CN106566561A - Preparation method of cyanophenyl pyrimidine type liquid crystal monomer - Google Patents
Preparation method of cyanophenyl pyrimidine type liquid crystal monomer Download PDFInfo
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
- C09K19/345—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing two nitrogen atoms
- C09K19/3458—Uncondensed pyrimidines
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
Abstract
The invention relates to a preparation method of a cyanophenyl pyrimidine type liquid crystal monomer. The preparation method includes the steps of: performing a Grignard reaction to bromoalkane and magnesium to prepare Grignard reagent; performing an alkylation reaction to the Grignard reagent and a compound represented as follows, wherein n is 1, 2 or 3; hydrolyzing the reaction product under acidic condition; and performing a coupling reaction to the hydrolyzed product with a compound represented as follows, wherein m is 1, 2 or 3 to finally produce the cyanophenyl pyrimidine type liquid crystal monomer. Compared with the prior art, usage of high-dangerous and high-pollution reagents is avoided, so that the preparation method is environment-friendly and pollution-free. The method has simple processes, is easy to carry out, has fewer steps, is high in yield, is low in production cost, and is beneficial to industrial production.
Description
Technical field
The present invention relates to field of liquid crystal display, more particularly to a kind of preparation method of cyano group benzene miazines liquid crystal monomer.
Background technology
Recently as economic fast development, the development of field of liquid crystal display is especially prominent, cyano group benzene pyrimidine be for
The important monomer of synthesis plurality of liquid crystals material, the compound of this kind of liquid crystal monomer synthesis has viscosity low, and resistivity is high, response speed
Degree is very fast, the advantages of can improve mixed crystal dielectric constant, is especially suitable for the liquid crystal display of TFT driving.Suchization
A compound part therein can use following structural formula to represent：
The R is C1～C9Straight chained alkyl, it is 1,2 or 3 that n is 1,2 or 3, m.
At present, the preparation method of such compound, such as patent CN101712654A, using to Brominal raw material is done, and leads to chlorine
Change hydrogen, ammonia is reacted, prepared to bromobenzene nitrile amidine salt, through cyclization, synthesize pyrimidine, then be coupled, finally carry out cyanogen
Base replaces, and prepares cyano-containing benzene pyrimidine compound, and the synthetic method needs to use high risk hydrogen chloride, ammonia, safety wind
Danger is big, and reactions steps are longer, and yield is also low, in addition, using cuprous cyanide in reaction, environmental pollution is larger, is unfavorable for work
Industry is produced.
The content of the invention
The technical problem to be solved is to provide a kind of preparation method of cyano group benzene miazines liquid crystal monomer, this
The cyano group benzene miazines liquid crystal monomer of bright preparation, for field of liquid crystal display, it is to avoid high-risk reagent and high pollution compound
Use, its preparation method is simple, and high income is environment friendly and pollution-free, be conducive to industrialized production, solve to be produced present in prior art
Thing yield is low, high pollution, is unfavorable for the problem of industrialized production.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：
A kind of cyano group benzene miazines liquid crystal monomer, with following structural formula：
R is C1-C9Straight chained alkyl, it is 1,2 or 3 that n is 1,2 or 3, m.
A kind of preparation method of cyano group benzene miazines liquid crystal monomer, comprises the following steps：
(1) under the conditions of 20-66 DEG C, brominated alkanes and ether organic solvent are added dropwise in magnesium, brominated alkanes structural formula is
R-Br, R are C1-C9Linear paraffin, carries out grignard reaction, and is incubated 2h, obtains chemical compounds I, and the chemical compounds I structural formula is R-
MgBr, R are C1-C9Linear paraffin；
(2) negate and answer starting compound II, compound ii structural formula isN is 1,2 or 3, to compound
Add tetrachloro furans and catalyst in II, and under the conditions of 56-66 DEG C, the chemical compounds I obtained in step (1) is added dropwise, carry out alkane
Glycosylation reaction, and insulation reaction 2h, wait to hydrolyze, and obtain reactant liquor；
(3) take the watery hydrochloric acid that mass fraction under the conditions of 1-5 DEG C is 10%, under the conditions of 0-40 DEG C to mass fraction be 10%
Watery hydrochloric acid in the reactant liquor obtained in step (2) is added dropwise, stir 0.5h, be hydrolyzed reaction, obtains compound III, compound
III structural formula isR is C1-C9Straight chained alkyl, n is 1,2 or 3；
(4) tetrahydrofuran, catalyst and the compounds Ⅳ, compounds Ⅳ structural formula is added to be in compound IIIM is 1,2 or 3, and it is 10% aqueous slkali to be warming up to 50-55 DEG C and mass fraction is added dropwise, then is warming up to
60-65 DEG C carries out coupling reaction, and the reaction time is 15-20h, obtains compound V, and the structural formula of compound V isR is C1-C9Straight chained alkyl, it is 1,2 or 3 that n is 1,2 or 3, m.
On the basis of above-mentioned technical proposal, the present invention can also do following improvement.
Further, the brominated alkanes in the step (1) and the mol ratio of magnesium are 1：(0.91-1)；Brominated alkanes and ethers
The mass ratio of organic solvent is 1:(3-10)；Ether organic solvent is in ether, methyl phenyl ethers anisole, tetrahydrofuran, methyltetrahydrofuran
One or more.
Further, the grignard reaction temperature in the step (1) is 56-66 DEG C.
Further, the compound ii in the step (2) and the mass ratio of tetrachloro furans are 1:(2-5)；Compound ii with
The mol ratio of catalyst is 1:(0.01-0.03)；Catalyst is in palladium bichloride, the triphenylphosphine of dichloro two conjunction palladium, palladium
Plant or several.
Further, the mass fraction in the step (3) is 10% watery hydrochloric acid and the mass ratio of compound ii is 1:
(0.25-0.5)。
Further, the catalyst in the step (4) is in palladium bichloride, the triphenylphosphine of dichloro two conjunction palladium, palladium
Plant or several；Compound III is 1 with the mol ratio of catalyst：(0.001-0.002)；The mass ratio of compound III and compounds Ⅳ
For 1:(0.8-1.5)；Compound III is 1 with the mass ratio of tetrahydrofuran：(5-10).
Further, the compound III in the step (4) and the mass ratio of aqueous slkali are 1：(16-22)；Aqueous slkali is carbon
One or more in sour potassium, sodium carbonate, potassium hydroxide, NaOH.
Further, all steps are carried out under the conditions of inert gas shielding.
The invention has the beneficial effects as follows：Avoid high-risk reagent and high pollution reagent is used, it is environment friendly and pollution-free, prepare work
Skill is simple, and easy to operate, reactions steps are few, high income, and low production cost is conducive to industrialized production.
Specific embodiment
The principle and feature of the present invention are described below, example is served only for explaining the present invention, is not intended to limit
Determine the scope of the present invention.
The preparation of 2- amyl group -5- (4- itrile group the benzene)-pyrimidine of embodiment 1
1) under nitrogen protection, 9.7g (0.4mol) magnesium, the 56 DEG C of dropwise additions of control interior temperature are added in the there-necked flask of clean dried
The mixed solution of 66.4g (0.44mol) bromo pentane silanes and 180g tetrahydrofurans, drop finishes carries out grignard reaction in 66 DEG C, and insulation 2 is little
When, obtain RMgBr stand-by.
2) under nitrogen protection, the chloro- 5- Bromopyrimidines of 48.4g (0.25mol) 2- are added in the there-necked flask of clean dried,
96.7g tetrachloro furans, 0.45g (0.0025mol) palladium bichloride, 60 DEG C of control interior temperature is added dropwise RMgBr in (1), and drop finishes in 60 DEG C
Reaction is alkylated, insulation reaction 2 hours, reaction is finished, and obtains reactant liquor, waits to hydrolyze.
3) under nitrogen protection, the watery hydrochloric acid that mass fraction under the conditions of 4 DEG C is 10% is added in the there-necked flask of clean dried
130g, is added dropwise reactant liquor in step (2) under the conditions of 14 DEG C, and drop finishes stirring 0.5 hour, and be hydrolyzed reaction, and stirring is finished, point
Layer, lower floor's water is merged organic phase and is washed to neutrality with toluene extraction, takes off dry solvent, obtains the chloro- 5- amyl groups pyrimidines of 2-, yield
93%.
4) under nitrogen protection, the chloro- 5- amyl groups pyrimidines of 43g (0.23mol) 2- are added in the there-necked flask of clean dried,
34.4g (0.23mol) is warming up to 50 DEG C to itrile group phenyl boric acid, 322.5g tetrahydrofurans, 0.05g (0.00023mol) palladium.
The sodium carbonate liquor that 688g mass fractions are 10% is weighed, 55 DEG C of control interior temperature instills aqueous sodium carbonate in reaction system,
Drop finishes, and is warming up to 60 DEG C, carries out coupling reaction, and insulation reaction 18 hours, insulation is finished, addition 140g toluene, 135g concentrated hydrochloric acids, point
Layer, water is merged organic phase and is washed to neutrality with toluene extraction, takes off dry solvent, obtains 2- amyl group -5- (4- itrile group benzene)-pyrimidine,
Yield 95%.
The preparation of the 4'- of embodiment 2 (5- butyl -2- pyrimidine radicals) -4- biphenylcarbonitriles
1) under nitrogen protection, 9.7g (0.4mol) magnesium, the 20 DEG C of dropwise additions of control interior temperature are added in the there-necked flask of clean dried
The mixed solution of 60.3g (0.44mol) NBBs and 180g tetrahydrofurans, drop finishes carries out grignard reaction in 56 DEG C, and insulation 2 is little
When, obtain RMgBr stand-by.
2) under nitrogen protection, the chloro- 5- Bromopyrimidines of 48.4g (0.25mol) 2- are added in the there-necked flask of clean dried,
96.7g tetrachloro furans, 0.45g (0.0025mol) palladium bichloride.60 DEG C of control interior temperature is added dropwise RMgBr in (1), and drop finishes in 66 DEG C
Reaction is alkylated, insulation reaction 2 hours, reaction is finished, and obtains reactant liquor, waits to hydrolyze.
3) under nitrogen protection, the watery hydrochloric acid that mass fraction under the conditions of 3 DEG C is 10% is added in the there-necked flask of clean dried
130g, is added dropwise reactant liquor in step (2) under the conditions of 24 DEG C, and drop finishes stirring 0.5 hour, and be hydrolyzed reaction, and stirring is finished, point
Layer, lower floor's water is merged organic phase and is washed to neutrality with toluene extraction, takes off dry solvent, obtains the chloro- 5- butyl pyrimidines of 2-, yield
96%.
4) under nitrogen protection, the chloro- 5- butyl pyrimidines of 40.9g (0.24mol) 2- are added in the there-necked flask of clean dried,
53.5g (0.24mol) 4 '-cyanobiphenyls -4- ylboronic acids, 306.8g tetrahydrofurans, 0.05g (0.00024mol) palladium rises
Temperature is to 53 DEG C.The sodium carbonate liquor that 818g mass fractions are 10% is weighed, 55 DEG C of control interior temperature instills aqueous sodium carbonate anti-
In answering system, drop finishes, and being warming up to 60 DEG C carries out coupling reaction, and insulation reaction 20 hours, insulation is finished, and adds 130g toluene, 130g
Concentrated hydrochloric acid, layering.Water is merged organic phase and is washed to neutrality with toluene extraction, takes off dry solvent, and (5- butyl -2- are phonetic to obtain 4'-
Piperidinyl) -4- biphenylcarbonitriles, yield 96%.
The preparation of the 4- of embodiment 3 (5- propyl group-[2,5'] Sulfadiazine Compound -2'- bases)-benzonitrile
1) under nitrogen protection, 12.2g (0.5mol) magnesium, the 46 DEG C of dropwise additions of control interior temperature are added in the there-necked flask of clean dried
The mixed solution of 67.6g (0.55mol) N-Propyl Bromides and 202.8g tetrahydrofurans, drop finishes carries out grignard reaction in 60 DEG C, and insulation 2 is little
When, obtain RMgBr stand-by.
2) under nitrogen protection, the chloro- 5- Bromopyrimidines of 58g (0.3mol) 2-, 116g tetra- are added in the there-necked flask of clean dried
Chlorine furans, 0.53g (0.003mol) palladium bichloride, 63 DEG C of control interior temperature is added dropwise RMgBr in (1), and drop finishes carries out alkyl in 56 DEG C
Change reaction, insulation reaction 2 hours, reaction is finished, and obtains reactant liquor, waits to hydrolyze.
3) under nitrogen protection, the watery hydrochloric acid that mass fraction under the conditions of 2 DEG C is 10% is added in the there-necked flask of clean dried
148g, is added dropwise reactant liquor in step (2) under the conditions of 34 DEG C, and drop finishes stirring 0.5 hour, and be hydrolyzed reaction, and stirring is finished, point
Layer, lower floor's water is merged organic phase and is washed to neutrality with toluene extraction, takes off dry solvent, obtains the chloro- 5- propyl group pyrimidines of 2-, yield
93%.
4) under nitrogen protection, the chloro- 5- propyl group pyrimidines of 43.8g (0.28mol) 2- are added in the there-necked flask of clean dried,
63g (0.28mol) 4- (5- boronates-pyrimidine -2-base)-benzonitrile, 328.5g tetrahydrofurans, 0.06g (0.00028mol) vinegar
Sour palladium, is warming up to 52 DEG C.The sodium carbonate liquor that 744.6g mass fractions are 10% is weighed, 53 DEG C of interior temperature of control is water-soluble by sodium carbonate
Drop enters in reaction system, and drop finishes, and is warming up to 65 DEG C, carries out coupling reaction, and insulation reaction 15 hours, insulation is finished, and is added
142.6g toluene, 137.5g concentrated hydrochloric acids, layering, water is merged organic phase and is washed to neutrality with toluene extraction, takes off dry solvent, is obtained
To 4- (5- propyl group-[2,5'] Sulfadiazine Compound -2'- bases)-benzonitrile, yield 92%.
The preparation of 2- amyl group -5- (4- itrile group the benzene)-pyrimidine of embodiment 4
1) under nitrogen protection, 10.6g (0.44mol) magnesium, 65 DEG C of drops of control interior temperature are added in the there-necked flask of clean dried
Plus the mixed solution of 72.8g (0.48mol) bromo pentane silanes and 218.4g tetrahydrofurans, drop finishes carries out grignard reaction in 64 DEG C, insulation 2
Hour, obtain RMgBr stand-by.
2) under nitrogen protection, the chloro- 5- Bromopyrimidines of 56.6g (0.29mol) 2- are added in the there-necked flask of clean dried,
113.2g tetrachloro furans, 0.52g (0.0029mol) palladium bichloride, 56 DEG C of control interior temperature is added dropwise RMgBr in (1), and drop finishes in 58
Reaction DEG C is alkylated, insulation reaction 2 hours, reaction is finished, and obtains reactant liquor, waits to hydrolyze.
3) under nitrogen protection, the watery hydrochloric acid that mass fraction under the conditions of 3 DEG C is 10% is added in the there-necked flask of clean dried
113.2g, is added dropwise reactant liquor in step (2) under the conditions of 6 DEG C, and drop finishes stirring 0.5 hour, and be hydrolyzed reaction, and stirring is finished, point
Layer, lower floor's water is merged organic phase and is washed to neutrality with toluene extraction, takes off dry solvent, obtains the chloro- 5- amyl groups pyrimidines of 2-, yield
91%.
4) under nitrogen protection, the chloro- 5- amyl groups pyrimidines of 43g (0.23mol) 2- are added in the there-necked flask of clean dried,
150 pairs of itrile group phenyl boric acids of 34.4g (0.23mol), 215g tetrahydrofurans, the palladiums of 0.05g (0.00023mol) 225 are warming up to
54 DEG C, the sodium carbonate liquor that 688g mass fractions are 10% is weighed, aqueous sodium carbonate is instilled reactant by 52 DEG C of interior temperature of control
In system, drop finishes, and is warming up to 60 DEG C, carries out coupling reaction, and insulation reaction 18 hours, insulation is finished, and adds 140g toluene, the dense salt of 135g
Acid, layering, water is merged organic phase and is washed to neutrality with toluene extraction, de- dry solvent, obtain 2- amyl group -5- (4- itrile group benzene) -
Pyrimidine, yield 93%.
The preparation of the 4'- of embodiment 5 (5- butyl -2- pyrimidine radicals) -4- biphenylcarbonitriles
1) under nitrogen protection, 10.3g (0.42mol) magnesium, 20 DEG C of drops of control interior temperature are added in the there-necked flask of clean dried
Plus the mixed solution of 60.3g (0.44mol) NBBs and 361.8g tetrahydrofurans, drop finishes carries out grignard reaction in 56 DEG C, insulation 2
Hour, obtain RMgBr stand-by.
2) under nitrogen protection, the chloro- 5- Bromopyrimidines of 48.4g (0.25mol) 2- are added in the there-necked flask of clean dried,
169.4g tetrachloro furans, 0.9g (0.005mol) palladium bichloride, 60 DEG C of control interior temperature is added dropwise RMgBr in (1), and drop finishes in 66 DEG C
Reaction is alkylated, insulation reaction 2 hours, reaction is finished, and obtains reactant liquor, waits to hydrolyze.
3) under nitrogen protection, the watery hydrochloric acid that mass fraction under the conditions of 3 DEG C is 10% is added in the there-necked flask of clean dried
145.2g, is added dropwise reactant liquor in step (2) under the conditions of 20 DEG C, and drop finishes stirring 0.5 hour, and be hydrolyzed reaction, and stirring is finished, point
Layer, lower floor's water is merged organic phase and is washed to neutrality with toluene extraction, takes off dry solvent, obtains the chloro- 5- butyl pyrimidines of 2-, yield
95%.
4) under nitrogen protection, the chloro- 5- butyl pyrimidines of 40.9g (0.24mol) 2- are added in the there-necked flask of clean dried,
45g (0.2mol) 4 '-cyanobiphenyls -4- ylboronic acids, 327.2g tetrahydrofurans, the palladiums of 0.08g (0.00036mol) 208.33,
It is warming up to 53 DEG C.The sodium carbonate liquor that 777.1g mass fractions are 10% is weighed, 55 DEG C of interior temperature of control drips aqueous sodium carbonate
In entering reaction system, drop finishes, and is warming up to 60 DEG C, carries out coupling reaction, and insulation reaction 20 hours, insulation is finished, and adds 130g toluene,
130g concentrated hydrochloric acids, layering, water is merged organic phase and is washed to neutrality with toluene extraction, de- dry solvent, obtain 4'- (5- butyl-
2- pyrimidine radicals) -4- biphenylcarbonitriles, yield 94%.
The preparation of the 4- of embodiment 6 (5- propyl group-[2,5'] Sulfadiazine Compound -2'- bases)-benzonitrile
1) under nitrogen protection, 13.4g (0.55mol) magnesium, 46 DEG C of drops of control interior temperature are added in the there-necked flask of clean dried
Plus the mixed solution of 67.6g (0.55mol) N-Propyl Bromides and 676g tetrahydrofurans, drop finishes carries out grignard reaction in 60 DEG C, and insulation 2 is little
When, obtain RMgBr stand-by.
2) under nitrogen protection, the chloro- 5- Bromopyrimidines of 58g (0.3mol) 2-, 290g tetra- are added in the there-necked flask of clean dried
Chlorine furans, 1.62g (0.009mol) palladium bichloride, 63 DEG C of control interior temperature is added dropwise RMgBr in (1), and drop finishes carries out alkyl in 56 DEG C
Change reaction, insulation reaction 2 hours, reaction is finished, and obtains reactant liquor, waits to hydrolyze.
3) under nitrogen protection, the watery hydrochloric acid of mass fraction 10% under the conditions of 2 DEG C is added in the there-necked flask of clean dried
232g, is added dropwise reactant liquor in step (2) under the conditions of 40 DEG C, and drop finishes stirring 0.5 hour, and be hydrolyzed reaction, and stirring is finished, point
Layer, lower floor's water is merged organic phase and is washed to neutrality with toluene extraction, takes off dry solvent, obtains the chloro- 5- propyl group pyrimidines of 2-, yield
92%.
4) under nitrogen protection, the chloro- 5- propyl group pyrimidines of 43.8g (0.28mol) 2- are added in the there-necked flask of clean dried,
65.7g (0.28mol) 4- (5- boronates-pyrimidine -2-base)-benzonitrile, 438g tetrahydrofurans, 0.12g (0.00056mol) vinegar
Sour palladium, is warming up to 52 DEG C, weighs the sodium carbonate liquor that 963.6g mass fractions are 10%, and 53 DEG C of interior temperature of control is water-soluble by sodium carbonate
Drop enters in reaction system, and drop finishes, and is warming up to 65 DEG C, carries out coupling reaction, and insulation reaction 15 hours, insulation is finished, and is added
142.6g toluene, 137.5g concentrated hydrochloric acids, layering, water is merged organic phase and is washed to neutrality with toluene extraction, takes off dry solvent, is obtained
To 4- (5- propyl group-[2,5'] Sulfadiazine Compound -2'- bases)-benzonitrile, yield 91%.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of spirit or essential attributes without departing substantially from the present invention, the present invention can be in other specific forms realized.Therefore, no matter
From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit is required rather than described above is limited, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.
The foregoing is only presently preferred embodiments of the present invention, not to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (9)
1. a kind of cyano group benzene miazines liquid crystal monomer, it is characterised in that the cyano group benzene miazines liquid crystal monomer, its structural formula is such as
Under：
R is C1-C9Straight chained alkyl, it is 1,2 or 3 that n is 1,2 or 3, m.
2. a kind of preparation method of cyano group benzene miazines liquid crystal monomer, it is characterised in that comprise the following steps：
(1) under the conditions of 20-66 DEG C, brominated alkanes and ether organic solvent are added dropwise in magnesium, brominated alkanes structural formula is R-Br,
R is C1-C9Linear paraffin, carries out grignard reaction, and is incubated 2h, obtains chemical compounds I, and the chemical compounds I structural formula is R-MgBr, R
For C1-C9Linear paraffin；
(2) negate and answer starting compound II, compound ii structural formula isN is 1,2 or 3, in compound ii
Addition tetrachloro furans and catalyst, and under the conditions of 56-66 DEG C, the chemical compounds I obtained in step (1) is added dropwise, it is alkylated
Reaction, and insulation reaction 2h, wait to hydrolyze, and obtain reactant liquor；
(3) take the watery hydrochloric acid that mass fraction under the conditions of 1-5 DEG C is 10%, under the conditions of 0-40 DEG C to mass fraction be 10% it is dilute
The reactant liquor obtained in step (2) is added dropwise in hydrochloric acid, 0.5h is stirred, be hydrolyzed reaction, obtain compound III, compound III knot
Structure formula isR is C1-C9Straight chained alkyl, n is 1,2 or 3；
(4) tetrahydrofuran, catalyst and the compounds Ⅳ, compounds Ⅳ structural formula is added to be in compound IIIM is 1,2 or 3, and it is 10% aqueous slkali to be warming up to 50-55 DEG C and mass fraction is added dropwise, then is warming up to
60-65 DEG C carries out coupling reaction, and the reaction time is 15-20h, obtains compound V, and the structural formula of compound V isR is C1-C9Straight chained alkyl, it is 1,2 or 3 that n is 1,2 or 3, m.
3. preparation method according to claim 2, it is characterised in that the brominated alkanes in the step (1) rub with magnesium
You are than being 1：(0.91-1)；Brominated alkanes are 1 with the mass ratio of ether organic solvent:(3-10)；Ether organic solvent be ether,
One or more in methyl phenyl ethers anisole, tetrahydrofuran, methyltetrahydrofuran.
4. preparation method according to claim 2, it is characterised in that the grignard reaction temperature in the step (1) is 56-
66℃。
5. preparation method according to claim 2, it is characterised in that the compound ii in the step (2) and tetrachloro furan
The mass ratio muttered is 1:(2-5)；Compound ii is 1 with the mol ratio of catalyst:(0.01-0.03)；Catalyst be palladium bichloride, two
The triphenylphosphine of chlorine two closes one or more in palladium, palladium.
6. preparation method according to claim 2, it is characterised in that the mass fraction in the step (3) is 10%
Watery hydrochloric acid is 1 with the mass ratio of compound ii:(0.25-0.5).
7. preparation method according to claim 2, it is characterised in that the catalyst in the step (4) be palladium bichloride, two
The triphenylphosphine of chlorine two closes one or more in palladium, palladium；Compound III is 1 with the mol ratio of catalyst：(0.001-
0.002)；Compound III is 1 with the mass ratio of compounds Ⅳ:(0.8-1.5)；Compound III is 1 with the mass ratio of tetrahydrofuran：
(5-10)。
8. preparation method according to claim 2, it is characterised in that the compound III and aqueous slkali in the step (4)
Mass ratio be 1：(16-22)；Aqueous slkali is one or more in potassium carbonate, sodium carbonate, potassium hydroxide, NaOH.
9. the preparation method according to claim 2-8 any one, it is characterised in that all steps are protected in inert gas
Carry out under the conditions of shield.
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| CN115417823A (en) * | 2022-08-27 | 2022-12-02 | 上海泰坦科技股份有限公司 | Preparation method of pyrimidine biphenyl aromatic ring compound |
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| CN115417823A (en) * | 2022-08-27 | 2022-12-02 | 上海泰坦科技股份有限公司 | Preparation method of pyrimidine biphenyl aromatic ring compound |
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