CN114989115B - Improved synthesis of alpha- (nitromethyl) -2-furanmethanol and method for maintaining catalyst activity in the process - Google Patents
Improved synthesis of alpha- (nitromethyl) -2-furanmethanol and method for maintaining catalyst activity in the process Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- KWOKMZBSAZNOBW-UHFFFAOYSA-N 1-(furan-2-yl)-2-nitroethanol Chemical compound [O-][N+](=O)CC(O)C1=CC=CO1 KWOKMZBSAZNOBW-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000008569 process Effects 0.000 title claims description 11
- 230000000694 effects Effects 0.000 title abstract description 4
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 238000003786 synthesis reaction Methods 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000003960 organic solvent Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012046 mixed solvent Substances 0.000 claims abstract description 5
- 238000001308 synthesis method Methods 0.000 claims abstract description 3
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 72
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- WVUICGOYGDHVBH-ONEGZZNKSA-N 2-[(e)-2-nitroethenyl]furan Chemical compound [O-][N+](=O)\C=C\C1=CC=CO1 WVUICGOYGDHVBH-ONEGZZNKSA-N 0.000 claims description 25
- 239000012535 impurity Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 16
- 238000004821 distillation Methods 0.000 claims description 16
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 239000011949 solid catalyst Substances 0.000 claims description 10
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- LYGJENNIWJXYER-BJUDXGSMSA-N nitromethane Chemical group [11CH3][N+]([O-])=O LYGJENNIWJXYER-BJUDXGSMSA-N 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 abstract description 18
- 229910001863 barium hydroxide Inorganic materials 0.000 abstract description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000001514 detection method Methods 0.000 description 11
- 238000004809 thin layer chromatography Methods 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZUDYPQRUOYEARG-UHFFFAOYSA-L barium(2+);dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Ba+2] ZUDYPQRUOYEARG-UHFFFAOYSA-L 0.000 description 9
- 239000007791 liquid phase Substances 0.000 description 9
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000002274 desiccant Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- JWQAFPHYLSGNSK-UHFFFAOYSA-N 2-amino-1-(furan-2-yl)ethanol Chemical compound NCC(O)C1=CC=CO1 JWQAFPHYLSGNSK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000006842 Henry reaction Methods 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- -1 nitromethyl Chemical group 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000825 ultraviolet detection Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical class N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 239000005499 Clomazone Substances 0.000 description 1
- 239000005588 Oxadiazon Substances 0.000 description 1
- CHNUNORXWHYHNE-UHFFFAOYSA-N Oxadiazon Chemical compound C1=C(Cl)C(OC(C)C)=CC(N2C(OC(=N2)C(C)(C)C)=O)=C1Cl CHNUNORXWHYHNE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- KIEDNEWSYUYDSN-UHFFFAOYSA-N clomazone Chemical compound O=C1C(C)(C)CON1CC1=CC=CC=C1Cl KIEDNEWSYUYDSN-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The application relates to an improved synthesis method of alpha- (nitromethyl) -2-furanmethanol, which uses a mixed solvent system of an organic solvent and water, takes aqueous barium hydroxide as a catalyst and synthesizes the alpha- (nitromethyl) -2-furanmethanol through the following reaction. The application also relates to a method for maintaining the activity of the catalyst in the method, water is added into the organic solvent used in the reaction, and the catalyst is aqueous barium hydroxide.
Description
Technical Field
The application relates to an improved synthesis method of a herbicide safener, namely a oxazazole intermediate alpha- (nitromethyl) -2-furanmethanol, and a method for maintaining catalytic activity in the method.
Background
In the prior art, as one of the synthetic methods of clomazone, the following reaction scheme is disclosed (see, for example, U.S. patent document US 5428172):
the first step of the reaction is to prepare alpha- (nitromethyl) -2-furanmethanol by using furfural and nitromethane as raw materials, barium hydroxide octahydrate as a catalyst and THF as a solvent.
The reaction has more byproducts, and the system after the reaction contains unreacted raw materials of furfural, nitromethane, byproducts and other impurities besides the product alpha- (nitromethyl) -2-furanmethanol.
In US5428172, the intermediate α - (nitromethyl) -2-furanmethanol is directly used in the next reaction without any purification treatment, which has an influence on the accuracy and reactivity of the feed in the next reaction.
In non-patent documents 1 and 2, as a purification method of the intermediate α - (nitromethyl) -2-furanmethanol obtained in this step, it is reported that a reduced pressure distillation is performed to remove a solvent (a solvent used in the reaction thereof includes ethanol, methylene chloride, ethyl acetate, and the like) and unreacted raw material nitromethane and furfural, followed by further purification by column chromatography. Column chromatography purification, although it can obtain intermediates of higher purity, is not suitable for industrial production.
Further, in the conventional production, barium hydroxide as a catalyst is directly removed by washing with water after use, and thus, the environmental load is large and the cost is high.
Non-patent literature 1：A new series of bipyridine based chiral organocatalysts for enantioselective Henry reaction.New Journal Of Chemistry.2016,40(8):7148-7156
Non-patent literature 2：Cu(II)-L-prolinamide:First catalytic application of metal-amidoamine complex in enantioselective Henry reaction.Catalysis Communications.2019,129.
Disclosure of Invention
The current reaction of preparing alpha- (nitromethyl) -2-furanmethanol using barium hydroxide octahydrate to catalyze furfural and nitromethane can be accomplished in the following two ways.
Mode 1: furfural and nitromethane are fed according to the mol ratio of 1 (8-10), the nitromethane is used as a reactant and a solvent, and the barium hydroxide octahydrate is used as a catalyst to react under the condition of not adding other solvents. After the reaction is finished and the solid catalyst is filtered out, the system contains a large amount of unreacted nitromethane and a little furfural, the product alpha- (nitromethyl) -2-furanmethanol, the main impurity 2- (2-nitrovinyl) -furan and other unknown impurities.
Mode 2: furfural and nitromethane are fed according to a molar ratio of 1:1, solvents such as tetrahydrofuran and the like are added as reaction media, barium hydroxide octahydrate is added for reaction under a stirring state, after a solid catalyst is filtered out after the reaction is finished, the system comprises tetrahydrofuran solvents, a little unreacted furfural and nitromethane, and a product alpha- (nitromethyl) -2-furol, main impurities 2- (2-nitrovinyl) -furan and other unknown impurities.
The present inventors have carried out the above reaction in the above manner and attempted recycling of the catalyst barium hydroxide, but have found that when the reaction is carried out using the recovered barium hydroxide in the above two manners, the recovered catalyst has no catalytic activity and the reaction does not proceed at all.
The inventor of the present application has studied to find that the catalyst has a property change before and after use and has tried to solve various measures of catalyst deactivation, and as a result, has found that the filtered catalyst barium hydroxide can be recycled after a small amount of water is added into the reaction system to change a single organic solvent system into a mixed system of organic solvent and water.
Accordingly, in one aspect, the present invention provides an improved process for the preparation of α - (nitromethyl) -2-furanmethanol using a mixed solvent system of an organic solvent and water, synthesized by the reaction of aqueous barium hydroxide as a catalyst:
On the other hand, the present inventors have found that, when the above reactants are separated and purified, the reduced pressure rectification can remove most of unreacted raw material furfural and nitromethane, but the product is at a higher temperature for a long time, which results in an increase in impurity 2- (2-nitrovinyl) -furan represented by the following formula (1), which has a higher boiling point (222.7.+ -. 15 ℃ C., 760 mmHg) and is not easily separated from the product, thereby greatly reducing the yield and purity of α - (nitromethyl) -2-furan. And, the alkene compound impurity can influence the subsequent nitro catalytic hydrogenation reduction reaction of alpha- (nitromethyl) -2-furanmethanol, and more new impurities are added to a hydrogenation reaction body.
In view of this, the present invention uses chemical treatment to purify the reaction product, and sodium bisulphite is added to remove unreacted raw material furfural and main byproduct impurity 2- (2-nitrovinyl) -furan.
Drawings
FIG. 1 is a TG (thermogravimetric) -DSC analysis of unused barium hydroxide octahydrate.
FIG. 2 is a TG (thermogravimetric) -DSC analysis chart of used barium hydroxide octahydrate
Detailed Description
In the present application, "%" means mass percent and "about" means within.+ -. 10% unless otherwise specified.
In one aspect, the invention relates to an improved synthesis of alpha- (nitromethyl) -2-furanmethanol by reacting furfural with nitromethane using a mixed solvent system of an organic solvent and water with aqueous barium hydroxide as a catalyst.
Specific examples of the organic solvent used in the process of the present invention include, but are not limited to, nitromethane, tetrahydrofuran, dioxane, and a mixed solvent of any two or three thereof, preferably nitromethane or tetrahydrofuran or a mixture thereof. When nitromethane is used, it serves as both a reaction raw material and a solvent.
Unlike available organic solvent system, the present invention can reuse barium hydroxide catalyst for over 2-3 times through adding small amount of water into organic solvent.
In some embodiments, the volume ratio of organic solvent to water is about (10-15): 1. The addition amount of water is too small to sufficiently ensure the activity of the catalyst; when the amount of water added is too large, barium hydroxide is dissolved, so that recycling is affected, or the catalyst is agglomerated, so that the reaction efficiency is affected.
Specific examples of aqueous barium hydroxide include, but are not limited to, ba (OH) 2˙8H2 O.
The catalyst is generally used in an amount effective to catalyze the reaction of the present invention, and the amount of aqueous barium hydroxide to furfural starting material may be 1 (8-12), preferably 1 (9-11), and more preferably about 1:10, on a molar basis.
Preferably, the above reaction is carried out at a temperature of 15 to 25 ℃.
Based on the results of the present inventors' study on the stability of α - (nitromethyl) -2-furanmethanol, the present application makes adjustments to the method of purifying the product of the above reaction. Thus, the improved process of the present application preferably further comprises the following purification steps: after the reaction, separating and removing the solid catalyst, decompressing and distilling to remove the organic solvent and unreacted nitromethane to obtain a concentrated solution, adding sodium bisulphite solution into the concentrated solution, and removing unreacted furfural and impurity 2- (2-nitrovinyl) -furan through chemical reaction.
Unlike the conventional method of removing an organic solvent, unreacted nitromethane and furaldehyde by reduced pressure distillation, only the organic solvent and nitromethane having a relatively low boiling point are removed by reduced pressure distillation, and the furaldehyde having a relatively high boiling point is removed not by reduced pressure distillation but by a chemical method. Thereby reducing the distillation temperature, shortening the distillation time and avoiding a great amount of alpha- (nitromethyl) -2-furanmethanol from self elimination reaction to become alkene impurities caused by long-time high-temperature exposure
The reduced pressure distillation is preferably performed at a temperature lower than 25℃so that the occurrence of self-elimination reaction of α - (nitromethyl) -2-furanmethanol to 2- (2-nitrovinyl) -furan as an impurity can be suppressed.
In some embodiments, the vacuum level of reduced pressure distillation is about 750 to 760mmHg, preferably 755 to 758mmHg.
In some embodiments, the sodium bisulfite solution is an aqueous sodium bisulfite solution having a concentration of 0.4 to 0.6g/mL, preferably about 0.5 g/mL. Too low a concentration can affect mass transfer between substrates, which in turn affects reaction efficiency, and too high a concentration can increase raw material consumption, increasing reaction costs.
In some embodiments, the reduced pressure distillation removes the organic solvent and unreacted nitromethane to obtain a concentrate and sodium bisulfite solution having a mass to volume ratio (g/mL) of 1 (1.1-6).
In the present application, "concentrated liquid" means concentrated liquid obtained by distillation under reduced pressure until the weight is substantially unchanged or until no distillate is present, and "substantially unchanged weight" means that the difference between the two weighed masses is less than 0.3mg within 10 minutes.
Preferably, the reaction temperature after adding sodium bisulphite solution to the concentrate is 10-15 ℃. At the temperature, the sodium bisulphite, the furfural and the 2- (2-nitrovinyl) -furan can be guaranteed to achieve good reaction efficiency, and more conversion of alpha- (nitromethyl) -2-furanmethanol into the 2- (2-nitrovinyl) -furan in the system can be avoided.
Preferably, the reaction time after adding the sodium bisulfite solution to the concentrate is more than 4 hours to ensure that the sodium bisulfite reacts completely with furfural, 2- (2-nitrovinyl) -furan. And judging whether the furfural and 2- (2-nitrovinyl) -furan in the reactant are completely reacted or not through detection means such as thin layer chromatography.
Furfural, 2- (2-nitrovinyl) -furan and sodium bisulphite react to generate sodium salt products which are easy to dissolve in water, the sodium salt products are removed by extraction and water washing, the water-soluble impurities in the organic phase obtained by extraction are removed by water washing, and then the organic phase is dried and distilled under reduced pressure to remove the organic extractant to obtain concentrated solution. The concentrated solution is the intermediate product alpha- (nitromethyl) -2-furanmethanol with higher purity.
Examples of the extractant include, but are not limited to, organic solvents such as methylene chloride, chloroform, ethyl acetate, dichloroethane, benzene, and the like.
Examples of such desiccants include, but are not limited to, anhydrous magnesium sulfate, calcium oxide, 4A molecular sieves, and the like solid desiccants.
The invention further provides a method for maintaining the catalytic activity in the method, water is added into the organic solvent used in the reaction, the catalyst is aqueous barium hydroxide,
In some embodiments, the organic solvent in the process is one or more selected from nitromethane, tetrahydrofuran and dioxane, preferably nitromethane or tetrahydrofuran or mixtures thereof.
Preferably, the volume ratio of organic solvent/water in the process is (5-15): 1, more preferably (8-12): 1, still more preferably about 10:1.
More preferably, the reaction temperature is 15 to 25 ℃.
Further preferably, the catalyst is used in the process in a molar ratio to the raw furfural of 1 (8-12), preferably 1 (9-11), more preferably about 1:10.
In some embodiments, the thin layer chromatography assay conditions referred to herein are: developing agent petroleum ether and ethyl acetate are 4:1, and an ultraviolet detection lamp (254 nm);
in some embodiments, the high performance liquid chromatography assay conditions referred to herein are: methanol: water=40:60, flow rate 1mL/min, detection wavelength 228nm &340nm, agilent C18 column.
According to the invention, on one hand, the catalyst barium hydroxide is effectively recycled, the cost is saved, the environment is protected, and on the other hand, the intermediate alpha- (nitromethyl) -2-furanmethanol is obtained with higher yield and purity, so that the quality of the final product of the subsequent reduction, cyclization and amidation reaction, namely the oxadiazon, is improved.
Examples
EXAMPLE 1 alpha- (nitromethyl) -2-furanmethanol stability Studies
A sample of α - (nitromethyl) -2-furanmethanol was dissolved in a liquid phase mobile phase (methanol: water=40:60), the solution was placed in a stability test chamber at a temperature of 5 ℃, 15 ℃, 25 ℃, and then the liquid phase was sampled at different time points to determine the concentration change of α - (nitromethyl) -2-furanmethanol and the concentration change of impurity 2- (2-nitrovinyl) -furan therein.
The detection results are shown in the following table 1.
Liquid phase conditions: mobile phase: methanol: water = 40:60, flow rate: 1.0mL/min, detection wavelength: 228nm &340nm, column: agilent C18 column.
TABLE 1
Note that: a is alpha- (nitromethyl) -2-furanmethanol; b is 2- (2-nitrovinyl) -furan.
As is clear from the results in Table 1, the concentration of the α - (nitromethyl) -2-furanmethanol was reduced after the reaction was allowed to stand for 1 hour at 25℃and the concentration of the impurity 2- (2-nitrovinyl) -furan was increased, and the change was more remarkable with the lapse of time; at 15 ℃, the concentration of alpha- (nitromethyl) -2-furanmethanol does not change obviously within 1h, and the concentration begins to decrease and the impurity concentration increases after 2 h; at 5 ℃, the concentration of alpha- (nitromethyl) -2-furanmethanol and the concentration of impurity 2- (2-nitrovinyl) -furan are not obviously changed within 8 hours.
Example 2 recovery and Property Change Studies of catalyst
According to the route described in US5428172, using furfural and nitromethane as raw materials, alpha- (nitromethyl) -2-furanmethanol is prepared by reacting in tetrahydrofuran in the presence of barium hydroxide octahydrate, and after the reaction is completed, the solid catalyst barium hydroxide is filtered out from the reaction mass and recycled.
Comparison of the virgin catalyst and the recovered catalyst shows that the catalyst has been converted from the original white monoclinic crystal into powder, and the results are shown in figures 1 and 2, wherein the novel barium hydroxide octahydrate has obvious endothermic peaks at 86.76 ℃ and 109.86 ℃ as shown in the results of TG-DSC, which means that part of water is evaporated to absorb heat, and the recovered catalyst has obvious endothermic peaks at 69.79 ℃ and 109.86 ℃, which means that part of organic solvent is adsorbed in the recovered catalyst, so that the temperature is reduced, the weight loss of the virgin catalyst and the weight loss of the recovered catalyst are obviously changed, the weight loss of the recovered catalyst is obviously lower than that of the virgin catalyst, and the appearance of the crystals added with the catalyst is obviously changed, which means that the catalyst is changed in nature before and after the use.
Measurement conditions of TG-DSC: the initial temperature is 20 ℃, the final temperature is 800 ℃, the heating rate is 10 ℃/min, and the analytical instrument is: a differential thermal re-combination apparatus of type SDT Q600, TA instruments, USA.
Example 3
2.00G of furfural, 7.32g of nitromethane, 0.65g of barium hydroxide as a solid catalyst recovered from the above, and 10.0mL of tetrahydrofuran were added to a 50mL three-necked flask at 20℃and 1.0mL of water was added thereto with stirring to react for 17.5 hours, and the reaction mixture and the α - (nitromethyl) -2-furanmethanol control were subjected to comparative detection by thin layer chromatography, followed by completion of the reaction after confirming that the product was no longer increased. High performance liquid phase detection is carried out on the reaction liquid, the content of alpha- (nitromethyl) -2-furanmethanol in the reaction liquid is 17.88 percent (containing organic solvent) according to an external standard method, and the yield is 87.00 percent; the content of 2- (2-nitrovinyl) -furan was 0.15% (containing an organic solvent), and the yield thereof was 0.84%.
Thin layer chromatography conditions: developing agent petroleum ether and ethyl acetate are 4:1, and an ultraviolet detection lamp (254 nm);
the liquid phase conditions were the same as in example 1.
Comparative example 1
According to the route described in US5428172, using furfural and nitromethane as raw materials, alpha- (nitromethyl) -2-furanmethanol is prepared by reacting in tetrahydrofuran in the presence of barium hydroxide octahydrate, and after the reaction is completed, the solid catalyst barium hydroxide is filtered out of the reaction mass for reuse.
To a 50mL three-necked flask, 2.00g of furfural, 7.32g of nitromethane, 0.65g of the above-recovered solid catalyst barium hydroxide, and 10.0mL of tetrahydrofuran were added at 20℃and the mixture was stirred for 18.5 hours. The reaction solution and the alpha- (aminomethyl) -2-furanmethanol reference substance were qualitatively analyzed by thin plate detection to find that no product point exists, and high performance liquid phase detection shows that no absorption peaks of alpha- (nitromethyl) -2-furanmethanol and 2- (2-nitrovinyl) -furan exist, indicating that the reaction does not proceed.
The thin layer chromatography and liquid phase conditions in this comparative example were the same as in example 3.
Example 4
Using the reaction solution obtained after the reaction in example 1, the solid catalyst was removed by filtration to obtain an organic phase filtrate, tetrahydrofuran and nitromethane in the organic phase were removed by distillation under reduced pressure at 25℃under a vacuum of 755 to 758mmHg, 12.32g of a concentrated solution was obtained, and the content of α - (aminomethyl) -2-furanmethanol in the concentrated solution was 63.3%, the content of 2- (2-nitrovinyl) -furan was 22.8%, the content of furfural was 12.4%, and the content of nitromethane was 2.4% by high performance liquid chromatography.
To a 50mL three-necked flask, the concentrated solution obtained above and 12.5mL of an aqueous sodium bisulfite solution having a concentration of 0.5g/mL were added, and when the reaction was carried out at 15℃for 1 hour, the spot where no furfural was observed was detected by thin layer chromatography, while the spot of 2- (2-nitrovinyl) -furan remained. After 4h of reaction, thin layer chromatography detection found that the furfural spot reappeared, while the 2- (2-nitrovinyl) -furan spot disappeared. Then, 5.0mL of aqueous solution of sodium bisulphite was added for further reaction for 1h, and all points of furfural and 2- (2-nitrovinyl) -furan were disappeared by thin layer chromatography detection. After the completion of the reaction, the organic phase was extracted with 40.0mL of methylene chloride, and the extracted organic phase was washed with 40.0mL of water 2 times to remove water-soluble matters in the organic phase. The organic phase was dried over anhydrous magnesium sulfate for 2h and filtered to separate out a solid desiccant. The extractant in the organic phase was removed by distillation under reduced pressure at 20℃and 710-720mmHg vacuum to give the final product. The content of alpha- (nitromethyl) -2-furanmethanol in the product is 94.5%, the content of 2- (2-nitrovinyl) -furan is 1.7%, the content of furfural is 1.1%, and the content of nitromethane is 2.6% as detected by high performance liquid chromatography.
The thin layer chromatography and liquid phase conditions in this example were the same as in example 3.
Comparative example 2
Using the reaction liquid obtained after the reaction in example 1, filtering to remove the solid catalyst to obtain an organic phase filtrate, and removing furfural by reduced pressure distillation (vacuum degree is less than or equal to 720 mmHg), wherein when the temperature in the kettle is 40 ℃, the reaction liquid is light yellow oily matter, the gas phase temperature is 20 ℃, and no fraction exists; when the temperature in the kettle is 60 ℃, the reaction liquid is yellow oily matter, the gas phase temperature is 20 ℃, and no fraction exists; when the temperature in the kettle is 80 ℃, the reaction liquid is brown oily matter, the gas phase temperature is 30 ℃, and no distillate is obtained; when the temperature in the kettle is 100 ℃, the reaction liquid is brown and has solid, the gas phase temperature is 35 ℃, and no fraction is distilled; when the temperature in the kettle is 120 ℃, the reaction liquid is solidified into a scorch black solid, the gas phase temperature is suddenly increased, the gas phase temperature is 60 ℃, and no fraction is distilled. After the reduced pressure distillation is finished, thin layer chromatography detection is carried out on the components at the bottom of the kettle, and the original point is found to generate a plurality of impurities (accounting for 6 to 12 percent of the total amount), the alpha- (nitromethyl) -2-furanmethanol is obviously reduced (accounting for 10 to 15 percent of the total amount), the main component of the black solid is 2- (2-nitrovinyl) -furan (accounting for 70 to 80 percent of the total amount), and the furfural accounts for 4 to 6 percent of the total amount. Therefore, when the vacuum degree is less than or equal to 720mmHg, furfural cannot be steamed out at a lower temperature, and impurities are generated in the system by reduced pressure distillation at a higher temperature, mainly alpha- (nitromethyl) -2-furanmethanol is dehydrated in molecules to generate 2- (2-nitrovinyl) -furan, so that the product content is reduced, the impurity content is increased, and in addition, some original point impurities are generated.
The thin layer chromatography and liquid phase conditions in this comparative example were the same as in example 3.
Claims (9)
1. The improved synthesis method of the alpha- (nitromethyl) -2-furanmethanol is characterized by using a mixed solvent system of an organic solvent and water, taking Ba (OH) 2˙8H2 O as a catalyst, and synthesizing the alpha- (nitromethyl) -2-furanmethanol through the following reaction:
the organic solvent is nitromethane or tetrahydrofuran or a mixture thereof,
The volume ratio of the organic solvent to the water is (8-12) 1,
The reaction temperature is 15-25 ℃.
2. The method of claim 1, wherein the volume ratio of organic solvent/water is 10:1.
3. The method according to claim 1 or 2, wherein the catalyst and the raw material furfural are used in a molar ratio of 1 (8-12).
4. The method according to claim 3, wherein the catalyst and the raw material furfural are used in a molar ratio of 1 (9-11).
5. A process according to claim 3, wherein the catalyst is used in a molar ratio to the raw material furfural of 1:10.
6. The method of claim 1 or 2, further comprising the purification step of: after the reaction, separating and removing the solid catalyst, decompressing and distilling to remove the organic solvent and unreacted nitromethane to obtain a concentrated solution, and then adding sodium bisulphite solution to remove furfural and impurity 2- (2-nitrovinyl) -furan through chemical reaction.
7. The method according to claim 6, wherein the sodium bisulfite solution is 0.4 to 0.6g/mL of sodium bisulfite aqueous solution.
8. The process of claim 6, wherein the reduced pressure distillation is performed at a temperature of less than 25 ℃.
9. The process according to claim 6, wherein the chemical reaction temperature after adding the sodium bisulphite solution is 10-15 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5428172A (en) * | 1993-09-21 | 1995-06-27 | Monsanto Company | Preparation of 3-dihaloacetyl oxazolidines |
| CN102617560A (en) * | 2011-01-30 | 2012-08-01 | 南京理工大学 | Preparation method of furilazole |
| CN110041294A (en) * | 2019-05-13 | 2019-07-23 | 河北科技大学 | The synthetic method and its application of the chloro- N- of 2,2- bis- [2- (2- furyl) -2- hydroxyethyl] acetamide |
| CN111689933A (en) * | 2020-06-10 | 2020-09-22 | 浙江工业大学 | Synthetic method of 5- [ (phenylamino) methyl ] -2-furanmethanol |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5428172A (en) * | 1993-09-21 | 1995-06-27 | Monsanto Company | Preparation of 3-dihaloacetyl oxazolidines |
| CN102617560A (en) * | 2011-01-30 | 2012-08-01 | 南京理工大学 | Preparation method of furilazole |
| CN110041294A (en) * | 2019-05-13 | 2019-07-23 | 河北科技大学 | The synthetic method and its application of the chloro- N- of 2,2- bis- [2- (2- furyl) -2- hydroxyethyl] acetamide |
| CN111689933A (en) * | 2020-06-10 | 2020-09-22 | 浙江工业大学 | Synthetic method of 5- [ (phenylamino) methyl ] -2-furanmethanol |
Non-Patent Citations (1)
| Title |
|---|
| 呋喃解草唑的合成研究;丁一;《科技创新导报》;第16卷;138-139 * |
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