CN100366591C - Prepn process of pyrethroid compound intermediate - Google Patents
Prepn process of pyrethroid compound intermediate Download PDFInfo
- Publication number
- CN100366591C CN100366591C CNB2003101224961A CN200310122496A CN100366591C CN 100366591 C CN100366591 C CN 100366591C CN B2003101224961 A CNB2003101224961 A CN B2003101224961A CN 200310122496 A CN200310122496 A CN 200310122496A CN 100366591 C CN100366591 C CN 100366591C
- Authority
- CN
- China
- Prior art keywords
- tetrafluoro
- solvent
- methyl
- hydroborate
- benzenediol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000002728 pyrethroid Substances 0.000 title claims abstract description 10
- 150000001875 compounds Chemical class 0.000 title abstract description 13
- 230000008569 process Effects 0.000 title description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 35
- 230000002829 reductive effect Effects 0.000 claims abstract description 24
- ZFHGXWPMULPQSE-SZGBIDFHSA-N (Z)-(1S)-cis-tefluthrin Chemical compound FC1=C(F)C(C)=C(F)C(F)=C1COC(=O)[C@@H]1C(C)(C)[C@@H]1\C=C(/Cl)C(F)(F)F ZFHGXWPMULPQSE-SZGBIDFHSA-N 0.000 claims abstract description 17
- 239000005939 Tefluthrin Substances 0.000 claims abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 63
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- -1 normal-butyl Chemical group 0.000 claims description 30
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 150000002170 ethers Chemical class 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 238000006722 reduction reaction Methods 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 9
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 9
- 229960004217 benzyl alcohol Drugs 0.000 claims description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052987 metal hydride Inorganic materials 0.000 claims description 6
- 150000004681 metal hydrides Chemical class 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- PJCSTULKVNHEGW-UHFFFAOYSA-N (2,3,5,6-tetrafluoro-4-methylphenyl)methanol Chemical compound CC1=C(F)C(F)=C(CO)C(F)=C1F PJCSTULKVNHEGW-UHFFFAOYSA-N 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 150000001263 acyl chlorides Chemical class 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 5
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 230000026030 halogenation Effects 0.000 claims description 4
- 238000005658 halogenation reaction Methods 0.000 claims description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 4
- 239000011877 solvent mixture Substances 0.000 claims description 4
- 229910015900 BF3 Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 3
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 125000005208 trialkylammonium group Chemical group 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- ZTXONRUJVYXVTJ-UHFFFAOYSA-N chromium copper Chemical compound [Cr][Cu][Cr] ZTXONRUJVYXVTJ-UHFFFAOYSA-N 0.000 claims description 2
- 229960004643 cupric oxide Drugs 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical group [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 2
- 150000003608 titanium Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 159000000013 aluminium salts Chemical class 0.000 claims 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims 1
- 150000003818 basic metals Chemical class 0.000 claims 1
- 150000003751 zinc Chemical class 0.000 claims 1
- 230000032050 esterification Effects 0.000 abstract description 8
- 238000005886 esterification reaction Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 2
- SDHKGYDQOGCLQM-UHFFFAOYSA-N [2,3,5,6-tetrafluoro-4-(hydroxymethyl)phenyl]methanol Chemical group OCC1=C(F)C(F)=C(CO)C(F)=C1F SDHKGYDQOGCLQM-UHFFFAOYSA-N 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000002140 halogenating effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000000543 intermediate Substances 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 6
- 150000005690 diesters Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000012279 sodium borohydride Substances 0.000 description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- WFNRNCNCXRGUKN-UHFFFAOYSA-N 2,3,5,6-tetrafluoroterephthalic acid Chemical compound OC(=O)C1=C(F)C(F)=C(C(O)=O)C(F)=C1F WFNRNCNCXRGUKN-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Chemical class 0.000 description 3
- 125000005233 alkylalcohol group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- 125000001475 halogen functional group Chemical group 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 3
- PCRSJGWFEMHHEW-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzene-1,4-dicarbonitrile Chemical compound FC1=C(F)C(C#N)=C(F)C(F)=C1C#N PCRSJGWFEMHHEW-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229930013930 alkaloid Natural products 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910000951 Aluminide Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 239000012448 Lithium borohydride Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical group OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- ZBALAEBQVZDYJG-UHFFFAOYSA-N dioctyl benzene-1,2-dicarboxylate toluene Chemical compound C1(=CC=CC=C1)C.C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC ZBALAEBQVZDYJG-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940059936 lithium bromide Drugs 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- XQDSCGOSSYGRSM-UHFFFAOYSA-N methyl 2,3,5,6-tetrafluoro-4-(hydroxymethyl)benzoate Chemical class COC(=O)C1=C(F)C(F)=C(CO)C(F)=C1F XQDSCGOSSYGRSM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
The present invention relates to a preparation method of a pyrethroid compound intermediate. The chemical name of the pyrethroid compound intermediate is 2, 3, 5, 6-tetrafluoro p-phenylenedimethanol prepared by that the 2, 3, 5, 6-tetrafluoro p-phenyl dicarboxylate is reduced; further, tefluthrin is obtained by halogenating, hydrogenation and esterification. The method has the characteristics of simple technological lines, high safety, favorable reliability and high quality yield.
Description
Technical field
The present invention relates to a kind of pyrethroid synthetic phenyl polyfluoride base alcohol 2,3,5 that is applied to, the 6-tetrafluoro is to the preparation method of Benzenediol, and it is the important intermediate of preparation pyrethroid, obtains tefluthrin through halo, hydrogenation, esterification.
Background technology
Cis-3-haloalkenyl group-2,2-dimethyl cyclopropane carboxylic acid and 4-methyl-2,3,5, the ester that 6-tetrafluoro phenyl alcohol forms, particularly tefluthrin [2,3,5,6-tetrafluoro-4-phenmethyl-cis-((Z)-2-chloro-3,3,3-three fluoro-third-1-thiazolinyl)-2,2-dimethyl cyclopropane carboxylic acid ester], be important sterilant and kill the mite product.Therefore need a kind of technology capable of being industrialized, effective to prepare and necessary resemble 2,3,5, the 6-tetrafluoro is to the such intermediate of Benzenediol.
Known preparation 2,3,5, the 6-tetrafluoro is to technology existing description in some patent of Benzenediol.In order further to improve yield and quality, require 2,3,5 of a kind of more high quality of invention and yield, the 6-tetrafluoro is to the industrial preparation process of Benzenediol.
Summary of the invention
The applicant has found a kind of preparation 2,3,5, and the 6-tetrafluoro can satisfy above-mentioned requirements to the method for Benzenediol, and safer with respect to existing this process of technology, is easy to control.This handicraft product uses simple solvent, does not need more processing step, and by-product is few, and the three wastes are handled simple, the product yield height, and purity reaches more than 97%.
Therefore, proposed below to be reduced into 2,3,5 by tetrafluoro dialkyl benzene carboxylicesters in the presence of reductive agent and solvent, the 6-tetrafluoro is to the technology of Benzenediol.
The R that mentions among the present invention
1Or R
2The straight or branched alkyl of identical or different 1-6 the carbon atom that is respectively is preferably methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, sec.-propyl, isobutyl-, the tertiary butyl or neo-pentyl.More preferably R
1And R
2Be identical, methyl particularly.Be R
1And R
2It all is the tetrafluoro dimethyl terephthalate (DMT) of methyl.
Intermediate (II) can separate, purify with using it for anything else or continuing to be reacted to target product (III).Structural formula (II) intermediate is a new discovery, also is another aspect of the present invention.
Parent material (I) can be very simply by tetrafluoro terephthalic acid and alkyl alcohol preferably the lower alkyl alcohol esterification make.The tetrafluoro terephthalic acid is a kind of intermediate for preparing sterilant, makes easily by the hydrolysis of tetrafluoro terephthalonitrile, and the yield height.The tetrafluoro terephthalonitrile can be made through fluoridizing easily by tetrachloro-p-phenylene's dintrile, and initial substance tetrachloro-p-phenylene dintrile is a kind of obtainable industrial goods.
The used appropriate reductant of this technology is a metal hydride, as the hydroborate of lithium, sodium, potassium or calcium, as POTASSIUM BOROHYDRIDE, sodium borohydride; A kind of aluminum hydride metal such as potassium hydride KH aluminium, lithium aluminium hydride; Alkoxyl group aluminum hydride metal such as MAlHx (OR) y, wherein, M-basic metal, R-alkanes, x, y can be independently 1,2,3, and x+y=4; The hydride of aluminium, boride; Hydrogen; A kind of hydrogen give body, as Virahol, ammonium formate, trialkyl ammonium formate or tetrahydrobenzene.
Using under the reduction reaction situation of metal hydride, the usage quantity of metal hydride all depends on the character of reductive agent itself except hydroborate, generally and the mol ratio of diester (I) at 1-3: 1, be preferably in 1-1.5: 1.For alkoxyl group aluminum hydride metal, with respect to the mol ratio of diester (I) at 4-12: 1, be preferably in 4-8: 1.Prepare the change of the intermediate of structure (II) if desired, the consumption of reductive agent generally reduces by half.
The solvent that reduction reaction is suitable has: alcohols; Glycols; Ethers; Gylcol ether; Second two ethers; Poly-second two ethers, polyether class, the mixture of a kind of lower alcohol (as methyl alcohol, ethanol), a kind of two-phase solvent mixture; Polar aprotic solvent; Organic acid; Ester; Water; Ether; The mixture of rudimentary anion surfactant.
Do with hydroborate in the reduction reaction of reductive agent, suitable solvent has alcohols, as: methyl alcohol, ethanol, Virahol; Glycols is as ethylene glycol or polyoxyethylene glycol; Also can be ethers, as: methyl ether, ether, methyl-phenoxide, acetic acid, two alkane, tetrahydrofuran (THF); The ester class: as ethyl acetate, ethyl formate.Gylcol ether, as 1, the 2-glycol dimethyl ether; Second two ethers are as diglyme; The polyether class; A kind of lower alkyl alcohol such as methyl alcohol, alcoholic acid mixture.Improve reaction yield and transformation efficiency for making reaction carry out to add a kind of auxiliary agent or catalyzer fully, or be used for reducing the usage quantity of hydroborate.Proper auxiliary agent is sex change metal-salt or boride.Best sex change metal-salt is aluminium, zinc, titanium salt such as aluminum chloride, zinc chloride, titanium tetrachloride etc.Boride such as boron trifluoride or alkyl boride.When using sodium borohydride, POTASSIUM BOROHYDRIDE, then can make auxiliary agent with lithiumation thing such as lithium chloride or lithiumbromide.General and the reductive agent mol ratio of amount of auxiliary is at 0.05-1: 1, and the best is 0.1-0.5: 1.Appropriate catalyst has salt, as tetraalkylammonium salt, phosphonate, open chain or the cyclic polyethers.Catalyst consumption is generally the 0.01-0.1 moles/mole of reductive agent.
When making reductive agent with hydroborate, also can use a kind of two-phase solvent mixture as solvent, by water and water-soluble or water-insoluble solvent such as aromatic hydrocarbon, particularly toluene is formed.In this case, generally need to add a kind of catalyzer and improve speed of reaction.Suitable catalyzer has cationic salts, as tetraalkylammonium salt, phosphonate, polyethylene glycol ether open chain or cyclic polyethers such as end closure, crown ether etc.
Be the aprotic, polar inert solvent than The suitable solvent when making reductive agent with the hydrogen aluminide, arene, as: toluene, methyl-phenoxide or ethers, as: two alkane, tetrahydrofuran (THF), ether, glycol dimethyl ether or relevant oligo-ether.
Reduction reaction can be carried out in the temperature range of solvent boiling point at-20 ℃, and generally at 30-120 ℃, better temperature range is 40-80 ℃, and the reaction times is depended on the activity of reductive agent, generally at 1-20 hour.This method prepares compound (III), and reaction is preferably uninterrupted continuously, and the content of guaranteeing compound (II) preferably is controlled in 1% less than 5%.
Another kind method is given body such as Virahol, ammonium formate, trialkyl ammonium formate or tetrahydrobenzene reduction diester with hydrogen or hydrogen, carries out under the effect of metal, metal oxide, mixed metal oxide, metal-salt or metal composite catalyst, diester is reduced to 2,3,5, the 6-tetrafluoro is to Benzenediol.If master metal group VIII metal as palladium, platinum, rhodium, rhenium, nickel, optionally is equipped with inert support, this carrier can be carbon, aluminum oxide, alkaline earth metal carbonate.Metal oxide has cupric oxide, chromic oxide.Mixed oxide such as chromiumcopper.Catalyst levels depends on the character of catalyzer.The group VIII metal, the consumption of salt or mixture is generally 0.01-5mol% of reductive agent, is preferably in 0.01-1mol%.The metal oxide of non-group VIII metal and mixed oxide are the 0.1-10wt% of reductive agent as catalyst consumption, are preferably in 0.1-1wt%.After reaction finishes, can reclaim catalyzer by routine techniques, as filtering, be adsorbed onto on the inert material or precipitation, in addition recovery set is used.If use hydrogen, pressure generally needs 1-200atm, preferably 10-50atm.Temperature is controlled at 50-200 ℃, is preferably in 50-120 ℃.If give body with hydrogen, reaction is generally carried out under solvent natural pressure and certain temperature condition.
The solvent that the catalytic hydrogenating reduction reaction is suitable for has alcohols, as methyl alcohol, Virahol; Aromatic hydrocarbon such as toluene, dimethylbenzene; Ethers such as THF, 1, the 2-glycol dimethyl ether; Or organic acid, as acetate; Or ester, as ethyl acetate, methyl acetate etc.Best solvent is Virahol or Virahol and aromatic mixed solvent.If preparation compound (II), the consumption of hydrogen is in a half termination reaction.
After the reduction reaction, should be undertaken by following one or multinomial step subsequently:
1, filtering separation catalyzer and recovery
2, water or organic acid or inorganic acid aqueous solution termination reaction
3, distillating recovering solvent
4, add a kind of different solvent
5, with water soluble acid or alkali extraction, remove water miscible inorganics or disposable reaction solvent.
6, by conventional means such as crystallization or evaporation recovery product.
Product also can be retained in the solvent, directly enters next step reaction, can shorten reactions steps.
The applicant is simultaneously through the following steps with 2,3,5, and the 6-tetrafluoro is converted into tefluthrin to Benzenediol.
1) with 2,3,5, halogenation obtains 2,3,5 to the 6-tetrafluoro to Benzenediol, 6-tetrafluoro-4-monochloromethyl phenylcarbinol;
This halogenation process is normally used to be that haloid acid family materials such as hydrochloric acid or Hydrogen bromide can carry out stable reaction.Used solvent is inert or not miscible with water solvent, arene for example, and the optimal temperature of reaction is between 50 ℃-150 ℃, optimum temps is 75 ℃-100 ℃.
2), obtain 4-methyl-2,3,5, the 6-tetrafluorobenzyl alcohol after 6-tetrafluoro-4-monochloromethyl phenylcarbinol hydrogenation with 2,3,5
Hydrogenation process in this step is used hydrogen and metal catalyst such as palladium, nickel, the hydrogen halide that cooperates alkaloids to emit in order to absorption reaction.Suitable alkaloids has alkali, alkaline earth metal oxide and carbonate.Alcohols, ester class and aromatic hydrocarbon are ideal solvents comparatively, and the optimal temperature of reaction is 0-60 ℃, and suitable pressure condition is that normal pressure is to 10atm.
3) with 4-methyl-2,3,5,6-tetrafluorobenzyl alcohol and cis-((Z)-2-chloro-3,3,3-three fluoro-third-1-thiazolinyl)-2,2-dimethylcyclopropane base acyl chlorides or cis-((Z)-2-chloro-3,3,3-three fluoro-third-1-thiazolinyl)-2, the synthetic tefluthrin that obtains of 2-dimethylcyclopropane yl carboxylic acid.
Just can obtain tefluthrin by esterification.The method of esterification process is: remove the HCl that produces by the physics method, catch up with as heating method or with inert blowing gas; Chemical process available bases such as pyridine neutralize.Esterification reacts completely if use the cyclopropane yl carboxylic acid can not use solvent or dewater to make under the strongly acidic catalyst effect with inert solvent such as toluene, dimethylbenzene or similar solvent.
In a word, principal character of the present invention is:
1, a kind of intermediate 2,3,5 of pyrethroid, the 6-tetrafluoro is to the preparation method of Benzenediol, and structural formula is
It is characterized in that with the tetrafluoro terephthalate be raw material, reduction preparation 2,3,5 under the effect of reductive agent and solvent, the 6-tetrafluoro is to Benzenediol, and its operational path is as follows:
R in the following formula
1Or R
2Be respectively the straight or branched alkyl of identical or different 1-6 carbon atom, wherein R
1And R
2Be not methyl simultaneously,
Solvent is: the mixture of the mixture of alcohols, glycols, ethers, second two ethers, gylcol ether, poly-second two ethers, polyether class, lower alcohol, two-phase solvent mixture, organic acid, ester, water, rudimentary anion surfactant,
Reductive agent is that metal hydride, borohydride aluminum hydride metal, aluminum borohydride, hydrogen or hydrogen are given body.
2, above-mentioned preparation method is characterized in that R
1Or R
2Be methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, sec.-propyl, isobutyl-, the tertiary butyl or neo-pentyl.
3, above-mentioned preparation method, it is characterized in that solvent is methyl alcohol, ethanol, Virahol, ethylene glycol, polyoxyethylene glycol, ether, 1,2-glycol dimethyl ether, tetrahydrofuran (THF), poly-second diether, methyl-phenoxide, acetic acid, ethyl acetate, ethyl formate, water, tetrahydrofuran (THF), methyl alcohol and alcoholic acid mixture.
4, above-mentioned preparation method is characterized in that the reductive agent borohydride is potassium borohydrid, sodium borohydride, lithium borohydride; The aluminum hydride metal is a lithium aluminium hydride, adds auxiliary agent or catalyzer simultaneously.
5, above-mentioned 4 described preparation methods, it is characterized in that proper auxiliary agent is sex change metal-salt or boride, the ratio of auxiliary dosage and reductive agent is 0.05-1: 1 moles/mole, appropriate catalyst be salt, open chain or the cyclic polyethers, the ratio of catalyst levels and reductive agent is 0.01-0.1: 1 moles/mole.
6, above-mentioned 5 described preparation methods is characterized in that the sex change metal-salt is an aluminum chloride, zinc chloride, titanium tetrachloride etc.; Boride is boron trifluoride or alkyl boride; Salt is tetraalkylammonium salt, phosphonate.
7, above-mentioned 5,6 described preparation methods is characterized in that solvent is methyl alcohol, ethanol, Virahol, ethylene glycol, polyoxyethylene glycol, ether, two alkane, tetrahydrofuran (THF), 1,2-glycol dimethyl ether, poly-second diether.
8, above-mentioned 1 described preparation method, when it is characterized in that using hydrogen as reductive agent, catalyzer is metal, metal oxide, mixed metal oxide, metal-salt or metal complex.
9, above-mentioned 8 described preparation methods is characterized in that solvent is alcohols, aromatic hydrocarbon, ethers, organic acid or ester.
10, according to above-mentioned arbitrary preparation method, it is characterized in that the temperature of reaction process is controlled at-20 ℃ in the temperature range of solvent boiling point, carry out.
11, above-mentioned 10 described preparation methods is characterized in that temperature of reaction is controlled at 40-80 ℃.
12, above-mentioned 1 described preparation method is characterized in that tetrafluoro obtains tefluthrin again to Benzenediol after halo, hydrogenation, esterification, can be through the following steps with 2,3,5, and the 6-tetrafluoro is converted into tefluthrin to Benzenediol
1) with 2,3,5, halogenation obtains 2,3,5 to the 6-tetrafluoro to Benzenediol, 6-tetrafluoro-4-monochloromethyl phenylcarbinol;
2), obtain 4-methyl-2,3,5, the 6-tetrafluorobenzyl alcohol after 6-tetrafluoro-4-monochloromethyl phenylcarbinol hydrogenation with 2,3,5;
3) with 4-methyl-2,3,5,6-tetrafluorobenzyl alcohol and cis-((Z)-2-chloro-3,3,3-three fluoro-third-1-thiazolinyl)-2,2-dimethylcyclopropane base acyl chlorides or cis-((Z)-2-chloro-3,3,3-three fluoro-third-1-thiazolinyl)-2, the synthetic tefluthrin that obtains of 2-dimethylcyclopropane yl carboxylic acid.
13, a kind of production 2,3,5, the 6-tetrafluoro is to the midbody compound (II) of Benzenediol
R wherein
2Methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, sec.-propyl, isobutyl-, the tertiary butyl or neo-pentyl for the straight or branched alkyl of 1-6 carbon atom.
14, above-mentioned 13 described compounds is characterized in that R
2Be methyl, this compound is 2,3,5,6-tetrafluoro-4-hydroxymethyl-benzoic acid methyl esters.
Embodiment
With some concrete examples the present invention is described below, but the present invention not only is confined to following embodiment:
Embodiment 1, and 3,5, the 6-tetrafluoro is to the preparation method (1) of Benzenediol
In the four-hole boiling flask of a 2000ml, drop into methyl alcohol 500ml, sodium borohydride 37g, be warming up to 50 ℃, be incubated after 1 hour, drop into tetrafluoro diethyl terephthalate 294g, continue under 50 ℃ temperature, to react 5 hours, be cooled to room temperature, with 30% hydrochloric acid 300ml hydrolysis, use the 500ml carbon tetrachloride extraction again, the tetrafluoro terephthalyl alcohol 167.2g that obtains the title of white solid behind the tetracol phenixin is sloughed in decompression, content is 97.7%, and yield is 77.8%
Embodiment 22, and 3,5, the 6-tetrafluoro is to the preparation method (2) of Benzenediol
In the four-hole boiling flask of a 2000ml, drop into ethanol 500ml, POTASSIUM BOROHYDRIDE 54g, be warming up to 50 ℃, be incubated after 1 hour, drop into tetrafluoro dimethyl terephthalate (DMT) 266g, continue under 50 ℃ temperature, to react 5 hours, be cooled to room temperature, with 30% hydrochloric acid 300ml hydrolysis, use the 500ml carbon tetrachloride extraction again, after sloughing tetracol phenixin, decompression obtains tetrafluoro terephthalyl alcohol 176.4g, content is 98.1%, and yield is 82.4%.
Embodiment 32, and 3,5, the 6-tetrafluoro is to the preparation method (3) of Benzenediol
Process is as described in (example one), and methyl alcohol is thrown 370ml, and the content of tetrafluoro terephthalyl alcohol is 93.1%, and yield is 76%
Embodiment 42, and 3,5, the 6-tetrafluoro is to the preparation method (4) of Benzenediol
In the autoclave of a 1000ml, add tetrafluoro to toluene dioctyl phthalate propyl ester 161g, active palladium 1.61g, methyl alcohol 500ml, logical hydrogen hydrogenating reduction under 60 ~ 70 ℃ temperature condition, pressure condition is 3.5atm.After waiting not have tangible absorption, be cooled to room temperature, suction filtration elimination Pd/c then, filtrate negative pressure precipitation, white solid tetrafluoro terephthalyl alcohol 85.6g, content is 97.5%, yield is 79.5%.
Embodiment 52, and 3,5, the 6-tetrafluoro is to the preparation method (5) of Benzenediol
Process is as described in (example four), and catalyzer Raney's nickel 1.61g, the content of tetrafluoro terephthalyl alcohol are 97.8%, and yield is 80.7%
Embodiment six 4-methylols-2,3,5, the preparation method of 6-tetrafluorobenzoic aid ester
In the 100ml of dried and clean flask, drop into tetrahydrofuran (THF) 20ml, glycol dimethyl ether 10ml, sodium borohydride 54g, controlled temperature slowly adds tetrafluoro to toluene dioctyl phthalate methyl esters 4.0g at 35 ℃, is warming up to 70 ℃, stir, insulation 5hr, sampling is regularly carried out the gas spectrum and is detected.Reactant leaves standstill to shake after 48hr lowers the temperature again and is warming up to, and analyze to show that reaction is incomplete, so add another part glycol dimethyl ether 10ml, and continuation concussion reaction 5hr.The gas spectrum shows that diester disappears, and the mixture water 100ml of Compound I I and compound III handles, again with ethyl acetate 50ml extraction 3 times.Extract obtains sticking white solid after merging processing.The gas spectrum shows that mixture is glycol 63% and monoesters 37%.Can get 4-methylol-2,3,5,6-tetrafluorobenzoic aid ester by the column chromatography purification.
It detects data: fusing point: 65.6 ℃, and purity: 97.6%
Nuclear magnetic resonance data: D
4In the methyl alcohol
19F-135.2 (polymorphic, 2F);-146.3 (polymorphic, 2F)
D
4In the methyl alcohol
1H 4.67 (singlet ,-CH2-, 2H); 3.90 (singlet, OCH3,3H) mass spectrum: molecular ion peak is at m/z238 (30%), and fragment ion peak is 207 (100%), and 187 (30%), 177 (25%), 159 (20%), 149 (22%), 131 (24%), 99 (24%), 81 (20%), 59 (17%)
Embodiment 7:
The preparation method (1) of tefluthrin [2,3,5,6-tetrafluoro-4-phenmethyl cis-((Z)-2-chloro-3,3,3-three fluoro-third-1-thiazolinyl)-2,2-dimethyl cyclopropane carboxylic acid ester]:
The first step: Synthetic 2,3,5,6-tetrafluoro-4-brooethyl phenylcarbinol
2,3,5, the 6-tetrafluoro joins in the 1L reactor the solution 80g of Benzenediol and methyl iso-butyl ketone (MIBK), and reactor is furnished with backflow and receiving device.Boil off solvent by distillation.Add toluene (303g) again, dewater by component distillation.Be heated to 60 ℃, keep 30min, add Silcolapse (0.2g) and 48% Hydrogen bromide (109.3g), be heated to 95 ℃, first backflow 30min is component distillation band water 5.5hr again.Add entry (150ml) and Hydrogen bromide (36.6g) then and cool to 55 ℃.Stir 15min at 55 ℃, separate water layer with 30min again.Oil reservoir washs layering with prefabricated solution (water 150ml+40% sodium acetate aqueous solution 36g), and toluene layer analyzes 2,3,5,6-tetrafluoro-4-brooethyl phenylcarbinol content, and yield is 96.2%
Second step: synthetic 4-methyl-2,3,5,6-tetrafluorobenzyl alcohol
Following process is carried out in the 1L glass autoclave (working volume 350-500mls) of a dispersion agitator of outfit (1000rpm), and the H2 charging is by inserting tube process Buchi Gas controller 6002 types.Heating and cooling control is bathed by Jelabo FP40 temperature.Methyl alcohol (362g), water (6g), 2,3,5,6-tetrafluoro-4-brooethyl phenylcarbinol (95.1g 100%wt.), MgO (18.1g), 5% palladium/carbon catalyst ((58 type) JohnsonMatthey company provides) (0.8g 100%wt.) joins in the reactor, adds a cover, and displaces O2 (near 0) with N2, be pressurized to 2.5bar with H2, stir,, make the entire reaction temperature be controlled at 50 ℃ by the temperature bath by Buchi controller control pressure 2.5bar.The H2 consumption is by the control of Buchi controller.Reaction until H2 no longer consume till (general 60--90min), release, and with the N2 displacement, blowing is with small amount of methanol (30g) flushing autoclave.Filtered and recycled spent catalyst and inorganic salt, (2 * 30g) wash filter cake with small amount of methanol.Merging filtrate, analytical calculation gets 2,3,5,6-tetrafluoro-4-methylbenzyl alcohol 60.4g, yield 89.4%
The 3rd step: synthetic tefluthrin
Cis-((Z)-2-chloro-3,3,3-three fluoro-third-1-thiazolinyl)-2,2-dimethylcyclopropane base acyl chlorides (257g) joins one to be furnished with in the four-hole boiling flask that disperses agitator, adds toluene (257g), lysed 2,3,5, add an amount of pyridine (51g) in the 6-tetrafluoro 4-methylbenzyl alcohol (188.1g) and place dropping funnel together, the solution that drips alcohol is gone in the acyl chlorides, temperature maintenance is at 35-45 ℃, drip and finish, be warming up to 95 ℃, be incubated 2 hours, be cooled to 60 ℃, add and boil off solvent behind the water-soluble salt and get tefluthrin 410.3g, content is 95.5%, and yield is 96.5%.
Embodiment 8: the preparation method (2) of tefluthrin [2,3,5,6-tetrafluoro-4-phenmethyl cis-((Z)-2-chloro-3,3,3-three fluoro-third-1-thiazolinyl)-2,2-dimethyl cyclopropane carboxylic acid ester]:
In the enamel high pressure still of 1000ml, throw methyl alcohol 250ml, sodium borohydride 20g.Controlled temperature slowly adds tetrafluoro terephthalic acid methyl esters 133g at 50 ℃, stir insulation 5hr, sampling analysis, gas spectrum show when diester has disappeared, add 30% HCL20ml in the mixture, carbon tetrachloride extraction with 250ml, tetracol phenixin is sloughed in decompression, adds toluene 300ml, 48% Hydrogen bromide (122.3g), be heated to 95 ℃, collect the azeotrope of toluene and water 95-100 ℃ of backflow after 30 minutes.React and be cooled to about 55 ℃ after 5.5 hours, with the washing of 5% sodium acetate aqueous solution once, slough solvent toluene, add methyl alcohol (450g), water (7.5g), 5% palladium/carbon catalyst (1.2g100%wt) in the residuum, the good seal device, approaching zero to oxygen level with nitrogen replacement, pressurized with hydrogen is to 2.5bar, and temperature of reaction is controlled at about 50 ℃.Till H2 no longer absorbed, nitrogen replacement was used in release, crossed catalyzer and inorganic salt that elimination was lost efficacy, and filtrate boils off solvent.Add toluene 150ml, pyridine 28.8g in the residuum, be warming up to 35-45 ℃, splash into cis-((Z)-2-chloro-3,3,3-three fluoro-third-1-thiazolinyl)-2,2-dimethylcyclopropane base formyl chloride (85.8g) drips and finishes, be warming up to 75-90 ℃, be incubated 2 hours, be cooled to 60 ℃, add and boil off solvent behind the water-soluble salt and get tefluthrin 71.1g, content is 94.9%, is 64.1% to the total recovery of tetrafluoro terephthalic acid methyl esters.
The applicant has invented a kind of new preparation method of intermediate of pyrethroid compound, this intermediate 2,3,5,6-tetrafluoro terephthalyl alcohol, and then obtaining tefluthrin by halo, hydrogenation, esterification, this technology has the advantages that operational path is simple, safe and reliable, mass yield is high, cost is low, is fit to very much suitability for industrialized production.The present invention has also found the compound of new intermediate simultaneously.
Claims (20)
1. the intermediate 2,3,5 of a pyrethroid, the 6-tetrafluoro is to the preparation method of Benzenediol, and its structural formula is
It is characterized in that with the tetrafluoro terephthalate shown in the formula (I) be raw material, at reductive agent be selected from and reduce 2,3,5 of preparation formula (III) under the effect of solvent of alcohols, the 6-tetrafluoro is to Benzenediol, and its operational path is as follows:
R wherein
1Or R
2It is respectively the straight or branched alkyl of identical or different 1-6 carbonatoms.
2. method according to claim 1 is characterized in that R
1Or R
2Be selected from is methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, sec.-propyl, isobutyl-, the tertiary butyl or neo-pentyl.
3. method according to claim 1, it is characterized in that reductive agent is that metal hydride, hydroborate, hydrogen or hydrogen are given body, prerequisite be when reductive agent be hydrogen or hydrogen when giving body, need have group VIII metal or its salt, cupric oxide, chromic oxide or chromiumcopper simultaneously.
4. method according to claim 3 is characterized in that metal hydride is potassium hydride KH aluminium, lithium aluminium hydride or MAlHx (OR) y, and wherein, M is a basic metal, and R is an alkyl, and x, y independently are 1,2,3, and x+y=4.
5. method according to claim 3 is characterized in that reductive agent is the hydroborate that hydroborate is selected from lithium, sodium, potassium or calcium.
6. method according to claim 3 is characterized in that hydrogen is selected from Virahol, ammonium formate, trialkyl ammonium formate or tetrahydrobenzene to body.
7. according to one of any described method of claim 1-6, it is characterized in that solvent is selected from the mixture of methyl alcohol, ethanol, Virahol, ethylene glycol, polyoxyethylene glycol or lower alcohol.
8. according to the described method of claim 7, it is characterized in that solvent is selected from methyl alcohol, the mixture of lower alcohol is methyl alcohol and alcoholic acid mixture.
9. method according to claim 1 is characterized in that reduction reaction carries out in the temperature range of solvent boiling point at-20 ℃.
10. according to the described method of claim 9, it is characterized in that reduction reaction carries out under 40-80 ℃.
11. the intermediate 2,3,5 of a pyrethroid, 6-tetrafluoro are to the preparation method of Benzenediol, its structural formula is
It is characterized in that with the tetrafluoro terephthalate shown in the formula (I) be raw material, hydroborate, solvent and be selected from the auxiliary agent of aluminium salt, zinc salt, titanium salt, boron trifluoride or alkyl boride or be selected from phosphonate or the effect of the catalyzer of open chain or cyclic polyethers under reduce 2 of preparation formula (III), 3,5, the 6-tetrafluoro is to Benzenediol, and slightly line is as follows for its technology:
R wherein
1Or R
2It is respectively the straight or branched alkyl of identical or different 1-6 carbonatoms.
12. method according to claim 11 is characterized in that R
1Or R
2Be selected from methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, sec.-propyl, isobutyl-, the tertiary butyl or neo-pentyl.
13. method according to claim 11 is characterized in that the two-phase solvent mixture that solvent is selected from alcohols, ethers, organic acid, ester, water and is made up of water and aromatic hydrocarbons.
14. method according to claim 13 is characterized in that alcohols is selected from the mixture of methyl alcohol, ethanol, Virahol, ethylene glycol, polyoxyethylene glycol or lower alcohol; Ethers is selected from ether, methyl-phenoxide, two alkane, tetrahydrofuran (THF); Glycol ether or poly-second diether; Aromatic hydrocarbons is toluene; Organic acid is an acetic acid; And ester is ethyl acetate or ethyl formate.
15., it is characterized in that hydroborate is selected from the hydroborate of lithium, sodium, potassium or calcium according to one of any described method of claim 11-14.
16. method according to claim 15 is characterized in that described auxiliary agent is selected from aluminum chloride, zinc chloride or titanium tetrachloride.
17. method according to claim 11, the mol ratio that it is characterized in that auxiliary agent and hydroborate is 0.05-1: 1, and the mol ratio of catalyzer and hydroborate is 0.01-0.1.
18. method according to claim 11 is characterized in that reduction reaction carries out in the temperature range of solvent boiling point at-20 ℃.
19. method according to claim 18 is characterized in that reduction reaction carries out under 40-80 ℃.
20. a method for preparing tefluthrin is characterized in that:
1) with claim 1 or the described method preparation 2,3,5 of claim 11, the 6-tetrafluoro is to Benzenediol;
2) with 2,3,5, halogenation obtains 2,3,5 to the 6-tetrafluoro to Benzenediol, 6-tetrafluoro-4-monochloromethyl phenylcarbinol;
3), obtain 4-methyl-2,3,5, the 6-tetrafluorobenzyl alcohol after 6-tetrafluoro-4-monochloromethyl phenylcarbinol hydrogenation with 2,3,5;
4) with 4-methyl-2,3,5,6-tetrafluorobenzyl alcohol and cis-((Z)-2-chloro-3,3,3-three fluoro-third-1-thiazolinyl)-2,2-dimethylcyclopropane base acyl chlorides or cis-((Z)-2-chloro-3,3,3-three fluoro-third-1-thiazolinyl)-2, the synthetic tefluthrin that obtains of 2-dimethylcyclopropane yl carboxylic acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2003101224961A CN100366591C (en) | 2003-12-26 | 2003-12-26 | Prepn process of pyrethroid compound intermediate |
| US10/575,420 US7312366B2 (en) | 2003-10-10 | 2004-01-13 | Preparation of one intermediate for pyrethroids |
| JP2006529548A JP4685779B2 (en) | 2003-10-10 | 2004-01-13 | Method for producing synthetic intermediate of pyrethroid compound |
| PCT/CN2004/000040 WO2005035474A1 (en) | 2003-10-10 | 2004-01-13 | Preparation of one intermediate for pyrethroids |
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| CN 200710079703 Division CN101125816B (en) | 2003-12-26 | 2003-12-26 | Alkyl 2,3,5,6-tetrafluoro-4-hydroxymethylbenzoate |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000068173A1 (en) * | 1999-05-07 | 2000-11-16 | Showa Denko K.K. | Process for producing tetrafluoro benzenemethanols |
| CN1458167A (en) * | 2003-06-02 | 2003-11-26 | 中国农业科学院哈尔滨兽医研究所 | Truncated expressed porcine circovirus II capsid protein antigen and use thereof |
| CN1605581A (en) * | 2003-10-10 | 2005-04-13 | 江苏扬农化工股份有限公司 | Preparation method for intermediate of pyrethroid compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000068173A1 (en) * | 1999-05-07 | 2000-11-16 | Showa Denko K.K. | Process for producing tetrafluoro benzenemethanols |
| CN1458167A (en) * | 2003-06-02 | 2003-11-26 | 中国农业科学院哈尔滨兽医研究所 | Truncated expressed porcine circovirus II capsid protein antigen and use thereof |
| CN1605581A (en) * | 2003-10-10 | 2005-04-13 | 江苏扬农化工股份有限公司 | Preparation method for intermediate of pyrethroid compound |
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