CN103396330A - Preparation method of N,N-dimethyl glycine ester based on silica gel sulfonic acid serving as catalyst - Google Patents
Preparation method of N,N-dimethyl glycine ester based on silica gel sulfonic acid serving as catalyst Download PDFInfo
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Abstract
The invention relates to preparation of N, N-dimethyl glycine ester chemical products, particularly relates to a preparation method of N,N-dimethyl glycine ester based on silica gel sulfonic acid serving as a catalyst, and belongs to the field of chemical industries. The preparation method is characterized in that carboxylic acid and alcohol are used as raw materials for carrying out esterification reaction so as to obtain the N,N-dimethyl glycine ester, the catalyst for esterification reaction is the silica gel sulfonic acid, the carboxylic acid is N,N-dimethyl glycine, and the alcohol is fatty alcohol with 1-12 carbon atoms. The synthesis of the silica gel sulfonic acid serving as the catalyst involved in the invention is simple, raw materials for synthesis of the catalyst are cheap and easily available, and the catalyst has high catalytic activity; the catalyst is recycled and reused through simple filtration, so that the production cost is saved; the corrosion of sulfuric acid, phosphoric acid and the like to equipment is avoided; by adopting the technology, the yield is high, and the conversion rate can reach above 95%; after completion of reaction, the follow-up treatment is simple; the atom economy in the whole reaction process is good, and no other waste products are generated except for water.
Description
Technical field
The present invention is directed to chemical field, relate to the preparation of DMG ester class Chemicals.
Background technology
Esterification is a class organic chemical reactions, is the reaction that alcohol and carboxylic acid/oxygen-containing inorganic acid generate ester and water.Esterification is divided into two classes, and a class is the Carboxylic acid and alcohol reaction, and another kind of is inorganic oxacid/inorganic acid and alcohol reaction.First kind esterification is reversible, and sluggish, usually with the vitriol oil, makes catalyzer.
DMG ester class, have another name called N, and N-dimethylamino acetic ester is the novel dermal osmosis accelerator of a class.This compounds can be applicable to creme, paste and the liniment in medicine, makeup, strengthens the osmotic absorption effect of medicine to skin, strengthens drug effect; Also can be applied in plant nutrition liquid, strengthen the absorption of Plant To Nutrient liquid, be with a wide range of applications.
About N, the synthetic method of N-dimethylamino acetic ester is a lot, and many documents are all to the synthetic thinking that provides of this compounds.
As the US4980378 patent, N is disclosed, N-dimethylamino acetic ester and N, the synthetic method of the compounds such as N-diethyl amino yl acetate.Its method is: Mono Chloro Acetic Acid and high fatty alcohol room temperature reaction 16 hours under triethylamine and anhydrous chloroform exist, make chloracetate, then make N with excessive decil ethereal solution or diethylamine reaction, N-disubstituted amido acetic ester, productive rate are 72%～94%.Its shortcoming is that the chloroform give solvent is used in the first step reaction, and triethylamine is as acid binding agent, and the reaction times is longer; Second step reaction is with the diethyl ether solution of the dimethylamine of 1mol/L, operates dangerously, is difficult to industrialization.And the CN02135085.X patent research shows, chloroform is unfavorable for chloroacetyl chloride and high fatty alcohol acylation reaction at room temperature, and toxicity is large, although triethylamine has played the effect of acid binding agent, the time of acidylating on the contrary increases.
And for example, CN1091122 has improved N, the synthetic method of N-dimethylamino acetic acid certain herbaceous plants with big flowers ester.The method is: at solvent-free or benzene, be under solvent, chloroacetyl chloride and 1-certain herbaceous plants with big flowers alcohol adopts 4～10 hours synthesis of chloroacetic acid certain herbaceous plants with big flowers esters of solid-liquid phase transfer catalysis reaction, then, with excessive dimethylamine gas reaction 2 hours, obtains N, N-dimethylamino acetic acid certain herbaceous plants with big flowers ester, productive rate 80.8%～86.1%.Its shortcoming is that the building-up reactions cost increases, complex operation.Show: the first step reaction, as phase-transfer catalyst, first stirs into pasty state with the mixture heating of certain herbaceous plants with big flowers alcohol, alkali and catalyzer with TBAI or PEG-400, is cooled to after room temperature just to drip chloroacetyl chloride and carry out acylation reaction; Catalyzer TBAI is more expensive, and PEG-400 is during as phase-transfer catalyst, and the reaction times is partially long; Second step reaction passes into dimethylamine gas with in the water-cooled reaction system of cryosel, need to increase dimethylamine gas and occur and e Foerderanlage, and with toluene as solvent.
For another example, CN1405147 has reported the synthetic method of DMG ester, and the method is: by chloroacetyl chloride and alcohol stirring at room reaction under condition of no solvent, made chloracetate in 1～3 hour.Then with excessive 1～2 hour synthetic DMG ester of dimethylamine agueous solution room temperature reaction, total recovery is 67%～96%.
The present invention is based on above-mentioned prior art, and for the deficiencies in the prior art, improves invention.
Summary of the invention
In view of this, the invention provides a kind of N of preparation, the method for N-dimethylamino acetic ester, the method has avoided the vitriol oil as catalyzer, and transformation efficiency is high.
For achieving the above object, technical scheme of the present invention is:
Be the preparation method of the DMG ester (N, N-dimethylamino acetic ester) of catalyzer based on silica gel sulfonic acid: esterification is carried out in described reaction take Carboxylic acid and alcohol as raw material, obtain the DMG ester; The catalyzer of described esterification is silica gel sulfonic acid, and described carboxylic acid is the DMG (N, N-dimethylamino acetic acid) of molecular formula as shown in I, and the molecular formula of described alcohol is as shown in II, and the molecular formula of described DMG ester is as shown in III.Described esterification reaction temperature is according to the boiling point of described alcohol in reaction and fixed.
Wherein, described alcohol is the fatty alcohol with 1～12 carbon atom, and the carbon atom in the R in molecular formula II and molecular formula III equals 1～12.
When temperature increases, N, the esterification rate of N-dimethylamino ethanamide is accelerated.The boiling point that surpasses medium for the temperature that makes reaction, this step can carry out having under pressure condition, and for example atmosphere is pressed onto 10 normal atmosphere.
In aforesaid method, catalyzer silica gel sulfonic acid (SiO
2-OSO
3H) as catalyzer, described silica gel sulfonic acid obtains by the following method: react in silica gel and the chlorsulfonic acid medium take methylene dichloride as solvent, deviate from hydrogenchloride,, except desolventizing, obtain silica gel sulfonic acid; Be specially: add the silica gel powder such as 1000 gram dryings in reactor, then add the methylene dichloride such as 2000 grams, stir, slowly add a certain amount of chlorsulfonic acid.Add complete after, continue at room temperature to stir 2 hours, the hydrogen chloride gas water of emitting absorbs.Standing static, remove methylene dichloride, obtained the silica gel sulfonic acid of certain immobilized sulfonic acid, dry, as to analyze its sulfonic acid supported quantity, obtain catalyzer silica gel sulfonic acid with standby.Silica gel sulfonic acid also can be replaced other high temperature resistant colloid sulfonic acid catalyst of solid phase carrier the most.
As preferred scheme, in described preparation method, described sulfonic acid represents with the weight ratio of chlorsulfonic acid, and the mass ratio of chlorsulfonic acid and silica gel is 15-40:100; The mass ratio that is preferably described chlorsulfonic acid and silica gel is 15%, 25% or 40%; See embodiment three for details.
As preferred scheme, in described preparation method, described N, N-dimethylamino acetic acid is DMG, and its concrete preparation method is: hydroxyacetonitrile and dimethylamine are reacted in water medium, and add potassium hydroxide further to react in reaction system, obtain the ammonia solution of DMG sodium salt, obtain N after deamination, N-N-methylsarcosine salts solution, regulating pH is 5 ± 0.5, obtains DMG; Specifically with reference to embodiment one.Or formaldehyde, sodium cyanide and dimethylamine are reacted in water medium, obtaining the ammonia solution of DMG (sodium) salt, deamination obtains the DMG sodium salt solution, and regulating pH is 5 ± 0.5, obtains DMG.Specifically with reference to embodiment two.
As preferred scheme, in described preparation method, when stating carboxylic acid is N, during the N-N-methylsarcosine, described DMG, described pure and mild described silica gel sulfonic acid are mixed, stirring heating refluxes, the water that esterification generates is taken reaction system out of by band water component distillation, and residuum is N, N-dimethylamino acetic ester.
As preferred scheme, 2-6 time capable of circulation of described preparation method, in producing several times, only need the amount recirculation of single silica gel sulfonic acid is used.Recycling of silica gel sulfonic acid, not only reduced the consumption of catalyzer, and avoided the vitriol oil in the product preparation process of traditional esterification to the corrosion of equipment may.
Preferably, the mass ratio of described silica gel sulfonic acid and described DMG is 5～20:100.
Preferably, described alcohol is the straight chain with 1～10 carbon atom; Or the branched fatty alcohol of 1～12 carbon atom arranged; As use Virahol.
In above-mentioned reaction, when described alcohol was low-boiling point alcohol, DMG was preferably 1:4～7 with the mol ratio of alcohol; When described alcohol is high-boiling point alcohol, add a certain amount of band aqua in described high-boiling point alcohol, with the mass ratio of aqua and DMG, be preferably 1:0.4～1, DMG is preferably 1:2～5 with the mol ratio of alcohol.Generate water because esterification is reversible reaction, in order to improve transformation efficiency, band aqua commonly used is separated water from reaction system, and the band aqua comprises toluene, benzene etc.
With gained N, the sweet amino ester underpressure distillation of N-dimethyl, or column chromatography wash-out, obtain highly purified N, N-dimethylamino acetic ester.
Two of purpose of the present invention is to provide the new application of silica gel sulfonic acid, and this application can be avoided N, and in N-dimethylamino acetic ester preparation process, the vitriol oil is as catalytic erosion equipment.
For achieving the above object, technical scheme of the present invention is:
The application of silica gel sulfonic acid in the catalyzer of preparation esterification, described esterification is N, the esterification that N-dimethylamino acetic acid and alcohol carry out.
Beneficial effect of the present invention is: 1) catalyzer silica gel sulfonic acid is synthetic simple, and raw material cheaply is easy to get, and has high catalytic activity; 2) catalyzer can pass through the simple filtration recovery, saves and produces production cost; Do not need simultaneously complicated aftertreatment, reduced the generation of refuse; 3) use solid acid as esterifying catalyst, avoided the corrosion to equipment such as sulfuric acid, phosphoric acid; 4) yield of this technique is high, and transformation efficiency can reach more than 95%; And the subsequent disposal after reaction is completed is simple; 5) whole reaction of atomic good economy performance, except generating water without other generation of waste materials.
Embodiment
Be described in detail hereinafter with reference to the preferred embodiments of the present invention.The experimental technique of unreceipted actual conditions in preferred embodiment, usually according to normal condition.
In the present invention, the DMG ester quasi-molecule formula that relates to is as shown in III, wherein R is 1～12, as DMG isopropyl ester, N, N-N-methylsarcosine butyl ester, the own ester of DMG, DMG monooctyl ester, N, N-N-methylsarcosine certain herbaceous plants with big flowers ester, N, N-dimethyl lauryl glycines etc., specifically depend on the number of C atom in the alcohol of molecular formula as shown in II, and R is 1～12, further, described alcohol is the straight chain with 1～10 carbon atom; Or the branched fatty alcohol of 1～12 carbon atom arranged.Wherein, alcohol is divided into low-boiling point alcohol and high-boiling point alcohol, and described esterification reaction temperature is according to the boiling point of described alcohol in reaction and fixed.
Embodiment one: DMG synthetic
hydroxyacetonitrile method: at room temperature, add 1000 gram 40% hydroxyl acetonitrile aqueous solutions in autoclave, then pass into 1435 gram 33% dimethylamine agueous solutions, then be warming up to 60 ℃, pressure reaches 7 kilograms (mPa), react after 30 minutes, stopped reaction, reaction solution is changed in the flask of 3000ml, adding the potassium hydroxide aqueous solution of 786 grams 50% in reaction solution, in 80 ℃ of insulations 5 hours, obtain N, the ammonia solution of N-N-methylsarcosine salt, deamination obtains N, N-N-methylsarcosine salts solution, add subsequently 37% salt acid for adjusting pH to 5.0, obtain N, the mixed solution of N-N-methylsarcosine and Repone K.Add 8 gram activated carbon decolorizings, the suction filtration gac, filtrate is cooled to 10 ℃, crystallization, the centrifugal potassium chloride of removing, filtrate crystallization purifying according to a conventional method can obtain DMG solid 656 grams, and purity reaches more than 99%, and folding hundred rear yields reach 91%.
Synthesizing of embodiment two DMGs
Formaldehyde, sodium cyanide and dimethylamine three component S trecker methods: add 1000 gram 37% formalins and 2215 gram 30% sodium cyanide solutions in reactor, then slowly drip 3363 gram 33% dimethylamine agueous solutions, dropwise, be warming up to 80 ℃, reacted 5 hours, obtain the ammonia solution of DMG sodium salt, deamination obtains N, N-N-methylsarcosine sodium salt solution, add subsequently 98% sulphur acid for adjusting pH to 5.0, obtain the mixed solution of DMG and sodium sulfate.Add 6 gram activated carbon decolorizings, the suction filtration gac, filtrate is cooled to 10 ℃, crystallization, the centrifugal sodium sulfate crystal of removing, filtrate crystallization purifying according to a conventional method can obtain N, N-N-methylsarcosine solid 646 grams, purity reaches more than 99%, and folding hundred rear yields reach 89%.
Embodiment three: the preparation of catalyzer silica gel sulfonic acid
The silica gel that adds 1000 gram 200～300 order dryings in reactor, then add the methylene dichloride of 2000 grams, and stirring at room, slowly add a certain amount of chlorsulfonic acid.Add complete after, continue at room temperature to stir 2 hours, the hydrogen chloride gas water of emitting absorbs.Static, remove methylene dichloride, obtained the silica gel sulfonic acid of certain immobilized sulfonic acid, dry, as to analyze its sulfonic acid supported quantity, obtain catalyzer silica gel sulfonic acid with standby.Described sulfonic acid all can take the mass ratio of the weighing scale of chlorsulfonic acid and silica gel as 15-40%.
| Catalyzer | Chlorsulfonic acid (gram) | Supported quantity (mmol/g) |
| Silica gel sulfonic acid A | 150 | 1.28 |
| Silica gel sulfonic acid B | 250 | 2.14 |
| Silica gel sulfonic acid C | 400 | 3.40 |
Embodiment four: DMG isopropyl ester synthetic
The DMG that adds 207 grams in reactor, Virahol 840 grams and silica gel sulfonic acid A20.7 gram, stirring heating refluxes, and the reactor bottom heating and temperature control is at 115 ℃, and head temperature, at 75 ℃, was kept this situation 7 hours.The exclusive segment distillment, and with the fresh Virahol of same quantity, replace., with the residual quantity of high-efficient liquid phase analysis DMG, when DMG is residual, be no more than 1%, stopped reaction.Cooling, filtering catalyst silica gel sulfonic acid.Light constituent is removed under low pressure distillation.Temperature by increasing vaporizer and pressure is reduced to mmHg continue evaporation, obtain 279 gram DMG isopropyl esters (colourless liquid), and purity is greater than 99%, and yield is 96%.
| Catalyzer | Catalytic amount (gram) | Yield |
| Silica gel sulfonic acid B | 10.35 | 96% |
| Silica gel sulfonic acid C | 10.35 | 97% |
Embodiment five: DMG butyl ester synthetic
The DMG that adds 207 grams in reactor, propyl carbinol 814 grams and silica gel sulfonic acid B 10.35 grams, stirring heating refluxes, and the reactor bottom heating and temperature control is at 115 ℃, and head temperature, at 75 ℃, was kept this situation 5 hours.The exclusive segment distillment, and with the fresh propyl carbinol of same quantity, replace., with the residual quantity of high-efficient liquid phase analysis DMG, when DMG is residual, be no more than 1%, stopped reaction.Cooling, filtering catalyst silica gel sulfonic acid.Light constituent is removed under low pressure distillation.Temperature by increasing vaporizer and pressure is reduced to mmHg continue evaporation, obtain the 303 positive butyl esters of gram DMG (colourless liquid), and purity is greater than 99%, and yield is 95%.
Embodiment six: the own ester of DMG synthetic
The DMG that adds 207 grams in reactor, the toluene of 500ml, n-hexyl alcohol 1020 grams and silica gel sulfonic acid B10.35 gram, stirring heating refluxes, and the reactor bottom heating and temperature control is at 115 ℃, and head temperature, at 75 ℃, was kept this situation 5 hours.The exclusive segment distillment., with the residual quantity of high-efficient liquid phase analysis DMG, when DMG is residual, be no more than 1%, stopped reaction.Cooling, filtering catalyst silica gel sulfonic acid.Light constituent is removed under low pressure distillation.Temperature by increasing vaporizer and pressure is reduced to mmHg continue evaporation, obtain the 377 just own esters of gram DMG (colourless liquid), and purity is greater than 99%, and yield is 92%.
Embodiment seven: DMG monooctyl ester synthetic
The DMG that adds 207 grams in reactor, the toluene of 500ml, n-Octanol 1040 grams and silica gel sulfonic acid B10.35 gram, stirring heating refluxes, and the exclusive segment distillment, held this situation 5 hours.With the residual quantity of high-efficient liquid phase analysis DMG, be no more than 1% when DMG is residual, stopped reaction, cooling, filtering catalyst silica gel sulfonic acid.Light constituent is removed under low pressure distillation.Temperature by increasing vaporizer and pressure is reduced to mmHg continue evaporation, obtain the 387 just own esters of gram DMG (colourless liquid), and purity is greater than 99%, and yield is 90%.
Embodiment eight: DMG certain herbaceous plants with big flowers ester synthetic
The DMG that adds 207 grams in reactor, the toluene of 500ml, positive certain herbaceous plants with big flowers alcohol 1264 grams and silica gel sulfonic acid B10.35 gram, stirring heating refluxes, and the exclusive segment distillment, held this situation 5 hours.With the residual quantity of high-efficient liquid phase analysis DMG, be no more than 1% when DMG is residual, stopped reaction, cooling, filtering catalyst silica gel sulfonic acid.Light constituent is removed under low pressure distillation.Residue is through rapid column chromatography (silica gel is the 100-300 order), and ethyl acetate, as eluent, is steamed except eluent, obtains 460 gram DMG certain herbaceous plants with big flowers esters (colourless liquid), and purity is greater than 99%, and yield is 88%.
Embodiment nine: DMG lauryl synthetic
The DMG that adds 207 grams in reactor, the toluene of 500ml, positive certain herbaceous plants with big flowers alcohol 1116 grams and silica gel sulfonic acid B10.35 gram, stirring heating refluxes, and the exclusive segment distillment, held this situation 7 hours.With the residual quantity of high-efficient liquid phase analysis DMG, be no more than 1% when DMG is residual, stopped reaction, cooling, filtering catalyst silica gel sulfonic acid.Light constituent is removed under low pressure distillation.Residue is through rapid column chromatography (silica gel is the 100-300 order), and ethyl acetate, as eluent, is steamed except eluent, obtains 477 gram DMG lauryls (colourless liquid), and purity is greater than 99%, and yield is 88%.
Embodiment ten: the recycled of catalyzer silica gel sulfonic acid B
The DMG that adds 207 grams in reactor, Virahol 840 grams and silica gel sulfonic acid B10.35 gram, stirring heating refluxes, and the reactor bottom heating and temperature control is at 115 ℃, and head temperature, at 75 ℃, was kept this situation 7 hours.The exclusive segment distillment, and with the fresh Virahol of same quantity, replace., with the residual quantity of high-efficient liquid phase analysis DMG, when DMG is residual, be no more than 1%, stopped reaction.Cooling, filtering catalyst silica gel sulfonic acid, oven dry, recycled.Light constituent is removed under low pressure distillation.Temperature by increasing vaporizer and pressure is reduced to mmHg continue evaporation, obtain 279 gram DMG isopropyl esters (colourless liquid), and purity is greater than 99%, and yield is 96%.
| Recycle number of times | Catalytic amount (gram) | Yield (%) |
| 1 | 10.35 | 96 |
| 2 | 10.35 | 96 |
| 3 | 10.35 | 96 |
| 4 | 10.35 | 96 |
| 5 | 10.35 | 96 |
| 6 | 10.35 | 95 |
| 7 | 10.35 | 94 |
| 8 | 10.35 | 90 |
[0053] Front 6 times of catalyzer silica gel sulfonic acid B circulation, the activity of catalyzer does not reduce, when recycling the 8th time, its N, the yield of N-N-methylsarcosine isopropyl ester obviously reduces, its reason is the increase along with cycle index, and immobilized sulfonic acid group on silica gel has occurred partly to come off, and causes its catalytic activity and descends.
Explanation is finally, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although with reference to preferred embodiment, the present invention is had been described in detail, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement technical scheme of the present invention, and not breaking away from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (11)
1. be the preparation method of the DMG ester of catalyzer based on silica gel sulfonic acid: esterification is carried out in described reaction take Carboxylic acid and alcohol as raw material, obtain the DMG ester; It is characterized in that: the catalyzer of described esterification is silica gel sulfonic acid, and described carboxylic acid is the DMG of molecular formula as shown in I, and the molecular formula of described alcohol is as shown in II, and the molecular formula of described DMG ester is as shown in III;
Wherein, described alcohol is the fatty alcohol with 1～12 carbon atom, and the carbon atom in the R in molecular formula II and molecular formula III equals 1～12.
2. preparation method according to claim 1, is characterized in that, described silica gel sulfonic acid obtains by the following method: react in silica gel and the chlorsulfonic acid medium take methylene dichloride as solvent, deviate from hydrogenchloride,, except desolventizing, obtain silica gel sulfonic acid.
3. preparation method according to claim 2, it is characterized in that: described sulfonic acid is in chlorsulfonic acid, and the mass ratio of chlorsulfonic acid and silica gel is 15-40:100.
4. preparation method according to claim 2, it is characterized in that: the preparation method of described DMG is:
Hydroxyacetonitrile and dimethylamine are reacted in water medium, the quaternization system, obtain the ammonia solution of DMG sodium salt, after deamination the DMG salts solution, regulating pH is 5 ± 0.5, obtains DMG;
Or formaldehyde, sodium cyanide and dimethylamine are reacted in water medium, obtaining the ammonia solution of DMG sodium salt, deamination obtains the DMG salts solution, and regulating pH is 5 ± 0.5, obtains DMG.
5. preparation method according to claim 1, is characterized in that: described DMG, described pure and mild described silica gel sulfonic acid are mixed, stir, reflux, the water that reaction generates is taken reaction system out of by band water component distillation, residuum is the DMG ester.
6. preparation method according to claim 1, is characterized in that: described silica gel sulfonic acid recirculation use 1-6 time.
7. preparation method according to claim 5, it is characterized in that: the mass ratio of described silica gel sulfonic acid and described DMG is 5～20:100.
8. preparation method according to claim 5, it is characterized in that: described alcohol is the straight chain fatty alcohol with 1～10 carbon atom; Or the branched fatty alcohol of 1～12 carbon atom arranged.
9. preparation method according to claim 8, it is characterized in that: when described alcohol was low-boiling point alcohol, the mol ratio of described DMG and described alcohol was 1:4～7; When described alcohol is high-boiling point alcohol, adding a certain amount of band aqua in described high-boiling point alcohol, is 1:0.4～1 with the mass ratio of aqua and DMG, and DMG is 1:2～5 with the mol ratio of alcohol.
10. preparation method according to claim 1 is characterized in that: gained DMG ester is purified, and the mode of described purification is underpressure distillation or column chromatography wash-out, obtains highly purified N, N-dimethylamino acetic ester.
11. the application of silica gel sulfonic acid in the catalyzer of preparation esterification, it is characterized in that: described esterification is N, the esterification that N-dimethylamino acetic acid and alcohol carry out.
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| CN103880691A (en) * | 2014-04-03 | 2014-06-25 | 重庆紫光国际化工有限责任公司 | Clean and environment-friendly production method of N,N-dialkylglycine |
| CN104610078A (en) * | 2014-10-27 | 2015-05-13 | 河北诚信有限责任公司 | Method for preparing high-purity N,N-dimethyl glycine |
| CN105521823A (en) * | 2016-01-07 | 2016-04-27 | 哈尔滨理工大学 | Mesoporous-silica-gel surface bonded alkylsulfonic acid catalyst and preparation and catalysis methods therefor |
| CN108410437A (en) * | 2018-05-09 | 2018-08-17 | 天津市大港渤中石油助剂有限公司 | Drilling fluid sealing agent low Poison sulfonated gilsonite |
| CN109467515A (en) * | 2018-10-11 | 2019-03-15 | 南京红杉生物科技有限公司 | The synthetic method of intermediate l-Alanine isopropyl ester hydrochloride |
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2013
- 2013-07-24 CN CN2013103136390A patent/CN103396330A/en active Pending
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880691A (en) * | 2014-04-03 | 2014-06-25 | 重庆紫光国际化工有限责任公司 | Clean and environment-friendly production method of N,N-dialkylglycine |
| CN104610078A (en) * | 2014-10-27 | 2015-05-13 | 河北诚信有限责任公司 | Method for preparing high-purity N,N-dimethyl glycine |
| CN104610078B (en) * | 2014-10-27 | 2017-07-11 | 河北诚信有限责任公司 | One kind prepares high purity N, the method for N dimethylglycines |
| CN105521823A (en) * | 2016-01-07 | 2016-04-27 | 哈尔滨理工大学 | Mesoporous-silica-gel surface bonded alkylsulfonic acid catalyst and preparation and catalysis methods therefor |
| CN108410437A (en) * | 2018-05-09 | 2018-08-17 | 天津市大港渤中石油助剂有限公司 | Drilling fluid sealing agent low Poison sulfonated gilsonite |
| CN109467515A (en) * | 2018-10-11 | 2019-03-15 | 南京红杉生物科技有限公司 | The synthetic method of intermediate l-Alanine isopropyl ester hydrochloride |
| CN109467515B (en) * | 2018-10-11 | 2021-08-13 | 南京红杉生物科技有限公司 | Synthesis method of intermediate L-alanine isopropyl ester hydrochloride |
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Application publication date: 20131120 |