CN111393256B - Synthetic method of 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl - Google Patents
Synthetic method of 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl Download PDFInfo
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- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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Abstract
The invention discloses a method for synthesizing 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl, and belongs to the technical field of chemical synthesis. 2,3,5,6-tetrafluoro-1,4-dibromobenzene reacts with magnesium metal in an inert solvent to obtain 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide, and then 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl is obtained through self-coupling reaction in an inert solvent under the action of a copper catalyst. The method has the advantages of cheap and easily obtained raw materials, short reaction steps, high synthesis yield, good product quality and the like, and is suitable for industrial production and application.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a synthetic method of 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl.
Background
2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl is a very important chemical intermediate, has a wide application prospect in the field of photoelectric materials, and can be used for preparing high-end photoelectric materials such as photoelectric solid materials, organic light emitting diodes, organic field effect transistors, solar cells and the like.
2,2',3,3',5,5',6,6' -octafluoro-4,4 '-dibromobiphenyl synthesis methods are rarely reported, and reference is made to similar structural compounds, such as 3,3',4,4',5,5',6,6 '-octafluoro-2,2' -dibromobiphenyl, which synthesis methods are as follows:
the synthesis method has harsh reaction conditions except that the reaction conditions are required to be-78 ℃ Besides the reaction at low temperature, n-butyllithium which is expensive and has higher safety risk is also needed to be used as a reaction reagent, and titanium tetrachloride with more than molar equivalent is also needed to be used as a coupling reagent, so that the synthesis cost is higher, and the method is not suitable for industrial production.
Disclosure of Invention
The invention aims to provide a simple, convenient and efficient synthetic method of 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl, and lays a foundation for industrial production. The synthesis method has the advantages of cheap and easily-obtained raw materials, short reaction steps, high synthesis yield, good product quality and the like, and is suitable for industrial production and application.
The technical scheme adopted by the invention is as follows:
a method for synthesizing 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl comprises the following steps:
(1) 2,3,5,6-tetrafluoro-1,4-dibromobenzene (I) reacts with magnesium metal in an inert solvent to obtain 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide (II);
(2) The obtained 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide (II) is subjected to self-coupling reaction in an inert solvent under the action of a copper catalyst to obtain 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl (III).
The technical route adopted by the invention can be shown by the following reaction formula:
the invention further provides that:
in the step (1):
the inert solvent is a solvent which does not generate side reaction with raw materials, intermediates, products and the like in the reaction process. The inert solvent is selected from one or more of the following: straight-chain or branched-chain alkane solvents such as n-pentane, n-hexane, n-heptane, n-octane, isooctane, etc.; cycloalkane-based solvents such as cyclopentane, cyclohexane, methylcyclohexane, decalin, and the like; aromatic hydrocarbon solvents such as benzene, toluene, xylene, etc.; ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, etc. Preferred inert solvents are ethereal solvents, represented by the general formula: R-O-R ', wherein R, R' is C1-C10 linear, branched or cyclic alkyl, C1-C10 linear, branched or cyclic alkoxyalkyl. Representative ether solvents are: diethyl ether, methyl propyl ether, ethyl propyl ether, methyl isopropyl ether, ethyl isopropyl ether, methyl n-butyl ether, ethyl n-butyl ether, methyl isobutyl ether, ethyl isobutyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, dimethoxymethane, diethoxymethane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, 1,1-dimethoxypropane, 1,1-diethoxypropane, 2,2-dimethoxypropane, 2,2-diethoxypropane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, cyclopentyl methyl ether, cyclohexyl methyl ether, and the like. The inert solvent used can be a single solvent or a mixed solvent consisting of two or more inert solvents, and the dosage of the solvent is 1 to 15 times of the mass of the compound (I).
The magnesium metal is required to be dry and fresh in surface without oxides, and is processed into a form with a higher specific surface area, such as magnesium chips, magnesium powder, magnesium strips and the like, so as to ensure good reaction activity. The ratio of the amount of the metallic magnesium to the amount of the compound (I) is (1-1.5): 1, and the preferable ratio of the amount of the metallic magnesium to the amount of the compound (I) is (1-1.2): 1.
The proper reaction temperature has an important influence on the smooth progress of the reaction. The reaction initiation can be promoted by properly increasing the reaction temperature, the accumulation of raw materials in a system caused by unsuccessful initiation in the early stage of the reaction is avoided, the safety risk is increased, meanwhile, the higher reaction temperature is also beneficial to accelerating the reaction speed, shortening the reaction time and reducing the residual quantity of the raw materials after the reaction is finished, but unnecessary side reactions can be caused by the excessively high reaction temperature, so that the product content and the reaction yield are reduced. The optional reaction temperature is (-30-100) deg.C, and the preferred reaction temperature is (-20-80) deg.C.
The reaction of this step is a reaction for preparing an aryl grignard reagent by reacting an aryl bromide with magnesium metal, and is required to be carried out under anhydrous conditions, so that the moisture content of raw materials, solvents and the like needs to be strictly controlled to ensure smooth initiation and normal operation of the reaction. In addition, before the reaction starts, a proper amount of elemental iodine, 1,2-dibromoethane and an alkyl Grignard reagent such as isopropyl magnesium chloride or an inert solvent solution of 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide prepared in advance can be added into the reaction system to be used as a reaction initiator to promote the successful initiation of the Grignard reaction.
In the step (2):
the inert solvent is a solvent which does not generate side reaction with raw materials, intermediates, products and the like in the reaction process. The inert solvent is selected from one or more of the following: straight-chain or branched-chain alkane solvents such as n-pentane, n-hexane, n-heptane, n-octane, isooctane, etc.; cycloalkane-based solvents such as cyclopentane, cyclohexane, methylcyclohexane, decalin, and the like; aromatic hydrocarbon solvents such as benzene, toluene, xylene, etc.; ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, etc. Preferred inert solvents are ethereal solvents, represented by the general formula: R-O-R ', wherein R, R' is C1-C10 linear, branched or cyclic alkyl, C1-C10 linear, branched or cyclic alkoxyalkyl. Representative ether solvents are: diethyl ether, methyl propyl ether, ethyl propyl ether, methyl isopropyl ether, ethyl isopropyl ether, methyl n-butyl ether, ethyl n-butyl ether, methyl isobutyl ether, ethyl isobutyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, dimethoxymethane, diethoxymethane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, 1,1-dimethoxypropane, 1,1-diethoxypropane, 2,2-dimethoxypropane, 2,2-diethoxypropane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, cyclopentyl methyl ether, cyclohexyl methyl ether, and the like. The inert solvent used may be a single solvent or a mixed solvent of two or more inert solvents, and may be the same as or different from the solvent used in step (1). The dosage of the solvent is 1 to 20 times of the mass of the compound (II).
The reaction in this step is a copper-catalyzed self-coupling reaction of a Grignard reagent. The copper catalyst can be inorganic copper compound, such as copper halide, cuprous halide, cupric oxide, cuprous oxide, etc., or organic copper compound, such as cupric acetate, cuprous acetate, etc., or elemental copper, such as copper powder. The preferred copper catalyst is an inorganic copper compound selected from one or more of the following: copper chloride, cuprous chloride, cupric bromide, cuprous bromide, cupric iodide, cuprous iodide, cupric sulfate, cuprous sulfate, cupric oxide, cuprous oxide. The mass ratio of the copper catalyst to the compound (II) is (0.1-3.0): 1, and the preferred mass ratio of the copper catalyst to the compound (II) is (0.3-1.5): 1.
The reaction can be carried out at low temperature, the optional reaction temperature is (-80-100) DEG C, and the preferred reaction temperature is (-70-80) DEG C.
Compared with the prior art, the invention has the beneficial effects that:
(1) A new route is developed for synthesizing 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl by using 2,3,5,6-tetrafluoro-1,4-dibromobenzene as a raw material through a Grignard reaction and a copper-catalyzed self-coupling reaction.
(2) The synthesis method has the advantages of cheap and easily-obtained raw materials, short reaction steps, high synthesis yield, good product quality and the like, and is suitable for industrial production and application.
The present invention will be further described with reference to the following embodiments. The following embodiments are only for the purpose of facilitating understanding of the present invention and do not limit the present invention. The present invention is not intended to be limited to the specific embodiments, and all the features mentioned in the description may be combined with each other to constitute a new embodiment as long as the features do not conflict with each other.
Detailed Description
Example one
Adding 2.87 g of fresh magnesium powder and 160 g of anhydrous ether into a 500 ml reaction bottle, stirring under the protection of nitrogen, cooling to (-5-0) DEG C by using a low-temperature bath, adding 0.5 ml of 2.0M isopropyl magnesium chloride solution through an injector, stirring for 10 minutes, dropwise adding a mixed solution of 30.79 g of 2,3,5,6-tetrafluoro-1,4-dibromobenzene and 120 g of anhydrous ether, and stirring and reacting for 10 hours at (-5-0) DEG C after dropwise adding to obtain 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide solution for later use.
And adding 14.5 g of cuprous chloride and 170 g of anhydrous ether into another 1L reaction bottle, starting stirring, cooling to (-50-55) DEG C, dropwise adding the prepared 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide solution, stirring at (-50-55) DEG C for reacting for 6 hours after the dropwise adding is finished, and stopping the reaction. Diluting the reaction liquid into 100 g of water, stirring at room temperature, adjusting the pH value to 1-2 by using concentrated hydrochloric acid, standing for layering, separating an upper organic phase, drying by using anhydrous sodium sulfate, concentrating to remove a solvent, decoloring the residue by using activated carbon, and recrystallizing to obtain 20.7 g of a white solid, namely 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl, wherein the yield is 90.8% and the purity is 99.4%.
Example two
Adding 3.76 g of fresh and sheared magnesium tape, 140 g of anhydrous 2-methyltetrahydrofuran and 140 g of nitrogen into a 500 ml reaction bottle, starting stirring, heating to 50-55 ℃, slowly dropwise adding a mixed solution of 46.2 g of 2,3,5,6-tetrafluoro-1,4-dibromobenzene and 180 g of anhydrous 2-methyltetrahydrofuran, stirring at 50-55 ℃ for reacting for 3 hours after dropwise adding is finished, obtaining 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide solution, and cooling for later use.
And adding 17.2 g of cuprous bromide and 150 g of anhydrous 2-methyltetrahydrofuran into another 1L reaction bottle, stirring, heating to 30-35 ℃, slowly dropwise adding the prepared 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide solution, and stirring at 30-35 ℃ for reaction for 2 hours after dropwise adding. Diluting the reaction liquid into 150 g of water, stirring at room temperature, adjusting the pH value to 1-2 by using 10% sulfuric acid solution, standing for layering, separating an upper organic phase, drying by using anhydrous sodium sulfate, concentrating to remove the solvent, decoloring the residue by using activated carbon, and recrystallizing to obtain 31.2 g of white solid, namely 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl, wherein the yield is 91.2%, and the purity is 99.3%.
EXAMPLE III
Adding 4.15 g of fresh and sheared magnesium tape, 50 g of anhydrous 1,4-dioxane and 0.1 g of iodine into a 250 ml reaction bottle under the protection of nitrogen, starting stirring, heating to (30-35) DEG C, slowly dropwise adding a mixed solution of 50 g of 2,3,5,6-tetrafluoro-1,4-dibromobenzene and 100 g of anhydrous 1,4-dioxane, and after dropwise adding, stirring at (30-35) DEG C for reaction for 5 hours to obtain 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide solution for later use.
And adding 15.6 g of cuprous iodide and 110 g of anhydrous 1,4-dioxane into a 500 ml reaction bottle, stirring, heating to 50-55 ℃, dropwise adding the prepared 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide solution, and stirring and reacting at 50-55 ℃ for 1 hour after dropwise adding. Diluting the reaction liquid into 150 g of 12% sulfuric acid solution, extracting twice by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, concentrating to remove the solvent, decoloring the residue by using activated carbon, and recrystallizing to obtain 33.58 g of white solid, namely 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl, wherein the yield is 90.7%, and the purity is 99.4%.
Example four
Adding 5.91 g of fresh magnesium powder, 210 g of anhydrous glycol dimethyl ether and nitrogen protection into a 1L reaction bottle, starting stirring, heating to 40-45 ℃, slowly dropwise adding a mixed solution of 70 g of 2,3,5,6-tetrafluoro-1,4-dibromobenzene and 140 g of anhydrous glycol dimethyl ether, stirring and reacting at 40-45 ℃ for 4 hours after dropwise adding is finished, obtaining 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide solution, and cooling for later use.
And adding 22.7 g of cuprous oxide and 100 g of anhydrous glycol dimethyl ether into another 1L reaction bottle, starting stirring, cooling to (-10-15) DEG C, dropwise adding the prepared 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide solution, and stirring at (-10-15) DEG C for reaction for 4 hours after dropwise adding. Diluting the reaction liquid into 250 g of water, adjusting the pH value to acidity by using 20% sulfuric acid solution, extracting twice by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, concentrating to remove a solvent, decoloring the residue by using activated carbon, and recrystallizing to obtain 47.17 g of white solid, namely 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl, wherein the yield is 91.0%, and the purity is 99.4%.
EXAMPLE five
Adding 8.68 g of fresh magnesium powder and 200 g of anhydrous tetrahydrofuran into a 1L reaction bottle, stirring at room temperature under the protection of nitrogen, slowly dropwise adding a mixed solution of 100 g of 2,3,5,6-tetrafluoro-1,4-dibromobenzene and 350 g of anhydrous tetrahydrofuran, and after dropwise adding, stirring at room temperature for reaction for 7 hours to obtain 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide solution for later use.
And adding 43.67 g of copper chloride and 100 g of anhydrous tetrahydrofuran into another 1L reaction bottle, starting stirring, cooling to (0-5) DEG C, dropwise adding the prepared 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide solution, and stirring and reacting at (0-5) DEG C for 3 hours after dropwise adding. The reaction solution is diluted to 200 g of 10% hydrochloric acid solution, extraction is carried out twice by ethyl acetate, organic phases are combined, the mixture is concentrated and removed of solvent after being dried by anhydrous sodium sulfate, residues are decolorized by active carbon and recrystallized to obtain 68.19 g of white solid, namely 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl, the yield is 92.1%, and the purity is 99.1%.
EXAMPLE six
Adding 7.25 g of fresh magnesium chips and 160 g of anhydrous dimethoxymethane into a 500 ml reaction bottle, stirring under nitrogen protection, cooling to (5-10) ° C, adding 0.5 ml of a 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide solution by using a syringe, stirring for 10 minutes, slowly dropwise adding a mixed solution of 80 g 2,3,5,6-tetrafluoro-1,4-dibromobenzene and 160 g of anhydrous dimethoxymethane, and after dropwise adding, stirring and reacting at (5-10) ° C for 8 hours to obtain 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide solution for later use.
And adding 34.8 g of cuprous sulfate and 300 g of anhydrous dimethoxymethane into another 1L reaction bottle, stirring, cooling to the temperature of (-30 to-35), dropwise adding the prepared 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide solution, and stirring at the temperature of (-30 to-35) for reaction for 5 hours after dropwise adding. Diluting the reaction liquid into 300 g of water, stirring at room temperature, adjusting the pH value to acidity by using a 10% hydrochloric acid solution, extracting twice by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, concentrating to remove the solvent, decoloring the residue by using activated carbon, and recrystallizing to obtain 53.84 g of white solid, namely 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl, wherein the yield is 90.9%, and the purity is 99.1%.
EXAMPLE seven
Adding 5.35 g of fresh magnesium chips and 60 g of anhydrous tetrahydrofuran into a 250 ml reaction bottle, stirring at room temperature under the protection of nitrogen, adding 0.2 g of dibromoethane into the reaction bottle by using a syringe, stirring for 15 minutes, slowly dropwise adding a mixed solution of 61.57 g 2,3,5,6-tetrafluoro-1,4-dibromobenzene and 60 g of anhydrous tetrahydrofuran, and after dropwise adding, stirring and reacting at room temperature for 6 hours to obtain 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide solution for later use.
And adding 23.75 g of cuprous chloride and 100 g of anhydrous tetrahydrofuran into another 500 ml reaction bottle, starting stirring, controlling the temperature of the system to be 10-15 ℃, dropwise adding the prepared 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide solution, and stirring and reacting for 3 hours at 10-15 ℃ after dropwise adding. The reaction solution is diluted to 150 g of 10% hydrochloric acid solution, extracted twice by ethyl acetate, organic phases are combined, dried by anhydrous sodium sulfate and concentrated to remove the solvent, and residues are decolorized by active carbon and recrystallized to obtain 42.08 g of white solid, namely 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl, the yield is 92.3% and the purity is 99.3%.
Claims (5)
1. A method for synthesizing 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl is characterized by comprising the following steps:
(1) 2,3,5,6-tetrafluoro-1,4-dibromobenzene reacts with metal magnesium at the temperature of-20-80 ℃ in an inert solvent to obtain 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide, wherein the ratio of the metal magnesium to the 2,3,5,6-tetrafluoro-1,4-dibromobenzene is 1-1.2;
(2) 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide is subjected to self-coupling reaction in an inert solvent at the temperature of-70-80 ℃ under the action of a copper catalyst to obtain 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl, wherein the copper catalyst is selected from one or more of the following: copper chloride, cuprous chloride, cupric bromide, cuprous iodide, cupric sulfate, cuprous sulfate, cupric oxide, cuprous oxide, the ratio of the amount of the copper catalyst to the amount of 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide is 0.3-1.5,
the reaction formula of the above reaction is described as follows:
2. the method of synthesizing 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl as claimed in claim 1, wherein: in the step (1), the inert solvent is an ether solvent and is represented by the following general formula: R-O-R ', wherein R, R' is C1-C10 linear chain, branched chain or cyclic alkyl, C1-C10 linear chain, branched chain or cyclic alkoxy alkyl, and the using amount of the solvent is 1-15 times of the weight of 2,3,5,6-tetrafluoro-1,4-dibromobenzene.
3. The method for synthesizing 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl according to claim 1, wherein: in the step (1), the inert solvent is selected from one or more of the following: diethyl ether, methyl propyl ether, ethyl propyl ether, methyl isopropyl ether, ethyl isopropyl ether, methyl n-butyl ether, ethyl n-butyl ether, methyl isobutyl ether, ethyl isobutyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, dimethoxymethane, diethoxymethane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, 1,1-dimethoxypropane, 1,1-diethoxypropane, 2,2-dimethoxypropane, 2,2-diethoxypropane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, cyclopentyl methyl ether, cyclohexyl methyl ether.
4. The method for synthesizing 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl according to claim 1, wherein: in the step (2), the inert solvent is an ether solvent and is represented by the following general formula: R-O-R ', wherein R, R' is C1-C10 linear chain, branched chain or cyclic alkyl, C1-C10 linear chain, branched chain or cyclic alkoxy alkyl, and the dosage of the solvent is 1-20 times of the weight of 2,3,5,6-tetrafluoro-4-bromophenyl magnesium bromide.
5. The method of synthesizing 2,2',3,3',5,5',6,6' -octafluoro-4,4 ' -dibromobiphenyl of claim 1, wherein: in the step (2), the inert solvent is selected from one or more of the following solvents: diethyl ether, methyl propyl ether, ethyl propyl ether, methyl isopropyl ether, ethyl isopropyl ether, methyl n-butyl ether, ethyl n-butyl ether, methyl isobutyl ether, ethyl isobutyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, dimethoxymethane, diethoxymethane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, 1,1-dimethoxypropane, 1,1-diethoxypropane, 2,2-dimethoxypropane, 2,2-diethoxypropane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, cyclopentyl methyl ether, cyclohexyl methyl ether.
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| CN113087592A (en) | 2021-07-09 |
| CN113087591A (en) | 2021-07-09 |
| CN111393256A (en) | 2020-07-10 |
| CN113087592B (en) | 2022-07-26 |
| CN112110789B (en) | 2022-05-03 |
| CN113087591B (en) | 2022-05-03 |
| CN113087590A (en) | 2021-07-09 |
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| CN112110789A (en) | 2020-12-22 |
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