CN108947811A - A kind of preparation method of benzene oxycarboxylic acid salt herbicide - Google Patents
A kind of preparation method of benzene oxycarboxylic acid salt herbicide Download PDFInfo
- Publication number
- CN108947811A CN108947811A CN201810225293.1A CN201810225293A CN108947811A CN 108947811 A CN108947811 A CN 108947811A CN 201810225293 A CN201810225293 A CN 201810225293A CN 108947811 A CN108947811 A CN 108947811A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oxycarboxylic acid
- benzene
- acid ester
- preparation
- 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.)
- Pending
Links
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 216
- 239000002253 acid Substances 0.000 title claims abstract description 94
- 150000003839 salts Chemical class 0.000 title claims abstract description 38
- 239000004009 herbicide Substances 0.000 title claims abstract description 34
- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 150000002148 esters Chemical class 0.000 claims abstract description 73
- 239000003054 catalyst Substances 0.000 claims abstract description 69
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 18
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 15
- 239000012320 chlorinating reagent Substances 0.000 claims abstract description 11
- 125000001118 alkylidene group Chemical group 0.000 claims abstract description 10
- 229930192474 thiophene Natural products 0.000 claims abstract description 10
- 238000006482 condensation reaction Methods 0.000 claims abstract description 9
- 239000002585 base Substances 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 150000003568 thioethers Chemical class 0.000 claims abstract description 6
- 150000003577 thiophenes Chemical class 0.000 claims abstract description 4
- 150000003557 thiazoles Chemical class 0.000 claims abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 82
- 238000006243 chemical reaction Methods 0.000 claims description 75
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 58
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 44
- -1 benzene oxygen Carboxylate Chemical class 0.000 claims description 35
- 229910052799 carbon Inorganic materials 0.000 claims description 33
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 31
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- 239000000460 chlorine Substances 0.000 claims description 17
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 13
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 12
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 10
- 239000001099 ammonium carbonate Substances 0.000 claims description 10
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- LNMBCRKRCIMQLW-UHFFFAOYSA-N 2-tert-butylsulfanyl-2-methylpropane Chemical compound CC(C)(C)SC(C)(C)C LNMBCRKRCIMQLW-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 6
- OVXHWSNIIKNEQD-UHFFFAOYSA-N 2,3,4-trichlorothiophene Chemical compound ClC1=CSC(Cl)=C1Cl OVXHWSNIIKNEQD-UHFFFAOYSA-N 0.000 claims description 5
- XPJACWOWEJJYRD-UHFFFAOYSA-N 2,5-dichloro-1,3-thiazole Chemical compound ClC1=CN=C(Cl)S1 XPJACWOWEJJYRD-UHFFFAOYSA-N 0.000 claims description 5
- CGZDWVZMOMDGBN-UHFFFAOYSA-N 2-Ethylthiazole Chemical compound CCC1=NC=CS1 CGZDWVZMOMDGBN-UHFFFAOYSA-N 0.000 claims description 5
- QVFXSOFIEKYPOE-UHFFFAOYSA-N 3,4-dichlorothiophene Chemical compound ClC1=CSC=C1Cl QVFXSOFIEKYPOE-UHFFFAOYSA-N 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 5
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-Me3C6H3 Natural products CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 4
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 claims description 4
- QMHIMXFNBOYPND-UHFFFAOYSA-N 4MTO Natural products CC1=CSC=N1 QMHIMXFNBOYPND-UHFFFAOYSA-N 0.000 claims description 4
- 229910007339 Zn(OAc)2 Inorganic materials 0.000 claims description 4
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 claims description 4
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 238000009333 weeding Methods 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- MJEPOVIWHVRBIT-UHFFFAOYSA-N 1-chloro-4-(4-chlorophenyl)sulfanylbenzene Chemical compound C1=CC(Cl)=CC=C1SC1=CC=C(Cl)C=C1 MJEPOVIWHVRBIT-UHFFFAOYSA-N 0.000 claims description 3
- XTMUXJBJCMRWPG-UHFFFAOYSA-N 3-chloropyridine-2-carboxylic acid Chemical compound OC(=O)C1=NC=CC=C1Cl XTMUXJBJCMRWPG-UHFFFAOYSA-N 0.000 claims description 3
- QUBJDMPBDURTJT-UHFFFAOYSA-N 3-chlorothiophene Chemical compound ClC=1C=CSC=1 QUBJDMPBDURTJT-UHFFFAOYSA-N 0.000 claims description 3
- SPRVGONRQZESPA-UHFFFAOYSA-N 4,5-dimethyl-1,2-thiazole Chemical compound CC=1C=NSC=1C SPRVGONRQZESPA-UHFFFAOYSA-N 0.000 claims description 3
- ZYXAPXCRZZMDQA-UHFFFAOYSA-N 5-chloro-1,2-thiazole Chemical compound ClC1=CC=NS1 ZYXAPXCRZZMDQA-UHFFFAOYSA-N 0.000 claims description 3
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- QOJMQILDLLFGEE-UHFFFAOYSA-N 2-butyl-1,3-thiazole Chemical compound CCCCC1=NC=CS1 QOJMQILDLLFGEE-UHFFFAOYSA-N 0.000 claims 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims 1
- JBZRLVKMCLOFLG-UHFFFAOYSA-N O=S=Cl Chemical compound O=S=Cl JBZRLVKMCLOFLG-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000002841 Lewis acid Substances 0.000 abstract description 5
- 150000007517 lewis acids Chemical group 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 150000003854 isothiazoles Chemical class 0.000 abstract 1
- 238000009413 insulation Methods 0.000 description 27
- 150000001721 carbon Chemical group 0.000 description 25
- 239000000047 product Substances 0.000 description 23
- BZCKRPHEZOHHBK-UHFFFAOYSA-N methyl 2-phenoxyacetate Chemical compound COC(=O)COC1=CC=CC=C1 BZCKRPHEZOHHBK-UHFFFAOYSA-N 0.000 description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- 238000004821 distillation Methods 0.000 description 16
- 238000011084 recovery Methods 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000012043 crude product Substances 0.000 description 15
- 239000012065 filter cake Substances 0.000 description 15
- 238000010992 reflux Methods 0.000 description 15
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 14
- 238000001914 filtration Methods 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 11
- 230000000630 rising effect Effects 0.000 description 11
- 150000002989 phenols Chemical class 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000009833 condensation Methods 0.000 description 9
- 230000005494 condensation Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- SXERGJJQSKIUIC-UHFFFAOYSA-N 2-Phenoxypropionic acid Chemical compound OC(=O)C(C)OC1=CC=CC=C1 SXERGJJQSKIUIC-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical group COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 description 7
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 7
- 239000001103 potassium chloride Substances 0.000 description 7
- 235000011164 potassium chloride Nutrition 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- IUQJDHJVPLLKFL-UHFFFAOYSA-N 2-(2,4-dichlorophenoxy)acetate;dimethylazanium Chemical compound CNC.OC(=O)COC1=CC=C(Cl)C=C1Cl IUQJDHJVPLLKFL-UHFFFAOYSA-N 0.000 description 6
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxyacetic acid Chemical compound OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 5
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 5
- YAVVGPBYBUYPSR-UHFFFAOYSA-N benzene;oxygen Chemical compound [O].C1=CC=CC=C1 YAVVGPBYBUYPSR-UHFFFAOYSA-N 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- 125000003944 tolyl group Chemical group 0.000 description 5
- SODPIMGUZLOIPE-UHFFFAOYSA-N (4-chlorophenoxy)acetic acid Chemical compound OC(=O)COC1=CC=C(Cl)C=C1 SODPIMGUZLOIPE-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910001510 metal chloride Inorganic materials 0.000 description 4
- HWIGZMADSFQMOI-UHFFFAOYSA-N methyl 2-(2,4-dichlorophenoxy)acetate Chemical class COC(=O)COC1=CC=C(Cl)C=C1Cl HWIGZMADSFQMOI-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- GVMOTDXEGIBMCK-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)butanoic acid Chemical compound CCC(C(O)=O)OC1=CC=C(Cl)C=C1C GVMOTDXEGIBMCK-UHFFFAOYSA-N 0.000 description 3
- KVHOVQBNKCVEEG-UHFFFAOYSA-N 2-methylpropyl 2-phenoxypropanoate Chemical compound CC(C)COC(=O)C(C)OC1=CC=CC=C1 KVHOVQBNKCVEEG-UHFFFAOYSA-N 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- QIIPQYDSKRYMFG-UHFFFAOYSA-N phenyl hydrogen carbonate Chemical compound OC(=O)OC1=CC=CC=C1 QIIPQYDSKRYMFG-UHFFFAOYSA-N 0.000 description 3
- 231100000004 severe toxicity Toxicity 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- AMFGTOFWMRQMEM-UHFFFAOYSA-N triazophos Chemical compound N1=C(OP(=S)(OCC)OCC)N=CN1C1=CC=CC=C1 AMFGTOFWMRQMEM-UHFFFAOYSA-N 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical compound CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 description 2
- QSGCJQBBHYWZHS-UHFFFAOYSA-N 2-methylpropyl 2-chloroacetate Chemical compound CC(C)COC(=O)CCl QSGCJQBBHYWZHS-UHFFFAOYSA-N 0.000 description 2
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 2
- DQAIZGWCKXJRSP-UHFFFAOYSA-N 2-tert-butyl-1,3-thiazole Chemical compound CC(C)(C)C1=NC=CS1 DQAIZGWCKXJRSP-UHFFFAOYSA-N 0.000 description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- QQOSUPHSTQYAOH-UHFFFAOYSA-N 6-methylheptyl 2-chloroacetate Chemical compound CC(C)CCCCCOC(=O)CCl QQOSUPHSTQYAOH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- BTMVHUNTONAYDX-UHFFFAOYSA-N butyl propionate Chemical compound CCCCOC(=O)CC BTMVHUNTONAYDX-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- PQROLKNPFDDLPB-UHFFFAOYSA-N ethyl 2-(4-chloro-2-methylphenoxy)butanoate Chemical compound CCOC(=O)C(CC)OC1=CC=C(Cl)C=C1C PQROLKNPFDDLPB-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- OSGZHKYFZSNKRI-UHFFFAOYSA-N methyl 2-(4-chlorophenoxy)acetate Chemical class COC(=O)COC1=CC=C(Cl)C=C1 OSGZHKYFZSNKRI-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- ZUGZAGVRSXHCOA-UHFFFAOYSA-N propan-2-yl 2-phenoxyacetate Chemical compound CC(C)OC(=O)COC1=CC=CC=C1 ZUGZAGVRSXHCOA-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- CETFXLWWGIUWAI-UHFFFAOYSA-M sodium;2-(4-chlorophenoxy)acetate Chemical compound [Na+].[O-]C(=O)COC1=CC=C(Cl)C=C1 CETFXLWWGIUWAI-UHFFFAOYSA-M 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- GAWAYYRQGQZKCR-REOHCLBHSA-N (S)-2-chloropropanoic acid Chemical compound C[C@H](Cl)C(O)=O GAWAYYRQGQZKCR-REOHCLBHSA-N 0.000 description 1
- 0 *c1cc(Cl)ccc1O*C(O*)=O Chemical compound *c1cc(Cl)ccc1O*C(O*)=O 0.000 description 1
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 description 1
- MZHCENGPTKEIGP-UHFFFAOYSA-N 2-(2,4-dichlorophenoxy)propanoic acid Chemical compound OC(=O)C(C)OC1=CC=C(Cl)C=C1Cl MZHCENGPTKEIGP-UHFFFAOYSA-N 0.000 description 1
- HMIAXVWVTBIGON-UHFFFAOYSA-N 2-chloro-1-(chloromethyl)-4-fluorobenzene Chemical compound FC1=CC=C(CCl)C(Cl)=C1 HMIAXVWVTBIGON-UHFFFAOYSA-N 0.000 description 1
- RVBUZBPJAGZHSQ-UHFFFAOYSA-N 2-chlorobutanoic acid Chemical compound CCC(Cl)C(O)=O RVBUZBPJAGZHSQ-UHFFFAOYSA-N 0.000 description 1
- GSFNQBFZFXUTBN-UHFFFAOYSA-N 2-chlorothiophene Chemical class ClC1=CC=CS1 GSFNQBFZFXUTBN-UHFFFAOYSA-N 0.000 description 1
- WOYWLLHHWAMFCB-UHFFFAOYSA-N 2-ethylhexyl acetate Chemical compound CCCCC(CC)COC(C)=O WOYWLLHHWAMFCB-UHFFFAOYSA-N 0.000 description 1
- IPLKGJHGWCVSOG-UHFFFAOYSA-N 4-chlorobutanoic acid Chemical compound OC(=O)CCCCl IPLKGJHGWCVSOG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- GUUNMTFSWQFNCZ-UHFFFAOYSA-I C(C=1C(C(=O)[O-])=CC=CC1)(=O)O.[K+].[C+4].C(C=1C(C(=O)[O-])=CC=CC1)(=O)O.C(C=1C(C(=O)[O-])=CC=CC1)(=O)O.C(C=1C(C(=O)[O-])=CC=CC1)(=O)O.C(C=1C(C(=O)[O-])=CC=CC1)(=O)O Chemical compound C(C=1C(C(=O)[O-])=CC=CC1)(=O)O.[K+].[C+4].C(C=1C(C(=O)[O-])=CC=CC1)(=O)O.C(C=1C(C(=O)[O-])=CC=CC1)(=O)O.C(C=1C(C(=O)[O-])=CC=CC1)(=O)O.C(C=1C(C(=O)[O-])=CC=CC1)(=O)O GUUNMTFSWQFNCZ-UHFFFAOYSA-I 0.000 description 1
- WNKGQCYVYDRMAL-UHFFFAOYSA-N C1(=CC=CC=C1)O.CC=1C=CC(=CC1)C(C)(C)C Chemical compound C1(=CC=CC=C1)O.CC=1C=CC(=CC1)C(C)(C)C WNKGQCYVYDRMAL-UHFFFAOYSA-N 0.000 description 1
- CYYSQTKXONGQKD-UHFFFAOYSA-N CNC.ClC1=CC(=C(OC(C(=O)O)CC)C=C1)C Chemical compound CNC.ClC1=CC(=C(OC(C(=O)O)CC)C=C1)C CYYSQTKXONGQKD-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 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
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PEZJICHLRCIEOF-UHFFFAOYSA-N [Na].OC(=O)COc1ccc(Cl)cc1 Chemical compound [Na].OC(=O)COc1ccc(Cl)cc1 PEZJICHLRCIEOF-UHFFFAOYSA-N 0.000 description 1
- MHIRBEIOVZPIDF-UHFFFAOYSA-N [O].ClC1=CC=CC=C1 Chemical compound [O].ClC1=CC=CC=C1 MHIRBEIOVZPIDF-UHFFFAOYSA-N 0.000 description 1
- 229940056218 acid gone Drugs 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N benzyl-alpha-carboxylic acid Natural products OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QEWYKACRFQMRMB-UHFFFAOYSA-N monofluoroacetic acid Natural products OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- VODRWDBLLGYRJT-UHFFFAOYSA-N propan-2-yl 2-chloroacetate Chemical compound CC(C)OC(=O)CCl VODRWDBLLGYRJT-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- QOUKSTJONOWRTR-UHFFFAOYSA-N propyl 2-phenoxyacetate Chemical compound CCCOC(=O)COC1=CC=CC=C1 QOUKSTJONOWRTR-UHFFFAOYSA-N 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
- 238000004064 recycling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- LNSAEWXPCBLGDX-UHFFFAOYSA-M sodium;2-(2,4-dichlorophenoxy)acetate;hydrate Chemical compound O.[Na+].[O-]C(=O)COC1=CC=C(Cl)C=C1Cl LNSAEWXPCBLGDX-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention provides a kind of preparation methods of benzene oxycarboxylic acid salt herbicide, comprising: S1, by phenol or o-cresol under alkaline matter effect, carry out condensation reaction with chlorinated carboxylic acid ester, obtain benzene oxycarboxylic acid ester；The chlorinated carboxylic acid ester general formula is ClR1COOR, R1For the alkylidene or alkylidene of C1~3, R is the alkyl of C1~10 or the naphthenic base of C3~10；S2, by the benzene oxycarboxylic acid ester under the first catalyst and the second catalyst action, with chlorinating agent carry out selective chlorination, obtain the ester of chlorobenzene oxycarboxylic acid shown in Formulas I；R3For H, Cl or CH3；First catalyst is selected from lewis acid, and the second catalyst is selected from thioether class, thiazoles, isothiazole class or the thiophenes of C5~22；S3, the chlorobenzene oxycarboxylic acid ester is mixed with alkali compounds, carries out Basic fluxing raction, obtains benzene oxycarboxylic acid salt herbicide.The present invention can improve product quality and production operation environment, and the three wastes are few.
Description
Technical field
The present invention relates to technical field of organic synthesis, more particularly, to a kind of preparation side of benzene oxycarboxylic acid salt herbicide
Method.
Background technique
Phenoxy carboxylic acid herbicides is a kind of important herbicide, due to its weeding fast speed, herbicidal spectrum is wider the advantages that,
Agriculturally it is being widely used.The necessary condition of phenoxy carboxylic acid reactive compound structure includes: a phenyl ring, an oxygen original on ring
Son replaces；The aliphatic chain being connected with oxygen atom and a carboxyl；Contain different substituent groups on phenyl ring, wherein taking with the 2nd, 4
The compound activity highest in generation.Due to the architectural difference of the groups such as benzene ring substitution group, different herbicide kinds can be formed；Agricultural
The more acid and esters for having such herbicide is used in production.This kind of herbicide includes the benzene oxygen carboxylic for having following structure general formula
Acid compounds:
In formula a, R1The alkylidene or alkylidene for being 1~3 for carbon atom number, R2For H, carbon atom number be 3~10 alkyl or
Naphthenic base, R3For H, Cl or CH3.But the water solubility of the chlorobenzene oxycarboxylic acid of this class formation is poor, thus use and also have
Certain difficulty.And the salt of chlorobenzene oxycarboxylic acid has if sodium salt, sylvite, ammonium salt or amine salt are preferable water-soluble due to having
Relatively broad application.Wherein, 4-chlorophenoxyacetic acid sodium, 2,4- Dichlorophenoxyacetic acid sodium, methoxone potassium,
2,4 dichlorophenoxyacetic acid dimethylamine salt, methoxone dimethylamine salt etc. are all widely used products.
The preparation method of the existing above-mentioned benzene oxycarboxylic acid salt herbicide being generally used mainly has following two step:
(1) using phenol as primary raw material, chlorinated phenol is made through chlorination；(2) chlorinated phenol carries out being condensed under alkaline condition with chlorinated carboxylic acid anti-
It answers, obtains condensation liquid.When the benzene oxycarboxylic acid salt herbicide of preparation is alkali metal salt, condensation liquid is directly filtered, after washing again
Drying, can be obtained benzene oxycarboxylic acid salt herbicide；And when the benzene oxycarboxylic acid salt herbicide of preparation be amine salt when, condensation liquid need through
Acidification, washing, drying, obtain phenoxy carboxylic acid herbicides, then react with ammonium carbonate, ammonium hydrogen carbonate, ammonia or organic amine, and benzene oxygen is made
Metal carboxylate herbicide.
In the above method, the chlorinated phenol of (1) step output has the penetrating odor of extremely difficult news, leads to production on-site environment
It is very poor, and chlorination is selectively poor.And in (2) step, it is intermolecular that Dichlorophenol or multi-chlorophenol in chlorinated phenol can occur two
Condensation can not only generate to generate hypertoxicity substance-dioxin of extremely difficult degradation and largely contain chlorinated phenol, chlorobenzene oxygen carboxylic
The dangerous waste of acid, and also contains dioxin in the benzene oxycarboxylic acid salt herbicide products of output, this is to environment and producers
Health brings great risk, and product quality is poor.In addition, dioxin can also be with benzene oxycarboxylic acid salt herbicide and its derivative
The use of product enters plant, air, soil and water source, and as food chain is enriched with, in turn results in more serious environment
And health hazard.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of preparation side of benzene oxycarboxylic acid salt herbicide
Method, this method can improve the operating environment of product quality and production scene.
The present invention provides a kind of preparation method of benzene oxycarboxylic acid salt herbicide, comprising the following steps:
S1, by phenol or o-cresol in the presence of alkaline substances, carry out condensation reaction with chlorinated carboxylic acid ester, obtain
Benzene oxycarboxylic acid ester；
The general formula of the chlorinated carboxylic acid ester is ClR1COOR, wherein R1The alkylidene or secondary alkane for being 1~3 selected from carbon atom number
Base, R are selected from the alkyl that carbon atom number is 1~10 or the naphthenic base that carbon atom number is 3~10；
S2, by the benzene oxycarboxylic acid ester existing for the first catalyst and the second catalyst under the conditions of, carried out with chlorinating agent
Selective chlorination obtains chlorobenzene oxycarboxylic acid ester shown in Formulas I；Wherein R3For H, Cl or CH3；First catalyst is selected from road
Lewis acid, the thiazole that second catalyst is selected from the thio-ether type compounds that carbon atom number is 5~22, carbon atom number is 5~22
The thiophenes that the different thiazoles compound or carbon atom number that class compound, carbon atom number are 5~22 are 5~22；
S3, the chlorobenzene oxycarboxylic acid ester is mixed with alkali compounds, carries out Basic fluxing raction, obtains benzene oxycarboxylic acid salt
Herbicide.
Preferably, in S1 step, the alkaline matter is sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, carbon
One of sour hydrogen sodium, saleratus, sodium carbonate and potassium carbonate are a variety of.
Preferably, in S1 step, the condensation reaction carries out in organic solvent, the organic solvent be benzene, toluene or
Dimethylbenzene；The setting-up point is 60~120 DEG C.
Preferably, in S2 step, first catalyst is selected from SnCl4、MgCl2、FeCl3、AlCl3、ZnCl2、TiCl4、
BF3、SbF5、Al2O3、Fe2O3、TiO2、Pb(OAc)2、Zn(OAc)2And Al2O(OAc)4One of or it is a variety of.
Preferably, in S2 step, second catalyst is selected from tertbutyl methyl thioether, tert-butylsulfide, diphenyl sulfide, 4,
4'- dichloro diphenyl sulfide, 2- methyl diphenyl sulfide, 2,4,6- trimethylbenzene thioether, 4,4'- thiobis (6- tert-butyl -3- methylbenzene
Phenol), thiazole, 2- ethyl thiazole, 2,5- dichloro thiazole, 4- methylthiazol, 2- tertiary butyl thiazole, isothiazole, 4,5- dimethyl it is different
Thiazole, 5- chloroisothiazole, 2,4,5- tri-tert isothiazole, thiophene, 2- methylthiophene, 2,5- thioxene, 3- chlorothiophene,
One of tri- chlorothiophene of 3,4- dichloro-thiophene and 2,3,4- is a variety of.
Preferably, in S2 step, the chlorinating agent is chlorine, thionyl chloride or chlorosulfuric acid.
Preferably, in S2 step, the dosage of first catalyst is the 0.05%~1.0% of benzene oxycarboxylic acid ester weight,
The dosage of second catalyst is the 0.05%~1.0% of benzene oxycarboxylic acid ester weight.
Preferably, in S2 step, the temperature of the selective chlorination reaction is -20~100 DEG C.
Preferably, in S3 step, the alkali compounds is sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, carbon
Potassium hydrogen phthalate, potassium carbonate, ammonium hydrogen carbonate, ammonium carbonate, ammonia or organic amine.
Preferably, in S3 step, the Basic fluxing raction temperature is 60~120 DEG C.
The present invention synthesizes benzene oxycarboxylic acid ester through condensation using phenol, and then selective chlorination synthesizes chlorobenzene oxycarboxylic acid ester, most
Alkaline hydrolysis synthesizes benzene oxycarboxylic acid salt herbicide afterwards.Compared with existing synthetic technology, the present invention is effectively avoided with unpleasant gas
The production and use of the chlorinated phenol of taste have fundamentally prevented the generation of the dioxin of severe toxicity, have greatly improved product quality
With the operating environment of production scene.Experiment display, gained benzene oxycarboxylic acid salt herbicide products content >=96.0%, total recovery >=
98%.The present invention, through condensation, selective chlorination and alkaline hydrolysis, has obtained the benzene oxycarboxylic acid salt weeding of high-quality using phenol as raw material
Agent, method of the invention efficiently avoid the loss of effective component, improve the yield of product.
In addition, the present invention by the innovation to process route, has effectively prevented the generation of high COD, high-salt wastewater, give up simultaneously
The quantum of output of salt (metal chloride) reduces 50% or more, and three wastes output has pole significantly to reduce, three-protection design cost
It declines to a great extent.
Specific embodiment
The present invention provides a kind of preparation methods of benzene oxycarboxylic acid salt herbicide, comprising the following steps:
S1, by phenol or o-cresol in the presence of alkaline substances, carry out condensation reaction with chlorinated carboxylic acid ester, obtain
Benzene oxycarboxylic acid ester；
The general formula of the chlorinated carboxylic acid ester is ClR1COOR, wherein R1The alkylidene or secondary alkane for being 1~3 selected from carbon atom number
Base, R are selected from the alkyl that carbon atom number is 1~10 or the naphthenic base that carbon atom number is 3~10；
S2, by the benzene oxycarboxylic acid ester existing for the first catalyst and the second catalyst under the conditions of, carried out with chlorinating agent
Selective chlorination obtains chlorobenzene oxycarboxylic acid ester shown in Formulas I；Wherein R3For H, Cl or CH3；First catalyst is selected from road
Lewis acid, the thiazole that second catalyst is selected from the thio-ether type compounds that carbon atom number is 5~22, carbon atom number is 5~22
The thiophenes that the different thiazoles compound or carbon atom number that class compound, carbon atom number are 5~22 are 5~22；
S3, the chlorobenzene oxycarboxylic acid ester is mixed with alkali compounds, carries out Basic fluxing raction, obtains benzene oxycarboxylic acid salt
Herbicide.
The preparation method of benzene oxycarboxylic acid salt herbicide provided by the invention can improve the operating environment of production scene, and
Have many advantages, such as that superior product quality, high income, the three wastes are few.
The embodiment of the present invention puts into a certain proportion of alkaline matter, under certain temperature using phenol as primary raw material thereto
Chlorinated carboxylic acid ester is added to be allowed to react, obtains benzene oxycarboxylic acid ester.Wherein, phenol of the present invention refers to phenol or o-cresol.
The general formula of chlorinated carboxylic acid ester of the present invention is ClR1COOR, R in formula1The alkylidene for being 1~3 selected from carbon atom number
Or alkylidene, specifically, R1=CH2、CH(CH3) or (CH2)3.R is selected from the alkyl that carbon atom number is 1~10 or carbon atom number is 3
~10 naphthenic base is preferably selected from the alkyl that carbon atom number is 1~4.In an embodiment of the present invention, the chlorinated carboxylic acid ester is
Methyl chloroacetate, ethyl chloroacetate, isopropyl chloracetate, Solid acid n-butyl chloroacete, iso-butyl chloroacetate, Isooctyl chloroacetate, chlorine
The positive last of the ten Heavenly stems ester of n-butyl propionate, chloropropionic acid, neoprene acid ethyl ester or the different monooctyl ester of chloro-butyric acid.
The present invention uses above-mentioned phenol and chlorinated carboxylic acid ester ClR1COOR synthesizes benzene oxycarboxylic acid ester, the benzene oxygen carboxylic through condensation
Acid esters refers to the substance having following structure:
The present invention carries out condensation reaction in the presence of alkaline substances, obtains chloride and benzene oxycarboxylic acid ester；It is described
Alkaline matter be preferably sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium bicarbonate, saleratus, sodium carbonate and
One of potassium carbonate is a variety of.
In an embodiment of the present invention, the condensation reaction can carry out in organic solvent, and reaction system is relatively uniform；
The organic solvent is preferably benzene, toluene or dimethylbenzene.The embodiment of the present invention puts into a certain proportion of alkali and organic molten into phenol
Agent, temperature rising reflux are dehydrated to biodiversity content≤0.5%, and chlorinated carboxylic acid ester is added dropwise thereto under certain temperature, are added dropwise
After at a temperature of this insulation reaction 0.5h, cooling filtering and suitable above-mentioned solvent is added, washs filter cake, drying obtains
Metal chloride and benzene oxycarboxylic acid ester crude product containing solvent, retortable recycling design, while obtaining benzene oxycarboxylic acid ester products.
Wherein, when the alkaline matter is sodium hydroxide, potassium hydroxide, sodium bicarbonate or saleratus, phenol and alkalinity
The molar ratio of substance can be 1:(1~1.08), preferred 1:(1~1.04), more preferable 1:(1.02~1.04)；When the basic species
Matter is calcium hydroxide, magnesium hydroxide, sodium carbonate or potassium carbonate, and the molar ratio of phenol and alkaline matter can be 1:(0.5~0.54), it is excellent
Select 1:(0.5~0.52), more preferable 1:(0.51~0.52).In reaction process, the dosage of the organic solvent is generally phenol weight
1~5 times, preferably 1.5~2.5 times of amount.
In the present invention, the molar ratio of phenol and chlorinated carboxylic acid ester can be 1:(1~1.08), preferred 1:(1~1.04), more excellent
Select 1:(1.02~1.04).The temperature of the condensation reaction can be 60~120 DEG C, preferably 60~100 DEG C, more preferable 80~100
℃.Gained condensation liquid is filtered and conventional wash and dries to obtain crude product；Wherein filtration temperature is generally 30~50 DEG C.
After obtaining benzene oxycarboxylic acid ester, a certain proportion of first catalyst and the second catalysis is added in the embodiment of the present invention thereto
Then a certain amount of chlorinating agent is added under certain temperature and carries out selective chlorination reaction for agent, addition finishes insulation reaction 0.5h,
Obtain chlorobenzene oxycarboxylic acid ester.
In the present invention, first catalyst is lewis acid.The substance of a usually acceptable electronics pair is exactly road
Lewis acid；Lewis acid catalyst of the present invention generally uses: (1) containing the chloride of Mg, Fe, Al, Zn, Ti or Sn；(2) contain
The oxide of Mg, Fe, Al, Zn, Ti or Sn；(3) fluoride, such as BF3、SbF5Deng；(4) phenylacetic acid compound, such as Pb (OAc)2、
Zn(OAc)2Deng.Specifically, first catalyst includes but are not limited to SnCl4、MgCl2、FeCl3、AlCl3、ZnCl2、
TiCl4、BF3、SbF5、Al2O3、Fe2O3、TiO2、Pb(OAc)2、Zn(OAc)2Or Al2O(OAc)4, preferably MgCl2、FeCl3、
ZnCl2、SbF5、TiO2、Pb(OAc)2, more preferably FeCl3、TiO2、Pb(OAc)2。
In the present invention, second catalyst be carbon atom number be 5~22 thio-ether type compounds, carbon atom number 5
The thiophene-based that the different thiazoles compound or carbon atom number that~22 thiazole compound, carbon atom number are 5~22 are 5~22
Thioether, thiazole, isothiazole, thiophene or their halo derivatives that conjunction object, preferably carbon atom number are 5~22, including but not
It is only limitted to tertbutyl methyl thioether, tert-butylsulfide, diphenyl sulfide, 4,4'- dichloro diphenyl sulfide, 2- methyl diphenyl sulfide, 2,4,6- tri-
Methyl diphenyl sulfide, 4,4'- thiobis (6- tert-butyl -3- methylphenol), thiazole, 2- ethyl thiazole, 2,5- dichloro thiazole, 4- first
Base thiazole, 2- tertiary butyl thiazole, isothiazole, 4,5- dimethyl isothiazole, 5- chloroisothiazole, 2,4,5- tri-tert isothiazole,
Thiophene, 2- methylthiophene, 2,5- thioxene, 3- chlorothiophene, 3,4- dichloro-thiophene, 2,3,4- tri- chlorothiophenes, wherein it is preferred that
Tert-butylsulfide, 2,4,6- trimethylbenzene thioether, 4,4'- thiobis (6- tert-butyl -3- methylphenol), 2- ethyl thiazole, 2,
5- dichloro thiazole, 2,4,5- tri-tert isothiazole, 4,5- dimethyl isothiazole, 3,4- dichloro-thiophene, 2,3,4- tri- chlorothiophenes,
More preferable tert-butylsulfide, 4,4'- thiobis (6- tert-butyl -3- methylphenol), 2,4,5- tri-tert isothiazole, 2,3,4-
Three chlorothiophenes.
In an embodiment of the present invention, first catalyst and/or the second catalyst can also be deposited in the form of load
In as loaded catalyst；Preferred catalyst carrier is silica gel (main component is silica), and catalyst passes through dipping
Method is loaded in catalyst carrier.The load factor of first catalyst and the second catalyst is respectively 10%~20%, 5%~
15%.
In the present invention, partially using be separated by distillation in the embodiment of unsupported catalyst catalyst and product from
And obtain chlorobenzene oxycarboxylic acid ester；It, can be with and in the embodiment that the first catalyst of part and the second catalyst are support type
It is not required to distillation and directly realizes the separation of catalyst and chlorobenzene oxycarboxylic acid ester by filtering, particularly, when by the first catalyst
When being fixed in reactor with the second catalyst, in this embodiment it is not even necessary to filtering can isolated chlorobenzene oxycarboxylic acid ester, this makes
The separation of catalyst and product becomes simple and easy, while improving the service efficiency of catalyst, saves a large amount of energy consumptions, and
It is particularly suitable for carrying out continuous operation.
In an embodiment of the present invention, the dosage of first catalyst can for benzene oxycarboxylic acid ester weight 0.05%~
1.0%, preferably 0.25%~1.0%, more preferably 0.5%~1.0%.The dosage of second catalyst can be benzene oxygen carboxylic
The 0.05%~1.0% of acid esters weight, preferably 0.2%~0.8%, more preferably 0.3%~0.5%.When the first catalyst
In the presence of in the form of loaded catalyst, the dosage of effective component is benzene oxycarboxylic acid ester weight in loaded catalyst
0.05%~1.0%, preferably 0.25%~1.0%, more preferably 0.5%~1.0%, having in loaded catalyst herein
Effect ingredient refers to the first catalyst being carried on carrier, the first catalyst of effective ingredient consumption=support type of the first catalyst
Usage amount × load factor.In the presence of the second catalyst is in the form of loaded catalyst, in loaded catalyst effectively at
Point dosage be benzene oxycarboxylic acid ester weight 0.05%~1.0%, preferably 0.2%~0.8%, more preferably 0.3%~
0.5%, the effective component in loaded catalyst refers to that the second catalyst being carried on carrier, the second catalyst have herein
Imitate usage amount × load factor of the second catalyst of Ingredient Amount=support type.
Chlorinating agent of the present invention is preferably chlorine, thionyl chloride or chlorosulfuric acid, more preferably chlorine or chlorosulfuric acid.This hair
The bright selective chlorination on the phenyl ring of synthesized benzene oxycarboxylic acid ester, obtains chlorobenzene oxycarboxylic acid ester.Selectivity of the present invention
Chlorination reaction temperature can be -20~100 DEG C, preferably -20~60 DEG C, more preferably -20~20 DEG C.Chlorobenzene oxygen carboxylic of the present invention
Acid esters refers to the substance having following structure:
The molar ratio of benzene oxycarboxylic acid ester and chlorinating agent of the present invention can be by following selection: when benzene oxycarboxylic acid ester is Formula II -1
And target product is when being -2 formula of Formulas I, is 1:(1.98~2.4 with the molar ratio of chlorinating agent), preferred 1:(2~2.2), more preferably
1:(2.02~2.06)；When benzene oxycarboxylic acid ester is Formula II -1 and target product is Formulas I -1, the molar ratio with chlorinating agent is 1:
(0.99~1.2), preferably 1:(1~1.1), more preferable 1:(1.01~1.03)；When benzene oxycarboxylic acid ester is Formula II -2, with chlorine
The molar ratio of agent is 1:(0.99~1.2), preferred 1:(1~1.1), more preferable 1:(1.01~1.03).
Benzene oxycarboxylic acid ester selective chlorination in the embodiment of the present invention obtains chlorobenzene oxycarboxylic acid ester shown in Formulas I.Then,
The chlorobenzene oxycarboxylic acid ester is subjected to Basic fluxing raction, obtains benzene oxycarboxylic acid salt herbicide.
A certain amount of alkali compounds is added into the chlorinated carboxylic acid ester in the embodiment of the present invention, the alkaline hydrolysis under certain temperature
2h~4h is reacted, the alcohol that reaction generates is steamed in reaction process simultaneously, is cooled to room temperature after completion of the reaction, obtains alkali solution liquid.When
When the alkali used is alkali metal compound, gained alkali solution liquid is filtered, and filter cake is dried to get benzene oxycarboxylic acid salt weeding
Agent, mother liquor reuse.When the alkali used is ammonium hydrogen carbonate, ammonium carbonate, ammonia or organic amine, gained alkali solution liquid is benzene oxycarboxylic acid salt
Class herbicide.Wherein, benzene oxycarboxylic acid salt herbicide yield in terms of phenol >=98%.
Alkali used in alkaline hydrolysis described in the embodiment of the present invention can be sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate,
Saleratus, potassium carbonate, ammonium hydrogen carbonate, ammonium carbonate, ammonia or the total number of carbon atoms are not more than 5 organic amine, wherein it is preferred that hydroxide
Sodium, potassium hydroxide, sodium bicarbonate, sodium carbonate, saleratus, potassium carbonate or dimethylamine.When alkali is monoacidic base, the chlorobenzene
The molar ratio of oxycarboxylic acid ester and alkali is 1:(1~1.2), preferred 1:(1~1.1), more preferable 1:(1.02~1.06)；When alkali is two
When first alkali, the molar ratio of the chlorobenzene oxycarboxylic acid ester and alkali is 1:(0.5~0.6), preferred 1:(0.5~0.55), more preferably
1:(0.51~0.53).In an embodiment of the present invention, the Basic fluxing raction temperature can be 60~120 DEG C, preferably 80~100
℃。
With traditional chlorobenzene oxycarboxylic acid sodium salt, sylvite synthesis technology compared with, the embodiment of the present invention will not generate difficulty
The mother liquor with high salt containing chlorinated phenol, chlorobenzene oxycarboxylic acid of reason, since chlorination is selectively high in the present invention, chloro obtained by chlorination
The content of benzene oxycarboxylic acid ester is high, and the chlorobenzene oxycarboxylic acid salt mother liquor that the present invention generates may be implemented to apply infinitely, simultaneously will
Stable product quality will not both generate a large amount of intractable mother liquor, will not lead to product quality in a high level
Decline.With traditional chlorobenzene oxycarboxylic acid ammonium salt, amine salt synthesis technology compared with, the present invention will not only generate intractable
Mother liquor with high salt containing chlorinated phenol, chlorobenzene oxycarboxylic acid, also improves the yield and utilization rate of chlorobenzene oxycarboxylic acid salt.It is below
Each target product and impurity situation (mass content) in some embodiments of the invention:
Each target product and impurity situation in 1 some embodiments of the invention of table
In conclusion the preparation method of benzene oxycarboxylic acid salt herbicide provided by the invention avoid chlorinated phenol production and
It uses, can fundamentally prevent the generation of the dioxin of severe toxicity, significantly improve the environment of product quality and Workplace, simultaneously
Improve yield.In addition, the present invention by the innovation to process route, has effectively prevented the generation of high COD, high-salt wastewater, simultaneously
The quantum of output of abraum salt (metal chloride) reduces 50% or more, and three wastes output has pole significantly to reduce, three-protection design at
Originally it declines to a great extent, is conducive to industrialization promotion.
In order to further illustrate the present invention, with reference to embodiments to benzene oxycarboxylic acid salt herbicide provided by the invention
Preparation method is described in detail.
In following embodiment, related raw material is commercially available.
Embodiment 1
Into the phenol of 95.06g purity 99%, the sodium hydroxide and 142.59g dimethylbenzene of 42.83g purity 99% is added,
Temperature rising reflux is dehydrated to moisture≤0.5%, and the methyl chloroacetate for being added dropwise to 116.20g purity 99% thereto at 90 DEG C is allowed to
Reaction, is added dropwise insulation reaction 0.5h at a temperature of this, is cooled to 40 DEG C, filters, and suitable dimethylbenzene washing filter is added
Cake dries to obtain sodium chloride and the methyl phenoxyacetate crude product containing dimethylbenzene later, is distilled to recover dimethylbenzene, while obtaining phenoxy acetic acid
Methyl esters 172.02g, content 96.1%.
Into distillation gained methyl phenoxyacetate, the tin tetrachloride and 0.60g purity 99% of 1.72g purity 99% is added
2,5- dichloro thiazoles, the chlorosulfuric acid that 279.41g purity 99% is added at 60 DEG C are allowed to react, and addition is finished to be protected at a temperature of this
Temperature reaction 0.5h, obtains 2,4- dichlorphenoxyacetic acid methyl esters 237.01g, content 98.17%.
To gained 2, in 4- dichlorphenoxyacetic acid methyl esters, the dimethylamine of 117.68g 40% is added, is reacted at 110 DEG C
4h, while the alcohol that reaction generates is steamed, end of reaction is cooled to room temperature, obtains 2,4- dichlorphenoxyacetic acid dimethylamine salt 318.07g,
Content 82.6%, total recovery in terms of phenol 98.68%.
Comparative example 1
Into the phenol of 95.06g purity 99%, the sodium hydroxide and 142.59g dimethylbenzene of 42.83g purity 99% is added,
Temperature rising reflux is dehydrated to moisture≤0.5%, and the methyl chloroacetate for being added dropwise to 116.20g purity 99% thereto at 90 DEG C is allowed to
Reaction, is added dropwise insulation reaction 0.5h at a temperature of this, is cooled to 40 DEG C, filters, and suitable dimethylbenzene washing filter is added
Cake dries to obtain sodium chloride and the methyl phenoxyacetate crude product containing dimethylbenzene later, is distilled to recover dimethylbenzene, while obtaining phenoxy acetic acid
Methyl esters 172.02g, content 96.1%.
Into distillation gained methyl phenoxyacetate, the tin tetrachloride of 1.72g purity 99% is added, is added at 60 DEG C
The chlorosulfuric acid of 279.41g purity 99% is allowed to react, and addition finishes insulation reaction 0.5h at a temperature of this, obtains 2,4- Dichlorophenoxy
Methyl acetate 237.23g, content 88.35%.
To gained 2, in 4- dichlorphenoxyacetic acid methyl esters, the dimethylamine of 117.68g 40% is added, is reacted at 110 DEG C
4h, while the alcohol that reaction generates is steamed, end of reaction is cooled to room temperature, obtains 2,4- dichlorphenoxyacetic acid dimethylamine salt 318.16g,
Content 74.1%, total recovery in terms of phenol 88.52%.
Comparative example 2
Into the phenol of 95.06g purity 99%, the sodium hydroxide and 142.59g dimethylbenzene of 42.83g purity 99% is added,
Temperature rising reflux is dehydrated to moisture≤0.5%, and the methyl chloroacetate for being added dropwise to 116.20g purity 99% thereto at 90 DEG C is allowed to
Reaction, is added dropwise insulation reaction 0.5h at a temperature of this, is cooled to 40 DEG C, filters, and suitable dimethylbenzene washing filter is added
Cake dries to obtain sodium chloride and the methyl phenoxyacetate crude product containing dimethylbenzene later, is distilled to recover dimethylbenzene, while obtaining phenoxy acetic acid
Methyl esters 172.02g, content 96.1%.
Into distillation gained methyl phenoxyacetate, 2, the 5- dichloro thiazole of 0.60g purity 99% is added, is added at 60 DEG C
The chlorosulfuric acid of 279.41g purity 99% is allowed to react, and addition finishes insulation reaction 0.5h at a temperature of this, obtains 2,4- Dichlorophenoxy
Methyl acetate 236.89g, content 78.54%.
To gained 2, in 4- dichlorphenoxyacetic acid methyl esters, the dimethylamine of 117.68g 40% is added, is reacted at 110 DEG C
4h, while the alcohol that reaction generates is steamed, end of reaction is cooled to room temperature, obtains 2,4- dichlorphenoxyacetic acid dimethylamine salt 318.33g,
Content 65.82%, total recovery in terms of phenol 78.65%.
Comparative example 3
Into the phenol of 95.06g purity 99%, the sodium hydroxide and 142.59g dimethylbenzene of 42.83g purity 99% is added,
Temperature rising reflux is dehydrated to moisture≤0.5%, and the methyl chloroacetate for being added dropwise to 116.20g purity 99% thereto at 90 DEG C is allowed to
Reaction, is added dropwise insulation reaction 0.5h at a temperature of this, is cooled to 40 DEG C, filters, and suitable dimethylbenzene washing filter is added
Cake dries to obtain sodium chloride and the methyl phenoxyacetate crude product containing dimethylbenzene later, is distilled to recover dimethylbenzene, while obtaining phenoxy acetic acid
Methyl esters 172.02g, content 96.1%.
The chlorosulfuric acid that 279.41g purity 99% is added into distillation gained methyl phenoxyacetate at 60 DEG C is allowed to react,
Addition finishes insulation reaction 0.5h at a temperature of this, obtains 2,4- dichlorphenoxyacetic acid methyl esters 237.43g, content 71.56%.
To gained 2, in 4- dichlorphenoxyacetic acid methyl esters, the dimethylamine of 117.68g 40% is added, is reacted at 110 DEG C
4h, while the alcohol that reaction generates is steamed, end of reaction is cooled to room temperature, obtains 2,4- dichlorphenoxyacetic acid dimethylamine salt 317.82g,
Content 60.0%, total recovery in terms of phenol 71.74%.
Embodiment 2
Into the o-cresol of 109.23g purity 99%, the potassium carbonate and 109.23g toluene of 69.80g purity 99% is added,
Temperature rising reflux is dehydrated to moisture≤0.5%, is added dropwise to the Solid acid n-butyl chloroacete of 152.14g purity 99% thereto at 120 DEG C
It is allowed to react, insulation reaction 0.5h at a temperature of this is added dropwise, be cooled to 30 DEG C, filter, and suitable toluene washing is added
Filter cake dries to obtain potassium chloride and methylphenoxyacetic acid N-butyl crude product containing toluene later, is distilled to recover toluene, while obtaining adjacent
Methylphenoxyacetic acid N-butyl 230.89g, content 95.9%.
Into distillation gained methylphenoxyacetic acid N-butyl, the iron chloride and 1.50g purity of 1.04g purity 99% is added
99% tertbutyl methyl thioether, the thionyl chloride that 118.46g purity 99% is added dropwise at 40 DEG C are allowed to react, and addition finishes
Insulation reaction 0.5h at a temperature of this obtains methoxone N-butyl 260.13g, content 98.01%.
Into gained methoxone N-butyl, the sodium hydroxide of 143.26g 32% is added, at 70 DEG C
4h is reacted, while steaming the alcohol that reaction generates, end of reaction is cooled to room temperature filtering, and filter cake drying obtains 4- chloro-2-methyl benzene oxygen
Acetic acid sodium salt 223.74g, content 98.5%, total recovery in terms of o-cresol 99.00%.
Embodiment 3
Into the phenol of 95.06g purity 99%, the sodium bicarbonate and 427.77g toluene of 91.65g purity 99% is added, rises
To moisture≤0.5%, the 2- chloropropionic acid N-butyl for being added dropwise to 179.62g purity 99% thereto at 80 DEG C makes warm reflux dewatering
Reaction, insulation reaction 0.5h at a temperature of this is added dropwise, is cooled to 50 DEG C, filtering, and suitable toluene washing filter is added
Cake dries to obtain sodium chloride and 2- phenoxy propionic acid N-butyl crude product containing toluene later, is distilled to recover toluene, while obtaining 2- benzene
Oxygroup n-butyl propionate 230.26g, content 96.0%.
Into distillation gained 2- phenoxy propionic acid N-butyl, the aluminium oxide and 0.12g purity of 1.73g purity 99% is added
99% tert-butylsulfide, the chlorine that 76.89g purity 99% is passed through at 100 DEG C are allowed to react, and addition finishes at a temperature of this
Insulation reaction 0.5h obtains 2- (4- chlorophenoxy) n-butyl propionate 257.60g, content 98.77%.
Into gained 2- (4- chlorophenoxy) n-butyl propionate, the ammonium hydroxide of 72.69g 25% is added, is reacted at 80 DEG C
3h, while the alcohol that reaction generates is steamed, end of reaction is cooled to room temperature, obtains 2- (4- chlorophenoxy) propionic acid ammonium salt 248.40g, contain
Amount 86.8%, total recovery in terms of phenol 99.00%.
Embodiment 4
Into the phenol of 95.06g purity 99%, the magnesium hydroxide and 285.18g benzene of 31.22g purity 99%, heating is added
To moisture≤0.5%, the positive last of the ten Heavenly stems ester of 2- chloropropionic acid for being added dropwise to 266.42g purity 99% thereto at 100 DEG C makes reflux dewatering
Reaction, insulation reaction 0.5h at a temperature of this is added dropwise, is cooled to 40 DEG C, filtering, and suitable benzene washing filter cake is added,
Magnesium chloride and the positive last of the ten Heavenly stems ester crude product of 2- phenoxy propionic acid containing benzene are dried to obtain later, are distilled to recover benzene, while obtaining 2- phenoxy group third
Sour positive last of the ten Heavenly stems ester 316.21g, content 96.1%.
Into the distillation gained positive last of the ten Heavenly stems ester of 2- phenoxy propionic acid, the magnesium chloride and 0.47g purity of 2.06g purity 99% is added
The 2 of 99%, 4,5- tri-tert isothiazole, the chlorine that 170.45g purity 99% is passed through at -20 DEG C are allowed to react, be added
Finish insulation reaction 0.5h at a temperature of this, obtains 2- (2,4- dichlorophenoxy) positive last of the ten Heavenly stems ester 379.59g of propionic acid, content 97.76%.
Into the positive last of the ten Heavenly stems ester of gained 2- (2,4- dichlorophenoxy) propionic acid, the isopropylamine of 174.46g 40% is added, in 100 DEG C
Lower reaction 2h, while the alcohol that reaction generates is steamed, end of reaction is cooled to room temperature, obtains 2- (2,4- dichlorophenoxy) propionic acid isopropyl
Amine salt 372.34g, content 77.9%, total recovery in terms of phenol 98.56%.
Embodiment 5
Into the phenol of 950.6g purity 99%, the sodium carbonate and 2376.5g dimethylbenzene of 556.7g purity 99% is added, rises
To moisture≤0.5%, the Isooctyl chloroacetate for being added dropwise to 2171.8g purity 99% thereto at 60 DEG C is allowed to warm reflux dewatering
Reaction, is added dropwise insulation reaction 0.5h at a temperature of this, is cooled to 40 DEG C, filters, and suitable dimethylbenzene washing filter is added
Cake dries to obtain sodium chloride and the different monooctyl ester crude product of phenoxy acetic acid containing dimethylbenzene later, is distilled to recover dimethylbenzene, while obtaining benzene oxygen
2-ethyl hexyl ethanoate 2728.6g, content 96.2%.
The chlorine that 45.5g load factor is 20% is separately added into thtee-stage shiplock flow reactor (each volume is 200ml)
4,4 '-dichloro diphenyl sulfides/silica gel supported catalyst that change zinc/silica gel supported catalyst and 60.7g load factor are 15%, to
The 20.0g distillation gained different monooctyl ester of phenoxy acetic acid is added in first stage reactor, then 10.0g is at the uniform velocity added at -20 DEG C in stirring
99% chlorosulfuric acid, to chlorosulfuric acid add followed by proportion at the uniform velocity be added 2708.6g obtained by the different monooctyl ester of phenoxy acetic acid and
The chlorosulfuric acid of 1357.2g 99%, as material is from the addition of the first stage reactor, the continuous overflow of material enters the second order reaction
Device and third stage reactor, it is -20 DEG C that its temperature is kept when second, third stage reactor also has material, and reaction mass is last
System is gone out by third level reactor overflow, obtains the different monooctyl ester of 4-chlorophenoxyacetic acid, and loaded catalyst is since density is larger, no
It can be with material outflow system.Heat preservation 30min is finished to all materials addition, by the material filtering in the first, second and third stage reactor
Merge with the different monooctyl ester of 4-chlorophenoxyacetic acid gone out by third level reactor overflow, obtains the different monooctyl ester 3020.1g of 4-chlorophenoxyacetic acid, contain
Amount 98.03%.
Into the different monooctyl ester of gained 4-chlorophenoxyacetic acid, the sodium hydroxide of 790.2g 50% is added, reacts 3h at 120 DEG C,
The alcohol that reaction generates is steamed simultaneously, and end of reaction is cooled to room temperature filtering, and filter cake drying obtains 4-chlorophenoxyacetic acid sodium salt
2083.1g, content 98.9%, total recovery in terms of phenol 98.77%.
Embodiment 6
Into the o-cresol of 109.23g purity 99%, the potassium hydroxide solid and 546.16g of 64.20g content 90% is added
Dimethylbenzene, temperature rising reflux are dehydrated to moisture≤0.5%, are added dropwise to the 4- neoprene of 156.71g purity 99% thereto at 70 DEG C
Acetoacetic ester is allowed to react, and insulation reaction 0.5h at a temperature of this is added dropwise, and is cooled to 30 DEG C, filters, and be added suitable two
Toluene washs filter cake, dries to obtain potassium chloride and the adjacent toluene oxy butyrate ethyl ester containing dimethylbenzene later, is distilled to recover diformazan
Benzene, while obtaining adjacent toluene oxy butyrate ethyl ester 230.35g, content 96.0%.
Into the adjacent toluene oxy butyrate ethyl ester of distillation gained, the iron oxide and 1.96g purity 99% of 0.35g purity 99% is added
2,4,6- trimethylbenzene thioethers, the chlorine that 78.40g purity 99% is passed through at 0 DEG C is allowed to react, and addition is finished in this temperature
Lower insulation reaction 0.5h obtains 4- chloro-2-methyl phenoxy butyric acid ethyl ester 259.15g, content 98.21%.
Into gained 4- chloro-2-methyl phenoxy butyric acid ethyl ester, the dimethylamine of 112.29g 40% is added, is reacted at 85 DEG C
2h, while the alcohol that reaction generates is steamed, end of reaction is cooled to room temperature, obtains 4- chloro-2-methyl phenoxy butyric acid dimethylamine salt
318.68g, content 84.9%, total recovery in terms of o-cresol 98.83%.
Embodiment 7
Into the o-cresol of 109.23g purity 99%, the saleratus and 218.46g first of 105.18g purity 99% is added
Benzene, temperature rising reflux are dehydrated to moisture≤0.5%, and the 4- chloro-butyric acid for being added dropwise to 246.66g purity 99% thereto at 90 DEG C is different
Monooctyl ester is allowed to react, and insulation reaction 0.5h at a temperature of this is added dropwise, and is cooled to 50 DEG C, filters, and suitable toluene is added
Filter cake is washed, dries to obtain potassium chloride and the different monooctyl ester crude product of adjacent toluene oxy butyrate containing toluene later, is distilled to recover toluene, simultaneously
Obtain the adjacent different monooctyl ester 318.89g of toluene oxy butyrate, content 95.8%.
Titanium dioxide, the 0.80g purity of 1.75g purity 99% are added into the different monooctyl ester of the adjacent toluene oxy butyrate of distillation gained
99% 2- ethyl thiazole, the chlorine that 85.67g purity 99% is passed through at 50 DEG C are allowed to react, and addition finishes at a temperature of this
Insulation reaction 0.5h obtains the different monooctyl ester 344.90g of 4- chloro-2-methyl phenoxy butyric acid, content 97.92%.
Into the different monooctyl ester of gained 4- chloro-2-methyl phenoxy butyric acid, saleratus, the 165.78g of 111.64g 99% is added
Water reacts 3h at 95 DEG C, while steaming the alcohol that reaction generates, and end of reaction is cooled to room temperature filtering, and filter cake drying obtains 4-
Chloro-2-methyl phenoxy butyric acid sylvite 267.56g, content 98.5%, total recovery in terms of o-cresol 98.7%.
Embodiment 8
Into the phenol of 95.06g purity 99%, 99% calcium hydroxide of 40.42g purity and 332.71g toluene, heating is added
For reflux dewatering to moisture≤0.5%, the methyl chloroacetate for being added dropwise to 118.40g purity 99% thereto at 80 DEG C is allowed to anti-
It answers, insulation reaction 0.5h at a temperature of this is added dropwise, be cooled to 30 DEG C, filter, and suitable toluene washing filter cake is added, it
Calcium chloride and methyl phenoxyacetate crude product containing toluene are dried to obtain afterwards, are distilled to recover toluene, while obtaining methyl phenoxyacetate
172.34g content 95.9%.
To distillation gained methyl phenoxyacetate in, be added 0.09g purity 99% lead acetate and 1.29g purity 99% 2,
3,4- tri- chlorothiophenes, the thionyl chloride that 118.34g purity 99% is added dropwise at 20 DEG C are allowed to react, and addition is finished in this temperature
Lower insulation reaction 0.5h obtains 4-chlorophenoxyacetic acid methyl esters 203.77g, content 97.63%.
Into gained 4-chlorophenoxyacetic acid methyl esters, sodium bicarbonate, the 129.30g water of 87.07g 99% is added, at 80 DEG C
2h is reacted, while steaming the alcohol that reaction generates, end of reaction is cooled to room temperature filtering, and filter cake drying obtains 4-chlorophenoxyacetic acid sodium
Salt 209.15g, content 98.6%, total recovery in terms of phenol 98.86%.
Embodiment 9
Into the phenol of 95.06g purity 99%, the potassium hydroxide solution and 190.12g of 116.88g concentration 48% is added
Benzene, temperature rising reflux are dehydrated to moisture≤0.5%, are added dropwise to the monoxone isopropyl of 137.97g purity 99% thereto at 110 DEG C
Ester is allowed to react, and insulation reaction 0.5h at a temperature of this is added dropwise, and is cooled to 40 DEG C, filters, and suitable benzene washing is added
Filter cake dries to obtain potassium chloride and the phenoxy acetic acid isopropyl ester crude product containing benzene later, is distilled to recover benzene, while it is different to obtain phenoxy acetic acid
Propyl ester 200.48g, content 96.1%.
Titanium tetrachloride/silica gel supported that 1.00g load factor is 10% is added into distillation gained phenoxy acetic acid isopropyl ester
Catalyst, 3,4- dichloro-thiophene/silica gel supported catalyst that 2.00g load factor is 5%, are added dropwise to 273.29g at 100 DEG C
The chlorosulfuric acid of purity 99% is allowed to react, and addition finishes insulation reaction 0.5h at a temperature of this, filters, obtains 2,4- Dichlorophenoxy second
Isopropyl propionate 265.80g, content 97.69%.
To gained 2, in 4- dichlorphenoxyacetic acid isopropyl ester, sodium carbonate, the 82.73g water of 55.71g 99% is added, in 60
4h is reacted at DEG C, while steaming the alcohol that reaction generates, and end of reaction is cooled to room temperature filtering, and filter cake drying obtains 2,4- dichloro-benzenes
Fluoroacetic acid sodium salt 241.94g, content 98.8%, total recovery in terms of phenol 98.38%.
Embodiment 10
Into the o-cresol of 109.23g purity 99%, be added 127.50g concentration 32% sodium hydroxide solution and
436.93g toluene, temperature rising reflux are dehydrated to moisture≤0.5%, are added dropwise to 155.18g purity 99% thereto at 100 DEG C
Iso-butyl chloroacetate is allowed to react, and insulation reaction 0.5h at a temperature of this is added dropwise, and is cooled to 50 DEG C, filters, and is added suitable
The toluene of amount washs filter cake, dries to obtain sodium chloride and methylphenoxyacetic acid isobutyl ester crude product containing toluene later, is distilled to recover
Toluene, while obtaining methylphenoxyacetic acid isobutyl ester 229.29g, content 96.3%.
Into distillation gained methylphenoxyacetic acid isobutyl ester, the aluminium chloride and 1.03g purity of 0.57g purity 99% is added
The 4 of 99%, 4 '-thiobis (6- tert-butyl -3- methylphenol), are added dropwise to the chlorosulfuric acid of 139.49g purity 99% at 80 DEG C
It is allowed to react, addition finishes insulation reaction 0.5h at a temperature of this, obtains methoxone isobutyl ester 258.11g, contains
Amount 98.16%.
Into gained methoxone isobutyl ester, the potassium hydroxide of 140.74g 40% is added, at 90 DEG C
4h is reacted, while steaming the alcohol that reaction generates, end of reaction is cooled to room temperature filtering, and filter cake drying obtains 4- chloro-2-methyl benzene oxygen
Potassium salt 237.74g, content 99.0%, total recovery in terms of o-cresol 98.58%.
Embodiment 11
Into the phenol of 950.6g purity 99%, the sodium hydroxide and 1425.9g dimethylbenzene of 428.3g purity 99% is added,
Temperature rising reflux is dehydrated to moisture≤0.5%, and the methyl chloroacetate for being added dropwise to 1162.0g purity 99% thereto at 90 DEG C is allowed to
Reaction, is added dropwise insulation reaction 0.5h at a temperature of this, is cooled to 40 DEG C, filters, and suitable dimethylbenzene washing filter is added
Cake dries to obtain sodium chloride and the methyl phenoxyacetate crude product containing dimethylbenzene later, is distilled to recover dimethylbenzene, while obtaining phenoxy acetic acid
Methyl esters 1720.2g, content 96.1%.
The oxygen that 20.1g load factor is 15% is separately added into thtee-stage shiplock flow reactor (each volume is 100ml)
Diphenyl sulfide/silica gel supported catalyst that change iron/silica gel supported catalyst and 30.1g load factor are 10%, it is anti-to the first order
It answers and 20.0g distillation gained methyl phenoxyacetate is added in device, then the sulfonyl of 32.5g 99% is at the uniform velocity added in stirring at 40 DEG C
Chlorine adds the sulphur that methyl phenoxyacetate and 2761.6g 99% obtained by 1700.2g are followed by the uniform velocity added in proportion to chlorosulfuric acid
Acyl chlorides, as material is from the addition of the first stage reactor, the continuous overflow of material enters the second stage reactor and third stage reactor,
It is 40 DEG C that its temperature is kept when second, third stage reactor also has material, and reaction mass is finally by third level reactor overflow
System out obtains 2,4- dichlorphenoxyacetic acid methyl esters, and loaded catalyst will not flow out system with material since density is larger
System.Heat preservation 30min is finished to all materials addition, by the material filtering in the first, second and third stage reactor and by third order reaction
2, the 4- dichlorphenoxyacetic acid methyl esters that device overflow goes out merges, and obtains 2,4- dichlorphenoxyacetic acid methyl esters 2365.5g, content 98.36%.
To gained 2, in 4- dichlorphenoxyacetic acid methyl esters, the dimethylamine of 1176.8g 40% is added, is reacted at 110 DEG C
4h, while the alcohol that reaction generates is steamed, end of reaction is cooled to room temperature, obtains 2,4- dichlorphenoxyacetic acid dimethylamine salt 3177.2g,
Content 82.8%, total recovery in terms of phenol 98.81%.
As seen from the above embodiment, benzene oxycarboxylic acid salt herbicide products content >=80.0% obtained by the embodiment of the present invention,
Total recovery >=98%, washing water and filtrate merge reuse.
Some target products and impurity situation are as follows in the embodiment of the present invention:
Some target products and impurity situation in 2 embodiment of the present invention of table
The present invention synthesizes benzene oxycarboxylic acid ester through condensation using phenol, and then selective chlorination synthesizes chlorobenzene oxycarboxylic acid ester, most
Alkaline hydrolysis synthesizes benzene oxycarboxylic acid salt herbicide afterwards.Present invention effectively avoids the production of the chlorinated phenol with bad smell and make
With, fundamentally prevented severe toxicity dioxin generation, greatly improve the operating environment of product quality and production scene.
Also, the present invention has effectively prevented the generation of high COD, high-salt wastewater, while the quantum of output of abraum salt (metal chloride) reduces
50% or more, significantly reduce three-protection design amount, three-protection design difficulty and processing cost.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of benzene oxycarboxylic acid salt herbicide, comprising the following steps:
S1, by phenol or o-cresol in the presence of alkaline substances, carry out condensation reaction with chlorinated carboxylic acid ester, obtain benzene oxygen
Carboxylate；
The general formula of the chlorinated carboxylic acid ester is ClR1COOR, wherein R1The alkylidene or alkylidene for being 1~3 selected from carbon atom number, R
Selected from carbon atom number be 1~10 alkyl or carbon atom number be 3~10 naphthenic base；
S2, by the benzene oxycarboxylic acid ester existing for the first catalyst and the second catalyst under the conditions of, selected with chlorinating agent
Property chlorination, obtains chlorobenzene oxycarboxylic acid ester shown in Formulas I；Wherein R3For H, Cl or CH3；First catalyst is selected from Louis
Acid, the thiazoles that second catalyst is selected from the thio-ether type compounds that carbon atom number is 5~22, carbon atom number is 5~22
Close object, the different thiazoles compound that carbon atom number is 5~22 or the thiophenes that carbon atom number is 5~22；
S3, the chlorobenzene oxycarboxylic acid ester is mixed with alkali compounds, carries out Basic fluxing raction, obtains benzene oxycarboxylic acid salt weeding
Agent.
2. preparation method according to claim 1, which is characterized in that in S1 step, the alkaline matter be sodium hydroxide,
One of potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium bicarbonate, saleratus, sodium carbonate and potassium carbonate are a variety of.
3. preparation method according to claim 2, which is characterized in that in S1 step, the condensation reaction is in organic solvent
Middle progress, the organic solvent are benzene, toluene or dimethylbenzene；The setting-up point is 60~120 DEG C.
4. preparation method according to claim 1, which is characterized in that in S2 step, first catalyst is selected from SnCl4、
MgCl2、FeCl3、AlCl3、ZnCl2、TiCl4、BF3、SbF5、Al2O3、Fe2O3、TiO2、Pb(OAc)2、Zn(OAc)2And Al2O
(OAc)4One of or it is a variety of.
5. preparation method according to claim 1, which is characterized in that in S2 step, second catalyst is selected from tertiary fourth
Methyl sulfide, tert-butylsulfide, diphenyl sulfide, 4,4'- dichloro diphenyl sulfide, 2- methyl diphenyl sulfide, 2,4,6- trimethylbenzene thioether,
4,4'- thiobis (6- tert-butyl -3- methylphenol), thiazole, 2- ethyl thiazole, 2,5- dichloro thiazole, 4- methylthiazol, uncle 2-
Butyl thiazole, isothiazole, 4,5- dimethyl isothiazole, 5- chloroisothiazole, 2,4,5- tri-tert isothiazole, thiophene, 2- methyl
One of thiophene, 2,5- thioxene, tri- chlorothiophene of 3- chlorothiophene, 3,4- dichloro-thiophene and 2,3,4- are a variety of.
6. preparation method according to claim 1, which is characterized in that in S2 step, the chlorinating agent is chlorine, thionyl
Chlorine or chlorosulfuric acid.
7. preparation method according to claim 1, which is characterized in that in S2 step, the dosage of first catalyst is
The 0.05%~1.0% of benzene oxycarboxylic acid ester weight, the dosage of second catalyst be benzene oxycarboxylic acid ester weight 0.05%~
1.0%.
8. preparation method according to any one of claims 1 to 7, which is characterized in that in S2 step, the selectivity chlorine
The temperature for changing reaction is -20~100 DEG C.
9. preparation method according to claim 1, which is characterized in that in S3 step, the alkali compounds is hydroxide
Sodium, potassium hydroxide, sodium bicarbonate, sodium carbonate, saleratus, potassium carbonate, ammonium hydrogen carbonate, ammonium carbonate, ammonia or organic amine.
10. preparation method according to claim 9, which is characterized in that in S3 step, the Basic fluxing raction temperature be 60~
120℃。
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