JPH0556339B2 - - Google Patents
Info
- Publication number
- JPH0556339B2 JPH0556339B2 JP8769685A JP8769685A JPH0556339B2 JP H0556339 B2 JPH0556339 B2 JP H0556339B2 JP 8769685 A JP8769685 A JP 8769685A JP 8769685 A JP8769685 A JP 8769685A JP H0556339 B2 JPH0556339 B2 JP H0556339B2
- Authority
- JP
- Japan
- Prior art keywords
- fluoro
- formula
- acetylamino
- general formula
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002253 acid Substances 0.000 claims description 18
- -1 alkali metal salt Chemical class 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 3
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000000243 solution Substances 0.000 description 17
- 239000002904 solvent Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 238000001953 recrystallisation Methods 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000000638 solvent extraction Methods 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- QYIGFZOHYGYBLX-UHFFFAOYSA-N 2-phenyl-2-sulfanylacetic acid Chemical class OC(=O)C(S)C1=CC=CC=C1 QYIGFZOHYGYBLX-UHFFFAOYSA-N 0.000 description 3
- HMMBJOWWRLZEMI-UHFFFAOYSA-N 4,5,6,7-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CCCC2=C1C(=O)OC2=O HMMBJOWWRLZEMI-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012024 dehydrating agentsâ Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- ZRPLXMHGCDGAQM-UHFFFAOYSA-N 2-(5-amino-2-chloro-4-fluorophenyl)ethanethioic s-acid Chemical compound NC1=CC(CC(O)=S)=C(Cl)C=C1F ZRPLXMHGCDGAQM-UHFFFAOYSA-N 0.000 description 2
- JJYPVYZAGBIUBU-UHFFFAOYSA-N 2-[3-(1,3-dioxo-3a,4,5,7a-tetrahydroisoindol-2-yl)phenyl]sulfanylacetic acid Chemical class OC(=O)CSC1=CC=CC(N2C(C3C=CCCC3C2=O)=O)=C1 JJYPVYZAGBIUBU-UHFFFAOYSA-N 0.000 description 2
- HUPFFHLRZXIFMI-UHFFFAOYSA-N 2-amino-2-phenylethanethioic s-acid Chemical class OC(=S)C(N)C1=CC=CC=C1 HUPFFHLRZXIFMI-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012320 chlorinating reagent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- ZHMMAPCWLTYCEK-UHFFFAOYSA-N n-(4-chloro-2-fluoro-5-sulfanylphenyl)acetamide Chemical compound CC(=O)NC1=CC(S)=C(Cl)C=C1F ZHMMAPCWLTYCEK-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 125000004454 (C1-C6) alkoxycarbonyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- RUIXOZUENDLCST-UHFFFAOYSA-N 2-(5-acetamido-2-bromo-4-fluorophenyl)ethanethioic s-acid Chemical compound CC(=O)NC1=CC(CC(O)=S)=C(Br)C=C1F RUIXOZUENDLCST-UHFFFAOYSA-N 0.000 description 1
- MXBCCJLXNHHIPN-UHFFFAOYSA-N 2-(5-acetamido-2-chloro-4-fluorophenyl)ethanethioic s-acid Chemical compound CC(=O)NC1=CC(CC(O)=S)=C(Cl)C=C1F MXBCCJLXNHHIPN-UHFFFAOYSA-N 0.000 description 1
- RMJDALAJXFKERY-UHFFFAOYSA-N 2-[2-bromo-5-(1,3-dioxo-4,5,6,7-tetrahydroisoindol-2-yl)-4-fluorophenyl]sulfanylacetic acid Chemical compound C1=C(Br)C(SCC(=O)O)=CC(N2C(C3=C(CCCC3)C2=O)=O)=C1F RMJDALAJXFKERY-UHFFFAOYSA-N 0.000 description 1
- TWICXRHICJCOGF-UHFFFAOYSA-N 2-[3-chloro-4-(1,3-dioxo-4,5,6,7-tetrahydroisoindol-2-yl)-5-fluorothiophen-2-yl]acetic acid Chemical compound ClC1=C(CC(=O)O)SC(F)=C1N1C(=O)C(CCCC2)=C2C1=O TWICXRHICJCOGF-UHFFFAOYSA-N 0.000 description 1
- HIULNHONUJTOTQ-UHFFFAOYSA-N 2-chloro-4-fluorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(F)C=C1Cl HIULNHONUJTOTQ-UHFFFAOYSA-N 0.000 description 1
- JIFAWAXKXDTUHW-UHFFFAOYSA-N 2-fluorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1F JIFAWAXKXDTUHW-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- SPAMRUYRVYMHPV-UHFFFAOYSA-N 3a,4,5,7a-tetrahydroisoindole-1,3-dione Chemical class C1=CCCC2C(=O)NC(=O)C21 SPAMRUYRVYMHPV-UHFFFAOYSA-N 0.000 description 1
- AFJWMGOTLUUGHF-UHFFFAOYSA-N 4,5,6,7-tetrahydroisoindole-1,3-dione Chemical compound C1CCCC2=C1C(=O)NC2=O AFJWMGOTLUUGHF-UHFFFAOYSA-N 0.000 description 1
- XRBWNHAYOYZIPT-UHFFFAOYSA-N 5-acetamido-2-bromo-4-fluorobenzenesulfonic acid Chemical compound CC(=O)NC1=CC(S(O)(=O)=O)=C(Br)C=C1F XRBWNHAYOYZIPT-UHFFFAOYSA-N 0.000 description 1
- NKKSARYWJOJMIS-UHFFFAOYSA-N 5-acetamido-2-bromo-4-fluorobenzenesulfonyl chloride Chemical compound CC(=O)NC1=CC(S(Cl)(=O)=O)=C(Br)C=C1F NKKSARYWJOJMIS-UHFFFAOYSA-N 0.000 description 1
- MCYNMHHOXKSIAC-UHFFFAOYSA-N 5-acetamido-2-chloro-4-fluorobenzenesulfonyl chloride Chemical compound CC(=O)NC1=CC(S(Cl)(=O)=O)=C(Cl)C=C1F MCYNMHHOXKSIAC-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003927 aminopyridines Chemical class 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- TVADFTBCWGPXSK-UHFFFAOYSA-N n-(3-sulfanylphenyl)acetamide Chemical compound CC(=O)NC1=CC=CC(S)=C1 TVADFTBCWGPXSK-UHFFFAOYSA-N 0.000 description 1
- HFMVEHCSFPQQFH-UHFFFAOYSA-N n-(4-bromo-2-fluoro-5-sulfanylphenyl)acetamide Chemical compound CC(=O)NC1=CC(S)=C(Br)C=C1F HFMVEHCSFPQQFH-UHFFFAOYSA-N 0.000 description 1
- BCYGKMDWQBWUSC-UHFFFAOYSA-N n-(4-bromo-2-fluorophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Br)C=C1F BCYGKMDWQBWUSC-UHFFFAOYSA-N 0.000 description 1
- GVRKNSAEOVXHOS-UHFFFAOYSA-N n-(4-chloro-2-fluorophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Cl)C=C1F GVRKNSAEOVXHOS-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003208 petroleum 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
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Indole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
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The present invention is based on the general formula [In the formula, X represents a chlorine atom or a bromine atom. ] The present invention relates to 5-(N-acetylamino)-4-fluoro-2-halobenzenesulfonyl chloride (hereinafter referred to as the compound of the present invention) represented by the following and a method for producing the same. reducing the compound of the present invention and reacting it with haloacetic acid;
General formula that can be produced by deacetylation, reaction with 3,4,5,6-tetrahydrophthalic anhydride, and then esterification [In the formula, R is a C1 - C6 alkyl group, a C3 - C7 cycloalkyl group, a C3 - C6 alkenyl group, a C3 - C6 alkynyl group, a C2 - C6 haloalkyl group, a C1- C6 It represents a C4 alkoxy ( C1 - C4 ) alkyl group, a C1 - C6 alkoxycarbonyl ( C1 - C3 ) alkyl group, or a phenyl group, and X has the same meaning as above. ] 2-substituted phenyl-4,5,6,7-
Tetrahydro-2H-isoindole-1,3-
Zion does not cause harmful chemical damage to major crops such as corn, soybeans, wheat, cotton, and rice, and exhibits sufficient herbicidal efficacy against many weeds (Japanese Patent Application Laid-Open No. 59-212472). . The compounds of the present invention are important as intermediates thereof. Compounds of the invention typically have the general formula [In the formula, X represents the same meaning as above. ] An alkali metal salt such as sodium or potassium or an organic base salt such as pyridine of 5-(N-acetylamino)-4-fluoro-2-halobenzenesulfonic acid represented by It can be produced by reacting a chlorinating agent such as phosphorus pentachloride or phosphorus oxychloride in a solvent or in the absence of a solvent at 0°C to 200°C for 0.5 to 5 hours and chlorinating it. Examples of the solvent include halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, and dichlorobenzene, or mixtures thereof. After completion of the reaction, the reaction solution is subjected to normal post-treatments such as extraction with an organic solvent and concentration, or further purified by chromatography, recrystallization, etc. as necessary to obtain the desired general formula. []
The compound of the present invention represented by can be obtained. 5-(N-acetylamino)-4-fluoro-2-halobenzenesulfonic acid represented by the general formula [], which is a raw material compound in the above method, can be efficiently produced by the following method. That is, the general formula [In the formula, X represents the same meaning as above. ] 2-fluoro-4-haloacetanilide and an equivalent to an excess amount of oleum relative to the 2-fluoro-4-haloacetanilide are heated at 0°C to 0°C without a solvent or in concentrated sulfuric acid as a solvent.
It can be produced by reacting at 100°C for 0.5 to 5 hours and sulfonating. After the reaction is complete, the reaction solution is added dropwise to ice or ice water, the precipitated crystals are collected, and the usual post-sulfonation treatment is performed, such as washing with cold water, etc., or if necessary, operations such as recrystallization are performed. The desired 5-(N-acetylamino)-4-
Fluoro-2-halobenzenesulfonic acid [ ] is obtained. In addition, the obtained 5-(N-acetylamino)-4
-Fluoro-2-halobenzenesulfonic acid []
To obtain the corresponding sulfonate, add an aqueous solution of sodium hydroxide, potassium hydroxide, sulfonic acid, etc., or a base such as pyridine, further concentrate under reduced pressure, and then wash the residue with cold water and filter it. be able to. In addition, 5-(N-acetylamino)-4-fluoro-2-halobenzenesulfonic acid [] obtained by sulfonating 2-fluoro-4-haloacetanilide [] can be chlorinated without isolating it. The following methods can be used to efficiently obtain compounds. That is, 2-fluoro-4-haloacetanilide [] is reacted with 1 to 20 equivalents of 20% or more fuming sulfuric acid in the absence of a solvent or in concentrated sulfuric acid as a solvent at 0°C to 20°C to sulfonate it. Then, the obtained sulfonic acid is not isolated, but is reacted with 1.0 to 10 equivalents of a chlorinating agent such as carbon tetrachloride, chloroform, or sulfur dichloride at 60°C to 65°C for 1 to 96 hours to undergo chlorination. It can be manufactured by After the completion of the reaction, the reaction solution is poured into ice water and subjected to usual post-treatments such as organic solvent extraction and concentration, or if necessary, purified by operations such as recrystallization to obtain the desired compound of the present invention. can get. In addition, 2-fluoro-4-haloacetanilide of the general formula [], which is a raw material compound, is
It can be produced by the production method described in Japanese Patent No. 51521. The present invention will be explained in more detail below using manufacturing examples. Production example 1 5-(N-acetylamino)-2-bromo-4-
175.8g of fluorobenzenesulfonic acid and pyridine
130 g was added and stirred for 1 hour, and the precipitated crystals were collected and washed with diethyl ether. 199.5 g of the pyridine salt of the sulfonic acid thus obtained
was suspended in 560 ml of chloroform, and 140.7 g of phosphorus pentachloride was added.
After adding, the mixture was stirred at 60°C to 70°C for 1 hour. The reaction solution was allowed to cool, water was added, and extracted with chloroform.
The extract was dried and concentrated to obtain 73.25 g of 5-(N-acetylamino)-2-bromo-4-fluorobenzenesulfonyl chloride. mp155âïœ156â Using the same method, 5-(N-acetylamino)-
From 2-chloro-4-fluorobenzenesulfonic acid, 5-(N-acetylamino)-2-chloro-4
-Fluorobenzenesulfonyl chloride was obtained. mp138âïœ139â Production Example 2 173.2g of N-(4-bromo-2-fluorophenyl)acetamide was suspended in 80ml of concentrated sulfuric acid and heated at 10â.
After dropping 340ml of 60% oleum at ~20â,
Stir for hours. After that, the reaction solution was added dropwise to 500 g of ice water at 10°C to 20°C, the precipitated crystals were removed, and the mixture was cooled with cold water.
Washed with 400ml. The crystals are dried under reduced pressure and heat,
175.8 g of 5-(N-acetylamino)-2-bromo-4-fluorobenzenesulfonic acid was obtained. mp300â or higher NMR (D 6 -DMSO) ÎŽppm2.0 (3H, s), 7.45 (1H, d) 8.3 (1H, d), 9.7 (1H, m) In the same manner, N-(4-chloro 5-(N-acetylamino)-2-chloro-4-fluorobenzenesulfonic acid was obtained from -2-fluorophenyl)acetamide. mp300â or higher NMR (D 6 -DMSO) ÎŽppm2.0 (3H, s), 7.2 (1H, d), 8.2 (1H, d), 9.6 (1H, m) Production example 3 4-chloro-2-fluoroacetanilide 100
g was added to 80 ml of concentrated sulfuric acid under ice cooling. 200 ml of 60% oleum was added dropwise to this at 0-10°C, and the mixture was stirred for 1 hour.
300 ml of carbon tetrachloride was added at room temperature and stirred at 60-65°C for 5 hours. After cooling to room temperature, add 300 ml of carbon tetrachloride.
ml and stirred at 60-65°C for 5 hours. After cooling, the reaction solution was poured into ice water and extracted with ethyl acetate. The extract was washed with water, dried, and concentrated to obtain 189 g of 4-chloro-2-fluoro-5-chlorosulfonylacetanilide. mp138-139â In the same manner, 4-bromo-2-fluoro-
5-chlorosulfonylacetanilide was obtained. mp155-156â In addition, from the compound of the present invention, by the following method,
2-substituted phenyl-4,5, with herbicidal activity
6,7-tetrahydro-2H-isoindole-
1,3-dione [ ] can be obtained. That is, the compound of the present invention has a 3.0
~20 equivalents of reducing agents such as zinc, stannous chloride, iron, etc.
By using 3.0 to a large excess of acid such as acetic acid, hydrochloric acid, sulfuric acid, etc., and reacting at 50°C to 100°C for 0.1 to 24 hours to reduce the general formula [In the formula, X represents the same meaning as above. ] 5-(N-acetylamino)-4-fluoro-2-halobenzenethiol can be obtained. After completion of the reaction, the reaction solution is subjected to conventional post-treatments such as organic solvent extraction and concentration, or further purified by operations such as chromatography and recrystallization, if necessary. Next, 5-(N-acetylamino)-4-fluoro-2-halobenzenethiol [ ] and the general formula YCH 2 COOH [ ] [where Y represents a chlorine atom or a bromine atom]. ] By reacting haloacetic acid represented by the general formula in a solvent in the presence of a dehydrohalogenating agent at 0°C to 100°C for 0.5 to 24 hours, [In the formula, X represents the same meaning as above. ] A phenylthioglycolic acid derivative represented by the following can be obtained. The amount of reagents used in this reaction is 5-(N-acetylamino)-4-fluoro-
With respect to 1 equivalent of 2-halobenzenethiol [], the amount of haloacetic acid [] is 1.0 to 1.2 equivalents, and the amount of the dehydrohalogenating agent is 1.0 to 1.2 equivalents. As a solvent, aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene,
Examples include ethers such as tetrahydrofuran, acid amides such as N,N-dimethylformamide, sulfur compounds such as dimethyl sulfoxide, water, and mixtures thereof. Examples of the dehydrohalogenation agent include organic bases such as pyridine and triethylamine, and inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, and potassium hydride. After completion of the reaction, the reaction solution is subjected to conventional post-treatments such as solvent extraction and concentration, and if necessary, purified by operations such as chromatography and recrystallization. Furthermore, the phenylthioglycolic acid derivative [] is reacted with 1.0 equivalent to a large excess of mineral acid in a solvent at 20°C to 100°C for 0.5 to 24 hours to deacetylate it. general formula [In the formula, X represents the same meaning as above. ] Aminophenylthioacetic acids represented by these can be obtained. Examples of mineral acids include hydrochloric acid, hydrobromic acid, and sulfuric acid, and examples of solvents include water, alcohol, acetic acid, and the like. After the reaction is completed, the reaction solution is adjusted to pH 1.5 to 4 with an aqueous sodium hydroxide solution, etc. After cooling, the resulting crystals are separated or subjected to usual post-treatments such as organic solvent extraction and concentration, and if necessary. For example, it is purified by operations such as chromatography and recrystallization. The obtained aminophenylthioacetic acid [] and
To this, 1.0 to 1.1 equivalents of 3,4,5,6-tetrahydrophthalic anhydride was added in a solvent at 80°C to 200°C.
By reacting for 0.5 to 12 hours at °C, the general formula [In the formula, X represents the same meaning as above. ] An N-(m-carboxymethylthiophenyl)tetrahydrophthalimide derivative represented by these can be obtained. Examples of the solvent include water, acetic acid, propionic acid, dioxane, etc., and mixtures thereof. After completion of the reaction, the reaction solution is subjected to conventional post-treatments such as organic solvent extraction and concentration, and if necessary, purified by operations such as chromatography and recrystallization. Furthermore, the obtained N-(m-carboxymethylthiophenyl)tetrahydrophthalimide derivative [] has the general formula R-OH [] [wherein R represents the same meaning as above]. ] In a solvent, in the presence of a dehydrating agent, if necessary, in the presence of a base, and if necessary, while removing water from the reaction system, react at 0°C to 200°C for 1 hour to 24 hours. 2-substituted phenyl-4,5,6,7-tetrahydro-2H-isoindole-1,3-dione [] can be obtained by The amount of reagents used in this reaction is N-
For 1 equivalent of (m-carboxymethylthiophenyl)tetrahydrophthalimide derivative [],
The alcohol [ ] is used in an amount of 1 to 10 equivalents, and the dehydrating agent and the base are used in a catalytic amount to 1 equivalent. Examples of solvents include aliphatic hydrocarbons such as hexane, heptane, ligroin, and petroleum ether, aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, and methylene chloride, and diethyl. Examples include ethers such as ether, diisopropyl ether, dioxane, tetrahydrofuran, and diethylene glycol dimethyl ether. Examples of the dehydrating agent include acids such as concentrated sulfuric acid and para-toluenesulfonic acid, and carbodiimides such as dicyclohexylcarbodiimide. Examples of the base include aminopyridines such as 4-N,N-dimethylaminopyridine. After completion of the reaction, the reaction solution is subjected to conventional post-treatments such as organic solvent extraction and concentration, and if necessary, purified by operations such as chromatography and recrystallization. Next, a production example of 2-substituted phenyl-4,5,6,7-sotrahydro-2H-isoindole-1,3-dione [] will be shown as a reference example. Reference example 1 [5-(N-acetylamino)-4-fluoro-
Production of 2-Halobenzenethiol [] 73.25 g of 4-bromo-2-fluoro-5-chlorosulfonylacetanilide was dissolved in 630 ml of acetic acid, and 289.7 g of zinc was added. Heating the reaction solution, 6
Refluxed for an hour. After cooling, water was added, extracted with ethyl acetate, washed with water, washed with sodium bicarbonate, dried, and concentrated to obtain 31.38 g of 2-bromo-4-fluoro-5-acetamino-thiophenol. mp157-158â 4-chloro-2-fluoro-5 in the same manner
2-chloro-4-fluoro-5-acetamino-thiophenol mp 156-158°C was obtained from -chlorosulfonylacetanilide. Reference Example 2 [Production of phenylthioglycolic acid derivative []] 8 g of 2-chloro-4-fluoro-5-acetaminothiophenol, 1.6 g of sodium hydroxide,
6 g of bromoacetic acid was added dropwise to a mixture of 25 ml of water at 0 to 5°C, and the mixture was refluxed until it became a lead acetate test paper (-). After cooling, the reaction solution was adjusted to pH=4 and extracted with ethyl acetate. The extract was dried and concentrated to obtain 8.8 g of 5-(N-acetylamino)-2-chloro-4-fluorophenylthioacetic acid. mp145-147â In the same manner, 2-bromo-4-fluoro-
From 5-acetaminothiophenol, 5-(N
-acetylamino)-2-bromo-4-fluorophenylthioacetic acid was obtained. mp173.1~174.1
°C Reference Example 3 [Production of aminophenylthioacetic acids] 5-(N-acetylamino)-2-chloro-4-
89.8 g of fluorophenylthioacetic acid was suspended in a 10% aqueous hydrochloric acid solution and heated under reflux for 2 hours. After the reaction solution has cooled down, add sodium hydroxide aqueous solution and adjust the pH to 4.
And so. After cooling with ice, the precipitated crystals were collected, washed with cold water, and air-dried to obtain 55.0 g of 5-amino-2-chloro-4-fluorophenylthioacetic acid. NMR (CDCl 3 + D 6 âDMSO) ÎŽppm3.55 (2H,
s), 6.75 (1H, d), 6.92 (1H, d), 6.2~
7.6 (2H, m), IRÎœcm -1 (liquid paraffin) 3400, 3300, 1670 In the same manner, 5-(N-acetylamino)-
5-amino-2-bromo-4-fluorophenylthioacetic acid was obtained from 2-bromo-4-fluorophenylthioacetic acid. NMR (CDCl 3 ) ÎŽppm3.6 (2H, s), 6.6 (2H,
m), 6.9 (1H, d), 7.1 (1H, d), IRÎœcm -1 (liquid paraffin) 3380, 3280, 1670 Reference example 4 [N-(m-carboxymethylthiophenyl)
Production of tetrahydrophthalimide derivative [] 55.0 g of 5-amino-2-chloro-4-fluorophenylthioacetic acid and 38.1 g of 3,4,5,6-tetrahydrophthalic anhydride were dissolved in 250 ml of acetic acid.
The mixture was heated under reflux for 1 hour. After the reaction mixture has cooled,
Water was added and extracted with ethyl acetate. After neutralizing the extract with an aqueous sodium bicarbonate solution, washing with water, and drying,
The solvent was distilled off under reduced pressure to give 2-(5-carboxylmethylthio-4-chloro-2-fluorophenyl).
46.8 g of -4,5,6,7-tetrahydro-2H-isoindole-1,3-dione was obtained. mp138-139â In the same manner, 5-amino-2-bromo-4
- From fluorophenylthioacetic acid, 2-(5-carboxylmethylthio-4-bromo-2-fluorophenyl)-4,5,6,7-tetrahydro-
2H-isoindole-1,3-dione was obtained. NMR (CDCl 3 ) ÎŽppm1.8 (4H, m), 2.4 (4H,
m), 3.65 (2H, s), 7.28 (1H, d), 7.45
(1H, s), 10.2 (1H, m) IRÎœcm -1 (neat) 1715 Reference example 5 [2-substituted phenyl-4,5,6,7-tetrahydro-2H-isoindole-1,3-dione] ] 2-(4-chloro-2-fluoro-5-carboxymethylthiophenyl)-4,5,6,7-tetrahydro-2H-isoindole-1,3-dione 1.2 g, ethanol 1.0 g Dissolve in 20ml of toluene, add a small amount of p-toluenesulfonic acid, reflux for 3 hours, add water, separate the toluene layer, dry,
Concentrate and purify the residue with a silica gel column to obtain 2-
(4-chloro-2-fluoro-5-ethoxycarbonylmethylthiophenyl)-4,5,6,7,-
Tetrahydro-2H-isoindole-1,3-
0.1 g of dione was obtained. n 18 D 1.5670 2-substituted phenyl- which can be produced by a similar method
Some of 4,5,6,7-tetrahydro-2H-isoindole-1,3-dione []
Shown in the table.
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Claims (1)
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é æ³ã[Claims] 1. General formula [In the formula, X represents a chlorine atom or a bromine atom. ] 5-(N-acetylamino)-4-fluoro-2-halobenzenesulfonyl chloride. 2 General formula [In the formula, X represents a chlorine atom or a bromine atom. ] A general formula characterized by reacting an alkali metal salt or organic base salt of 5-(N-acetylamino)-4-fluoro-2-halobenzenesulfonic acid with phosphorus pentachloride or phosphorus oxychloride. [In the formula, X represents the same meaning as above. ] A method for producing 5-(N-acetylamino)-4-fluoro-2-halobenzenesulfonyl chloride. 3 General formula [In the formula, X represents a chlorine atom or a bromine atom. ] The general formula obtained by reacting 2-fluoro-4-haloacetanilide with fuming sulfuric acid [In the formula, X represents the same meaning as above. ] 5-(N-acetylamino)-4-fluoro-2-halobenzenesulfonic acid represented by is converted into an alkali metal salt or an organic base salt, and then reacted with phosphorus pentachloride or phosphorus oxychloride. general formula [In the formula, X represents the same meaning as above. ] A method for producing 5-(N-acetylamino)-4-fluoro-2-halobenzenesulfonyl chloride. 4 General formula [In the formula, X represents a chlorine atom or a bromine atom. ] The general formula obtained by reacting 2-fluoro-4-haloacetanilide with fuming sulfuric acid [In the formula, X represents the same meaning as above. ] without isolating 5-(N-acetylamino)-4-fluoro-2-halobenzenesulfonic acid represented by
General formula characterized by reacting carbon tetrachloride, chloroform or sulfur dichloride [In the formula, X represents the same meaning as above. ] A method for producing 5-(N-acetylamino)-4-fluoro-2-halobenzenesulfonyl chloride.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA000453116A CA1210771A (en) | 1983-05-16 | 1984-04-30 | 2-substituted phenyl-4,5,6,7-tetrahydro-2h-isoindole- 1,3-diones, and their production and use |
CA453116 | 1984-04-30 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60248657A JPS60248657A (en) | 1985-12-09 |
JPH0556339B2 true JPH0556339B2 (en) | 1993-08-19 |
Family
ID=4127752
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8769685A Granted JPS60248657A (en) | 1984-04-30 | 1985-04-24 | 5-(n-acetylamino)-4-fluoro-2-halobenzenesulfonyl chloride and its preparation |
JP60087697A Pending JPS60248663A (en) | 1984-04-30 | 1985-04-24 | Aminophenylthioacetic acid compound and its preparation |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60087697A Pending JPS60248663A (en) | 1984-04-30 | 1985-04-24 | Aminophenylthioacetic acid compound and its preparation |
Country Status (1)
Country | Link |
---|---|
JP (2) | JPS60248657A (en) |
-
1985
- 1985-04-24 JP JP8769685A patent/JPS60248657A/en active Granted
- 1985-04-24 JP JP60087697A patent/JPS60248663A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
JPS60248657A (en) | 1985-12-09 |
JPS60248663A (en) | 1985-12-09 |
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