CN101062887A - Method for synthesizing o-phenylphenol - Google Patents
Method for synthesizing o-phenylphenol Download PDFInfo
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Abstract
The invention discloses a synthesizing method of orthoxenol with amino benzenes compound, which comprises the following steps: choosing amino benzenes compound as raw material; diazotizing; coupling; generating diphenyl compound; hydrolyzing; getting the orthoxenol. This invention possesses simple operation, low cost and high receiving ratio, which adopts a new route to proceed.
Description
Technical field
The present invention relates to a kind of important organic chemical industry and the synthetic route of pharmaceutical prod and intermediate orthoxenol, belong to meticulous organic chemical industry (medicine is synthetic) field.
Background technology
As a kind of important fine chemical product, orthoxenol (III) is widely used in industries such as medicine, dyestuff.Orthoxenol (III) is mainly synthetic by partition method and synthesis method at present.Partition method is to reclaim to produce from the distillation residue of being produced phenol by sulfonation method, owing to be subjected to resource limit, output is limited, and along with eliminating gradually of sulfonation method phenol process, the amount of orthoxenol can not be met the need of market; Synthesis method relates generally to the catalytic dehydrogenation of the dimer 2-hexamethylene alkylidene group pimelinketone and 2-(1-cyclohexenyl) pimelinketone (II) of pimelinketone (I), but the catalyst themselves of catalytic dehydrogenation costs an arm and a leg, and it is higher that the life-span causes production cost than short-range missile.And the efficient of gas-phase dehydrogenation is higher, but the equipment installation cost is bigger, the operational requirement strictness, and the technology of dehydrogenation in liquid phase is comparatively simple, and shortcoming is that the recovery and reuse of catalyzer are relatively more difficult, all is unsuitable for large-scale production.
Summary of the invention
The invention provides a kind of route novelty, simple to operate, the novel method of preparation orthoxenol with low cost.
Described synthetic method comprises following steps: formula (IV) compound or its salt under the effect of phase-transfer catalyst, under acidic conditions with diazo reagent in corresponding coupling reagent in-20-100 ℃ diazotization reaction; Diazonium salt (V) again under the catalysis of coupling catalyst, generates biphenol compound (VI) in 0-100 ℃ with coupling reagent directly or after filtering; Biphenol compound (VI) promptly gets orthoxenol (III) through alkalescence or acidic conditions hydrolysis.
R is hydrogen, fluorine, chlorine, bromine or iodine atom in its Chinese style (IV), is preferably chlorine, bromine atoms; Described coupling reagent Ph-R
1Middle R
1For corresponding hydrogen atom or methoxyl group, oxyethyl group, be preferably methoxyl group; R in the described biphenol compound (VI)
2Be fluorine, chlorine, bromine, iodine atom or methoxyl group, oxyethyl group.
Described corresponding coupling reagent Ph-R
1Consumption be calculated as 1～5ml by every 1g formula (IV) compound.
Phase-transfer catalyst is benzyltriethylammoinium chloride (TEBA) in described diazotization and the linked reaction, 18 hats, 6 (18-C-6), caproic acid potassium, tetrabutyl ammonium sulfate etc., be preferably TEBA and 18-C-6, catalyst consumption is the 0.1-10% of reaction raw materials formula (IV) compound quality, is preferably 0.5-5%.
Used an acidic catalyst is one of following or more than one arbitrary combination in the described diazotization reaction: the hydrochloride of the vitriol oil, trichoroacetic acid(TCA), trifluoroacetic acid or corresponding formula (IV) compound is preferably the hydrochloride and the vitriol oil of compound (IV).The equivalence ratio of the consumption of described acid and formula (IV) compound is 1-10: 1, be preferably 1-4: 1.
Diazo reagent such as Sodium Nitrite, nitrous acid isopropyl ester, nitrous acid straight butyl, n-amyl nitrite are preferably Sodium Nitrite in the described diazotization reaction.The equivalence ratio of the consumption of described diazo reagent and formula (IV) compound is 0.6-3: 1, be preferably 0.9-1.5: 1.
If R is fluorine, chlorine, bromine or iodine atom, then select for use benzene in the above-mentioned formula (IV), simultaneously solvent for reacting as coupling reagent; Diazotization and coupling can be adopted the method for the treatment of different things alike, and directly obtain biphenol compound (VI) in the presence of coupling catalyst, yield 60-90%, R in its Chinese style (VI)
2Be fluorine, chlorine, bromine or iodine atom.Biphenol compound (VI) hydrolysis under alkaline condition obtains orthoxenol (III), yield 40-60%.
Described diazotization reaction an acidic catalyst is preferably the mixed acid of the hydrochloride and the vitriol oil of formula (IV), and the equivalence ratio of the hydrochloride of the vitriol oil and formula (IV) is 0.1-0.5: 1, be preferably 0.2-0.3: 1.
Described diazotization and linked reaction temperature be-20-100 ℃, be preferably 40-80 ℃.
Described coupling catalyst is copper powder, cuprous chloride, cupric chloride, is preferably copper powder; Catalyst consumption is the 2-20% of formula (IV) compound quality, is preferably 5-10%.
Described hydrolysis reaction carries out under alkaline condition, and described alkali is sodium hydroxide, potassium hydroxide, is preferably sodium hydroxide.The concentration of aqueous solution of described alkali is 10-50%, is preferably 35-45%; The consumption of described alkali is 2-10 for the equivalence ratio with formula (VI): 1, be preferably 3-5: 1.
Described hydrolysis reaction carries out under Red copper oxide, cuprous chloride catalysis, is preferably Red copper oxide; The mass ratio of catalyzer and halogenated biphenyl is 5-20%, is preferably 10%.
Described hydrolysis reaction carries out at 180-250 ℃, is preferably 230-240 ℃; Pressure is 15-30atm, is preferably 20-25atm.
If R is a hydrogen atom, then select methyl-phenoxide for use in the above-mentioned formula (IV), phenyl ethyl ether is a coupling reagent, is preferably methyl-phenoxide.Join coupling under catalyst in the coupling reagent after the diazonium salt of gained can filter once more, obtain biphenol compound (VI) yield 60-80%, wherein R
2Be methoxyl group, oxyethyl group.Biphenol compound (VI) hydrolysis under acidic conditions obtains orthoxenol (III) yield 60-90%.
Described diazotization reaction temperature is-20-100 ℃, be preferably 0-25 ℃.
Described coupling catalyst is Potassium ethanoate, sodium-acetate, salt of wormwood, is preferably Potassium ethanoate; The equivalence ratio of catalyzer and formula (IV) is 1-5: 1, be preferably 2: 1.
Described linked reaction temperature is 0-100 ℃, is preferably 0-40 ℃.
Described hydrolysis reaction carries out under acidic conditions, optional Hydrogen bromide, and the aqueous solution such as hydroiodic acid HI are preferably Hydrogen bromide; Concentration is 20-60%, is preferably 45-55%; The aqueous acid consumption is calculated as 5-20ml by every 1g formula (VI) compound, is preferably 10-15ml.
Described hydrolysising reacting temperature is 60-100 ℃, is preferably 90-100 ℃.
Synthetic method of the present invention generates biphenyl compound (VI) with the diazotization and the linked reaction of amino benzenes compounds (IV) under acid catalysis by diazo reagent in organic coupling reagent, hydrolysis afterwards generates orthoxenol (III).Method provided by the present invention has the route novelty, and cost is low and simple to operate---and can save the separation drying step, reduce the characteristics such as Hazard Factor in the diazonium salt drying process.
Embodiment:
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this.
Embodiment 1
The 6.4g o-chloroaniline hydrochloride is joined in the there-necked flask that contains 30mL benzene, room temperature (25 ℃) adds 3.0g anhydrous magnesium sulfate and 0.1g copper powder, (0.05gTEBA benzyltriethylammoinium chloride), add the 3.3g Sodium Nitrite afterwards, be heated to 60 ℃ of reaction 24h, add the 1.0g vitriol oil afterwards, continue reaction 12h.Reacting liquid filtering, solid washes twice with benzene, and filtrate water is given a baby a bath on the third day after its birth inferior, reclaims benzene, gets adjacent chlordiphenyl 5.6g, yield 76.16%.
Embodiment 2
The 6.4g o-chloroaniline hydrochloride is joined in the there-necked flask that contains 30mL benzene, and room temperature (25 ℃) adds 2.0g anhydrous magnesium sulfate and 0.1g copper powder, 0.05gTEBA, add the 3.3g Sodium Nitrite afterwards, be heated to 60 ℃ of reaction 30h, add the 1.0g vitriol oil afterwards, continue reaction 15h.Reacting liquid filtering, solid washes twice with benzene, and filtrate water is given a baby a bath on the third day after its birth inferior, reclaims benzene, gets adjacent chlordiphenyl 5.3g, yield 72.11%.
Embodiment 3
The 6.4g o-chloroaniline hydrochloride is joined in the there-necked flask that contains 30mL benzene, and room temperature (25 ℃) adds 3.0g anhydrous magnesium sulfate and 0.5g copper powder, 0.05gTEBA, add the 3.3g Sodium Nitrite afterwards, be heated to 60 ℃ of reaction 20h, add the 1.0g vitriol oil afterwards, continue reaction 12h.Reacting liquid filtering, solid washes twice with benzene, and filtrate water is given a baby a bath on the third day after its birth inferior, reclaims benzene, gets adjacent chlordiphenyl 5.7g, yield 77.55%.
Embodiment 4
The 6.4g o-chloroaniline hydrochloride is joined in the there-necked flask that contains 30mL benzene, and room temperature (25 ℃) adds 3.0g anhydrous magnesium sulfate and 0.1g copper powder, adds the 3.3g Sodium Nitrite afterwards, is heated to 60 ℃ of reaction 48h, adds the 1.0g vitriol oil afterwards, continues reaction 24h.Reacting liquid filtering, solid washes twice with benzene, and filtrate water is given a baby a bath on the third day after its birth inferior, reclaims benzene, gets adjacent chlordiphenyl 4.5g, yield 61.22%.
Embodiment 5
The 6.4g o-chloroaniline hydrochloride is joined in the there-necked flask that contains 30mL benzene, and room temperature (25 ℃) adds 3.0g anhydrous magnesium sulfate and 0.1g cuprous chloride, 0.05gTEBA, add the 3.3g Sodium Nitrite afterwards, be heated to 60 ℃ of reaction 24h, add the 1.0g vitriol oil afterwards, continue reaction 12h.Reacting liquid filtering, solid washes twice with benzene, and filtrate water is given a baby a bath on the third day after its birth inferior, reclaims benzene, gets adjacent chlordiphenyl 5.5g, yield 74.83%.
Embodiment 6
The 6.4g o-chloroaniline hydrochloride is joined in the there-necked flask that contains 30mL benzene, and room temperature (25 ℃) adds 3.0g anhydrous magnesium sulfate and 0.1g copper powder, 0.05g 18-C-6, add the 3.3g Sodium Nitrite afterwards, be heated to 60 ℃ of reaction 24h, add the 1.0g vitriol oil afterwards, continue reaction 12h.Reacting liquid filtering, solid washes twice with benzene, and filtrate water is given a baby a bath on the third day after its birth inferior, reclaims benzene, gets adjacent chlordiphenyl 5.9g%, yield 80.27%.
Embodiment 7
The 6.4g o-chloroaniline hydrochloride is joined in the there-necked flask that contains 30mL benzene, and room temperature (25 ℃) adds 3.0g anhydrous magnesium sulfate and 0.1g copper powder, 0.05gTEBA, add the 4.0g Sodium Nitrite afterwards, be heated to 60 ℃ of reaction 24h, add the 1.0g vitriol oil afterwards, continue reaction 12h.Reacting liquid filtering, solid washes twice with benzene, and filtrate water is given a baby a bath on the third day after its birth inferior, reclaims benzene, gets adjacent chlordiphenyl 5.6g, yield 76.16%.
Embodiment 8
The 6.4g o-chloroaniline hydrochloride is joined in the there-necked flask that contains 30mL benzene, and room temperature (25 ℃) adds 3.0g anhydrous magnesium sulfate and 0.1g copper powder, 0.05gTEBA, add the 3.3g Sodium Nitrite afterwards, be heated to 40 ℃ of reaction 30h, add the 1.0g vitriol oil afterwards, continue reaction 15h.Reacting liquid filtering, solid washes twice with benzene, and filtrate water is given a baby a bath on the third day after its birth inferior, reclaims benzene, gets adjacent chlordiphenyl 5.1g, 69.39%.
Embodiment 9
8.3g o-bromoaniline hydrochloride is joined in the there-necked flask that contains 30mL benzene, and room temperature (25 ℃) adds 3.0g anhydrous magnesium sulfate and 0.1g copper powder, 0.05gTEBA, add the 3.3g Sodium Nitrite afterwards, be heated to 60 ℃ of reaction 24h, add the 1.5g vitriol oil afterwards, continue reaction 12h.Reacting liquid filtering, solid washes twice with benzene, and filtrate water is given a baby a bath on the third day after its birth inferior, reclaims benzene, gets adjacent chlordiphenyl 7.9g, yield 85.22%.
Embodiment 10
8.3g o-bromoaniline hydrochloride is joined in the there-necked flask that contains 40mL benzene, and room temperature (25 ℃) adds 3.0g anhydrous magnesium sulfate and 0.1g copper powder, 0.05g 18-C-6, add the 3.3g Sodium Nitrite afterwards, be heated to 60 ℃ of reaction 20h, add the 1.0g vitriol oil afterwards, continue reaction 5h.Reacting liquid filtering, solid washes twice with benzene, and filtrate water is given a baby a bath on the third day after its birth inferior, reclaims benzene, gets adjacent bromo biphenyl 8.3g, yield 89.54%.
Embodiment 11
Adjacent chlordiphenyl 31.3g joined in 40% the NaOH aqueous solution (67g+100mL), add 3.0g Red copper oxide, heat 240 ℃ of reactions, self pressure reaches 20-25atm, reacts 72h.Filter, use the concentrated hydrochloric acid acidifying afterwards, with three times (100mL*3) of toluene extraction, the combining methylbenzene layer is used the NaOH aqueous solution extraction, merge the alkali layer, wash twice with toluene, the concentrated hydrochloric acid acidifying of alkali layer with toluene extraction (50mL*3), merges once more, drying concentrates, and gets product 11.5g, yield 40.48%.
Embodiment 12
Adjacent chlordiphenyl 31.3g joined in 50% the NaOH aqueous solution (100g+100mL), add 3.0g Red copper oxide, heat 240 ℃ of reactions, self pressure reaches 20-25atm, reacts 72h.Filter, use the concentrated hydrochloric acid acidifying afterwards, with three times (100mL*3) of toluene extraction, the combining methylbenzene layer is used the NaOH aqueous solution extraction, merge the alkali layer, wash twice with toluene, the concentrated hydrochloric acid acidifying of alkali layer with toluene extraction (50mL*3), merges once more, drying concentrates, and gets product 15.2g, yield 53.50%.
Embodiment 13
Adjacent bromo biphenyl 11.6g joined in 40% the NaOH aqueous solution (67g+100mL), add 1.0g Red copper oxide, heat 240 ℃ of reactions, self pressure reaches 20-25atm, reacts 72h.Filter, use the concentrated hydrochloric acid acidifying afterwards, with three times (100mL*3) of toluene extraction, the combining methylbenzene layer is used the NaOH aqueous solution extraction, merge the alkali layer, wash twice with toluene, the concentrated hydrochloric acid acidifying of alkali layer with toluene extraction (50mL*3), merges once more, drying concentrates, and gets product 4.9g, yield 57.92%.
Embodiment 14
Adjacent bromo biphenyl 11.6g joined in 40% the NaOH aqueous solution (67g+100mL), add 1.0g Red copper oxide, heat 200 ℃ of reactions, self pressure reaches 20-25atm, reacts 72h.Filter, use the concentrated hydrochloric acid acidifying afterwards, with three times (100mL*3) of toluene extraction, the combining methylbenzene layer is used the NaOH aqueous solution extraction, merge the alkali layer, wash twice with toluene, the concentrated hydrochloric acid acidifying of alkali layer with toluene extraction (50mL*3), merges once more, drying concentrates, and gets product 4.5g, yield 53.19%.
Embodiment 15
Adjacent bromo biphenyl 11.6g joined in 40% the NaOH aqueous solution (67g+100mL), add 2.0g Red copper oxide, heat 240 ℃ of reactions, self pressure reaches 20-25atm, reacts 72h.Filter, use the concentrated hydrochloric acid acidifying afterwards, with three times (100mL*3) of toluene extraction, the combining methylbenzene layer is used the NaOH aqueous solution extraction, merge the alkali layer, wash twice with toluene, the concentrated hydrochloric acid acidifying of alkali layer with toluene extraction (50mL*3), merges once more, drying concentrates, and gets product 5.0g, yield 59.10%.
Embodiment 16
5.0g aniline, 30ml methyl-phenoxide are joined in the there-necked flask, and ice bath is cooled to below 5 ℃, slowly drips the 8.0g vitriol oil, adds 0.05gTEBA afterwards, the 4.5g Sodium Nitrite, and 25 ℃ are stirred 2h, filter, and solid washes twice with methyl-phenoxide, reclaims methyl-phenoxide.Solid joins in the there-necked flask that contains the 30ml methyl-phenoxide, adds the 12.0g Potassium ethanoate, and stirring at normal temperature 20h filters, and concentrates and reclaims methyl-phenoxide, gets 2-methoxyl biphenyl 7.6g, yield 76%.
Embodiment 17
5.0g aniline, 30ml methyl-phenoxide are joined in the there-necked flask, and ice bath is cooled to below 5 ℃, slowly drips the 12.0g vitriol oil, adds 0.05gTEBA afterwards, the 4.5g Sodium Nitrite, and 25 ℃ are stirred 2h, filter, and solid washes twice with methyl-phenoxide, reclaims methyl-phenoxide.Solid joins in the there-necked flask that contains the 30ml methyl-phenoxide, adds the 12.0g Potassium ethanoate, and stirring at normal temperature 20h filters, and concentrates and reclaims methyl-phenoxide, gets 2-methoxyl biphenyl 7.8g, yield 78%.
Embodiment 18
5.0g aniline, 30ml methyl-phenoxide are joined in the there-necked flask, and ice bath is cooled to below 5 ℃, slowly drips the 8.0g vitriol oil, adds 0.05gTEBA afterwards, the 5.6g Sodium Nitrite, and 25 ℃ are stirred 2h, filter, and solid washes twice with methyl-phenoxide, reclaims methyl-phenoxide.Solid joins in the there-necked flask that contains the 30ml methyl-phenoxide, adds the 12.0g Potassium ethanoate, and stirring at normal temperature 20h filters, and concentrates and reclaims methyl-phenoxide, gets 2-methoxyl biphenyl 7.3g, yield 73%.
Embodiment 19
5.0g aniline, 30ml methyl-phenoxide are joined in the there-necked flask, and ice bath is cooled to below 5 ℃, slowly drips the 8.0g vitriol oil, adds 0.05gTEBA afterwards, the 5.6g Sodium Nitrite, and 40 ℃ are stirred 2h, filter, and solid washes twice with methyl-phenoxide, reclaims methyl-phenoxide.Solid joins in the there-necked flask that contains the 30ml methyl-phenoxide, adds the 12.0g Potassium ethanoate, and stirring at normal temperature 20h filters, and concentrates and reclaims methyl-phenoxide, gets 2-methoxyl biphenyl 6.8g, yield 68%.
Embodiment 20
2-methoxyl biphenyl 0.40g is joined in the there-necked flask that contains 20ml HBr (content 〉=40%) reflux 15h, cooling, reaction solution dilutes with 40ml water, extract 10ml*3 with toluene, the combining methylbenzene layer is used the 40%NaOH aqueous solution extraction, 5ml*4, merge the alkali layer, wash 5m,l*2 twice, use the concentrated hydrochloric acid acidifying afterwards with toluene, extract 5ml*4 with toluene, the toluene layer anhydrous magnesium sulfate drying.Filter, reclaim toluene, get orthoxenol 0.19g, yield 51.41%.
Embodiment 21
2-methoxyl biphenyl 0.40g is joined in the there-necked flask that contains 20ml HBr (content 〉=55%) reflux 7h, cooling, reaction solution dilutes with 40ml water, extract 10ml*3 with toluene, the combining methylbenzene layer is used the 40%NaOH aqueous solution extraction, 5ml*4, merge the alkali layer, wash 5m,l*2 twice, use the concentrated hydrochloric acid acidifying afterwards with toluene, extract 5ml*4 with toluene, the toluene layer anhydrous magnesium sulfate drying.Filter, reclaim toluene, get orthoxenol 0.32g, yield 86.49%.
Claims (12)
1. preparation method suc as formula (III) orthoxenol, it is characterized in that: it comprises the steps:
Formula (IV) compound or its salt under the effect of phase-transfer catalyst, under acidic conditions with diazo reagent at corresponding coupling reagent Ph-R
1Middle 20-100 ℃ of diazotization; Diazonium salt (V) directly or after filtering again under the catalysis of coupling catalyst, 0-100 ℃ down with coupling reagent generation biphenol compound (VI); Biphenol compound (VI) through alkalescence or acidic conditions hydrolysis, promptly gets orthoxenol (III) under certain temperature and pressure; R is hydrogen, fluorine, chlorine, bromine or iodine atom in its Chinese style (IV); R in the described coupling reagent
1Be corresponding hydrogen atom or methoxyl group, oxyethyl group; R in the described biphenol compound (VI)
2Be fluorine, chlorine, bromine, iodine atom or methoxyl group, oxyethyl group.
2. preparation method as claimed in claim 1 is characterized in that: described coupling reagent consumption is every gram formula (IV) compound coupling reagent 1～5ml; Phase-transfer catalyst is Bian TEBA (TEBA), 18 hat 6 (18-C-6), caproic acid potassium or tetrabutyl ammonium sulfate in described diazotization and the linked reaction, and the mass ratio of catalyzer and reaction raw materials formula (IV) compound is 0.005-0.05: 1.
3. preparation method as claimed in claim 1 is characterized in that: used an acidic catalyst is one of following acid or more than one arbitrary combination in the diazotization reaction: the hydrochloride of the vitriol oil, trichoroacetic acid(TCA), trifluoroacetic acid or corresponding formula (IV) compound; Acid is 1-10 with the equivalence ratio of formula (IV) compound in the diazotization reaction: 1; Diazo reagent is Sodium Nitrite, nitrous acid isopropyl ester, nitrous acid straight butyl, n-amyl nitrite in the described diazotization reaction; The equivalence ratio of diazo reagent and formula (IV) compound is 0.6-3 in the described diazotization reaction: 1.
4. preparation method as claimed in claim 1 is characterized in that: if R is fluorine, chlorine, bromine or iodine atom, compound (III) is got by following step preparation: select for use benzene as coupling reagent, simultaneously the solvent for reacting in the described formula (IV); Diazotization and coupling can be adopted the method for the treatment of different things alike, and temperature of reaction is 40-80 ℃, directly obtain biphenol compound (VI) under an acidic catalyst and coupling catalyst catalysis, R in its Chinese style (VI)
2Be fluorine, chlorine, bromine or iodine atom; Biphenol compound (VI) hydrolysis under alkaline condition, hydrolysising reacting temperature is 180-250 ℃, reaction pressure is 15-30atm, obtains orthoxenol (III).
5. preparation method as claimed in claim 4 is characterized in that: described an acidic catalyst is hydrochloride and vitriol oil nitration mixture, and the equivalence ratio of the hydrochloride of the described vitriol oil and formula (IV) is 0.1-0.5: 1.
6. preparation method as claimed in claim 4 is characterized in that: described coupling catalyst is copper powder, cuprous chloride, cupric chloride, and the mass ratio of described coupling catalyst and formula (IV) compound is 0.02-0.2: 1.
7. preparation method as claimed in claim 4 is characterized in that: described hydrolysis reaction carries out under alkaline condition, and wherein used alkali is sodium hydroxide, potassium hydroxide, and the aqueous solution mass percent concentration of alkali is 10-50%; Alkali and formula (VI) equivalence ratio is 2-10: 1.
8. preparation method as claimed in claim 4 is characterized in that: the used catalyzer of described hydrolysis reaction is Red copper oxide, cuprous chloride, and the mass ratio of catalyzer and halogenated biphenyl is 5-20: 100.
9. preparation method as claimed in claim 1, it is characterized in that: in the described formula (IV) if R be hydrogen atom, compound (III) is got by following step preparation: in corresponding coupling reagent Chinese style (IV) and diazo reagent diazotization, the diazotization reaction temperature is-20-100 ℃, join once more in the coupling reagent after the diazonium salt of gained filters and under the coupling catalyst effect, linked reaction takes place, the linked reaction temperature is 0-100 ℃, obtains biphenol compound (VI); Biphenol compound (VI) hydrolysis under acidic conditions, the temperature of reaction of hydrolysis reaction is 60-100 ℃, obtains orthoxenol (III).
10. preparation method as claimed in claim 9 is characterized in that: described corresponding coupling reagent is methyl-phenoxide, phenyl ethyl ether.
11. preparation method as claimed in claim 9 is characterized in that: described coupling catalyst is Potassium ethanoate, sodium-acetate, salt of wormwood, and the equivalence ratio of described catalyzer and formula (IV) compound is 1-5: 1.
12. preparation method as claimed in claim 9, it is characterized in that: described hydrolysis reaction carries out under acidic conditions, optional Hydrogen bromide, hydriodic acid aqueous solution, wherein Suan mass percent concentration is 20-60%, and the aqueous acid consumption is calculated as 5-20ml by every 1g formula (VI) compound.
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| CN101955415A (en) * | 2010-08-20 | 2011-01-26 | 绍兴文理学院 | Method for preparing 2-hydroxyl biphenyl compound |
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| CN109796312A (en) * | 2019-02-12 | 2019-05-24 | 上海阿拉丁生化科技股份有限公司 | A kind of synthetic method of 3- xenol |
| CN111362782A (en) * | 2020-03-16 | 2020-07-03 | 内蒙古大中实业化工有限公司 | Method for preparing m-trifluoromethylphenol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101955415A (en) * | 2010-08-20 | 2011-01-26 | 绍兴文理学院 | Method for preparing 2-hydroxyl biphenyl compound |
| CN101955415B (en) * | 2010-08-20 | 2013-06-19 | 绍兴文理学院 | Method for preparing 2-hydroxyl biphenyl compound |
| CN104649869A (en) * | 2013-11-18 | 2015-05-27 | 江苏扬农化工股份有限公司 | Method for preparing 2,5-dichlorophenols by using 2,5-dichlorphenol ether |
| CN104649869B (en) * | 2013-11-18 | 2016-07-13 | 江苏扬农化工股份有限公司 | A kind of method that the 2,5-of utilization dichloro 2, 2-Oxydiphenol prepares 2,5-chlorophenesic acid |
| CN109796312A (en) * | 2019-02-12 | 2019-05-24 | 上海阿拉丁生化科技股份有限公司 | A kind of synthetic method of 3- xenol |
| CN111362782A (en) * | 2020-03-16 | 2020-07-03 | 内蒙古大中实业化工有限公司 | Method for preparing m-trifluoromethylphenol |
| CN111362782B (en) * | 2020-03-16 | 2022-06-07 | 内蒙古大中实业化工有限公司 | Method for preparing m-trifluoromethylphenol |
| CN113620774A (en) * | 2021-08-17 | 2021-11-09 | 上海应用技术大学 | Method for synthesizing biphenyl compounds by adopting microchannel reactor |
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