CN106631839B - A kind of preparation method of thifluzamide key intermediate -2,6- bis- bromo- 4- (trifluoromethoxy) aniline - Google Patents
A kind of preparation method of thifluzamide key intermediate -2,6- bis- bromo- 4- (trifluoromethoxy) aniline Download PDFInfo
- Publication number
- CN106631839B CN106631839B CN201611038897.2A CN201611038897A CN106631839B CN 106631839 B CN106631839 B CN 106631839B CN 201611038897 A CN201611038897 A CN 201611038897A CN 106631839 B CN106631839 B CN 106631839B
- Authority
- CN
- China
- Prior art keywords
- preparation
- temperature
- bromo
- added dropwise
- hydrogen peroxide
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/09—Bromine; Hydrogen bromide
- C01B7/093—Hydrogen bromide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of thifluzamide key intermediate -2, the preparation method of 6- bis- bromo- 4- (trifluoromethoxy) aniline, this method includes following operating procedure: (1) putting into water in reaction flask, stirring is lower to instill the concentrated sulfuric acid, metal bromide and catalyst are put into again, then 4- trifluoro-methoxyaniline is added, 30min is stirred;(2) at 30 DEG C, hydrogen peroxide is added dropwise, controls rate of addition, so that reaction temperature is slowly increased to 50 DEG C, and with temperature in coolant liquid control reaction flask continue that hydrogen peroxide, after being added dropwise, 2~3.0h of insulation reaction at 50~55 DEG C is added dropwise at 50~55 DEG C;(3) reaction is finished, and adds water and stirs, off-white color 2, the bromo- 4- trifluoro-methoxyaniline of 6- bis- is obtained by filtration.Synthetic method of the invention has the characteristics of environmental protection, safety, no three wastes, synthesis yield height, good product quality.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to a kind of bromo- 4- (three of thifluzamide key intermediate -2,6- bis-
Fluorine methoxyl group) aniline synthetic method.
Background technique
Thifluzamide is developed 1992 by Monsanto at first, is sold within 1994 Rhom and Hass and is developed, and 2001
Year, ROHM AND HAAS was incorporated to The Dow Agrosciences, LLC., and trade name expires fringe.Full fringe is a kind of new thiazole carboxyl N- benzamides
Broad-spectrum germicide has special efficacy to many Basidiomycetes diseases on rice, wheat, other field crops and lawn, grassland.
Currently, the process route of preparation 2,6- bis- bromo- 4- (trifluoromethoxy) aniline is mainly selected with 4- trifluoro methoxy
Base aniline is raw material, is obtained and bromination reaction occurs in different system bodies.
It is the key intermediate for preparing thifluzamide that US5045554, which discloses 2,6- bis- bromo- 4- (trifluoromethoxy) aniline,
It discloses using bromine as bromating agent, synthesis 2 of the glacial acetic acid for dicyandiamide solution, the method for 6- bis- bromo- 4- (trifluoromethoxy) aniline,
Although reaction can be gone on smoothly, acetic acid dosage is big, and bromo element waste is serious, not environmentally and uneconomical, is suitble to industrialized production.
US6114584, which is disclosed, makees solvent with water, uses bromine as bromating agent, since the hydrogen bromide that reaction generates cannot have
Effect utilizes, and causes the waste of bromine atom, has violated economy principle, simultaneously as being heterogeneous reaction, reaction cannot be thorough, receives
Rate is relatively low, uneconomical.
" Organic fluoride industry " the 3rd phase in 2008,34-36 pages discloses using bromine-hydrogen peroxide as bromating agent, with organic solvent
Method with water as dicyandiamide solution synthesis 2,6- bis- bromo- 4- (trifluoromethoxy) aniline, this method bromo element obtain preferably
It utilizes, because introducing organic solvent, so that reaction can carry out under homogeneous phase condition, reaction is more thoroughly.But it is organic molten due to using
Agent, so that synthesis process becomes complicated, while organic solvent also can generate pollution to water body and atmosphere, through agent and environmental-protecting performance
It is all bad.
ZL 2,011 1 0406829.8 is disclosed using bromine-hydrogen peroxide as bromating agent, is added with water as reaction medium
The method of inert abrasive media synthesis 2,6- bis- bromo- 4- (trifluoromethoxy) aniline is entered, the method increase the benefits of bromine
With rate, the use of organic solvent is avoided, there is no the consumption of organic solvent and environmental issues, simultaneously as joined inert
Abrasive media is warded off and has exempted from intermediate package, improves product yield.But this method is heterogeneous reaction, and the reaction time is long, in work
The separation of inert media and finished product is relatively difficult in the production of industry metaplasia, while making on a large scale because bromine toxicity is big, steam is volatile
With to environmental protection and safety requirements it is higher.
Although above method has an example of industrialized production, but environmental protection, safety, in terms of cannot be simultaneous
It cares for, therefore develops a kind of safe and environment-friendly, economic synthesis 2, the method for 6- bis- bromo- 4- (trifluoromethoxy) aniline is that have very much
Meaning.
Summary of the invention
A kind of 2,6- bis- bromo- 4- (trifluoromethoxy) aniline is provided the invention mainly solves the technical problem of providing a kind of
Preparation method, this method, as bromating agent, made using metal bromide (sodium bromide or potassium bromide), sulfuric acid and hydrogen peroxide with water
It is avoided using tetrabutylammonium bromide as phase transfer catalyst using bromine, organic solvent for reaction medium, solves reaction
It is not thorough problem.
In order to solve the above technical problems, one technical scheme adopted by the invention is that:
A kind of preparation method of thifluzamide key intermediate -2,6- bis- bromo- 4- (trifluoromethoxy) aniline, feature
It is that this method includes following operating procedure:
(1) water is put into reaction flask, stirs the lower instillation concentrated sulfuric acid, then put into metal bromide and catalyst, then again
4- trifluoro-methoxyaniline is added, stirs 30 min;
(2) at 30 DEG C, hydrogen peroxide is added dropwise, controls rate of addition, reaction temperature is made to be slowly increased to 50 DEG C, and 50~
55 DEG C with temperature in coolant liquid control reaction flask are continued that hydrogen peroxide, after being added dropwise, the insulation reaction 2 at 50~55 DEG C is added dropwise
~3.0h;
(3) reaction is finished, and adds water and stirs, off-white color 2, the bromo- 4- trifluoro-methoxyaniline of 6- bis- is obtained by filtration;It is filtered
Mother liquor is cooled to 0 degree, and sodium sulphate or potassium sulfate crystal is precipitated, refilter it is mother liquid obtained can directly apply, catalyst is in mother liquor set
With not adding in the process.
Further, the metal bromide is sodium bromide or potassium bromide, preferably sodium bromide.
Further, the catalyst is tetrabutylammonium bromide.
Further, the molar ratio of trifluoro-methoxyaniline is 1.8~2.3: 1.
Further, the molar ratio of the metal bromide and sulfuric acid is 2.0~2.2: 1.
Further, the molar ratio of the hydrogen peroxide and metal bromide is 0. 9~1.5: 1.
Further, the molar ratio of the catalyst tetrabutylammonium bromide and 4- trifluoro-methoxyaniline be 0.002~
0.01: 1.
Further, mother liquor can directly be applied to system after paying production sulfate by decrease temperature crystalline method.
Further, it is 30~65 degree that hydrogen peroxide temperature, which is added dropwise, and best dropping temperature is 50~55 degree.
As the 7th kind of restriction of the invention, the feeding sequence is water --- sulfuric acid --- sodium bromide or bromination
--- hydrogen peroxide is added dropwise in catalyst --- 4- trifluoro-methoxyaniline --- to potassium, first by this feeding sequence 4- trifluoro-methoxyaniline
The bromate of white is formed, the bromine after hydrogen peroxide in hydrogen bromide is added dropwise and is oxidized to that bromine is monatomic, in the work of phase transfer catalyst
With the monatomic rapid hydrogen atom for replacing amido ortho position on 4- trifluoro-methoxyaniline phenyl ring of lower bromine, liquid list bromo-derivative is formed,
Single bromo-derivative by bromo, generates two bromo-derivatives and is precipitated in solid form again, is filtered out finished product, and sulphur is precipitated in mother liquor decrease temperature crystalline
After hydrochlorate, mother liquor is applied in reaction system again, finally bromo element is fully utilized, and avoids the waste of resource, more suitable
For industrialized production.
Shown in the following chemical formula of the principle of the present invention:
Due to the adoption of the above technical solution, compared with prior art, the present invention acquired technological progress is:
The present invention uses sodium bromide or potassium bromide to react for metal bromide, dilute sulfuric acid and 4- trifluoro-methoxyaniline and generates
Acid salt, then reacted with hydrogen peroxide and carry out bromination reaction, the insecurity factor caused by production using bromine is avoided, and use water
Make medium, using phase transfer catalyst, becomes reaction rapidly thoroughly, safer environmental protection is more suitable for industrialized production, this hair
Bright preparation method preparation method more reported at present is improved on yield and purity, and specifically, yield can reach
To 98.0% or more, purity can reach 99.2~99.8%.
The present invention is applicable in the preparation of the key intermediate of agriculture chemicals fungicide thifluzamide, is also applied for herbicide and insecticide
The preparation of important intermediate.
Specific embodiment
Embodiment 1
The preparation method of 2,6- of one kind bis- bromo- 4- (trifluoromethoxy) aniline, including following operating procedure:
250g water is put into 1000mL there-necked flask, stirring is started and instills 17.5 (0.175mol) sulfuric acid, then put into
Then the potassium bromide (0.378moL) and tetrabutylammonium bromide 0.3g of 45g puts into 30g (99%, 0.168mol) 4- trifluoro methoxy again
Base aniline adjusts temperature to 30 DEG C or more, starts that 35% hydrogen peroxide 38g is added dropwise, temperature rises when dropwise addition, when temperature rises to 50
DEG C when, by control coolant liquid control dropping temperature between 50~55 DEG C, keep the temperature to drip off, drip off heat preservation 3 hours, drop
Temperature is to 30 DEG C or so, filtering, and filter cake drying obtains white crystals 2, the bromo- 4- trifluoro-methoxyaniline 55.6g of 6- bis-, purity
99.8%(HPLC), yield 99%.
It filters mother liquor and cools to 0 degree, refilter, obtain filter cake 10g, mother liquor 310g.
Embodiment 2
The preparation method of 2,6- of one kind bis- bromo- 4- (trifluoromethoxy) aniline, including following operating procedure:
By in the mother liquor 310g investment 1000mL there-necked flask for filtering off potassium sulfate crystallization in example 1, starts stirring and instill
17.5 (0.175mol) sulfuric acid, then put into the potassium bromide (0.365moL) and 30g (99%, 0.168mol) 4- trifluoro methoxy of 43.5g
Base aniline adjusts temperature to 30 DEG C or more, starts that 35% hydrogen peroxide 38g (0.391mol) is added dropwise, and temperature rises when dropwise addition, works as temperature
When degree rises to 50 DEG C, dropping temperature is controlled between 50~55 DEG C by control coolant liquid, keeps the temperature to drip off, drips off guarantor
Temperature 3.5 hours is cooled to 30 DEG C or so, and filtering, filter cake drying obtains white crystals 2, the bromo- 4- trifluoro-methoxyaniline of 6- bis-
55.3g, purity 99.7%(HPLC), yield 98.4%.
It filters mother liquor and cools to 0 degree, refilter, obtain filter cake 30.5g, mother liquor 350g.
Embodiment 3
The preparation method of 2,6- of one kind bis- bromo- 4- (trifluoromethoxy) aniline, including following operating procedure:
By in the mother liquor 350g investment 1000mL there-necked flask for filtering off potassium sulfate crystallization in example 2, starts stirring and instill
17.5 (0.175mol) sulfuric acid, then put into the potassium bromide (0.365moL) and 30g (99%, 0.168mol) 4- trifluoro methoxy of 43.5g
Base aniline adjusts temperature to 30 DEG C or more, starts that 35% hydrogen peroxide 38g (0.391mol) is added dropwise, and temperature rises when dropwise addition, works as temperature
When degree rises to 50 DEG C, dropping temperature is controlled between 50~55 DEG C by control coolant liquid, keeps the temperature to drip off, drips off guarantor
Temperature 3.5 hours is cooled to 30 DEG C or so, and filtering, filter cake drying obtains white crystals 2, the bromo- 4- trifluoro-methoxyaniline of 6- bis-
55.4g, purity 99.2%(HPLC), yield 98.1%.
It filters mother liquor and cools to 0 degree, refilter, obtain filter cake 31g, mother liquor 389g.
Embodiment 4
The preparation method of 2,6- of one kind bis- bromo- 4- (trifluoromethoxy) aniline, including following operating procedure:
130g water is put into 250mL four-hole bottle, stirring is started and instills 17.5 (0.175mol) sulfuric acid, put into 40g's
Sodium bromide (0.388moL) and tetrabutylammonium bromide 0.3g, then 30g (99%, 0.168mol) 4- trifluoro-methoxyaniline is put into, it adjusts
Temperature is saved to 30 DEG C or more, starts that 35% hydrogen peroxide 38g is added dropwise, temperature rises when dropwise addition, when temperature rises to 50 DEG C, passes through
Coolant liquid control dropping temperature is controlled between 50~55 DEG C, keeps the temperature to drip off, drips off heat preservation 3 hours, be cooled to 30 DEG C
Left and right, filtering, filter cake drying obtain white crystals 2,6- bis- bromo- 4- trifluoro-methoxyaniline 56g, purity 99.7%(HPLC),
Yield 99.6%.
It filtering mother liquor and cools to 0 degree, filtering obtains filter cake 40g, and 156 grams of mother liquor.
Embodiment 5
The preparation method of 2,6- of one kind bis- bromo- 4- (trifluoromethoxy) aniline, including following operating procedure:
It will be filtered off in embodiment 4 in sulfate crystal mother liquor 156g investment 250mL four-hole bottle, start stirring and instill
17.5 (0.175mol) sulfuric acid, then the sodium bromide (0.354moL) of 36.5g is put into, then put into 30g (99%, 0.168mol) 4- tri-
Fluorine methoxyl group aniline adjusts temperature to 30 DEG C or more, starts that 35% hydrogen peroxide 38g is added dropwise, temperature rises when dropwise addition, when in temperature
When being raised to 50 DEG C, dropping temperature is controlled between 50~55 DEG C by control coolant liquid, keeps the temperature to drip off, drips off heat preservation 3
Hour, it is cooled to 30 DEG C or so, filtering, filter cake drying obtains white crystals 2, the bromo- 4- trifluoro-methoxyaniline 55.8g of 6- bis-,
Purity 99.6%(HPLC), yield 99.2%.
It filters mother liquor and cools to 0 degree, refilter, obtain filter cake 56.5g, 163 grams of mother liquor.
Embodiment 6
The preparation method of 2,6- of one kind bis- bromo- 4- (trifluoromethoxy) aniline, including following operating procedure:
It will be filtered off in embodiment 5 in 163 g of sulfate crystal mother liquor investment 250mL four-hole bottle, start stirring and instill
17.5 (0.175mol) sulfuric acid, then the sodium bromide (0.354moL) of 36.5g is put into, then put into 30g (99%, 0.168mol) 4- tri-
Fluorine methoxyl group aniline adjusts temperature to 30 DEG C or more, starts that 35% hydrogen peroxide 38g is added dropwise, temperature rises when dropwise addition, when in temperature
When being raised to 50 DEG C, dropping temperature is controlled between 50~55 DEG C by control coolant liquid, keeps the temperature to drip off, drips off heat preservation 3
Hour, it is cooled to 30 DEG C or so, filtering, filter cake drying obtains white crystals 2, the bromo- 4- trifluoro-methoxyaniline 55.5g of 6- bis-,
Purity 99.7%(HPLC), yield 98.7%.
It filters mother liquor and cools to 0 degree, refilter, obtain filter cake 57g, 169 grams of mother liquor.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks
Domain is included within the scope of the present invention.
Claims (8)
1. a kind of preparation method of thifluzamide key intermediate -2,6- bis- bromo- 4- (trifluoromethoxy) aniline, feature exist
In this method include following operating procedure:
Water is put into reaction flask, the lower instillation concentrated sulfuric acid is stirred, then put into metal bromide and catalyst, then adds 4- tri-
Fluorine methoxyl group aniline stirs 30 min;
At 30 DEG C, hydrogen peroxide is added dropwise, controls rate of addition, reaction temperature is made to be slowly increased to 50 DEG C, and 50~55 DEG C with
Coolant liquid control reaction flask in temperature continue be added dropwise hydrogen peroxide, after being added dropwise, at 50~55 DEG C insulation reaction 2~
3.0h ;
Reaction is finished, and adds water and stirs, off-white color 2, the bromo- 4- trifluoro-methoxyaniline of 6- bis- is obtained by filtration;Filtered mother liquor drop
Temperature to 0 degree, be precipitated sodium sulfate crystal, refilter it is mother liquid obtained can directly apply, catalyst does not add during mother liquid recycle;
Wherein, the metal bromide is sodium bromide;
The catalyst is tetrabutylammonium bromide.
2. preparation method according to claim 1, it is characterised in that the metal bromide and 4- trifluomethoxybenzene
The molar ratio of amine is 1.8~2.3: 1.
3. preparation method according to claim 1, it is characterised in that the molar ratio of the metal bromide and sulfuric acid is
2.0~2.2: 1.
4. preparation method according to claim 1, it is characterised in that the molar ratio of the hydrogen peroxide and metal bromide
It is 0. 9~1.5: 1.
5. preparation method according to claim 1, it is characterised in that the catalyst tetrabutylammonium bromide and 4- trifluoro
The molar ratio of aminoanisole is 0.002~0.01: 1.
6. preparation method according to claim 1, it is characterised in that mother liquor obtains by-product sulphur by decrease temperature crystalline method
After hydrochlorate, it is directly applied to system.
7. preparation method according to claim 1, it is characterised in that it is 30~65 DEG C that hydrogen peroxide temperature, which is added dropwise,.
8. preparation method according to claim 7, it is characterised in that it is 50~55 DEG C that hydrogen peroxide temperature, which is added dropwise,.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611038897.2A CN106631839B (en) | 2016-11-23 | 2016-11-23 | A kind of preparation method of thifluzamide key intermediate -2,6- bis- bromo- 4- (trifluoromethoxy) aniline |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611038897.2A CN106631839B (en) | 2016-11-23 | 2016-11-23 | A kind of preparation method of thifluzamide key intermediate -2,6- bis- bromo- 4- (trifluoromethoxy) aniline |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106631839A CN106631839A (en) | 2017-05-10 |
CN106631839B true CN106631839B (en) | 2019-03-12 |
Family
ID=58812519
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201611038897.2A Active CN106631839B (en) | 2016-11-23 | 2016-11-23 | A kind of preparation method of thifluzamide key intermediate -2,6- bis- bromo- 4- (trifluoromethoxy) aniline |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106631839B (en) |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6114584A (en) * | 1999-09-29 | 2000-09-05 | Occidental Chemical Corporation | Method of preparing brominated substituted anilines |
WO2000069810A1 (en) * | 1999-05-17 | 2000-11-23 | Novo Nordisk A/S | Glucagon antagonists/inverse agonists |
JP2001199943A (en) * | 2000-01-21 | 2001-07-24 | Kemikurea:Kk | Method for producing 2,6-dibromo-4- trifluoromethoxyaniline |
CN102234220A (en) * | 2010-05-04 | 2011-11-09 | 南通天泽化工有限公司 | Method for preparing 4-bromo-1,2-xylene |
CN102285878A (en) * | 2011-06-24 | 2011-12-21 | 昆明制药集团股份有限公司 | Method for preparing 2-halo-4,5-dimethoxy benzoic acid |
CN102491910A (en) * | 2011-12-09 | 2012-06-13 | 盐城利民化工有限公司 | Method for synthesizing 2,6-dibromo-4-(trifluoromethoxy) aniline by water-phase method |
CN103570566A (en) * | 2013-11-12 | 2014-02-12 | 河北科技大学 | Method for preparing 2,6-dibromo-4-trifluoromethoxyaniline |
CN103965094A (en) * | 2013-01-31 | 2014-08-06 | 江苏道博化工有限公司 | N-methyl-4-amino-5-bromo-phthalimide synthesis method |
CN105399712A (en) * | 2015-12-07 | 2016-03-16 | 潍坊玉成化工有限公司 | Preparation method of 4-bromo phthalic anhydride |
-
2016
- 2016-11-23 CN CN201611038897.2A patent/CN106631839B/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000069810A1 (en) * | 1999-05-17 | 2000-11-23 | Novo Nordisk A/S | Glucagon antagonists/inverse agonists |
US6114584A (en) * | 1999-09-29 | 2000-09-05 | Occidental Chemical Corporation | Method of preparing brominated substituted anilines |
JP2001199943A (en) * | 2000-01-21 | 2001-07-24 | Kemikurea:Kk | Method for producing 2,6-dibromo-4- trifluoromethoxyaniline |
CN102234220A (en) * | 2010-05-04 | 2011-11-09 | 南通天泽化工有限公司 | Method for preparing 4-bromo-1,2-xylene |
CN102285878A (en) * | 2011-06-24 | 2011-12-21 | 昆明制药集团股份有限公司 | Method for preparing 2-halo-4,5-dimethoxy benzoic acid |
CN102491910A (en) * | 2011-12-09 | 2012-06-13 | 盐城利民化工有限公司 | Method for synthesizing 2,6-dibromo-4-(trifluoromethoxy) aniline by water-phase method |
CN103965094A (en) * | 2013-01-31 | 2014-08-06 | 江苏道博化工有限公司 | N-methyl-4-amino-5-bromo-phthalimide synthesis method |
CN103570566A (en) * | 2013-11-12 | 2014-02-12 | 河北科技大学 | Method for preparing 2,6-dibromo-4-trifluoromethoxyaniline |
CN105399712A (en) * | 2015-12-07 | 2016-03-16 | 潍坊玉成化工有限公司 | Preparation method of 4-bromo phthalic anhydride |
Non-Patent Citations (2)
Title |
---|
2,6-二溴-4-三氟甲氧基苯胺的合成;杜汉权;《有机氟工业》;20081231(第3期);第34-36页 |
Quaternary Ammonium Salts as Bifunctional Catalysts in the Oxybromination of Aromatic Compounds by Aqueous Hydrogen BromidelHydrogen Peroxide;Yoel Sasson等;《Journal of the Chemical Society, Chemical Communications》;19871231(第19期);第1421-2页 |
Also Published As
Publication number | Publication date |
---|---|
CN106631839A (en) | 2017-05-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104230803B (en) | Preparation method of hydroxychloroquine sulfate | |
CN104610071B (en) | A kind of chlorine direct chlorination and hydrogen peroxide oxidation chlorination are prepared the method for 2,6-Dichloro-4-nitroaniline simultaneously | |
CN112707836B (en) | Preparation method of m-diamide compound | |
WO2019041462A1 (en) | Method for preparing 1,1'-ethylene-2,2'-bipyridyl dichloride salt | |
CN111100044B (en) | Preparation method of alkyl zinc sulfinate series compounds | |
US11981616B2 (en) | Method for preparing 3,3′-diaminobenzidine | |
CN106631839B (en) | A kind of preparation method of thifluzamide key intermediate -2,6- bis- bromo- 4- (trifluoromethoxy) aniline | |
CN105017232B (en) | A kind of synthetic method of triazole bactericidal agent | |
JP3575839B2 (en) | Method for producing 5-acetoacetylamino-2-benzimidazolone | |
CN110845371B (en) | Method for synthesizing o-sulfobenzaldehyde under normal pressure | |
CN110305037B (en) | Synthesis method of selective isochromic isomer of wave-absorbing material 2, 4-bis (phenylazo) resorcinol | |
CN114685300A (en) | Preparation method of o-chlorophenylglycine | |
CN107501141A (en) | A kind of preparation method to methylsulfonyltoluene | |
CN110092783B (en) | Preparation method of thiamethoxam | |
CN107216287A (en) | The preparation method of Boscalid | |
CN108203368A (en) | A kind of production technology of high-quality trimethyl orthoacetate | |
CN107827821B (en) | Continuous flow clean production process of pyrazolone series products | |
CN107033102B (en) | The synthetic method of mefenacet | |
CN103739421B (en) | 1,1-diphenyl ethylene derivatives and preparation method thereof | |
CN113121335A (en) | Preparation method of 2, 4-dichlorophenoxyacetic acid | |
CH390271A (en) | Process for the preparation of diarylaminoaromatic dicarboxylic acids | |
CN115073299B (en) | Method for preparing 2-fluoro-3-trifluoromethyl aniline | |
CN103086962A (en) | Synthetic method for 5-chlorine-2,4-dyhydroxyl pyridine | |
CN115385904A (en) | Green synthesis method of thiamethoxam | |
CN108276328A (en) | A kind of preparation method of Sorafenib |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |