CN108046984A - A kind of preparation method of halogen-substituted class compound - Google Patents
A kind of preparation method of halogen-substituted class compound Download PDFInfo
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- CN108046984A CN108046984A CN201711455444.4A CN201711455444A CN108046984A CN 108046984 A CN108046984 A CN 108046984A CN 201711455444 A CN201711455444 A CN 201711455444A CN 108046984 A CN108046984 A CN 108046984A
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- 0 CC1(C)c(cc(cc2)-c3cc(-c(cc4)ccc4[N+]([O-])=O)cc(OS(C(F)(F)F)(=O)=O)c3)*2-c2ccccc12 Chemical compound CC1(C)c(cc(cc2)-c3cc(-c(cc4)ccc4[N+]([O-])=O)cc(OS(C(F)(F)F)(=O)=O)c3)*2-c2ccccc12 0.000 description 1
- VNGQJGHDLPGQSG-UHFFFAOYSA-N CC1(C)c2cc(-c3cc(-c(cc4)ccc4-c4ccccc4)cc(-c(cc4)ccc4[N+]([O-])=O)c3)ccc2-c2ccccc12 Chemical compound CC1(C)c2cc(-c3cc(-c(cc4)ccc4-c4ccccc4)cc(-c(cc4)ccc4[N+]([O-])=O)c3)ccc2-c2ccccc12 VNGQJGHDLPGQSG-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation methods of compound shown in formula 1, comprise the following steps：(1) condensation reaction：(2) ring-closure reaction：(3) substitution reaction：(4) coupling reaction：(5) reduction reaction：(6) diazo-reaction：
Description
Technical field
The invention belongs to organic synthesis field more particularly to a kind of preparation methods of halogen-substituted class compound.
Background technology
Compound containing phenyl group is important organic chemical industry's material, can be with after being substituted on benzene by different substituent groups
It applies in medicine, pesticide, dyestuff, display chemicals various aspects.Compound shown in formula A is an important oled below
The intermediate of material.
The content of the invention
The present invention provides a kind of preparation method of halogen-substituted class compound, the halogen-substituted class compound bags
It includes with lower structure：
Wherein X is selected from F, Cl, Br, I.
Compound synthesis route is as follows shown in formula 1：
(1) condensation reaction：
(2) ring-closure reaction：
(3) substitution reaction：
(4) coupling reaction：
(5) reduction reaction：
(6) diazo-reaction：
Wherein X is selected from F, Cl, Br, I
In diazo-reaction, amino-compound is initially formed diazol, then carries out sandmeyer reaction, obtains corresponding
The benzene-like compounds of halogen substitution.
Compound synthesis route is as follows shown in formula 2：
(1) condensation reaction：
(2) ring-closure reaction：
(3) substitution reaction：
(4) coupling reaction：
(5) reduction reaction：
(6) diazo-reaction：
Wherein X is selected from F, Cl, Br, I.
In diazo-reaction, amino-compound is initially formed diazol, then carries out sandmeyer reaction, obtains corresponding
The benzene-like compounds of halogen substitution.
Compound synthesis route is as follows shown in formula 3：
(1) condensation reaction：
(2) ring-closure reaction：
(3) substitution reaction：
(4) coupling reaction：
(5) reduction reaction：
(6) diazo-reaction：
Wherein X is selected from F, Cl, Br, I.
In diazo-reaction, amino-compound is initially formed diazol, then carries out sandmeyer reaction, obtains corresponding
The benzene-like compounds of halogen substitution.
Compound synthesis route is as follows shown in formula 4：
(1) condensation reaction：
(2) ring-closure reaction：
(3) substitution reaction：
(4) coupling reaction：
(5) reduction reaction：
(6) diazo-reaction：
Wherein X is selected from F, Cl, Br, I.
In diazo-reaction, amino-compound is initially formed diazol, then carries out sandmeyer reaction, obtains corresponding
The benzene-like compounds of halogen substitution.
Compound synthesis route is as follows shown in formula 5：
(1) condensation reaction：
(2) ring-closure reaction：
(3) substitution reaction：
(4) coupling reaction：
(5) reduction reaction：
(6) diazo-reaction：
Wherein X is selected from F, Cl, Br, I.
In diazo-reaction, amino-compound is initially formed diazol, then carries out sandmeyer reaction, obtains corresponding
The benzene-like compounds of halogen substitution.
The present invention has the beneficial effect that：
The present invention provides a kind of preparation methods of new halogen-substituted class compounds compound.
Specific embodiment
The optional factor that the preparation method of halogen-substituted class compound provides according to the present invention is more, according to the present invention
Claim can be combined into different embodiments, and embodiment is only used for that the present invention is described further, not to this hair
It is bright to be construed as limiting.The present invention is further detailed below in conjunction with embodiment.
The synthesis of compound shown in 1 formula 1 of embodiment
(1) condensation reaction
500 milliliters of there-necked flasks, nitrogen protection, 300 ml methanols of addition, 10.6 grams of (0.1mol) benzaldehydes, 16.5 grams
(0.1mol) p-nitroacetophenone is slowly heated to 40 degree, and the solution of 3 grams of water of 1 gram of (0.025mol) sodium hydroxide is added dropwise, adds
Finish be to slowly warm up to back flow reaction 4 it is small when, be down to room temperature, be concentrated under reduced pressure into dry, add in dichloromethane and moisture liquid, organic layer carbon
Silica gel post separation after sour potassium drying, petroleum ether：Ethyl acetate=4：1 (volume ratio) elution separation, obtain 1- (4- nitrobenzophenones)-
6.6 grams of 3- phenyl -2- propylene -1- ketone, yield 26.08%.
Mass Spectrometer Method has been carried out to obtained 1- (4- nitrobenzophenones) -3- phenyl -2- propylene -1- ketone, has measured molecular weight
For 253.
(2) ring-closure reaction
In 1000 milliliters of there-necked flasks, 300 milliliters of absolute ethyl alcohols, 25.3 grams of (0.1mol) 1- (4- nitrobenzophenones) -3- are added in
Phenyl -2- propylene -1- ketone, 32.4 grams of (0.15mol) 1- (2- oxopropyls) pyridine -1- bromides, 20.2 grams (0.2mol)
Triethylamine, be heated to 60 degree of reactions 24 it is small when, be down to room temperature, add in dichloromethane and moisture liquid, organic layer washing, anhydrous slufuric acid
Silica gel post separation after magnesium drying, petroleum ether：Ethyl acetate=4：1 (volume ratio) elution separation, obtains 4- nitros-[1,1':3',
1 "-terphenyl] 17.6 grams of -5'- phenol, yield 60.48%.
To obtained 4- nitros-[1,1':3', 1 "-terphenyl] -5'- phenol carried out Mass Spectrometer Method, and measuring molecular weight is
291。
To obtained 4- nitros-[1,1':3', 1 "-terphenyl] -5'- phenol carried out nuclear-magnetism detection, obtained nuclear-magnetism solution
It is as follows to analyse data：
1HNMR (500MHz, CDCl3)：δ 8.29 (m, 2H), δ 7.89 (m, 2H), δ 7.77 (m, 2H), δ 7.62 (t, 1H), δ
7.49 (m, 2H), δ 7.40 (m, 1H), δ 7.22 (d, 2H) δ 4.85 (s, 1H).
(3) substitution reaction
500 milliliters of there-necked flasks, nitrogen protection, 200 milliliters of dichloromethane of addition, 29.1 grams of (0.1mol) 4- nitros-[1,
1':3', 1 "-terphenyl] -5'- phenol, 0 degree is cooled to, 0~5 degree of temperature is controlled, 16.8 grams of (0.1mol) fluoroforms is slowly added dropwise
Sulfonic acid chloride, finish be slowly increased to room temperature reaction 6 it is small when, add moisture liquid, organic layer concentration washing, anhydrous sodium sulfate drying, then
It is concentrated to dryness, petroleum ether and ethyl acetate mixed solvent recrystallization obtain trifluoromethanesulfonic acid 4- nitros-[1,1':3', 1 "-three connection
Benzene] 36.7 grams of -5'- phenol esters, yield 86.76%.
(4) coupling reaction
500 milliliters of there-necked flasks add in 4.23 grams of (0.01mol) trifluoromethanesulfonic acid 4- nitros-[1,1':3', 1 "-three connection
Benzene] -5'- phenol esters, 1.45 grams of (0.012mol) phenyl boric acids, 0.35 gram of (0.0003mol) tetra-triphenylphosphine palladium, 2.76 grams
(0.02mol) potassium carbonate, 200 milliliters of toluene, 100 milliliters of ethyl alcohol, 80 milliliters of water, under nitrogen protection, heating reflux reaction 8 is small
When, cooling, liquid separation, after organic layer washing, anhydrous sodium sulfate drying, silica gel column chromatography separates, and petroleum ether elution obtains 4- nitre
Base -5'- phenyl -1,1':3', 2.8 grams of 1 "-terphenyl, yield 79.77%.
To obtained 4- nitros -5'- phenyl -1,1':3', 1 "-terphenyl have carried out Mass Spectrometer Method, measure molecular weight and are
351。
(5) reduction reaction
In 500 milliliters of autoclaves, 200 milliliters of ethyl alcohol, 3.51 grams of (0.01mol) 4- nitro -5'- phenyl -1,1' are added in:
3', 1 "-terphenyl, 0.4 gram 5% of Pd/C control temperature 60 C, and pressure 0.2MPa carries out hydro-reduction reaction, and reaction finishes,
Cooling, nitrogen displacement after reacting liquid filtering, are concentrated to dryness, ethyl acetate and toluene Mixed Solvent recrystallization, obtain 5'- phenyl-
[1,1':3', 1 "-terphenyl] 3.06 grams of -4- amine, yield 95.33%.
To obtained 5'- phenyl-[1,1':3', 1 "-terphenyl] -4- amine progress Mass Spectrometer Method, product m/e：321.
(6) diazo-reaction
500 milliliters of there-necked flasks add in 3.21 grams of (0.01mol) 5'- phenyl-[1,1':3', 1 "-terphenyl] -4- amine, 10
The hydrobromic acid of milliliter 47%, 10 milliliter 95% of the concentrated sulfuric acid are to slowly warm up to 80 degree and are kept for 10 minutes, be then cooled to 5 degree, add
Enter 0.2 gram of cuprous bromide, control 2 milliliters of aqueous solutions of 0~5 degree of dropwise addition, 0.69 gram of (0.01mol) sodium nitrite, finish, keep 0
~5 degree 30 minutes, be slowly increased to 20~25 degree reaction 1 it is small when, then heat to 60~65 degree keep 3 it is small when, cool down, add water,
Obtained solid is filtered, after solid is dried, silica gel column chromatography separation, petroleum ether elution obtains the bromo- 5'- of 4- shown in formula 1-1
Phenyl -1,1':3', 2.6 grams of 1 "-terphenyl, yield 67.53%.
5'- phenyl -1,1' bromo- to 4- shown in obtained formula 1-1:3', 1 "-terphenyl have carried out Mass Spectrometer Method, measure
Molecular weight is 385 (m/e 384,386).
Therein 47% hydrobromic acid is simply changed into 36% hydrochloric acid, by it by the synthesis of compound with reference to shown in formula 1-1
In cuprous bromide change stannous chloride into, synthesized the chloro- 5'- phenyl -1,1' of 4- shown in formula 1-2:3', 1 "-terphenyl.
5'- phenyl -1,1' chloro- to 4- shown in obtained formula 1-2:3', 1 "-terphenyl have carried out Mass Spectrometer Method, measure
Molecular weight is 340.
Therein 47% hydrobromic acid is simply changed into 50% hydroiodic acid by the synthesis of compound with reference to shown in formula 1-1, will
Cuprous bromide therein changes cuprous iodide into, has synthesized the iodo- 5'- phenyl -1,1' of 4- shown in formula 1-3:3', 1 "-terphenyl.
5'- phenyl -1,1' iodo- to 4- shown in obtained formula 1-3:3', 1 "-terphenyl have carried out Mass Spectrometer Method, measure
Molecular weight is 432.
The synthesis of compound shown in 2 formula 2 of embodiment
The synthesis of synthetic method compound with reference to shown in formula 1, simply in first step condensation reaction, by benzaldehyde therein
Change biphenylcarboxaldehyde into, you can obtain compound shown in formula 2.
Specific synthesis following compounds：
Mass Spectrometer Method is carried out to compound shown in obtained formula 2-1, it is 416 to measure molecular weight.
Mass Spectrometer Method is carried out to compound shown in obtained formula 2-2, measure molecular weight is 461 (m/e 460,462).
Mass Spectrometer Method is carried out to compound shown in obtained formula 2-3, it is 508 to measure molecular weight.
The synthesis of compound shown in 3 formula 3 of embodiment
The synthesis of synthetic method compound with reference to shown in formula 1, simply in first step condensation reaction, by benzaldehyde therein
Change -2 formaldehyde of 9,9- dimethyl fluorenes into, you can obtain compound shown in formula 3.
Specific synthesis following compounds：
Mass Spectrometer Method is carried out to compound shown in obtained formula 3-1, it is 456 to measure molecular weight.
Mass Spectrometer Method is carried out to compound shown in obtained formula 3-2, measure molecular weight is 501 (m/e 500,502).
Mass Spectrometer Method is carried out to compound shown in obtained formula 3-3, it is 548 to measure molecular weight.
The synthesis of compound shown in 4 formula 4 of embodiment
The synthesis of synthetic method compound with reference to shown in formula 3, simply in the coupling reaction of the 4th step, by benzene boron therein
Acid changes biphenylboronic acid into, you can obtains compound shown in formula 4.
Specific synthesis following compounds：
Mass Spectrometer Method is carried out to compound shown in obtained formula 4-1, it is 533 to measure molecular weight.
Mass Spectrometer Method is carried out to compound shown in obtained formula 4-2, measure molecular weight is 577 (m/e 576,579).
Mass Spectrometer Method is carried out to compound shown in obtained formula 4-3, it is 624 to measure molecular weight.
The synthesis of compound shown in 5 formula 5 of embodiment
The synthesis of synthetic method compound with reference to shown in formula 3, simply in the coupling reaction of the 4th step, by benzene boron therein
Acid changes 9,9- dimethyl fluorene -2- boric acid into, you can obtains compound shown in formula 5.
Specific synthesis following compounds：
Mass Spectrometer Method is carried out to compound shown in obtained formula 5-1, it is 572 to measure molecular weight.
Mass Spectrometer Method is carried out to compound shown in obtained formula 5-2, measure molecular weight is 617 (m/e 616,618).
Mass Spectrometer Method is carried out to compound shown in obtained formula 5-3, it is 664 to measure molecular weight.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
God and scope.In this way, if these modifications and changes of the present invention belongs to the scope of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to comprising including these modification and variations.
Claims (6)
1. the preparation method of compound, comprises the following steps shown in a kind of formula 1：
(1) condensation reaction：
(2) ring-closure reaction：
(3) substitution reaction：
(4) coupling reaction：
(5) reduction reaction：
(6) diazo-reaction：
Wherein X is selected from F, Cl, Br, I.
2. the preparation method of compound, comprises the following steps shown in a kind of formula 2：
(1) condensation reaction：
(2) ring-closure reaction：
(3) substitution reaction：
(4) coupling reaction：
(5) reduction reaction：
(6) diazo-reaction：
Wherein X is selected from F, Cl, Br, I.
3. the preparation method of compound, comprises the following steps shown in a kind of formula 3：
(1) condensation reaction：
(2) ring-closure reaction：
(3) substitution reaction：
(4) coupling reaction：
(5) reduction reaction：
(6) diazo-reaction：
Wherein X is selected from F, Cl, Br, I.
4. the preparation method of compound, comprises the following steps shown in a kind of formula 4：
(1) condensation reaction：
(2) ring-closure reaction：
(3) substitution reaction：
(4) coupling reaction：
(5) reduction reaction：
(6) diazo-reaction：
Wherein X is selected from F, Cl, Br, I.
5. the preparation method of compound, comprises the following steps shown in a kind of formula 5：
(1) condensation reaction：
(2) ring-closure reaction：
(3) substitution reaction：
(4) coupling reaction：
(5) reduction reaction：
(6) diazo-reaction：
Wherein X is selected from F, Cl, Br, I.
6. application of the preparation method described in Claims 1 to 5 in oled materials synthesis.
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| CN201711455444.4A CN108046984A (en) | 2017-12-27 | 2017-12-27 | A kind of preparation method of halogen-substituted class compound |
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| CN201711455444.4A CN108046984A (en) | 2017-12-27 | 2017-12-27 | A kind of preparation method of halogen-substituted class compound |
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