CN117402184B - Preparation method of diethyl methoxyborane - Google Patents
Preparation method of diethyl methoxyborane Download PDFInfo
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- CN117402184B CN117402184B CN202311723737.1A CN202311723737A CN117402184B CN 117402184 B CN117402184 B CN 117402184B CN 202311723737 A CN202311723737 A CN 202311723737A CN 117402184 B CN117402184 B CN 117402184B
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- FESAXEDIWWXCNG-UHFFFAOYSA-N diethyl(methoxy)borane Chemical compound CCB(CC)OC FESAXEDIWWXCNG-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 54
- 239000007788 liquid Substances 0.000 claims abstract description 95
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims abstract description 82
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 66
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- LTPNVDMBVZGYRA-UHFFFAOYSA-L [Na+].[Na+].[O-][AsH]([O-])=O Chemical compound [Na+].[Na+].[O-][AsH]([O-])=O LTPNVDMBVZGYRA-UHFFFAOYSA-L 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 34
- -1 arsine sodium acetate Chemical compound 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 18
- 238000003860 storage Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 238000013112 stability test Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000002572 peristaltic effect Effects 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 3
- 229910000085 borane Inorganic materials 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- FJLGEFLZQAZZCD-MCBHFWOFSA-M (3R,5S)-fluvastatin(1-) Chemical compound C12=CC=CC=C2N(C(C)C)C(\C=C\[C@@H](O)C[C@@H](O)CC([O-])=O)=C1C1=CC=C(F)C=C1 FJLGEFLZQAZZCD-MCBHFWOFSA-M 0.000 description 1
- MHUWZNTUIIFHAS-XPWSMXQVSA-N 9-octadecenoic acid 1-[(phosphonoxy)methyl]-1,2-ethanediyl ester Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C\CCCCCCCC MHUWZNTUIIFHAS-XPWSMXQVSA-N 0.000 description 1
- XUKUURHRXDUEBC-KAYWLYCHSA-N Atorvastatin Chemical compound C=1C=CC=CC=1C1=C(C=2C=CC(F)=CC=2)N(CC[C@@H](O)C[C@@H](O)CC(O)=O)C(C(C)C)=C1C(=O)NC1=CC=CC=C1 XUKUURHRXDUEBC-KAYWLYCHSA-N 0.000 description 1
- XUKUURHRXDUEBC-UHFFFAOYSA-N Atorvastatin Natural products C=1C=CC=CC=1C1=C(C=2C=CC(F)=CC=2)N(CCC(O)CC(O)CC(O)=O)C(C(C)C)=C1C(=O)NC1=CC=CC=C1 XUKUURHRXDUEBC-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- DFOTYIBNFBKXBR-UHFFFAOYSA-N CCBOC Chemical compound CCBOC DFOTYIBNFBKXBR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940124350 antibacterial drug Drugs 0.000 description 1
- 229960005370 atorvastatin Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960003765 fluvastatin Drugs 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- BPRHUIZQVSMCRT-VEUZHWNKSA-N rosuvastatin Chemical compound CC(C)C1=NC(N(C)S(C)(=O)=O)=NC(C=2C=CC(F)=CC=2)=C1\C=C\[C@@H](O)C[C@@H](O)CC(O)=O BPRHUIZQVSMCRT-VEUZHWNKSA-N 0.000 description 1
- 229960000672 rosuvastatin Drugs 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229940047047 sodium arsenate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention provides a preparation method of diethyl methoxyborane, and belongs to the field of diethyl methoxyborane. The preparation method of the diethyl methoxyborane comprises the following steps: preparing a first liquid, preparing a second liquid and reacting; selecting ethylene glycol dimethyl ether as a solvent, and adding triethylboron to prepare a first liquid; adding arsonic acid sodium salt into ethylene glycol dimethyl ether containing methanol to prepare a second liquid; the first liquid and the second liquid are contacted and reacted to prepare the diethyl methoxyborane solution. The preparation method of the diethyl methoxyborane can effectively improve the purity and the yield of the prepared diethyl methoxyborane product, further improve the stability of the prepared diethyl methoxyborane product and can be stably stored for a long time.
Description
Technical Field
The invention relates to the field of diethyl methoxyborane, in particular to a preparation method of diethyl methoxyborane.
Background
The reduction of organic substances such as esters, acids or ketones to alcohols, and the reduction of amides, nitriles or imides to amines are key transformations for the development of drugs, such as the preparation of antibacterial drugs, key intermediates for certain veterinary drugs, etc. The aforementioned reduction reactions are difficult to accomplish under specific conditions, and there is a general need in the art to employ related means capable of reducing the aforementioned organic substrates, particularly esters and amides, and lower boranes can be used as reducing agents in the aforementioned organic syntheses to solve the aforementioned problems.
However, in the conventional lower boranes, diborane is liable to spontaneously ignite as a gas, unstable in nature, and easily oxidized to form higher boranes, and further reduced in reducibility, and generally needs to be stored under anhydrous and anaerobic conditions, which is very unfavorable for use. The triethylboron is used as a substitute thereof, so that the stability is greatly improved, the transportation, the storage and the use are facilitated, and the triethylboron is widely applicable to various scientific research projects at present; however, triethylboron is still relatively active as an organoboride, and the practical use performance under specific conditions is still not ideal.
Diethyl methoxyborane (diethylmethoxyborane, CAS 7397-46-8) of the formula C 5H13 BO. The diethyl methoxyborane can be used as a reducing agent in organic synthesis, and various defects of diborane and triethylboron can be avoided. Meanwhile, the diethyl methoxyborane has wide application in the aspects of asymmetric reduction, asymmetric catalytic coupling, free radical reaction and the like. In addition, diethyl methoxyborane can also act as a non-corresponding selective reducing agent, capable of reducing beta-hydroxy ketone to diol; is used in the synthesis of active pharmaceutical ingredients such as atorvastatin, rosuvastatin, fluvastatin, etc.
However, the existing production process of diethyl methoxyborane has the defects that the purity and yield of the prepared diethyl methoxyborane product are not ideal; meanwhile, the diethyl methoxyborane product has poor stability and cannot be stably stored for a long time.
Chinese patent CN103483366a provides a process for preparing diethyl methoxyborane, which comprises adding an ether solution of magnesium and boron trifluoride under nitrogen protection, then adding bromoethane, and dropping the reactant into an ether solution containing methanol after the reaction is completed, thereby obtaining diethyl methoxyborane. According to the preparation method of the ethylmethoxy borane, the prepared product contains partial impurities, and the purity and stability of the product are low; and may affect the production efficiency in the actual production process.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention aims to provide a preparation method of diethyl methoxyborane, which can effectively improve the purity and yield of the prepared diethyl methoxyborane product, further improve the stability of the prepared diethyl methoxyborane product and can be stably stored for a long time.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
The preparation method of the diethyl methoxyborane comprises the following steps: preparing a first liquid, preparing a second liquid and reacting;
The method for preparing the first liquid comprises the steps of uniformly mixing triethylboron and ethylene glycol dimethyl ether to prepare the first liquid;
adding methanol into ethylene glycol dimethyl ether, continuously adding arsine sodium acetate, and uniformly mixing to obtain a second liquid;
the method of the reaction is that the first liquid is added into the second liquid; after the first liquid is added, the reaction is continued, and solids are separated and removed to prepare the diethyl methoxyborane solution.
Preferably, in the preparation method, the weight percentage content of each raw material is as follows:
67-71% of ethylene glycol dimethyl ether;
Triethylboron 20%;
8% of methanol;
1-5% of arsonic acid sodium acetate.
Preferably, in the preparation of the first liquid, the weight ratio of the triethylboron to the ethylene glycol dimethyl ether is 1:2.35-2.55.
Preferably, in the preparation of the second liquid, the weight ratio of the methanol to the ethylene glycol dimethyl ether is 4:10.
Preferably, in the preparation of the second liquid, the weight ratio of the arsonic acid sodium salt to the ethylene glycol dimethyl ether is 0.5-2.5:10.
Preferably, the weight ratio of the ethylene glycol dimethyl ether in the first liquid to the ethylene glycol dimethyl ether in the second liquid is 235-255:100.
Preferably, in the reaction, the first liquid is added to the second liquid at a rate of 4-6mL/min; more preferably 5mL/min.
Preferably, in the reaction, the reaction temperature is controlled to be 10-15 ℃.
Preferably, in the reaction, after the addition of the first liquid is completed, the reaction is continued for 3 to 3.5 hours; more preferably 3h.
Further, in the reaction, the purity of the prepared diethyl methoxyborane solution is more than 28 weight percent.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method of diethyl methoxyborane, ethylene glycol dimethyl ether is selected as a solvent, and triethylboron is added to prepare a first liquid; adding arsonic acid sodium salt into ethylene glycol dimethyl ether containing methanol to prepare a second liquid; the first liquid and the second liquid are contacted and reacted to finally obtain a diethyl methoxyborane solution with high yield and high purity; by adopting the sodium arsonate acetate salt to be matched with other technical means, the purity and the yield of the prepared diethyl methoxyborane product can be effectively improved, the stability of the prepared diethyl methoxyborane product is further improved, and the diethyl methoxyborane product can be stably stored for a long time.
(2) According to the preparation method of the diethyl methoxyborane, the prepared diethyl methoxyborane solution is colorless liquid, the purity of the diethyl methoxyborane is 28.09-30.28wt%, and the yield of the diethyl methoxyborane is 90.15-95.49%.
(3) Through experiments, the diethyl methoxyborane solution prepared by the preparation method of the diethyl methoxyborane has smaller difference between the purity of the diethyl methoxyborane in the solution and the purity of the diethyl methoxyborane in the solution during initial storage after sealed storage for 6 months in the environment of 5 ℃; the preparation method of the diethyl methoxyborane can effectively improve the stability of the prepared diethyl methoxyborane solution, and the diethyl methoxyborane solution can be stably stored for a long time.
Drawings
FIG. 1 is a gas chromatogram of a diethylmethoxyborane solution prepared in example 4.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
The embodiment provides a preparation method of diethyl methoxyborane, which specifically comprises the following steps:
① Preparation of materials
The materials are prepared according to the following raw and auxiliary material formula:
355.00g (71 wt%) of ethylene glycol dimethyl ether;
100.00g (20 wt%) of triethylboron;
40g (8 wt%) of methanol;
Arsinic acid acetic acid sodium salt 5g (1 wt%).
② Preparation of the first liquid
255G of ethylene glycol dimethyl ether is taken in a four-mouth bottle with 1L, 100g of triethylboron is added, and the mixture is uniformly dispersed to prepare a first liquid.
③ Preparation of the second liquid
40G of methanol was added to 100g of ethylene glycol dimethyl ether, and then 5g of arsonic acid sodium acetate was added thereto, followed by stirring for 30 minutes, to prepare a second liquid.
④ Reaction
Adding the first liquid into the second liquid at a feeding speed of 5mL/min by adopting a peristaltic pump under the temperature condition of 15 ℃; after the addition of the first liquid is completed, the reaction is continued at 15 ℃ for 3 hours, and after the detection reaction is completed by adopting gas chromatography, solids are separated and removed, so that the diethyl methoxyborane solution is prepared.
According to the preparation method of the diethyl methoxyborane, the prepared diethyl methoxyborane solution is colorless liquid, the purity of the diethyl methoxyborane is 28.09wt%, and the yield of the diethyl methoxyborane is 90.15%.
Example 2
The embodiment provides a preparation method of diethyl methoxyborane, which specifically comprises the following steps:
① Preparation of materials
The materials are prepared according to the following raw and auxiliary material formula:
350.00g (70 wt%) of ethylene glycol dimethyl ether;
100.00g (20 wt%) of triethylboron;
40g (8 wt%) of methanol;
arsinic acid acetic acid sodium salt 10g (2 wt%).
② Preparation of the first liquid
250G of ethylene glycol dimethyl ether is taken in a four-mouth bottle with 1L, 100g of triethylboron is added, and the mixture is uniformly dispersed to prepare a first liquid.
③ Preparation of the second liquid
40G of methanol was added to 100g of ethylene glycol dimethyl ether, and then 10g of arsonic acid sodium acetate was added thereto, followed by stirring for 30 minutes, to prepare a second liquid.
④ Reaction
Adding the first liquid into the second liquid at a feeding speed of 6mL/min by adopting a peristaltic pump under the temperature condition of 12 ℃; after the addition of the first liquid is completed, the reaction is continued at the temperature of 12 ℃ for 3 hours, and after the detection reaction is completed by adopting gas chromatography, solids are separated and removed, so that the diethyl methoxyborane solution is prepared.
According to the preparation method of the diethyl methoxyborane, the prepared diethyl methoxyborane solution is colorless liquid, the purity of the diethyl methoxyborane is 29.15wt%, and the yield of the diethyl methoxyborane is 91.88%.
Example 3
The embodiment provides a preparation method of diethyl methoxyborane, which specifically comprises the following steps:
① Preparation of materials
The materials are prepared according to the following raw and auxiliary material formula:
345.00g (69 wt%) of ethylene glycol dimethyl ether;
100.00g (20 wt%) of triethylboron;
40g (8 wt%) of methanol;
arsinic acid acetic acid sodium salt 15g (3 wt%).
② Preparation of the first liquid
245G of ethylene glycol dimethyl ether is taken in a four-mouth bottle with 1L, 100g of triethylboron is added, and the mixture is uniformly dispersed to prepare a first liquid.
③ Preparation of the second liquid
40G of methanol was added to 100g of ethylene glycol dimethyl ether, followed by 15g of arsonic acid sodium acetate, and stirred for 30 minutes to prepare a second liquid.
④ Reaction
Adding the first liquid into the second liquid at a feeding speed of 4mL/min by adopting a peristaltic pump under the temperature condition of 10 ℃; after the addition of the first liquid is completed, the reaction is continued for 3.5 hours at the temperature of 10 ℃, and after the detection of the reaction is completed by adopting gas chromatography, solids are separated and removed, so that the diethyl methoxyborane solution is prepared.
According to the preparation method of the diethyl methoxyborane, the prepared diethyl methoxyborane solution is colorless liquid, the purity of the diethyl methoxyborane is 30.01wt%, and the yield of the diethyl methoxyborane is 92.51%.
Example 4
The embodiment provides a preparation method of diethyl methoxyborane, which specifically comprises the following steps:
① Preparation of materials
The materials are prepared according to the following raw and auxiliary material formula:
340.00g (68 wt%) of ethylene glycol dimethyl ether;
100.00g (20 wt%) of triethylboron;
40g (8 wt%) of methanol;
20g (4 wt%) of arsinic acid sodium acetate.
② Preparation of the first liquid
240G of ethylene glycol dimethyl ether is taken in a four-mouth bottle with 1L, 100g of triethylboron is added, and the mixture is uniformly dispersed to prepare a first liquid.
③ Preparation of the second liquid
40G of methanol was added to 100g of ethylene glycol dimethyl ether, followed by addition of 20g of arsonic acid sodium acetate salt and stirring for 30min, to prepare a second liquid.
④ Reaction
Adding the first liquid into the second liquid at a feeding speed of 5mL/min by adopting a peristaltic pump under the temperature condition of 15 ℃; after the addition of the first liquid is completed, the reaction is continued at 15 ℃ for 3 hours, and after the detection reaction is completed by adopting gas chromatography, solids are separated and removed, so that the diethyl methoxyborane solution is prepared.
According to the preparation method of the diethyl methoxyborane, the prepared diethyl methoxyborane solution is colorless liquid; as shown in FIG. 1, the peak area 97.29% of the diethylmethoxyborane solution with a retention time of 13.285min was substituted into the diethylmethoxyborane standard curve to obtain a diethylmethoxyborane solution with a diethylmethoxyborane purity of 30.28wt% and a diethylmethoxyborane yield of 95.49%.
Example 5
The embodiment provides a preparation method of diethyl methoxyborane, which specifically comprises the following steps:
① Preparation of materials
The materials are prepared according to the following raw and auxiliary material formula:
335.00g (67 wt%) of ethylene glycol dimethyl ether;
100.00g (20 wt%) of triethylboron;
40g (8 wt%) of methanol;
25g (5 wt%) of arsonic acid sodium acetate salt.
② Preparation of the first liquid
235G of ethylene glycol dimethyl ether is taken in a 1L four-mouth bottle, 100g of triethylboron is added, and the mixture is uniformly dispersed to prepare a first liquid.
③ Preparation of the second liquid
40G of methanol was added to 100g of ethylene glycol dimethyl ether, followed by 25g of arsonic acid sodium acetate, and stirred for 30 minutes to prepare a second liquid.
④ Reaction
Adding the first liquid into the second liquid at a feeding speed of 5mL/min by adopting a peristaltic pump under the temperature condition of 15 ℃; after the addition of the first liquid is completed, the reaction is continued at 15 ℃ for 3 hours, and after the detection reaction is completed by adopting gas chromatography, solids are separated and removed, so that the diethyl methoxyborane solution is prepared.
According to the preparation method of the diethyl methoxyborane, the prepared diethyl methoxyborane solution is colorless liquid, the purity of the diethyl methoxyborane is 29.19wt%, and the yield of the diethyl methoxyborane is 93.09%.
Comparative example 1
The technical scheme of comparative example 1 is the same as that of example 1, except that: the sodium arsenate acetate salt in the second liquid was omitted and ethylene glycol dimethyl ether was used to make up parts by weight.
The preparation method of the diethyl methoxyborane in the comparative example 1 specifically comprises the following steps:
① Preparation of materials
The materials are prepared according to the following raw and auxiliary material formula:
360.00g (72 wt%) of ethylene glycol dimethyl ether;
100.00g (20 wt%) of triethylboron;
40g (8 wt%) of methanol.
② Preparation of the first liquid
255G of ethylene glycol dimethyl ether is taken in a four-mouth bottle with 1L, 100g of triethylboron is added, and the mixture is uniformly dispersed to prepare a first liquid.
③ Preparation of the second liquid
40G of methanol is added into 100g of ethylene glycol dimethyl ether and stirred uniformly to prepare a second liquid.
④ Reaction
Adding the first liquid into the second liquid at a feeding speed of 5mL/min by adopting a peristaltic pump under the temperature condition of 15 ℃; after the addition of the first liquid is completed, the reaction is continued at 15 ℃ for 3 hours, and after the detection reaction is completed by adopting gas chromatography, solids are separated and removed, so that the diethyl methoxyborane solution is prepared.
The purity of the obtained diethyl methoxyborane solution was 15.68wt% and the diethyl methoxyborane yield was 74.13% by the method of preparation of diethyl methoxyborane of comparative example 1.
It can be seen that the purity of the diethyl methoxyborane solution prepared in examples 1-5 is more than 28wt% and completely meets the requirements of diethyl methoxyborane products; in the example 4, 4wt% of sodium arsonate acetate is adopted, the reaction effect is optimal, the purity of the prepared diethyl methoxyborane solution can reach 30.28wt%, and the yield of the diethyl methoxyborane can reach 95.49%; according to the preparation method of the diethyl methoxyborane, the first liquid is prepared by adopting the ethylene glycol dimethyl ether and the triethylboron, the second liquid is prepared by adopting the methanol, the ethylene glycol dimethyl ether and the sodium arsonate acetate, and the diethyl methoxyborane is prepared by the contact reaction of the first liquid and the second liquid, so that the purity and the yield of the prepared diethyl methoxyborane product can be effectively improved.
Test example 1
Stability test of diethyl methoxyborane solution: the diethyl methoxyborane solutions prepared in examples 1-5 and comparative example 1 are placed in a temperature environment of 5 ℃ respectively, and are stored in a sealing way; and detecting the purity of the diethyl methoxyborane solution after 1 month of sealed storage, 2 months of sealed storage, 3 months of sealed storage, 4 months of sealed storage, 5 months of sealed storage and 6 months of sealed storage respectively.
The stability test results of the diethylmethoxyborane solution prepared in example 1 are shown in the following table:
。
the stability test results of the diethylmethoxyborane solution prepared in example 2 are shown in the following table:
。
the stability test results of the diethylmethoxyborane solution prepared in example 3 are shown in the following table:
。
the stability test results of the diethylmethoxyborane solution prepared in example 4 are shown in the following table:
。
the stability test results of the diethylmethoxyborane solution prepared in example 5 are shown in the following table:
。
the stability test results of the diethyl methoxyborane solution prepared in comparative example 1 are shown in the following table:
。
According to the preparation method of the diethyl methoxyborane, the stability of the prepared diethyl methoxyborane solution can be effectively improved through combination in the technical means, the purity attenuation of the diethyl methoxyborane is not obvious in the long-term storage process, and the diethyl methoxyborane solution can be stably stored for a long time; the comparative example 1 has the advantages that after omitting the corresponding technical characteristics, the stability of the prepared diethyl methoxyborane solution is obviously poor, and the purity of the diethyl methoxyborane solution is obviously attenuated in the long-time sealed storage process, and the purity of the diethyl methoxyborane solution in the solution is attenuated by more than 55% after being placed for 6 months, so that the diethyl methoxyborane solution cannot be stored at long-time temperature.
The percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. The preparation method of the diethyl methoxyborane is characterized by comprising the following steps of: preparing a first liquid, preparing a second liquid and reacting;
The method for preparing the first liquid comprises the steps of uniformly mixing triethylboron and ethylene glycol dimethyl ether to prepare the first liquid;
In the preparation of the first liquid, the weight ratio of the triethylboron to the ethylene glycol dimethyl ether is 1:2.35-2.55;
adding methanol into ethylene glycol dimethyl ether, continuously adding arsine sodium acetate, and uniformly mixing to obtain a second liquid;
In the preparation of the second liquid, the weight ratio of the arsonic acid sodium salt to the ethylene glycol dimethyl ether is 0.5-2.5:10;
The method of the reaction is that the first liquid is added into the second liquid; after the first liquid is added, continuing to react, and separating and removing solids to prepare diethyl methoxy borane solution;
In the reaction, the weight ratio of the ethylene glycol dimethyl ether in the first liquid to the ethylene glycol dimethyl ether in the second liquid is 235-255:100;
In the reaction, the reaction temperature is controlled to be 10-15 ℃; after the first liquid is added, the reaction time is continued for 3 to 3.5 hours;
In the preparation method, the weight percentage content of each raw material is as follows: 67-71% of ethylene glycol dimethyl ether; triethylboron 20%; 8% of methanol; 1-5% of arsonic acid sodium acetate.
2. The method for preparing diethyl methoxyborane according to claim 1, wherein the weight ratio of methanol to ethylene glycol dimethyl ether in the second liquid is 4:10.
3. The process for preparing diethylmethoxyborane according to claim 1, wherein the first liquid is added to the second liquid at a rate of 4-6mL/min.
4. The process for preparing diethylmethoxyborane according to claim 1, wherein the purity of the resulting diethylmethoxyborane solution in the reaction is > 28wt%.
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