WO2020259078A1 - Procédé de préparation d'un dérivé de triphénylamine contenant de l'adamantyle - Google Patents

Procédé de préparation d'un dérivé de triphénylamine contenant de l'adamantyle Download PDF

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WO2020259078A1
WO2020259078A1 PCT/CN2020/087870 CN2020087870W WO2020259078A1 WO 2020259078 A1 WO2020259078 A1 WO 2020259078A1 CN 2020087870 W CN2020087870 W CN 2020087870W WO 2020259078 A1 WO2020259078 A1 WO 2020259078A1
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carbon atoms
groups
reaction
adamantyl
chemical formula
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李应文
马天天
冯震
沙荀姗
孙占义
王亚龙
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陕西莱特光电材料股份有限公司
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Publication of WO2020259078A1 publication Critical patent/WO2020259078A1/fr

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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
    • C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C07C17/2637—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions between a compound containing only oxygen and possibly halogen as hetero-atoms and a halogenated hydrocarbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
    • 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
    • C07C37/16—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 by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
    • 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
    • C07C37/18—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 by condensation involving halogen atoms of halogenated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
    • C07C2603/74—Adamantanes

Definitions

  • the invention belongs to the field of electroluminescence, and relates to a preparation method of organic electroluminescence compounds. More specifically, the invention relates to a preparation method of adamantyl-containing triphenylamine derivatives.
  • Electroluminescence also known as electroluminescence, or EL for short
  • EL electroluminescence
  • OLED organic electroluminescent devices
  • OLED organic electroluminescent devices
  • the organic thin film is a film of organic light-emitting material formed on a substrate by evaporation or spin coating. Compared with traditional display technology, it has great advantages in terms of voltage characteristics, luminous brightness, luminous efficiency, color quality, response speed and viewing angle, and low cost, so it has a broad market prospect.
  • adamantane derivatives such as triphenylamine derivatives containing adamantyl groups.
  • triphenylamine derivatives containing adamantyl groups When the adamantyl-containing triphenylamine derivatives are prepared in a one-pot reaction, the yield of the target product is very low due to too many impurities. For this reason, researchers have studied a stepwise reaction method.
  • the conventional preparation method of triphenylamine derivatives containing adamantyl group is to use aryl halide adamantane or aryl menthol esters to react with a first-grade aromatic amine, and then through post-treatment, separation, and purification to obtain higher purity
  • the intermediate (secondary aromatic amine compound) is then used to react with another halogenated aromatic hydrocarbon to produce the target product (tertiary aromatic amine compound).
  • the present invention provides a method for preparing adamantyl-containing triphenylamine derivatives, which improves the yield.
  • a preparation method of adamantyl-containing triphenylamine derivatives specifically includes the following steps:
  • Step 1 Add the compound of Chemical Formula 2, the compound of Chemical Formula 3, the base, the ligand, and the catalyst to the solvent to carry out the reaction;
  • Step 2 Put the compound represented by Chemical Formula 4 directly into the reaction solution obtained by the reaction in Step 1, and then continue the reaction to obtain the adamantyl-containing triphenylamine derivative represented by Chemical Formula 1;
  • X is selected from Cl, Br, I and CF 3 SO 3 ;
  • Y is selected from Cl, Br and I;
  • L is selected from substituted or unsubstituted arylene groups with 6-30 carbon atoms, substituted or unsubstituted heteroarylene groups with 6-30 carbon atoms;
  • Ar 1 and Ar 2 are the same or different, and are independently selected from substituted or unsubstituted alkyl groups having 1 to 35 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 35 carbon atoms, substituted or unsubstituted The alkynyl groups with 2-35 carbon atoms, substituted or unsubstituted cycloalkyl groups with 3-35 carbon atoms, substituted or unsubstituted heterocycloalkyl groups with 2-35 carbon atoms, substituted or unsubstituted Substituted aralkyl groups with 7-40 carbon atoms, substituted or unsubstituted heteroaralkyl groups with 2-40 carbon atoms, substituted or unsubstituted aryl groups with 6-40 carbon atoms, substituted or Unsubstituted heteroaryl groups with 1-40 carbon atoms;
  • the substituents of Ar 1 and Ar 2 are the same or different, and are independently selected from hydrogen, deuterium, halogen, cyano, nitro, alkyl with 1-40 carbon atoms, alkenyl with 2-40 carbon atoms, Alkynyl groups with 2-40 carbon atoms, aryl groups with 6-60 carbon atoms, heteroaryl groups with 5-60 carbon atoms, aryloxy groups with 6-60 carbon atoms, and carbon atoms 1-40 alkoxy, 6-60 arylamino, 3-40 cycloalkyl, 3-40 heterocycloalkyl, carbon 1 -40 alkylsilyl group, alkylboron group with 1-40 carbon atoms, arylboron group with 6-60 carbon atoms, arylphosphino group with 6-60 carbon atoms and the number of carbon atoms Substitution with 6-60 arylsilyl groups;
  • the substituent of L is selected from hydrogen, deuterium, halogen, cyano, nitro, alkyl with 1-40 carbon atoms, alkenyl with 2-40 carbon atoms, alkynyl with 2-40 carbon atoms, carbon Aryl groups with 6 to 60 atoms, heteroaryl groups with 5 to 60 carbon atoms, aryloxy groups with 6 to 60 carbon atoms, alkoxy groups with 1 to 40 carbon atoms, carbon atoms It is an arylamino group with 6-60 carbon atoms, a cycloalkyl group with 3-40 carbon atoms, a heterocycloalkyl group with 3-40 carbon atoms, an alkylsilyl group with 1-40 carbon atoms, and a carbon atom Alkyl boron group with 1-40, aryl boron with 6-60 carbon atoms, arylphosphino with 6-60 carbon atoms, and arylsilyl group with 6-60 carbon atoms .
  • the reaction temperature is 100-105°C, and the reaction time is 2-24h; in step 2, the reaction temperature is 100-105°C, and the reaction time is 2-48h.
  • chemical formula 2 is obtained by reacting 1-adamantanol with the compound shown in chemical formula 5 for 2-3h, and the reaction formula is as follows:
  • reaction formula 2 is synthesized by using the compound shown in chemical formula 6 and trifluoromethanesulfonic anhydride, the reaction formula is as follows:
  • the solvent is selected from toluene and xylene
  • the base is selected from potassium phosphate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, cesium carbonate, sodium tert-butoxide and potassium tert-butoxide.
  • the catalyst is selected from Pd 2 dba 3 , Pd(OAc) 2 and Pd(dppf)Cl 2 .
  • the ligand is selected from (t-Bu) 3 P, x-PHOS and s-PHOS.
  • the molar ratio of the compounds represented by Chemical Formula 2, Chemical Formula 3 and Chemical Formula 4 is 1:1:0.98.
  • L is selected from 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, dibenzofuran and diphenyl And thiophene.
  • L is selected from 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, dibenzofuranyl, Dibenzothienyl, N-phenylcarbazolyl, or a group formed by connecting any two or three of the above groups through a single bond.
  • Ar 1 and Ar 2 are each independently selected from 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl , Dibenzofuranyl, dibenzothienyl, N-phenylcarbazolyl, or a group formed by connecting two or three of the above groups through a single bond.
  • the compound represented by Chemical Formula 1 is selected from the compounds represented by the following structures:
  • aryl refers to an optional functional group or substituent derived from an aromatic carbocyclic ring.
  • the aryl group can be a monocyclic aryl group or a polycyclic aryl group.
  • the aryl group can be a monocyclic aryl group, a condensed ring aryl group, two or more monocyclic aryl groups conjugated by carbon-carbon bonds, A monocyclic aryl group and a fused ring aryl group conjugated by carbon-carbon bonds, and two or more fused ring aryl groups conjugated by a carbon-carbon bond. That is, two or more aromatic groups conjugated through carbon-carbon bonds can also be regarded as aryl groups in the present application.
  • the aryl group does not contain heteroatoms such as B, N, O, S, P, and Si.
  • biphenyl, terphenyl, etc. are aryl groups.
  • aryl groups may include, but are not limited to, phenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl, biphenyl, terphenyl, tetraphenyl, pentaphenyl, benzo[9,10] Phenanthryl, pyrenyl, benzofluoranthene, Base etc.
  • the substituted aryl group may be one or more hydrogen atoms in the aryl group, such as deuterium atom, halogen group, -CN, aryl, heteroaryl, trialkylsilyl, alkyl, Cycloalkyl, alkoxy, alkylthio, haloalkyl, aryloxy, arylthio, silyl, alkylamino, arylamino, heterocyclic and other groups are substituted.
  • aryl group such as deuterium atom, halogen group, -CN, aryl, heteroaryl, trialkylsilyl, alkyl, Cycloalkyl, alkoxy, alkylthio, haloalkyl, aryloxy, arylthio, silyl, alkylamino, arylamino, heterocyclic and other groups are substituted.
  • heteroaryl-substituted aryl groups include, but are not limited to, dibenzofuranyl-substituted phenyl groups, dibenzothiophene-substituted phenyl groups, pyridine-substituted phenyl groups, and the like.
  • the number of carbon atoms of a substituted aryl group refers to the total number of carbon atoms of the aryl group and the substituents on the aryl group.
  • a substituted aryl group with 18 carbon atoms refers to an aryl group and its The total number of carbon atoms of the substituent is 18.
  • a heteroaryl group refers to a monovalent aromatic ring containing at least one heteroatom in the ring or a derivative thereof.
  • the heteroatom may be at least one of B, O, N, P, Si, and S.
  • the heteroaryl group can be a monocyclic heteroaryl group or a polycyclic heteroaryl group.
  • the heteroaryl group can be a single aromatic ring system or multiple aromatic ring systems conjugated by carbon-carbon bonds, and any aromatic
  • the ring system is an aromatic monocyclic ring or an aromatic fused ring.
  • the "heteroaryl group” in this application may include 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 heteroatoms selected from B, O, N, P, Si, Se and S
  • the number of carbon atoms can be 3-40. In some embodiments, the number of carbon atoms of the heteroaryl group can be 3-30. In other embodiments, the number of carbon atoms of the heteroaryl group can be 3-20. , Or 3-18, or 3-12, or 12-18. For example, the number of carbon atoms of the heteroaryl group can also be 5, 8, 9, 12, 18, 20 or 40. Of course, the number of carbon atoms can also be other numbers, which will not be repeated here. List one by one.
  • aryl can be applied to arylene
  • heteroaryl can be applied to heteroarylene
  • alkyl can be applied to alkylene
  • cycloalkyl can be Applied to cycloalkylene
  • heteroaryl groups may include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, Acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazine Azinyl, isoquinolinyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thiophene Thienyl, benzofur
  • thienyl, furanyl, phenanthrolinyl, etc. are heteroaryl groups of a single aromatic ring system type, and N-arylcarbazolyl and N-heteroarylcarbazolyl are multiple groups conjugated through carbon-carbon bonds. Ring system type heteroaryl.
  • aryl-substituted heteroaryl groups include, but are not limited to, phenyl-substituted dibenzofuranyl, phenyl-substituted dibenzothienyl, phenyl-substituted pyridyl, and the like.
  • the number of carbon atoms of the substituted heteroaryl group refers to the total number of carbon atoms of the heteroaryl group and the substituent on the heteroaryl group.
  • the present invention has the following beneficial technical effects:
  • the present invention first adopts the reaction of aryl halide adamantane or aryl masticate and the first-grade aromatic amine, without separating and purifying after the reaction, directly throwing in halogenated aromatic hydrocarbon for reaction.
  • the steps of the present invention are simple, the raw materials used are basic chemical raw materials, and the yield is high.
  • the final product has high purity. It is much better than the prior art in terms of raw material cost, actual operability and man-hours required for operation, and is very applicable For industrial production.
  • the preparation method of adamantane derivatives needs to be synthesized through multiple steps, and the Suzuki coupling reaction is often used in the synthesis of the target product.
  • the Suzuki reaction rate of most chlorinated compounds is very slow, the yield is very low, and each step needs to be separated and purified, the catalyst utilization rate is low, resulting in increased costs.
  • 4-(adamantan-1-yl)benzene trifluoromethanesulfonate is used to react with 4'-chloro-4-ylbiphenylboronic acid to obtain aryl halide adamantane.
  • the present invention aims to provide a method for preparing triphenylamine derivatives containing adamantyl groups. Under the condition that the pH is greater than or equal to 10, using aryl halide adamantane or aryl mantane ester, first-class aromatic amine as raw materials, using alkali, catalyst, ligand, toluene or xylene as solvent, reflux reaction 2-24 Hours; cooling down, adding water, extracting with organic solvent, washing with water, drying, and removing the solvent to obtain the crude product, which is then purified by column or recrystallization.
  • An organic electroluminescent device includes an anode, a cathode, and an organic layer between the anode and the cathode.
  • the organic layer includes at least one layer, and at least one of the above-mentioned organic layers includes the preparation method of the present invention.
  • the organic layer containing the above compound is selected from a hole injection layer, a hole transport layer, a red light enhancement layer, an electron blocking layer, an electron transport layer, an electron injection layer, a lifetime improvement layer, a light-emitting layer, and a light-emitting auxiliary layer.
  • MC refers to CH 2 Cl 2 , dichloromethane.
  • Example 4 The method of Example 4 was used to synthesize 2-bromo-7-adamantyl-9,9-dimethylfluorene.
  • Example 4 The method of Example 4 was used to synthesize 2-bromo-7-adamantyl-9,9-dimethylfluorene.
  • Example 3 The method of Example 3 was used to synthesize 4-bromo-4'-adamantyl biphenyl.
  • Comparative literature uses four-step reaction to synthesize compound 110 (compound 1 of the present invention), and the specific process is as follows:
  • Comparative literature uses a four-step reaction to synthesize compound 110 (that is, compound 1 synthesized in Example 1 of the present invention), the number of steps is longer, and the overall synthesis process takes longer.
  • the compound 1 synthesis method provided by the method of the present invention is a two-step synthesis, which greatly simplifies the route, improves the total yield, reduces the preparation time, and is very suitable for industrial production.
  • N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine in the last step of the comparison literature is used directly, but those skilled in the art know N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine itself requires the use of 2-amino-9,9-dimethylfluorene and 4-bromobiphenyl or 2-bromo-9,9-dimethylfluorene and 4-aminobiphenyl are reacted to prepare. Therefore, in general, the prior art requires two steps to prepare tertiary amine compounds from primary amine compounds.
  • the comparative literature uses a three-step reaction to synthesize intermediate 1-(4"-chloro-[1,1':4',1"-terphenyl]-4-yl)adamantane, with a total yield of 61.2% in the three steps.
  • the method of the present invention is synthesized in one step with a yield of 68%. Obviously better than the comparative literature.
  • the comparative literature adopts a one-step reaction to synthesize compound 40 (that is, compound 13 synthesized in Example 13 of the present invention), it actually requires two-step synthesis because 9,9-dimethyl-N-(4-phenylnaphthalene-1-yl) )-9H-fluoren-2-amine needs to be synthesized by a primary amine compound.
  • the single-step yield is as high as 77%, the overall yield of the total synthesis process is low (estimated to be about 60%), which indirectly causes high costs and is not conducive to mass production.
  • the synthesis method of compound 13 (ie compound 40 provided in the reference document) in the present invention is a one-step synthesis. From the perspective of the total synthesis process, the number of steps is reduced by one step, the total yield is higher, and the preparation time is reduced, which is very suitable For industrial production.
  • Table 1 shows the comparison of the final target product yields of the same compounds in the examples of the present invention and the comparative documents.
  • the yield of the one-pot reaction is very low; while the complete sub-step reaction has reduced impurities, but due to the separation and purification operation of the intermediate process, some products are lost, resulting in the final product
  • the yield is not high.
  • the method of the invention can not only avoid the problem of a large amount of impurities caused by a one-pot reaction, but also avoid the loss of the intermediate process, so that the yield of the final product is obviously improved.

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Abstract

L'invention concerne un procédé de préparation d'un dérivé de triphénylamine contenant de l'adamantyle, le procédé comprenant d'abord la réaction d'un adamantane aryle ou d'un ester d'adamantane aryle halogéné avec une amine aromatique primaire sans séparation ou purification après une réaction, et l'ajout direct d'un hydrocarbure aromatique halogéné pour la réaction. Le procédé présente non seulement moins d'étapes de réaction et peut assurer une séparation et une purification finales, mais peut également réduire la teneur en impuretés, augmente davantage le rendement du produit, et prépare le produit cible avec un rendement plus élevé. En outre, les étapes selon la présente invention sont simples, les matières premières utilisées sont des matières premières chimiques basiques, le rendement est élevé, et le produit final préparé présente une pureté élevée. Le procédé est supérieur à l'état de la technique en termes de coût de matières premières, de l'exploitabilité réelle et des heures de travail requises pour l'opération , et est très approprié pour une production industrielle.
PCT/CN2020/087870 2019-06-24 2020-04-29 Procédé de préparation d'un dérivé de triphénylamine contenant de l'adamantyle WO2020259078A1 (fr)

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