CN108191600A - A kind of preparation method of halogen-substituted class compound - Google Patents

A kind of preparation method of halogen-substituted class compound Download PDF

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Publication number
CN108191600A
CN108191600A CN201711455443.XA CN201711455443A CN108191600A CN 108191600 A CN108191600 A CN 108191600A CN 201711455443 A CN201711455443 A CN 201711455443A CN 108191600 A CN108191600 A CN 108191600A
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赵东敏
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration

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  • Chemical & Material Sciences (AREA)
  • 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 class compound halogen-substituted shown in formula 1, include the following steps：(1) condensation reaction：(2) ring-closure reaction：(3) substitution reaction：(4) coupling reaction：(5) reduction reaction：(6) diazo-reaction：

Description

A kind of preparation method of halogen-substituted class compound
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 replaced 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.
Invention content
The present invention provides a kind of preparation method of halogen-substituted class compound, the halogen-substituted class compound packets 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.
The present invention has the beneficial effect that：
The present invention provides a kind of preparation methods of new halogen-substituted class compound.
Specific embodiment
It is more according to the optional factor that the preparation method of the halogen-substituted class compound of the present invention provides, it is 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, 12.0 grams (0.1mol) acetophenone 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, and finishes slowly It is warming up to back flow reaction 4 hours, is down to room temperature, be concentrated under reduced pressure into dry, addition dichloromethane and moisture liquid, organic layer dry potassium carbonate Silica gel post separation, petroleum ether after dry：Ethyl acetate=4：1 (volume ratio) elution separation, obtains 1,3- diphenyl -2- propylene -1- 7.7 grams of ketone, yield 37.02%.
Mass Spectrometer Method is carried out to obtained benzylideneacetophenone, it is 208 to measure molecular weight.
(2) ring-closure reaction
In 1000 milliliters of there-necked flasks, 300 milliliters of absolute ethyl alcohols of addition, 20.8 grams of (0.1mol) 1,3- diphenyl -2- propylene - 1- ketone, 32.4 grams of (0.15mol) 1- (2- oxopropyls) pyridine -1- bromides, 20.2 grams of (0.2mol) triethylamines are heated to 60 degree are reacted 24 hours, are down to room temperature, add in dichloromethane and moisture liquid, organic layer washing, silica gel after anhydrous magnesium sulfate drying Post separation, petroleum ether：Ethyl acetate=4：1 (volume ratio) elution separation, obtains 11.1 grams of 3,5- diphenyl phenol, yield 45.12%.
Obtained 3,5- diphenyl phenol is carried out and Mass Spectrometer Method, measure molecular weight are 246.
Nuclear-magnetism detection is carried out to obtained 3,5- diphenyl phenol, obtained nuclear-magnetism parsing data are as follows：
1HNMR (500MHz, CDCl3)：δ 7.77 (m, 4H), δ 7.61 (t, 1H), δ 7.50 (m, 4H), δ 7.40 (m, 2H), δ 7.22 (d, 2H), δ 4.88 (s, 1H).
(3) substitution reaction
500 milliliters of there-necked flasks, nitrogen protection, add in 200 milliliters of dichloromethane, 24.6 grams of (0.1mol) 3,5- diphenyl benzenes Phenol is cooled to 0 degree, controls 0~5 degree of temperature, 16.8 grams of (0.1mol) trifluoromethanesulfchloride chlorides are slowly added dropwise, finishes and is slowly increased to room Temperature reaction 6 hours, adds moisture liquid, organic layer concentration washing, then anhydrous sodium sulfate drying is concentrated to dryness, petroleum ether and acetic acid Acetate mixed solvent recrystallizes, and obtains trifluoromethanesulfonic acid 3,30.1 grams of 5- diphenyl phenyl ester, yield 79.63%.
(4) coupling reaction
500 milliliters of there-necked flasks, 3.78 grams of (0.01mol) trifluoromethanesulfonic acids 3 of addition, 5- diphenyl phenyl esters, 1.99 grams (0.012mol) p-nitrophenyl boric acid, 0.35 gram of (0.0003mol) tetra-triphenylphosphine palladium, 2.76 grams of (0.02mol) potassium carbonate, 200 milliliters of toluene, 100 milliliters of ethyl alcohol, 80 milliliters of water, under nitrogen protection, heating reflux reaction 8 hours cools down, and liquid separation is organic After layer washing, anhydrous sodium sulfate drying, silica gel column chromatography detaches, and petroleum ether elution obtains 4- nitro -5'- phenyl -1,1':3', 2.0 grams of 1 "-terphenyl, yield 56.98%.
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, reaction solution filtering after, be 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 react 1 hour, then heat to 60~65 degree keep 3 hours, 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/e384,386).
Therein 47% hydrobromic acid is only 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 only 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, only 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, only 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.
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 range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies Within, then the present invention is also intended to include these modifications and variations.

Claims (4)

1. the preparation method of compound, includes 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, includes 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, includes 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. application of the preparation method described in claims 1 to 3 in oled materials synthesis.
CN201711455443.XA 2017-12-27 2017-12-27 A kind of preparation method of halogen-substituted class compound Withdrawn CN108191600A (en)

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Application publication date: 20180622