CN108409585A - A kind of tri-arylamine group compound and preparation method thereof with dihydroxy active site - Google Patents
A kind of tri-arylamine group compound and preparation method thereof with dihydroxy active site Download PDFInfo
- Publication number
- CN108409585A CN108409585A CN201810233572.2A CN201810233572A CN108409585A CN 108409585 A CN108409585 A CN 108409585A CN 201810233572 A CN201810233572 A CN 201810233572A CN 108409585 A CN108409585 A CN 108409585A
- Authority
- CN
- China
- Prior art keywords
- compound
- formula
- preparation
- indicates
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/68—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members 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 ring carbon atoms
- C07D309/10—Oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This application involves a kind of preparation method of the tri-arylamine group compound with dihydroxy active site, this method includes esterification, reduction reaction, hydroxyl protection, halogen amino coupling reaction, the acquisition of hydroxyl deprotection steps.The preparation method of the application is by using the raw material being relatively easily available as reactant, and using relatively mild reaction condition, and reaction route is simple.
Description
Technical field
This application involves technical field of organic synthesis.It particularly relates to a kind of three virtues with dihydroxy active site
Aminated compounds and preparation method thereof.
Background technology
Tri-arylamine group compound is a kind of extraordinary organic hole transport material, is widely used in organic photoconductor, has
Field effect transistors, Organic Light Emitting Diode, dye-sensitized solar cells, on organic polymer solar cell.It is organic
Hole mobile material is one of important materials of organic electroluminescence device, with the fast development of organic electroluminescent technology,
The edge of industrialization is had been approached, market prospects are very good.
Currently, the relevant report of preparation method about the tri-arylamine group compound with dihydroxy active site is seldom.
Japanese Patent Laid-Open JP2010085832 discloses a kind of electronics according to the manufacturing method of photoreceptor coating, and one kind is described
The preparation method of the similar tri-arylamine group compound with dihydroxy active site, specifically, amino-compound and acetyl group
The iodide of protection pass through coupling reaction, then are deprotected deacetylate by hydroxyl and obtain having the three of dihydroxy active site
Aromatic amine compounds, still, in the preparation method, raw material is not easy to start with, and the reaction temperature of two steps is all higher, needs more severe
The reaction condition at quarter.
For this purpose, there is an urgent need in the art to a kind of preparation sides of the new tri-arylamine group compound with dihydroxy active site
Method solves the above problems.
Invention content
The application's is designed to provide a kind of preparation of the new tri-arylamine group compound with dihydroxy active site
Method, come solve it is above-mentioned in the prior art the technical issues of.Specifically, the application is as starting material, to pass through bromo-hydrocinnamic acid
Over-churning, reduction, hydroxyl protection, halogen-amino coupled, hydroxyl are deprotected five steps and one kind are obtained by the reaction with dihydroxy active sites
The tri-arylamine group compound of point.
The purpose of the application also reside in provide it is a kind of by method as described above prepare have dihydroxy active site
Tri-arylamine group compound.
To achieve the goals above, the application provides following technical proposals.
In the first aspect, the application provides a kind of preparation method of the acetyl derivatives of styrene, including：
A kind of preparation method of the tri-arylamine group compound with dihydroxy active site, which is characterized in that by following
It is prepared by method：
S1：In the presence of the first catalyst, to the carboxyl progress esterification for the compound that formula 1 indicates, obtain
The compound that formula 2 indicates；
S2：Reduction reaction is carried out to the ester group of the compound of the expression of formula 2 and obtains the compound that formula 3 indicates；
S3：Hydroxyl protection is carried out to the hydroxyl of the compound of the expression of formula 3 and obtains the compound that formula 4 indicates；
S4：Halogen amino coupling reaction is carried out to the compound that formula 4 indicates and obtains the compound that formula 5 indicates；
S5：In the presence of the second catalyst, 6 table of hydroxyl deprotection acquisition formula is carried out to the compound that formula 5 indicates
The compound shown；
X-Ar-ROOH formulas 1
X-Ar- ROO- formulas 2
X-Ar-ROH formulas 3
In formula, X is halogen atom, and R is the alkylidene of C1~10, and Ar is aryl, and the X and R are that the X and Ar are adjacent
Position, contraposition or meta position.
In some embodiments, the halogen atom is chlorine, bromine or iodine, and the alkylidene is methylene, ethylidene, Asia
Propyl, butylidene, pentylidene, hexylidene, heptamethylene, octamethylene, nonylene or decylene, the aryl be phenyl, naphthalene or
Anthryl, the X and Ar are ortho position or contraposition.
In some embodiments, the halogen atom be chlorine or bromine, the alkylidene be ethylidene or propylidene, it is described
Aryl is phenyl, and the X and Ar are ortho position or contraposition.
In some embodiments, the halogen atom be chlorine or bromine, the alkylidene be ethylidene or propylidene, it is described
Aryl is phenyl, and the X and Ar are contrapositions.
In some embodiments, in the step S1, using thionyl chloride as the first catalyst.
In some embodiments, in the step S2, using sodium borohydride and/or alchlor as reducing agent.
In some embodiments, in the step S3, the compound that 3,4-2H- dihydropyran indicates formula 3 is added
Carry out hydroxyl protection.
In some embodiments, in the step S4, nitrogen displacement is carried out to reaction system.
In some embodiments, in the step S5, using p-methyl benzenesulfonic acid as the second catalyst, at normal temperatures
It is reacted.
In second aspect, the application is provided according to three virtues with dihydroxy active site made from the preparation method
Aminated compounds.
That is, the application using to bromo-hydrocinnamic acid as starting material, through over-churning, reduction, hydroxyl protection, halogen amino
Coupling, hydroxyl are deprotected five step reactions and obtain a kind of tri-arylamine group compound with dihydroxy active site.
Compared with prior art, the advantageous effect of the application is that the preparation method of the application is obtained by using relatively easy
The raw material arrived is as reactant, and using relatively mild reaction condition, and reaction route is simple, can be synthesis tri-arylamine group
Organic hole transport material intermediate provides the synthetic route for reference.
Description of the drawings
Fig. 1 shows the final products DP1's of the embodiment of the present invention 11H-NMR collection of illustrative plates.
Specific implementation mode
Unless otherwise indicated, from context cues or belong to the convention of the prior art, otherwise number all in the application
It is all based on weight with percentage, and test and characterizing method used is all synchronous with the submission date of the application.It is being applicable in
In the case of, any patent, patent application or disclosure involved in the application are fully incorporated in this as reference, and its
Patent families of equal value are also introduced into as reference, disclosed by these special documents about the synthetic technology in this field, product
With the definition of fabrication design, polymer, comonomer, initiator or catalyst etc..If the specific art disclosed in the prior art
Defining for language is inconsistent with any definition provided herein, then term provided herein of being subject to defines.
Digital scope in the application is approximation, therefore unless otherwise stated, it may include the number other than range
Value.Numberical range include with the increased all numerical value from lower limiting value to upper limit value of 1 unit, condition be any lower value with
There are the intervals of at least two unit between arbitrary high value.For example, if compositional, physics or other property (such as molecules
Amount, melt index (MI) etc.) it is 100 to 1000, it is meant that clearly list all single numbers, such as 100,101,102 etc., with
And all subranges, such as 100 to 166,155 to 170,198 to 200 etc..For comprising less than 1 numerical value or comprising big
In the range of 1 score (such as 1.1,1.5 etc.), then suitably regard 1 unit as 0.0001,0.001,0.01 or 0.1.
For including the range of the units less than 10 (such as 1 to 5), usually regarding 1 unit as 0.1., these are only intended to table
The specific example of the content reached, and all possible combination of the numerical value between cited minimum and peak is all recognized
In this application for clear record.
About chemical compound in use, unless explicitly stated otherwise, otherwise odd number includes all isomeric forms, otherwise also
So (for example, " hexane " either individually or collectively includes whole isomers of hexane).In addition, unless explicitly stated otherwise, otherwise using
"one", the noun that "an" or "the" are described also includes its plural form.
Term "comprising", " comprising ", " having " and their derivative are not excluded for any other component, step or mistake
The presence of journey, and whether disclose in this application with these other components, step or process unrelated.To eliminate any query,
Unless expressly stated, otherwise all in the application to use term "comprising", " comprising ", or the composition of " having " can include to appoint
What additional additive, auxiliary material or compound.On the contrary, in addition to necessary to operating characteristics those, term " substantially by ...
Composition " excludes any other component, step or process except the hereinafter described range of any term.Term " by ...
Composition " does not include any component, step or the process for not specifically describing or listing.Unless expressly stated, otherwise term "or" refers to
The separate member listed or any combination thereof.
Term defines
As used herein, term " alkylidene " refers to from shape after the hydrogen atom or group that alkane structure eliminates two monovalencies
At substituent group.
As used herein, the carbon atom number that term " alkylidenes of C1~10 " refers to alkylidene is 1~10, and alkylidene
Carbon atom arrangement can be linear structure or branched structure.
As used herein, term " aryl " refers to any functional group derived from simple aromatic rings or substituent group.
As used herein, term " yield " refers to the product amount obtained in chemical reaction.Yield is typically expressed as reacting
The percentage of theoretical yield.
It is carried out as follows in the preparation method of the tri-arylamine group compound with dihydroxy active site of the application：
In step sl：After the compound and methanol that formula 1 indicates are added in reaction bulb, stirring is warming up to 45~55 DEG C,
Thionyl chloride is slowly added dropwise, is heated to reflux 1.5~2.5 hours, reaction terminates, and stops reaction.With methanol has been steamed, obtain thick
Product.80~90 DEG C of fractions are being collected in oil pump vacuum distillation, obtain the compound that formula 2 indicates.
In step s 2：The compound that formula 2 indicates is added in reaction bulb, glycol dimethyl ether, sodium borohydride stir, often
Alchlor is added portionwise in temperature, adds within 1.5~2.5 hours, system automatic heating, finally keeps the temperature 45~55 DEG C 1.5~2.5 small
When, sample point plate analysis, reaction terminates, and stops reaction.It pours into ice water and hydrolyzes, PH=2 or so is adjusted to sulfuric acid, with acetic acid second
Ester extracts, and 10% sodium bicarbonate is washed till neutrality, and liquid separation obtains the compound that formula 3 indicates with solvent has been steamed.
In step s3：Compound, the dichloromethane of the expression of the formula 3 are added in reaction bulb, adds to entering to first under room temperature
Benzene sulfonic acid, stirring are added dropwise 3,4-2H- dihydropyran, add within 0.5~1.5 hour, and system temperature can be increased slightly, and heat preservation 25~
35 minutes, it is down to room temperature, is stirred 9~11 hours, sampling analysis, raw material after reaction, is washed once, water with 10% sodium bicarbonate
Layer is extracted with dichloromethane, is merged organic phase, has been rotated solvent, and the compound of the expression of crude product formula 4 is obtained.Crude product is not necessarily to purity, can
It is directly used in next step.
In step s 4：Compound, aniline, toluene, the palladium of the expression of the formula 4, stirring, nitrogen are added in reaction bulb
Tri-tert phosphorus is added in displacement 3 times, stirs 0.25~0.75 hour, and potassium tert-butoxide is added, and nitrogen is replaced 3 times, is heated to back
Stream, is stirred overnight (about 15 hours), and sampling analysis, reaction terminates, and stops reaction.After washing is added, aqueous layer with ethyl acetate carries
It taking primary, merges organic layer, silica gel is crossed after organic layer concentration is dry, solvent washing is concentrated and dried, and crosses silicagel column, with solvent washing,
It is spin-dried for solvent, obtains the compound of the expression of formula 5.
In step s 5：Be added in reaction bulb the formula 5 expression compound, methanol, p-methyl benzenesulfonic acid, stirring at normal temperature
Overnight, sampling analysis, reaction terminates, and stops reaction.After being washed with 10% sodium bicarbonate, ethyl acetate extracts 2~3 times, is spin-dried for
Solvent crosses silicagel column and is spin-dried for solvent with solvent washing, obtains the compound of the expression of final products formula 6.
In the above-described embodiment, in step sl, thionyl chloride is added dropwise has very exothermic, need to be slowly added dropwise.In step
In S2, alchlor is added to have very exothermic, needs to be added portionwise.In step s3,3,4-2H- dihydropyran is added dropwise has in the process
A small amount of heat release, temperature can be increased slightly, after continuing for some time, be down to room temperature naturally.The product cannot distill, and otherwise can occur
It is decomposed into raw material, it may be possible to which the acid in system, which does not eliminate, to be caused.In step s 4, in order to avoid air and moisture, nitrogen is used
Air displacement is clean.The salt in system is washed off before crossing silica gel, silica gel of being otherwise sorry.
Embodiment
Below in conjunction with embodiments herein, clear and complete description is carried out to the technical solution of the application.Such as nothing
It illustrates, reagent used and raw material can all be bought by commercial sources.
Embodiment 1
The first step：It is added in 5L reaction bulbs to bromo-hydrocinnamic acid 500g, methanol 2000g, stirring is warming up to 50 DEG C, slowly
Thionyl chloride 7g is added dropwise, is added dropwise 10 minutes or so, is heated to reflux 2 hours, reaction terminates, and stops reaction.With having steamed methanol,
Obtain 530 grams of crude product.80~90 DEG C of fractions are being collected in oil pump vacuum distillation, obtain intermediate M1 (507g, molar yield
95.5%, HPLC purity 98.5%).
Second step：M1 300g, glycol dimethyl ether 2000g, sodium borohydride 70g are added in 5L reaction bulbs, stirs, often
Alchlor 82g is added portionwise in temperature, adds within 2 hours, system automatic heating, finally keeps the temperature 50 DEG C 2 hours, sample point plate analysis,
Reaction terminates, and stops reaction.It pours into ice water and hydrolyzes, be adjusted to PH=2 or so with sulfuric acid, be extracted with ethyl acetate, 10% carbonic acid
Hydrogen sodium is washed till neutrality, and liquid separation obtains intermediate M2 (319g, molar yield 90%, HPLC purity with solvent has been steamed
98.6%).
Third walks：It is added the M2 128g in 5L reaction bulbs, dichloromethane 2000g, under room temperature plus to entering to toluene sulphur
Sour 2g, stirring are added dropwise 3,4-2H- dihydropyran 60g, add within 1 hour, and system temperature can be increased slightly, keep the temperature 30 minutes, are down to
Room temperature stirs 10 hours, and sampling analysis, raw material after reaction, is washed once, water layer dichloro with 10% sodium bicarbonate 500ml
Methane extracts, and merges organic phase, has rotated solvent, obtained crude product M3 (180g, HPLC purity 87%).Crude product, can be straight without purification
It connects in next step.
4th step：The M3 209g, aniline 29.6g, toluene 1350g are added in 5L reaction bulbs, palladium 2.2g is stirred
It mixes, nitrogen is replaced 3 times, and tri-tert phosphorus 6.17g is added, and is stirred 0.5 hour, and potassium tert-butoxide 107g is added, and nitrogen is replaced 3 times,
It is heated to flowing back, is stirred overnight (about 15 hours), sampling analysis, reaction terminates, and stops reaction.After 1000g washings are added, water layer
It is primary with ethyl acetate 200g extractions, merge organic layer, silica gel, solvent (ethyl acetate are crossed after organic layer concentration is dry：N-hexane v/
V=1:1) it rinses, is concentrated and dried, silicagel column is crossed, with solvent (ethyl acetate：N-hexane v/v=10:1) it rinses, is spin-dried for solvent,
Obtain intermediate M4 (109g, HPLC purity 73%).
5th step：The M4 145g, methanol 700g, p-methyl benzenesulfonic acid 2.5g, stirring at normal temperature mistake are added in 2L reaction bulbs
At night, (0.5%) middle control 1, raw material are less than sampling analysis, reaction terminates, and stop reaction.After being washed with 10% sodium bicarbonate, acetic acid
Ethyl ester extracts 2 times, is spin-dried for solvent, silicagel column is crossed, with solvent (n-hexane：Ethyl acetate v/v=3:2) it rinses, is spin-dried for solvent, obtains
Final products DP1 (1H-NMR collection of illustrative plates is as shown in Figure 1), (55g, HPLC purity 97.3%).
Above-mentioned reaction process is as follows
It is shown：
Embodiment 2
The first step：It is added in 5L reaction bulbs to bromo-acid 450g, methanol 1800g, stirring is warming up to 50 DEG C, slowly
Thionyl chloride 7g is added dropwise, is added dropwise 10 minutes or so, is heated to reflux 2 hours, reaction terminates, and stops reaction.With having steamed methanol,
Obtain 500 grams of crude product.80~90 DEG C of fractions are being collected in oil pump vacuum distillation, obtain intermediate N1 (489g, molar yield
95.0%, HPLC purity 98.0%).
Second step：N1 290g, glycol dimethyl ether 1900g, sodium borohydride 68g are added in 5L reaction bulbs, stirs, often
Alchlor 80g is added portionwise in temperature, adds within 2 hours, system automatic heating, finally keeps the temperature 50 DEG C 2 hours, sample point plate analysis,
Reaction terminates, and stops reaction.It pours into ice water and hydrolyzes, be adjusted to PH=2 or so with sulfuric acid, be extracted with ethyl acetate, 10% carbonic acid
Hydrogen sodium is washed till neutrality, and liquid separation obtains intermediate N2 (308g, molar yield 91%, HPLC purity with solvent has been steamed
98.0%).
Third walks：It is added the N2 120g in 5L reaction bulbs, dichloromethane 1920g, under room temperature plus to entering to toluene sulphur
Sour 2g, stirring are added dropwise 3,4-2H- dihydropyran 58g, add within 1 hour, and system temperature can be increased slightly, keep the temperature 30 minutes, are down to
Room temperature stirs 10 hours, and sampling analysis, raw material after reaction, is washed once, water layer dichloro with 10% sodium bicarbonate 500ml
Methane extracts, and merges organic phase, has rotated solvent, obtained crude product N3 (170g, HPLC purity 88%).Crude product, can be straight without purification
It connects in next step.
4th step：The N3 170g, aniline 27.2g, toluene 1280g are added in 5L reaction bulbs, palladium 2.2g is stirred
It mixes, nitrogen is replaced 3 times, and tri-tert phosphorus 6.17g is added, and is stirred 0.5 hour, and potassium tert-butoxide 102g is added, and nitrogen is replaced 3 times,
It is heated to flowing back, is stirred overnight (about 15 hours), sampling analysis, reaction terminates, and stops reaction.After 1000g washings are added, water layer
It is primary with ethyl acetate 200g extractions, merge organic layer, silica gel, solvent (ethyl acetate are crossed after organic layer concentration is dry：N-hexane v/
V=1:1) it rinses, is concentrated and dried, silicagel column is crossed, with solvent (ethyl acetate：N-hexane v/v=10:1) it rinses, is spin-dried for solvent,
Obtain intermediate N4 (89g, HPLC purity 76%).
5th step：The M4 120g, methanol 650g, p-methyl benzenesulfonic acid 2.5g, stirring at normal temperature mistake are added in 2L reaction bulbs
At night, (0.5%) middle control 1, raw material are less than sampling analysis, reaction terminates, and stop reaction.After being washed with 10% sodium bicarbonate, acetic acid
Ethyl ester extracts 2 times, is spin-dried for solvent, silicagel column is crossed, with solvent (n-hexane：Ethyl acetate v/v=3:2) it rinses, is spin-dried for solvent, obtains
Final products DP2 (50g, HPLC purity 98.1%).
Embodiment 3
The first step：It is added in 5L reaction bulbs to bromo-hydrocinnamic acid 550g, methanol 2200g, stirring is warming up to 50 DEG C, slowly
Thionyl chloride 7g is added dropwise, is added dropwise 10 minutes or so, is heated to reflux 2 hours, reaction terminates, and stops reaction.With having steamed methanol,
Obtain 540 grams of crude product.80~90 DEG C of fractions are being collected in oil pump vacuum distillation, obtain intermediate P1 (518g, molar yield
96.0%, HPLC purity 97.9%).
Second step：M1 310g, glycol dimethyl ether 2100g, sodium borohydride 72g are added in 5L reaction bulbs, stirs, often
Alchlor 84g is added portionwise in temperature, adds within 2 hours, system automatic heating, finally keeps the temperature 50 DEG C 2 hours, sample point plate analysis,
Reaction terminates, and stops reaction.It pours into ice water and hydrolyzes, be adjusted to PH=2 or so with sulfuric acid, be extracted with ethyl acetate, 10% carbonic acid
Hydrogen sodium is washed till neutrality, and liquid separation obtains intermediate P2 (324g, molar yield 91%, HPLC purity with solvent has been steamed
98.2%).
Third walks：It is added the M2 130g in 5L reaction bulbs, dichloromethane 2000g, under room temperature plus to entering to toluene sulphur
Sour 2g, stirring are added dropwise 3,4-2H- dihydropyran 60g, add within 1 hour, and system temperature can be increased slightly, keep the temperature 30 minutes, are down to
Room temperature stirs 10 hours, and sampling analysis, raw material after reaction, is washed once, water layer dichloro with 10% sodium bicarbonate 500ml
Methane extracts, and merges organic phase, has rotated solvent, obtained crude product P3 (181g, HPLC purity 86%).Crude product, can be straight without purification
It connects in next step.
4th step：The M3 210g, amino naphthalenes 30.0g, toluene 1360g, palladium 2.2g are added in 5L reaction bulbs,
Stirring, nitrogen are replaced 3 times, and tri-tert phosphorus 6.18g is added, and are stirred 0.5 hour, and potassium tert-butoxide 108g, nitrogen displacement 3 is added
It is secondary, it is heated to flowing back, is stirred overnight (about 15 hours), sampling analysis, reaction terminates, and stops reaction.After 1000g washings are added,
Aqueous layer with ethyl acetate 200g extractions are primary, merge organic layer, silica gel, solvent (ethyl acetate are crossed after organic layer concentration is dry：Just oneself
Alkane v/v=1:1) it rinses, is concentrated and dried, silicagel column is crossed, with solvent (ethyl acetate：N-hexane v/v=10:1) it rinses, is spin-dried for molten
Agent obtains intermediate P4 (110g, HPLC purity 74%).
5th step：The M4 148g, methanol 708g, p-methyl benzenesulfonic acid 2.6g, stirring at normal temperature mistake are added in 2L reaction bulbs
At night, (0.5%) middle control 1, raw material are less than sampling analysis, reaction terminates, and stop reaction.After being washed with 10% sodium bicarbonate, acetic acid
Ethyl ester extracts 2 times, is spin-dried for solvent, silicagel column is crossed, with solvent (n-hexane：Ethyl acetate v/v=3:2) it rinses, is spin-dried for solvent, obtains
Final products DP (55.8g, HPLC purity 97.1%).
The above-mentioned description to embodiment is that this Shen can be understood and applied for the ease of those skilled in the art
Please.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiments without paying performing creative labour.Therefore, the application is not limited to implementation here
Example, those skilled in the art make according to herein disclosed content in the case where not departing from the application scope and spirit
It improves and changes within all scope of the present application.
Claims (10)
1. a kind of preparation method of the tri-arylamine group compound with dihydroxy active site, which is characterized in that pass through following sides
It is prepared by method：
S1：In the presence of the first catalyst, to carboxyl progress esterification acquisition 2 table of formula for the compound that formula 1 indicates
The compound shown；
S2：Reduction reaction is carried out to the ester group of the compound of the expression of formula 2 and obtains the compound that formula 3 indicates；
S3：Hydroxyl protection is carried out to the hydroxyl of the compound of the expression of formula 3 and obtains the compound that formula 4 indicates；
S4：Halogen amino coupling reaction is carried out to the compound that formula 4 indicates and obtains the compound that formula 5 indicates；
S5：In the presence of the second catalyst, what hydroxyl deprotection acquisition formula 6 indicated is carried out to the compound that formula 5 indicates
Compound；
X-Ar-ROOH formulas 1
X-Ar-ROH- formulas 2
X-Ar-ROH formulas 3
In formula, X is halogen atom, and R is the alkylidene of C1~10, and Ar is aryl, and the X and R are ortho position, contraposition or meta position.
2. preparation method as described in claim 1, which is characterized in that the halogen atom is chlorine, bromine or iodine, the alkylidene
It is described for methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, heptamethylene, octamethylene, nonylene or decylene
Aryl is phenyl, naphthalene or anthryl, and the X and Ar are ortho position or contraposition.
3. preparation method as described in claim 1, which is characterized in that the halogen atom is chlorine or bromine, and the alkylidene is
Ethylidene or propylidene, the aryl are phenyl, and the X and Ar are ortho position or contraposition.
4. preparation method as described in claim 1, which is characterized in that the halogen atom is chlorine or bromine, and the alkylidene is
Ethylidene or propylidene, the aryl are phenyl, and the X and Ar are contrapositions.
5. preparation method as described in any one of claims 1 to 4, it is characterised in that:In the step S1, using chlorination
Sulfoxide is as the first catalyst.
6. preparation method as described in any one of claims 1 to 4, it is characterised in that：In the step S2, boron hydrogen is used
Change sodium and/or alchlor as reducing agent.
7. preparation method as described in any one of claims 1 to 4, it is characterised in that：In the step S3,3,4- are added
2H- dihydropyran carries out hydroxyl protection to the compound that formula 3 indicates.
8. preparation method as described in any one of claims 1 to 4, it is characterised in that：In the step S4, to reactant
System carries out nitrogen displacement.
9. preparation method as described in any one of claims 1 to 4, it is characterised in that：In the step S5, using to first
Benzene sulfonic acid is reacted at normal temperatures as the second catalyst.
10. three virtues with dihydroxy active site made from the preparation method according to any one of claim 1~9
Aminated compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810233572.2A CN108409585A (en) | 2018-03-21 | 2018-03-21 | A kind of tri-arylamine group compound and preparation method thereof with dihydroxy active site |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810233572.2A CN108409585A (en) | 2018-03-21 | 2018-03-21 | A kind of tri-arylamine group compound and preparation method thereof with dihydroxy active site |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108409585A true CN108409585A (en) | 2018-08-17 |
Family
ID=63133022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810233572.2A Pending CN108409585A (en) | 2018-03-21 | 2018-03-21 | A kind of tri-arylamine group compound and preparation method thereof with dihydroxy active site |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108409585A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1734356A (en) * | 2004-08-04 | 2006-02-15 | 施乐公司 | Polycarbonates and photoconductive imaging members |
| CN102712613A (en) * | 2010-06-14 | 2012-10-03 | 株式会社理光 | New tetrahydropyranyl compound and method for producing the tetrahydropyranyl compound |
| CN103329046A (en) * | 2011-01-21 | 2013-09-25 | 株式会社理光 | Electrophotographic photoconductor, image forming method, image forming apparatus, and process cartridge |
| JP2016184004A (en) * | 2015-03-25 | 2016-10-20 | 富士ゼロックス株式会社 | Electrophotographic photoreceptor, process cartridge, and image forming apparatus |
| US20180009733A1 (en) * | 2016-07-06 | 2018-01-11 | Lexmark International, Inc. | Two step method of producing triarlyamine compounds having two alkyl alcohols in a single reaction vessel |
-
2018
- 2018-03-21 CN CN201810233572.2A patent/CN108409585A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1734356A (en) * | 2004-08-04 | 2006-02-15 | 施乐公司 | Polycarbonates and photoconductive imaging members |
| CN102712613A (en) * | 2010-06-14 | 2012-10-03 | 株式会社理光 | New tetrahydropyranyl compound and method for producing the tetrahydropyranyl compound |
| CN103329046A (en) * | 2011-01-21 | 2013-09-25 | 株式会社理光 | Electrophotographic photoconductor, image forming method, image forming apparatus, and process cartridge |
| JP2016184004A (en) * | 2015-03-25 | 2016-10-20 | 富士ゼロックス株式会社 | Electrophotographic photoreceptor, process cartridge, and image forming apparatus |
| US20180009733A1 (en) * | 2016-07-06 | 2018-01-11 | Lexmark International, Inc. | Two step method of producing triarlyamine compounds having two alkyl alcohols in a single reaction vessel |
Non-Patent Citations (2)
| Title |
|---|
| JIANBING JIANG等: "One-Step Trimethylstannylation of Benzyl and Alkyl Halides", 《J.ORG.CHEM.》 * |
| JIN XIE等: "Antiproliferative activity and SARs of caffeic acid esters with mono-substituted phenylethanols moiety", 《BIOORGANIC & MEDICINAL CHEMISTRY LETTERS》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112679420B (en) | Preparation method of 2,5-dibromopyridine | |
| CN104744303B (en) | Bromomethylbiphenyls of 2 R 4 ' and preparation method thereof | |
| CN113651784B (en) | Synthesis method of 3,3', 4' -biphenyl tetracarboxylic dianhydride | |
| CN108409585A (en) | A kind of tri-arylamine group compound and preparation method thereof with dihydroxy active site | |
| CN108191858B (en) | A kind of intermediate preparing pyrroloquinoline quinone and preparation method | |
| US4758380A (en) | Substituted 1,1,1-triaryl-2,2,2-trifluoroethanes and processes for their synthesis | |
| JPH09502164A (en) | Synthesis of substituted triphenylene useful as discotic liquid crystals | |
| CN107501077A (en) | A kind of preparation method of 2 (4 bromomethyl) phenylpropionic acids | |
| CN100545136C (en) | A kind of preparation method of pentabromobenzyl bromine | |
| US4327036A (en) | Chlorination process | |
| JP2021195344A (en) | Method for producing 5-bromo-2-halogenated benzoic acid | |
| CN105968013B (en) | A kind of π-copolymer and preparation method thereof | |
| CN105503884B (en) | A kind of synthetic method for being used to synthesize the key intermediate of BET protein inhibitors | |
| CN115124410B (en) | Preparation method of 2-fluoro-4-hydroxybenzaldehyde | |
| CN108503553A (en) | A kind of tri-arylamine group compound and preparation method thereof with tetrahydroxy active site | |
| CN102101827B (en) | Method for preparing Prasugrel intermediate alpha-cyclopropyl carbonyl-2-fluorobenzyl halide | |
| JP2004203770A (en) | Aromatic carboxylic acid derivative and acid chloride derivative thereof | |
| CN112851468A (en) | Preparation method of 3, 5-dimethoxy-4-methylbenzoic acid | |
| CN102558196A (en) | Method for preparing (3,4)-1,4-dioxoethylidene thiophene-2'-methanol | |
| CN111349052B (en) | Synthesis method of mosapride citrate | |
| KR100807454B1 (en) | Aromatic carboxylic acids, acid halides thereof and processes for preparing both | |
| US5861540A (en) | Substituted 1,1,1-triaryl-2,2,2-trifuoroethanes and processes for their synthesis | |
| CN117843580A (en) | Preparation method of apixitan and intermediate | |
| JPS6041059B2 (en) | Novel phenylpropionate derivative | |
| US5011955A (en) | Substituted 1,1,1-triaryl-2,2,2-trifluoroethanes and processes for their synthesis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20181109 Address after: 221003 chemical agglomeration area of Pizhou Economic Development Zone, Xuzhou, Jiangsu Applicant after: B&C (Xuzhou) Chemical Co., Ltd. Address before: 201614 3M, 9 building, 1158 Central Road, Songjiang District, Shanghai. Applicant before: Shanghai Bo Chemical Technology Co., Ltd. |
|
| TA01 | Transfer of patent application right | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180817 |
|
| RJ01 | Rejection of invention patent application after publication |