CN106146551B - The preparation method of insecticide orthene - Google Patents
The preparation method of insecticide orthene Download PDFInfo
- Publication number
- CN106146551B CN106146551B CN201610673837.1A CN201610673837A CN106146551B CN 106146551 B CN106146551 B CN 106146551B CN 201610673837 A CN201610673837 A CN 201610673837A CN 106146551 B CN106146551 B CN 106146551B
- Authority
- CN
- China
- Prior art keywords
- orthene
- solutions
- mixed liquor
- insecticide
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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 System
- 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 a kind of preparation method of insecticide orthene, including：Phosgene and O, O, O trimethyl sulfydryl phosphate react 1~4h under the effect of the catalyst, remove extra phosgene, vacuum distillation removal methylchloroformate through nitrogen purging after reaction, and gained liquid is O, S solutions of dimethyl phosphoryl chlorine；Acetamide is added drop-wise to O, in the toluene solution of S solutions of dimethyl phosphoryl chlorine after add in acid binding agent, be heated to 20~60 DEG C and be stirred to react after 2~6h being down to room temperature and obtaining mixed liquor, it is post-treated up to orthene.The present invention prepares the reaction process of insecticide orthene simply 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 simply filtering, crystallizing, and the substantially emission problem of non-environmental-pollution waste liquid and exhaust gas, meet the requirement of environmental protection and energy saving.
Description
Technical field
The present invention relates to insecticide preparing technical fields.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 acephatemet
Change derivative.It is synthesized first by Beyer Co., Ltd within 1964.The formal commercialization of Chevron Chemical companies of the U.S. in 1972.
China has more plant produceds.Orthene does not pollute the environment, quickly by plant and soil microbial degradation after,
Orthene or its metabolite excrete quickly, will not all accumulate in vivo, therefore, before having wide application
Scape.
At present, orthene production method is prepared into being further after spermine by base stock of phosphorus thiochloride
Preparing becomes orthene (CN104262390；CN104558024).This process route wastewater discharge is big, high energy consumption,
Atom utilization is low.Therefore, original acephate producing process route has not adapted to wanting for social environment protection from now on
Ask, social environment protection and business economic contradiction have become it is very prominent, it is in the urgent need to address the problem of.How to use simpler
It is single, cost is less expensive, synthesis condition milder method prepares insecticide orthene is the subject studied at present.
Invention content
The object of the present invention is to provide a kind of preparation method of insecticide orthene, and provide and at least will be described later
The advantages of.
In order to realize these purposes and other advantages according to the present invention, a kind of system of insecticide orthene is provided
Preparation Method includes the following steps：
Step 1: phosgene and O, O, O- trimethyl sulfydryl phosphate, react 1~4h, reaction knot under the effect of the catalyst
Shu Houjing nitrogen purging removes extra phosgene, vacuum distillation removal methylchloroformate, and gained liquid is O, S- dimethyl phosphorus
Acyl chlorides, wherein, the catalyst is triethylamine or triethylene diamine；
Step 2: by O, S- solutions of dimethyl phosphoryl chlorine, which is dissolved in toluene solution and is cooled to 5 DEG C, obtains O, S- solutions of dimethyl phosphoryl chlorine
Acetamide is added drop-wise to O, obtains reaction mixture in the toluene solution of S- solutions of dimethyl phosphoryl chlorine, acid binding agent is added in by toluene solution
After being stirred into reaction mixture, be heated to after 5 DEG C of isothermal reaction 5-10min 20~60 DEG C be stirred to react 2~6h after drop
Mixed liquor is obtained to room temperature, it is post-treated up to orthene.
Preferably, the molar ratio of phosgene, O in step 1, O, O- trimethyl phosphorothioates and catalyst is 1.1
~1.5:1:0.01~0.1.
Preferably, the reaction temperature of step 1 is 55~110 DEG C.
Preferably, the toluene solution of O described in step 2, S- solutions of dimethyl phosphoryl chlorine is according to the O of every 1mol, S- dimethyl
The toluene that phosphoryl chloride phosphorus oxychloride is dissolved in 200mL is made.
Preferably, post processing described in step 2 is specially that the toluene of mixed liquor total volume half is added in mixed liquor
And crystal seed, it is sufficiently stirred after solid is precipitated, filters to take solid, obtained solid heating is dissolved in what 1-1.2 times of mixed liquor total volume was measured
Methanol, filtering and impurity removing, gained filtrate are concentrated into 2/5ths postcoolings of the volume for former filtrate volume to room temperature, crystallize, filtering
White crystal, as orthene are obtained, wherein, the crystal seed is orthene crystal.
Preferably, acid binding agent described in step 2 is one kind in potassium carbonate, sodium carbonate and triethylamine.
Preferably, O in step 2, O, the molar ratio of O- trimethyl phosphorothioates, acetamide and acid binding agent are
1:1~1.5:1~1.5.
Preferably, 1-3 drops are added dropwise in every 1s in the rate of addition control of acetamide in step 2.
The present invention includes at least following advantageous effect：The present invention prepare insecticide orthene reaction process it is simple and
Mild condition reduces the consumption of reagent and energy, and last handling process is simple, without extraction process, by simply filtering, tying
Crystalline substance can be obtained by final product, and the substantially emission problem of non-environmental-pollution waste liquid and exhaust gas, meet environmental protection and energy saving
Requirement.
Part is illustrated to embody by further advantage, target and the feature of the present invention by following, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, to enable those skilled in the art with reference to specification
Word can be implemented according to this.
It should be noted that experimental method described in following embodiments, is conventional method unless otherwise specified, institute
Reagent and material are stated, unless otherwise specified, is commercially obtained.
Embodiment 1
The preparation method of insecticide orthene of the present invention, is as follows：
The first step adds in O, O, O- in the 1000mL reaction bulbs equipped with mechanical agitation, thermometer, thang-kng pipe and condenser
Trimethyl sulfydryl phosphate 156.1g (1mol), triethylamine 5.1g (0.05mol), stirring are uniformly mixed it and heat up 100 DEG C,
Phosgene 148.3g (1.5mol) is passed through by thang-kng pipe, after phosgene of having friendly relations, control temperature reacts 2h, then through nitrogen at 100 DEG C
Purging removes extra phosgene, and vacuum distillation removes the by-product methylchloroformate generated, and residual income liquid is O, S- diformazans
Base phosphoryl chloride phosphorus oxychloride 141.2g, content 98%, yield 88%；
The reaction equation of O, S- solutions of dimethyl phosphoryl chlorine synthesis：
Second step adds in O, S- in the 1000mL reaction bulbs equipped with mechanical agitation, thermometer, addition funnel and condenser
Solutions of dimethyl phosphoryl chlorine 141.2g (0.88mol) adds in toluene 176mL afterwards, is sufficiently stirred and is cooled to 5 DEG C, is then added dropwise 1 with 1s
The speed of drop is added dropwise acetamide 51.9g (0.88mol) and obtains reaction mixture, and sodium carbonate 93.28g (0.88mol) is added to instead
It answers in mixed liquor and is sufficiently stirred, control temperature is cooled at 5 DEG C, insulation reaction 5min after being heated to 50 DEG C the reaction was continued 4h
Room temperature obtains mixed liquor, and the toluene of mixed liquor total volume half and 4-6g crystal seeds are added in mixed liquor, is sufficiently stirred precipitation solid
Afterwards, solid is filtered to take, obtained solid heating is dissolved in the methanol of 1 times of amount of mixed liquor total volume, filtering and impurity removing, and gained filtrate is concentrated into
Volume be 2/5ths postcoolings of former filtrate volume to room temperature, white crystal, as orthene are filtered to obtain in crystallization,
In, the crystal seed is orthene crystal, obtains final 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, is as follows：
The first step adds in O, O, O- in the 1000mL reaction bulbs equipped with mechanical agitation, thermometer, thang-kng pipe and condenser
Trimethyl sulfydryl phosphate 156.1g (1mol), triethylamine 10.2g (0.1mol), stirring are uniformly mixed it and heat up 80 DEG C,
Phosgene 119.2g (1.2mol) is passed through by thang-kng pipe, after phosgene of having friendly relations, control temperature reacts 4h, then through nitrogen at 80 DEG C
Purging removes extra phosgene, and vacuum distillation removes the by-product methylchloroformate generated, and residual income liquid is O, S- diformazans
Base phosphoryl chloride phosphorus oxychloride 136.4g, content 98%, yield 86%；
The reaction equation of O, S- solutions of dimethyl phosphoryl chlorine synthesis：
Second step adds in O, S- in the 1000mL reaction bulbs equipped with mechanical agitation, thermometer, addition funnel and condenser
Solutions of dimethyl phosphoryl chlorine 136.4g (0.87mol) adds in toluene 174mL afterwards, is sufficiently stirred and is cooled to 5 DEG C, is then added dropwise 2 with 1s
The speed acetamide 59.1g (1mol) of drop obtains reaction mixture, and potassium carbonate 138.3g (1mol) is added in reaction mixture
And be sufficiently stirred, at 5 DEG C, insulation reaction 5min, being heated to 60 DEG C the reaction was continued to cool to room temperature after 6h must mix control temperature
Liquid adds in the toluene of mixed liquor total volume half and 4-6g crystal seeds in mixed liquor, is sufficiently stirred after solid is precipitated, and filters to take solid
Body, obtained solid heating are dissolved in 1 crystalline substance of mixed liquor total volume, filter to obtain white crystal, as orthene, wherein, the crystalline substance
Kind is orthene crystal, obtains final 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, is as follows：
The first step adds in O, O, O- in the 1000mL reaction bulbs equipped with mechanical agitation, thermometer, thang-kng pipe and condenser
Trimethyl sulfydryl phosphate 156.1g (1mol), triethylene diamine 112.4g (0.05mol), stirring make it be uniformly mixed and heat up
110 DEG C, phosgene 138.5g (1.4mol) is passed through by thang-kng pipe, after phosgene of having friendly relations, control temperature reacts 3h, then at 110 DEG C
Extra phosgene is removed through nitrogen purging, vacuum distillation removes the by-product methylchloroformate generated, and residual income liquid is O,
S- solutions of dimethyl phosphoryl chlorine 138g, content 98%, yield 86%；
The reaction equation of O, S- solutions of dimethyl phosphoryl chlorine synthesis：
Second step adds in O, S- in the 1000mL reaction bulbs equipped with mechanical agitation, thermometer, addition funnel and condenser
Solutions of dimethyl phosphoryl chlorine 138g (0.86mol) adds in toluene 172mL afterwards, is sufficiently stirred and is cooled to 5 DEG C, and 3 drops then are added dropwise with 1s
Speed be added dropwise acetamide 76.2g (1.29mol) reaction mixture, by triethylamine 101.2g (1mol) be added to reaction mixing
It in liquid and is sufficiently stirred, control temperature is heated to 20 DEG C the reaction was continued to cool to room temperature after 2h and obtain at 5 DEG C, insulation reaction 5min
Mixed liquor adds in the toluene of mixed liquor total volume half and 4-6g crystal seeds in mixed liquor, is sufficiently stirred after solid is precipitated, filtering
Solid is taken, obtained solid heating is dissolved in the methanol of 1.2 times of amounts of mixed liquor total volume, filtering and impurity removing, and gained filtrate is concentrated into volume
For 2/5ths postcoolings for former filtrate volume to room temperature, white crystal, as orthene are filtered to obtain in crystallization, wherein, institute
Crystal seed is stated as orthene crystal, obtains final 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, is as follows：
The first step adds in O, O, O- in the 1000mL reaction bulbs equipped with mechanical agitation, thermometer, thang-kng pipe and condenser
Trimethyl sulfydryl phosphate 156.1g (1mol), triethylene diamine 22.4g (0.01mol), stirring make it be uniformly mixed and heat up
55 DEG C, phosgene 108.8g (1.1mol) is passed through by thang-kng pipe, after phosgene of having friendly relations, control temperature reacts 4h, Ran Houjing at 55 DEG C
Nitrogen purging removes extra phosgene, and vacuum distillation removes the by-product methylchloroformate generated, and residual income liquid is O, S-
Solutions of dimethyl phosphoryl chlorine 139.6g, content 98%, yield 87%；
The reaction equation of O, S- solutions of dimethyl phosphoryl chlorine synthesis：
Second step adds in O, S- in the 1000mL reaction bulbs equipped with mechanical agitation, thermometer, addition funnel and condenser
Solutions of dimethyl phosphoryl chlorine 139.6g (0.87mol) adds in toluene 174mL afterwards, is sufficiently stirred and is cooled to 5 DEG C, is then added dropwise 1 with 1s
The speed of drop is added dropwise acetamide 77.1g (1.3mol) and obtains reaction mixture, and acid binding agent sodium carbonate 92.2g (0.87mol) is added in
After being stirred into reaction mixture, control temperature is dropped at 5 DEG C, insulation reaction 5min after being heated to 40 DEG C the reaction was continued 5h
Temperature obtains mixed liquor to room temperature, and the toluene of mixed liquor total volume half and 4-6g crystal seeds are added in mixed liquor, is sufficiently stirred precipitation
After solid, solid is filtered to take, obtained solid, which heats, is dissolved in 1 times of methanol measured of mixed liquor total volume, filtering and impurity removing, and gained filtrate is dense
2/5ths postcoolings that volume is former filtrate volume are reduced to room temperature, white crystal, as acetyl methylamine are filtered to obtain in crystallization
Phosphorus, wherein, the crystal seed is orthene crystal, obtains final 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, is as follows：
The first step adds in O, O, O- in the 1000mL reaction bulbs equipped with mechanical agitation, thermometer, thang-kng pipe and condenser
Trimethyl sulfydryl phosphate 156.1g (1mol), triethylene diamine 17.9g (0.08mol), stirring make it be uniformly mixed and heat up
60 DEG C, phosgene 149g (1.5mol) is passed through by thang-kng pipe, after phosgene of having friendly relations, control temperature reacts 3h, then through nitrogen at 60 DEG C
Extra phosgene is removed in air-blowing cleaning, and vacuum distillation removes the by-product methylchloroformate generated, and residual income liquid is O, S- bis-
Methyl phosphoryl chloride phosphorus oxychloride 142.8g, content 98%, yield 89%；
The reaction equation of O, S- solutions of dimethyl phosphoryl chlorine synthesis：
Second step adds in O, S- in the 1000mL reaction bulbs equipped with mechanical agitation, thermometer, addition funnel and condenser
Solutions of dimethyl phosphoryl chlorine 142.8g (0.89mol) adds in toluene 178mL afterwards, is sufficiently stirred and is cooled to 5 DEG C, is then added dropwise 1 with 1s
The speed of drop is added dropwise acetamide 59.1g (1mol) and obtains reaction mixture, and triethylamine 1.1.2g (1mol) is added to reaction mixing
It in liquid and is sufficiently stirred, control temperature is heated to 30 DEG C the reaction was continued to cool to room temperature after 5h and obtain at 5 DEG C, insulation reaction 5min
Mixed liquor adds in the toluene of mixed liquor total volume half and 4-6g crystal seeds in mixed liquor, is sufficiently stirred after solid is precipitated, filtering
Solid is taken, obtained solid heating is dissolved in the methanol of 1.2 times of amounts of mixed liquor total volume, filtering and impurity removing, and gained filtrate is concentrated into volume
For 2/5ths postcoolings for former filtrate volume to room temperature, white crystal, as orthene are filtered to obtain in crystallization, wherein, institute
Crystal seed is stated as orthene crystal, obtains final product orthene 136.9g, content 98%, yield 84%.
The reaction equation of orthene synthesis：
Although the embodiments of the present invention have been disclosed as above, but its be not restricted in specification and embodiment it is listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, it is of the invention and unlimited
In specific details.
Claims (5)
1. a kind of preparation method of insecticide orthene, which is characterized in that include the following steps：
Step 1: phosgene and O, O, O- trimethyl sulfydryl phosphate, react 1~4h, after reaction under the effect of the catalyst
Extra phosgene, vacuum distillation removal methylchloroformate are removed through nitrogen purging, gained liquid is O, S- solutions of dimethyl phosphoryl chlorine,
Wherein, the catalyst is triethylamine or triethylene diamine；
Step 2: by O, S- solutions of dimethyl phosphoryl chlorine, which is dissolved in toluene solution and is cooled to 5 DEG C, obtains O, the toluene of S- solutions of dimethyl phosphoryl chlorine
Acetamide is added drop-wise to O, obtains reaction mixture in the toluene solution of S- solutions of dimethyl phosphoryl chlorine, acid binding agent is added to instead by solution
Answer after being stirred in mixed liquor, be heated to after 5 DEG C of isothermal reaction 5-10min 20~60 DEG C be stirred to react 2~6h after be down to room
It is warm to obtain mixed liquor, post-treated orthene to obtain the final product；
Wherein, the molar ratio of phosgene, O in step 1, O, O- trimethyl phosphorothioates and catalyst is 1.1~1.5:1:
0.01~0.1；
The reaction temperature of step 1 is 55~110 DEG C；
O in step 2, O, the molar ratio of O- trimethyl phosphorothioates, acetamide and acid binding agent is 1:1~1.5:1~
1.5。
2. the preparation method of insecticide orthene as described in claim 1, which is characterized in that O described in step 2, S-
According to the O of every 1mol, the toluene that S- solutions of dimethyl phosphoryl chlorine is dissolved in 200mL is made the toluene solution of solutions of dimethyl phosphoryl chlorine.
3. the preparation method of insecticide orthene as described in claim 1, which is characterized in that locate after described in step 2
Reason is specially that the toluene and crystal seed of mixed liquor total volume half are added in mixed liquor, is sufficiently stirred after solid is precipitated, filters to take
Solid, obtained solid heating are dissolved in the methanol that 1-1.2 times of mixed liquor total volume is measured, filtering and impurity removing, and gained filtrate is concentrated into volume
For 2/5ths postcoolings for former filtrate volume to room temperature, white crystal, as orthene are filtered to obtain in crystallization, wherein, institute
Crystal seed is stated as orthene crystal.
4. the preparation method of insecticide orthene as described in claim 1, which is characterized in that acid is tied up described in step 2
Agent is one kind in potassium carbonate, sodium carbonate and triethylamine.
5. the preparation method of insecticide orthene as described in claim 1, which is characterized in that acetamide in step 2
1-3 drops are added dropwise in every 1s in rate of addition control.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610673837.1A CN106146551B (en) | 2016-08-16 | 2016-08-16 | The preparation method of insecticide orthene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610673837.1A CN106146551B (en) | 2016-08-16 | 2016-08-16 | The preparation method of insecticide orthene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106146551A CN106146551A (en) | 2016-11-23 |
| CN106146551B true CN106146551B (en) | 2018-06-08 |
Family
ID=57330318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610673837.1A Active CN106146551B (en) | 2016-08-16 | 2016-08-16 | The preparation method of insecticide orthene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106146551B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112979699A (en) * | 2021-02-24 | 2021-06-18 | 湖南沅江赤蜂农化有限公司 | Acephate synthesizer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2016
- 2016-08-16 CN CN201610673837.1A patent/CN106146551B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| "Chemistry of Thiono- and Selenonophosphoranes. A Mechanistic Study of Chlorination Reactions of Phosphorus Thionoesters >P(S)OR: Reactive Intermediates and Stereochemistry";J Michalski. et al;《Journal of the American Chemical Society》;19780816;第100卷(第17期);第5386-5390页 * |
| "乙酰甲胺磷的生产新工艺及其表征";刘章伟等;《农药》;20120430;第51卷(第4期);第255页左栏 * |
| "固体光气"一锅法"合成卡莫氟";张庆伟等;《化学试剂》;20091231;第31卷(第4期);第301-302页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106146551A (en) | 2016-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2738839C (en) | A process for preparing n-(hydrocarbyl)phosphoric or thiophosphoric triamides | |
| CN101591284B (en) | Method for preparing chlorfenapyr and analog thereof | |
| DE102012208982A1 (en) | Process for the preparation of lithium sulfide | |
| CN106146551B (en) | The preparation method of insecticide orthene | |
| CN101684107A (en) | New febuxostat crystal form and preparing method thereof | |
| CN104370957A (en) | Microchannel synthesis technology for N-(n-Butyl)thiophosphoric triamide | |
| CN104788505B (en) | A kind of DMCoF/DMMnF heterojunction materials of metal organic frame single crystal epitaxial growth and preparation method thereof | |
| CN105254678A (en) | Preparation method for fire retardant high in phosphorus content | |
| CN104892664A (en) | Method for preparing phosphocholine chloride calcium salt tetrahydrate | |
| CN104326512B (en) | A kind of preparation method of nickelous fluoride | |
| JP5805742B2 (en) | Slow-acting liquid fertilizer and method for producing the same | |
| Kumar et al. | The role of a weakly coordinating thioether group in ligation controlled molecular self-assemblies and their inter-conversions in Ni (ii) complexes of l-methionine derived ligand | |
| CN104292121B (en) | A kind of reduce the method for by-product during adjacent methyl-acetoacetanilide produces | |
| RU2511271C2 (en) | Zinc complex of asymmetric ethylenediamine-n,n-dipropyonic acid dichloride and method of its obtaining | |
| CN108299392B (en) | Nicosulfuron crystal form and preparation method thereof | |
| CN109503494A (en) | 1,1 '-diamino -4,4 ', 5,5 '-tetranitros -2,2 '-bisglyoxaline novel crystal forms and preparation method | |
| CN102963923B (en) | Large-scale production method for preparing gallium nitrate by using gallium | |
| CN105820047A (en) | Three isomorphic complexes based on aromatic dicarboxylic acid ligand and synthesis method thereof | |
| US20110105786A1 (en) | Creatinol o-phosphate and synthesis method thereof | |
| CN103787895A (en) | Production process for synthesizing 4-bromo-2-methylaniline | |
| CN104151185A (en) | N-(2,4-dimethyl phenyl)-3-hydroxyl-2-naphthamide and preparation method thereof | |
| CN103613615A (en) | Preparation method of N-(phosphonomethyl) iminodiacetic acid | |
| CN104788506B (en) | A kind of DMMnF/DMCoF heterojunction materials of metal organic frame single crystal epitaxial growth and preparation method thereof | |
| CN106117087A (en) | A kind of creatinol method for production of phosphate salt | |
| CN104788507B (en) | A kind of mg-doped metal organic frame DMMg0.5Mn0.5F monocrystal materials and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |