CN106146551A - The preparation method of insecticide orthene - Google Patents
The preparation method of insecticide orthene Download PDFInfo
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- CN106146551A CN106146551A CN201610673837.1A CN201610673837A CN106146551A CN 106146551 A CN106146551 A CN 106146551A CN 201610673837 A CN201610673837 A CN 201610673837A CN 106146551 A CN106146551 A CN 106146551A
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- Prior art keywords
- orthene
- preparation
- solutions
- insecticide
- mixed liquor
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- YASYVMFAVPKPKE-UHFFFAOYSA-N acephate Chemical compound COP(=O)(SC)NC(C)=O YASYVMFAVPKPKE-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000002917 insecticide Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 24
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 23
- CVNMBKFJYRAHPO-UHFFFAOYSA-N [chloro(methyl)phosphoryl]methane Chemical compound CP(C)(Cl)=O CVNMBKFJYRAHPO-UHFFFAOYSA-N 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 8
- 230000006837 decompression Effects 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 238000010926 purge Methods 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims abstract description 3
- 230000000694 effects Effects 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 230000001186 cumulative effect Effects 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 10
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000002386 leaching Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- BOKOVLFWCAFYHP-UHFFFAOYSA-N dihydroxy-methoxy-sulfanylidene-$l^{5}-phosphane Chemical compound COP(O)(O)=S BOKOVLFWCAFYHP-UHFFFAOYSA-N 0.000 claims 1
- -1 phosgene and O Chemical compound 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 238000011109 contamination Methods 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000013019 agitation Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 3
- BZCGWAXQDLXLQM-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O.ClP(Cl)(Cl)=O BZCGWAXQDLXLQM-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- PFNFFQXMRSDOHW-UHFFFAOYSA-N spermine Chemical compound NCCCNCCCCNCCCN PFNFFQXMRSDOHW-UHFFFAOYSA-N 0.000 description 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QDJVSIBBXBDDOX-UHFFFAOYSA-N [P].C(C)(=O)NC Chemical compound [P].C(C)(=O)NC QDJVSIBBXBDDOX-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229940063675 spermine Drugs 0.000 description 1
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/2479—Compounds containing the structure P(=X)n-N-acyl, P(=X)n-N-heteroatom, P(=X)n-N-CN (X = O, S, Se; n = 0, 1)
- C07F9/2487—Compounds containing the structure P(=X)n-N-acyl, P(=X)n-N-heteroatom, P(=X)n-N-CN (X = O, S, Se; n = 0, 1) containing the structure P(=X)n-N-C(=X) (X = O, S, Se; n = 0, 1)
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the preparation method of a kind of insecticide orthene, including: phosgene and O, O, O trimethyl sulfydryl phosphate, reacting 1～4h under the effect of catalyst, reaction removes unnecessary phosgene through nitrogen purging after terminating, and methylchloroformate is removed in decompression distillation, gained liquid is O, S solutions of dimethyl phosphoryl chlorine；Add acid binding agent after being added drop-wise to by acetamide in the toluene solution of O, S solutions of dimethyl phosphoryl chlorine, be down to room temperature after being heated to 20～60 DEG C of stirring reactions 2～6h and obtain mixed liquor, post-treated i.e. obtain orthene.The present invention prepares that the course of reaction of insecticide orthene is simple and mild condition, reduce the consumption of reagent and energy, last handling process is simple, without extraction, final product is can be obtained by by simple filtration, crystallization, and substantially free of environmental contamination waste liquid and the emission problem of waste gas, meet the requirement of environmental protection and energy saving.
Description
Technical field
The present invention relates to insecticide preparing technical field.It is more particularly related to a kind of insecticide acetyl methylamine
The preparation method of phosphorus.
Background technology
Orthene is a kind of efficient, low toxicity, low-residual, broad-spectrum organic insecticide.It is the acetyl of Bayer 71628
Change derivant.Within 1964, first synthesized by Beyer Co., Ltd.The formal commercialization of Chevron Chemical company of the U.S. in 1972.?
Existing many plant produced of China.Orthene does not pollutes the environment, quickly by plant and soil microbial degradation after using,
Orthene or its metabolite quickly excrete, all without accumulating in vivo, therefore, before having wide application
Scape.
At present, orthene production method is with phosphorus thiochloride as base stock. after being prepared into as spermine further
Preparation becomes orthene (CN104262390；CN104558024).Process route wastewater discharge is big, energy consumption is high for this,
Atom utilization is low.Therefore, original acephate producing process route does not the most adapt to wanting of the protection of social environment from now on
Asking, social environment protection has become as the most prominent with the contradiction of business economic, problem in the urgent need to address.How with simpler
Single, cost method less expensive, synthesis condition milder prepares the problem that insecticide orthene is research at present.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of insecticide orthene, and offer at least will be described later
Advantage.
In order to realize according to object of the present invention and further advantage, it is provided that the system of a kind of insecticide orthene
Preparation Method, comprises the following steps:
Step one, phosgene and O, O, O-trimethyl sulfydryl phosphate, under the effect of catalyst, react 1～4h, reaction knot
Shu Houjing nitrogen purging removes unnecessary phosgene, and methylchloroformate is removed in decompression distillation, and gained liquid is O, S-dimethyl phosphorus
Acyl chlorides, wherein, described catalyst is triethylamine or triethylene diamine；
Step 2, O, S-solutions of dimethyl phosphoryl chlorine is dissolved in toluene solution and be cooled to 5 DEG C O, S-solutions of dimethyl phosphoryl chlorine
Toluene solution, is added drop-wise in the toluene solution of O, S-solutions of dimethyl phosphoryl chlorine to obtain reaction mixture by acetamide, is added by acid binding agent
In reaction mixture after stirring mixing, 5 DEG C of isothermal reaction 5-10min post-heating drop to 20～60 DEG C of stirring reactions 2～6h
Obtain mixed liquor to room temperature, post-treated i.e. obtain orthene.
Preferably, phosgene, O in step one, the molar ratio of O, O-trimethyl phosphorothioate and catalyst is 1.1
～1.5:1:0.01～0.1.
Preferably, the reaction temperature of step one is 55～110 DEG C.
Preferably, the toluene solution of O described in step 2, S-solutions of dimethyl phosphoryl chlorine is according to O, the S-dimethyl of every 1mol
Phosphoryl chloride phosphorus oxychloride is dissolved in the toluene of 200mL and prepares.
Preferably, post processing described in step 2 is specially the toluene adding mixed liquor cumulative volume half in mixed liquor
And crystal seed, after being sufficiently stirred for separating out solid, cross leaching solid, the heating of gained solid is dissolved in mixed liquor cumulative volume 1-1.2 times amount
Methanol, filtering and impurity removing, gained filtrate be concentrated into that volume is former filtrate volume 2/5ths after be cooled to room temperature, crystallization, filter
Obtaining white crystal, be orthene, wherein, described crystal seed is orthene crystal.
Preferably, the one during acid binding agent described in step 2 is potassium carbonate, sodium carbonate and triethylamine.
Preferably, O in step 2, the molar ratio of O, O-trimethyl phosphorothioate, acetamide and acid binding agent is
1:1～1.5:1～1.5.
Preferably, in step 2, the rate of addition of acetamide controls to drip at every 1s dropping 1-3.
The present invention at least includes following beneficial effect: the present invention prepare the course of reaction of insecticide orthene simple and
Mild condition, reduces the consumption of reagent and energy, and last handling process is simple, it is not necessary to extraction process, by simple filtration, knot
Crystalline substance can be obtained by final product, and substantially free of environmental contamination waste liquid and the emission problem of waste gas, meets environmental protection and energy saving
Requirement.
Part is embodied by the further advantage of the present invention, target and feature by description below, and part also will be by this
Invention research and practice and be understood by the person skilled in the art.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, to make those skilled in the art with reference to description
Word can be implemented according to this.
It should be noted that experimental technique described in following embodiment, if no special instructions, it is conventional method, institute
State reagent and material, if no special instructions, the most commercially obtain.
Embodiment 1
The preparation method of insecticide orthene of the present invention, it specifically comprises the following steps that
The first step, adds O, O, O-in the 1000mL reaction bulb equipped with mechanical agitation, thermometer, logical light pipe and condenser
Trimethyl sulfydryl phosphate 156.1g (1mol), triethylamine 5.1g (0.05mol), stirring makes its mix homogeneously and heats up 100 DEG C,
Being passed through phosgene 148.3g (1.5mol) by logical light pipe, after phosgene of having friendly relations, control temperature, at 100 DEG C, reacts 2h, then through nitrogen
Purging removes unnecessary phosgene, and decompression is distilled off the by-product methylchloroformate produced, and residual income liquid is O, S-diformazan
Base phosphoryl chloride phosphorus oxychloride 141.2g, content 98%, yield 88%；
The reaction equation that O, S-solutions of dimethyl phosphoryl chloro becomes:
Second step, adds O, S-in equipped with the 1000mL reaction bulb of mechanical agitation, thermometer, addition funnel and condenser
Solutions of dimethyl phosphoryl chlorine 141.2g (0.88mol) adds toluene 176mL afterwards, is sufficiently stirred for and is cooled to 5 DEG C, then drips 1 with 1s
Speed dropping acetamide 51.9g (0.88mol) dripped obtains reaction mixture, is joined instead by sodium carbonate 93.28g (0.88mol)
Answer in mixed liquor and be sufficiently stirred for, control temperature at 5 DEG C, insulation reaction 5min, be heated to 50 DEG C continue reaction 4h after cool to
Room temperature obtains mixed liquor, adds toluene and the 4-6g crystal seed of mixed liquor cumulative volume half in mixed liquor, is sufficiently stirred for separating out solid
After, cross leaching solid, the heating of gained solid is dissolved in the methanol of mixed liquor cumulative volume 1 times amount, and filtering and impurity removing, gained filtrate is concentrated into
Volume be former filtrate volume 2/5ths after be cooled to room temperature, crystallization, filter to obtain white crystal, be orthene, its
In, described crystal seed is orthene crystal, obtains end product orthene 132.2g, content 98%, yield 82%.
The reaction equation of orthene synthesis:
Embodiment 2
The preparation method of insecticide orthene of the present invention, it specifically comprises the following steps that
The first step, adds O, O, O-in the 1000mL reaction bulb equipped with mechanical agitation, thermometer, logical light pipe and condenser
Trimethyl sulfydryl phosphate 156.1g (1mol), triethylamine 10.2g (0.1mol), stirring makes its mix homogeneously and heats up 80 DEG C,
Being passed through phosgene 119.2g (1.2mol) by logical light pipe, after phosgene of having friendly relations, control temperature, at 80 DEG C, reacts 4h, then through nitrogen
Purging removes unnecessary phosgene, and decompression is distilled off the by-product methylchloroformate produced, and residual income liquid is O, S-diformazan
Base phosphoryl chloride phosphorus oxychloride 136.4g, content 98%, yield 86%；
The reaction equation that O, S-solutions of dimethyl phosphoryl chloro becomes:
Second step, adds O, S-in equipped with the 1000mL reaction bulb of mechanical agitation, thermometer, addition funnel and condenser
Solutions of dimethyl phosphoryl chlorine 136.4g (0.87mol) adds toluene 174mL afterwards, is sufficiently stirred for and is cooled to 5 DEG C, then drips 2 with 1s
Speed acetamide 59.1g (1mol) dripped obtains reaction mixture, is joined in reaction mixture by potassium carbonate 138.3g (1mol)
And be sufficiently stirred for, control temperature is at 5 DEG C, and insulation reaction 5min, cooling to room temperature after being heated to 60 DEG C of continuation reaction 6h must mix
Liquid, adds toluene and the 4-6g crystal seed of mixed liquor cumulative volume half in mixed liquor, after being sufficiently stirred for separating out solid, crosses leaching solid
Body, it is brilliant that the heating of gained solid is dissolved in mixed liquor cumulative volume 1, filters to obtain white crystal, is orthene, wherein, described crystalline substance
Planting is orthene crystal, obtains end product orthene 133.8g, content 98%, yield 84%.
The reaction equation of orthene synthesis:
Embodiment 3
The preparation method of insecticide orthene of the present invention, it specifically comprises the following steps that
The first step, adds O, O, O-in the 1000mL reaction bulb equipped with mechanical agitation, thermometer, logical light pipe and condenser
Trimethyl sulfydryl phosphate 156.1g (1mol), triethylene diamine 112.4g (0.05mol), stirring makes its mix homogeneously and heats up
110 DEG C, being passed through phosgene 138.5g (1.4mol) by logical light pipe, after phosgene of having friendly relations, control temperature, at 110 DEG C, reacts 3h, then
Removing unnecessary phosgene through nitrogen purging, decompression is distilled off the by-product methylchloroformate produced, and residual income liquid is O,
S-solutions of dimethyl phosphoryl chlorine 138g, content 98%, yield 86%；
The reaction equation that O, S-solutions of dimethyl phosphoryl chloro becomes:
Second step, adds O, S-in equipped with the 1000mL reaction bulb of mechanical agitation, thermometer, addition funnel and condenser
Solutions of dimethyl phosphoryl chlorine 138g (0.86mol) adds toluene 172mL afterwards, is sufficiently stirred for and is cooled to 5 DEG C, then drips 3 with 1s
Speed dropping acetamide 76.2g (1.29mol) reaction mixture, triethylamine 101.2g (1mol) is joined reaction mixing
In liquid and be sufficiently stirred for, control temperature at 5 DEG C, insulation reaction 5min, be heated to 20 DEG C continue reaction 2h after cool to room temperature and obtain
Mixed liquor, adds toluene and the 4-6g crystal seed of mixed liquor cumulative volume half in mixed liquor, after being sufficiently stirred for separating out solid, filters
Taking solid, the heating of gained solid is dissolved in the methanol of mixed liquor cumulative volume 1.2 times amount, and filtering and impurity removing, gained filtrate is concentrated into volume
It is cooled to room temperature after 2/5ths of former filtrate volume, crystallization, filter to obtain white crystal, be orthene, wherein, institute
Stating crystal seed is orthene crystal, obtains end product orthene 127.6g, content 98%, yield 81%.
The reaction equation of orthene synthesis:
Embodiment 4
The preparation method of insecticide orthene of the present invention, it specifically comprises the following steps that
The first step, adds O, O, O-in the 1000mL reaction bulb equipped with mechanical agitation, thermometer, logical light pipe and condenser
Trimethyl sulfydryl phosphate 156.1g (1mol), triethylene diamine 22.4g (0.01mol), stirring makes its mix homogeneously and heats up
55 DEG C, being passed through phosgene 108.8g (1.1mol) by logical light pipe, after phosgene of having friendly relations, control temperature, at 55 DEG C, reacts 4h, then warp
Nitrogen purging removes unnecessary phosgene, and decompression is distilled off the by-product methylchloroformate produced, and residual income liquid is O, S-
Solutions of dimethyl phosphoryl chlorine 139.6g, content 98%, yield 87%；
The reaction equation that O, S-solutions of dimethyl phosphoryl chloro becomes:
Second step, adds O, S-in equipped with the 1000mL reaction bulb of mechanical agitation, thermometer, addition funnel and condenser
Solutions of dimethyl phosphoryl chlorine 139.6g (0.87mol) adds toluene 174mL afterwards, is sufficiently stirred for and is cooled to 5 DEG C, then drips 1 with 1s
Speed dropping acetamide 77.1g (1.3mol) dripped obtains reaction mixture, is added by acid binding agent sodium carbonate 92.2g (0.87mol)
In reaction mixture stirring mixing after, control temperature at 5 DEG C, insulation reaction 5min, be heated to 40 DEG C continue reaction 5h after drop
Temperature obtains mixed liquor to room temperature, adds toluene and the 4-6g crystal seed of mixed liquor cumulative volume half in mixed liquor, is sufficiently stirred for separating out
After solid, crossing leaching solid, the heating of gained solid is dissolved in the methanol of mixed liquor cumulative volume 1 times amount, and filtering and impurity removing, gained filtrate is dense
It is cooled to room temperature after be reduced to that volume is former filtrate volume 2/5ths, crystallization, filter to obtain white crystal, be acetyl methylamine
Phosphorus, wherein, described crystal seed is orthene crystal, obtains end product orthene 129.1g, content 98%, yield
81%.
The reaction equation of orthene synthesis:
Embodiment 5
The preparation method of insecticide orthene of the present invention, it specifically comprises the following steps that
The first step, adds O, O, O-in the 1000mL reaction bulb equipped with mechanical agitation, thermometer, logical light pipe and condenser
Trimethyl sulfydryl phosphate 156.1g (1mol), triethylene diamine 17.9g (0.08mol), stirring makes its mix homogeneously and heats up
60 DEG C, being passed through phosgene 149g (1.5mol) by logical light pipe, after phosgene of having friendly relations, control temperature, at 60 DEG C, reacts 3h, then through nitrogen
Air-blowing cleaning goes unnecessary phosgene, decompression that the by-product methylchloroformate that produce is distilled off, and residual income liquid is O, S-bis-
Methyl phosphoryl chloride phosphorus oxychloride 142.8g, content 98%, yield 89%；
The reaction equation that O, S-solutions of dimethyl phosphoryl chloro becomes:
Second step, adds O, S-in equipped with the 1000mL reaction bulb of mechanical agitation, thermometer, addition funnel and condenser
Solutions of dimethyl phosphoryl chlorine 142.8g (0.89mol) adds toluene 178mL afterwards, is sufficiently stirred for and is cooled to 5 DEG C, then drips 1 with 1s
Speed dropping acetamide 59.1g (1mol) dripped obtains reaction mixture, and triethylamine 1.1.2g (1mol) joins reaction mixing
In liquid and be sufficiently stirred for, control temperature at 5 DEG C, insulation reaction 5min, be heated to 30 DEG C continue reaction 5h after cool to room temperature and obtain
Mixed liquor, adds toluene and the 4-6g crystal seed of mixed liquor cumulative volume half in mixed liquor, after being sufficiently stirred for separating out solid, filters
Taking solid, the heating of gained solid is dissolved in the methanol of mixed liquor cumulative volume 1.2 times amount, and filtering and impurity removing, gained filtrate is concentrated into volume
It is cooled to room temperature after 2/5ths of former filtrate volume, crystallization, filter to obtain white crystal, be orthene, wherein, institute
Stating crystal seed is orthene crystal, obtains end product orthene 136.9g, content 98%, yield 84%.
The reaction equation of orthene synthesis:
Although embodiment of the present invention are disclosed as above, but it is not restricted in description and embodiment listed
Using, it can be applied to various applicable the field of the invention completely, for those skilled in the art, and can be easily
Realizing other amendment, therefore under the general concept limited without departing substantially from claim and equivalency range, the present invention does not limit
In specific details.
Claims (8)
1. the preparation method of an insecticide orthene, it is characterised in that comprise the following steps:
Step one, phosgene and O, O, O-trimethyl sulfydryl phosphate, under the effect of catalyst, react 1～4h, after reaction terminates
Removing unnecessary phosgene through nitrogen purging, methylchloroformate is removed in decompression distillation, and gained liquid is O, S-solutions of dimethyl phosphoryl chlorine,
Wherein, described catalyst is triethylamine or triethylene diamine；
Step 2, O, S-solutions of dimethyl phosphoryl chlorine is dissolved in toluene solution and be cooled to 5 DEG C the toluene of O, S-solutions of dimethyl phosphoryl chlorine
Solution, is added drop-wise to acetamide in the toluene solution of O, S-solutions of dimethyl phosphoryl chlorine to obtain reaction mixture, is joined instead by acid binding agent
Answering in mixed liquor after stirring mixing, 5 DEG C of isothermal reaction 5-10min post-heating are down to room to 20～60 DEG C of stirring reactions 2～6h
Warm mixed liquor, post-treated i.e. obtains orthene.
2. the preparation method of insecticide orthene as claimed in claim 1, it is characterised in that phosgene, O in step one,
The molar ratio of O, O-trimethyl phosphorothioate and catalyst is 1.1～1.5:1:0.01～0.1.
3. the preparation method of insecticide orthene as claimed in claim 1, it is characterised in that the reaction temperature of step one
It it is 55～110 DEG C.
4. the preparation method of insecticide orthene as claimed in claim 1, it is characterised in that O described in step 2, S-
The toluene that the toluene solution of solutions of dimethyl phosphoryl chlorine is dissolved in 200mL according to the O of every 1mol, S-solutions of dimethyl phosphoryl chlorine prepares.
5. the preparation method of insecticide orthene as claimed in claim 1, it is characterised in that place after described in step 2
Reason is specially toluene and the crystal seed adding mixed liquor cumulative volume half in mixed liquor, after being sufficiently stirred for separating out solid, crosses leaching
Solid, the heating of gained solid is dissolved in the methanol of mixed liquor cumulative volume 1-1.2 times amount, and filtering and impurity removing, gained filtrate is concentrated into volume
It is cooled to room temperature after 2/5ths of former filtrate volume, crystallization, filter to obtain white crystal, be orthene, wherein, institute
Stating crystal seed is orthene crystal.
6. the preparation method of insecticide orthene as claimed in claim 1, it is characterised in that tie up acid described in step 2
Agent is the one in potassium carbonate, sodium carbonate and triethylamine.
7. the preparation method of insecticide orthene as claimed in claim 1, it is characterised in that O in step 2, O, O-tri-
The molar ratio of methylphosphorothioate, acetamide and acid binding agent is 1:1～1.5:1～1.5.
8. the preparation method of insecticide orthene as claimed in claim 1, it is characterised in that acetamide in step 2
Rate of addition controls to drip at every 1s dropping 1-3.
Priority Applications (1)
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| CN101429213A (en) * | 2007-11-06 | 2009-05-13 | 李坚 | O,S-dimethyl thiophosphoryl chloride, preparation and uses thereof |
| CN102336783A (en) * | 2010-07-18 | 2012-02-01 | 李坚 | Isomerization reaction |
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| CN101429213A (en) * | 2007-11-06 | 2009-05-13 | 李坚 | O,S-dimethyl thiophosphoryl chloride, preparation and uses thereof |
| CN102336783A (en) * | 2010-07-18 | 2012-02-01 | 李坚 | Isomerization reaction |
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| CN112979699A (en) * | 2021-02-24 | 2021-06-18 | 湖南沅江赤蜂农化有限公司 | Acephate synthesizer |
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