CN109912455A - A method of preparing 4- hydroxyl -4 '-cyanobiphenyl - Google Patents
A method of preparing 4- hydroxyl -4 '-cyanobiphenyl Download PDFInfo
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- CN109912455A CN109912455A CN201910250252.2A CN201910250252A CN109912455A CN 109912455 A CN109912455 A CN 109912455A CN 201910250252 A CN201910250252 A CN 201910250252A CN 109912455 A CN109912455 A CN 109912455A
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Abstract
A method of 4- hydroxyl -4'- cyanobiphenyl is prepared, the technical field of Synthetic Organic Chemistry is belonged to, using p bromophenol as raw material, substituted boracic acid is first prepared, is then prepared into 4- hydroxyl -4'- cyanobiphenyl again, the substituted boracic acid is
Description
Technical field
The invention belongs to the technical fields of Synthetic Organic Chemistry, are related to the preparation of liquid crystal intermediates, and in particular to a kind of system
The method of standby -4 '-cyanobiphenyl of 4- hydroxyl.
Background technique
PDLC is the abbreviation of English Polymer Dispersed Liquid Crystal, and Chinese name is polymer dispersion liquid
It is brilliant.Polymer dispersed liquid crystals (PDLC) is by low molecular weight liquid crystal (liquid crystal, be abbreviated as LC) and prepolymer Kuer
UV65 glue mixes, under certain condition aggregated reaction, forms micron-sized liquid crystal droplet and is evenly dispersed in high score subnet
In network, the dielectric anisotropy of liquid crystal molecule is recycled to obtain the material with electro-optic response characteristic, it operates mainly in scattering
Between state and transparent state and there is certain gray scale.Polymer dispersed liquid crystal film is that liquid crystal and polymer are combined obtained one kind
The membrane material of excellent combination property.Liquid crystal molecule imparts the significant electro-optical characteristic of polymer dispersed liquid crystal film, receives it
Extensive concern, and have broad application prospects.For conventional display device, polymer dispersion type liquid crystal display device
With lot of advantages, such as it is not required to polarizing film and oriented layer, preparation process is simple, can be easily made large area flexible display etc..
At present optical modulator, temperature-sensitive and pressure-sensitive device, automatically controlled glass, light valve, Projection Display, in terms of obtain it is extensive
Using.
Common liquid crystal molecule has that Δ n is smaller, the lower alkyl biphenyl nitrile of clearing point and alkoxy biphenyl nitrile in PDLC；Also
Have is exactly Δ n larger, the higher alkyl terphenyl nitrile of clearing point or alkyl cyclohexyl biphenyl nitrile；And clearing point is high, solubility
AlrightEstersMonomer.
Wherein 4- hydroxyl -4 '-cyanobiphenyl (abbreviation xenol nitrile) is important intermediate, it can be used for preparing alcoxyl
Base biphenyl nitrile, it can also be used to part esters monomer is prepared, such as:And in other liquid
In brilliant material preparation, also there is important purposes, can such as prepare 4- hydroxyl -4 '-diphenic acidIt
It is to prepare a major class alkoxy diphenic acid esters liquid crystalKey intermediate.
Xenol nitrile is in current preparation method, usually with 4- xenolFor raw material, preparation
Method is as follows:
Method A:4- xenol reacts into amide with ammonia, later thionyl after pair gram acylation of trichloro-acetic chloride
Chlorine is dehydrated into nitrile and obtains product, and yield is 51.9%~56.7%.
Method B:4- xenol protects hydroxyl by acetic anhydride, implements by the route of similar approach 1, wherein at amide
Step sloughs protecting group, yield 47.7%.
Method C: biphenyl is raw material, is first acylated with chloroacetic chloride pair gram and bromination reaction of connecting is obtained to bromo biphenyl ethyl ketone,
Bayer-Villiger oxidation resets and obtains 4 '-bromo- 4- xenols later, finally reacts to obtain product with cuprous cyanide, yield is
33%.
With the development of coupling reaction technology in recent years, gradually have through coupling mode synthetic method, e.g.,
Appl Organometal Chem.2017；Use is coupled a step with to cyanophenylboronic acid to iodophenol in e3778
Obtain 4- hydroxyl -4 '-cyanobiphenyl, the reaction time for 24 hours, but yield only 76%, and expensive starting materials are not easy to obtain.
4- hydroxyl -4 '-cyano is obtained with to one step of cyanophenylboronic acid coupling using p bromophenol in WO2006072015A2
Biphenyl has used high activity ligand tri-tert-butylphosphine, reaction time 48h, but yield only 55%.
It is coupled using to methoxyphenylboronic acid with to Brominal in WO2016008561A1, then demethylation, obtains 4- hydroxyl-
4 '-cyanobiphenyls are easy to get although raw material is opposite in fact, and demethylation complicated condition needs -78 DEG C of ultralow temperature.
In Bioorganic&Medicinal Chemistry 11 (2003) 3457-3474, has and passed through using p bromophenol
Silica reagent protection, exchanges by lithium halogen, boronation later, hydrolysis, is coupled (yield: 100% × 65% × 91% afterwards and to Brominal
=59%).Gross production rate is not high in the method, and organolithium reagent is expensive, severe reaction conditions, opposite to Brominal price
It is higher, so and being not suitable for industrial.
Above method all has apparent disadvantage, such as classical way general steps length, low yield, three wastes discharge amount
Greatly, comprehensive yied is below 60%.Although coupling method process is simple, the raw material used is not easy to obtain, and considers raw material such as to hydroxyl
Base phenyl boric acid, the synthesis to cyanophenylboronic acid etc., from the gross production rate of most initial raw material p bromophenol meter also about 60% or so.
Summary of the invention
The object of the present invention is to provide it is a kind of simple, efficiently, convenient for industrial production 4- hydroxyl -4 '-cyanobiphenyl method.
The present invention be realize its purpose the technical solution adopted is that:
A method of 4- hydroxyl -4 '-cyanobiphenyl is prepared using p bromophenol as raw material, and substituted boracic acid is first prepared,
Then it is prepared into 4- hydroxyl -4 '-cyanobiphenyl again, the substituted boracic acid isWherein PG is to protect
Group is protected, by the substituted boracic acid with to 6-chlorophenyl nitrile, Suzuki coupling reaction is carried out in the presence of solvent, alkali and catalyst, is taken off
Protection, obtains 4- hydroxyl -4 '-cyanobiphenyl, and control p bromophenol is 1.0:(1.0~1.5 to the molar ratio of 6-chlorophenyl nitrile, alkali):
(2.0~4.0), the temperature of Suzuki coupling reaction are 50-120 DEG C.
The mass ratio of catalyst and p bromophenol is (0.00001~0.02): 1.
The preparation of substituted boracic acid the following steps are included:
A, p bromophenol solvent and acid binding agent effect under, reacted with protecting group reagent, obtain hydroxyl protection to bromobenzene
PhenolPG represents blocking group；
B, by the p bromophenol of the obtained hydroxyl protection of step A be added magnesium chips generate Grignard Reagent and with boronate reagent it is anti-
It answers, hydrolysis obtains substituted boracic acidPG represents blocking group.
In step A, p bromophenol is 1.0:(1.0~2.0 with the molar ratio of protecting group reagent and acid binding agent): (1.0~
2.5)。
In step B, the molar ratio of p bromophenol and magnesium chips, borate is 1.0:(1.0~2.0): (1.2~2.5).
In step A, control reaction temperature is -10~50 DEG C.
In step B, the reaction temperature that control Grignard Reagent is reacted with boronate reagent is -15~80 DEG C.
In step A, solvent is dimethylbenzene, toluene, benzene, tetrahydrofuran, 2- methyltetrahydrofuran, dioxane, ethylene glycol
One or more of combination in dimethyl ether；Protecting group reagent is dihydropyran, trim,ethylchlorosilane, tert-butyldimethylsilyl chloride silicon
Alkane, phenyldimethylchlorosilane, one or more of combination in tri isopropyl chlorosilane；Acid binding agent uses triethylamine, pyridine, miaow
Azoles, tetramethylethylenediamine, sodium carbonate, potassium carbonate, sodium hydroxide, combination one or more of in potassium hydroxide.
In step B, boronate reagent is trimethylborate, one in triethyl borate, triisopropyl borate ester, butyl borate
Kind or several combinations.Step B is also to carry out under solvent condition, and solvent for use is dimethylbenzene, toluene, benzene, tetrahydrofuran, 2-
Methyltetrahydrofuran, dioxane, combination one or more of in glycol dimethyl ether；Concentration is added when hydrolysis and is lower than 1mol/L
Hydrochloric acid, sulfuric acid, phosphoric acid or formic acid, acetic acid, ammonium chloride, ammonium phosphate, ammonium sulfate, ammonium bromide aqueous solution be hydrolyzed.
In Suzuki coupling reaction, solvent is dimethylbenzene, toluene, benzene, tetrahydrofuran, 2- methyltetrahydrofuran, dioxy six
One or more of combination in ring, glycol dimethyl ether；Alkali is sodium carbonate, sodium bicarbonate, potassium carbonate, saleratus, hydroxide
Sodium, potassium hydroxide, sodium fluoride, combination one or more of in potassium fluoride；Catalyst is the combination of equivalent palladium catalyst and ligand,
Wherein palladium catalyst is tetrakis triphenylphosphine palladium, palladium chloride, palladium acetate, group one or more of in bis-triphenylphosphipalladium palladium dichloride
It closes, ligand is X-Phos, S-Phos, tri-tert-butylphosphine, two (1- adamantyl) butyl phosphines, one or more of in tricyclohexyl phosphine
Combination.
The beneficial effects of the present invention are:
1, the preparation of para hydroxybenzene boric acid (or phenyl boric acid of blocking group protection), substantially, as raw material, to show to Brominal
Have that the yield of technology is very low (30-60%), the present invention is not separated by the selection of design solvent and is directly used in reaction, reduced
Loss in treatment process.And be fine chemicals to Brominal, market capacity is small, and price is high, and production process is complicated, the three wastes
Discharge capacity is big, and to 6-chlorophenyl nitrile, it is medical pesticide dyestuff intermediate, it is from a wealth of sources, it is cheap.
2, present invention is alternatively directed to reaction conditions to study for a long period of time, and reaction process is simplified, can in commodity production
It is reduced to minimum two reaction kettles and completes production process.And the gross production rate started with p bromophenol is up to 85% or more！From production
In efficiency to three wastes discharge amount, it is much better than existing production technology.
3, in the present invention, after dissolving p bromophenol in a solvent in first reaction vessel, add acid binding agent and protection
Base reagent adds water quenching to go out and dissolves the salt of generation after completion of the reaction, and after branch vibration layer, organic layer is that phenolic hydroxyl group is protected
The solution of p bromophenol.In second reaction vessel, add magnesium chips and solvent, the protected p bromophenol of phenolic hydroxyl group is added dropwise later
Solution be prepared into Grignard Reagent, by borate be added after again weak acid hydrolyze, branch vibration layer, organic layer is that phenolic hydroxyl group is protected
The para hydroxybenzene boric acid solution of shield.Do not have to change container later, be added wherein to 6-chlorophenyl nitrile and aqueous slkali and catalyst, heating hair
Raw coupling reaction, is completed at the same time Deprotection.It is post-treated to obtain product 4- hydroxyl -4 '-cyanobiphenyl, white crystal.
4, it is an advantage of the current invention that the solvent being added is through entire reaction process, and process does not have to isolate and purify, and subtracts
Loss during the separation process is lacked, process is simple, and three wastes discharge amount is small.Overcome existing method insufficient, improves Suzuki friendship
The existing method of coupling reaction is pitched, what is be simple and efficient has obtained product, is convenient for industrial production.
Specific embodiment
The present invention is to solve shortcomings in the prior art, provides a kind of suitable industrialized production 4- being simple and efficient
Hydroxyl -4 '-cyanobiphenyl method.Using p bromophenol as raw material, experience phenolic hydroxyl group protection, grignard reaction, boronation and hydrolysis, idol
The several steps of connection-deprotection complete preparation process in primary organic solvent system of the same race.Combined with specific embodiments below
The present invention is further illustrated.
Embodiment 1
500ml there-necked flask reaction unit is assembled, by p bromophenol 34.6g (0.2mol), pyridine 19.75g (0.25mol),
It is placed in there-necked flask, 2- methyltetrahydrofuran 100ml is added, trimethyl is added dropwise under nitrogen protection less than 10 DEG C in ice-water bath temperature control
The 50ml2- methyltetrahydrofuran solution of chlorosilane 25.92g (0.24mol), temperature control are no more than 20 DEG C, and drop finishes, temperature control 15-20
DEG C, reaction is terminated after reacting 2h, with the washing reaction liquid of saturated salt solution 50ml × 2,10g anhydrous magnesium sulfate drying for standby.
Separately take 1000ml there-necked flask, be added 5.76g (0.24mol) magnesium chips, 30 DEG C of water-bath, in dropwise addition step prepare to three
Methyl siloxy bromobenzene 2- methyltetrahydrofuran solution causes preparation Grignard Reagent, drips 30-35 DEG C of reaction 2h of Bi Jixu temperature control,
Ice salt bath is cooled to -15 DEG C, the 100ml2- methyltetrahydrofuran solution of trimethylborate 41.6g (0.4mol) is added dropwise, temperature control is not
More than 0 DEG C, drop, which finishes, warms naturally to 20 DEG C, is hydrolyzed with saturated ammonium chloride 21.4g (0.4mol) aqueous solution (50ml water), stands and divide
Liquid remove water phase, in organic phase be added to 6-chlorophenyl nitrile 30.25g (0.22mol), potassium fluoride 11.6g (0.2mol), water 50ml,
Four (triphenylphosphine palladium) 0.02g, X-Phos0.02g, are warming up to 50 DEG C, react 8h, are down to room temperature, with 30% concentrated hydrochloric acid 50ml,
Water 50ml is configured to dilute hydrochloric acid and hydrolyzes, temperature rising reflux 1h, liquid separation while hot, and water phase is thrown aside.Organic phase condensing crystallizing can obtain off-white color
Product xenol nitrile 33.18g, purity 99.72%, total recovery 85.1%.
Embodiment 2 (industrially scalable)
It cleans 500L reaction kettle device and dries, p bromophenol 34.6kg, dihydropyran 20.19kg are placed in reaction kettle
In, dimethylbenzene 100L is added, freezing liquid temperature control is less than -10 DEG C, the 50L of trim,ethylchlorosilane 25.92kg is added dropwise under nitrogen protection
Xylene solution, temperature control are no more than 0 DEG C, and drop finishes, -5~5 DEG C of freezing liquid temperature control system temperature, terminate reaction, saturation after reacting 4h
The washing reaction liquid of saline solution 50L × 2,10kg anhydrous magnesium sulfate drying for standby.
In the 1000L reaction kettle of another drying, 5.76kg magnesium chips is added, is heated to 30 DEG C, step prepares in dropwise addition
To trimethylsiloxy group bromobenzene xylene solution, cause preparation Grignard Reagent, drips 30-35 DEG C of reaction 4h of Bi Jixu temperature control, freezing
Liquid is cooled to -10 DEG C, and the 100L xylene solution of trimethylborate 41.6kg is added dropwise, and temperature control is no more than 0 DEG C, drop Bi Ziran heating
It to 20 DEG C, is hydrolyzed with saturated ammonium chloride 21.4kg aqueous solution (50L water), stands liquid separation and remove water phase, the addition pair in organic phase
6-chlorophenyl nitrile 30.25kg, potassium carbonate 27.6kg, water 50L, four (triphenylphosphine palladium) 20g, X-Phos20g are warming up to 120 DEG C, reaction
12h is down to room temperature, is configured to dilute hydrochloric acid hydrolysis with 30% concentrated hydrochloric acid 50L, water 50L, is warming up to 100 DEG C of reaction 2h, divides while hot
Liquid, water phase are thrown aside.Organic phase condensing crystallizing can obtain off-white color product xenol nitrile 33.4kg, purity 99.68%, total recovery
85.64%.
Embodiment 3 (industrially scalable)
It cleans 500L reaction kettle device and dries, p bromophenol 34.6kg, imidazoles 17kg are placed in reaction kettle, be added
The 50L dioxy of tri isopropyl chlorosilane 46.08kg is added dropwise less than 20 DEG C in dioxane 100L, freezing liquid temperature control under nitrogen protection
Six ring solution, temperature control are no more than 30 DEG C, and drop finishes, and 15~25 DEG C of water-bath temperature control, terminate reaction after reacting 4h, use saturated salt solution
The washing reaction liquid of 50L × 2,10kg anhydrous magnesium sulfate drying for standby.
Another drying 1000L reaction kettle in, be added 6kg magnesium chips, be heated to 40 DEG C, in dropwise addition step prepare to three
Isopropyl siloxy bromobenzene dioxane solution causes preparation Grignard Reagent, drips 50-60 DEG C of reaction 4h of Bi Jixu temperature control, freezing
Liquid is cooled to 20 DEG C, and the 100L dioxane solution of triisopropyl borate ester 45.12kg is added dropwise, and temperature control is no more than 30 DEG C, drips Bi Sheng
Temperature is configured to the hydrolysis of 100L dilute hydrochloric acid with 30% concentrated hydrochloric acid 50L, stands liquid separation and remove water phase, in organic phase to 80 DEG C of reaction 4h
Middle addition is warming up to reflux to 6-chlorophenyl nitrile 30.25kg, potassium carbonate 27.6kg, water 50L, palladium acetate 10g, tri-tert-butylphosphine 20g,
12h is reacted, room temperature is down to, is configured to dilute hydrochloric acid hydrolysis, temperature rising reflux 2h, while hot liquid separation, water with 30% concentrated hydrochloric acid 50L, water 50L
Mutually throw aside.Organic phase condensing crystallizing can obtain off-white color product xenol nitrile 34.1kg, purity 99.58%, total recovery
87.2%.
Embodiment 4 (industrially scalable)
It cleans 500L reaction kettle device and dries, p bromophenol 34.6kg, sodium carbonate 12kg are placed in reaction kettle, are added
Entering toluene 100L, the 50L toluene solution of trim,ethylchlorosilane 25.92kg is added dropwise less than 10 DEG C in freezing liquid temperature control under nitrogen protection,
Temperature control is no more than 20 DEG C, and drop finishes, and terminates and reacts after 20-25 DEG C of reaction 3h of temperature control, with the washing reaction liquid of saturated salt solution 50L × 2,
10kg anhydrous magnesium sulfate drying for standby.
In the 1000L reaction kettle of another drying, 5.76kg magnesium chips is added, is heated to 30 DEG C, step prepares in dropwise addition
To trimethylsiloxy group bromobenzene toluene solution, causes preparation Grignard Reagent, drip 35-40 DEG C of reaction 3h of Bi Jixu temperature control, freezing liquid
- 15 DEG C are cooled to, the 100L toluene solution of trimethylborate 41.6kg is added dropwise, temperature control is no more than 0 DEG C, and drop finishes, 40 DEG C are warming up to,
It is hydrolyzed with saturated ammonium chloride 21.4kg aqueous solution (50L water), stands liquid separation and remove water phase, be added in organic phase to 6-chlorophenyl nitrile
30.25kg, potassium carbonate 27.6kg, water 50L, four (triphenylphosphine palladium) 1.73g, X-Phos1.73g are warming up to 80 DEG C, reaction
10h is down to room temperature, is configured to dilute hydrochloric acid hydrolysis, temperature rising reflux 1.5h, while hot liquid separation, water phase with 30% concentrated hydrochloric acid 50L, water 50L
It throws aside.Organic phase condensing crystallizing can obtain off-white color product xenol nitrile 33.2kg, purity 99.62%, total recovery 85.13%.
Embodiment 5 (industrially scalable)
It cleans 2000L reaction kettle device and dries, p bromophenol 138.4kg, imidazoles 65kg are placed in reaction kettle, are added
Enter toluene 400L, for freezing liquid temperature control less than 10 DEG C, the 200L toluene that trim,ethylchlorosilane 103.7kg is added dropwise under nitrogen protection is molten
Liquid, temperature control are no more than 20 DEG C, and drop finishes, and reaction is terminated after 20-25 DEG C of reaction 3h of temperature control, are washed with saturated salt solution 200L × 2 anti-
Answer liquid, 40kg anhydrous magnesium sulfate drying for standby.
In the 3000L reaction kettle of another drying, 22.7kg magnesium chips is added, is heated to 30 DEG C, step prepares in dropwise addition
To trimethylsiloxy group bromobenzene toluene solution, cause preparation Grignard Reagent, drips and finish 30-35 DEG C of reaction 3h of temperature control, freezing liquid cooling
To -10 DEG C, the 400L toluene solution of trimethylborate 166.4kg is added dropwise, temperature control is no more than 0 DEG C, and drop, which finishes, is warming up to 20 DEG C, temperature control
It 20-30 DEG C, reacts 5 hours, is then hydrolyzed with saturated ammonium chloride 85.6kg aqueous solution (200L water), stand liquid separation and remove water phase,
It is added in organic phase to 6-chlorophenyl nitrile 121kg, potassium carbonate 110.4kg, water 200L, four (triphenylphosphine palladium) 1.384g, two (1- gold
Rigid alkyl) butyl phosphine 1.384g, it is warming up to reflux, 10h is reacted, is down to room temperature, is configured to 30% concentrated hydrochloric acid 200L, water 200L
Dilute hydrochloric acid hydrolysis, heats up 80 DEG C and reacts 1.5h, liquid separation while hot, water phase is thrown aside.Organic phase condensing crystallizing can obtain off-white color product hydroxyl
Base biphenyl nitrile 134.1kg, purity 99.71%, total recovery 85.96%.
Claims (10)
1. using p bromophenol as raw material substituted boracic acid is first prepared, so in a kind of method for preparing 4- hydroxyl -4'- cyanobiphenyl
It is prepared into 4- hydroxyl -4'- cyanobiphenyl again afterwards, which is characterized in that the substituted boracic acid isIts
Middle PG is blocking group, and by the substituted boracic acid with to 6-chlorophenyl nitrile, Suzuki coupling is carried out in the presence of solvent, alkali and catalyst
Reaction, deprotection obtain 4- hydroxyl -4'- cyanobiphenyl, and control p bromophenol is 1.0:(1.0 to the molar ratio of 6-chlorophenyl nitrile, alkali
~1.5): (2.0~4.0), the temperature of Suzuki coupling reaction are 50-120 DEG C.
2. a kind of method for preparing 4- hydroxyl -4'- cyanobiphenyl according to claim 1, which is characterized in that catalyst with
The mass ratio of p bromophenol is (0.00001~0.02): 1.
3. a kind of method for preparing 4- hydroxyl -4'- cyanobiphenyl according to claim 1, which is characterized in that substituted boracic acid
Preparation the following steps are included:
A, p bromophenol reacts with protecting group reagent under solvent and acid binding agent effect, obtains the p bromophenol of hydroxyl protectionPG represents blocking group；
B, magnesium chips generation Grignard Reagent is added in the p bromophenol of the obtained hydroxyl protection of step A and is reacted with boronate reagent,
Hydrolysis obtains substituted boracic acidPG represents blocking group.
4. a kind of method for preparing 4- hydroxyl -4'- cyanobiphenyl according to claim 3, which is characterized in that in step A,
The molar ratio of p bromophenol and protecting group reagent and acid binding agent is 1.0:(1.0~2.0): (1.0~2.5).
5. a kind of method for preparing 4- hydroxyl -4'- cyanobiphenyl according to claim 3, which is characterized in that in step B,
The molar ratio of p bromophenol and magnesium chips, borate is 1.0:(1.0~2.0): (1.2~2.5).
6. a kind of method for preparing 4- hydroxyl -4'- cyanobiphenyl according to claim 3, which is characterized in that in step A,
Controlling reaction temperature is -10~50 DEG C.
7. a kind of method for preparing 4- hydroxyl -4'- cyanobiphenyl according to claim 3, which is characterized in that in step B,
The reaction temperature that control Grignard Reagent is reacted with boronate reagent is -15~80 DEG C.
8. a kind of method for preparing 4- hydroxyl -4'- cyanobiphenyl according to claim 3, which is characterized in that in step A,
Solvent is dimethylbenzene, toluene, benzene, tetrahydrofuran, 2- methyltetrahydrofuran, dioxane, a kind of or several in glycol dimethyl ether
The combination of kind；Protecting group reagent is dihydropyran, trim,ethylchlorosilane, tert-butyl chloro-silicane, pheiiyldimetliyl chlorine silicon
Alkane, one or more of combination in tri isopropyl chlorosilane；Acid binding agent using triethylamine, pyridine, imidazoles, tetramethylethylenediamine,
Sodium carbonate, potassium carbonate, sodium hydroxide, combination one or more of in potassium hydroxide.
9. a kind of method for preparing 4- hydroxyl -4'- cyanobiphenyl according to claim 3, which is characterized in that in step B,
Boronate reagent is trimethylborate, triethyl borate, triisopropyl borate ester, combination one or more of in butyl borate.
10. a kind of method for preparing 4- hydroxyl -4'- cyanobiphenyl according to claim 1, which is characterized in that solvent is
Dimethylbenzene, toluene, benzene, tetrahydrofuran, 2- methyltetrahydrofuran, dioxane, group one or more of in glycol dimethyl ether
It closes；Alkali is sodium carbonate, sodium bicarbonate, potassium carbonate, saleratus, sodium hydroxide, potassium hydroxide, sodium fluoride, a kind of in potassium fluoride
Or several combination；Catalyst is the combination of equivalent palladium catalyst and ligand, and wherein palladium catalyst is tetrakis triphenylphosphine palladium, chlorine
Change palladium, palladium acetate, combination one or more of in bis-triphenylphosphipalladium palladium dichloride, ligand is X-Phos, S-Phos, tri-tert
Phosphine, two (1- adamantyl) butyl phosphines, combination one or more of in tricyclohexyl phosphine.
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| CN110016028A (en) * | 2019-04-17 | 2019-07-16 | 上海大学 | Naphthyridines bigeminy azole compounds and preparation method thereof |
| CN114262263A (en) * | 2021-12-28 | 2022-04-01 | 河北美星化工有限公司 | Preparation method of 4-iodophenol |
| CN114262263B (en) * | 2021-12-28 | 2024-04-19 | 河北美星化工有限公司 | Preparation method of 4-iodophenol |
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