CN104628666B - The synthetic method of the net serial herbicide of sym-trinitrobenzene - Google Patents
The synthetic method of the net serial herbicide of sym-trinitrobenzene Download PDFInfo
- Publication number
- CN104628666B CN104628666B CN201510024982.2A CN201510024982A CN104628666B CN 104628666 B CN104628666 B CN 104628666B CN 201510024982 A CN201510024982 A CN 201510024982A CN 104628666 B CN104628666 B CN 104628666B
- Authority
- CN
- China
- Prior art keywords
- trinitrobenzene
- sym
- compound
- sodium methyl
- synthetic method
- 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
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/48—Two nitrogen atoms
- C07D251/52—Two nitrogen atoms with an oxygen or sulfur atom attached to the third ring carbon atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of synthetic method of the net serial herbicide of sym-trinitrobenzene, using sym-trinitrobenzene Tianjin serial herbicide and sodium methyl mercaptide as raw material, the net serial herbicide active compound of sym-trinitrobenzene is synthesized in confined conditions.The present invention solves the problems such as the difficult control of existing process smell, wastewater treatment complexity, improves reaction efficiency and yield, reduces power and raw materials consumption, reduce production cost, reaction raw materials are easy to get, and course of reaction is closed, odor control, without using catalyst, environmental protection, have the advantages that easily-controllable, efficient, environmentally friendly, products obtained therefrom quality is good, high income, with relatively more a wide range of application value, considerable economic benefit and social benefit will be brought after realizing industrialization.
Description
Technical field
The present invention relates to a kind of synthetic method of triazine herbicide, and in particular to a kind of sym-trinitrobenzene is only serial
The synthetic method of herbicide, belongs to herbicide preparing technical field.
Technical background
Triazine herbicide is one of most important type in modern herbicide, and since nineteen fifty-two A.Gast, find can
The activity of weeding of happy Tianjin (Chlorazine) has simultaneously been delivered after first report in nineteen fifty-five, has just started sym-trinitrobenzene weeding
The research of agent, particularly 1956 year find the height activity of weeding of Simanex (Simazine) and trietazine (Trietazine)
Afterwards, such herbicide is just developed rapidly.Triazine herbicide structural formula is as follows, is equal when the X in formula is-Cl-
Triazine Tianjin serial herbicide, is the net serial herbicide of sym-trinitrobenzene when X is-S-.
Net serial herbicide research and development and Time To Market are all relatively more early, including terbutryn, ametryn, put out net, symetryne, cyanogen
Grass is net, it is net to put out(Prometryn)Etc. kind.Wherein, put out and listed only in 1962, terbutryn goes out in nineteen sixty-five list marketing, green bristlegrass
It is net to start list marketing in 1966, at present, with ametryn and put out be only net serial herbicide main product.
Ametryn is the product that Switzerland J.R Geigy companies developed and promoted first the beginning of the sixties.Israel's Ah sweet's chemistry
Company started to be approved registration in China in 1994, and into Chinese market, trade name Ah going out is net.Using ametryn as the net of representative
The synthetic route of serial herbicide product is substantially all identical, and the method that the country is generally used at present is sodium methyl mercaptide method, i.e.,:With equal
Triazine Tianjin serial herbicide active compound and sodium methyl mercaptide are raw material, and reaction is carried out in the presence of amines catalyst and is made corresponding
The net serial herbicide of sym-trinitrobenzene.This method is primarily present following shortcoming:One is that sodium methyl mercaptide has foul odour, should
The uncontrollable smell diffusion of technique;Two be that the use of amines catalyst causes waste water stink not handle thoroughly;Three be to be produced into
This is of a relatively high, and raw material puts into many, low yield.In particular with society to environmental protection more stringent requirement, old life
Production. art faces great environmental protection pressure, the main difficulty produced as net class herbicide.
The content of the invention
The various shortcoming of net serial herbicide is produced for sodium methyl mercaptide method now, the invention provides a kind of s-triazine
The synthetic method of the net serial herbicide of class, this method environmental protection, solve the wastewater treatment that sodium methyl mercaptide method now is present it is difficult,
The defects such as sodium methyl mercaptide stink hardly possible control.
The invention provides the synthetic method of the net serial herbicide of part sym-trinitrobenzene, disclosed below equal of the present invention
The net serial herbicide of triazine, refers to the herbicide with following structural formula:
。
The synthetic method of the present invention, concrete technical scheme is as follows:
A kind of synthetic method of the net serial herbicide of sym-trinitrobenzene, it is characterized in that:Using compound A and sodium methyl mercaptide as original
Material, synthesizes the net serial herbicide active compound of sym-trinitrobenzene in confined conditions;The structural formula of the compound A as shown in following formula I,
The structural formula of the net serial herbicide of sym-trinitrobenzene is as shown in following formula II, and the R1 wherein in formula I and formula II is alkyl, R2It is
Alkyl or;
。
Reaction equation of the present invention is:
In above-mentioned synthetic method, R1And R2Can be with identical, can also be different.
In above-mentioned synthetic method, R1During for alkyl, carbon atom number is 1-4, R2 During for alkyl, carbon atom number is also
1-4。
In above-mentioned synthetic method, R1And R2 During for alkyl, ethyl, isopropyl or the tert-butyl group, R can be selected from1And R2Can be with
It is identical, can also be different.
In above-mentioned synthetic method, compound A and sodium methyl mercaptide are reacted in the absence of catalyst, reduce catalyst
Pollution to waste water and environment, it is to avoid catalyst has the problem of being difficult to handle in waste water.
In above-mentioned synthetic method, when compound A and sodium methyl mercaptide react, system temperature is 100-130 DEG C, preferably 115-
130℃。
In above-mentioned synthetic method, the reaction time of compound A and sodium methyl mercaptide is 30-90min, preferably 40-80min.
In above-mentioned synthetic method, the mol ratio of compound A and sodium methyl mercaptide is 1:0.8-1.0, preferably 1:0.95-0.99.
Sodium methyl mercaptide owes amount or equimolar amounts is used, and can completely be reacted, reduce the residual of smell.
In above-mentioned synthetic method, compound A and sodium methyl mercaptide are reacted in organic solvent, and organic solvent is that reaction is situated between
Matter, selection is not reacted with reactant and product, and the good solvent of dissolubility, preferably isopropanol, tert-butyl alcohol etc., is had
Consumption those skilled in the art of machine solvent can rule of thumb with need to be selected.
In above-mentioned synthetic method, reactant is reacted in enclosed system, in conditions such as temperature, reactant, solvents
Under effect, in reaction, system has certain pressure itself, and catalyst can be added without in the presence of this pressure
It can be reacted, so as to solve the intractable problem of waste water.Meanwhile, enclosed system also avoid the diffusion of sodium methyl mercaptide, make
Smell will not be leaked in air in building-up process.Improve synthetic environment.According to lot of experiment validation, system pressure is in 0.2-
Preferably, in 0.3-0.5MPa, effect is more preferable for synthetic effect during 0.6MPa.Certainly, when reaction condition is unable to reach the pressure,
Certain inert gas can also be added to meet the optimum pressure condition.
In above-mentioned synthetic method, the compound A is sym-trinitrobenzene Tianjin serial herbicide, and preferably Garagard, green bristlegrass is gone
Tianjin, Kusatsu, Simanex, cyanazine are flutterred, its corresponding net serial herbicide of sym-trinitrobenzene is terbutryn, ametryn, it is net to put out,
Symetryne, cyanatryn.
In above-mentioned synthetic method, the reaction solution cooling obtained after reaction divides decrease temperature crystalline after liquid, organic phase recycling design, obtains
The net serial herbicide of sym-trinitrobenzene.
In above-mentioned synthetic method, following steps are specifically included:
(1)Solvent and compound A are mixed in a kettle., sodium methyl mercaptide is then added, airtight heating is reacted, instead
Cool after should terminating;
(2)By reaction solution stratification, lower aqueous layer is separated;
(3)By upper strata oil reservoir(That is organic layer)Applied mechanically by being distilled to recover solvent, the residue after distillation is by knot
It is brilliant, crush to obtain the net serial herbicide active compound of sym-trinitrobenzene.
The present invention solves the problems such as the difficult control of existing process smell, wastewater treatment complexity, improves reaction efficiency and receipts
Rate, reduces power and raw materials consumption, reduces production cost, and reaction raw materials are easy to get, and course of reaction is closed, odor control,
Without using catalyst, environmental protection has the advantages that easily-controllable, efficient, environmentally friendly, and products obtained therefrom quality is good, high income, with comparing
A wide range of application value, considerable economic benefit and social benefit will be brought after realizing industrialization.
Embodiment
For the further instruction present invention, a series of specific embodiments are set forth below, these embodiments only play explanation
Effect, is not limited the scope of the present invention.Unless otherwise instructed, following material contents are weight/mass percentage composition.
Embodiment 1
In 1L reactor, isopropanol 350mL, 20wt% sodium methyl mercaptide liquid 245.88g and 97wt% green bristlegrass is put into respectively
Remove Tianjin 160.00g, it is closed after stirring mixing be warming up to during 115 DEG C of insulation reaction 50min, insulation reaction that pressure is in kettle
0.34MPa, reaction end is cooled to 60 DEG C.Stand, point water, water layer is almost tasteless after being distilled to recover solvent.Oil reservoir is transferred to
Solvent is distilled to recover in 500mL four-hole boiling flasks, residue pours into pallet and crushed through crystallisation by cooling, obtains white powder 163.02g,
It is 97.62% through HPLC detection ametryn contents, using atrazine rate of collecting as 97.31%.
Embodiment 2
In 1L reactor, put into isopropanol 350mL, 20wt% sodium methyl mercaptide liquid 247.14g respectively and 97% green bristlegrass is gone
Tianjin 160.00g, it is closed after stirring mixing be warming up to during 120 DEG C of insulation reaction 45min, insulation reaction that pressure is in kettle
0.37MPa, reaction end is cooled to 62 DEG C.Stand, point water, water layer free from extraneous odour after being distilled to recover solvent.Oil reservoir is transferred to 500mL
Solvent is distilled to recover in four-hole boiling flask, residue pours into pallet and crushed through crystallisation by cooling, obtains white powder 164.81g, passed through
HPLC detection ametryn contents are 96.88%, using atrazine rate of collecting as 97.63%.
Embodiment 3
In 1L reactor, put into isopropanol 350mL, 20wt% sodium methyl mercaptide liquid 249.66g respectively and 97% green bristlegrass is gone
Tianjin 160.00g, it is closed after stirring mixing be warming up to during 118 DEG C of insulation reaction 50min, insulation reaction that pressure is in kettle
0.35MPa, reaction end is cooled to 60 DEG C.Stand, point water, water layer is almost tasteless after being distilled to recover solvent.Oil reservoir is transferred to
Solvent is distilled to recover in 500mL four-hole boiling flasks, residue pours into pallet and crushed through crystallisation by cooling, obtains white powder 165.48g,
It is 96.97% through HPLC detection ametryn contents, using atrazine rate of collecting as 98.12%.
Embodiment 4
In 1L reactor, put into isopropanol 350mL, 20wt% sodium methyl mercaptide liquid 248.41g respectively and 97% green bristlegrass is gone
Tianjin 160.00g, it is closed after stirring mixing be warming up to during 118 DEG C of insulation reaction 80min, insulation reaction that pressure is in kettle
0.34MPa, reaction end is cooled to 60 DEG C.Stand, point water, water layer is almost tasteless after being distilled to recover solvent.Oil reservoir is transferred to
Solvent is distilled to recover in 500mL four-hole boiling flasks, residue pours into pallet and crushed through crystallisation by cooling, obtains white powder 164.42g,
It is 97.13% through HPLC detection ametryn contents, using atrazine rate of collecting as 97.65%.
Embodiment 5
In 1L reactor, put into isopropanol 350mL, 20wt% sodium methyl mercaptide liquid 247.21g respectively and 97% green bristlegrass is gone
Tianjin 160.00g, it is closed after stirring mixing be warming up to during 114 DEG C of insulation reaction 60min, insulation reaction that pressure is in kettle
0.32MPa, reaction end is cooled to 60 DEG C.Stand, point water, water layer is almost tasteless after being distilled to recover solvent.Oil reservoir is transferred to
Solvent is distilled to recover in 500mL four-hole boiling flasks, residue pours into pallet and crushed through crystallisation by cooling, obtains white powder 165.38g,
It is 96.21% through HPLC detection ametryn contents, using atrazine rate of collecting as 97.29%.
Embodiment 6
In 1L reactor, put into isopropanol 350mL, 20wt% sodium methyl mercaptide liquid 201.75g respectively and 97% green bristlegrass is gone
Tianjin 160.00g, it is closed after stirring mixing be warming up to during 114 DEG C of insulation reaction 65min, insulation reaction that pressure is in kettle
0.32MPa, reaction end is cooled to 60 DEG C.Stand, point water, water layer is through being distilled to recover solvent, containing a small amount of unreacted atrazine
It is recovered by filtration.Oil reservoir, which is transferred in 500mL four-hole boiling flasks, is distilled to recover solvent, and residue pours into pallet and crushed through crystallisation by cooling, obtains
To white powder 141.68g, detect that ametryn content is 92.01% through HPLC, using atrazine rate of collecting as 79.71%.
Embodiment 7
In 1L reactor, put into isopropanol 350mL, 20wt% sodium methyl mercaptide liquid 229.49g respectively and 97% green bristlegrass is gone
Tianjin 160.00g, it is closed after stirring mixing be warming up to during 116 DEG C of insulation reaction 65min, insulation reaction that pressure is in kettle
0.33MPa, reaction end is cooled to 60 DEG C.Stand, point water, water layer is through being distilled to recover solvent, waste water free from extraneous odour.Oil reservoir is transferred to
Solvent is distilled to recover in 500mL four-hole boiling flasks, residue pours into pallet and crushed through crystallisation by cooling, obtains white powder 154.68g,
It is 96.13% through HPLC detection ametryn contents, using atrazine rate of collecting as 90.92%.
Embodiment 8
In 1L reactor, put into isopropanol 350mL, 20wt% sodium methyl mercaptide liquid 252.18g respectively and 97% green bristlegrass is gone
Tianjin 160.00g, it is closed after stirring mixing be warming up to during 118 DEG C of insulation reaction 58min, insulation reaction that pressure is in kettle
0.34MPa, reaction end is cooled to 60 DEG C.Stand, point water, water layer is through being distilled to recover solvent, waste water odor control.Oil reservoir is transferred to
Solvent is distilled to recover in 500mL four-hole boiling flasks, residue pours into pallet and crushed through crystallisation by cooling, obtains white powder 164.31g,
It is 97.55% through HPLC detection ametryn contents, using atrazine rate of collecting as 98.01%.
Embodiment 9
In 1000L reactor, isopropanol 350L, 20wt% sodium methyl mercaptide liquid 248.40kg and 97% green bristlegrass are put into respectively
Remove Tianjin 160.00kg, it is closed after stirring mixing be warming up to during 120 DEG C of insulation reaction 50min, insulation reaction that pressure is in kettle
0.36MPa, reaction end is cooled to 60 DEG C.Stand, point water, water layer is almost tasteless after being distilled to recover solvent.Oil reservoir is transferred to
Recycling design in 500L enamel stills, residue is put into stainless steel tank and crushed through crystallisation by cooling, obtains white powder 165.81kg,
It is 96.64% through HPLC detection ametryn contents, using atrazine rate of collecting as 97.98%.
Embodiment 10
In 1000L reactor, isopropanol 350L, 20wt% sodium methyl mercaptide liquid 232.10kg and 97% is put into respectively and is flutterred
Go out Tianjin 160.00kg, it is closed after stirring mixing be warming up to during 126 DEG C of insulation reaction 80min, insulation reaction that pressure is in kettle
0.47MPa, reaction end is cooled to 60 DEG C.Stand, point water, water layer is almost tasteless after being distilled to recover solvent.Oil reservoir is transferred to
Recycling design in 500L enamel stills, residue is put into stainless steel tank and crushed through crystallisation by cooling, obtains white powder 164.24kg,
It is 96.88% through HPLC detection prometryn contents, using propazine rate of collecting as 97.57%.
Embodiment 11
In 1000L reactor, isopropanol 350L, 20wt% sodium methyl mercaptide liquid 233.75kg and 97% is put into respectively special
Fourth Tianjin 160.00kg, it is closed after stirring mixing be warming up to during 125 DEG C of insulation reaction 80min, insulation reaction that pressure is in kettle
0.46MPa, reaction end is cooled to 60 DEG C.Stand, point water, water layer is almost tasteless after being distilled to recover solvent.Oil reservoir is transferred to
Recycling design in 500L enamel stills, residue is put into stainless steel tank and crushed through crystallisation by cooling, obtains white powder 165.53kg,
It is 96.58% through HPLC detection terbutryn contents, using Garagard rate of collecting as 98.04%.
Embodiment 12
In 1000L reactor, the west of isopropanol 350L, 20wt% sodium methyl mercaptide liquid 262.96kg and 97% is put into respectively
Agate Tianjin 160.00kg, it is closed after stirring mixing be warming up to during 123 DEG C of insulation reaction 30min, insulation reaction that pressure is in kettle
0.45MPa, reaction end is cooled to 60 DEG C.Stand, point water, water layer is almost tasteless after being distilled to recover solvent.Oil reservoir is transferred to
Recycling design in 500L enamel stills, residue is put into stainless steel tank and crushed through crystallisation by cooling, obtains white powder 165.81kg,
It is 96.33% through HPLC detection symetryne contents, using Simanex rate of collecting as 97.32%.
Embodiment 13
In 1000L reactor, isopropanol 350L, 20wt% sodium methyl mercaptide liquid 216.96kg and 97% cyanogen are put into respectively
Kusatsu 160.00kg, it is closed after stirring mixing be warming up to during 123 DEG C of insulation reaction 90min, insulation reaction that pressure is in kettle
0.45MPa, reaction end is cooled to 60 DEG C.Stand, point water, water layer is almost tasteless after being distilled to recover solvent.Oil reservoir is transferred to
Recycling design in 500L enamel stills, residue is put into stainless steel tank and crushed through crystallisation by cooling, obtains white powder 160.42kg,
It is 97.13% through HPLC detection cyanatryn contents, using cyanazine rate of collecting as 95.78%.
Comparative example
In 1000L reactor, isopropanol 400L, 20wt% sodium methyl mercaptide liquid 290.01kg, 30% 3 are put into respectively
Reflux condenser is connected after methylamine water solution 5.4kg and 97% atrazine 160.00kg, reactor, mixing is stirred after the end that feeds intake
Backflow is warming up to, reflux temperature is in the range of 78-81 DEG C, back flow reaction 80min, there be by force condenser gaseous phase outlet in course of reaction
The fishy odor of strong trimethylamine, reaction end is cooled to 60 DEG C.Stand, point water, water layer is after being distilled to recover solvent, waste water band
There is the smell of trimethylamine and sodium methyl mercaptide.Oil reservoir is transferred to recycling design in 500L enamel stills, and residue is put into warp in stainless steel tank
Crystallisation by cooling is crushed, and obtains white powder 160.21kg, detects that ametryn content is 96.08% through HPLC, with atrazine rate of collecting
For 94.12%, gained ametryn product carries the smell of methyl mercaptan, and the product obtained using new technology of the present invention is nonirritant
Smell.
Claims (6)
1. a kind of synthetic method of the net serial herbicide of sym-trinitrobenzene, it is characterized in that:Using compound A and sodium methyl mercaptide as original
Material, reacted in the presence of airtight condition, without catalyst, synthesize the net serial herbicide active compound of sym-trinitrobenzene, compound A and
Sodium methyl mercaptide is reacted in organic solvent, and the organic solvent is isopropanol or the tert-butyl alcohol, compound A and sodium methyl mercaptide
Mol ratio is 1:0.8-1.0, compound A and sodium methyl mercaptide reaction temperature are 100-130 DEG C, compound A and sodium methyl mercaptide reaction
When, system pressure is 0.2-0.6MPa;The structural formula of the compound A is as shown in following formula I, the net serial herbicide of sym-trinitrobenzene
Structural formula as shown in following formula II, the R wherein in formula I and formula II1It is alkyl, R2Be alkyl or, R1For
During alkyl, carbon atom number is 1-4;R2 During for alkyl, carbon atom number is 1-4;
。
2. synthetic method according to claim 1, it is characterized in that:R1And R2 In alkyl be selected from ethyl, isopropyl or
The tert-butyl group.
3. synthetic method according to claim 1 or 2, it is characterized in that:The mol ratio of compound A and sodium methyl mercaptide is 1:
0.95-0.99。
4. synthetic method according to claim 1 or 2, it is characterized in that:The reaction time of compound A and sodium methyl mercaptide is
30-90min。
5. synthetic method according to claim 1 or 2, it is characterized in that:The compound A is Garagard, atrazine, put out
Tianjin, Simanex or cyanazine, the net serial herbicide of sym-trinitrobenzene are terbutryn, ametryn, prometryn, symetryne or cyanogen grass
Only.
6. synthetic method according to claim 1 or 2, it is characterized in that:The reaction solution cooling point liquid obtained after reaction, it is organic
Decrease temperature crystalline after phase recycling design, obtains the net serial herbicide of sym-trinitrobenzene.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510024982.2A CN104628666B (en) | 2015-01-19 | 2015-01-19 | The synthetic method of the net serial herbicide of sym-trinitrobenzene |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510024982.2A CN104628666B (en) | 2015-01-19 | 2015-01-19 | The synthetic method of the net serial herbicide of sym-trinitrobenzene |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104628666A CN104628666A (en) | 2015-05-20 |
CN104628666B true CN104628666B (en) | 2017-08-29 |
Family
ID=53207957
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510024982.2A Active CN104628666B (en) | 2015-01-19 | 2015-01-19 | The synthetic method of the net serial herbicide of sym-trinitrobenzene |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104628666B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108341787A (en) * | 2017-01-23 | 2018-07-31 | 浙江中山化工集团股份有限公司 | A kind of ametryn production method of no catalyst |
CN111018799B (en) * | 2018-10-09 | 2022-06-10 | 山东润博生物科技有限公司 | Continuous production method of sym-triazine net series herbicide |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1326931A (en) * | 2000-06-02 | 2001-12-19 | 长兴县中山化工有限公司 | Method for producing ametryn |
CN101157659A (en) * | 2007-11-13 | 2008-04-09 | 山东潍坊润丰化工有限公司 | Method for synthesizing weed killer terbutryn |
-
2015
- 2015-01-19 CN CN201510024982.2A patent/CN104628666B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN104628666A (en) | 2015-05-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101357895B (en) | Method for synthesizing methoxamine hydrochloride | |
CN101503375B (en) | Method for synthesizing methoxy amine hydrochlorate | |
CN104628666B (en) | The synthetic method of the net serial herbicide of sym-trinitrobenzene | |
CN101538208B (en) | Method for preparing mixture of 4-(alpha, alpha-dimethylbenzyl) diphenylamine and 4,4-bis (alpha, alpha-dimethylbenzyl) diphenylamine | |
CN108752159B (en) | Method for separating benzene-toluene-cyclohexane ternary azeotropic system by double-thermal coupling ternary extractive distillation | |
CN111099990A (en) | Method for recycling mother liquor of long carbon chain dicarboxylic acid refining crystallization | |
CN105418469A (en) | Preparation method for antioxidant 2,4-bi(n-octyl sulfur methylene)-6-methylphenol | |
WO2023241727A1 (en) | Method for separating ethylene glycol from ethylene glycol diacetate by using sulfolane as entrainer | |
CN105541550A (en) | Method for preparing high-purity potassium tert-butoxide with tert-butanol-water azeotropic solution and potassium hydroxide | |
CN107311861A (en) | A kind of 4 methoxyl group ethyl acetoacetates and its synthetic method | |
CN105820111B (en) | The method that a kind of preparation method of catalyst and its catalysis prepare 2,2- bipyridyls | |
CN107501143A (en) | A kind of preparation method of the methylphenol of antioxidant 2,4 2 (n-octylthiomethylene) 6 | |
CN109705048B (en) | Clean preparation method of tebuconazole | |
CN101948374B (en) | Method for synthesizing alpha-bromoketone and coproducing bromohydrocarbon | |
CN106854157A (en) | The method for synthesizing cyclopropane ester in low-alcohols solubility solvent | |
CN101955435A (en) | New method for preparing tyramine | |
CN105439870B (en) | A kind of N of recovery, the method for N ' dicyclohexylurea (DCU)s recycling | |
CN108191731A (en) | A kind of novel butyrolactam preparation process based on biomass material aminobutyric acid | |
CN106588678B (en) | A kind of preparation method of 5- (2- ethoxys) amino o-cresol | |
CN109748826B (en) | Synthetic method of indoxacarb intermediate hydrazinobenzyl formate | |
CN108586183B (en) | Supercritical technology-based method for separating and purifying high-purity alpha-methylnaphthalene | |
CN102757454A (en) | Preparation method of trimethyl gallium | |
CN106631687B (en) | A method of with synthesizing leaf alcohol under silane-Lewis acid catalytic systems | |
CN104945234B (en) | The preparation method of the methoxy benzophenone of 2,2 ' dihydroxy 4 | |
CN108623508A (en) | The method of purification of N-phenylmaleimide |
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 | ||
CP02 | Change in the address of a patent holder | ||
CP02 | Change in the address of a patent holder |
Address after: No. 03001, chlor alkali Road, Weifang Coastal Economic Development Zone, Shandong, Shandong Patentee after: Shandong Weifang Rainbow Chemical Co.,Ltd. Address before: Haiyuan Binhai Economic Development Zone, Shandong province Weifang city 262737 Street No. 600 Patentee before: Shandong Weifang Rainbow Chemical Co.,Ltd. |