CN102643299B - Method for preparing aliphatic boric acid by ethylene diamine tetraacetic acid (EDTA) trisodium salt - Google Patents
Method for preparing aliphatic boric acid by ethylene diamine tetraacetic acid (EDTA) trisodium salt Download PDFInfo
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Abstract
The invention belongs to the technical field of chemical industry. A method for preparing aliphatic boric acid by ethylene diamine tetraacetic acid (EDTA) trisodium salt includes adding a solution of a Grignard reagent into double alkyl substituted amino boron chloride at the temperature between 5 DEG C below zero and 0 DEG C and obtaining a mixture, stirring the mixture for 2-3 hours at the room temperature after the addition, adding an aqueous solution of the EDTA trisodium salt at the temperature between 0 DEG C and 10 DEG C after a reaction until the solution is clear and layered, dropwise adding concentrated hydrochloric acid at the temperature of aqueous layers between 0-10 DEG C, adjusting potential of hydrogen (pH) of the solution ranges from 2 to 3, precipitating white solids of EDTA during the period, filtering and recycling the white solids of EDTA, extracting a filter liquor by an organic solvent 1, obtaining a crude product by concentrating an organic layer, dissolving repeatedly by adding an organic solvent 2, removing undissolved substances by a filtration, concentrating a filter liquor, pulping by a non-polar varsol, filtering and drying to obtain an organic boric acid. The method for preparing the aliphatic boric acid by the ethylene diamine tetraacetic acid (EDTA) trisodium salt has the advantages that the method is safe and environmental-friendly, the cost is low, the used EDTA trisodium salt is easy to recycle to obtain the EDTA, and the recycle rate is high, thereby the method is suitable for the industrialized production.
Description
Technical field
The invention belongs to chemical technology field, relate to a kind of sequestrant EDTA trisodium salt and be applied in the method for synthesizing in organic boronic.
Background technology
For micromolecular aliphatic category boric acid as methyl-boron-dihydroxide, ethyl-boron dihydroxide, usually adopt Grignard reagent or lithium reagent and boric acid lipid to react under the cold condition of about-78 DEG C, acidified and purifying obtains product.But easily produce trimethyl-boron or the boron triethyl of spontaneous combustion in reaction process, before acidifying, trialkylboron is exist with the form of complex compound in the basic conditions, dissociates out, easily cause and catch fire after acidifying.There is following shortcoming in this way: temperature condition is harsh, yield is lower, and easily produces the pyrophoric gas of corresponding trimethylammonium borine or boron triethyl in the process of acidifying, causes and catches fire, there is potential safety hazard, this fatefulue shortcoming limits suitability for industrialized production.
Summary of the invention
The object of the invention is to solve the problem, provide a kind of EDTA trisodium salt to prepare the method for fats boric acid, temperature of reaction easily reaches, and yield is high, and process safety is reliable, is suitable for suitability for industrialized production.
The technical scheme that the present invention is used for achieving the above object is: a kind of EDTA trisodium salt prepares the method for fats boric acid, under-5 DEG C ~ 0 DEG C temperature condition, the solution of Grignard reagent is added drop-wise in two alkyl-substituted amino boron chloride, drip complete stirring at room temperature 2 ~ 3 hours, at reaction terminates latter 0 DEG C ~ 10 DEG C, the aqueous solution adding EDTA trisodium salt is clarified to solution, layering, dripping concentrated hydrochloric acid acid adjustment to solution ph at water layer 0 ~ 10 DEG C is 2 ~ 3, period separates out white solid EDTA, filter, white solid EDTA reclaims, filtrate organic solvent 1 extracts, organic layer concentrates to obtain crude product, add organic solvent 2 heavy molten, filtering insolubles, filtrate concentrates, non-polar hydrocarbon kind solvent is pulled an oar, filter, obtain organic boronic.
Described fats boric acid is methyl-boron-dihydroxide or ethyl-boron dihydroxide.
The solution of described Grignard reagent be the tetrahydrofuran solution of methyl Grignard, the tetrahydrofuran solution of ethyl Grignard reagent or.
Described pair of alkyl-substituted amino boron chloride is two dimethylamino boron chlorides or two diisopropylaminoethyl boron chloride.
Described Grignard reagent is 1 ~ 1.5:1 with the mol ratio of two amino boron chloride, and wherein 1:1 is best.
The mol ratio of described EDTA trisodium salt and Grignard reagent is 1:1.
The mass concentration of the described EDTA trisodium salt aqueous solution is 25% ~ 35%.
Described organic solvent 1 is methyl tertiary butyl ether, ethyl acetate or 2-methyltetrahydrofuran.
Described organic solvent 2 is tetrahydrofuran (THF) or methyl tertiary butyl ether.
Described non-polar hydrocarbon kind solvent is normal heptane or normal hexane.
Use in the present invention EDTA trisodium salt mechanism: EDTA (ethylenediamine tetraacetic acid (EDTA)) and EDETATE SODIUM salt can carry out complexing with magnesium ion, generate water-soluble products, water-soluble poor due to EDTA, its natrium brine dissolubility is good, wherein EDETATE SODIUM salt brine solution shows slightly acidic pH value and is about 4-6, the aobvious weakly alkaline pH value of the EDTA trisodium salt aqueous solution is that the aobvious strong basicity pH value of 7-8, the EDTA tetra-na salt aqueous solution is for being greater than 12.
Exist with the form of complex compound in the basic conditions to make to prepare the pyrophoric gas trialkylborane produced in small molecules fats boric acid, avoid spilling of dissociating, the present invention have selected water-soluble good weakly alkaline EDTA trisodium salt and magnesium ion and carries out complexing and generate water-soluble products.Do not select the reason of EDTA tetra-na salt to be that its aobvious strong basicity, produces throw out with magnesium ion, make reaction cannot layering; The reason of EDETATE DISODIUM is not selected to be that it is aobvious acid, and trialkylborane can be made to overflow.Thus before making small molecules fats boric acid aftertreatment acidifying, the complex compound of trimethyl-boron is stayed in organic phase, aqueous phase, at aqueous phase, is carried out acidifying and obtains product methyl-boron-dihydroxide, avoid the spilling of trimethyl-boron, eliminate potential safety hazard by borate like this.
To sum up useful achievement of the present invention is: temperature of reaction is-5 DEG C ~ 0 DEG C-and easily reaches, avoid deep cooling low temperature, yield is high, and EDTA used is recyclable to be reused, and process safety is reliable, is suitable for suitability for industrialized production.
embodiment:
Below by specific examples, the present invention is further detailed, but is not limited to the content of specific embodiment.
Embodiment 1
A kind of EDTA trisodium salt prepares the method for fats boric acid; to in the 1L four-hole bottle of magnetic agitation; under argon shield, add 67.2g dimethylamino boron chloride (0.50mol, 1eq); tetrahydrofuran solution (the 2.0mmol/g of 250g methylmagnesium-chloride is loaded in dropping funnel; 0.50mol, 1eq), drip Grignard reagent at 0 ~-5 DEG C; 3h drips complete, insulation 2h.Temperature control 0 ~ 10 DEG C, drips 627g 30%EDTA trisodium-salt solution, precipitates and tail off gradually in reaction solution, drip and finish, solution clarification after stirring at room temperature 1h, and pH value about 8 is static.Layering, drips 161g concentrated hydrochloric acid adjust ph to about 2 ~ 3 at water layer 0 ~ 10 DEG C, filter, filtrate MTBE extracts (300g × 6), concentrate and to obtain crude product, add 20gTHF and weigh molten, filtering insolubles, filtrate concentrates, 35g normal hexane is pulled an oar, and filters, dry white products methyl-boron-dihydroxide 16.8g, GC:98%, yield: 56.1%.
Embodiment 2
A kind of EDTA trisodium salt prepares the method for fats boric acid; to in the 1L four-hole bottle of magnetic agitation; under argon shield, add 123.0g diisopropylaminoethyl boron chloride (0.50mol, 1eq); tetrahydrofuran solution (the 2.0mmol/g of 250g methylmagnesium-chloride is loaded in dropping funnel; 0.50mol, 1eq), drip Grignard reagent at 0 ~-5 DEG C; 3h drips complete, insulation 2h.Temperature control 0 ~ 10 DEG C, drips 627g 30%EDTA trisodium-salt solution, precipitates and tail off gradually in reaction solution, drip and finish, solution clarification after stirring at room temperature 1h, and pH value about 8 is static.Layering, drips 168g concentrated hydrochloric acid adjust ph to about 2 ~ 3 at water layer 0 ~ 10 DEG C, filter, filtrate MTBE extracts (300g × 6), concentrate to obtain crude product, add 45g methyl tertiary butyl ether, filtering insolubles, filtrate concentrates, 35g normal hexane is pulled an oar, and filters, dry white products methyl-boron-dihydroxide 16.1g, GC:> 98%, yield: 53.8%.
Embodiment 3
A kind of EDTA trisodium salt prepares the method for fats boric acid; to in the 1L four-hole bottle of magnetic agitation; under argon shield, add 67.2g dimethylamino boron chloride (0.50mol, 1eq); tetrahydrofuran solution (the 2.0mmol/g of 375g methylmagnesium-chloride is loaded in dropping funnel; 0.75mol, 1.5eq), drip Grignard reagent at 0 ~-5 DEG C; 3h drips complete, insulation 2h.Temperature control 0 ~ 10 DEG C, drips 940.5g 30%EDTA trisodium-salt solution, precipitates and tail off gradually in reaction solution, drip and finish, solution clarification after stirring at room temperature 1h, and pH value about 8 is static.Layering, drips 241.5g concentrated hydrochloric acid adjust ph to about 2 ~ 3 at water layer 0 ~ 10 DEG C, filter, filtrate MTBE extracts (300g × 6), concentrate and to obtain crude product, add 20gTHF and weigh molten, filtering insolubles, filtrate concentrates, 35g normal hexane is pulled an oar, and filters, dry white products methyl-boron-dihydroxide 15.1g, GC:98%, yield: 50.5%.
Embodiment 4
A kind of EDTA trisodium salt prepares the method for fats boric acid; to in the 1L four-hole bottle of magnetic agitation; under argon shield, add 67.2g dimethylamino boron chloride (0.50mol, 1eq); tetrahydrofuran solution (the 2.0mmol/g of 300g methylmagnesium-chloride is loaded in dropping funnel; 0.60mol, 1eq), drip Grignard reagent at 0 ~-5 DEG C; 3h drips complete, insulation 2h.Temperature control 0 ~ 10 DEG C, drips 627g 30%EDTA trisodium-salt solution, precipitates and tail off gradually in reaction solution, drip and finish, solution clarification after stirring at room temperature 1h, and pH value about 8 is static.Layering, drips 161g concentrated hydrochloric acid adjust ph to about 2 ~ 3 at water layer 0 ~ 10 DEG C, filter, filtrate extraction into ethyl acetate (300g × 6), concentrate and to obtain crude product, add 20gTHF and weigh molten, filtering insolubles, filtrate concentrates, 35g normal hexane is pulled an oar, and filters, dry white products methyl-boron-dihydroxide 17.2g, GC:98%, yield: 57.4%.
Embodiment 5
A kind of EDTA trisodium salt prepares the method for fats boric acid; to in the 1L four-hole bottle of magnetic agitation; under argon shield, add 123.0g diisopropylaminoethyl boron chloride (0.50mol, 1eq); tetrahydrofuran solution (the 2.0mmol/g of 250g methylmagnesium-chloride is loaded in dropping funnel; 0.50mol, 1eq), drip Grignard reagent at 0 ~-5 DEG C; 3h drips complete, insulation 2h.Temperature control 0 ~ 10 DEG C, drips 627g 30%EDTA trisodium-salt solution, precipitates and tail off gradually in reaction solution, drip and finish, solution clarification after stirring at room temperature 1h, and pH value about 8 is static.Layering, drips 168g concentrated hydrochloric acid adjust ph to about 2 ~ 3 at water layer 0 ~ 10 DEG C, filter, filtrate 2-methyltetrahydrofuran extraction (300g × 6), concentrate to obtain crude product, add 45g methyl tertiary butyl ether, filtering insolubles, filtrate concentrates, 35g normal heptane is pulled an oar, and filters, dry white products methyl-boron-dihydroxide 16.4g, GC:> 98%, yield: 54.8%.
Embodiment 6
A kind of EDTA trisodium salt prepares the method for fats boric acid; to in the 1L four-hole bottle of magnetic agitation; under argon shield, add 67.2g dimethylamino boron chloride (0.50mol, 1eq); tetrahydrofuran solution (the 2.5mmol/g of 200g ethylmagnesium bromide is loaded in dropping funnel; 0.50mol, 1eq), drip Grignard reagent at 0 ~-5 DEG C; 3h drips complete, insulation 2h.Temperature control 0 ~ 10 DEG C, drips 627g 30%EDTA trisodium-salt solution, precipitates and tail off gradually in reaction solution, drip and finish, solution clarification after stirring at room temperature 1h, and pH value about 8 is static.Layering, drips 154g concentrated hydrochloric acid adjust ph to about 2 ~ 3 at water layer 0 ~ 10 DEG C, filter, filtrate MTBE extracts (300g × 6), concentrate and to obtain crude product, add 20gTHF and weigh molten, filtering insolubles, filtrate concentrates, 35g normal hexane is pulled an oar, and filters, dry white products ethyl-boron dihydroxide 25.3g, GC:> 98%, yield: 68.3%.
Embodiment 7
A kind of EDTA trisodium salt prepares the method for fats boric acid; to in the 1L four-hole bottle of magnetic agitation; under argon shield, add 67.2g dimethylamino boron chloride (0.50mol, 1eq); tetrahydrofuran solution (the 2.5mmol/g of 200g ethylmagnesium bromide is loaded in dropping funnel; 0.50mol, 1eq), drip Grignard reagent at 0 ~-5 DEG C; 3h drips complete, insulation 2h.Temperature control 0 ~ 10 DEG C, drips 627g 30%EDTA trisodium-salt solution, precipitates and tail off gradually in reaction solution, drip and finish, solution clarification after stirring at room temperature 1h, and pH value about 8 is static.Layering, drips 154g concentrated hydrochloric acid adjust ph to about 2 ~ 3 at water layer 0 ~ 10 DEG C, filter, filtrate 2-methyltetrahydrofuran extraction (300g × 6), concentrate and to obtain crude product, add 45g methyl tertiary butyl ether and weigh molten, filtering insolubles, filtrate concentrates, 35g normal heptane is pulled an oar, and filters, dry white products ethyl-boron dihydroxide 26.4g, GC:> 98%, yield: 71.3%.
Embodiment 8
A kind of EDTA trisodium salt prepares the method for fats boric acid; to in the 1L four-hole bottle of magnetic agitation; under argon shield, add 123.0g diisopropylaminoethyl boron chloride (0.50mol, 1eq); tetrahydrofuran solution (the 2.5mmol/g of 200g ethylmagnesium bromide is loaded in dropping funnel; 0.50mol, 1eq), drip Grignard reagent at 0 ~-5 DEG C; 3h drips complete, insulation 2h.Temperature control 0 ~ 10 DEG C, drips 627g 30%EDTA trisodium-salt solution, precipitates and tail off gradually in reaction solution, drip and finish, solution clarification after stirring at room temperature 1h, and pH value about 8 is static.Layering, drips 170g concentrated hydrochloric acid adjust ph to about 2 ~ 3 at water layer 0 ~ 10 DEG C, filter, filtrate MTBE extracts (300g × 6), concentrate and to obtain crude product, add 45g methyl tertiary butyl ether and weigh molten, filtering insolubles, filtrate concentrates, 35g normal hexane is pulled an oar, and filters, dry white products methyl-boron-dihydroxide 24.9g, GC:> 98%, yield: 67.2%.
Embodiment 9
A kind of EDTA trisodium salt prepares the method for fats boric acid; to in the 1L four-hole bottle of magnetic agitation; under argon shield, add 123.0g diisopropylaminoethyl boron chloride (0.50mol, 1eq); tetrahydrofuran solution (the 2.5mmol/g of 300g ethylmagnesium bromide is loaded in dropping funnel; 0.75mol, 1eq), drip Grignard reagent at 0 ~-5 DEG C; 3h drips complete, insulation 2h.Temperature control 0 ~ 10 DEG C, drips 940.5g 30%EDTA trisodium-salt solution, precipitates and tail off gradually in reaction solution, drip and finish, solution clarification after stirring at room temperature 1h, and pH value about 8 is static.Layering, drips 255g concentrated hydrochloric acid adjust ph to about 2 ~ 3 at water layer 0 ~ 10 DEG C, filter, filtrate MTBE extracts (300g × 6), concentrate and to obtain crude product, add 20gTHF and weigh molten, filtering insolubles, filtrate concentrates, 35g normal hexane is pulled an oar, and filters, dry white products methyl-boron-dihydroxide 23.7g, GC:> 98%, yield: 64.0%.
Embodiment 10
A kind of EDTA trisodium salt prepares the method for fats boric acid; to in the 1L four-hole bottle of magnetic agitation; under argon shield, add 123.0g diisopropylaminoethyl boron chloride (0.50mol, 1eq); tetrahydrofuran solution (the 2.5mmol/g of 200g ethylmagnesium bromide is loaded in dropping funnel; 0.50mol, 1eq), drip Grignard reagent at 0 ~-5 DEG C; 3h drips complete, insulation 2h.Temperature control 0 ~ 10 DEG C, drips 627g 30%EDTA trisodium-salt solution, precipitates and tail off gradually in reaction solution, drip and finish, solution clarification after stirring at room temperature 1h, and pH value about 8 is static.Layering, drips 170g concentrated hydrochloric acid adjust ph to about 2 ~ 3 at water layer 0 ~ 10 DEG C, filter, filtrate extraction into ethyl acetate (300g × 6), concentrate and to obtain crude product, add 20gTHF and weigh molten, filtering insolubles, filtrate concentrates, 35g normal heptane is pulled an oar, and filters, dry white products methyl-boron-dihydroxide 25.4g, GC:> 98%, yield: 68.5%.
Claims (6)
1. prepare the method for fats boric acid with EDTA trisodium salt for one kind, it is characterized in that: under-5 DEG C ~ 0 DEG C temperature condition, the solution of Grignard reagent is joined in two alkyl-substituted amino boron chloride, add complete stirring at room temperature 2 ~ 3 hours, at reaction terminates latter 0 DEG C ~ 10 DEG C, the aqueous solution adding EDTA trisodium salt is clarified to solution, layering, dripping concentrated hydrochloric acid acid adjustment to solution ph at water layer 0 ~ 10 DEG C is 2 ~ 3, period separates out white solid EDTA, filter, white solid EDTA reclaims, filtrate organic solvent 1 extracts, organic layer concentrates to obtain crude product, add organic solvent 2 heavy molten, filtering insolubles, filtrate concentrates, non-polar hydrocarbon kind solvent is pulled an oar, filter, dry organic boronic,
The solution of wherein said Grignard reagent is the tetrahydrofuran solution of methylmagnesium-chloride or the tetrahydrofuran solution of ethylmagnesium bromide;
Described pair of alkyl-substituted amino boron chloride is dimethylamino boron chloride or diisopropylaminoethyl boron chloride;
Described organic solvent 1 is methyl tertiary butyl ether, ethyl acetate or 2-methyltetrahydrofuran;
Described organic solvent 2 is tetrahydrofuran (THF) or methyl tertiary butyl ether;
Described non-polar hydrocarbon kind solvent is normal heptane or normal hexane.
2. a kind of EDTA trisodium salt according to claim 1 prepares the method for fats boric acid, it is characterized in that: fats boric acid is methyl-boron-dihydroxide or ethyl-boron dihydroxide.
3. a kind of EDTA trisodium salt according to claim 1 prepares the method for fats boric acid, it is characterized in that: Grignard reagent is 1 ~ 1.5:1 with the mol ratio of two alkyl-substituted amino boron chloride.
4. a kind of EDTA trisodium salt according to claim 1 prepares the method for fats boric acid, it is characterized in that: Grignard reagent is 1:1 with the mol ratio of two alkyl-substituted amino boron chloride.
5. a kind of EDTA trisodium salt according to claim 1 prepares the method for fats boric acid, it is characterized in that: the mol ratio of EDTA trisodium salt and Grignard reagent is 1:1.
6. a kind of EDTA trisodium salt according to claim 1 prepares the method for fats boric acid, it is characterized in that: the concentration of the EDTA trisodium salt aqueous solution is 25% ~ 35%.
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CN103030660A (en) * | 2012-12-20 | 2013-04-10 | 大连联化化学有限公司 | Technological method for synthesizing methylboronic acid |
CN104163825B (en) * | 2013-05-20 | 2016-09-28 | 重庆圣华曦药业股份有限公司 | A kind of methyl-boric acid preparation method of improvement |
CN105153210A (en) * | 2015-07-22 | 2015-12-16 | 蚌埠中实化学技术有限公司 | Preparation method for isobutaneboronic acid |
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Non-Patent Citations (4)
Title |
---|
Preparation of some organo-bis(diisopropylamino)boranes and their application to the synthesis of oxazaborolidines;P.Y.Chavant et al;《Journal of Organometallic Chemistry》;19921221;第455卷;第37-46页 * |
取代基苯硼酸的合成与应用进展;蒋欢妹等;《材料导报》;20070501;第21卷(第5A期);第223-226页 * |
高产率制备甲基硼酸;李恒光等;《化学试剂》;19970628;第19卷(第3期);第185页和第149页 * |
黄世文等.杂芳基硼化合物的合成.《武汉大学学报(自然科学版)》.1999,第45卷(第2期),第160-164页. * |
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