CN1267402C - Synthetic method for 3,5-dichloro-2,4-difluoronitrobenzene and teflubenzuron - Google Patents
Synthetic method for 3,5-dichloro-2,4-difluoronitrobenzene and teflubenzuron Download PDFInfo
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- CN1267402C CN1267402C CN 200510049360 CN200510049360A CN1267402C CN 1267402 C CN1267402 C CN 1267402C CN 200510049360 CN200510049360 CN 200510049360 CN 200510049360 A CN200510049360 A CN 200510049360A CN 1267402 C CN1267402 C CN 1267402C
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- CJDWRQLODFKPEL-UHFFFAOYSA-N teflubenzuron Chemical compound FC1=CC=CC(F)=C1C(=O)NC(=O)NC1=CC(Cl)=C(F)C(Cl)=C1F CJDWRQLODFKPEL-UHFFFAOYSA-N 0.000 title abstract description 18
- 239000005938 Teflubenzuron Substances 0.000 title abstract description 17
- OWALCRQILZGQDH-UHFFFAOYSA-N 1,3-dichloro-2,4-difluoro-5-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(Cl)=C(F)C(Cl)=C1F OWALCRQILZGQDH-UHFFFAOYSA-N 0.000 title abstract 4
- 238000010189 synthetic method Methods 0.000 title description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- RJXOVESYJFXCGI-UHFFFAOYSA-N 2,4-difluoro-1-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1F RJXOVESYJFXCGI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000007259 addition reaction Methods 0.000 claims abstract description 3
- -1 benzoyl urea compound Chemical class 0.000 claims description 29
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 239000000460 chlorine Substances 0.000 claims description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 239000002798 polar solvent Substances 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- CTVBVNKEMCGZDF-UHFFFAOYSA-N 2-chloro-1,3-difluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C(Cl)=C1F CTVBVNKEMCGZDF-UHFFFAOYSA-N 0.000 claims description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 239000011630 iodine Substances 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000005660 chlorination reaction Methods 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 7
- 238000006396 nitration reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 abstract 3
- KLECNQGLBJHVSH-UHFFFAOYSA-N 3,5-dichloro-2,4-difluoroaniline Chemical compound NC1=CC(Cl)=C(F)C(Cl)=C1F KLECNQGLBJHVSH-UHFFFAOYSA-N 0.000 abstract 2
- ZRJSABISRHPRSB-UHFFFAOYSA-N 2,6-difluorobenzoyl isocyanate Chemical compound FC1=CC=CC(F)=C1C(=O)N=C=O ZRJSABISRHPRSB-UHFFFAOYSA-N 0.000 abstract 1
- 239000003139 biocide Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- HRYILSDLIGTCOP-UHFFFAOYSA-N N-benzoylurea Chemical compound NC(=O)NC(=O)C1=CC=CC=C1 HRYILSDLIGTCOP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GBDZXPJXOMHESU-UHFFFAOYSA-N 1,2,3,4-tetrachlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1Cl GBDZXPJXOMHESU-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- GIMOSWIWKCENFV-UHFFFAOYSA-N 1-(3,5-dichloro-2,4-difluorophenyl)-3-[(2,6-difluorophenyl)methyl]urea Chemical compound FC1=CC=CC(F)=C1CNC(=O)NC1=CC(Cl)=C(F)C(Cl)=C1F GIMOSWIWKCENFV-UHFFFAOYSA-N 0.000 description 1
- AJCSNHQKXUSMMY-UHFFFAOYSA-N 1-chloro-2,4-difluorobenzene Chemical compound FC1=CC=C(Cl)C(F)=C1 AJCSNHQKXUSMMY-UHFFFAOYSA-N 0.000 description 1
- AVRQBXVUUXHRMY-UHFFFAOYSA-N 2,6-difluorobenzamide Chemical compound NC(=O)C1=C(F)C=CC=C1F AVRQBXVUUXHRMY-UHFFFAOYSA-N 0.000 description 1
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to synthesis methods for a biocidal agent of teflubenzuron and an intermediate compound of 3, 5-dichloro-2, 4-difluoronitrobenzene thereof. The chemical synthesis method of the 3, 5-dichloro-2, 4-difluoronitrobenzene comprises that 2, 4-difluoronitrobenzene is chlorinated to obtain the product. The preparation process for the teflubenzuron comprises the following steps: 2, 4-difluoronitrobenzene is chlorinated to prepare 3, 5-dichloro-2, 4-difluoronitrobenzene and is hydrogenized for reduction to prepare 3, 5-dichloro-2, 4-difluoroaniline, and the 3, 5-dichloro-2, 4-difluoroaniline and 2, 6-difluorobenzoyl isocyanate take an addition reaction to obtain the product. Compared with the prior art, the present invention solves the problem of nitration isomer generation in the process of 1, 2, 4-trichloro-benzene, reduces reaction steps, has simple synthesis processes, easy material acquirement and mild reaction conditions and has great implementing values, social benefits and economic benefits.
Description
(1) technical field
The present invention relates to a kind of sterilant Teflubenzuron and intermediate 3 thereof, 5-two chloro-2, the synthetic method of 4-difluoro nitrobenzene.
(2) background technology
Teflubenzuron (Teflubenzuron) is by Celamerck GmbH ﹠amp; Co. (now being Shell Agrar GmbH) was in benzoyl urea (BPUs) sterilant in Thailand's exploitation in 1984.Chemical name is 1-(3,5-two chloro-2,4 difluorobenzene bases)-3-(2, the 6-difluoro benzoyl) urea; English name be 1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzyl) urea; CAS record number: [83121-18-0]; Molecular formula: C
14H
6Cl
2F
4N
2O
2222～223 ℃ of fusing points; Molecular weight: 381.1; Chemical structural formula:
Teflubenzuron is a kind of new process for preparation of benzoylurea compounds, and it is better especially organophosphorus, pyrethroid, carbamate three insecticides to have been produced the pest controling effect of resistance.Benzoyl urea (BPUs) compound is confirmed in effect obtained aspect the Crop protection with its unique insecticidal activity as the topmost chitin synthesis inhibitor of insect.The main method of existing synthetic insecticide sulphur has:
1, with 1,2, the 4-trichlorobenzene is a raw material, through nitrated, chlorination, fluoridize and step such as reduction makes key intermediate 3,5-two chloro-2,4 difluorobenzene amine; 2,6-difluorobenzamide and triphosgene reaction make 2, the 6-difluoro benzoyl isocyanate, and again with 3,5-two chloro-2,4 difluorobenzene amine additions obtain the sterilant Teflubenzuron.Reaction principle is as follows:
Though this route has bibliographical information, when trichlorobenzene is nitrated, there is more nitration isomer, and also the not easily separated direct intermediate 3 that influences, the quality of 5-two chloro-2,4 difluorobenzene amine, industrialization has little significance.
2, with 1,2,3, the 4-tetrachlorobenzene is a raw material, through nitrated, fluoridize, step such as reduction makes key intermediate 3,5-two chloro-2,4 difluorobenzene amine, this intermediate are again with 2, the addition of 6-difluoro benzoyl isocyanate obtains the sterilant Teflubenzuron.Reaction principle is as follows:
This route has patent report, though nitrated polarization is good, does not have nitration isomer, and 1,2,3,4-tetrachlorobenzene raw material is difficult to obtain, and costs an arm and a leg, and only rests on the laboratory study stage.
By as can be seen above-mentioned, being of synthetic Teflubenzuron most critical is synthetic 3,5-two chloro-2,4-difluoro nitrobenzene.
(3) summary of the invention
In order to overcome complex process in the prior art, shortcoming that cost is high, the invention provides a kind of 3,5-two chloro-2, the synthetic method of 4-difluoro nitrobenzene.
Described 3,5-two chloro-2, the chemical synthesis process of 4-difluoro nitrobenzene comprises 2, the chlorination of 4-difluoro nitrobenzene gets described product.
Further, described synthetic method comprises: with iodine catalyzer, and 2, in 120～160 ℃ of reaction 1～10h, separation and purification promptly gets described product in polar solvent for 4-difluoro nitrobenzene and chlorine.
Above-mentioned iodine and 2, the weight ratio of 4-difluoro nitrobenzene is preferably 0.02～0.07: 1, chlorine and 2, the mol ratio of 4-difluoro nitrobenzene is preferably 1～10: 1.
Further, described synthetic method comprises: with 2,4-difluoro nitrobenzene and iodine are dissolved in the polar solvent, are warming up to 120～160 ℃ and begin to feed chlorine, and reaction 6～8h stops logical chlorine, and the reaction solution separation and purification gets described product.
Described polar solvent is preferably intensive polar solvent, as the vitriol oil, dimethyl sulfoxide (DMSO), dimethyl formamide, tetramethylene sulfone, the more preferably vitriol oil.
A kind of preparation method suc as formula the benzoyl urea compound shown in (I) is characterized in that comprising the steps:
A, with 2, the chlorination of 4-difluoro nitrobenzene makes 3,5-two chloro-2, the 4-difluoro nitrobenzene makes 3 through hydrogenating reduction again, 5-two chloro-2,4 difluorobenzene amine;
B, 3,5-two chloro-2,4 difluorobenzene amine and 2, the addition reaction of 6-difluoro benzoyl isocyanate gets described benzoyl urea compound.
Among the described step a, can make 3,5-two chloro-2,4 difluorobenzene amine: 1. iron powder by one of following catalyst hydrogenation reduction; 2. Raney's nickel; 3. palladium carbon.
Recommend to prepare benzoyl urea compound with processing parameter as follows:
A, be catalyzer with iodine, 2,4-difluoro nitrobenzene and chlorine in polar solvent in 120～160 ℃ of reaction 6～8h, separation and purification and 3,5-two chloro-2,4-difluoro nitrobenzene, make 3,5-two chloro-2,4 difluorobenzene amine by one of following catalyst hydrogenation reduction again: 1. iron powder; 2. Raney's nickel; 3. palladium carbon; Described solvent is one of following: the 1. vitriol oil; 2. dimethyl sulfoxide (DMSO); 3. dimethyl formamide; 4. tetramethylene sulfone;
B, with 3,5-two chloro-2,4 difluorobenzene amine are dissolved in the organic solvent, reflux slowly drips 2 while stirring, 6-difluoro benzoyl isocyanate, back flow reaction 4～8h.Cool off, filter, dry described benzoyl urea compound; Described organic solvent is one of following: 1. toluene; 2. benzene; 3. dimethylbenzene; 4. chlorobenzene.
The present invention has compared with prior art solved 1,2, and reactions steps has been lacked in the generation of the nitration isomer of 4-trichlorobenzene technology, and its synthesis technique is simple, raw material is easy to get, the reaction conditions gentleness, has big implementary value and economic results in society.
(4) description of drawings
Fig. 1 is that embodiment 1 makes 3,5-two chloro-2, the infrared spectrum of 4-difluoro nitrobenzene.
Fig. 2 is that embodiment 1 makes 3,5-two or two chloro-2, the mass spectrum of 4-difluoro nitrobenzene.
(5) embodiment
The invention will be further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited to this.
With 2,4-difluoro nitrobenzene 31.8g (0.2mol) and 2.0g iodine are dissolved in the vitriol oil of 50mL 98%, are warming up to 160 ℃ and begin logical chlorine, reaction 8h stops logical chlorine, and reaction solution is poured in the frozen water, organic phase is washed till neutrality with the NaOH aqueous solution and obtains 3,5-two chloro-2,4-difluoro nitrobenzene.Above-mentioned 3,5-two chloro-2, the infrared spectrum of 4-difluoro nitrobenzene and mass spectrum are respectively as depicted in figs. 1 and 2.
IR (cm
-1): 3096 (aromatic ring=C-H), 1543 (aromatic ring C=C), 1343 (NO
2Nitrogen-oxygen bond), 1266 (C-F), 1166 (C-Cl).
75mL industrial alcohol, 50mL water, 2.5mL Glacial acetic acid, 1.0g ammonium chloride and the 22.5g reduced iron powder 0.5h that under reflux state, refluxes, drip 3,5-two chloro-2,4-difluoro nitrobenzene 22.8g (0.1mol), back flow reaction 5h adds sodium carbonate solution and regulates pH=9～10, and steam distillation steams 3,5-two chloro-2,4 difluorobenzene amine.
With 19.8g (0.1mol) 3,5-two chloro-2,4 difluorobenzene amine are dissolved in the 50mL toluene, and reflux slowly drips 2 while stirring, and the 6-difluoro benzoyl isocyanate continues back flow reaction 4h.Cool off, filter, dry white crystal Teflubenzuron 35.7g, yield is 93.7%, fusing point is 222.1～223.3 ℃.
Embodiment 2
3,5-two chloro-2, the synthetic operation of 4-difluoro nitrobenzene are with embodiment 1, and solvent is selected 80mL dimethyl sulfoxide (DMSO) (DMSO) for use, 120 ℃ of temperature of reaction, reaction times 6h.
With 3,5-two chloro-2,4-difluoro nitrobenzene 22.8g (0.1mol), the palladium-carbon catalyst of 10g 5%, 100mLDMF places and inhales hydrogen reactor, under the room temperature, feeds hydrogen in reaction mixture, carries out hydrogenation reaction to no longer inhaling till the hydrogen.Filter, the filtrate decompression distillation obtains 3,5-two chloro-2,4 difluorobenzene amine.
The synthetic operation of Teflubenzuron is with embodiment 1, and solvent is selected 60mL benzene for use, and back flow reaction 8h gets white crystal 34.5g, and yield is 90.6%, and fusing point is 222.5～223.8 ℃.
Embodiment 3
3,5-two chloro-2, the synthetic operation of 4-difluoro nitrobenzene are with embodiment 1, and solvent is selected 100mL dimethyl formamide (DMF) for use, 140 ℃ of temperature of reaction, reaction times 7h.
With 3,5-two chloro-2,4-difluoro nitrobenzene 22.8g (0.1mol), 80mL DMF and 8g Raney nickel drop in the autoclave, sealing, feed hydrogen to 1.25MPa, be warming up to 50 ℃, behind the reaction 3h, cooling, filter, the filtrate decompression distillation obtains 3,5-two chloro-2,4 difluorobenzene amine.
The synthetic operation of Teflubenzuron is with embodiment 1, and solvent is selected 60mL dimethylbenzene for use, and back flow reaction 6h gets white crystal Teflubenzuron 35.5g, and yield is 93.2%, and fusing point is 222.2～223.6 ℃.
Embodiment 4
3,5-two chloro-2, the synthetic operation of 4-difluoro nitrobenzene is with embodiment 1, and solvent is selected the 70mL tetramethylene sulfone for use, 130 ℃ of temperature of reaction, reaction times 7h.
3, the synthetic operation of 5-two chloro-2,4 difluorobenzene amine is with embodiment 1.
The synthetic operation of Teflubenzuron is with embodiment 1, and solvent is selected the 60mL chlorobenzene for use, and back flow reaction 6h gets white crystal Teflubenzuron 35.8g, and yield is 94.0%, and fusing point is 222.8～224.1 ℃.
Claims (10)
1, a kind of 3,5-two chloro-2, the chemical synthesis process of 4-difluoro nitrobenzene comprises 2, the chlorination of 4-difluoro nitrobenzene gets described product.
2, chemical synthesis process as claimed in claim 1 is characterized in that comprising: with iodine catalyzer, and 2, in 120～160 ℃ of reaction 1～10h, separation and purification promptly gets described product in polar solvent for 4-difluoro nitrobenzene and chlorine.
3, chemical synthesis process as claimed in claim 2 is characterized in that described polar solvent is one of the following 1. vitriol oil; 2. dimethyl sulfoxide (DMSO); 3. dimethyl formamide; 4. tetramethylene sulfone.
4, chemical synthesis process as claimed in claim 3 is characterized in that described polar solvent is the vitriol oil.
5, as the described chemical synthesis process of one of claim 1～4, it is characterized in that: with 2,4-difluoro nitrobenzene and iodine are dissolved in the polar solvent, be warming up to 120～160 ℃ and begin to feed chlorine, reaction 6～8h stops logical chlorine, and the reaction solution separation and purification gets described product.
6, chemical synthesis process as claimed in claim 5, it is characterized in that: with 2,4-difluoro nitrobenzene and iodine are dissolved in 98% the vitriol oil, be warming up to 160 ℃ and begin logical chlorine, reaction 8h stops logical chlorine, reaction solution is poured in the frozen water, organic phase obtains 3 with aqueous sodium hydroxide washes to neutrality, 5-two chloro-2,4-difluoro nitrobenzene.
7, a kind of preparation method suc as formula the benzoyl urea compound shown in (I) is characterized in that comprising the steps:
A, with 2, the chlorination of 4-difluoro nitrobenzene makes 3,5-two chloro-2, the 4-difluoro nitrobenzene makes 3 through hydrogenating reduction again, 5-two chloro-2,4 difluorobenzene amine;
B, 3,5-two chloro-2,4 difluorobenzene amine and 2, the addition reaction of 6-difluoro benzoyl isocyanate gets described benzoyl urea compound.
8, the preparation method of benzoyl urea compound as claimed in claim 7, it is characterized in that among the described step a: with 2, the chlorination of 4-difluoro nitrobenzene makes 3,5-two chloro-2, the 4-difluoro nitrobenzene, make 3,5-two chloro-2,4 difluorobenzene amine by one of following catalyst hydrogenation reduction again: 1. iron powder; 2. Raney's nickel; 3. palladium carbon.
9, the preparation method of benzoyl urea compound as claimed in claim 7; it is characterized in that among the described step b: with 3; 5-two chloro-2; the 4-difluoroaniline is dissolved in the organic solvent; reflux slowly drips 2 while stirring, the 6-difluoro benzoyl isocyanate; back flow reaction 4～8h, cool off, filter, dry described product.
10,, it is characterized in that comprising the steps: as the preparation method of the described benzoyl urea compound of one of claim 7～9
A, be catalyzer with iodine, 2,4-difluoro nitrobenzene and chlorine in polar solvent in 120～160 ℃ of reaction 6～8h, separation and purification and 3,5-two chloro-2,4-difluoro nitrobenzene, make 3,5-two chloro-2,4 difluorobenzene amine by one of following catalyst hydrogenation reduction again: 1. iron powder; 2. Raney's nickel; 3. palladium carbon; Described polar solvent is one of following: the 1. vitriol oil; 2. dimethyl sulfoxide (DMSO); 3. dimethyl formamide; 4. tetramethylene sulfone;
B, with 3,5-two chloro-2,4 difluorobenzene amine are dissolved in the organic solvent, reflux slowly drips 2 while stirring, the 6-difluoro benzoyl isocyanate, back flow reaction 4～8h, cool off, filter, dry described benzoyl urea compound; Described organic solvent is one of following: 1. toluene; 2. benzene; 3. dimethylbenzene; 4. chlorobenzene.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510049360 CN1267402C (en) | 2005-03-11 | 2005-03-11 | Synthetic method for 3,5-dichloro-2,4-difluoronitrobenzene and teflubenzuron |
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|---|---|---|---|
| CN 200510049360 CN1267402C (en) | 2005-03-11 | 2005-03-11 | Synthetic method for 3,5-dichloro-2,4-difluoronitrobenzene and teflubenzuron |
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|---|---|
| CN1683318A CN1683318A (en) | 2005-10-19 |
| CN1267402C true CN1267402C (en) | 2006-08-02 |
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| CN 200510049360 Expired - Fee Related CN1267402C (en) | 2005-03-11 | 2005-03-11 | Synthetic method for 3,5-dichloro-2,4-difluoronitrobenzene and teflubenzuron |
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| CN102617360B (en) * | 2012-03-01 | 2013-11-06 | 江西吉翔医药化工有限公司 | Synthetic method of 3, 5-dichloro-2, 4-difluoroaniline |
| CN102796003B (en) * | 2012-07-11 | 2014-05-28 | 常州大学 | Preparation method of 2-fluoro-4,5-dichloronitrobenzene |
| CN102863340B (en) * | 2012-09-24 | 2014-05-21 | 浙江禾田化工有限公司 | Preparation and purifying method of 2, 3, 4, 5-tetrachloronitrobenzene |
| CN105801429B (en) * | 2014-12-31 | 2019-09-24 | 安徽新北卡化学有限公司 | A kind of preparation method of the chloro- 2,4 difluorobenzene amine of 3,5- bis- |
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