CN1656894A - Diphenyl ether herbicide and its preparation method - Google Patents
Diphenyl ether herbicide and its preparation method Download PDFInfo
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- CN1656894A CN1656894A CN 200410013568 CN200410013568A CN1656894A CN 1656894 A CN1656894 A CN 1656894A CN 200410013568 CN200410013568 CN 200410013568 CN 200410013568 A CN200410013568 A CN 200410013568A CN 1656894 A CN1656894 A CN 1656894A
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000004009 herbicide Substances 0.000 title claims abstract description 34
- 230000002363 herbicidal effect Effects 0.000 title claims description 24
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 13
- LZCLXQDLBQLTDK-BYPYZUCNSA-N ethyl (2S)-lactate Chemical compound CCOC(=O)[C@H](C)O LZCLXQDLBQLTDK-BYPYZUCNSA-N 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- RVYGYYVGWSCWGY-UHFFFAOYSA-N 4-fluoro-3-methylphenol Chemical compound CC1=CC(O)=CC=C1F RVYGYYVGWSCWGY-UHFFFAOYSA-N 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 22
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 230000006837 decompression Effects 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 13
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 claims description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- DGRVQOKCSKDWIH-UHFFFAOYSA-N 1-chloro-2-(trifluoromethyl)benzene Chemical class FC(F)(F)C1=CC=CC=C1Cl DGRVQOKCSKDWIH-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 239000005711 Benzoic acid Substances 0.000 claims description 5
- 235000010233 benzoic acid Nutrition 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- -1 carrene Chemical compound 0.000 claims description 3
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 2
- 229940072033 potash Drugs 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- XILPLWOGHPSJBK-UHFFFAOYSA-N 1,2-dichloro-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(Cl)C(Cl)=C1 XILPLWOGHPSJBK-UHFFFAOYSA-N 0.000 abstract 1
- 238000006640 acetylation reaction Methods 0.000 abstract 1
- 241000196324 Embryophyta Species 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000007726 management method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 240000006541 Dactyloctenium aegyptium Species 0.000 description 1
- 244000058871 Echinochloa crus-galli Species 0.000 description 1
- 240000006927 Foeniculum vulgare Species 0.000 description 1
- 235000004204 Foeniculum vulgare Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 241001251949 Xanthium sibiricum Species 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of diphenylether herbicides is prepared through reaction between 3,4-dichlorotrifluoro toluene, 4-fluoro-3-methylphenol and acid trap in solvent to obtain brown liquid, reaction on oxidizing agent and concentrated nitric and to obtain light yellows powder, acetylation reaction in solvent, adding L-ethyl lactate, and reaction under action of alkaline catalyst.
Description
Technical field: the present invention relates to diphenyl ether herbicide and synthesis technique thereof, be specifically related to O-[2-fluoro-5-(2-chloro-α, α, α-trifluoro p-methoxyphenyl) benzoyl]-L-ethyl lactate weed killer herbicide and synthesis technique thereof.
Background technology: at present the kind of weed killer herbicide is a lot, but all there is consumption big (the per hectare consumption is up to 2～10 kilograms) in most of weed killer herbicides, and there is the shortcoming of unsafe factor in crops, and they have also caused bigger destruction to environment.In order to reach the purpose of highly effective and safe, people develop diphenyl ether compound in recent years, but the product synthesis technique complexity developed, yield is low, manufacturing cost is high, and its preparation method is difficult for realizing large-scale industrial production.
Summary of the invention: the present invention provides a kind of diphenyl ether herbicide and preparation method thereof in order to solve the shortcoming that the prior art consumption is big, cost is high, yield is low, and it has the advantage safe, efficient, that consumption is few.Diphenyl ether herbicide of the present invention is O-[2-fluoro-5-(2-chloro-α, α, a α-trifluoro p-methoxyphenyl) benzoyl]-L-ethyl lactate weed killer herbicide, its structural formula is
It is prepared by following step: a, condensation reaction: with 3,4-two chlorobenzotrifluorides, 4-fluoro-3-methylphenol and acid binding agent are (0.8～1.5) according to mol ratio: 1: 2 ratio joins in the solvent, the control reaction temperature was reacted 1～20 hour down at 140～180 ℃, decompression and solvent recovery then, the residue that obtains is a brown liquid, be 2-fluoro-5-(2-chloro-α, α, α-trifluoro p-methoxyphenyl) toluene (I); B, oxidation reaction: in the brown liquid that a step obtains, add oxidant and red fuming nitric acid (RFNA), wherein the mol ratio of brown liquid, red fuming nitric acid (RFNA) and oxidant is 1: 14: (0.02～0.05), the control reaction temperature was reacted 2～10 hours down at 165～175 ℃, then the decompression, suction filtration, the gained solid is carried out obtaining buff powder, i.e. 2-fluoro-5-(2-chloro-α after soda acid handles, α, α-trifluoro p-methoxyphenyl) benzoic acid (II); C; esterification: buff powder and acylating agent are joined in the solvent; the control reaction temperature was reacted 1～10 hour to the solvent refluxing temperature at 20 ℃; remove excessive acylating agent; add the L-ethyl lactate then; to the solvent refluxing temperature, reacted 2～15 hours at 0 ℃ in control reaction temperature under the effect of base catalyst; buff powder wherein; acylating agent; the mol ratio of L-ethyl lactate and base catalyst is 1: (1～2): 1.1: 1; decompression then; suction filtration; filtrate is washed; dry; distillation; obtain brown viscous liquid at last; be O-[2-fluoro-5-(2-chloro-α; α, α-trifluoro p-methoxyphenyl) benzoyl]-L-ethyl lactate (III).Its synthetic route is as follows:
Weed killer herbicide of the present invention has safety, efficient, consumption is few, cost is low advantage, and its preparation method has that technology is simple, synthetic reaction is rapid, total recovery high (55.4%), low cost of manufacture, be convenient to the advantage of large-scale industrial production.
Embodiment one: the diphenyl ether herbicide of present embodiment is O-[2-fluoro-5-(2-chloro-α, α, a α-trifluoro p-methoxyphenyl) benzoyl]-L-ethyl lactate weed killer herbicide, its structural formula is
It is prepared by following step: a, condensation reaction: with 3,4-two chlorobenzotrifluorides, 4-fluoro-3-methylphenol and acid binding agent are (0.8～1.5) according to mol ratio: 1: 2 ratio joins in the solvent, the control reaction temperature was reacted 1～20 hour down at 140～180 ℃, decompression and solvent recovery then, the residue that obtains is a brown liquid, i.e. 2-fluoro-5-(2-chloro-α, α, α-trifluoro p-methoxyphenyl) toluene (I); B, oxidation reaction: in the brown liquid that a step obtains, add oxidant and red fuming nitric acid (RFNA), wherein the mol ratio of brown liquid, red fuming nitric acid (RFNA) and oxidant is 1: 14: (0.02～0.05), the control reaction temperature was reacted 2～10 hours down at 165～175 ℃, then the decompression, suction filtration, the gained solid is carried out obtaining buff powder, i.e. 2-fluoro-5-(2-chloro-α after soda acid handles, α, α-trifluoro p-methoxyphenyl) benzoic acid (II); C; esterification: buff powder and acylating agent are joined in the solvent; the control reaction temperature was reacted 1～10 hour to the solvent refluxing temperature at 20 ℃; remove excessive acylating agent; add the L-ethyl lactate then; to the solvent refluxing temperature, reacted 2～15 hours at 0 ℃ in control reaction temperature under the effect of base catalyst; buff powder wherein; acylating agent; the mol ratio of L-ethyl lactate and base catalyst is 1: (1～2): 1.1: 1; decompression then; suction filtration; filtrate is washed; dry; distillation; obtain brown viscous liquid at last; be O-[2-fluoro-5-(2-chloro-α; α, α-trifluoro p-methoxyphenyl) benzoyl]-L-ethyl lactate (III).Described acid binding agent is a kind of or any several mixture in potash, sodium carbonate, sodium hydroxide and the potassium hydroxide; Solvent in a step is dimethyl sulfoxide (DMSO), N, a kind of or any several mixture in dinethylformamide, toluene, dimethylbenzene and the chlorobenzene; Oxidant is one or both the mixture in vanadium pentoxide and the manganese dioxide; Acylating agent is a kind of or any several mixture in thionyl chloride, phosphorus trichloride and the phosphorus oxychloride; Solvent in the b step is a kind of or any several mixture in toluene, benzene, dimethylbenzene, carrene, chloroform and the carbon tetrachloride; Base catalyst is triethylamine, pyridine, N, a kind of or any several mixture in accelerine, sodium carbonate and the sodium bicarbonate.
Embodiment two: the diphenyl ether herbicide of present embodiment is O-[2-fluoro-5-(2-chloro-α, α, a α-trifluoro p-methoxyphenyl) benzoyl]-L-ethyl lactate weed killer herbicide, its structural formula is
It is prepared by following step: a, condensation reaction: with 3,4-two chlorobenzotrifluorides, 4-fluoro-3-methylphenol and acid binding agent are that 1.1: 1: 2 ratio joins in the solvent according to mol ratio, the control reaction temperature was reacted 1～20 hour down at 140～180 ℃, decompression and solvent recovery then, residue is a brown liquid, be 2-fluoro-5-(2-chloro-α, α, α-trifluoro p-methoxyphenyl) toluene (I); B, oxidation reaction: in a, add oxidant and red fuming nitric acid (RFNA) in the brown liquid, wherein the mol ratio of brown liquid, red fuming nitric acid (RFNA) and oxidant is 1: 14: 0.03, the control reaction temperature was reacted 2～10 hours down at 165～175 ℃, then the decompression, suction filtration, the gained solid is carried out obtaining buff powder, i.e. 2-fluoro-5-(2-chloro-α after soda acid handles, α, α-trifluoro p-methoxyphenyl) benzoic acid (II); C; esterification: buff powder and acylating agent are joined in the solvent; the control reaction temperature was reacted 1～10 hour to the solvent refluxing temperature at 20 ℃; remove excessive acylating agent; add the L-ethyl lactate then; to the solvent refluxing temperature, reacted 2～15 hours at 0 ℃ in control reaction temperature under the effect of base catalyst; buff powder wherein; acylating agent; the mol ratio of L-ethyl lactate and base catalyst is 1: 1.5: 1.1: 1; decompression then; suction filtration; filtrate is washed; dry; distillation; obtain brown viscous liquid at last; be O-[2-fluoro-5-(2-chloro-α; α, α-trifluoro p-methoxyphenyl) benzoyl]-L-ethyl lactate (III).
Embodiment three: present embodiment is prepared by following step: a, condensation reaction: add 126g 4-fluoro-3-methylphenol, 236.5g 3 in the 400g dimethyl sulfoxide (DMSO), 4-two chlorobenzotrifluorides and 212g Anhydrous potassium carbonate, under 140～180 ℃ of temperature, reacted 1～20 hour, the recovered under reduced pressure dimethyl sulfoxide (DMSO), the gained residue disperses in water, obtains brown liquid 267.6g, be 2-fluoro-5-(2-chloro-α, α, α-trifluoro p-methoxyphenyl) toluene (I), yield is 88%; B, oxidation reaction: get 152g brown liquid, 4.6g vanadium pentoxide and 678.5g red fuming nitric acid (RFNA), under 165～175 ℃ of temperature, reacted 2～10 hours, steam about 30% red fuming nitric acid (RFNA), add big water gaging then, decompression, suction filtration, the gained solid is carried out after soda acid handles, obtain buff powder 111.9g, i.e. 2-fluoro-5-(2-chloro-α, α, α-trifluoro p-methoxyphenyl) benzoic acid (II), yield is 67%; C, esterification: in 300ml toluene, add the 83.5g buff powder, at room temperature drip the 44.3g thionyl chloride, react to the reflux temperature of toluene at 20 ℃ and to obtain acyl chlorides in 1～10 hour, remove excessive thionyl chloride and most of toluene then under reduced pressure, standby; Other adding 34.1g purity in 100ml toluene is 90% L-ethyl lactate and 25.3g triethylamine; under 0 ℃, be added drop-wise in the above-mentioned solution of acid chloride; the control temperature was reacted 2～15 hours to the solvent refluxing temperature at 0 ℃; cooling; decompression, suction filtration; filtrate is washed; use anhydrous magnesium sulfate drying; remove solvent with steam distillation then; obtain brown viscous liquid 102.2g at last, i.e. O-[2-fluoro-5-(2-chloro-α, α; α-trifluoro p-methoxyphenyl) benzoyl]-L-ethyl lactate (III), yield is 94%.Brown viscous liquid is defined as O-[2-fluoro-5-(2-chloro-α through infrared, nuclear-magnetism, Mass Spectrometer Method; α; α-trifluoro p-methoxyphenyl) benzoyl]-the L-ethyl lactate; carry out before the seedling and activity of weeding test behind the seedling to the composition of this chemical structural formula; wherein Ce Shi weeds are barnyard grass grass, Siberian cocklebur, lady's-grass, fennel fiber crops and duck grass etc., and the crop of test is soybean, wheat, peanut.At sectional area is 100cm
2The ceramic whiteware basin in sowing germinate target examination assortment consistent, cover the thick table soil of 0.5cm, behind the suppression trickle, management method is cultivated routinely, treat respectively to try the material plant and grow to required growth period, carrying out the cauline leaf spraying by experimental scheme dosage with crawler type crop sprayer handles, processing is placed in the greenhouse and cultivates by the normal management method, routine observation examination material growth and development of plants situation, and in handling back 15 days, the range estimation medicament is to the growth inhibition situation of examination material plant, this inorganic agent is higher to the broad leaved weed activity, to the weed growth inhibiting rate more than 90%, safe to crop, consumption is little, and the per hectare consumption is no more than 20 grams.
Claims (10)
1, diphenyl ether herbicide is characterized in that it is O-[2-fluoro-5-(2-chloro-α, α, a α-trifluoro p-methoxyphenyl) benzoyl]-L-ethyl lactate weed killer herbicide, its structural formula is
2, the preparation method of diphenyl ether herbicide, it is characterized in that it is prepared by following step: a, condensation reaction: with 3,4-two chlorobenzotrifluorides, 4-fluoro-3-methylphenol and acid binding agent are (0.8～1.5) according to mol ratio: 1: 2 ratio joins in the solvent, the control reaction temperature was reacted 1～20 hour down at 140～180 ℃, decompression and solvent recovery then, the residue that obtains is a brown liquid, i.e. 2-fluoro-5-(2-chloro-α, α, α-trifluoro p-methoxyphenyl) toluene; B, oxidation reaction: in the brown liquid that a step obtains, add oxidant and red fuming nitric acid (RFNA), wherein the mol ratio of brown liquid, red fuming nitric acid (RFNA) and oxidant is 1: 14: (0.02～0.05), the control reaction temperature was reacted 2～10 hours down at 165～175 ℃, then the decompression, suction filtration, the gained solid is carried out obtaining buff powder, i.e. 2-fluoro-5-(2-chloro-α after soda acid handles, α, α-trifluoro p-methoxyphenyl) benzoic acid; C; esterification: buff powder and acylating agent are joined in the solvent; the control reaction temperature was reacted 1～10 hour to the solvent refluxing temperature at 20 ℃; remove excessive acylating agent; add the L-ethyl lactate then; to the solvent refluxing temperature, reacted 2～15 hours at 0 ℃ in control reaction temperature under the effect of base catalyst; buff powder wherein; acylating agent; the mol ratio of L-ethyl lactate and base catalyst is 1: (1～2): 1.1: 1; decompression then; suction filtration; filtrate is washed; dry; distillation; obtain brown viscous liquid at last; be O-[2-fluoro-5-(2-chloro-α; α, α-trifluoro p-methoxyphenyl) benzoyl]-the L-ethyl lactate.
3, the preparation method of diphenyl ether herbicide according to claim 2 is characterized in that acid binding agent is a kind of or any several mixture in potash, sodium carbonate, sodium hydroxide and the potassium hydroxide.
4, the preparation method of diphenyl ether herbicide according to claim 2 is characterized in that the solvent in a step is dimethyl sulfoxide (DMSO), N, a kind of or any several mixture in dinethylformamide, toluene, dimethylbenzene and the chlorobenzene; Solvent in the b step is a kind of or any several mixture in toluene, benzene, dimethylbenzene, carrene, chloroform and the carbon tetrachloride.
5, the preparation method of diphenyl ether herbicide according to claim 2 is characterized in that oxidant is one or both the mixture in vanadium pentoxide and the manganese dioxide.
6, the preparation method of diphenyl ether herbicide according to claim 2 is characterized in that acylating agent is a kind of or any several mixture in thionyl chloride, phosphorus trichloride and the phosphorus oxychloride.
7, the preparation method of diphenyl ether herbicide according to claim 2 is characterized in that base catalyst is triethylamine, pyridine, N, a kind of or any several mixture in accelerine, sodium carbonate and the sodium bicarbonate.
8, the preparation method of diphenyl ether herbicide according to claim 2 is characterized in that 3 in a step, and 4-two chlorobenzotrifluorides, 4-fluoro-3-methylphenol and acid binding agent are 1.1: 1: 2 according to mol ratio.
9, the preparation method of diphenyl ether herbicide according to claim 2, the mol ratio that it is characterized in that brown liquid, red fuming nitric acid (RFNA) and oxidant in the b step is 1: 14: 0.03.
10, the preparation method of diphenyl ether herbicide according to claim 2 is characterized in that the mol ratio of buff powder, acylating agent, L-ethyl lactate and base catalyst in the c step is 1: 1.5: 1.1: 1.
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| CN 200410013568 CN1656894A (en) | 2004-02-19 | 2004-02-19 | Diphenyl ether herbicide and its preparation method |
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| CN 200410013568 CN1656894A (en) | 2004-02-19 | 2004-02-19 | Diphenyl ether herbicide and its preparation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407462B (en) * | 2007-10-09 | 2011-07-20 | 中国中化股份有限公司 | Diphenyl ether compound and use thereof |
| CN101747202B (en) * | 2008-12-11 | 2013-03-27 | 中国中化股份有限公司 | 2-chloro-benzoate compound and application thereof |
| CN103342630A (en) * | 2013-07-30 | 2013-10-09 | 黑龙江大学 | Method for synthesizing diaryl ether compounds |
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2004
- 2004-02-19 CN CN 200410013568 patent/CN1656894A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407462B (en) * | 2007-10-09 | 2011-07-20 | 中国中化股份有限公司 | Diphenyl ether compound and use thereof |
| CN101747202B (en) * | 2008-12-11 | 2013-03-27 | 中国中化股份有限公司 | 2-chloro-benzoate compound and application thereof |
| CN103342630A (en) * | 2013-07-30 | 2013-10-09 | 黑龙江大学 | Method for synthesizing diaryl ether compounds |
| CN103342630B (en) * | 2013-07-30 | 2015-01-21 | 黑龙江大学 | Method for synthesizing diaryl ether compounds |
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