CN103724233B - Synthesis method of novaluron - Google Patents
Synthesis method of novaluron Download PDFInfo
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- CN103724233B CN103724233B CN201310561651.3A CN201310561651A CN103724233B CN 103724233 B CN103724233 B CN 103724233B CN 201310561651 A CN201310561651 A CN 201310561651A CN 103724233 B CN103724233 B CN 103724233B
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- trifluoromethoxy
- fluoro
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- benzene
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- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 title abstract description 4
- 238000001308 synthesis method Methods 0.000 title abstract 2
- -1 and finally Chemical compound 0.000 claims abstract description 34
- BOFRXDMCQRTGII-UHFFFAOYSA-N 619-08-9 Chemical compound OC1=CC=C([N+]([O-])=O)C=C1Cl BOFRXDMCQRTGII-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000007259 addition reaction Methods 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZRJSABISRHPRSB-UHFFFAOYSA-N 2,6-difluorobenzoyl isocyanate Chemical compound FC1=CC=CC(F)=C1C(=O)N=C=O ZRJSABISRHPRSB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000002829 reductive effect Effects 0.000 claims abstract description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 3
- 150000007529 inorganic bases Chemical class 0.000 claims abstract 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 76
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 32
- AUVLKYVTAAKSDM-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenylsulfanyl)ethene Chemical compound FC(F)=C(F)SC(F)=C(F)F AUVLKYVTAAKSDM-UHFFFAOYSA-N 0.000 claims description 21
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 21
- 238000010189 synthetic method Methods 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 18
- 239000011737 fluorine Substances 0.000 claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 13
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000002798 polar solvent Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 7
- 239000011707 mineral Substances 0.000 claims description 7
- 235000010755 mineral Nutrition 0.000 claims description 7
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 7
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical group CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 3
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims 4
- 238000000034 method Methods 0.000 abstract description 13
- 238000007086 side reaction Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 4
- DUQYSTOFYBWCDV-UHFFFAOYSA-N 3-chloro-4-[1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy]aniline Chemical compound NC1=CC=C(OC(F)(F)C(F)OC(F)(F)F)C(Cl)=C1 DUQYSTOFYBWCDV-UHFFFAOYSA-N 0.000 abstract 2
- YYKYTWQQDTYZMW-UHFFFAOYSA-N 2-chloro-4-nitro-1-[1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy]benzene Chemical compound ClC1=C(C=CC(=C1)[N+](=O)[O-])OC(C(OC(F)(F)F)F)(F)F YYKYTWQQDTYZMW-UHFFFAOYSA-N 0.000 abstract 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 abstract 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical class COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 8
- 241000238631 Hexapoda Species 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000012485 toluene extract Substances 0.000 description 4
- 238000009423 ventilation Methods 0.000 description 4
- 229920002101 Chitin Polymers 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- HRYILSDLIGTCOP-UHFFFAOYSA-N N-benzoylurea Chemical class NC(=O)NC(=O)C1=CC=CC=C1 HRYILSDLIGTCOP-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 210000002615 epidermis Anatomy 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- UPLPHRJJTCUQAY-WIRWPRASSA-N 2,3-thioepoxy madol Chemical compound C([C@@H]1CC2)[C@@H]3S[C@@H]3C[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@](C)(O)[C@@]2(C)CC1 UPLPHRJJTCUQAY-WIRWPRASSA-N 0.000 description 1
- 241000243818 Annelida Species 0.000 description 1
- 241000238421 Arthropoda Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000237852 Mollusca Species 0.000 description 1
- 241000244206 Nematoda Species 0.000 description 1
- 241001012098 Omiodes indicata Species 0.000 description 1
- 241000233654 Oomycetes Species 0.000 description 1
- 241000251539 Vertebrata <Metazoa> Species 0.000 description 1
- 241000607479 Yersinia pestis Species 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GFKHCUPBADPSDI-UHFFFAOYSA-N benzene;hydrazine Chemical compound NN.C1=CC=CC=C1 GFKHCUPBADPSDI-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of novaluron. P-nitrophenol is taken as a starting material, and hydrogen peroxide and hydrochloric acid chloro are used for preparing 2-chloro-4-nitrophenol; an inorganic base catalyst and perfluorinated vinyl methyl ether are used for addition reaction, 2-chloro-4-nitro-1-(1, 1, 2-trifluoro-2-(trifluoro methoxy) ethoxy) benzene is obtained, then nitro is reduced to obtain 3-chloro-4-(1, 1, 2-trifluoro-2-(trifluoro methoxy) ethoxy) aniline, and finally, 3-chloro-4-(1, 1, 2-trifluoro-2-(trifluoro methoxy) ethoxy) aniline reacts with 2, 6-difluorobenzoyl isocyanate to obtain novaluron. According to the method, raw materials are low in cost and easy to obtain, the operation is simple and convenient, the cost is low, the side reaction is few, and the method is suitable for industrial production.
Description
Technical field
The present invention relates to the preparation of the organic compound as agricultural chemicals; be specifically related to a kind of fluorine uride (N-[[chloro-4-[1 of 3-; the fluoro-2-of 1,2-tri-(trifluoromethoxy) oxyethyl group] phenyl] formamyl]-2,6-two fluorobenzamides) synthetic method.
Background technology
Fluorine uride, has another name called Rimon, is a kind of high-efficient low toxicity insecticide important in process for preparation of benzoylurea compounds, mainly through the object suppressing chitinous synthesis to reach kill pests.Chitin is a widely distributed ammonia polysaccharide, contains in a large number in invertebrates particularly arthropods (insect, crustacean) body, and relative less in mollusk, annelid and nematode.Chitin is the primary structural composition of the chitin-protein complexes such as insect cuticle and peritrophic membrane, but is not present in plant and vertebrates simultaneously or the integration composition of fungi (except oomycetes) and some alga cells walls.Just because of this difference, chitin is counted as a safety and has the sterilant target compared with strong selectivity.Chitinous synthesis in acyl group ureas strongly inhibited insect new epidermis forming process, by affecting the basic chitin-protein structure of insect exoskeleton and havoc insect molting, result makes epidermis fragile and soft, finally causes insect to dewater and dead.Fluorine uride is process for preparation of benzoylurea compounds of new generation, controls fruit, vegetables, the lepidopteran of cotton and corn, aleyrodid and leaf worm.Due to the biological activity that it is higher, and more friendly to people and animals, be one of pesticide species of desirable update.The development and utilization of fluorine uride is conducive to the development of China's green agriculture.
What the synthetic method of fluorine uride was seen in report is is published in " He'nan University of Technology's journal (natural science edition) " 29 volumes the 1st phase 64-67 page of 2008, take p-NP as raw material, the chloro-4-nitrophenols of the 2-generated after chloro adopts iron powder that nitroreduction is become amino, obtain the chloro-PAP of 2-, addition reaction is carried out again with perfluorovinyl sulfide methyl ether, the perfluor aniline obtained and 2,6-difluoro benzoyl isocyanate react and generate fluorine uride.The method mainly contains following drawback: 1. adopt iron powder to make reductive agent, the three wastes enormous amount that industrial production produces, be difficult to process, larger to environmental hazard; 2., in the chloro-PAP of 2-and the addition reaction of perfluorovinyl sulfide methyl ether, except phenolic hydroxyl group reaction, also have the amino side reaction occurred with perfluor raw material.Because perfluorovinyl sulfide methyl ether is expensive, the content not only increasing impurity of side reaction herein and too increase the consumption of expensive perfluor raw material, adds cost.
Summary of the invention
Technical problem to be solved by this invention is to overcome above-mentioned weak point, and research and design purity is high, yield is high, the synthetic method of stay-in-grade fluorine uride.
The invention provides a kind of synthetic method of fluorine uride.
The inventive method take p-NP as starting raw material, obtains the chloro-4-nitrophenols of 2-in hydrochloric acid and hydrogen peroxide through chlorination; The chloro-4-nitrophenols of 2-and perfluorovinyl sulfide methyl ether generation addition reaction, obtained 2-chloro-4-nitro-1-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene; Hydrazine hydrate reduction again through metal catalytic obtains the chloro-4-of 3-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) aniline; Fluorine uride is obtained further with 2,6-difluoro benzoyl isocyanate generation condensation reaction.
The inventive method comprises the steps:
(1) chloro: take p-NP as starting raw material, prepares the chloro-4-nitrophenols of 2-with hydrogen peroxide and hydrochloric acid chloro.Particularly, be dissolved in by p-NP in hydrochloric acid, drip hydrogen peroxide in 35 ~ 40 DEG C, reaction 3-4 hour, obtains the chloro-4-nitrophenols of 2-after filtration.
(2) addition: adopt mineral alkali catalysis and perfluorovinyl sulfide methyl ether generation addition reaction, obtain 2-chloro-4-nitro-1-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene.Particularly, chloro-for 2-4-nitrophenols is dissolved in the mixed system of benzene kind solvent and polar solvent, reacts with perfluorovinyl sulfide methyl ether under the catalysis of mineral alkali, obtain the chloro-4-nitro of 2--1-(1, the fluoro-2-of 1,2-tri-(trifluoromethoxy) oxyethyl group) benzene.
(3) reduce: obtain the chloro-4-of 3-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) aniline with hydrazine hydrate reduction nitro afterwards.Particularly, the chloro-4-nitro of 2--1-(1,1, the fluoro-2-of 2-tri-(trifluoromethoxy) oxyethyl group) benzene uses hydrazine hydrate for reductive agent under metal catalytic, obtain the chloro-4-of 3-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) aniline.
(4) condensation: last and 2,6-difluoro benzoyl isocyanates carry out condensation reaction and obtain fluorine uride.Particularly, chloro-for 3-4-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) aniline and 2,6-difluoro benzoyl isocyanate are reacted, filter afterwards, drying can obtain fluorine uride.
In the synthetic route reported, be that chloro-for 2-4-nitrophenols is first used metallic reducing agent, as iron powder, zinc powder etc., be amino by nitroreduction, and then carry out addition reaction with perfluorovinyl sulfide methyl ether.In the method, the metal catalyst used on the one hand, the three wastes enormous amount produced in the industrial production, and be difficult to process, the harm produced environment is larger; On the other hand, after chloro-for 2-4-nitrophenols is reduced to the chloro-PAP of 2-, then when reacting with perfluorovinyl sulfide methyl ether, except the reaction of the phenolic hydroxyl group that normally occurs and perfluor raw material, also have and aminoly to occur with the side reaction of perfluor raw material.So, the reaction of this step not only can produce impurity, and increases the consumption of perfluor raw material.Due to the raw material that perfluor raw material is the most expensive in whole route, the unit consumption increase of this raw material will certainly cause the increase of whole raw materials cost.
The synthesis technique of the present invention to fluorine uride improves, and is first reacted with perfluorovinyl sulfide methyl ether by chloro-for 2-4-nitrophenols, avoids the generation of side reaction; Ensuing reduction reaction uses hydrazine hydrate as reductive agent, avoids the use of metallic reducing agent, greatly reduces three wastes generation, be beneficial to industrial production and environment protection.
The solvent of the chloro-4-nitrophenols of step of the present invention (2) 2-and the addition of perfluorovinyl sulfide methyl ether is the mixed system of benzene kind solvent and polar solvent, and benzene kind solvent is selected from benzene, toluene or dimethylbenzene; Polar solvent is selected from methyl-sulphoxide, acetonitrile, dioxane, DMF, N-Methyl pyrrolidone or N,N-dimethylacetamide, and the mixed volume per-cent of benzene kind solvent and polar solvent is 0.1:1 ~ 4:1, is preferably 1:1 ~ 2.3:1.
The chloro-4-nitrophenols of 2-and the solvent load of perfluorovinyl sulfide methyl ether addition reaction and the weight ratio of substrate are 2.0 ~ 40:1, are preferably 5.0 ~ 30:1.
The mineral alkali of the chloro-4-nitrophenols of 2-and the addition reaction of perfluorovinyl sulfide methyl ether is sodium hydroxide, potassium hydroxide, hydrated barta, salt of wormwood, sodium carbonate or cesium carbonate.Mol ratio 0.05 ~ the 0.8:1 of the consumption of mineral alkali and the chloro-4-nitrophenols of 2-, is preferably 0.1 ~ 0.6:1.
The temperature of reaction of the chloro-4-nitrophenols of 2-and the addition reaction of perfluorovinyl sulfide methyl ether is-50 ~ 50 DEG C, is preferably-10 ~ 10 DEG C; Reaction times is 0.5 ~ 24 hour, is preferably 5 ~ 10 hours.
The solvent selected from methanol of the reduction reaction of step of the present invention (3) 2-chloro-4-nitro-1-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene, ethanol, Virahol, the trimethyl carbinol or isopropylcarbinol; The weight ratio of reaction solvent consumption and substrate is 2.0 ~ 30:1, is preferably 5.0 ~ 10.0:1; Temperature of reaction is the boiling point that room temperature arrives solvent for use.
The metal catalyst that reduction reaction uses is selected from Raney's nickel, palladium-carbon catalyst, palladium chloride, tetrakis triphenylphosphine palladium, iron trichloride or [two (diphenylphosphine) ferrocene of 1,1-] palladium chloride; The weight ratio of catalyst levels and substrate is 0.001 ~ 0.3:1.
The reductive agent that reduction reaction uses is the hydrazine hydrate of 85%; The weight ratio of hydrazine hydrate consumption and substrate is 1.0 ~ 10:1, preferably 2.0 ~ 5.0:1.
The chloro-4-(1 of step of the present invention (4) 3-, 1, the fluoro-2-of 2-tri-(trifluoromethoxy) oxyethyl group) solvent of condensation reaction of aniline and 2,6-difluoro benzoyl isocyanate is selected from methylene dichloride, 1,2-ethylene dichloride, chlorobenzene or dichlorobenzene; The weight ratio of solvent load and the chloro-4-of 3-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) aniline is 2.0 ~ 30:1, preferably 5.0 ~ 20:1.
The temperature of reaction of condensation reaction is-10 ~ 20 DEG C; Reaction times is 1 ~ 10 hour.
The inventive method advantage: 1, the chloro-4-nitrophenols of 2-and perfluorovinyl sulfide methyl ether generation addition reaction, avoid the generation of side reaction, reduce the generation of impurity in production, also reduce the consumption of expensive raw material perfluorovinyl sulfide methyl ether simultaneously, reduce cost; 2, the chloro-4-nitro of 2--1-(1, the fluoro-2-of 1,2-tri-(trifluoromethoxy) oxyethyl group) hydrazine hydrate reduction of metal catalytic that the reduction reaction of benzene adopts, avoid use metallic reducing agent, greatly reduce the generation of the three wastes, environmental friendliness; 3, each step safety simple to operate, convenient post-treatment, equipment requirements is low, is applicable to industrialized production.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but and unrestricted range of application of the present invention.
Embodiment 1: the chloro-4-nitrophenols of preparation 2-:
In 500ml flask, add p-NP 35 grams, concentrated hydrochloric acid 205 grams, stir lower dropping 26 grams, hydrogen peroxide, control temperature, below 30 DEG C, reacts after 3 hours, and filter, filter cake washes with water to neutrality, after drying, use ethylene dichloride recrystallization, obtain 35g yellow solid, productive rate 80%.
Embodiment 2: preparation 2-chloro-4-nitro-1-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene:
In 250ml flask, add the chloro-4-nitrophenols of 2-3.48 grams, toluene 40mL, methyl-sulphoxide 40mL and 0.37 gram, potassium hydroxide, stir borehole cooling to 5 DEG C, pass into perfluorovinyl sulfide methyl ether 3.32 grams, after ventilation terminates, be incubated 0-10 DEG C of reaction 10 hours, add 50mL water, layering, aqueous phase 20mL toluene extracts once, merges organic phase, anhydrous sodium sulfate drying, filters, concentrated, obtain brown solid 5.86 grams, productive rate 86%.
1HNMR(400MHz，CDCl
3)：δ5.97(dt，J=56.0，4.0Hz，1H)，7.48(d，J=9.2Hz，1H)，8.13(dd，J=2.8，9.2Hz，1H)，8.32(d，J=2.8Hz，1H)；
19FNMRδppm-144.84，-86.40，-59.75。
Embodiment 3: preparation 2-chloro-4-nitro-1-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene:
In 100ml flask, add the chloro-4-nitrophenols of 2-6.96 grams, dimethylbenzene 20mL, methyl-sulphoxide 20mL and 1 gram, potassium hydroxide, stir borehole cooling to 5 DEG C, pass into perfluorovinyl sulfide methyl ether 6.64 grams, after ventilation terminates, be incubated 0-10 DEG C of reaction 10 hours, add 100mL water, layering, aqueous phase 50mL toluene extracts once, merges organic phase, anhydrous sodium sulfate drying, filters, concentrated, obtain brown solid 10.38 grams, productive rate 76.2%.
Embodiment 4: preparation 2-chloro-4-nitro-1-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene:
In 100ml flask, add the chloro-4-nitrophenols of 2-8.71 grams, toluene 33mL, DMF 15mL and 1.5 grams, potassium hydroxide, stir borehole cooling to 5 DEG C, pass into perfluorovinyl sulfide methyl ether 5.0 grams, after ventilation terminates, be incubated 0-10 DEG C of reaction 10 hours, add 100mL water, layering, aqueous phase 50mL toluene extracts once, merge organic phase, anhydrous sodium sulfate drying, filter, concentrated, obtain brown solid 15.2 grams, productive rate 89%.
Embodiment 5: preparation 2-chloro-4-nitro-1-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene:
In 100ml flask, add the chloro-4-nitrophenols of 2-3.48 grams, toluene 36mL, acetonitrile 18mL and 1.06 grams, sodium carbonate, stir borehole cooling to 5 DEG C, pass into perfluorovinyl sulfide methyl ether 3.32 grams, after ventilation terminates, intensification 40-45 DEG C is reacted 10 hours, adds 100mL water, layering, aqueous phase 50mL toluene extracts once, merges organic phase, anhydrous sodium sulfate drying, filters, concentrated, obtain brown solid 4.17 grams, productive rate 61.4%.
Embodiment 6: preparation 3-chloro-4-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) aniline
In 100mL flask, add the chloro-4-nitro of 2--1-(1,1, the fluoro-2-of 2-tri-(trifluoromethoxy) oxyethyl group) benzene 6.79g, ethanol 48mL and iron trichloride 105mg, reflux, drip hydrazine hydrate 16.5mL, dropwise rear back flow reaction 24 hours, filtered while hot, filter cake washing with alcohol, filtrate concentrates, filtration obtains brown solid, and vacuum-drying obtains 5.14g, productive rate 83%.
1HNMR(400MHz，CDCl
3)：δ3.75(bs，2H)，5.96(dt，J=54.4，3.2Hz，1H)，6.52(dd，J=2.8，8.8Hz，1H)，6.73(d，J=2.8Hz，1H)，7.08(d，J=8.8Hz，1H)。
Embodiment 7: preparation 3-chloro-4-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) aniline
In 250mL flask, add the chloro-4-nitro of 2--1-(1,1, the fluoro-2-of 2-tri-(trifluoromethoxy) oxyethyl group) benzene 17g, methyl alcohol 90mL and palladium chloride 170mg, reflux, drip hydrazine hydrate 49.4mL, dropwise rear back flow reaction 24 hours, filtered while hot, filter cake methanol wash, filtrate concentrates, filtration obtains brown solid, and vacuum-drying obtains 13.3g, productive rate 85.8%.
Embodiment 8: prepare fluorine uride
In 100mL flask, add the chloro-4-of 3-(1,1, the fluoro-2-of 2-tri-(trifluoromethoxy) oxyethyl group) aniline 6.19g and ethylene dichloride 60mL, be cooled to-5 DEG C, drip 2,6-difluoro benzoyl isocyanate 4g, after dropwising, rises to 10 DEG C, react 10 hours, filter, solid ethylene dichloride recrystallization, dry, obtain off-white color solid 8.38g, productive rate 85%.
Embodiment 9: prepare fluorine uride
In 100mL flask, add the chloro-4-of 3-(1,1, the fluoro-2-of 2-tri-(trifluoromethoxy) oxyethyl group) aniline 7.43g and orthodichlorobenzene 75mL, be cooled to-5 DEG C, drip 2,6-difluoro benzoyl isocyanate 5g, after dropwising, rises to 10 DEG C, react 10 hours, filter, solid ethylene dichloride recrystallization, dry, obtain off-white color solid 8.02g, productive rate 67.8%.
Claims (16)
1. a synthetic method for fluorine uride, it comprises the following steps:
(1) chloro: take p-NP as starting raw material, prepares the chloro-4-nitrophenols of 2-with hydrogen peroxide and hydrochloric acid chloro;
(2) addition: adopt mineral alkali catalysis and perfluorovinyl sulfide methyl ether generation addition reaction, obtain 2-chloro-4-nitro-1-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene;
(3) reduce: obtain the chloro-4-of 3-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) aniline with hydrazine hydrate reduction nitro afterwards; Described reduction is carried out under metal catalyst catalysis, metal catalyst is wherein selected from Raney's nickel, palladium-carbon catalyst, palladium chloride, tetrakis triphenylphosphine palladium, iron trichloride or [two (diphenylphosphine) ferrocene of 1,1-] palladium chloride;
(4) condensation: last and 2,6-difluoro benzoyl isocyanates carry out condensation reaction and obtain fluorine uride.
2. synthetic method according to claim 1, is characterized in that each step is specially:
(1) chloro: be dissolved in by p-NP in hydrochloric acid, drips hydrogen peroxide in 35 ~ 40 DEG C, and reaction 3-4 hour, obtains the chloro-4-nitrophenols of 2-after filtration;
(2) addition: chloro-for 2-4-nitrophenols is dissolved in the mixed system of benzene class and polar solvent, react with perfluorovinyl sulfide methyl ether under the catalysis of mineral alkali, obtain 2-chloro-4-nitro-1-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene;
(3) reduce: the chloro-4-nitro of 2--1-(1,1, the fluoro-2-of 2-tri-(trifluoromethoxy) oxyethyl group) benzene uses hydrazine hydrate for reductive agent under the catalysis of metal catalyst, obtain the chloro-4-(1 of 3-, the fluoro-2-of 1,2-tri-(trifluoromethoxy) oxyethyl group) aniline;
(4) condensation: chloro-for 3-4-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) aniline and 2,6-difluoro benzoyl isocyanate are reacted, filter afterwards, drying can obtain fluorine uride.
3., according to the synthetic method of any one of claim 1-2, it is characterized in that the mineral alkali in described step (2) is selected from sodium hydroxide, potassium hydroxide, hydrated barta, salt of wormwood, sodium carbonate or cesium carbonate.
4., according to the synthetic method of any one of claim 1-2, it is characterized in that described step (2) uses the mixed system of benzene class and polar solvent, benzene kind solvent is selected from benzene, toluene or dimethylbenzene; Polar solvent is selected from methyl-sulphoxide, acetonitrile, dioxane, DMF, N-Methyl pyrrolidone or N,N-dimethylacetamide, and the mixed volume per-cent of benzene class and polar solvent is 0.1/1 ~ 4/1.
5. synthetic method according to claim 4, wherein, the mixed volume per-cent of benzene class and polar solvent is 1/1 ~ 2.3/1.
6. according to the synthetic method of any one of claim 1-2, it is characterized in that in described step (2), the mol ratio of the consumption of inorganic base catalyst and the chloro-4-nitrophenols of 2-is 0.05 ~ 0.8:1.
7. synthetic method according to claim 6, is characterized in that the consumption of inorganic base catalyst and the mol ratio of the chloro-4-nitrophenols of 2-are 0.1 ~ 0.6:1.
8., according to the synthetic method of any one of claim 1-2, it is characterized in that the weight ratio of solvent load and the chloro-4-nitrophenols of 2-in described step (2) is 2.0 ~ 40:1.
9. synthetic method according to claim 8, is characterized in that the weight ratio of solvent load and the chloro-4-nitrophenols of 2-in described step (2) is 5.0 ~ 30:1.
10., according to the synthetic method of any one of claim 1-2, it is characterized in that the temperature of reaction of described step (2) is-50 ~ 50 DEG C; Time is 0.5 ~ 24 hour.
11. synthetic methods according to claim 10, is characterized in that the temperature of reaction of described step (2) is-10 ~ 10 DEG C; Time is 5 ~ 10 hours.
12. according to the synthetic method of any one of claim 1-2, it is characterized in that described step (3) is carried out under metal catalyst catalysis, metal catalyst is wherein selected from Raney's nickel, palladium-carbon catalyst, palladium chloride, tetrakis triphenylphosphine palladium, iron trichloride or [two (diphenylphosphine) ferrocene of 1,1-] palladium chloride; Solvent is methyl alcohol, ethanol, Virahol, isopropylcarbinol or the trimethyl carbinol; The temperature of reaction by room temperature to the boiling point of use solvent.
13. according to the synthetic method of any one of claim 1-2, it is characterized in that described step (3), the weight ratio of the consumption of metal catalyst and 2-chloro-4-nitro-1-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene is 0.001 ~ 0.3:1; The weight ratio of the consumption of hydrazine hydrate and 2-chloro-4-nitro-1-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene is 1.0 ~ 10:1; The weight ratio of solvent load and 2-chloro-4-nitro-1-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene is 2.0 ~ 30:1.
14. synthetic methods according to claim 13, is characterized in that the consumption of hydrazine hydrate and the weight ratio of 2-chloro-4-nitro-1-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene are 2.0 ~ 5.0:1; The weight ratio of solvent load and 2-chloro-4-nitro-1-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene is 5.0 ~ 10:1.
15., according to the synthetic method of any one of claim 1-2, is characterized in that the solvent of described step (4) condensation is selected from methylene dichloride, 1,2-ethylene dichloride, chlorobenzene, dichlorobenzene; The weight ratio of solvent load and the chloro-4-of 3-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) aniline is 2.0 ~ 30:1; The temperature of reaction of described step (4) is-10 ~ 20 DEG C; 1 ~ 10 hour reaction times;
16. synthetic methods according to claim 15, is characterized in that the weight ratio of solvent load and the chloro-4-of 3-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) aniline is 5.0 ~ 20:1.
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