CN103951627A - Method for synthesizing sulfentrazone midbody and sulfentrazone - Google Patents
Method for synthesizing sulfentrazone midbody and sulfentrazone Download PDFInfo
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- CN103951627A CN103951627A CN201410186717.XA CN201410186717A CN103951627A CN 103951627 A CN103951627 A CN 103951627A CN 201410186717 A CN201410186717 A CN 201410186717A CN 103951627 A CN103951627 A CN 103951627A
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- 238000000034 method Methods 0.000 title claims abstract description 23
- OORLZFUTLGXMEF-UHFFFAOYSA-N sulfentrazone Chemical compound O=C1N(C(F)F)C(C)=NN1C1=CC(NS(C)(=O)=O)=C(Cl)C=C1Cl OORLZFUTLGXMEF-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 101
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- -1 2,4-difluoro-5-(4-difluoro methyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazole-1-yl) phenyl Chemical group 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006722 reduction reaction Methods 0.000 claims abstract description 13
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 11
- 238000005694 sulfonylation reaction Methods 0.000 claims abstract description 10
- 230000006103 sulfonylation Effects 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 7
- 238000006396 nitration reaction Methods 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 claims description 18
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- 239000000460 chlorine Substances 0.000 claims description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 13
- 235000015320 potassium carbonate Nutrition 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 10
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 10
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 9
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Chemical group 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims description 7
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-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
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical group 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 150000003003 phosphines Chemical class 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000002334 glycols Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000000802 nitrating effect Effects 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 3
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 11
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 150000003983 crown ethers Chemical class 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000002202 Polyethylene glycol Substances 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 230000011987 methylation Effects 0.000 abstract 1
- 238000007069 methylation reaction Methods 0.000 abstract 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 abstract 1
- QDVFAGFTHUWITN-UHFFFAOYSA-N methylsulfonylmethane;hydrochloride Chemical compound Cl.CS(C)(=O)=O QDVFAGFTHUWITN-UHFFFAOYSA-N 0.000 abstract 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 150000002576 ketones Chemical class 0.000 description 7
- 150000002828 nitro derivatives Chemical class 0.000 description 7
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- WJIYVZOJKPPMDO-UHFFFAOYSA-N C1(=CC=CC=C1)C1(C(=O)O)CC(C(=O)O)(CC=C1)C Chemical compound C1(=CC=CC=C1)C1(C(=O)O)CC(C(=O)O)(CC=C1)C WJIYVZOJKPPMDO-UHFFFAOYSA-N 0.000 description 5
- UHKMRAOFYCTDQJ-UHFFFAOYSA-N 6-(difluoromethyl)-1-methyl-3-phenylcyclohex-4-ene-1,3-dicarboxylic acid Chemical compound C1(=CC=CC=C1)C1(C(=O)O)CC(C(=O)O)(C(C=C1)C(F)F)C UHKMRAOFYCTDQJ-UHFFFAOYSA-N 0.000 description 4
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 0 CC(C)=NN([C@@]1OC1N)C1=CC=CC*=C1 Chemical compound CC(C)=NN([C@@]1OC1N)C1=CC=CC*=C1 0.000 description 2
- SNOKIIWKOBEJKY-UHFFFAOYSA-N CC1(CC(C=CC1C(F)F)(C2=CC(=C(C=C2Cl)Cl)N)C(=O)O)C(=O)O Chemical compound CC1(CC(C=CC1C(F)F)(C2=CC(=C(C=C2Cl)Cl)N)C(=O)O)C(=O)O SNOKIIWKOBEJKY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- RCFKEIREOSXLET-UHFFFAOYSA-N disulfamide Chemical compound CC1=CC(Cl)=C(S(N)(=O)=O)C=C1S(N)(=O)=O RCFKEIREOSXLET-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/12—Oxygen or sulfur atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing a sulfentrazone midbody and sulfentrazone. The method comprises the following steps: preparing the sulfentrazone midbody (III) from 1-phenyl-3-methyl-1H-1,2,4-triazole-5-ketone used as a raw material in an aprotic solvent in the presence of a compound (A) or a compound (B) and alkali, performing difluoro methylation to obtain a midbody (IV), performing chlorination, nitration and reduction, and further performing methyl sulfone chloride sulfonylation to obtain a final product, namely, N(2,4-difluoro-5-(4-difluoro methyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazole-1-yl) phenyl) sulfamide. The method has the main beneficial effects that due to an adopted catalytic hydrogenation process, the nitroreduction is not only high in chemical selectivity, but also is more environment-friendly, efficient, safe and reliable, as triphenylphosphine, polyethylene glycol or crown ether is used as a catalyst which takes the place of a conventional used catalyst such as DMF (Dimethyl Formamide) in the sulfonylation reaction, less side reaction is caused, and the yield is high. The overall process is simple and convenient, the reaction condition is gentle, the yield is high, the product quality is high, and the industrial production is facilitated.
Description
Technical field
The present invention relates to the synthetic method of organofluorine compound, relate in particular to a kind of method of synthetic sulfentrazone intermediate and sulfentrazone.
Background technology
Sulfentrazone is a kind of weedicide that belongs to triazolineone.Chemical name is N-(the chloro-5-(4-of 2,4-bis-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) phenyl) Toluidrin.Its chemical structural formula shows below:
1-phenyl-4-difluoromethyl-3-methyl isophthalic acid H-1,2,4-triazole-5-ketone (IV) is the main intermediate of synthetic sulfentrazone.US5438149 discloses the preparation method of this intermediate: taking difluorochloromethane as difluoromethyl reagent, salt of wormwood is acid binding agent, and DMF is reaction solvent, in enclosed high pressure reactor, at 160-200oC temperature, reacts.High-temperature high-voltage reaction, there in suitability for industrialized production, have to be many unfavorable: for example (1) adds methylene fluoride and is not easy under High Temperature High Pressure; (2) after acid binding agent salt of wormwood absorbing hydrogen chloride, become saleratus, saleratus is so decomposing water outlet under high temperature.This water byproduct plays many destructive effects under High Temperature High Pressure, as with product on N-difluoromethyl or difluoromethyl reagent itself rise hydrolysis reaction produce inorganic fluoride, the latter understands corrosion reacting kettle; (3) reaction solvent DMF is at high temperature, has especially water can decomposite dimethylamine gas under existing, the latter not only can with difluoromethyl reagent react, and in the time of post-reaction treatment, give off foul odour; (4) by product that high temperature preparation method brings into thus, brings detrimentally affect to follow-up nitrated and reduction reaction.
It is solvent that US5756755 uses glyme to replace DMF, although successfully solved aforementioned the 3rd problem, other problem still exists.
Related genera has been reported (J. Agri. Food. Chem. 2008,56,2118) like Triazolinones difluoromethylization reaction under phase-transfer catalysis.This reaction is taking THF as solvent, but this condition is to substrate sensitivity, and uses greatly excessive difluoromethyl reagent, produces a large amount of oxygen-difluoromethyl by products simultaneously, need separate with silica gel column chromatography, hindered the industrial application of technique.
US4818275 uses iron powder successfully nitro-compound (VII) to be reduced into wanted aniline product (VIII).Although iron powder used is cheap, a large amount of scrap iron slags that produce are large environmental issues.
Li MeiFang (modern, 2010,9,28) has reported and has used metallic nickel (Ni) for catalyzer hydro-reduction nitro-compound (VII).This reactive chemistry selectivity good (reducing hydrogenation dehalogenation).But the spontaneous combustion attribute of metallic nickel is a safety worries in industrial production.
US4818275 discloses 1-(5-amino-2; 4-dichlorophenyl)-4-difluoromethyl-3-methyl isophthalic acid H-1; 2; 4-triazole-5(4 hydrogen) ketone (VIII) and methylsulfonyl chloride be taking halogenated alkane as solvent; taking triethylamine as alkali XianCheng, two Toluidrins are then sloughed a part methylsulfonyl and are obtained product under sodium hydroxide effect.But there are problems in this technique, as excessive triethylamine or pyridine produce a large amount of waste water; The methylsulfonyl chloride that consumes 2 equivalents, Atom economy is poor; Yield is low etc.The solubility salt catalysis sulfonylations such as US5990315 discloses quaternary ammonium salt, quaternary alkylphosphonium salt, the method has solved direct sulfonylation, but catalyzer is more expensive, and yield is low.US7169952 discloses the direct sulfonylation of the high boiling point acid amides such as DMF and tertiary amine catalytic, and the cheap catalyzer of the method utilization has solved the problem of direct sulfonylation, but produces methane amide impurity, has affected product quality or yield.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of method of synthetic sulfentrazone intermediate and sulfentrazone is provided.
The method of synthetic sulfentrazone comprises: taking compound (II) as raw material; under compound (A) effect or under compound (B) and alkali effect; in aprotic solvent, carry out difluoromethyl through compound (III) and obtain intermediate (IV); through chlorination; nitrated, under catalyzer C, hydro-reduction obtains intermediate (VIII), has carapax et plastruw testudinis sulfonylation at catalyzer D and solvent; target product (I), be expressed as follows with reaction formula:
Wherein R1, R2, R3, R4 is C1-C18 alkyl or C6-C10 aryl, R1, R2, R3, R4 group can be identical or different; X is halogen; Y is halogen or HSO4, and described catalyzer C is transition-metal catalyst, and described catalyzer D is organic phosphine compounds, crown ether compound or polyoxyethylene glycol PEG compounds.
The R1 of described compound (A), R2, R3, R4 is preferably normal-butyl; Compound (A) is preferably 0.1～1.2:1 with the mol ratio of compound (II); Described temperature of reaction is preferably 50～150 DEG C.The R1 of described compound (B), R2, R3, R4 is preferably normal-butyl, and Y is preferably bromine; The mol ratio of compd B and compound (II) is preferably 0.1～1.2:1.Described alkali is alkali metal hydroxide or carbonate, and described alkali metal hydroxide is preferably potassium hydroxide, and described carbonate is preferably salt of wormwood; The mol ratio of potassium hydroxide and compound (II) is preferably 1～1.5:1, and the mol ratio of salt of wormwood and compound (II) is preferably 0.5～1.5:1.Described X is preferably chlorine or bromine; The aprotic solvent of described difluoromethyl is preferably toluene, DMF; Difluoromethyl reagent and compound (II) mol ratio is preferably 1～2:1, and described difluoromethyl temperature is preferably 20～160 DEG C; Described chlorination reagent is chlorine; Described chlorination is carried out in two steps, preferably 0～40 DEG C of described the first step chlorination reaction temperature; The first step chlorination chlorine and compound (IV) mol ratio is preferably 1～2:1; Described the first step chlorinated solvent is preferably DMF; Described second step chlorination reaction temperature is preferably 50～100 DEG C; Second step chlorination chlorine and compound (IV) mol ratio is preferably 1～2:1; Described second step chlorinated solvent is preferably one or more of acetic acid, water.Described nitrating agent is nitric acid and sulfuric acid mixture; The mol ratio of nitric acid and compound (VI) is preferably 1～1.5:1, and the mol ratio of sulfuric acid and compound (VI) is preferably 3～20:1, and nitration reaction temperature is preferably 0～60 DEG C.The transition-metal catalyst of described hydro-reduction reaction is preferably Pt or Pd, and the amount of catalyzer C is preferably 3%～0.1% of compound (VII); Described hydroborating reagent is hydrogen; Hydrogen and compound (VII) mol ratio is preferably 3～6:1; Described reduction reaction temperature is preferably 20～90 DEG C.Described methylsulfonyl chloride reagent is methylsulfonyl chloride, and methylsulfonyl chloride and compound (VIII) mol ratio is preferably 1～1.5:1; Described methylsulfonyl chlorination temperature is preferably 50～150 DEG C; Described organic phosphine compounds is preferably triphenylphosphine, tributylphosphine or tri octyl phosphine; Described crown ether compound is hexaoxacyclooctadecane-6-6; Described polyoxyethylene glycol compounds PEG, number-average molecular weight scope is 600～2000; The mol ratio of described catalyzer D and compound (VIII) is 0.005～0.03:1; Described methylsulfonyl solvent is preferably toluene, dimethylbenzene or diethylbenzene.
Triazole quinoline ketone compound (III) structural formula is as follows:
Wherein R1, R2, R3, R4 is C1-C18 alkyl or C6-C10 aryl, R1, R2, R3, R4 group is identical or different.The R1 of described compound (III), R2, R3, R4 is preferably normal-butyl.
The preparation method of compound (III) comprising: taking compound (II) as raw material, at compound (A) or under compound (B) and alkali effect, in aprotic solvent, reacts and obtains,
Wherein R1, R2, R3, R4 is C1-C18 alkyl or C6-C10 aryl, R1, R2, R3, R4 group is identical or different.
The R1 of described compound (A), R2, R3, R4 is preferably normal-butyl; Compound (A) is preferably 0.1～1.2:1 with the mol ratio of compound (II); Described temperature of reaction is preferably 50～150 DEG C.The R1 of described compound (B), R2, R3, R4 is preferably normal-butyl, and Y is preferably bromine; The mol ratio of compd B and compound (II) is preferably 0.1～1.2:1.Described alkali is alkali metal hydroxide or carbonate, and described alkali metal hydroxide is preferably potassium hydroxide, and described carbonate is preferably salt of wormwood; The mol ratio of potassium hydroxide and compound (II) is preferably 1～1.5:1, and the mol ratio of salt of wormwood and compound (II) is preferably 0.5～1.5:1.
The beneficial effect that the present invention compared with prior art has:
Taking compound (II) as raw material, at compound (A) or under compound (B) and alkali effect, in aprotic solvent, carry out difluoromethyl through compound (III) and obtain intermediate (IV), this difluoromethylization reaction more convenient safety under lesser temps and pressure is carried out.
Because difluoromethyl quality product improves, follow-up nitrated and catalytic hydrogenation reduction reaction and product separation are purified and be more prone to carry out.
Use catalytic hydrogenation technique, nitroreduction not only chemo-selective is high, simultaneously more green, efficient, safe and reliable.The catalyzer that sulfonylation adopts is triphenylphosphine, polyoxyethylene glycol or crown ether, and the catalyzer such as the DMF having used before having replaced, side reaction is few, has obtained highly purified product with high yield.Integrated artistic is easy, reaction conditions gentleness, and yield is high, and quality product is high, is conducive to suitability for industrialized production.
Brief description of the drawings
Fig. 1 is compound of the present invention (III) 1-phenyl-3-methyl isophthalic acid, 2,4-triazole-5-ketone TBuA) H1NMR spectrogram (solvent D2O).
Embodiment
The method of synthetic sulfentrazone comprises: taking compound (II) as raw material; under compound (A) effect or under compound (B) and alkali effect; in aprotic solvent, carry out difluoromethyl through compound (III) and obtain intermediate (IV); through chlorination; nitrated, under catalyzer C, hydro-reduction obtains intermediate (VIII), has carapax et plastruw testudinis sulfonylation at catalyzer D and solvent; target product (I), be expressed as follows with reaction formula:
Wherein R1, R2, R3, R4 is C1-C18 alkyl or C6-C10 aryl, R1, R2, R3, R4 group can be identical or different; X is halogen; Y is halogen or HSO4, and described catalyzer C is transition-metal catalyst, and described catalyzer D is organic phosphine compounds, crown ether compound or polyoxyethylene glycol PEG compounds.
The R1 of described compound (A), R2, R3, R4 is preferably normal-butyl; Compound (A) is preferably 0.1～1.2:1 with the mol ratio of compound (II); Described temperature of reaction is preferably 50～150 DEG C.The R1 of described compound (B), R2, R3, R4 is preferably normal-butyl, and Y is preferably bromine; The mol ratio of compd B and compound (II) is preferably 0.1～1.2:1.Described alkali is alkali metal hydroxide or carbonate, and described alkali metal hydroxide is preferably potassium hydroxide, and described carbonate is preferably salt of wormwood; The mol ratio of potassium hydroxide and compound (II) is preferably 1～1.5:1, and the mol ratio of salt of wormwood and compound (II) is preferably 0.5～1.5:1.Described X is preferably chlorine or bromine; The aprotic solvent of described difluoromethyl is preferably toluene, DMF; Difluoromethyl reagent and compound (II) mol ratio is preferably 1～2:1, and described difluoromethyl temperature is preferably 20～160 DEG C; Described chlorination reagent is chlorine; Described chlorination is carried out in two steps, preferably 0～40 DEG C of described the first step chlorination reaction temperature; The first step chlorination chlorine and compound (IV) mol ratio is preferably 1～2:1; Described the first step chlorinated solvent is preferably DMF; Described second step chlorination reaction temperature is preferably 50～100 DEG C; Second step chlorination chlorine and compound (IV) mol ratio is preferably 1～2:1; Described second step chlorinated solvent is preferably one or more of acetic acid, water.Described nitrating agent is nitric acid and sulfuric acid mixture; The mol ratio of nitric acid and compound (VI) is preferably 1～1.5:1, and the mol ratio of sulfuric acid and compound (VI) is preferably 3～20:1, and nitration reaction temperature is preferably 0～60 DEG C.The transition-metal catalyst of described hydro-reduction reaction is preferably Pt or Pd, and the amount of catalyzer C is preferably 3%～0.1% of compound (VII); Described hydroborating reagent is hydrogen; Hydrogen and compound (VII) mol ratio is preferably 3～6:1; Described reduction reaction temperature is preferably 20～90 DEG C.Described methylsulfonyl chloride reagent is methylsulfonyl chloride, and methylsulfonyl chloride and compound (VIII) mol ratio is preferably 1～1.5:1; Described methylsulfonyl chlorination temperature is preferably 50～150 DEG C; Described organic phosphine compounds is preferably triphenylphosphine, tributylphosphine or tri octyl phosphine; Described crown ether compound is hexaoxacyclooctadecane-6-6; Described polyoxyethylene glycol compounds PEG, number-average molecular weight scope is 600～2000; The mol ratio of described catalyzer D and compound (VIII) is 0.005～0.03:1; Described methylsulfonyl solvent is preferably toluene, dimethylbenzene or diethylbenzene.
Triazole quinoline ketone compound (III) structural formula is as follows:
Wherein R1, R2, R3, R4 is C1-C18 alkyl or C6-C10 aryl, R1, R2, R3, R4 group is identical or different.The R1 of described compound (III), R2, R3, R4 is preferably normal-butyl.
The preparation method of compound (III) comprising: taking compound (II) as raw material, at compound (A) or under compound (B) and alkali effect, in aprotic solvent, reacts and obtains,
Wherein R1, R2, R3, R4 is C1-C18 alkyl or C6-C10 aryl, R1, R2, R3, R4 group is identical or different.
The R1 of described compound (A), R2, R3, R4 is preferably normal-butyl; Compound (A) is preferably 0.1～1.2:1 with the mol ratio of compound (II); Described temperature of reaction is preferably 50～150 DEG C.The R1 of described compound (B), R2, R3, R4 is preferably normal-butyl, and Y is preferably bromine; The mol ratio of compd B and compound (II) is preferably 0.1～1.2:1.Described alkali is alkali metal hydroxide or carbonate, and described alkali metal hydroxide is preferably potassium hydroxide, and described carbonate is preferably salt of wormwood; The mol ratio of potassium hydroxide and compound (II) is preferably 1～1.5:1, and the mol ratio of salt of wormwood and compound (II) is preferably 0.5～1.5:1.
Example below further for example understands features more of the present invention, but the present invention applies for that content and the scope protected are not subject to the restriction of following embodiment.
Embodiment 1:
In 100mL flask, drop into 1-phenyl-3-methyl isophthalic acid H-1,2,4-triazole-5-ketone (2g), toluene (40mL), TBAH aqueous solution 11.6g(content 25%).Reaction mixture stirs and is warmed up to 110 DEG C of reactions, and the band water that refluxes, and vacuum-drying obtains compound (III, 1-phenyl-3-methyl isophthalic acid, 2,4-triazole-5-ketone TBuA) (4.7g).1HNMR（400MHz，D2O）δ7.49（2H，d,J?=?7.6?Hz），7.36（2H，dd,J?=?7.6?,7.6?Hz），7.18（1H，d,J?=?7.6?Hz），2.98（8H，t，J?=?8.4?Hz），2.03（3H，s），1.46（8H，m）,1.19（8H，m）,1.19（8H，m）,0.80（12H，t，J?=?8.4?Hz）。
Embodiment 2:
In 1000mL flask, drop into 1-phenyl-3-methyl isophthalic acid H-1,2,4-triazole-5-ketone (50g), toluene (300mL), TBAH aqueous solution 296g(content 25%).Reaction mixture stirs temperature reaction, and refluxes after band water, and at 80-90 DEG C, logical difluorochloromethane is to having reacted, precipitation, add water (200mL) stirs, and filters, be dried to obtain 1-phenyl-4-difluoromethyl-3-methyl isophthalic acid H-1,2,4-triazole-5-ketone (60g).
Embodiment 3:
In 1000mL there-necked flask, drop into 1-phenyl-3-methyl isophthalic acid H-1,2,4-triazole-5-ketone (80g), DMF (430mL), salt of wormwood (55g), Tetrabutyl amonium bromide (22g).Reaction mixture stirs and is warmed up to 120 DEG C of reactions, and decompression dehydration, logical difluorochloromethane reaction 1 hour, common enter difluorochloromethane 47g.After completion of the reaction, be cooled to about 50 DEG C filtrations.Filtrate precipitation, add water (300mL) stirs, and filters, and is dried to obtain 1-phenyl-4-difluoromethyl-3-methyl isophthalic acid H-1,2,4-triazole-5-ketone (94g).
Embodiment 4:
In 250mL reaction flask, add 1-phenyl-4-difluoromethyl-3-methyl isophthalic acid H-1,2,4-triazole-5-ketone 31g and 160gDMF solution, ice bath passes into chlorine after cooling to 5 DEG C, reacts and is warmed up to 8 DEG C after 1 hour, stop passing into chlorine, common enter chlorine 13g, decompression adds 80g water washing solid after precipitation, obtains 1-(4-chloro-phenyl-after oven dry)-4-difluoromethyl-3-methyl isophthalic acid H-1,2,4-triazole-5-ketone 35g
Embodiment 5: add 1-(4-chloro-phenyl-in 500mL reaction flask)-4-difluoromethyl-3-methyl isophthalic acid H-1,2,4-triazole-5-ketone 35g, acetic acid 180g and water 180g, heating for dissolving, after cooling to 85 DEG C, pass into chlorine, react cool to room temperature after 2 hours, common enter chlorine 15g, filter, water 65g washing, obtains 1-(4-chloro-phenyl-after oven dry)-4-difluoromethyl-3-methyl isophthalic acid H-1,2,4-triazole-5-ketone 33g obtains 1-(2 after drying, 4-dichlorophenyl)-4-difluoromethyl-3-methyl isophthalic acid H-1,2,4-triazole-5-ketone 34g.
Embodiment 5:
In 250mL reaction flask, drop into 1-(2,4 dichloro benzene base)-4-difluoromethyl-3-methyl isophthalic acid H-1,2,4-triazole-5-ketone (34g) and oleum (173g).After stirring and dissolving, be cooled to below 50 DEG C, start slowly to drip nitrosonitric acid (8.6g), after dropping finishes, continue to stir 2 hours, then under agitation slowly pour in 320mL frozen water, solid is separated out, filter, with 320mL water washing solid, dry to obtain product 1-(5-nitro-2,4 dichloro benzene base)-4-difluoromethyl-3-methyl isophthalic acid H-1,2,4-triazole-5-ketone 37g.
Embodiment 6:
In 250mL autoclave, drop into above-mentioned gained 1-(5-nitro-2,4-dichlorophenyl)-4-difluoromethyl-3-methyl isophthalic acid H-1,2,4-triazole-5-ketone 37g, add again catalyzer (Pd/C, 0.3g) and methyl alcohol (150mL), at 0.5MPa and 60 DEG C, stir hydrogenation 2 hours, use altogether 0.9g hydrogen, after reaction finishes, filter, with 50mL methanol wash solid, filtrate decompression boils off methyl alcohol, obtain 1-(5-amino-2,4-dichlorophenyl)-4-difluoromethyl-3-methyl isophthalic acid H-1,2,4-triazole-5-ketone (31.9g).
Embodiment 7:
In three-necked flask, add 1-(5-amino-2,4-dichlorophenyl)-4-difluoromethyl-3-methyl isophthalic acid hydrogen-1,2,4-triazole-5-ketone 31g, 150mL toluene, under stirring, be warming up to 100oC, add 0.25g triphenylphosphine, drip 13.5g methylsulfonyl chloride, after dropwising, keep system temperature 100oC, react stopped reaction after 12 hours, cooling, suction filtration, washing, dries, and obtains N-(2, the chloro-5-of 4-bis-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) phenyl) Toluidrin 36.2g.
Claims (10)
1. the method for a synthetic sulfentrazone; it is characterized in that; taking compound (II) as raw material, under compound (A) effect or under compound (B) and alkali effect, in aprotic solvent, carry out difluoromethyl through compound (III) and obtain intermediate (IV); through chlorination; nitrated, under catalyzer C, hydro-reduction obtains intermediate (VIII), has carapax et plastruw testudinis sulfonylation at catalyzer D and solvent; target product (I), be expressed as follows with reaction formula:
Wherein R
1, R
2, R
3, R
4for C1-C18 alkyl or C6-C10 aryl, R
1, R
2, R
3, R
4group can be identical or different; X is halogen; Y is halogen or HSO
4, described catalyzer C is transition-metal catalyst, described catalyzer D is organic phosphine compounds, crown ether compound or polyoxyethylene glycol PEG compounds.
2. method according to claim 1, is characterized in that, described X is preferably chlorine or bromine;
The aprotic solvent of described difluoromethyl is preferably toluene or DMF; Difluoromethyl reagent and compound (II) mol ratio is preferably 1～2:1, and described difluoromethyl temperature is preferably 20～160 DEG C.
3. method according to claim 1, is characterized in that, described chlorination reagent is chlorine; Described chlorination is carried out in two steps, preferably 0～40 DEG C of described the first step chlorination reaction temperature; The first step chlorination chlorine and compound (IV) mol ratio is preferably 1～2:1; Described the first step chlorinated solvent is preferably DMF; Described second step chlorination reaction temperature is preferably 50～100 DEG C; Second step chlorination chlorine and compound (IV) mol ratio is preferably 1～2:1; Described second step chlorinated solvent is preferably one or more of acetic acid, water.
4. method according to claim 1, is characterized in that, described nitrating agent is nitric acid and sulfuric acid mixture; The mol ratio of nitric acid and compound (VI) is preferably 1～1.5:1, and the mol ratio of sulfuric acid and compound (VI) is preferably 3～20:1, and nitration reaction temperature is preferably 0～60 DEG C.
5. method according to claim 1, is characterized in that, the transition-metal catalyst of described hydro-reduction reaction is preferably Pt or Pd, and the amount of catalyzer C is preferably 0.1%～3% of compound (VII); Described hydroborating reagent is hydrogen; Hydrogen and compound (VII) mol ratio is preferably 3～6:1; Described reduction reaction temperature is preferably 20～90 DEG C.
6. method according to claim 1, is characterized in that, described methylsulfonyl chloride reagent is methylsulfonyl chloride, and methylsulfonyl chloride and compound (VIII) mol ratio is preferably 1～1.5:1; Described methylsulfonyl chlorination temperature is preferably 50～150 DEG C; Described organic phosphine compounds is preferably triphenylphosphine, tributylphosphine or tri octyl phosphine; Described crown ether compound is hexaoxacyclooctadecane-6-6; Described polyoxyethylene glycol compounds PEG, number-average molecular weight scope is 600～2000; The mol ratio of described catalyzer D and compound (VIII) is 0.005～0.03:1; Described methylsulfonyl solvent is preferably toluene, dimethylbenzene or diethylbenzene.
7. a triazole quinoline ketone compound (III), is characterized in that structural formula is as follows:
Wherein R
1, R
2, R
3, R
4for C1-C18 alkyl or C6-C10 aryl, R
1, R
2, R
3, R
4group is identical or different.
8. compound according to claim 7, is characterized in that, the R of described compound (III)
1, R
2, R
3, R
4preferably be normal-butyl.
9. a preparation method for compound as claimed in claim 7 (III), is characterized in that, taking compound (II) as raw material, at compound (A) or under compound (B) and alkali effect, in aprotic solvent, react and obtain,
Wherein R
1, R
2, R
3, R
4for C1-C18 alkyl or C6-C10 aryl, R
1, R
2, R
3, R
4group is identical or different.
10. according to the method described in claim 1 or 9, it is characterized in that the R of described compound (A)
1, R
2, R
3, R
4preferably be normal-butyl; Compound (A) is preferably 0.1～1.2:1 with the mol ratio of compound (II); Described temperature of reaction is preferably 50～150 DEG C;
The R of described compound (B)
1, R
2, R
3, R
4preferably be normal-butyl, Y is preferably bromine; The mol ratio of compd B and compound (II) is preferably 0.1～1.2:1;
Described alkali is alkali metal hydroxide or carbonate, and described alkali metal hydroxide is preferably potassium hydroxide, and described carbonate is preferably salt of wormwood; The mol ratio of potassium hydroxide and compound (II) is preferably 1～1.5:1, and the mol ratio of salt of wormwood and compound (II) is preferably 0.5～1.5:1.
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