CN101423460A - Method for preparing chlorinated diphenyl ether - Google Patents
Method for preparing chlorinated diphenyl ether Download PDFInfo
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- CN101423460A CN101423460A CNA2008102437436A CN200810243743A CN101423460A CN 101423460 A CN101423460 A CN 101423460A CN A2008102437436 A CNA2008102437436 A CN A2008102437436A CN 200810243743 A CN200810243743 A CN 200810243743A CN 101423460 A CN101423460 A CN 101423460A
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Abstract
The invention discloses a method for preparing chloro-substituted diphenyl ether or polychloro-substituted diphenyl ether. A target compound is generated by dichlorobenzene and phenol or fortified phenol which are added or not added with an organic solvent in the presence of a chlorine hydride absorbent for an Ullmann reaction under the catalysis of a catalyst; the chlorine hydride absorbent is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate; the solvent is a polar or non-polar organic solvent, and the using amount of the solvent accounts for 0 to 50 percent of total reaction materials; and the catalyst is iodide or a copper compound or a mixture of the iodide and the copper compound. The method has the advantages that the method adopts the optimized mixture ratio of raw materials, a mixed solvent system and a copper catalyst with a nano-grain diameter, and ensures that the reaction rate is accelerated and a product has high yield.
Description
Technical field
The preparation method of a kind of phenyl ether that the present invention relates to.More specifically, relate to the preparation method of a kind of chloro or many chlorinated diphenyl ethers.
Background technology
Two aryl oxide compounds are important agricultural chemicals and medicine intermediates, wherein, chlorinated diphenyl ether is a kind of special phenyl ether, but chlorine is reactive group, can be converted into (synthetic chemistries such as amido, 2003,11,37), can as intermediate prepare medicine, (EP 0051235 for agricultural chemicals, 0065485,126430), difenoconazole wherein (DE 3140277) compounds is the agricultural chemicals that a kind of consumption is big and sterilization effect is good; And, also can be used for making plant-growth regulator (USP4124370) or hydraulic efficiency oil (USP3472782); Or replace polychlorinated biphenyl to be used for making electrical condenser; Simultaneously many chlorinated diphenyl ethers and downstream product polyamines yl diphenyl ether thereof can also be as the monomers of synthetic macromolecular compound, so chlorinated diphenyl ether has important use and is worth.
There are some diverse ways can be used for preparing diphenyl ether compound, wherein convenient and commonly used with the Ullmann reaction.The Ullmann reaction is a raw material with halo aryl oxide and phenates, is catalyzer with metallic copper or mantoquita, gets through the pyrocondensation reaction.Discover: wherein the activity of halo aryl oxide wants high, in general, iodo thing and bromo-derivative are than the reactive behavior height of chloro thing, under copper catalyst and phase-transfer catalyst condition, react 4-chlorodiphenyl ether (the Tetrahedron Letters that can obtain 90% yield as phenol with to chloroiodobenzone, 2008
49, 2018), but to chloroiodobenzone preparation difficulty, price is very high; Simultaneously, it is also higher to contain the fragrant halogen reactive behavior of strong electron-withdrawing group group (as nitro, trifluoromethyl) on the phenyl ring.And reaction is very slow during with common chlorinated aromatic hydrocarbons.
Therefore in the reaction process, usually add the complex compound of mantoquita, copper, the compound that reaches nickel and palladium is a catalyzer, and certain cocatalysts comes accelerated reaction, the raising efficiency of pcr product.As aspect the preparation chlorinated diphenyl ether, USP3472782,3371120 reports are catalyzer with CuCl/KI, prepare 3,4 '-dichloro-diphenyl ether with p-dichlorobenzene and 3-diclophenac sodium.EP 0051235 report is that catalyzer carries out the Ullmann reaction with the lipid acid mantoquita of ventilation breather or low carbon chain.But the control of reaction yield, reaction and reaction times are all undesirable, and under at copper oxide catalyzation, para-chlorophenol salt reacts 24h with Meta Dichlorobenzene at 150 ℃, 3, and the productive rate of 4 '-dichloro-diphenyl ether only is 10～20%.Sometimes also add some phase-transfer catalysts improve reaction speed (Tetrahedron Letters, 2008,
49, 2018)
Because the Ullmann reaction is a nucleophilic substitution reaction, non-proton intensive polar solvent can increase the nucleophilic attack ability of ArO-negative ion, therefore uses dimethyl sulfoxide (DMSO) or N mostly, and dinethylformamide etc. are as solvent.Simultaneously, the reaction product chlorinated diphenyl ether is also produced by products such as trimerization or four polyethers together with the phenolate reaction, the temperature of reaction height, and then by product is many.
Summary of the invention
The present invention relates to the preparation method of a kind of chlorinated diphenyl ether or many chlorinated diphenyl ethers,, improve reactive behavior, shorten the reaction times, improve product selectivity and yield by realizing that simply industrial method prepares chlorinated diphenyl ether.
Technical scheme of the present invention is as follows:
The preparation method of a kind of chlorinated diphenyl ether or many chlorinated diphenyl ethers, it is characterized in that: by dichlorobenzene and phenol or fortified phenol under the condition that chlorine hydride absorbent exists, the Ullmann reaction is carried out in interpolation or not adding machine solvent again under catalyst, generate target compound; Chlorine hydride absorbent is one or more in sodium hydroxide, potassium hydroxide, yellow soda ash or the salt of wormwood; Solvent is polarity or nonpolar organic solvent, including, but not limited to toluene, dimethylbenzene, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol dibutyl ether and dibutyl ethylene glycol ether, or the mixture of two or more above-mentioned solvents, its consumption accounts for 0～50% of total reaction material; Catalyzer is iodide or copper compound, or the mixture of the two.
The preparation method of described chlorinated diphenyl ether or many chlorinated diphenyl ethers is characterized in that: dichlorobenzene refers to santochlor or Meta Dichlorobenzene; Fortified phenol, its chemical structural formula is:
Wherein, R
1, R
2Be alone the saturated or unsaturated alkyl of H, straight or branched respectively, as methyl, ethyl, propyl group or sec.-propyl, butyl or isobutyl-, vinyl, phenyl or other inactive substituted radical; R
2Also be chosen as chlorine; R
1, R
2Position on phenyl ring can be in phenolic hydroxyl group optional position in addition.
The preparation method of described chlorinated diphenyl ether or many chlorinated diphenyl ethers is characterized in that: the mol ratio of dichlorobenzene and phenol or fortified phenol is 3～5:1.
The preparation method of described chlorinated diphenyl ether or many chlorinated diphenyl ethers is characterized in that: the Ullmann reaction conditions is: carry out under normal pressure, negative pressure or certain pressure; Temperature of reaction is 80～250 ℃; Reaction times is for being 5～30h; Quantity of solvent is 0～30% of a total reaction material.
The preparation method of described chlorinated diphenyl ether or many chlorinated diphenyl ethers, it is characterized in that: dichlorobenzene refers to Meta Dichlorobenzene, and when fortified phenol referred to para-chlorophenol, target compound was 3, during 4 '-dichloro-diphenyl ether, Meta Dichlorobenzene: the mol ratio of para-chlorophenol is 2～10:1; The mixture that adopts polar solvent and azeotropic dehydration solvent is as solvent, and the volume ratio of the two is 2～8:8～2, adopts toluene or dimethylbenzene as the azeotropic dehydration solvent, and adopting dimethyl formamide or dimethyl formamide is the mixture of polar solvent.
The preparation method of described chlorinated diphenyl ether or many chlorinated diphenyl ethers is characterized in that: described copper compound refers to copper hydroxide, cupric oxide, Red copper oxide, cupric chloride, cuprous chloride, cupric iodide, copper carbonate or ventilation breather; Or the mixture of two or more above-mentioned mantoquitas, add-on is 0.1～2%; Described iodide are meant sodium iodide or potassiumiodide, and its consumption is 0.02～1% of a total reactant amount.
The preparation method of described chlorinated diphenyl ether or many chlorinated diphenyl ethers is characterized in that: copper compound is the ultra-fine cuprous chloride of median size＜1 μ m, and its add-on is 0.1～2% of a reactant.
The preparation method of described chlorinated diphenyl ether or many chlorinated diphenyl ethers is characterized in that: described Meta Dichlorobenzene: the para-chlorophenol mol ratio is 3～5:1, and solvent boiling point is 100～250 ℃.
The preparation method of described chlorinated diphenyl ether or many chlorinated diphenyl ethers is characterized in that: the ratio of two kinds of solvents is 3:7～4:6.
Dichlorobenzene, its chemical structural formula is:
Two chlorine atoms position or contrapositions between the position on the phenyl ring is, promptly A can be Meta Dichlorobenzene, or is santochlor.
Chlorine hydride absorbent, but the hydrogenchloride that neutralization reaction is emitted are sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood etc.
Reaction can be carried out under normal pressure, decompression or certain pressure, generally carries out under normal pressure.
Temperature of reaction is 80～250 ℃, and the reaction times is 5～30h.
In particular:
What the present invention relates to is a kind of method for preparing chlorinated diphenyl ether or many chlorinated diphenyl ethers, as the 3-chlorodiphenyl ether, 4-chlorodiphenyl ether, 3,3 '-dichloro-diphenyl ether, 3,4 '-dichloro-diphenyl ether, 2,4 '-dichloro-diphenyl ether, 4, the preparation method of 4 '-dichloro-diphenyl ether etc. reacts by Ullmann and to prepare.
According to the structure of product, select suitable phenol and chlorobenzene, it is synthetic that a kind of compound has several routes, as prepare 3, and 4 '-dichloro-diphenyl ether can be a raw material with Meta Dichlorobenzene and para-chlorophenol, can be raw material with santochlor and m-Chlorophenol also.
Owing to contain chlorine substituent in the reaction product, can also continue reaction with phenol and produce by products such as trimerization or four polyethers, must control two kinds of proportion of raw materials when therefore reacting, with the generation of control side reaction, improve yield and guarantee the purity of product.As with Meta Dichlorobenzene and para-chlorophenol being raw material synthetic 3, during 4 '-dichloro-diphenyl ether, two kinds of stock yard dichlorobenzene: the para-chlorophenol mol ratio is that 2～10:1 is comparatively suitable, considers comprehensive factors such as equipment efficiency of usage, and preferred Meta Dichlorobenzene: the para-chlorophenol material molar ratio is 3～5:1.
Reaction raw materials phenol can be converted into phenates earlier, with the chlorinated benzene reaction, can adopt sodium hydroxide or potassium hydroxide and its reaction, and then the water that generates is distilled out system then.Certainly, also can use yellow soda ash or salt of wormwood, constantly dehydration in reaction process, but speed of response is slower.
Dehydration can be used organic solvent such as azeotropic dehydrations such as toluene or dimethylbenzene, also can constantly feed the rare gas element dehydration to system, and wherein azeotropic dehydration speed is fast.
Extra solvent can not be added in reaction, directly carries out in excessive material system.But for the concentration of controlling reactive material and the viscosity of system, the moisture that reaction is emitted can in time be got rid of system and fast reaction speed, preferably adds suitable solvent.On choice of Solvent, except not participating in reaction, mainly consider the boiling point and the polarity of solvent.
When the boiling point of solvent was too low, temperature of reaction did not increase, and the reaction reflux temperature is low, and speed of response is slow.But solvent boiling point is too high, too near the boiling point of product, can cause the separation difficulty with product.So suitable solvent boiling point is 100～250 ℃.
According to the characteristics of Ullmann reaction, the polarity of solvent height can improve speed of response, but product selectivity is had certain influence.
To consider also that simultaneously phenol and alkali reaction can emit water, and the existence of water can influence the carrying out of reaction, so must make water exclude reaction system completely, the present invention adopts a kind of azeotropic dehydration solvent, constantly water is in time distilled the discharge reaction system in initial reaction stage and reaction process.
Take all factors into consideration above-mentioned factor, patent of the present invention adopts the mixture of a kind of polar solvent and a kind of azeotropic dehydration solvent, as the mixed solvent with the same dimethyl formamide of toluene (or dimethylbenzene) (or dimethyl formamide).The ratio of these two kinds of solvents is 2:8～8:2, is preferably 3:7～4:6.
It is too big that the ratio of whole solvent and reactant is difficult for, otherwise can influence the utilising efficiency of conversion unit, be generally reactant 0～50% between, being preferably is 0～25%.
The Ullmann reaction will be added the carrying out that catalyzer comes accelerated reaction sometimes, is generally copper catalyst, as copper hydroxide, cupric oxide, Red copper oxide, cupric chloride, cuprous chloride, cupric iodide, copper carbonate, ventilation breather etc.; It also can be the mixture of two or more above-mentioned mantoquitas.Can also be sodium iodide or potassiumiodide simultaneously, or the mixture of they and one or more above-mentioned mantoquitas.
This patent adopts the ultra-fine cuprous chloride catalyst of a kind of particle diameter at 100～800nm, because particle diameter is little, is easy to disperse in system, has improved catalytic effect, has accelerated speed of response.Its add-on is 0.1～2% of a reactant, is preferably 0.2～0.5%.
Also can add a spot of promotor salt compounded of iodine in the reaction, be sodium iodide or potassiumiodide, preferred potassiumiodide.Its consumption is 0.02～1% of a reactant, is preferably 0.05～0.5%
Reaction can be carried out under normal pressure, decompression or certain pressure, generally carries out under normal pressure for easy to operate.
According to factors such as the activity of reactant and boiling points, temperature of reaction is 80～250 ℃, preferably 120～160 ℃.Reaction times is generally 5～30h, owing to improved speed of response, can shorten the reaction times, and the therefore preferred reaction times is 10～20h.
In reaction process, can take a sample and carry out the content of gas chromatographic analysis product in system, to understand the degree of carrying out of reaction.
Advantage of the present invention is: adopt the copper catalyst of proportioning raw materials, mixed solvent system and the nanometer particle size optimized, make speed of response accelerate the product yield height.
Following some examples that pass through further describe content of the present invention, but do not constitute the restriction to other protection domain of this patent.
Embodiment
Embodiment 1:
The preparation of 4-chloro-phenyl ether
94g phenol, 650g santochlor, 1g median size are that cuprous chloride, 0.5g potassiumiodide, 150g N,N-DIMETHYLACETAMIDE and the 50mL dimethylbenzene of 600nm adds in the four-necked bottle, stir down to wherein adding 40g sodium hydroxide, heat up gradually then, to 120 ℃ of beginnings of interior temperature azeotropic, in temperature time dehydration finishes to 160 ℃, continue stirring reaction 12h at 160～165 ℃ then, stop heating, leave standstill cooling, filter.The filtrate decompression distillation, the cut of 135～138 ℃/6mmHg of collection obtains colourless transparent liquid 164.8g.4-chloro-phenyl ether yield (in phenol) is 80.6%, and through gas chromatographic analysis, content is 99.3%.
Embodiment 2:
The preparation of 3-chlorodiphenyl ether
94g phenol, 650g Meta Dichlorobenzene, 2.5g median size are that cuprous chloride, salt of wormwood, 150 gram N,N-DIMETHYLACETAMIDEs and the 50mL dimethylbenzene of 600nm adds in the four-necked bottle, 140 ℃ of beginnings of temperature azeotropic in being warming up to gradually, slowly be warmed up to 160～165 ℃ then and continue stirring reaction 12h, stop heating, leave standstill cooling, filter.The filtrate decompression distillation, the cut of 128～132 ℃/5mmHg of collection gets colourless transparent liquid 175.3g.3-chloro-phenyl ether yield (in phenol) is 85.7%, and through gas chromatographic analysis, content is 99.5%.
Embodiment 3:
3, the preparation of 4 '-dichloro-diphenyl ether
130g para-chlorophenol, 600g Meta Dichlorobenzene and toluene 100mL add in the four-necked bottle, to wherein adding 41g sodium hydroxide, 120～140 ℃ of azeotropic dehydrations, the dehydration condistillation goes out most of 65mL toluene, adding the 1.5g median size then in system is the cuprous chloride of 600nm, and the 60g diethylene glycol diethyl ether, be warmed up to 170 ℃, continue at 170 ℃ of stirring reaction 20h.Reaction finishes postcooling to room temperature, with the filtrate decompression distillation, collects the cut of 146 ℃/5mmHg after the filtration, gets colourless transparent liquid 219g.3,4 '-dichloro-diphenyl ether yield (in para-chlorophenol) is 90.6%, and through gas chromatographic analysis, content is 99.2%.
Embodiment 4:
3, the preparation of 4 '-dichloro-diphenyl ether
M-Chlorophenol with equivalent replaces para-chlorophenol, and santochlor replaces Meta Dichlorobenzene, N, the N-diethylformamide replaces diethylene glycol diethyl ether, repeats embodiment 3,3,4 '-dichloro-diphenyl ether yield (in m-Chlorophenol) is 89.1%, and through gas chromatographic analysis, content is 99.0%.
Embodiment 5:
4, the preparation of 4 '-dichloro-diphenyl ether
130g para-chlorophenol, 700g santochlor and toluene 100mL add in the four-necked bottle, to wherein adding 57g potassium hydroxide, 100～140 ℃ of azeotropic dehydrations, the dehydration condistillation goes out most of 70mL toluene, adding the 2.0g median size then in system is the cuprous chloride of 600nm, and the 60g N,N-DIMETHYLACETAMIDE, be warmed up to 170 ℃, continue at 170 ℃ of stirring reaction 15h.Reaction finishes postcooling to room temperature, leaves standstill, and with the filtrate decompression distillation, collects the cut of 149～151 ℃/5mmHg after the filtration, gets colourless transparent liquid 226g.4,4 '-dichloro-diphenyl ether yield (in para-chlorophenol) is 83.4%, and through gas chromatographic analysis, content is 99.4%.
Claims (9)
1, the preparation method of a kind of chlorinated diphenyl ether or many chlorinated diphenyl ethers, it is characterized in that: by dichlorobenzene and phenol or fortified phenol under the condition that chlorine hydride absorbent exists, the Ullmann reaction is carried out in interpolation or not adding machine solvent again under catalyst, generate target compound; Chlorine hydride absorbent is one or more in sodium hydroxide, potassium hydroxide, yellow soda ash or the salt of wormwood; Solvent is polarity or nonpolar organic solvent, including, but not limited to toluene, dimethylbenzene, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol dibutyl ether and dibutyl ethylene glycol ether, or the mixture of two or more above-mentioned solvents, its consumption accounts for 0～50% of total reaction material; Catalyzer is iodide or copper compound, or the mixture of the two.
2, the preparation method of chlorinated diphenyl ether according to claim 1 or many chlorinated diphenyl ethers is characterized in that: dichlorobenzene refers to santochlor or Meta Dichlorobenzene; Fortified phenol, its chemical structural formula is:
Wherein, R
1, R
2Be alone the saturated or unsaturated alkyl of H, straight or branched respectively, as methyl, ethyl, propyl group or sec.-propyl, butyl or isobutyl-, vinyl, phenyl or other inactive substituted radical; R
2Also be chosen as chlorine; R
1, R
2Position on phenyl ring can be in phenolic hydroxyl group optional position in addition.
3, the preparation method of chlorinated diphenyl ether according to claim 1 or many chlorinated diphenyl ethers is characterized in that: the mol ratio of dichlorobenzene and phenol or fortified phenol is 3～5:1.
4, the preparation method of chlorinated diphenyl ether according to claim 1 or many chlorinated diphenyl ethers is characterized in that: the Ullmann reaction conditions is: carry out under normal pressure, negative pressure or certain pressure; Temperature of reaction is 80～250 ℃; Reaction times is for being 5～30h; Quantity of solvent is 0～30% of a total reaction material.
5, the preparation method of chlorinated diphenyl ether according to claim 1 or many chlorinated diphenyl ethers, it is characterized in that: dichlorobenzene refers to Meta Dichlorobenzene, and when fortified phenol referred to para-chlorophenol, target compound was 3, during 4 '-dichloro-diphenyl ether, Meta Dichlorobenzene: the mol ratio of para-chlorophenol is 2～10:1; The mixture that adopts polar solvent and azeotropic dehydration solvent is as solvent, and the volume ratio of the two is 2～8:8～2, adopts toluene or dimethylbenzene as the azeotropic dehydration solvent, and adopting dimethyl formamide or dimethyl formamide is the mixture of polar solvent.
6, according to the preparation method of the described chlorinated diphenyl ether of one of claim 1-5 or many chlorinated diphenyl ethers, it is characterized in that: described copper compound refers to copper hydroxide, cupric oxide, Red copper oxide, cupric chloride, cuprous chloride, cupric iodide, copper carbonate or ventilation breather; Or the mixture of two or more above-mentioned mantoquitas, add-on is 0.1～2%; Described iodide are meant sodium iodide or potassiumiodide, and its consumption is 0.02～1% of a total reactant amount.
7, the preparation method of chlorinated diphenyl ether according to claim 6 or many chlorinated diphenyl ethers is characterized in that: copper compound is the ultra-fine cuprous chloride of median size＜1 μ m, and its add-on is 0.1～2% of a reactant.
8, the preparation method of chlorinated diphenyl ether according to claim 5 or many chlorinated diphenyl ethers is characterized in that: described Meta Dichlorobenzene: the para-chlorophenol mol ratio is 3～5:1, and solvent boiling point is 100～250 ℃.
9, the preparation method of chlorinated diphenyl ether according to claim 5 or many chlorinated diphenyl ethers is characterized in that: the ratio of two kinds of solvents is 3:7～4:6.
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| CN108069834A (en) * | 2016-11-18 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of method that serialization prepares 3,4 ' dichloro-diphenyl ethers |
| CN108069834B (en) * | 2016-11-18 | 2020-11-10 | 中国科学院大连化学物理研究所 | Method for continuously preparing 3, 4' -dichlorodiphenyl ether |
| CN111097524A (en) * | 2019-12-12 | 2020-05-05 | 广东省石油与精细化工研究院 | UiO-67 solid-supported Cu salt catalyst and preparation method and application thereof |
| CN111153772A (en) * | 2020-01-08 | 2020-05-15 | 安徽禾宸化学科技有限公司 | Preparation method for constructing diphenyl ether structure compound |
| CN115087642A (en) * | 2020-03-10 | 2022-09-20 | 株式会社吴羽 | Preparation method of azole derivative, preparation method of bromohydrin derivative and bromohydrin derivative, and preparation method of 1-chloro-3- (4-chlorophenoxy) benzene |
| CN115087642B (en) * | 2020-03-10 | 2023-05-05 | 株式会社吴羽 | Process for producing azole derivative, process for producing bromohydrin derivative and process for producing bromohydrin derivative, and process for producing 1-chloro-3- (4-chlorophenoxy) benzene |
| US11739038B2 (en) | 2020-03-10 | 2023-08-29 | Kureha Corporation | Method for producing azole derivative, bromohydrin derivative and method for producing same, and method for producing 1-chloro-3-(4-chlorophenoxy)benzene |
| CN113636917A (en) * | 2021-08-10 | 2021-11-12 | 宁夏瑞泰科技股份有限公司 | Synthetic method of 3, 4' -dichlorodiphenyl ether |
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