21] GC-MS t R : 35.97 min, 41.73 min, 48.77 min (11, Exact mass: 478.3 m/z, found: 478.4 m/z), 22.88 min, 24.29 min, 24.45 min, 26.14 min (30, Exact mass: 390.3 m/z, found: 390.3 m/z), 18.15 min, 18.68 min, 19.22 min (21, Ex
- Example 25 A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [11], (E,E/Z,Z) - 1-(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)-4-(1-isobutoxyprop-1-en-2- yl)benzene [31], and (E,E/Z,Z) - 1,4-bis(1-isobutoxyprop-1-en-2- yl)benzene [22] GC-MS t R : 36.01 min, 41.71 min, 48.67 min (11, Exact mass: 478.3 m/z, found: 478.4 m/z), 22.21 min, 23.51 min, 23.63 min, 25.13 min (31, Exact mass: 390.3 m/z, found: 390.3 m/z), 17.60 min, 18.08 min,
- Example 26 A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [17], (E,E/Z,Z) - 1-(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)-3-(1-propoxyprop-1-en-2- yl)benzene [35], and (E,E/Z,Z) - 1,3-bis(1-propoxyprop-1-en-2-yl)benzene [32] GC-MS t R : 27.34 min, 29.70 min, 32.94 min (17, Exact mass: 450.3 m/z, found: 450.4 m/z), 20.09 min, 20.60 min, 20.88 min, 21.58 min (35, Exact mass: 362.2 m/z, found: 362.3 m/z),16.80 min, 17.16 min, 17.46 min (32, Exact mass
- Example 27 A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [17] (E,E/Z,Z) - 1-(1- butoxyprop-1-en-2-yl)-3-(1-(2-(2-propoxyethoxy)ethoxy)prop-1-en-2- yl)benzene [36], and (E,E/Z,Z) - 1,3-bis(1-butoxyprop-1-en-2-yl)benzene [33] GC-MS t R : 27.35 min, 29.69 min, 32.96 min (17, Exact mass: 450.3 m/z, found: 450.4 m/z), 20.79 min, 21.62 min, 21.77 min, 22.84 min (36, Exact mass: 376.3 m/z, found: 376.3 m/z), 17.71 min, 18.18 min, 18.68 min (33, Exact mass:
- Example 28 A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [17], (E,E/Z,Z) - 1-(1- isobutoxyprop-1-en-2-yl)-3-(1-(2-(2-propoxyethoxy)ethoxy)prop-1-en-2- yl)benzene [37], and (E,E/Z,Z) - 1,3-bis(1-isobutoxyprop-1-en-2- yl)benzene [34]
- Example 29 A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- isopropoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [45], (E,E/Z,Z) - 1-(1-(2- (2-isopropoxyethoxy)ethoxy)prop-1-en-2-yl)-3-(1-propoxyprop-1-en-2- yl)benzene [38], and (E,E/Z,Z) - 1,3-bis(1-propoxyprop-1-en-2-yl)benzene [32] GC-MS t R : 25.17 min, 26.96 min, 29.48 min (45, Exact mass: 450.3 m/z, found: 450.4 m/z), 19.66 min, 20.12 min, 20.38 min, 20.98 min (38, Exact mass: 362.2 m/z, found: 362.3 m/z), 16.79 min, 17.13 min, 17.45 min (32,
- Example 30 A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- isopropoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [45], (E,E/Z,Z) - 1-(1- butoxyprop-1-en-2-yl)-3-(1-(2-(2-isopropoxyethoxy)ethoxy)prop-1-en-2- yl)benzene [39], and (E,E/Z,Z) - 1,3-bis(1-butoxyprop-1-en-2-yl)benzene [33] GC-MS t R : 25.16 min, 26.91 min, 29.46 min (45, Exact mass: 450.3 m/z, found: 450.4 m/z), 20.29 min, 21.07 min, 21.19 min, 22.14 min (39, Exact mass: 376.3 m/z, found: 376.3 m/z), 17.67 min, 18.17 min, 18.67 min (33
- Example 31 A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- isopropoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [45], (E,E/Z,Z) - 1-(1- isobutoxyprop-1-en-2-yl)-3-(1-(2-(2-isopropoxyethoxy)ethoxy)prop-1-en- 2-yl)benzene [40], and (E,E/Z,Z) - 1,3-bis(1-isobutoxyprop-1-en-2- yl)benzene [34] GC-MS t R : 25.18 min, 26.96 min, 29.51 min (45, Exact mass: 450.3 m/z, found: 450.4 m/z), 19.88 min, 20.58 min, 20.70 min, 21.54 min (40, Exact mass: 376.3 m/z, found: 376.3 m/z), 17.16 min, 17.63 min, 18.05
- Example 32 A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [18], (E,E/Z,Z) - 1-(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)-3-(1-propoxyprop-1-en-2- yl)benzene [41], and (E,E/Z,Z) - 1,3-bis(1-propoxyprop-1-en-2-yl)benzene [32] GC-MS t R : 32.75 min, 36.17 min, 41.29 min (18, Exact mass: 478.3 m/z, found: 478.4 m/z), 20.95 min, 21.58 min, 21.95 min, 22.72 min (41, Exact mass: 376.3 m/z, found: 376.3 m/z), 16.82 min, 17.16 min, 17.48 min (32,
- Example 33 A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [18], (E,E/Z,Z) - 1-(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)-3-(1-butoxyprop-1-en-2-yl)benzene [42], and (E,E/Z,Z) - 1,3-bis(1-butoxyprop-1-en-2-yl)benzene [33]
- Example 34 A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [18], (E,E/Z,Z) - 1-(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)-3-(1-isobutoxyprop-1-en-2- yl)benzene [43], and (E,E/Z,Z) - 1,3
- Example 35 A mixture of (E,E/Z,Z) - 1,4-bis(1-((1-methoxypropan-2- yl)oxy)prop-1-en-2-yl)benzene [46], (E,E/Z,Z) - 1-(1-((1-methoxypropan-2- yl)oxy)prop-1-en-2-yl)-4-(1-propoxyprop-1-en-2-yl)benzene [47], and (E,E/Z,Z) - 1,4-bis(1-propoxyprop-1-en-2-yl)benzene [20] GC-MS t R : 19.77 min (46, Exact mass: 334.2 m/z, found: 334.2 m/z),18.28 min, 18.41 min, 18.69 min (47, Exact mass: 304.2 m/z, found: 304.1 m/z), 17.23 min, 17.49 min, 17.64 min (20, Exact mass: 274.2 m/z, found: 274.2 m
- Example 36 A mixture of (E,E/Z,Z) - 1,4-bis(1-((1-methoxypropan-2- yl)oxy)prop-1-en-2-yl)benzene [46], (E,E/Z,Z) - 1-(1-butoxyprop-1-en-2-yl)- 4-(1-((1-methoxypropan-2-yl)oxy)prop-1-en-2-yl)benzene [48], and (E,E/Z,Z) - 1,4-bis(1-butoxyprop-1-en-2-yl)benzene [21] GC-MS t R : 19.79 min (46, Exact mass: 334.2 m/z, found: 334.2 m/z), 18.88 min, 18.95 min, 19.04 min, 19.50 min (48, Exact mass: 318.2 m/z, found: 318.2 m/z), 18.16 min, 18.70 min, 19.20 min (21, Exact mass: 302.2 m/z
- Example 37 (E,E/Z,Z) - 1,4-bis(1-((1-methoxypropan-2-yl)oxy)prop-1-en- 2-yl)benzene [46], (E,E/Z,Z) - 1-(1-isobutoxyprop-1-en-2-yl)-4-(1-((1- methoxypropan-2-yl)oxy)prop-1-en-2-yl)benzene [49], and (E,E/Z,Z) - 1,4- bis(1-isobutoxyprop-1-en-2-yl)benzene [22] GC-MS t R : 19.77 min (46, Exact mass: 334.2 m/z, found: 334.2 m/z), 18.15 min, 18.24 min, 18.69 min, 19.40 min (49, Exact mass: 318.2 m/z, found: 318.2 m/z), 17.58 min, 17.64 min (22, Exact mass: 302.2 m/z, found: 30
- Example 38 A mixture of (E,E/Z,Z) - 1,3-bis(1-((1-methoxypropan-2- yl)oxy)prop-1-en-2-yl)benzene [50], (E,E/Z,Z) - 1-(1-((1-methoxypropan-2- yl)oxy)prop-1-en-2-yl)-3-(1-propoxyprop-1-en-2-yl)benzene [51], and (E,E/Z,Z) - 1,3-bis(1-propoxyprop-1-en-2-yl)benzene [32]
- Example 39 A mixture of (E,E/Z,Z) - 1,3-bis(1-((1-methoxypropan-2- yl)oxy)prop-1-en-2-yl)benzene [50], (E,E/Z,Z) - 1-(1-butoxyprop-1-en-2-yl)- 3-(1-((1-methoxypropan-2-yl)oxy)prop-1-en-2-yl)benzene [52], and (E,E/Z,Z) - 1,3-bis(1-butoxyprop-1-en-2-yl)benzene [33] GC-MS t R : 19.06 min (50, Exact mass: 334.2 m/z, found: 334.2 m/z), 17.86 min, 18.37 min, 18.91 min (52, Exact mass: 318.2 m/z, found: 318.2 m/z), 17.68 min, 18.21 min, 18.73 min (33, Exact mass: 302.2 m/z, found: 30
- Example 40 A mixture of (E,E/Z,Z) - 1,3-bis(1-((1-methoxypropan-2- yl)oxy)prop-1-en-2-yl)benzene [50], (E,E/Z,Z) - 1-(1-isobutoxyprop-1-en-2- yl)-3-(1-((1-methoxypropan-2-yl)oxy)prop-1-en-2-yl)benzene [53], and (E,E/Z,Z) - 1,3-bis(1-isobutoxyprop-1-en-2-yl)benzene [34] GC-MS t R : 18.46 min, 19.07 min (50, Exact mass: 334.2 m/z, found: 334.2 m/z), 17.96 min (53, Exact mass: 318.2 m/z, found: 318.2 m/z), 17.14 min, 17.69 min (34, Exact mass: 302.2 m/z, found: 302.1 m
- Example 41 A mixture of (E,E/Z,Z) - 1,4-bis(1-(3-methoxypropoxy)prop- 1-en-2-yl)benzene [54], (E,E/Z,Z) - 1-(1-(3-methoxypropoxy)prop-1-en-2- yl)-4-(1-propoxyprop-1-en-2-yl)benzene [55], and (E,E/Z,Z) - 1,4-bis(1- propoxyprop-1-en-2-yl)benzene [20] GC-MS t R : 19.71 min, 20.54 min, 21.42 min (54, Exact mass: 334.2 m/z, found: 334.2 m/z), 18.31 min, 18.75 min, 18.90 min, 19.34 min (55, Exact mass: 304.2 m/z, found: 304.1 m/z), 17.19 min, 17.54 min, 17.83 min (20, Exact mass: 274.2 m/z, found: 274.1 m/z
- Example 42 A mixture of (E,E/Z,Z) - 1,4-bis(1-(3-methoxypropoxy)prop- 1-en-2-yl)benzene [54], (E,E/Z,Z) - 1-(1-butoxyprop-1-en-2-yl)-4-(1-(3- methoxypropoxy)prop-1-en-2-yl)benzene [56], and (E,E/Z,Z) - 1,4-bis(1- butoxyprop-1-en-2-yl)benzene [21] GC-MS t R : 19.71 min, 20.51 min, 21.41 min (54, Exact mass: 334.2 m/z, found: 334.2 m/z), 18.87 min, 19.50 min, 20.22 min (56, Exact mass: 318.2 m/z, found: 318.2 m/z), 18.14 min, 18.69 min, 19.24 min (21, Exact mass: 302.2 m/z, found: 302.1 m/
- Example 43 (E,E/Z,Z) - 1,4-bis(1-(3-methoxypropoxy)prop-1-en-2- yl)benzene [54], (E,E/Z,Z) - 1-(1-isobutoxyprop-1-en-2-yl)-4-(1-(3- methoxypropoxy)prop-1-en-2-yl)benzene [57], and (E,E/Z,Z) - 1,4-bis(1- isobutoxyprop-1-en-2-yl)benzene [22]
- Example 44 A mixture of (E,E/Z,Z) - 1,3-bis(1-(3-methoxypropoxy)prop- 1-en-2-yl)benzene [58], 1-(1-(3-methoxypropoxy)prop-1-en-2-yl)-3-(1- propoxyprop-1-en-2-yl)benzene [59], and (E,E/Z,Z) - 1,3-bis(1- propoxyprop-1-en-2-yl)benzene [32] GC-MS t R : 19.05 min, 19.74 min, 20.53 min (58, Exact mass: 334.2 m/z, found: 334.2 m/z), 17.83 min, 18.19 min, 18.36 min, 18.75 min (59, Exact mass: 304.2 m/z, found: 304.1 m/z), 16.73 min, 17.14 min, 17.42 min (32, Exact mass: 274.2 m/z, found: 274.1 m/z).
- Example 45 A mixture of (E,E/Z,Z) - 1,3-bis(1-(3-methoxypropoxy)prop- 1-en-2-yl)benzene [58], (E,E/Z,Z) - 1-(1-butoxyprop-1-en-2-yl)-3-(1-(3- methoxypropoxy)prop-1-en-2-yl)benzene [60], and (E,E/Z,Z) - 1,3-bis(1- butoxyprop-1-en-2-yl)benzene [33] GC-MS t R : 19.06 min, 19.72 min, 20.53 min (58, Exact mass: 334.2 m/z, found: 334.2 m/z), 18.33 min, 18.86 min, 18.89 min, 19.50 min (60, Exact mass: 318.2 m/z, found: 318.2 m/z), 17.65 min, 18.15 min, 18.68 min (33, Exact mass: 302.2 m/z, found: 302.1
- Example 46 A mixture of (E,E/Z,Z) - 1,3-bis(1-(3-methoxypropoxy)prop- 1-en-2-yl)benzene [58], (E,E/Z,Z) - 1-(1-isobutoxyprop-1-en-2-yl)-3-(1-(3- methoxypropoxy)prop-1-en-2-yl)benzene [61], and (E,E/Z,Z) - 1,3-bis(1- isobutoxyprop-1-en-2-yl)benzene [34] GC-MS t R : 19.06 min, 19.74 min, 20.51 min (58, Exact mass: 334.2 m/z, found: 334.2 m/z), 18.06 min, 18.55 min, 18.58 min, 19.15 min (61, Exact mass: 318.2 m/z, found: 318.2 m/z), 17.11 min, 17.61 min, 18.04 min (34, Exact mass: 302.2 m/z, found
- Example 47 A mixture of (E,E/Z,Z) - 1,4-bis(1-(3-methoxybutoxy)prop-1- en-2-yl)benzene [62], (E,E/Z,Z) - 1-(1-(3-methoxybutoxy)prop-1-en-2-yl)-4- (1-propoxyprop-1-en-2-yl)benzene [63], and (E,E/Z,Z) - 1,4-bis(1- propoxyprop-1-en-2-yl)benzene [20] GC-MS t R : 20.25 min, 21.33 min, 22.72 min (62, Exact mass: 362.2 m/z, found: 362.3 m/z), 18.52 min, 18.94 min, 19.27 min, 19.75 min (63, Exact mass: 318.2 m/z, found: 318.2 m/z), 17.16 min, 17.54 min, 17.83 min (20, Exact mass: 274.2 m/z, found: 274.1
- Example 48 A mixture of (E,E/Z,Z) - 1,4-bis(1-(3-methoxybutoxy)prop-1- en-2-yl)benzene [62], (E,E/Z,Z) - 1-(1-butoxyprop-1-en-2-yl)-4-(1-(3- methoxybutoxy)prop-1-en-2-yl)benzene [64], and (E,E/Z,Z) - 1,4-bis(1- butoxyprop-1-en-2-yl)benzene [21]
- Example 49 (E,E/Z,Z) - 1,4-bis(1-(3-methoxybutoxy)prop-1-en-2- yl)benzene [62], (E,E/Z,Z) - 1-(1-isobutoxyprop-1-en-2-yl)-4-(1-(3- methoxybutoxy)prop-1-en-2-yl)benzene [65], and (E,E/Z,Z) - 1,4-bis(1- isobutoxyprop-1-en-2-yl)benzene [22] GC-MS t R : 20.29 min, 21.33 min, 22.74 min (62, Exact mass: 362.2 m/z, found: 362.3 m/z), 18.75 min, 19.34 min, 19.53 min, 20.22 min (65, Exact mass: 332.2 m/z, found: 332.3 m/z), 17.58 min, 18.06 min, 18.53 min (22, Exact mass: 302.2 m/z, found: 302.1
- Example 50 A mixture of (E,E/Z,Z) - 1,3-bis(1-(3-methoxybutoxy)prop-1- en-2-yl)benzene [66], (E,E/Z,Z) - 1-(1-(3-methoxybutoxy)prop-1-en-2-yl)-3- (1-propoxyprop-1-en-2-yl)benzene [67], and (E,E/Z,Z) - 1,3-bis(1- propoxyprop-1-en-2-yl)benzene [32] GC-MS t R : 19.52 min, 20.39 min, 21.54 min (66, Exact mass: 362.2 m/z, found: 362.3 m/z), 18.03 min, 18.40 min, 18.68 min, 19.09 min (67, Exact mass: 318.2 m/z, found: 318.2 m/z), 16.76 min, 17.09 min, 17.42 min (32, Exact mass: 274.2 m/z, found: 274.1
- Example 51 A mixture of (E,E/Z,Z) - 1,3-bis(1-(3-methoxybutoxy)prop-1- en-2-yl)benzene [66], (E,E/Z,Z) - 1-(1-butoxyprop-1-en-2-yl)-3-(1-(3- methoxybutoxy)prop-1-en-2-yl)benzene [68], and (E,E/Z,Z) - 1,3-bis(1- butoxyprop-1-en-2-yl)benzene [33] GC-MS t R : 19.52 min, 20.39 min, 21.54 min (66, Exact mass: 362.2 m/z, found: 362.3 m/z), 18.52 min, 19.08 min, 19.25 min, 19.89 min (68, Exact mass: 332.2 m/z, found: 332.3 m/z), 17.67 min, 18.15 min, 18.67 min (33, Exact mass: 302.2 m/z, found: 302.1 m/
- Example 52 A mixture of (E,E/Z,Z) - 1,3-bis(1-(3-methoxybutoxy)prop-1- en-2-yl)benzene [66], (E,E/Z,Z) - 1-(1-isobutoxyprop-1-en-2-yl)-3-(1-(3- methoxybutoxy)prop-1-en-2-yl)benzene [69], and (E,E/Z,Z) - 1,3-bis(1- isobutoxyprop-1-en-2-yl)benzene [34] GC-MS t R : 19.54 min, 20.42 min, 21.52 min (66, Exact mass: 362.2 m/z, found: 362.3 m/z), 18.21 min, 18.75 min, 18.93 min, 19.47 min (69, Exact mass: 332.2 m/z, found: 332.2 m/z), 17.11 min, 17.57 min, 18.05 min (34, Exact mass: 302.2 m/z, found:
- Example 53 A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-propoxyethoxy)prop-1- en-2-yl)benzene [70], (E,E/Z,Z) - 1-(1-(2-propoxyethoxy)prop-1-en-2-yl)-4- (1-propoxyprop-1-en-2-yl)benzene [71], and (E,E/Z,Z) - 1,4-bis(1- propoxyprop-1-en-2-yl)benzene [20]
- Example 54 A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-propoxyethoxy)prop-1- en-2-yl)benzene [70], (E,E/Z,Z) - 1-(1-butoxyprop-1-en-2-yl)-4-(1-(2- propoxyethoxy)prop-1-en-2-yl)benzene [72], and (E,E/Z,Z) - 1,4-bis(1- butoxyprop-1-en-2-yl)benzene [21] GC-MS t R : 20.76 min, 21.61 min, 22.64 min (70, Exact mass: 362.2 m/z, found: 362.3 m/z), 19.29 min, 19.94 min, 20.66 min(72, Exact mass: 332.2 m/z, found: 332.3 m/z), 18.11 min, 18.67 min, 19.22 min (21, Exact mass: 302.2 m/z, found: 302.1 m/z).
- Example 55 (E,E/Z,Z) - 1,4-bis(1-(2-propoxyethoxy)prop-1-en-2- yl)benzene [70], (E,E/Z,Z) - 1-(1-isobutoxyprop-1-en-2-yl)-4-(1-(2- propoxyethoxy)prop-1-en-2-yl)benzene [73], and (E,E/Z,Z) - 1,4-bis(1- isobutoxyprop-1-en-2-yl)benzene [22] GC-MS t R : 20.73 min, 21.58 min, 22.64 min (70, Exact mass: 362.2 m/z, found: 362.3 m/z), 18.91 min, 19.57 min, 20.20 min (73, Exact mass: 332.2 m/z, found: 332.3 m/z), 17.55 min, 18.06 min, 18.53 min (22, Exact mass: 302.2 m/z, found: 302.1 m/z).
- Example 56 A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-propoxyethoxy)prop-1- en-2-yl)benzene [74], (E,E/Z,Z) - 1-(1-(2-propoxyethoxy)prop-1-en-2-yl)-3- (1-propoxyprop-1-en-2-yl)benzene [75], and (E,E/Z,Z) - 1,3-bis(1- propoxyprop-1-en-2-yl)benzene [32] GC-MS t R : 19.92 min, 20.60 min, 21.51 min (74, Exact mass: 362.2 m/z, found: 362.3 m/z), 18.19 min, 18.56 min, 18.67 min, 19.10 min (75, Exact mass: 318.2 m/z, found: 318.2 m/z), 16.78 min, 17.11 min, 17.42 min (32, Exact mass: 274.2 m/z, found: 274.1 m
- Example 57 A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-propoxyethoxy)prop-1- en-2-yl)benzene [74], (E,E/Z,Z) -1-(1-butoxyprop-1-en-2-yl)-3-(1-(2- propoxyethoxy)prop-1-en-2-yl)benzene [76], and (E,E/Z,Z) - 1,3-bis(1- butoxyprop-1-en-2-yl)benzene [33] GC-MS t R : 19.95 min, 20.60 min, 21.49 min (74, Exact mass: 362.2 m/z, found: 362.3 m/z), 18.71 min, 19.24 min, 19.88 min(76, Exact mass: 332.2 m/z, found: 332.3 m/z), 17.67 min, 18.15 min, 18.64 min (33, Exact mass: 302.2 m/z, found: 302.1 m/z).
- Example 58 A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-propoxyethoxy)prop-1- en-2-yl)benzene [74], (E,E/Z,Z) - 1-(1-isobutoxyprop-1-en-2-yl)-3-(1-(2- propoxyethoxy)prop-1-en-2-yl)benzene [77], and (E,E/Z,Z) - 1,3-bis(1- isobutoxyprop-1-en-2-yl)benzene [34] GC-MS t R : 19.91 min, 20.59 min, 21.51 min (74, Exact mass: 362.2 m/z, found: 362.3 m/z), 18.37 min, 18.89 min, 19.52 min(77, Exact mass: 332.2 m/z, found: 33 m/z), 17.14 min, 17.58 min, 18.04 min (34, Exact mass: 302.2 m/z, found: 302.1 m/z).
- Example 59 A mixture of (E,E/Z,Z) - 1,4-bis(1-(4-methoxybutoxy)prop-1- en-2-yl)benzene [78], (E,E/Z,Z) - 1-(1-(4-methoxybutoxy)prop-1-en-2-yl)-4- (1-propoxyprop-1-en-2-yl)benzene [79], and (E,E/Z,Z) - 1,4-bis(1- propoxyprop-1-en-2-yl)benzene [20]
- Example 60 A mixture of (E,E/Z,Z) - 1,4-bis(1-(4-methoxybutoxy)prop-1- en-2-yl)benzene [78], (E,E/Z,Z) - 1-(1-butoxyprop-1-en-2-yl)-4-(1-(4- methoxybutoxy)prop-1
- Example 62 A mixture of (E,E/Z,Z) - 1,3-bis(1-(4-methoxybutoxy)prop-1- en-2-yl)benzene [82], (E,E/Z,Z) - 1-(1-(4-methoxybutoxy)prop-1-en-2-yl)-3- (1-propoxyprop-1-en-2-yl)benzene [83], and (E,E/Z,Z) - 1,3-bis(1- propoxyprop-1-en-2-yl)benzene [32]
- Example 63 A mixture of (E,E/Z,Z) - 1,3-bis(1-(4-methoxybutoxy)prop-1- en-2-yl)benzene [82], (E,E/Z,Z) -1-(1-butoxyprop-1-en-2-yl)-3-(1-(4- methoxybutoxy)prop-1-en-2-yl)benzene [84], and (E,E/Z,Z
- Example 67 (E,E/Z,Z) - 1,4-bis(1-(3-ethoxypropoxy)prop-1-en-2- yl)benzene [86], (E,E/Z,Z) - 1-(1-(3-ethoxypropoxy)prop-1-en-2-yl)-4-(1- isobutoxyprop-1-en-2-yl)benzene [89], and (E,E/Z,Z) - 1,4-bis(1- isobutoxyprop-1-en-2-yl)benzene [22]
- Example 68 A mixture of (E,E/Z,Z) - 1,3-bis(1-(3-ethoxypropoxy)prop-1- en-2-yl)benzene [90], (E,E/Z,Z) - 1-(1-(3-ethoxypropoxy)prop-1-en-2-yl)-3- (1-propoxyprop-1-en-2-yl)benzene [91], and (E,E/Z,
- Mass spectra were collected using electrospray ionization in both the positive-ion and negative ion modes.
- Ammonium acetate 50 mM in MeOH
- ES+/ES- scan range was 60- 3300 amu (25 and 75V).
- Methyl palmitate t R 16.6 min using the above method.
- compounds 58, 66 and 74 were compared against Texanol TM and Optifilm Enhancer 400 TM (OE 400) both available commercially from Eastman Chemical Company.
- MFFT efficiency testing was based on ASTM D2354. The model instrument used was an MFFT-90 bar which allows samples to be tested from -10°C to 90°C. For waterborne latexes, reaching a temperature of 2°C is the primary goal. To reach that temperature, the MFFT bar was set to range from 0°C to 18°C.
- Tg values for waterborne latexes somewhat correlate with their coinciding MFFT value.
- Neat commercial architectural latexes typically fall within this temperature range when testing for MFFT efficiency.
- the range can be adjusted accordingly to determine the film’s MFFT.
- the ultimate goal for the final paint is to form a continuous film at a low temperature (2°C). To achieve this, the MFFT of the neat latex material is first determined.
- the reactive film-hardening additive is added at different phr (% additive based on latex solids) levels to allow the latex to reach 2°C. To reach that temperature, a linear regression of the phr levels is performed. In turn, the appropriate amount of reactive film-hardening additive to add to the final paint formulation can be determined. The results are shown in Table 2 below:
Abstract
Disclosed are aromatic enol ether compounds that have utility as film- hardening additives for coating formulations. The aromatic enol ether compounds have particular utility as film-hardening additives for water-based coating formulations. The aromatic enol ether compounds provide improvements in hardness and hardness related properties such as block resistance, without contributing to the volatile organic content of the coating formulation.
Description
AROMATIC ENOL ETHERS FIELD OF THE INVENTION [0001] This application relates to chemistry generally. In particular, this application relates to enol ethers and more particularly to aromatic enol ethers. BACKGROUND OF THE INVENTION [0002] Enol ethers are useful in a variety of chemical applications such as plasticizers, diluents, wetting agents and paint additives and as intermediates in chemical processes. Plasticizers, diluents, wetting agents and paint additives often are volatile and evaporate into the atmosphere during use. For example, coalescing aids that are added to water-based paints, aid in film formation in latex emulsions. The coalescing aids lower the glass transition temperature (Tg) of the latex polymer and as the paint dries, the polymers that have been softened by the coalescing aid are allowed to flow together and form a film after the water has left the system. Coalescing aids that are volatile evaporate out of the film. This allows the polymer to return to the original Tg thereby giving harder films for better block and print resistant coatings. [0003] Due to environmental concerns, the use of volatile materials such as paint additives, plasticizers, diluents, wetting agents and coalescing aids are increasing undesirable. There is a need for materials that can be used as plasticizers, diluents, wetting agents and paint additives that exhibit low volatility. SUMMARY OF THE INVENTION [0004] The invention is set forth in the appended claims. [0005] The present application relates to an enol ether compound according to Formula I:
wherein: A is (C8-20) alkylaryl; R1a and R1b are independently (C1-12)alkyl, (C2-12)alkenyl, (C3- 8)cycloalkyl, or 5- to 9-membered aryl or
each R4 is independently (C1-12)alkyl, or -C(O)R5; each R5 is (C1-12)alkyl unsubstituted or substituted by R6, (C2-12)alkenyl unsubstituted or substituted by R6, (C3-8)cycloalkyl, or 5- to 9- membered aryl; each R6 is (C1-4)alkoxy, or oxo; and each n is independently an integer from 1 to 15 or
each R7 is independently (C1-12)alkyl. In another embodiment the present application relates to an enol ether compound according to Formula I:
wherein:
A is (C8-20) alkylaryl; R1a and R1b are independently (C1-12)alkyl, (C2-12)alkenyl, (C3- 8)cycloalkyl, or 5- to 9-membered aryl or
each R4 is independently (C1-12)alkyl, or -C(O)R5; each R5 is (C1-12)alkyl unsubstituted or substituted by R6, (C2-12)alkenyl unsubstituted or substituted by R6, (C3-8)cycloalkyl, or 5- to 9- membered aryl; each R6 is (C1-4)alkoxy, or oxo; and each n is independently an integer from 1 to 15 or
each R7 is independently (C1-12)alkyl each z is an integer from 1 to 4. In another embodiment the present invention relates to a coating composition comprising: a. at least one latex compound; and b. at least one aromatic enol ether having Formula I:
wherein: A is (C8-20) alkylaryl; R1a and R1b are independently (C1-12)alkyl, (C2-12)alkenyl, (C3- 8)cycloalkyl, or 5- to 9-membered aryl or
each R4 is independently (C1-12)alkyl, or -C(O)R5; each R5 is (C1-12)alkyl unsubstituted or substituted by R6, (C2-12)alkenyl unsubstituted or substituted by R6, (C3-8)cycloalkyl, or 5- to 9- membered aryl; each R6 is (C1-4)alkoxy, or oxo; and each n is independently an integer from 1 to 15 or
each R7 is independently (C1-12)alkyl. In another embodiment the present invention relates to a coating composition comprising: a. at least one latex compound; and b. at least one aromatic enol ether having Formula I:
wherein: A is (C8-20) alkylaryl; R1a and R1b are independently (C1-12)alkyl, (C2-12)alkenyl, (C3- 8)cycloalkyl, or 5- to 9-membered aryl or
each R4 is independently (C1-12)alkyl, or -C(O)R5; each R5 is (C1-12)alkyl unsubstituted or substituted by R6, (C2-12)alkenyl unsubstituted or substituted by R6, (C3-8)cycloalkyl, or 5- to 9- membered aryl; each R6 is (C1-4)alkoxy, or oxo; and each n is independently an integer from 1 to 15 or
each R7 is independently (C1-12)alkyl each z is an integer from 1 to 4. DETAILED DESCRIPTION Definitions: [0006] In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the following meanings. [0007] “Alkyl” means an aliphatic hydrocarbon. The alkyl can specify the number of carbon atoms, for example (C1-5)alkyl. Unless otherwise specified, the alkyl group can be unbranched or branched. In some embodiments, the alkyl group is branched. In some embodiments, the alkyl group is unbranched. Non-limiting examples of alkanes include methane, ethane, propane, isopropyl (i.e., branched propyl), butyl, and the like. [0008] “Alkenyl” means an aliphatic hydrocarbon with one or more unsaturated carbon-carbon bonds. The alkenyl can specify the number of carbon atoms, for example (C2-12)alkenyl. Unless otherwise specified, the alkyl group can be unbranched or branched. In some embodiments, the alkyl group is branched. In some embodiments, the alkyl group is unbranched. Non-limiting examples of alkanes include ethenyl, propenyl, butenyl, hexa-3,5- dienyl, and the like. [0009] “Alcohol” means a chemical containing one or more hydroxyl groups.
[0010] “Aldehyde” means a chemical containing one or more -C(O)H groups. [0011] “Cycloalkyl” means a cyclic hydrocarbon compound. The cycloalkyl can specify the number of carbon atoms in ring system, for example (C3- 8)cycloalkyl. Non-limiting examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclohexyl, and cyclooctyl. [0012] “Aryl” means a ring system made up carbon atoms that has at least one ring that is aromatic. The carbon units making up the aryl ring may be specified, for example 5- to 9-membered aryl. Non-limiting examples of aryl include phenyl, naphthyl, 2,3-dihydro-1H-indene, and 1,2,3,4- tetrahydronaphthalene. [0013] Values may be expressed as “about” or “approximately” a given number. Similarly, ranges may be expressed herein as from “about” one particular value and/or to “about” or another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect. [0014] As used herein, the terms “a,” “an,” and “the” mean one or more. [0015] As used herein, the term “and/or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed. For example, if a compound is described as containing components A, B, and/or C, the compound can contain A alone; B alone; C alone; A and B in combination; A and C in combination, B and C in combination; or A, B, and C in combination. [0016] As used herein, the terms “comprising,” “comprises,” and “comprise” are open-ended transition terms used to transition from a subject recited before the term to one or more elements recited after the term, where the element or elements listed after the transition term are not necessarily the only elements that make up the subject. [0017] As used herein, the terms “having,” “has,” and “have” have the
same open-ended meaning as “comprising,” “comprises,” and “comprise” provided above. [0018] As used herein, the terms “including,” “includes,” and “include” have the same open-ended meaning as “comprising,” “comprises,” and “comprise” provided above. [0019] “Chosen from” as used herein can be used with “or” or “and.” For example, Y is chosen from A, B, and C means Y can be individually A, B, or C. Alternatively, Y is chosen from A, B, or C means Y can be individually A, B, or C; or a combination of A and B, A and C, B and C, or A, B, and C. [0020] Presented herein are novel enol ethers which can be used in applications such as (but not limited to) plasticizers, diluents, wetting agents, coalescing aids and paint additives. [0021] In some embodiments the invention is a compound according to Formula I:
wherein: A is (C8-20) alkylaryl; R1a and R1b are independently (C1-12)alkyl, (C2-12)alkenyl, (C3- 8)cycloalkyl, or 5- to 9-membered aryl or
each R4 is independently (C1-12)alkyl, or -C(O)R5; each R5 is (C1-12)alkyl unsubstituted or substituted by R6, (C2-12)alkenyl unsubstituted or substituted by R6, (C3-8)cycloalkyl, or 5- to 9- membered aryl; each R6 is (C1-4)alkoxy, or oxo; and
each n is independently an integer from 1 to 15 or
each R7 is independently (C1-12)alkyl. [0022] In some embodiments, A in Formulas I, is 1,2-, 1,3-, or 1,4- disubstituted phenyl. In some embodiments, each n is an integer from 1 to 3. [0023] In some embodiments of Formulas I, each R4 is hydrogen. In some embodiments, each R4 is (C1-12)alkyl. In some embodiments, each R4 is independently ethyl. In some embodiments, each R4 is (C2-12)alkenyl. In some embodiments, each R4 is -C(O)R5. [0024] In some embodiments of Formulas I, each R5 is (C1-12)alkyl unsubstituted or substituted by R6. In some embodiments, each R5 is (C1- 12)alkenyl unsubstituted or substituted by R6. In some embodiments, each R5 is (C3-8)cycloalkyl. In some embodiments, each R5 is 5- to 9-membered aryl. [0025] In some embodiments of Formulas I each n is an integer from 1 to 2. In some embodiments, each n is an integer from 1 to 3. In some embodiments, each n is an integer from 1 to 4. In some embodiments, each n is an integer from 1 to 5. In some embodiments, n is an integer from 1 to 6. In some embodiments, n is an integer from 1 to 7. In some embodiments, n is an integer from 1 to 8. In some embodiments, n is an integer from 1 to 9. In some embodiments, n is an integer from 1 to 10. In some embodiments, n is an integer from 1 to 11. In some embodiments, n is an integer from 1 to 12. In some embodiments, n is an integer from 1 to 13. In some embodiments, n is an integer from 1 to 14. In some embodiments, n is an integer from 1 to 15. [0026] In another embodiment the present application relates to an enol ether compound according to Formula I:
wherein: A is (C8-20) alkylaryl; R1a and R1b are independently (C1-12)alkyl, (C2-12)alkenyl, (C3- 8)cycloalkyl, or 5- to 9-membered aryl or
each R4 is independently (C1-12)alkyl, or -C(O)R5; each R5 is (C1-12)alkyl unsubstituted or substituted by R6, (C2-12)alkenyl unsubstituted or substituted by R6, (C3-8)cycloalkyl, or 5- to 9- membered aryl; each R6 is (C1-4)alkoxy, or oxo; and each n is independently an integer from 1 to 15 or
each R7 is independently (C1-12)alkyl each z is an integer from 1 to 4. [0027] In some embodiments, A in Formulas I, is 1,2-, 1,3-, or 1,4- disubstituted phenyl. In some embodiments, each n is an integer from 1 to 3. [0028] In some embodiments of Formulas I, each R4 is hydrogen. In some embodiments, each R4 is (C1-12)alkyl. In some embodiments, each R4 is independently ethyl. In some embodiments, each R4 is (C2-12)alkenyl. In some embodiments, each R4 is -C(O)R5. [0029] In some embodiments of Formulas I, each R5 is (C1-12)alkyl unsubstituted or substituted by R6. In some embodiments, each R5 is (C1- 12)alkenyl unsubstituted or substituted by R6. In some embodiments, each R5 is (C3-8)cycloalkyl. In some embodiments, each R5 is 5- to 9-membered aryl. [0030] In some embodiments of Formulas I each n is an integer from 1 to 2. In some embodiments, each n is an integer from 1 to 3. In some
embodiments, each n is an integer from 1 to 4. In some embodiments, each n is an integer from 1 to 5. In some embodiments, n is an integer from 1 to 6. In some embodiments, n is an integer from 1 to 7. In some embodiments, n is an integer from 1 to 8. In some embodiments, n is an integer from 1 to 9. In some embodiments, n is an integer from 1 to 10. In some embodiments, n is an integer from 1 to 11. In some embodiments, n is an integer from 1 to 12. In some embodiments, n is an integer from 1 to 13. In some embodiments, n is an integer from 1 to 14. In some embodiments, n is an integer from 1 to 15. [0031] In some embodiments, the compounds of Formulas I have a volatile organic content of less than 50 wt % according to ASTM D6886. In some embodiments, the volatile organic content is less than 30 wt %. In some embodiments, the volatile organic content is less than 10 wt %. In some embodiments, the volatile organic content is less than 5 wt %. In some embodiments, the volatile organic content is less than 3 wt %. In some embodiments, the volatile organic content is less than 2 wt %. In some embodiments, the volatile organic content is less than 1 wt %. In some embodiments, the volatile organic content is less than 0.8 wt %. Compounds [0032] The enol ether compounds disclosed in the present application exhibit a low volatile organic content (less than 50 wt %, but as low as 0.7 wt % according to ASTM D6886). The enol ethers can be used as reactive film- hardening compounds. Reactive film-hardening compounds react with components in coating compositions to form crosslinks in the films providing improved film properties. When we say that the enol ether compounds of this invention can be used as reactive film-hardening additives, we mean when added to a coating composition, that a harder film is obtained upon curing the composition than is obtained in the absence of the invention enol ether additives, or that the coating composition exhibits a higher gel fraction than in the absence of the enol ether additive, or that both coating composition hardness and increased gel fraction properties are improved by the addition of the enol ether reactive film-hardening additives.
[0033] Not wishing to be bound by any theory, the increase in hardness observed in a coating that contains the enol ether additives described herein may be the result of a chemical reaction, so that the additives described herein may be described as “reactive” enol ether film-hardening additives. [0034] The enol ether materials described herein can also facilitate the individual latex particles coming together to form a continuous film at a given temperature by reducing the minimum film-forming temperature (MFFT) of the latex polymer. [0035] The enol ethers of the present invention are expected to have particular utility in latex coating compositions such as in acrylic polymer, vinyl acrylic polymer, styrene butadiene polymer and styrene acrylic latex polymer compositions, and mixtures thereof. [0036] More particularly, the enol ethers of the present invention are expected to have particular utility in latex coating compositions including, but not limited to styrene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2- ethylhexyl acrylate, isoprene, octyl acrylate, octyl methacrylate, iso-octyl acrylate, iso-octyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, O-methyl styrene, vinyl naphthalene, vinyl toluene, chloromethyl styrene, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, acrylonitrile, glycidyl methacrylate, acetoacetoxyethyl methacrylate, acetoacetoxy ethyl acrylate, vinyl chloride, vinylidene chloride, vinyl acetate, butyl acrylamide, or ethyl acrylamide polymer compositions and mixtures thereof. [0037] In some embodiments, the compounds of Formula I are enol ethers represented by Formulas 20-93:
and isomers thereof. [0038] The enol ethers depicted by Formulas 20-93 are representative of the enol ethers claimed herein. Isomers of the enol ethers depicted by Formulas 20-93 are expected to be produced during synthesis of the enol ethers depicted by Formulas 20-93. All isomers of the enol ethers depicted by Formulas 20-93 and are within the scope of the claims set forth herein. [0039] The compounds depicted by Formulas I include those having a weight percent volatile content of less than 50%, as measured according to ASTM Method D6886. This test may be conducted generally by heating the sample in a forced air oven at 110°C. for 60 minutes. The weight loss after the test is deemed to result from a loss of volatiles originally present in the sample; the percent volatile present in the original sample may then be calculated. Although the cited test can be conducted on coating compositions containing other components such as latex polymers, the values cited herein may be obtained from a sample of the additive itself. The weight percent volatile of a film-hardening aid may be used herein as a yardstick to measure the amount of VOC the additive would contribute to the VOC in a particular end use such as a component of a coating composition. EXAMPLES [0040] This invention can be further illustrated by the following examples thereof, although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated. In particular more than one method to make enol ethers is available to the skilled artisan. Methods A, B, and C are described herein.
Abbreviations: [0041] mL is milliliter; wt % is weight percent; eq is equivalent(s); hrs or h is hour(s); mm is millimeter; m is meter; GC is gas chromatography;°C is degree Celsius; min is minute; tR is retention time; VOC is volatile organic compound; MeP is methyl palmitate; w/v is weight/volume; µL is microliter. RFHA is reactive film-hardening additive. Preparation of dicarbinol [1] and 2,2'-(1,4-phenylene)dipropanal [2]
Preparation of dicarbinol 1: [0042] KOH (49.2 g, 788 mmol) was dissolved in MeOH (400 mL) contained within a 1L, 4-necked round-bottom flask fitted with thermocouple, overhead stirrer, and nitrogen inlet atop a reflux condenser. During the addition of KOH, internal temperature reached 60 °C and was maintained there by heating mantle. The solid di-epoxide was added over the course of 1.5 hrs. The reaction was monitored by 1H NMR (aliquot was taken and dissolved in DMSO-d6. Once di-epoxide was completely consumed, the reaction was cooled to ambient temperature, and acetic acid (47.3g, 788 mmol) was added dropwise. Once addition was complete, the volatiles were removed under reduced pressure using a rotary evaporator. The residue was taken up in 250 mL of toluene and then washed with 250 mL of water. The aqueous layer was back-extracted with 250 mL of EtOAc (ethyl acetate). The organics were combined, dried with MgSO4 and simultaneously treated with 5g of activated carbon. The mixture was filtered and volatiles were removed under reduced pressure using a rotary evaporator. Dicarbinol 1 was isolated as a white solid. LC-MS (Column A) tR : 3.80 min (Exact mass : 254.15 m/z, found 254.2 m/z ).
Preparation of 2,2'-(1,4-phenylene)dipropanal [2]: [0043] The dicarbinol 1 was then dissolved in formic acid (88%, 98.0 g) contained within a 500 mL, 4-necked round-bottom flask fitted with thermocouple, overhead stirrer, and nitrogen inlet atop a reflux condenser. The mixture was heated to 100 °C. After 6 hrs, additional formic acid was added (98.0 g). After an additional 2 hrs, GC indicated >99% conversion to dialdehyde 2. The volatiles were then removed under reduced pressure using a rotary evaporator. The residue was taken up in 250 mL of toluene and then washed with a saturated solution of NaHCO3. After layer separation, the organics were dried with MgSO4, filtered, and then concentrated. The crude material was then Kugelrohr – distilled at 150 °C/1 mm Hg to isolate the di- aldehyde 2 as a colorless oil. GC-MS tR : 14.47 min (Exact mass: 190.10 m/z, found: 190.1 m/z). Preparation of 2,2'-(1,3-phenylene)dipropanal 4
[0044] Dicarbinol 3 was prepared in a similar manner to di-carbinol 2 using procedure described in Method A. [LC-MS (Column B) tR : 4.55 min, 4.68 min (Exact mass: 254.15 m/z, found 254.2 m/z)]. Di-aldehyde 4 was prepared in a similar manner to di-aldehyde 2 using Method A. GC-MS tR : 14.22 min (Exact mass: 190.10 m/z, found: 190.1 m/z). Method A: [0045] Di-aldehyde was added to a nitrogen-swept, round-bottom flask fitted with overhead-stirrer, thermocouple, and Dean-Stark. Glycol alcohol solvent (5 equiv.) was added all at once, followed by the addition of toluene (2x mass of aldehyde used). Sodium methanesulfonate (0.025 equiv.) was added to the flask, followed by the addition of methanesulfonic acid (0.025
equiv.). The reaction was heated to reflux and held at that temperature for 15 hrs. Toluene was removed under reduced pressure using a rotary evaporator. Then 50% caustic (0.024 equiv.) was added all at once. The mixture was fractionally distilled under reduced pressure. Example 1: Preparation of (E,E/Z,Z) - 1,4-bis(1-(2-butoxyethoxy)prop-1- en-2-yl)benzene [5]
GC-MS tR : 22.83 min, 24.34 min, 26.08 min (Exact mass: 390.28 m/z, found 390.3 m/z). Example 2: Preparation of (E,E/Z,Z) - 1,4-bis(1-((1-((1-methoxypropan-2- yl)oxy)propan-2-yl)oxy)prop-1-en-2-yl)benzene [6]
GC-MS tR : 25.8 min, 26.2 min, 28.3 min, 28.9 min (Exact mass: 450.30 m/z, found 450 m/z).
Method B: [0046] To a 4-necked round-bottom flask fitted with an overhead stirrer, thermocouple, and nitrogen inlet was added acetic anhydride (5 equiv.) and sodium bisulfate monohydrate (0.025 equiv.). The mixture was then heated to 65 °C and held for 30 minutes. The dicarbinol was then added dropwise over the course of 4-5 hrs via a pressure-equalizing addition funnel. Once the addition was complete, the reaction was checked by GC. Once complete, the mix was transferred to a 1-neck round-bottom flask and the excess acetic anhydride/acetic acid was removed under reduced pressure using a rotary evaporatory. The crude was taken up in toluene. The organics were then washed with 10% caustic (x2) solution and then 5% ammonium hydroxide solution. The mixture was dried with MgSO4 and simultaneously treated with activated carbon. After filtration, the volatiles were removed under reduced pressure using a rotary evaporator. Light-boiling impurities were removed by distillation. The enol ether / 1,1-disubstituted olefin was Kugelrohr-distilled to afford product blends. Example 3: A mixture of (E,E/Z,Z) - 1,4-bis(1-((1-((1-methoxypropan-2- yl)oxy)propan-2-yl)oxy)prop-1-en-2-yl)benzene [6a], (E,Z) - 1-(1-((1-((1- methoxypropan-2-yl)oxy)propan-2-yl)oxy)prop-1-en-2-yl)-4-(3-((1-((1- methoxypropan-2-yl)oxy)propan-2-yl)oxy)prop-1-en-2-yl)benzene [6b], and 1,4-bis(3-((1-((1-methoxypropan-2-yl)oxy)propan-2-yl)oxy)prop-1-en- 2-yl)benzene [6c]
GC-MS tR : 25.80 min, 26.28 min, 26.80 min, 27.30 min, 28.38 min, 28.94 min (Exact mass: 450.30 m/z, found: 450.4 m/z). Example 4: A mixture of (E,E/Z,Z) - 1,4-bis(4,7,10-trimethyl-2,5,8,11- tetraoxatetradec-12-en-13-yl)benzene [7a], (E,Z) - 4,7,10-trimethyl-13-(4- (4,7,10-trimethyl-2,5,8,11-tetraoxatetradec-13-en-13-yl)phenyl)-2,5,8,11- tetraoxatetradec-12-ene [7b], and 1,4-bis(4,7,10-trimethyl-2,5,8,11- tetraoxatetradec-13-en-13-yl)benzene [7c]
GC-MS tR : 43.08 (broad peak), 69.53 min (broad peak) (Exact mass: 566.38 m/z, found: 566.5 m/z). Example 5: A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- methoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [8a], (E,Z) - 1-(1-(2-(2- methoxyethoxy)ethoxy)prop-1-en-2-yl)-4-(3-(2-(2- methoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [8b], and 1,4-bis(3-(2-(2- methoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [8c]
GC-MS tR : 23.9 min, 24.29 min, 24.48 min, 25.64 min, 25.96 min, 27.63 min (Exact mass: 394.24 m/z, found: 394.3 m/z). Example 6: a mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- ethoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [9a], (E/Z) - 1-(1-(2-(2- ethoxyethoxy)ethoxy)prop-1-en-2-yl)-4-(3-(2-(2- ethoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [9b], and 1,4-bis(3-(2-(2- ethoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [9c].
GC-MS tR : 25.64 min, 26.23 min, 26.55 min, 28.00 min, 28.47 min, 30.67 min (Exact mass: 422.27 m/z, found: 422.3 m/z). Example 7: A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [10a], (E,Z) - 1-(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)-4-(3-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [10b], 1,4-bis(3-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [10c].
GC-MS tR : 29.70 min, 30.67 min, 31.30 min, 33.27 min, 34.18 min, 37.58 min (Exact mass: 450.30 m/z, found: 450.3 m/z). Example 8: A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [11a], (E,Z) - 1-(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)-4-(3-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [11b], 1,4-bis(3-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [11c].
GC-MS tR : 36.07 min, 37.71 min, 38.86 min, 41.45 min (Exact mass: 478.33 m/z, found: 478.4 m/z). Example 9: A mixture of (E,E/Z,Z) - 1,4-di(2,5,8,11-tetraoxatetradec-12- en-13-yl)benzene [12a], (E,Z) - 13-(4-(2,5,8,11-tetraoxatetradec-13-en-13- yl)phenyl)-2,5,8,11-tetraoxatetradec-12-ene [12b], and 1,4-di(2,5,8,11- tetraoxatetradec-13-en-13-yl)benzene [12c].
GC-MS tR : 39.51 min, 41.51 min, 42.78 min, 46.43 min, 48.26 min, 55.04 min (Exact mass: 482.29 m/z, found: 482.4 m/z). Example 10: A mixture of (E,E/Z,Z) - 1,3-bis(1-((1-((1-methoxypropan-2- yl)oxy)propan-2-yl)oxy)prop-1-en-2-yl)benzene [13a], (E/Z) - 1-(1-((1-((1- methoxypropan-2-yl)oxy)propan-2-yl)oxy)prop-1-en-2-yl)-3-(3-((1-((1- methoxypropan-2-yl)oxy)propan-2-yl)oxy)prop-1-en-2-yl)benzene [13b], and 1,3-bis(3-((1-((1-methoxypropan-2-yl)oxy)propan-2-yl)oxy)prop-1-en- 2-yl)benzene [13c].
GC-MS tR : 22.78 min, 23.14 min, 23.45 min, 23.91 min, 24.27 min, 24.59 min, 25.17 min, 25.58 min, 26.05 min (Exact mass: 450.30 m/z, found: 450.4 m/z). Example 11: A mixture of (E,E/Z,Z) - 1,3-bis(4,7,10-trimethyl-2,5,8,11- tetraoxatetradec-12-en-13-yl)benzene [14a], (E/Z) - 4,7,10-trimethyl-13-(3- (4,7,10-trimethyl-2,5,8,11-tetraoxatetradec-13-en-13-yl)phenyl)-2,5,8,11- tetraoxatetradec-12-ene [14b], and 1,3-bis(4,7,10-trimethyl-2,5,8,11- tetraoxatetradec-13-en-13-yl)benzene [14c]
GC-MS tR : 41.84 – 43.72 min (broad peak) (Exact mass: 566.38 m/z, found: 566.5 m/z). Example 12: A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- methoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [15a], (E/Z) - 1-(1-(2-(2- methoxyethoxy)ethoxy)prop-1-en-2-yl)-3-(3-(2-(2- methoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [15b], 1,3-bis(3-(2-(2- methoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [15c].
GC-MS tR : 22.57 min, 22.91 min, 23.08 min, 23.79 min, 24.08 min, 25.43 min (Exact mass: 394.24 m/z, found: 394.3 m/z). Example 13-1 and Example 13-2: A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- ethoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [16a], (E/Z) - 1-(1-(2-(2- ethoxyethoxy)ethoxy)prop-1-en-2-yl)-3-(3-(2-(2-
ethoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [16b], and 1,3-bis(3-(2-(2- ethoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [16c].
GC-MS tR : 24.07 min, 24.73 min, 24.80 min, 25.72 min, 25.87 min, 27.78 min (Exact mass: 422.27 m/z, found: 422.3 m/z). 0.05 equiv. of sodium bisulfate used. Example 13-1: 0.025 equiv. of sodium bisulfate used. Ratio of 16a:16b:16c = 1.0:1.7:3.6. Example 13-2: 0.50 equiv. of sodium bisulfate used. Ratio of 16a:16b:16c = 1.0:2.7:10. Example 14: A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [17a], (E/Z) - 1-(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)-3-(3-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [17b], and 1,3-bis(3-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [17c]
GC-MS tR : 27.42 min, 28.16 min, 28.63 min, 29.80 min, 30.61 min, 33.20 min (Exact mass: 450.30 m/z, found: 450.4 m/z). Example 15: A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [18a], (E/Z) - 1-(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)-3-(3-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [18b], and 1,3-bis(3-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [18c].
GC-MS tR : 32.75 min, 33.89 min, 34.68 min, 36.20 min, 37.42 min, 41.29 min (Exact mass: 478.33 m/z, found: 478.4 m/z). Example 16: A mixture of (E,E/Z,Z) - 1,3-di(2,5,8,11-tetraoxatetradec-12- en-13-yl)benzene [19a], (E/Z) - 13-(3-(2,5,8,11-tetraoxatetradec-13-en-13- yl)phenyl)-2,5,8,11-tetraoxatetradec-12-ene [19b], and 1,3-di(2,5,8,11- tetraoxatetradec-13-en-13-yl)benzene [19c].
GC-MS tR : 35.57 min, 36.92 min, 37.81 min, 39.66 min, 41.11 min, 45.59 min (Exact mass: 482.29 m/z, found: 482.3 m/z). Method C: [0047] To a 4-necked round-bottom flask fitted with an overhead stirrer, thermocouple, and nitrogen inlet was added dialdehyde 2 or 4 (1 equiv.), glycol ether solvent (5 equiv.) and lower-boiling, aliphatic alcohol (5 equiv.). Phosphoric acid (0.5 equiv., 85% in water) was added all at once. A liquid level was marked on the reaction flask. The mixture was sparged (sub- surface) with nitrogen at a flow rate of 250 mL/min. The system was then pulled under vacuum. The reaction mixture was heated to 75°C. The lower- boiling alcohol component was continuously removed from the reaction to facilitate water-removal. Over the course of the reaction, fresh lower-boiling alcohol component was added back to the reaction flask such that the liquid volume was maintained up to the marked liquid level on the flask. Once GC and NMR confirmed >99.5% conversion of aldehyde, the reaction mixture was cooled to ambient temperature and then diluted with a minimal amount of toluene. This mixture was then poured into water containing 1.25 equiv. of NaOH. The layers were separated and the organics were washed with water three times. After washing, the organics were dried with MgSO4, filtered, and the volatiles were removed under reduced pressure. The mixture was then transferred to a 4-necked flask containing glass boiling chips and fitted with a thermocouple and short-path condenser. The excess, unreacted alcohols were first removed under reduced pressure with heat. Once complete, 0.05
equiv. of phosphoric acid was added to the reactor. The mixture was further heated to facilitate conversion to enol ether. The reaction was heated until the rate of alcohol production dropped substantially and NMR or GC analysis indicated >95% conversion to the desired product. Example 17: A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [10], (E,E/Z,Z) - 1-(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)-4-(1-propoxyprop-1-en-2- yl)benzene [23], and (E,E/Z,Z) - 1,4-bis(1-propoxyprop-1-en-2-yl)benzene [20]
GC-MS tR : 29.61 min, 33.23 min, 37.51 min (10, Exact mass: 450.3 m/z, found: 450.4 m/z), 20.85 min, 21.57 min, 21.83 min, 22.75 min (23, Exact mass: 362.2 m/z, found: 362.3 m/z), 17.20 min, 17.52 min, 17.83 min (20, Exact mass: 274.2 m/z, found: 274.1 m/z). Example 18: A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [10], (E,E/Z,Z) - 1-(1- butoxyprop-1-en-2-yl)-4-(1-(2-(2-propoxyethoxy)ethoxy)prop-1-en-2- yl)benzene [24], and (E,E/Z,Z) - 1,4-bis(1-butoxyprop-1-en-2-yl)benzene [21]
GC-MS tR : 29.65 min, 33.18 min, 37.42 min (10, Exact mass: 450.3 m/z, found: 450.4 m/z), 21.71 min, 22.84 min, 22.97 min, 24.34 min (24, Exact mass: 376.3 m/z, found: 376.3 m/z), 18.15 min, 18.68 min, 19.22 min (21, Exact mass: 302.2 m/z, found: 302.3 m/z). Example 19: A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [10], (E,E/Z,Z) - 1-(1- isobutoxyprop-1-en-2-yl)-4-(1-(2-(2-propoxyethoxy)ethoxy)prop-1-en-2- yl)benzene [25], and (E,E/Z,Z) - 1,4-bis(1-isobutoxyprop-1-en-2- yl)benzene [22]
GC-MS tR : 29.60 min, 33.18 min, 37.48 min (10, Exact mass: 450.3 m/z, found: 450.4 m/z), 21.17 min, 22.28 min, 23.51 min (25, Exact mass: 376.3 m/z, found: 376.3 m/z), 17.58 min, 18.06 min, 18.55 min (22, Exact mass: 302.2 m/z, found: 302.3 m/z).
Example 20: A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- isopropoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [44], (E,E/Z,Z) - 1-(1-(2- (2-isopropoxyethoxy)ethoxy)prop-1-en-2-yl)-4-(1-propoxyprop-1-en-2- yl)benzene [26], and (E,E/Z,Z) - 1,4-bis(1-propoxyprop-1-en-2-yl)benzene [20]
GC-MS tR : 27.02 min, 29.68 min, 32.85 min (44, Exact mass: 450.3 m/z, found: 450.4 m/z), 20.32 min, 21.01 min, 21.23 min, 21.98 min (26, Exact mass: 362.2 m/z, found: 362.3 m/z), 17.17 min, 17.55 min, 17.84 min (20, Exact mass: 274.2 m/z, found: 274.1 m/z). Example 21: A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- isopropoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [44], (E,E/Z,Z) - 1-(1- butoxyprop-1-en-2-yl)-4-(1-(2-(2-isopropoxyethoxy)ethoxy)prop-1-en-2- yl)benzene [27], and (E,E/Z,Z) - 1,4-bis(1-butoxyprop-1-en-2-yl)benzene [21]
GC-MS tR : 26.94 min, 29.67 min, 32.88 min (44, Exact mass: 450.3 m/z, found: 450.4 m/z), 21.08 min, 22.19 min, 23.43 min (27, Exact mass: 376.3 m/z, found: 376.3 m/z), 18.14 min, 18.68 min, 19.22 min (21, Exact mass: 302.2 m/z, found: 302.3 m/z). Example 22: A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- isopropoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [44], (E,E/Z,Z) - 1-(1- isobutoxyprop-1-en-2-yl)-4-(1-(2-(2-isopropoxyethoxy)ethoxy)prop-1-en- 2-yl)benzene [28], and (E,E/Z,Z) - 1,4-bis(1-isobutoxyprop-1-en-2- yl)benzene [22]
GC-MS tR : 27.00 min, 29.67 min, 32.92 min (44, Exact mass: 450.3 m/z, found: 450.4 m/z), 20.59 min, 21.61 min, 21.74 min, 22.71 min (28, Exact mass: 376.3 m/z, found: 376.3 m/z), 17.63 min, 18.06 min, 18.55 min (22, Exact mass: 302.2 m/z, found: 302.1 m/z). Example 23: A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [11], (E,E/Z,Z) - 1-(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)-4-(1-propoxyprop-1-en-2- yl)benzene [29], and (E,E/Z,Z) - 1,4-bis(1-propoxyprop-1-en-2-yl)benzene [20]
GC-MS tR : 39.95 min, 41.67 min, 48.54 min (11, Exact mass: 478.3 m/z, found: 478.4 m/z), 21.82 min, 22.69 min, 23.13 min, 24.10 min (29, Exact mass: 376.3 m/z, found: 376.3 m/z), 17.20 min, 17.57 min, 17.86 min (20, Exact mass: 274.2 m/z, found: 274.1 m/z). Example 24: A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [11], (E,E/Z,Z) - 1-(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)-4-(1-butoxyprop-1-en-2-yl)benzene [30], and (E,E/Z,Z) - 1,4-bis(1-butoxyprop-1-en-2-yl)benzene [21]
GC-MS tR : 35.97 min, 41.73 min, 48.77 min (11, Exact mass: 478.3 m/z, found: 478.4 m/z), 22.88 min, 24.29 min, 24.45 min, 26.14 min (30, Exact mass: 390.3 m/z, found: 390.3 m/z), 18.15 min, 18.68 min, 19.22 min (21, Exact mass: 302.2 m/z, found: 302.1 m/z).
Example 25: A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [11], (E,E/Z,Z) - 1-(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)-4-(1-isobutoxyprop-1-en-2- yl)benzene [31], and (E,E/Z,Z) - 1,4-bis(1-isobutoxyprop-1-en-2- yl)benzene [22]
GC-MS tR : 36.01 min, 41.71 min, 48.67 min (11, Exact mass: 478.3 m/z, found: 478.4 m/z), 22.21 min, 23.51 min, 23.63 min, 25.13 min (31, Exact mass: 390.3 m/z, found: 390.3 m/z), 17.60 min, 18.08 min, 18.56 min (22, Exact mass: 302.2 m/z, found: 302.1 m/z). Example 26: A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [17], (E,E/Z,Z) - 1-(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)-3-(1-propoxyprop-1-en-2- yl)benzene [35], and (E,E/Z,Z) - 1,3-bis(1-propoxyprop-1-en-2-yl)benzene [32]
GC-MS tR : 27.34 min, 29.70 min, 32.94 min (17, Exact mass: 450.3 m/z, found: 450.4 m/z), 20.09 min, 20.60 min, 20.88 min, 21.58 min (35, Exact mass: 362.2 m/z, found: 362.3 m/z),16.80 min, 17.16 min, 17.46 min (32, Exact mass: 274.2 m/z, found: 274.1 m/z). Example 27: A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [17] (E,E/Z,Z) - 1-(1- butoxyprop-1-en-2-yl)-3-(1-(2-(2-propoxyethoxy)ethoxy)prop-1-en-2- yl)benzene [36], and (E,E/Z,Z) - 1,3-bis(1-butoxyprop-1-en-2-yl)benzene [33]
GC-MS tR : 27.35 min, 29.69 min, 32.96 min (17, Exact mass: 450.3 m/z, found: 450.4 m/z), 20.79 min, 21.62 min, 21.77 min, 22.84 min (36, Exact mass: 376.3 m/z, found: 376.3 m/z), 17.71 min, 18.18 min, 18.68 min (33, Exact mass: 302.2 m/z, found: 302.1 m/z). Example 28: A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- propoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [17], (E,E/Z,Z) - 1-(1- isobutoxyprop-1-en-2-yl)-3-(1-(2-(2-propoxyethoxy)ethoxy)prop-1-en-2- yl)benzene [37], and (E,E/Z,Z) - 1,3-bis(1-isobutoxyprop-1-en-2- yl)benzene [34]
GC-MS tR : 27.35 min, 29.71 min, 32.95 min (17, Exact mass: 450.3 m/z, found: 450.4 m/z), 20.35 min, 21.08 min, 21.24 min, 22.18 min (37, Exact mass: 376.3 m/z, found: 376.3 m/z), 17.16 min, 17.61 min, 18.05 min (34, Exact mass: 302.2 m/z, found: 302.1 m/z). Example 29: A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- isopropoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [45], (E,E/Z,Z) - 1-(1-(2- (2-isopropoxyethoxy)ethoxy)prop-1-en-2-yl)-3-(1-propoxyprop-1-en-2- yl)benzene [38], and (E,E/Z,Z) - 1,3-bis(1-propoxyprop-1-en-2-yl)benzene [32]
GC-MS tR : 25.17 min, 26.96 min, 29.48 min (45, Exact mass: 450.3 m/z, found: 450.4 m/z), 19.66 min, 20.12 min, 20.38 min, 20.98 min (38, Exact mass: 362.2 m/z, found: 362.3 m/z), 16.79 min, 17.13 min, 17.45 min (32, Exact mass: 274.2 m/z, found: 274.1 m/z).
Example 30: A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- isopropoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [45], (E,E/Z,Z) - 1-(1- butoxyprop-1-en-2-yl)-3-(1-(2-(2-isopropoxyethoxy)ethoxy)prop-1-en-2- yl)benzene [39], and (E,E/Z,Z) - 1,3-bis(1-butoxyprop-1-en-2-yl)benzene [33]
GC-MS tR : 25.16 min, 26.91 min, 29.46 min (45, Exact mass: 450.3 m/z, found: 450.4 m/z), 20.29 min, 21.07 min, 21.19 min, 22.14 min (39, Exact mass: 376.3 m/z, found: 376.3 m/z), 17.67 min, 18.17 min, 18.67 min (33, Exact mass: 302.2 m/z, found: 302.1 m/z). Example 31: A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- isopropoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [45], (E,E/Z,Z) - 1-(1- isobutoxyprop-1-en-2-yl)-3-(1-(2-(2-isopropoxyethoxy)ethoxy)prop-1-en- 2-yl)benzene [40], and (E,E/Z,Z) - 1,3-bis(1-isobutoxyprop-1-en-2- yl)benzene [34]
GC-MS tR : 25.18 min, 26.96 min, 29.51 min (45, Exact mass: 450.3 m/z, found: 450.4 m/z), 19.88 min, 20.58 min, 20.70 min, 21.54 min (40, Exact mass: 376.3 m/z, found: 376.3 m/z), 17.16 min, 17.63 min, 18.05 min (34, Exact mass: 302.2 m/z, found: 302.1 m/z). Example 32: A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [18], (E,E/Z,Z) - 1-(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)-3-(1-propoxyprop-1-en-2- yl)benzene [41], and (E,E/Z,Z) - 1,3-bis(1-propoxyprop-1-en-2-yl)benzene [32]
GC-MS tR : 32.75 min, 36.17 min, 41.29 min (18, Exact mass: 478.3 m/z, found: 478.4 m/z), 20.95 min, 21.58 min, 21.95 min, 22.72 min (41, Exact mass: 376.3 m/z, found: 376.3 m/z), 16.82 min, 17.16 min, 17.48 min (32, Exact mass: 274.2 m/z, found: 274.1 m/z). Example 33: A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [18], (E,E/Z,Z) - 1-(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)-3-(1-butoxyprop-1-en-2-yl)benzene [42], and (E,E/Z,Z) - 1,3-bis(1-butoxyprop-1-en-2-yl)benzene [33]
GC-MS tR : 32.70 min, 36.14 min, 41.21 min (18, Exact mass: 478.3 m/z, found: 478.4 m/z), 21.83 min, 22.77 min, 23.02 min, 24.29 min (42, Exact mass: 390.3 m/z, found: 390.3 m/z), 17.73 min, 18.18 min, 18.69 min (33, Exact mass: 302.2 m/z, found: 302.1 m/z), Example 34: A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [18], (E,E/Z,Z) - 1-(1-(2-(2- butoxyethoxy)ethoxy)prop-1-en-2-yl)-3-(1-isobutoxyprop-1-en-2- yl)benzene [43], and (E,E/Z,Z) - 1,3-bis(1-isobutoxyprop-1-en-2- yl)benzene [34]
GC-MS tR : 32.67 min, 36.22 min, 41.37 min (18, Exact mass: 478.3 m/z, found: 478.4 m/z), 21.27 min, 22.14 min, 22.36 min, 23.47 min (43, Exact mass: 390.3 m/z, found: 390.3 m/z), 17.18 min, 17.64 min, 18.06 min (34, Exact mass: 302.2 m/z, found: 302.1 m/z).
Example 35: A mixture of (E,E/Z,Z) - 1,4-bis(1-((1-methoxypropan-2- yl)oxy)prop-1-en-2-yl)benzene [46], (E,E/Z,Z) - 1-(1-((1-methoxypropan-2- yl)oxy)prop-1-en-2-yl)-4-(1-propoxyprop-1-en-2-yl)benzene [47], and (E,E/Z,Z) - 1,4-bis(1-propoxyprop-1-en-2-yl)benzene [20]
GC-MS tR : 19.77 min (46, Exact mass: 334.2 m/z, found: 334.2 m/z),18.28 min, 18.41 min, 18.69 min (47, Exact mass: 304.2 m/z, found: 304.1 m/z), 17.23 min, 17.49 min, 17.64 min (20, Exact mass: 274.2 m/z, found: 274.2 m/z). Example 36: A mixture of (E,E/Z,Z) - 1,4-bis(1-((1-methoxypropan-2- yl)oxy)prop-1-en-2-yl)benzene [46], (E,E/Z,Z) - 1-(1-butoxyprop-1-en-2-yl)- 4-(1-((1-methoxypropan-2-yl)oxy)prop-1-en-2-yl)benzene [48], and (E,E/Z,Z) - 1,4-bis(1-butoxyprop-1-en-2-yl)benzene [21]
GC-MS tR : 19.79 min (46, Exact mass: 334.2 m/z, found: 334.2 m/z), 18.88 min, 18.95 min, 19.04 min, 19.50 min (48, Exact mass: 318.2 m/z, found: 318.2 m/z), 18.16 min, 18.70 min, 19.20 min (21, Exact mass: 302.2 m/z, found: 302.2 m/z). Example 37: (E,E/Z,Z) - 1,4-bis(1-((1-methoxypropan-2-yl)oxy)prop-1-en- 2-yl)benzene [46], (E,E/Z,Z) - 1-(1-isobutoxyprop-1-en-2-yl)-4-(1-((1- methoxypropan-2-yl)oxy)prop-1-en-2-yl)benzene [49], and (E,E/Z,Z) - 1,4- bis(1-isobutoxyprop-1-en-2-yl)benzene [22]
GC-MS tR : 19.77 min (46, Exact mass: 334.2 m/z, found: 334.2 m/z), 18.15 min, 18.24 min, 18.69 min, 19.40 min (49, Exact mass: 318.2 m/z, found: 318.2 m/z), 17.58 min, 17.64 min (22, Exact mass: 302.2 m/z, found: 302.1 m/z). Example 38: A mixture of (E,E/Z,Z) - 1,3-bis(1-((1-methoxypropan-2- yl)oxy)prop-1-en-2-yl)benzene [50], (E,E/Z,Z) - 1-(1-((1-methoxypropan-2- yl)oxy)prop-1-en-2-yl)-3-(1-propoxyprop-1-en-2-yl)benzene [51], and (E,E/Z,Z) - 1,3-bis(1-propoxyprop-1-en-2-yl)benzene [32]
GC-MS tR : 18.54 min, 19.04 min (50, Exact mass: 334.2 m/z, found: 334.2 m/z), 17.78 min, 17.85 min (51, Exact mass: 304.2 m/z, found: 304.1 m/z), 16.75 min, 17.14 min, 17.46 min (32, Exact mass: 274.2 m/z, found: 274.1 m/z). Example 39: A mixture of (E,E/Z,Z) - 1,3-bis(1-((1-methoxypropan-2- yl)oxy)prop-1-en-2-yl)benzene [50], (E,E/Z,Z) - 1-(1-butoxyprop-1-en-2-yl)- 3-(1-((1-methoxypropan-2-yl)oxy)prop-1-en-2-yl)benzene [52], and (E,E/Z,Z) - 1,3-bis(1-butoxyprop-1-en-2-yl)benzene [33]
GC-MS tR : 19.06 min (50, Exact mass: 334.2 m/z, found: 334.2 m/z), 17.86 min, 18.37 min, 18.91 min (52, Exact mass: 318.2 m/z, found: 318.2 m/z), 17.68 min, 18.21 min, 18.73 min (33, Exact mass: 302.2 m/z, found: 302.2 m/z).
Example 40: A mixture of (E,E/Z,Z) - 1,3-bis(1-((1-methoxypropan-2- yl)oxy)prop-1-en-2-yl)benzene [50], (E,E/Z,Z) - 1-(1-isobutoxyprop-1-en-2- yl)-3-(1-((1-methoxypropan-2-yl)oxy)prop-1-en-2-yl)benzene [53], and (E,E/Z,Z) - 1,3-bis(1-isobutoxyprop-1-en-2-yl)benzene [34]
GC-MS tR : 18.46 min, 19.07 min (50, Exact mass: 334.2 m/z, found: 334.2 m/z), 17.96 min (53, Exact mass: 318.2 m/z, found: 318.2 m/z), 17.14 min, 17.69 min (34, Exact mass: 302.2 m/z, found: 302.1 m/z). Example 41: A mixture of (E,E/Z,Z) - 1,4-bis(1-(3-methoxypropoxy)prop- 1-en-2-yl)benzene [54], (E,E/Z,Z) - 1-(1-(3-methoxypropoxy)prop-1-en-2- yl)-4-(1-propoxyprop-1-en-2-yl)benzene [55], and (E,E/Z,Z) - 1,4-bis(1- propoxyprop-1-en-2-yl)benzene [20]
GC-MS tR : 19.71 min, 20.54 min, 21.42 min (54, Exact mass: 334.2 m/z, found: 334.2 m/z), 18.31 min, 18.75 min, 18.90 min, 19.34 min (55, Exact mass: 304.2 m/z, found: 304.1 m/z), 17.19 min, 17.54 min, 17.83 min (20, Exact mass: 274.2 m/z, found: 274.1 m/z). Example 42: A mixture of (E,E/Z,Z) - 1,4-bis(1-(3-methoxypropoxy)prop- 1-en-2-yl)benzene [54], (E,E/Z,Z) - 1-(1-butoxyprop-1-en-2-yl)-4-(1-(3- methoxypropoxy)prop-1-en-2-yl)benzene [56], and (E,E/Z,Z) - 1,4-bis(1- butoxyprop-1-en-2-yl)benzene [21]
GC-MS tR : 19.71 min, 20.51 min, 21.41 min (54, Exact mass: 334.2 m/z, found: 334.2 m/z), 18.87 min, 19.50 min, 20.22 min (56, Exact mass: 318.2 m/z, found: 318.2 m/z), 18.14 min, 18.69 min, 19.24 min (21, Exact mass: 302.2 m/z, found: 302.1 m/z). Example 43: (E,E/Z,Z) - 1,4-bis(1-(3-methoxypropoxy)prop-1-en-2- yl)benzene [54], (E,E/Z,Z) - 1-(1-isobutoxyprop-1-en-2-yl)-4-(1-(3- methoxypropoxy)prop-1-en-2-yl)benzene [57], and (E,E/Z,Z) - 1,4-bis(1- isobutoxyprop-1-en-2-yl)benzene [22]
GC-MS tR : 19.74 min, 20.54 min, 21.42 min (54, Exact mass: 334.2 m/z, found: 334.2 m/z), 18.61 min, 19.16 min, 19.76 min (57, Exact mass: 318.2 m/z, found: 318.2 m/z), 17.57 min, 18.06 min, 18.53 min (22, Exact mass: 302.2 m/z, found: 302.1 m/z). Example 44: A mixture of (E,E/Z,Z) - 1,3-bis(1-(3-methoxypropoxy)prop- 1-en-2-yl)benzene [58], 1-(1-(3-methoxypropoxy)prop-1-en-2-yl)-3-(1- propoxyprop-1-en-2-yl)benzene [59], and (E,E/Z,Z) - 1,3-bis(1- propoxyprop-1-en-2-yl)benzene [32]
GC-MS tR : 19.05 min, 19.74 min, 20.53 min (58, Exact mass: 334.2 m/z, found: 334.2 m/z), 17.83 min, 18.19 min, 18.36 min, 18.75 min (59, Exact mass: 304.2 m/z, found: 304.1 m/z), 16.73 min, 17.14 min, 17.42 min (32, Exact mass: 274.2 m/z, found: 274.1 m/z).
Example 45: A mixture of (E,E/Z,Z) - 1,3-bis(1-(3-methoxypropoxy)prop- 1-en-2-yl)benzene [58], (E,E/Z,Z) - 1-(1-butoxyprop-1-en-2-yl)-3-(1-(3- methoxypropoxy)prop-1-en-2-yl)benzene [60], and (E,E/Z,Z) - 1,3-bis(1- butoxyprop-1-en-2-yl)benzene [33]
GC-MS tR : 19.06 min, 19.72 min, 20.53 min (58, Exact mass: 334.2 m/z, found: 334.2 m/z), 18.33 min, 18.86 min, 18.89 min, 19.50 min (60, Exact mass: 318.2 m/z, found: 318.2 m/z), 17.65 min, 18.15 min, 18.68 min (33, Exact mass: 302.2 m/z, found: 302.1 m/z). Example 46: A mixture of (E,E/Z,Z) - 1,3-bis(1-(3-methoxypropoxy)prop- 1-en-2-yl)benzene [58], (E,E/Z,Z) - 1-(1-isobutoxyprop-1-en-2-yl)-3-(1-(3- methoxypropoxy)prop-1-en-2-yl)benzene [61], and (E,E/Z,Z) - 1,3-bis(1- isobutoxyprop-1-en-2-yl)benzene [34]
GC-MS tR : 19.06 min, 19.74 min, 20.51 min (58, Exact mass: 334.2 m/z, found: 334.2 m/z), 18.06 min, 18.55 min, 18.58 min, 19.15 min (61, Exact mass: 318.2 m/z, found: 318.2 m/z), 17.11 min, 17.61 min, 18.04 min (34, Exact mass: 302.2 m/z, found: 302.1 m/z). Example 47: A mixture of (E,E/Z,Z) - 1,4-bis(1-(3-methoxybutoxy)prop-1- en-2-yl)benzene [62], (E,E/Z,Z) - 1-(1-(3-methoxybutoxy)prop-1-en-2-yl)-4- (1-propoxyprop-1-en-2-yl)benzene [63], and (E,E/Z,Z) - 1,4-bis(1- propoxyprop-1-en-2-yl)benzene [20]
GC-MS tR : 20.25 min, 21.33 min, 22.72 min (62, Exact mass: 362.2 m/z, found: 362.3 m/z), 18.52 min, 18.94 min, 19.27 min, 19.75 min (63, Exact mass: 318.2 m/z, found: 318.2 m/z), 17.16 min, 17.54 min, 17.83 min (20, Exact mass: 274.2 m/z, found: 274.1 m/z). Example 48: A mixture of (E,E/Z,Z) - 1,4-bis(1-(3-methoxybutoxy)prop-1- en-2-yl)benzene [62], (E,E/Z,Z) - 1-(1-butoxyprop-1-en-2-yl)-4-(1-(3- methoxybutoxy)prop-1-en-2-yl)benzene [64], and (E,E/Z,Z) - 1,4-bis(1- butoxyprop-1-en-2-yl)benzene [21]
GC-MS tR : 20.25 min, 21.32 min, 22.71 min (62, Exact mass: 362.2 m/z, found: 362.3 m/z), 19.08 min, 19.74 min, 19.94 min, 20.72 min (64, Exact mass: 332.2 m/z, found: 332.3 m/z),18.12 min, 18.67 min, 19.22 min (21, Exact mass: 302.2 m/z, found: 302.1 m/z). Example 49: (E,E/Z,Z) - 1,4-bis(1-(3-methoxybutoxy)prop-1-en-2- yl)benzene [62], (E,E/Z,Z) - 1-(1-isobutoxyprop-1-en-2-yl)-4-(1-(3- methoxybutoxy)prop-1-en-2-yl)benzene [65], and (E,E/Z,Z) - 1,4-bis(1- isobutoxyprop-1-en-2-yl)benzene [22]
GC-MS tR : 20.29 min, 21.33 min, 22.74 min (62, Exact mass: 362.2 m/z, found: 362.3 m/z), 18.75 min, 19.34 min, 19.53 min, 20.22 min (65, Exact mass: 332.2 m/z, found: 332.3 m/z), 17.58 min, 18.06 min, 18.53 min (22, Exact mass: 302.2 m/z, found: 302.1 m/z).
Example 50: A mixture of (E,E/Z,Z) - 1,3-bis(1-(3-methoxybutoxy)prop-1- en-2-yl)benzene [66], (E,E/Z,Z) - 1-(1-(3-methoxybutoxy)prop-1-en-2-yl)-3- (1-propoxyprop-1-en-2-yl)benzene [67], and (E,E/Z,Z) - 1,3-bis(1- propoxyprop-1-en-2-yl)benzene [32]
GC-MS tR : 19.52 min, 20.39 min, 21.54 min (66, Exact mass: 362.2 m/z, found: 362.3 m/z), 18.03 min, 18.40 min, 18.68 min, 19.09 min (67, Exact mass: 318.2 m/z, found: 318.2 m/z), 16.76 min, 17.09 min, 17.42 min (32, Exact mass: 274.2 m/z, found: 274.1 m/z). Example 51: A mixture of (E,E/Z,Z) - 1,3-bis(1-(3-methoxybutoxy)prop-1- en-2-yl)benzene [66], (E,E/Z,Z) - 1-(1-butoxyprop-1-en-2-yl)-3-(1-(3- methoxybutoxy)prop-1-en-2-yl)benzene [68], and (E,E/Z,Z) - 1,3-bis(1- butoxyprop-1-en-2-yl)benzene [33]
GC-MS tR : 19.52 min, 20.39 min, 21.54 min (66, Exact mass: 362.2 m/z, found: 362.3 m/z), 18.52 min, 19.08 min, 19.25 min, 19.89 min (68, Exact mass: 332.2 m/z, found: 332.3 m/z), 17.67 min, 18.15 min, 18.67 min (33, Exact mass: 302.2 m/z, found: 302.1 m/z). Example 52: A mixture of (E,E/Z,Z) - 1,3-bis(1-(3-methoxybutoxy)prop-1- en-2-yl)benzene [66], (E,E/Z,Z) - 1-(1-isobutoxyprop-1-en-2-yl)-3-(1-(3- methoxybutoxy)prop-1-en-2-yl)benzene [69], and (E,E/Z,Z) - 1,3-bis(1- isobutoxyprop-1-en-2-yl)benzene [34]
GC-MS tR : 19.54 min, 20.42 min, 21.52 min (66, Exact mass: 362.2 m/z, found: 362.3 m/z), 18.21 min, 18.75 min, 18.93 min, 19.47 min (69, Exact mass: 332.2 m/z, found: 332.2 m/z), 17.11 min, 17.57 min, 18.05 min (34, Exact mass: 302.2 m/z, found: m/z). Example 53: A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-propoxyethoxy)prop-1- en-2-yl)benzene [70], (E,E/Z,Z) - 1-(1-(2-propoxyethoxy)prop-1-en-2-yl)-4- (1-propoxyprop-1-en-2-yl)benzene [71], and (E,E/Z,Z) - 1,4-bis(1- propoxyprop-1-en-2-yl)benzene [20]
GC-MS tR : 20.70 min, 21.59 min, 22.64 min (70, Exact mass: 362.2 m/z, found: 362.3 m/z), 18.71min, 19.13 min, 19.25 min, 19.72 min (71, Exact mass: 318.2 m/z, found: 318.2 m/z), 17.19 min, 17.54 min, 17.83 min (20, Exact mass: 274.2 m/z, found: 274.1 m/z). Example 54: A mixture of (E,E/Z,Z) - 1,4-bis(1-(2-propoxyethoxy)prop-1- en-2-yl)benzene [70], (E,E/Z,Z) - 1-(1-butoxyprop-1-en-2-yl)-4-(1-(2- propoxyethoxy)prop-1-en-2-yl)benzene [72], and (E,E/Z,Z) - 1,4-bis(1- butoxyprop-1-en-2-yl)benzene [21]
GC-MS tR : 20.76 min, 21.61 min, 22.64 min (70, Exact mass: 362.2 m/z, found: 362.3 m/z), 19.29 min, 19.94 min, 20.66 min(72, Exact mass: 332.2 m/z, found: 332.3 m/z), 18.11 min, 18.67 min, 19.22 min (21, Exact mass: 302.2 m/z, found: 302.1 m/z). Example 55: (E,E/Z,Z) - 1,4-bis(1-(2-propoxyethoxy)prop-1-en-2- yl)benzene [70], (E,E/Z,Z) - 1-(1-isobutoxyprop-1-en-2-yl)-4-(1-(2-
propoxyethoxy)prop-1-en-2-yl)benzene [73], and (E,E/Z,Z) - 1,4-bis(1- isobutoxyprop-1-en-2-yl)benzene [22]
GC-MS tR : 20.73 min, 21.58 min, 22.64 min (70, Exact mass: 362.2 m/z, found: 362.3 m/z), 18.91 min, 19.57 min, 20.20 min (73, Exact mass: 332.2 m/z, found: 332.3 m/z), 17.55 min, 18.06 min, 18.53 min (22, Exact mass: 302.2 m/z, found: 302.1 m/z). Example 56: A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-propoxyethoxy)prop-1- en-2-yl)benzene [74], (E,E/Z,Z) - 1-(1-(2-propoxyethoxy)prop-1-en-2-yl)-3- (1-propoxyprop-1-en-2-yl)benzene [75], and (E,E/Z,Z) - 1,3-bis(1- propoxyprop-1-en-2-yl)benzene [32]
GC-MS tR : 19.92 min, 20.60 min, 21.51 min (74, Exact mass: 362.2 m/z, found: 362.3 m/z), 18.19 min, 18.56 min, 18.67 min, 19.10 min (75, Exact mass: 318.2 m/z, found: 318.2 m/z), 16.78 min, 17.11 min, 17.42 min (32, Exact mass: 274.2 m/z, found: 274.1 m/z).
Example 57: A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-propoxyethoxy)prop-1- en-2-yl)benzene [74], (E,E/Z,Z) -1-(1-butoxyprop-1-en-2-yl)-3-(1-(2- propoxyethoxy)prop-1-en-2-yl)benzene [76], and (E,E/Z,Z) - 1,3-bis(1- butoxyprop-1-en-2-yl)benzene [33]
GC-MS tR : 19.95 min, 20.60 min, 21.49 min (74, Exact mass: 362.2 m/z, found: 362.3 m/z), 18.71 min, 19.24 min, 19.88 min(76, Exact mass: 332.2 m/z, found: 332.3 m/z), 17.67 min, 18.15 min, 18.64 min (33, Exact mass: 302.2 m/z, found: 302.1 m/z). Example 58: A mixture of (E,E/Z,Z) - 1,3-bis(1-(2-propoxyethoxy)prop-1- en-2-yl)benzene [74], (E,E/Z,Z) - 1-(1-isobutoxyprop-1-en-2-yl)-3-(1-(2- propoxyethoxy)prop-1-en-2-yl)benzene [77], and (E,E/Z,Z) - 1,3-bis(1- isobutoxyprop-1-en-2-yl)benzene [34]
GC-MS tR : 19.91 min, 20.59 min, 21.51 min (74, Exact mass: 362.2 m/z, found: 362.3 m/z), 18.37 min, 18.89 min, 19.52 min(77, Exact mass: 332.2 m/z, found: 33 m/z), 17.14 min, 17.58 min, 18.04 min (34, Exact mass: 302.2 m/z, found: 302.1 m/z).
The inventors believe the prophetic examples 59-93 described below are within the spirit and scope of this invention. Example 59: A mixture of (E,E/Z,Z) - 1,4-bis(1-(4-methoxybutoxy)prop-1- en-2-yl)benzene [78], (E,E/Z,Z) - 1-(1-(4-methoxybutoxy)prop-1-en-2-yl)-4- (1-propoxyprop-1-en-2-yl)benzene [79], and (E,E/Z,Z) - 1,4-bis(1- propoxyprop-1-en-2-yl)benzene [20]
Example 60: A mixture of (E,E/Z,Z) - 1,4-bis(1-(4-methoxybutoxy)prop-1- en-2-yl)benzene [78], (E,E/Z,Z) - 1-(1-butoxyprop-1-en-2-yl)-4-(1-(4- methoxybutoxy)prop-1-en-2-yl)benzene [80], and (E,E/Z,Z) - 1,4-bis(1- butoxyprop-1-en-2-yl)benzene [21]
Example 61: (E,E/Z,Z) - 1,4-bis(1-(4-methoxybutoxy)prop-1-en-2- yl)benzene [78], (E,E/Z,Z) - 1-(1-isobutoxyprop-1-en-2-yl)-4-(1-(4- methoxybutoxy)prop-1-en-2-yl)benzene [81], and (E,E/Z,Z) - 1,4-bis(1- isobutoxyprop-1-en-2-yl)benzene [22]
Example 62: A mixture of (E,E/Z,Z) - 1,3-bis(1-(4-methoxybutoxy)prop-1- en-2-yl)benzene [82], (E,E/Z,Z) - 1-(1-(4-methoxybutoxy)prop-1-en-2-yl)-3- (1-propoxyprop-1-en-2-yl)benzene [83], and (E,E/Z,Z) - 1,3-bis(1- propoxyprop-1-en-2-yl)benzene [32]
Example 63: A mixture of (E,E/Z,Z) - 1,3-bis(1-(4-methoxybutoxy)prop-1- en-2-yl)benzene [82], (E,E/Z,Z) -1-(1-butoxyprop-1-en-2-yl)-3-(1-(4- methoxybutoxy)prop-1-en-2-yl)benzene [84], and (E,E/Z,Z) - 1,3-bis(1- butoxyprop-1-en-2-yl)benzene [33]
Example 64: A mixture of (E,E/Z,Z) - 1,3-bis(1-(4-methoxybutoxy)prop-1- en-2-yl)benzene [74], (E,E/Z,Z) - 1-(1-isobutoxyprop-1-en-2-yl)-3-(1-(4- methoxybutoxy)prop-1-en-2-yl)benzene [85], and (E,E/Z,Z) - 1,3-bis(1- isobutoxyprop-1-en-2-yl)benzene [34]
Example 65: A mixture of (E,E/Z,Z) - 1,4-bis(1-(3-ethoxypropoxy)prop-1- en-2-yl)benzene [86], (E,E/Z,Z) - 1-(1-(3-ethoxypropoxy)prop-1-en-2-yl)-4- (1-propoxyprop-1-en-2-yl)benzene [87], and (E,E/Z,Z) - 1,4-bis(1- propoxyprop-1-en-2-yl)benzene [20]
Example 66: A mixture of (E,E/Z,Z) - 1,4-bis(1-(3-ethoxypropoxy)prop-1- en-2-yl)benzene [86], (E,E/Z,Z) - 1-(1-butoxyprop-1-en-2-yl)-4-(1-(3- ethoxypropoxy)prop-1-en-2-yl)benzene [88], and (E,E/Z,Z) - 1,4-bis(1- butoxyprop-1-en-2-yl)benzene [21]
Example 67: (E,E/Z,Z) - 1,4-bis(1-(3-ethoxypropoxy)prop-1-en-2- yl)benzene [86], (E,E/Z,Z) - 1-(1-(3-ethoxypropoxy)prop-1-en-2-yl)-4-(1- isobutoxyprop-1-en-2-yl)benzene [89], and (E,E/Z,Z) - 1,4-bis(1- isobutoxyprop-1-en-2-yl)benzene [22]
Example 68: A mixture of (E,E/Z,Z) - 1,3-bis(1-(3-ethoxypropoxy)prop-1- en-2-yl)benzene [90], (E,E/Z,Z) - 1-(1-(3-ethoxypropoxy)prop-1-en-2-yl)-3- (1-propoxyprop-1-en-2-yl)benzene [91], and (E,E/Z,Z) - 1,3-bis(1- propoxyprop-1-en-2-yl)benzene [32]
Example 69: A mixture of (E,E/Z,Z) - 1,3-bis(1-(3-ethoxypropoxy)prop-1- en-2-yl)benzene [90], (E,E/Z,Z) -1-(1-butoxyprop-1-en-2-yl)-3-(1-(3- ethoxypropoxy)prop-1-en-2-yl)benzene [92], and (E,E/Z,Z) - 1,3-bis(1- butoxyprop-1-en-2-yl)benzene [33]
Example 69: A mixture of (E,E/Z,Z) - 1,3-bis(1-(3-ethoxypropoxy)prop-1- en-2-yl)benzene [90], (E,E/Z,Z) -1-(1-(3-ethoxypropoxy)prop-1-en-2-yl)-3- (1-isobutoxyprop-1-en-2-yl)benzene [93], and (E,E/Z,Z) - 1,3-bis(1- isobutoxyprop-1-en-2-yl)benzene [34]
[0048] The examples 3-52 described above were defined as non-VOC by ASTM D6886. This method uses MeP as a standard – if compound tR > MeP tR, compound is defined as non-VOC. Prophetic examples 59-93 are also expected to be non-VOC by ASTM D6886. Conditions - Agilent 1100 LC • Sample Prep: 2-3 mg/mL in DMSO • Column A: Zorbax XDB-C18 x 4.6 mm, 5 µm
• Column B: Poroshell EC-C1850 x 4.6 mm, 2.7 µm • Column Temp: 40 °C • Injection Volume: 2 µL • DAD: 190-600 nm collection • Pump Conditions: Initial – 97% water (2.5 mM NH4OAc) (Solvent A) and 3% acetonitrile (Solvent B) • Gradient: Table 1
• Mass spectra were acquired with a Micromass LCT mass spectrometer, which was coupled to the LC. Mass spectra were collected using electrospray ionization in both the positive-ion and negative ion modes. Ammonium acetate (50 mM in MeOH) was added post column (0.1 mL/min) to enhance ionization efficiency. ES+/ES- scan range was 60- 3300 amu (25 and 75V). GC-MS Instrument Parameters – Agilent 6890N GC with Agilent 5975B VL MSD [0049] Sample Prep: 100 µL sample diluted to 1 mL with toluene; Column: DB-5 30 m x 0.25 mm x 0.25 µm; Oven Ramp: 0-4.5 mins at 40 °C; Ramp 20C/min to 280C, Hold 53.5 mins; Injector: Temperature – 250 °C; Split Flow – 65 mL/min; Carrier Flow Rate – 1.3 mL/min; Volume – 1.0 µL; MS: Transfer
Line – 280 °C; Ion Source Temp – 230 °C; Mass Range – 34 -700 amu. Methyl palmitate tR = 16.6 min using the above method. [0050] To demonstrate utility in a latex formulation, compounds 58, 66 and 74 were compared against TexanolTM and Optifilm Enhancer 400TM (OE 400) both available commercially from Eastman Chemical Company. Minimum film-forming temperature (MFFT) screening: ASTM D2354-10e [0051] MFFT efficiency testing was based on ASTM D2354. The model instrument used was an MFFT-90 bar which allows samples to be tested from -10°C to 90°C. For waterborne latexes, reaching a temperature of 2°C is the primary goal. To reach that temperature, the MFFT bar was set to range from 0°C to 18°C. This range is important since those Tg values for waterborne latexes somewhat correlate with their coinciding MFFT value. The higher the Tg value, the higher the MFFT value and vice versa. Neat commercial architectural latexes typically fall within this temperature range when testing for MFFT efficiency. Depending on the Tg of the material being tested, the range can be adjusted accordingly to determine the film’s MFFT. [0052] The ultimate goal for the final paint is to form a continuous film at a low temperature (2°C). To achieve this, the MFFT of the neat latex material is first determined. If the neat latex material is above an MFFT of 2°C, the reactive film-hardening additive is added at different phr (% additive based on latex solids) levels to allow the latex to reach 2°C. To reach that temperature, a linear regression of the phr levels is performed. In turn, the appropriate amount of reactive film-hardening additive to add to the final paint formulation can be determined. The results are shown in Table 2 below:
Table 2
[0053] Parts per hundred resin (PHR) of Texanol, OE400, or reactive film- hardening additive required to lower MFFT to 4 °C and 0 °C in Rhoplex SG-30 and Acronal 296 D model coating systems. [0054] The results show that enol ethers of the present invention provide good performance as film hardening additives in latex coating formulations. [0055] The invention has been described in detail with reference to the embodiments disclosed herein, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
Claims
CLAIMS 1. A compound according to Formula I:
wherein: A is (C8-20) alkylaryl; R1a and R1b are independently (C1-12)alkyl, (C2-12)alkenyl, (C3- 8)cycloalkyl, or 5- to 9-membered aryl or
each R4 is independently (C1-12)alkyl, or -C(O)R5; each R5 is (C1-12)alkyl unsubstituted or substituted by R6, (C2-12)alkenyl unsubstituted or substituted by R6, (C3-8)cycloalkyl, or 5- to 9- membered aryl; each R6 is (C1-4)alkoxy, or oxo; and each n is independently an integer from 1 to 15 or
each R7 is independently (C1-12)alkyl. 2. The compound of claim 1 wherein A is 1,
2-, 1,3-, or 1,4-disubstituted phenyl, having a volatile organic content of less than 50 wt% according to
ASTM D6886, wherein R4 is hydrogen or ethyl, and wherein n is an integer from 1 to 4.
4. A compound according to formula I:
wherein: A is (C8-20) alkylaryl; R1a and R1b are independently (C1-12)alkyl, (C2-12)alkenyl, (C3- 8)cycloalkyl, or 5- to 9-membered aryl or
each R4 is independently (C1-12)alkyl, or -C(O)R5; each R5 is (C1-12)alkyl unsubstituted or substituted by R6, (C2-12)alkenyl unsubstituted or substituted by R6, (C3-8)cycloalkyl, or 5- to 9- membered aryl; each R6 is (C1-4)alkoxy, or oxo; and each n is independently an integer from 1 to 15 or
each R7 is independently (C1-12)alkyl each z is an integer from 1 to 4.
5. The compound of claim 4 having a volatile organic content of less than 50 wt% according to ASTM D6886, wherein A is 1,2-, 1,3-, or 1,4- disubstituted phenyl, wherein R4 is hydrogen or ethyl and wherein, n is an integer from 1 to 4.
6. A coating composition comprising: a. at least one latex compound; and b. at least one aromatic enol ether having Formula I:
wherein: A is (C8-20) alkylaryl; R1a and R1b are independently (C1-12)alkyl, (C2-12)alkenyl, (C3- 8)cycloalkyl, or 5- to 9-membered aryl or
each R4 is independently (C1-12)alkyl, or -C(O)R5; each R5 is (C1-12)alkyl unsubstituted or substituted by R6, (C2-12)alkenyl unsubstituted or substituted by R6, (C3-8)cycloalkyl, or 5- to 9- membered aryl; each R6 is (C1-4)alkoxy, or oxo; and each n is independently an integer from 1 to 15 or
each R7 is independently (C1-12)alkyl.
7. The aromatic enol ether of claim 6 having a volatile organic content of less than 50 wt% according to ASTM D6886 wherein A is 1,2-, 1,3-, or 1,4- disubstituted phenyl, wherein R4 is hydrogen or ethyl and wherein, n is an integer from 1 to 4.
8. The coating composition of claim 6 wherein said latex compound is an acrylic polymer, a vinyl acrylic polymer, a styrene butadiene polymer or a styrene acrylic latex polymer, or a mixture thereof.
9. The coating composition of claim 6 wherein said latex compound is a styrene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, isoprene, octyl acrylate, octyl methacrylate, iso-octyl acrylate, iso- octyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, O-methyl styrene, vinyl naphthalene, vinyl toluene, chloromethyl styrene, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, acrylonitrile, glycidyl methacrylate, acetoacetoxyethyl methacrylate, acetoacetoxy ethyl acrylate, vinyl chloride, vinylidene chloride, vinyl acetate, butyl acrylamide, or ethyl acrylamide polymer or mixture thereof.
10 A coating composition comprising: a. at least one latex compound; and b. at least one aromatic enol ether having Formula I:
wherein: A is (C8-20) alkylaryl; R1a and R1b are independently (C1-12)alkyl, (C2-12)alkenyl, (C3- 8)cycloalkyl, or 5- to 9-membered aryl or
each R4 is independently (C1-12)alkyl, or -C(O)R5; each R5 is (C1-12)alkyl unsubstituted or substituted by R6, (C2-12)alkenyl unsubstituted or substituted by R6, (C3-8)cycloalkyl, or 5- to 9- membered aryl; each R6 is (C1-4)alkoxy, or oxo; and each n is independently an integer from 1 to 15 or
each R7 is independently (C1-12)alkyl each z is an integer from 1 to 4.
11. The aromatic enol ether of claim 10 having a volatile organic content of less than 50 wt% according to ASTM D6886, wherein A is 1,2-, 1,3-, or 1,4- disubstituted phenyl, wherein R4 is hydrogen or ethyl and wherein, n is an integer from 1 to 4.
12. The coating composition of claim 10 wherein said latex compound is an acrylic polymer, a vinyl acrylic polymer, a styrene butadiene polymer or a styrene acrylic latex polymer, or a mixture thereof.
13. The coating composition of claim 10 wherein said latex compound is a styrene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, isoprene, octyl acrylate, octyl methacrylate, iso-octyl acrylate, iso- octyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, O-methyl styrene, vinyl naphthalene, vinyl toluene, chloromethyl styrene, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, acrylonitrile, glycidyl methacrylate, acetoacetoxyethyl methacrylate, acetoacetoxy ethyl acrylate, vinyl chloride, vinylidene chloride, vinyl acetate, butyl acrylamide, or ethyl acrylamide polymer or mixture thereof.
15. The coating composition of claim 14wherein said latex compound is a styrene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, isoprene, octyl acrylate, octyl methacrylate, iso-octyl acrylate, iso- octyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, O-methyl styrene, vinyl naphthalene, vinyl toluene, chloromethyl styrene, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, acrylonitrile, glycidyl methacrylate, acetoacetoxyethyl methacrylate, acetoacetoxy ethyl acrylate, vinyl chloride, vinylidene chloride, vinyl acetate, butyl acrylamide, or ethyl acrylamide polymer or mixture thereof.
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WO2018102463A1 (en) * | 2016-11-30 | 2018-06-07 | Christopher Duke | Free radical-and reactive oxygen species-reacting compounds |
US10858304B1 (en) * | 2019-09-04 | 2020-12-08 | Eastman Chemical Company | Aromatic enol ethers |
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US4248957A (en) * | 1978-07-05 | 1981-02-03 | Hoechst Aktiengesellschaft | Acid degradable radiation-sensitive mixture |
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