CN109776351A - A kind of diazonium acetate is continuously synthesizing to method - Google Patents
A kind of diazonium acetate is continuously synthesizing to method Download PDFInfo
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Abstract
The invention discloses a kind of diazonium acetates to be continuously synthesizing to method, glycine ester hydrochloride aqueous solution, sodium nitrite in aqueous solution, organic solvent is carried out two-stage diazotising synthetic reaction, for product through stratification, oil reservoir removes diazo liquid Lower tank, and water layer removes extraction kettle；Continue stratification after adding extractant to be extracted into extraction kettle, water layer removes acidification reflux kettle, and oil reservoir goes diazo liquid Lower tank to merge to obtain diazoacetic acid ester solution.Water layer in acidification reflux kettle, acidified reflux, cooling, resin adsorption, negative pressure letter is steamed, dehydration is concentrated, sodium chloride wet basis and centrifuge mother liquor are obtained after centrifugation, centrifuge mother liquor is back in acidification reflux kettle and applies, and sodium chloride wet basis obtains industrial grade sodium chloride after drying.The method of the present invention carry out reaction can sufficiently obtaining in high yield, and the high slat-containing wastewater that simultaneous reactions generate is by recycling sodium chloride after processing；And test the continuous production of entire technique.Realize the clean manufacturing discharged without waste water,waste gas and industrial residue.
Description
Technical field
The present invention relates to a kind of diazoacetic acid Lipase absobed serialization clean preparation methods, and in particular to a kind of pyrethroid
The clean preparation method of important intermediate diazoacetic acid Lipase absobed, belongs to chemosynthesis technical field in production.
Background technique
Diazonium carbonyls is a kind of high activity reaction reagent as carbene precursor, in transistion metal compound or
Under the catalysis of Lewis acid, cycloaddition reaction, etherification reaction can occur and insertion of C-H bond etc. is much reacted.For multiclass
The synthesis of organic compound.The cycloaddition reaction of diazonium acetate and alkene has been used for the industrial production of cyclopropanecarboxylcompound.By
In the latent instability and explosivity of diazonium acetate, such compound needs now-making-now-using.It is anti-with the pair of diazo-reaction
Impurity caused by answering often will affect the selectivity that diazonium compound participates in reaction in next step.The weight of high-purity is used under study for action
Nitrogen reagent is to improve the selectivity of reaction.Although there are many purification process in the lab, in the industrial production, to quick-fried
The purifying of the diazonium compound of fried property is then more difficult, can not be purified with the distillating method of low cost.One important channel is to adopt
Diazonium compound is synthesized with highly selective reaction, as few as possible to introducing impurity in solution.
The method that document has reported a variety of synthesis diazonium acetates, wherein being carried out in acid medium using amino-acid ester
Diazo-reaction be method that is the most succinct and being most widely used.Since diazonium compound is to the unstability of heat.It is difficult to
By distillation purifying in large-scale production, generally reacted with its solution.Thus, how to guarantee that reacting balance carries out, is same
The purity and yield of Shi Tigao diazonium acetate are critical issue of the compound as Industrial intermediates.But diazonium acetate
Synthesis yield only has 90% or so, and has a large amount of high ammonia nitrogen and high brine waste to discharge, wastewater biochemical low efficiency, it is difficult to biochemical
Processing.
Summary of the invention
The technical problem to be solved by the present invention is to be directed to the deficiencies in the prior art, and provide a kind of diazoacetic acid
Ester (diazoacetic acid methyl esters or ethyl diazoacetate) is continuously synthesizing to method；This method makes reaction that can sufficiently carry out obtaining
In high yield, the high slat-containing wastewater that simultaneous reactions generate is by recycling sodium chloride after processing；And test the serialization of entire technique
Production.Realize the clean manufacturing discharged without waste water,waste gas and industrial residue.
To achieve the goals above, the present invention adopts the following technical scheme that (unless otherwise instructed, following % concentration is matter
Measure percentage concentration):
A kind of diazonium acetate is continuously synthesizing to method, and flow chart is as shown in Figure 1, comprising the following steps:
(1) diazo compounds at: by glycine ester hydrochloride aqueous solution, sodium nitrite in aqueous solution, organic solvent put into level-one
In diazotising synthesis reactor, carried out at 0-20 DEG C level-one diazo compounds at, level-one diazo compounds at reaction time be within 5h；
Level-one diazotising synthetic product overflow carries out second level diazo compounds into second level into second level diazotising synthesis reactor at 0-20 DEG C
Diazo compounds at reaction time be 5h within；Second level diazotising synthetic product overflow, which carries out standing into level-one subsider, to divide
Layer, oil reservoir go diazo liquid Lower tank, water layer overflow to extraction kettle；Extractant is added into extraction kettle to be extracted, is stirred
The extract liquor overflow formed afterwards is into secondary settling tank；Extract liquor carries out stratification in secondary settling tank, and water layer overflow is extremely
Acidification reflux kettle, oil reservoir continue to obtain oil reservoir after diazo liquid Lower tank and level-one subsider stratification to mix, and obtain diazonium
Acetate solution；
(2) react the processing recycling of water layer: dense salt is added in water layer of the last overflow into acidification reflux kettle in step (1)
Acid for adjusting pH is 1~6, and being then heated to boiling point makes its boiling reflux, and tail gas is absorbed using 10%~30% aqueous solution of urea；
Reflux 1~4 hour, the water layer liquid after reflux enter in cooling kettle, enter in resin adsorption tower after cooling down, use suction
Anion exchange resin in attached tower is adsorbed, and negative pressure letter steaming is then carried out, and dehydration is concentrated into visible a small amount of crystal and is precipitated；It is de-
Preparation of the water jacket out for glycine ester hydrochloride aqueous solution, sodium nitrite in aqueous solution in step (1)；Production after negative pressure letter steaming
Object after being cooled to room temperature after be centrifuged, obtain sodium chloride wet basis and centrifuge mother liquor, centrifuge mother liquor is back to and is acidified back
It is applied in stream kettle, sodium chloride wet basis obtains industrial grade sodium chloride after drying.
In above-mentioned technical proposal, in step (1), the glycinate refers to glycine methyl ester or glycine ethyl ester；
Glycine ester hydrochloride refers to glycine methyl ester hydrochloride or glycine ethyl ester hydrochloride；
It is molten to refer to that corresponding glycine ester hydrochloride is dissolved in weak acid buffer for the glycine ester hydrochloride aqueous solution
The aqueous solution being formulated in liquid, wherein the mass fraction of glycine ester hydrochloride accounts for the 20-50% of entire aqueous solution,
Preferably 30-45%, further preferably 40-45%；
The weak acid buffer solution is acetic acid/sodium acetate, in formic acid/sodium formate, citric acid/sodium citrate buffer solution
Any one, the pH value of buffer solution is 4-6；Preferably acetic acid/sodium acetate buffer solution.
In above-mentioned technical proposal, in step (1), in the sodium nitrite in aqueous solution, the mass fraction of sodium nitrite is
20-50%, preferably 30-45%, further preferably 40-45%.
Glycinate hydrochloric acid in above-mentioned technical proposal, in step (1), in the glycine ester hydrochloride aqueous solution
Sodium nitrite in salt, with sodium nitrite in aqueous solution, molar ratio be 1:1.05~1:1.35, preferably 1:1.1~1:1.3, into
One step is preferably 1:1.15~1:1.25.
In above-mentioned technical proposal, in step (1), the organic solvent is the big halogenated alkane of density ratio water, halogenated ring
Alkane solvents；The preferably mixture of one of methylene chloride, chloroform, dichloroethanes or two kinds or more；It is described
Organic solvent dosage, be 1:1~3:1 with the weight ratio of the sodium nitrite in aqueous solution initially to feed intake.
In above-mentioned technical proposal, in step (1), the extractant is the big halogenated alkane of density ratio water, halogenated cycloalkanes
Hydro carbons extractant；The preferably mixture of one of methylene chloride, chloroform, dichloroethanes or two kinds or more；Extraction
The range of choice of agent is preferably formed with same type used in reaction and proportion with above-mentioned organic solvent；The extractant
The weight ratio of water layer is 0.5:1~3:1 in dosage, with extraction kettle.
In above-mentioned technical proposal, in step (1), the reaction temperature in level-one diazotising synthesis reactor is preferably 0-10 DEG C, instead
Preferably 1-2h between seasonable.
In above-mentioned technical proposal, in step (1), the reaction temperature in second level diazotising synthesis reactor is preferably 0-10 DEG C, instead
Preferably 1-2h between seasonable.
In above-mentioned technical proposal, in step (2), the anion exchange resin is large pore anion resin, preferably
310 resin anion (R.A.) of DG301, DG311 or DG；Anion exchange resin after adsorption saturation can use the sodium hydroxide of 5-20%
It is recycled after lye parsing.
In above-mentioned technical proposal, in step (2), acidification is preferably added to 20%~30% concentrated hydrochloric acid when flowing back, and adjusts pH
Preferably 3-4.
The advantages of technical solution of the present invention, is:
(1) present invention in diazonium acetate waste water can be recycled sodium chloride and deviate from water jacket with hydrochloride configuration and Asia sodium
Configuration, entire technique do not generate any high slat-containing wastewater；High ammonia nitrogen and high brine waste, byproduct sodium chloride are not generated；
(2) synthesis of product diazonium acetate of the invention realizes that continuous production, product are 10-30% diazonium acetate
Solution can be directly as the raw material of downstream product, and synthesis yield reaches 97% or more；
(3) present invention provides a kind of clean preparation method of pyrethroid intermediate diazonium acetate, and this method makes
Reaction can be carried out sufficiently to obtain in high yield, and the high slat-containing wastewater that simultaneous reactions generate is by recycling sodium chloride simultaneously after processing
And the continuous production of the entire technique of experiment.Realize the clean manufacturing discharged without waste water,waste gas and industrial residue.
Detailed description of the invention
Fig. 1 is the process flow chart of the method for the present invention.
Specific embodiment
The specific embodiment of technical solution of the present invention is described in detail below, but the present invention is not limited in being described below
Hold:
Embodiment 1:
A kind of clean preparation method that pyrethroid intermediate diazonium acetate is continuously synthesizing to:
(1) by 75kg hydrochloric acid saline solution, (acetic acid of glycine methyl ester hydrochloride and 0.1M/sodium acetate buffer solution are prepared
Form, pH value is adjusted to 4.3, wherein glycine methyl ester hydrochloride mass fraction be 35%), the Asia 45kg sodium water solution (nitrous acid
Sodium mass fraction be 35%), 70kg solvent chloroform is put into togerther in level-one diazotising synthesis reactor, wherein hydrochloride is water-soluble
The molar ratio of glycine methyl ester hydrochloride in liquid and the sodium nitrite in sub- sodium water solution is 1:1.09；One is carried out at 12 DEG C
Grade diazo compounds are at reaction 4h；Level-one diazotising synthetic product overflow carries out two into second level diazotising synthesis reactor at 8 DEG C
Grade diazo compounds are at reaction time 4h；Second level diazotising synthetic product overflow carries out stratification into level-one subsider, oil
Layer goes diazonium night Lower tank, water layer overflow to extraction kettle；50kg extractant chloroform is added into extraction kettle to be extracted, on
The extract layer overflow of layer is into secondary settling tank；Extract layer carries out stratification, water layer overflow to acidification in secondary settling tank
Flow back kettle, and oil reservoir continues to obtain oil reservoir after diazonium night Lower tank and level-one subsider stratification to mix, and obtains diazoacetic acid
Methyl ester solution 135.7kg, gas spectrum analysis wherein diazoacetic acid methyl ester content 15.3%, reaction yield 97.9%.
(2) water layer about 50kg of the overflow into acidification reflux kettle in step (1), in acidification reflux while being added 30% dense salt
Sour 2kg is adjusted after pH is 1.3 and is carried out temperature rising reflux, and tail gas is absorbed using 20% aqueous solution of urea；Product after reflux into
Enter into cooling kettle, enters in resin adsorption tower after cooling down；DG311 type yin after cooling in product utilization resin adsorption tower from
Sub-exchange resin is adsorbed, and negative pressure letter steaming is then carried out at low vacuum 100mmHg, the water jacket of abjection is in step (1)
Prepare hydrochloric acid saline solution, sub- sodium water solution；Product after negative pressure letter is steamed is centrifuged after cooling down, and it is wet to obtain sodium chloride
Base and centrifuge mother liquor, centrifuge mother liquor are back in acidification reflux kettle and apply, and sodium chloride wet basis obtains sodium chloride butt after drying
8.2kg。
The resin of adsorption saturation can be parsed with 15% sodium hydroxide lye, and per kilogram resin uses 2 kilograms of desorbed solutions, leaching
It steeps 24 hours and parses.
Embodiment 2:
(1) by 8kg hydrochloric acid saline solution, (acetic acid of glycine ethyl ester hydrochloride and 0.1M/sodium acetate buffer solution are prepared
Form, pH value is adjusted to 4.2, wherein glycine ethyl ester hydrochloride mass fraction be 40%), the Asia 45kg sodium water solution (nitrous acid
Sodium mass fraction be 45%), 45kg solvent 1,2- dichloroethanes is put into togerther in level-one diazotising synthesis reactor, wherein hydrochloride
The molar ratio of glycine ethyl ester hydrochloride in aqueous solution and the nitrous acid in sub- sodium water solution is 1:1.28；It carries out at 5 DEG C
Level-one diazo compounds are at reaction 2h；Level-one diazotising synthetic product overflow carries out at 5 DEG C into second level diazotising synthesis reactor
Second level diazo compounds are at reaction time 2h；Second level diazotising synthetic product overflow carries out stratification into level-one subsider,
Oil reservoir goes diazonium night Lower tank, water layer overflow to extraction kettle；60kg extractant 1,2- dichloroethanes is added into extraction kettle to carry out
Extraction, the extract layer overflow on upper layer is into secondary settling tank；Extract layer carries out stratification, water layer overflow in secondary settling tank
It flows back kettle to acidification, oil reservoir continues to obtain oil reservoir after diazonium night Lower tank and level-one subsider stratification to mix, and obtains again
Nitrogen ethyl acetate solution 125.8kg, gas spectrum analysis wherein ethyl diazoacetate content 20.5%, reaction yield 98.2%.
(2) water layer of the overflow into acidification reflux kettle in step (1), flowing back in acidification while 28% concentrated hydrochloric acid is added is adjusted
PH carries out temperature rising reflux after being 3, tail gas is absorbed using 30% aqueous solution of urea；Product after reflux enters cooling kettle
In, enter in resin adsorption tower after cooling down；DG310 type anion exchange resin after cooling in product utilization resin adsorption tower
It is adsorbed, negative pressure letter steaming is then carried out at low vacuum 100mmHg, the water jacket of abjection is for preparing hydrochloride in step (1)
Aqueous solution, sub- sodium water solution；Product after negative pressure letter is steamed is centrifuged after cooling down, and obtains sodium chloride wet basis and centrifugation is female
Liquid, centrifuge mother liquor are back in acidification reflux kettle and apply, and sodium chloride wet basis obtains sodium chloride butt after drying.
Embodiment 3:
(1) by the 80kg hydrochloric acid saline solution (formic acid of glycine ethyl ester hydrochloride and 0.1M/sodium formate buffer preparation
Form, pH value is adjusted to 4.3, wherein glycine ethyl ester hydrochloride mass fraction be 40%), the Asia 40kg sodium water solution (nitrous acid
Sodium mass fraction be 50%), 60kg methylene chloride is put into togerther in level-one diazotising synthesis reactor, wherein hydrochloride is water-soluble
The molar ratio of glycine ethyl ester hydrochloride in liquid and the nitrous acid in sub- sodium water solution is 1:1.26；Level-one is carried out at 3 DEG C
Diazo compounds are at reaction 1h；Level-one diazotising synthetic product overflow carries out second level into second level diazotising synthesis reactor at 3 DEG C
Diazo compounds are at reaction time 3h；Second level diazotising synthetic product overflow carries out stratification, oil reservoir into level-one subsider
Go diazonium night Lower tank, water layer overflow to extraction kettle；60kg extractant methylene chloride is added into extraction kettle to be extracted, upper layer
Extract layer overflow into secondary settling tank；Extract layer carries out stratification in secondary settling tank, and water layer overflow is extremely acidified back
Flow kettle, oil reservoir continues to obtain oil reservoir after diazonium night Lower tank and level-one subsider stratification to mix, and obtains diazoacetic acid second
Ester solution 143.7kg, gas spectrum analysis wherein ethyl diazoacetate content 17.9%, reaction yield 98.4%.
(2) water layer of the overflow into acidification reflux kettle in step (1), flowing back in acidification while 25% concentrated hydrochloric acid is added is adjusted
PH carries out temperature rising reflux after being 3.5, tail gas is absorbed using 30% aqueous solution of urea；Product after reflux enters cooling kettle
In, enter in resin adsorption tower after cooling down；DG310 type anion exchange resin after cooling in product utilization resin adsorption tower
It is adsorbed, negative pressure letter steaming is then carried out at low vacuum 110mmHg, the water jacket of abjection is for preparing hydrochloride in step (1)
Aqueous solution, sub- sodium water solution；Product after negative pressure letter is steamed is centrifuged after cooling down, and obtains sodium chloride wet basis and centrifugation is female
Liquid, centrifuge mother liquor are back in acidification reflux kettle and apply, and sodium chloride wet basis obtains sodium chloride butt after drying.
Embodiment 4:
(1) by 80kg hydrochloric acid saline solution (the citric acid/sodium citrate buffer solution of glycine ethyl ester hydrochloride and 0.2M
Be formulated, pH value is adjusted to 4.6, wherein glycine ethyl ester hydrochloride mass fraction be 20%), the Asia 30kg sodium water solution it is (sub-
Sodium nitrate mass fraction be 30%), 40kg solvent chloroform is put into togerther in level-one diazotising synthesis reactor, wherein hydrochloride
The molar ratio of glycine ethyl ester hydrochloride in aqueous solution and the nitrous acid in sub- sodium water solution is 1:1.13；It is carried out at 2 DEG C
Level-one diazo compounds are at reaction 4h；Level-one diazotising synthetic product overflow carries out at 1 DEG C into second level diazotising synthesis reactor
Second level diazo compounds are at reaction time 2h；Second level diazotising synthetic product overflow carries out stratification into level-one subsider,
Oil reservoir goes diazonium night Lower tank, water layer overflow to extraction kettle；40kg extractant chloroform is added into extraction kettle to be extracted,
The extract layer overflow on upper layer is into secondary settling tank；Extract layer carries out stratification, water layer overflow to acid in secondary settling tank
Change reflux kettle, oil reservoir continues to obtain oil reservoir after diazonium night Lower tank and level-one subsider stratification to mix, and obtains diazonium second
Acetate solution 89.8Kg, gas spectrum analysis wherein ethyl diazoacetate content 14.2%, reaction yield 97.4%.
(2) water layer of the overflow into acidification reflux kettle in step (1), flowing back in acidification while 25% concentrated hydrochloric acid is added is adjusted
PH carries out temperature rising reflux after being 2, tail gas is absorbed using 30% aqueous solution of urea；Product after reflux enters cooling kettle
In, enter in resin adsorption tower after cooling down；DG301 type anion exchange resin after cooling in product utilization resin adsorption tower
It is adsorbed, negative pressure letter steaming is then carried out at low vacuum 110mmHg, the water jacket of abjection is for preparing hydrochloride in step (1)
Aqueous solution, sub- sodium water solution；Product after negative pressure letter is steamed is centrifuged after cooling down, and obtains sodium chloride wet basis and centrifugation is female
Liquid, centrifuge mother liquor are back in acidification reflux kettle and apply, and sodium chloride wet basis obtains sodium chloride butt after drying.
Comparative example 1:
Into the three-necked bottle of 250mL be added 13.95g glycine ethyl ester hydrochloride, 20mL water, 3mL 0.5mol/L sulfuric acid,
30mL l, 2- dichloroethanes, is cooled to 10 DEG C, and stir, and the sodium nitrite in aqueous solution of 15mL 8mol/L is added dropwise.And keep anti-
Answer temperature at 10 DEG C or so, 20min is added, and stirs 120min.Reaction solution is transferred in separatory funnel, organic phase, water phase are separated
Extracted with (8mL × 2) 1,2- dichloroethanes, organic phase after merging through sodium bicarbonate solution (10mL × 2) washing, with anhydrous sulphur
It weighs after sour sodium is dry, measures ethyl diazoacetate content, yield only 94.8%.
Examples detailed above is technical conception and technical characteristics to illustrate the invention, can not be limited with this of the invention
Protection scope.The equivalent transformation or modification that all essence according to the present invention is done, should all cover in protection scope of the present invention
Within.
Claims (7)
1. a kind of diazonium acetate is continuously synthesizing to method, which comprises the following steps:
(1) diazo compounds at: by glycine ester hydrochloride aqueous solution, sodium nitrite in aqueous solution, organic solvent put into level-one diazonium
Be combined in kettle, carried out at 0-20 DEG C level-one diazo compounds at, level-one diazo compounds at reaction time be within 5h；Level-one
The overflow of diazotising synthetic product carries out second level diazo compounds into second level diazonium into second level diazotising synthesis reactor at 0-20 DEG C
The reaction time being combined to is within 5h；Second level diazotising synthetic product overflow carries out stratification into level-one subsider, oil
Layer goes diazo liquid Lower tank, water layer overflow to extraction kettle；Extractant is added into extraction kettle to be extracted, is formed after being stirred
Extract liquor overflow into secondary settling tank；Extract liquor carries out stratification in secondary settling tank, and water layer overflow is extremely acidified back
Flow kettle, oil reservoir continues to obtain oil reservoir after diazo liquid Lower tank and level-one subsider stratification to mix, and obtains diazonium acetate
Solution；
(2) react the processing recycling of water layer: concentrated hydrochloric acid tune is added in water layer of the last overflow into acidification reflux kettle in step (1)
Saving pH is 1~6, and being then heated to boiling point makes its boiling reflux, and tail gas is absorbed using 10%~30% aqueous solution of urea；Reflux
1~4 hour, the water layer liquid after reflux entered in cooling kettle, enters in resin adsorption tower after cooling down, uses adsorption tower
In anion exchange resin adsorbed, then carry out negative pressure letter steaming, dehydration is concentrated into visible a small amount of crystal and is precipitated；Abjection
Preparation of the water jacket for glycine ester hydrochloride aqueous solution, sodium nitrite in aqueous solution in step (1)；Product after negative pressure letter is steamed passes through
It is centrifuged after being cooled to after room temperature, obtains sodium chloride wet basis and centrifuge mother liquor, centrifuge mother liquor is back to acidification reflux kettle
In apply, sodium chloride wet basis obtains industrial grade sodium chloride after drying.
2. synthetic method according to claim 1, it is characterised in that: in step (1), the glycine ester hydrochloride water
Solution refers to that glycine methyl ester hydrochloride or glycine ethyl ester hydrochloride are dissolved in the water being formulated in weak acid buffer solution
Property solution, wherein the mass fraction of glycine ester hydrochloride accounts for the 20-50% of entire aqueous solution.
3. synthetic method according to claim 2, it is characterised in that: the weak acid buffer solution be acetic acid/sodium acetate,
Any one in formic acid/sodium formate, citric acid/sodium citrate buffer solution, the pH value of buffer solution are 4-6.
4. synthetic method according to claim 1, it is characterised in that: in step (1), the sodium nitrite in aqueous solution
In, the mass fraction of sodium nitrite is 20-50%.
5. synthetic method according to claim 1, it is characterised in that: in step (1), the glycine ester hydrochloride water
Glycine ester hydrochloride in solution, with the sodium nitrite in sodium nitrite in aqueous solution, molar ratio is 1:1.05~1:1.35.
6. synthetic method according to claim 1, it is characterised in that: in step (1), the organic solvent is density ratio
The big halogenated alkane of water, halogenated cycloalkane solvent；The dosage of organic solvent, the weight with the sodium nitrite in aqueous solution initially to feed intake
Amount is than being 1:1~3:1.
7. synthetic method according to claim 1, it is characterised in that: in step (1), the extractant is density ratio water
Big halogenated alkane, halogenated cycloalkane extractant；The dosage of extractant, with the weight ratio of water layer in extraction kettle be 0.5:1~
3:1。
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| CN112979579A (en) * | 2021-03-17 | 2021-06-18 | 乐威医药(天津)有限公司 | Low-temperature diazonium salt continuous preparation method of halogenated thiazole compound |
Citations (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2691650A (en) * | 1951-12-14 | 1954-10-12 | Nat Distillers Prod Corp | Diazotizing of glycine esters |
| US2691649A (en) * | 1951-12-14 | 1954-10-12 | Nat Distillers Prod Corp | Diazotizing of glycine esters |
| JPS48103514A (en) * | 1972-04-08 | 1973-12-25 | ||
| DE2400188A1 (en) * | 1974-01-03 | 1975-07-17 | Basf Ag | Alkyl diazoacetate prepn. by diazotising alkyl glycine esters - in aq. soln. at acid pH in presence of extractor solvent |
| US3897478A (en) * | 1970-05-21 | 1975-07-29 | Stauffer Chemical Co | Continuous process for the manufacture of alkyl chrysanthemate esters |
| JPS5182244A (en) * | 1974-12-03 | 1976-07-19 | Ici Ltd | 3 *2 22 jikurorubiniru * 2 22 jimechirushikuropuropankarubonsanesuteruno seizohoho |
| GB1467687A (en) * | 1974-11-25 | 1977-03-16 | Ucb Sa | Monoester monochlorides of 2-chloromalonic acid |
| GB1533381A (en) * | 1975-10-30 | 1978-11-22 | Wellcome Found | Preparation of esters of cyclopropane carboxylic acids |
| US4233213A (en) * | 1977-09-17 | 1980-11-11 | Bayer Aktiengesellschaft | Process for the continuous indirect diazotization of aromatic amines |
| JPH01115904A (en) * | 1987-10-28 | 1989-05-09 | Kuraray Co Ltd | Modified low-molecular weight conjugated diene polymer and curable composition made from said polymer |
| JPH05194323A (en) * | 1991-07-05 | 1993-08-03 | Dai Ichi Seiyaku Co Ltd | Production of fluorocyclopropanecarboxylic acid derivative |
| JP2008139299A (en) * | 2006-11-10 | 2008-06-19 | National Institute Of Advanced Industrial & Technology | High-sensitivity molecule probe for detecting membrane microdomain or cholesterol recognition protein |
| JP2010047496A (en) * | 2008-08-20 | 2010-03-04 | National Institute Of Advanced Industrial Science & Technology | Organism-related material-measuring device, and surface modification material for artificial organ |
| CN101844984A (en) * | 2010-06-08 | 2010-09-29 | 浙江大学 | Preparation method of 1,2,3-cyclopropyl tricarboxylate |
| CN102216243A (en) * | 2008-11-14 | 2011-10-12 | Dsm精细化学奥地利Nfg两合公司 | Process for the production of cyclopropane derivatives |
| WO2012128985A1 (en) * | 2011-03-18 | 2012-09-27 | Sigma-Aldrich Co. Llc | Continuous flow process for the production of diazo esters |
| CN102770415A (en) * | 2009-10-01 | 2012-11-07 | 艾米拉医药股份有限公司 | Polycyclic compounds as lysophosphatidic acid receptor antagonists |
| JP2012232904A (en) * | 2011-04-28 | 2012-11-29 | National Institute Of Advanced Industrial Science & Technology | Methoxy oligoethyleneglycol-silane compound surface modification material |
| WO2013052526A1 (en) * | 2011-10-06 | 2013-04-11 | Merck Sharp & Dohme Corp. | Triazolyl pde10 inhibitors |
| CN103189346A (en) * | 2010-11-01 | 2013-07-03 | 帝斯曼知识产权资产管理有限公司 | Continuous production and reaction of a diazo compound |
| CN203187607U (en) * | 2013-03-12 | 2013-09-11 | 浙江迪邦化工有限公司 | Automatic-control continuous production device for diazo compound |
| CN103664683A (en) * | 2012-09-21 | 2014-03-26 | 浙江龙盛集团股份有限公司 | Continuous diazotization production process of aromatic amine |
| EP2788333B1 (en) * | 2011-12-08 | 2016-03-23 | Boehringer Ingelheim International GmbH | 1,2,4-triazoles as allosteric modulators of mglu5 receptor activity for the treatment of schizophrenia of dementia |
| CN106316845A (en) * | 2016-08-24 | 2017-01-11 | 江苏优普生物化学科技股份有限公司 | Preparing method of cis, trans-ethyl 2, 2-dimethyl-3-(1-isobutenyl)cyclopropane-1-carboxylate |
| CN106396228A (en) * | 2016-09-18 | 2017-02-15 | 内蒙古久科康瑞环保科技有限公司 | Device and method for treating industrial wastewater with high salt content |
-
2017
- 2017-11-15 CN CN201711129836.1A patent/CN109776351B/en active Active
Patent Citations (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2691650A (en) * | 1951-12-14 | 1954-10-12 | Nat Distillers Prod Corp | Diazotizing of glycine esters |
| US2691649A (en) * | 1951-12-14 | 1954-10-12 | Nat Distillers Prod Corp | Diazotizing of glycine esters |
| US3897478A (en) * | 1970-05-21 | 1975-07-29 | Stauffer Chemical Co | Continuous process for the manufacture of alkyl chrysanthemate esters |
| JPS48103514A (en) * | 1972-04-08 | 1973-12-25 | ||
| DE2400188A1 (en) * | 1974-01-03 | 1975-07-17 | Basf Ag | Alkyl diazoacetate prepn. by diazotising alkyl glycine esters - in aq. soln. at acid pH in presence of extractor solvent |
| GB1467687A (en) * | 1974-11-25 | 1977-03-16 | Ucb Sa | Monoester monochlorides of 2-chloromalonic acid |
| JPS5182244A (en) * | 1974-12-03 | 1976-07-19 | Ici Ltd | 3 *2 22 jikurorubiniru * 2 22 jimechirushikuropuropankarubonsanesuteruno seizohoho |
| GB1459285A (en) * | 1974-12-03 | 1976-12-22 | Ici Ltd | Process for the preparation of cyclopropane carboxylic acid esters |
| GB1533381A (en) * | 1975-10-30 | 1978-11-22 | Wellcome Found | Preparation of esters of cyclopropane carboxylic acids |
| US4233213A (en) * | 1977-09-17 | 1980-11-11 | Bayer Aktiengesellschaft | Process for the continuous indirect diazotization of aromatic amines |
| JPH01115904A (en) * | 1987-10-28 | 1989-05-09 | Kuraray Co Ltd | Modified low-molecular weight conjugated diene polymer and curable composition made from said polymer |
| JPH05194323A (en) * | 1991-07-05 | 1993-08-03 | Dai Ichi Seiyaku Co Ltd | Production of fluorocyclopropanecarboxylic acid derivative |
| JP2008139299A (en) * | 2006-11-10 | 2008-06-19 | National Institute Of Advanced Industrial & Technology | High-sensitivity molecule probe for detecting membrane microdomain or cholesterol recognition protein |
| JP2010047496A (en) * | 2008-08-20 | 2010-03-04 | National Institute Of Advanced Industrial Science & Technology | Organism-related material-measuring device, and surface modification material for artificial organ |
| CN102216243A (en) * | 2008-11-14 | 2011-10-12 | Dsm精细化学奥地利Nfg两合公司 | Process for the production of cyclopropane derivatives |
| CN102770415A (en) * | 2009-10-01 | 2012-11-07 | 艾米拉医药股份有限公司 | Polycyclic compounds as lysophosphatidic acid receptor antagonists |
| CN101844984A (en) * | 2010-06-08 | 2010-09-29 | 浙江大学 | Preparation method of 1,2,3-cyclopropyl tricarboxylate |
| CN103189346A (en) * | 2010-11-01 | 2013-07-03 | 帝斯曼知识产权资产管理有限公司 | Continuous production and reaction of a diazo compound |
| WO2012128985A1 (en) * | 2011-03-18 | 2012-09-27 | Sigma-Aldrich Co. Llc | Continuous flow process for the production of diazo esters |
| JP2012232904A (en) * | 2011-04-28 | 2012-11-29 | National Institute Of Advanced Industrial Science & Technology | Methoxy oligoethyleneglycol-silane compound surface modification material |
| WO2013052526A1 (en) * | 2011-10-06 | 2013-04-11 | Merck Sharp & Dohme Corp. | Triazolyl pde10 inhibitors |
| EP2788333B1 (en) * | 2011-12-08 | 2016-03-23 | Boehringer Ingelheim International GmbH | 1,2,4-triazoles as allosteric modulators of mglu5 receptor activity for the treatment of schizophrenia of dementia |
| CN103664683A (en) * | 2012-09-21 | 2014-03-26 | 浙江龙盛集团股份有限公司 | Continuous diazotization production process of aromatic amine |
| CN203187607U (en) * | 2013-03-12 | 2013-09-11 | 浙江迪邦化工有限公司 | Automatic-control continuous production device for diazo compound |
| CN106316845A (en) * | 2016-08-24 | 2017-01-11 | 江苏优普生物化学科技股份有限公司 | Preparing method of cis, trans-ethyl 2, 2-dimethyl-3-(1-isobutenyl)cyclopropane-1-carboxylate |
| CN106396228A (en) * | 2016-09-18 | 2017-02-15 | 内蒙古久科康瑞环保科技有限公司 | Device and method for treating industrial wastewater with high salt content |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112979579A (en) * | 2021-03-17 | 2021-06-18 | 乐威医药(天津)有限公司 | Low-temperature diazonium salt continuous preparation method of halogenated thiazole compound |
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