CN107382756A - Quaternary carboxylic acid N, N, N ', the synthetic method of N ' four (4 carboxy vinyl phenyl) 1,4 phenylenediamines - Google Patents
Quaternary carboxylic acid N, N, N ', the synthetic method of N ' four (4 carboxy vinyl phenyl) 1,4 phenylenediamines Download PDFInfo
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- CN107382756A CN107382756A CN201710689928.9A CN201710689928A CN107382756A CN 107382756 A CN107382756 A CN 107382756A CN 201710689928 A CN201710689928 A CN 201710689928A CN 107382756 A CN107382756 A CN 107382756A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
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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
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/10—Formation of amino groups in compounds containing carboxyl groups with simultaneously increasing the number of carbon atoms in the carbon skeleton
Abstract
The quaternary carboxylic acid of the present inventionN,N,N′,NThe synthetic method of ' tetra- (4 carboxy vinyl phenyl) Isosorbide-5-Nitrae phenylenediamines, Isosorbide-5-Nitrae dibromobenzene reacts with diphenylamines through aryl amination to be generatedN,N,N′,N' tetraphenyl Isosorbide-5-Nitrae phenylenediamine (A), A and NBS reactions generateN,N,N′,N' tetra- (4 bromophenyl) 1,4 phenylenediamines (B).Compound B adds catalyst reaction generation with methyl acrylate under the conditions of inert gas shieldingN,N,N′,N' tetra- (4 methoxycarbonylvinyl phenyl) 1,4 phenylenediamines (C).Compound C generates target compound D through hydrolysis：N,N,N′,N' tetra- (4 carboxy vinyl phenyl) 1,4 phenylenediamines.Present invention synthesis one there is no literature reported on more phenyl ring fragrant four carboxylic acid compounds, have synthetic method simple, synthesis cost is low, the advantages of yield is high, product purity is high.Target compound D such as following formulas.
Description
Technical field
The present invention relates to quaternary carboxylic acidN,N,N′,NThe synthesis side of '-four (4- carboxy vinyls phenyl) -1,4- phenylenediamines
Method.
Background technology
The rigid aromatic carboxylic acids class part of extension is widely used in the structure of MOFs materials, and this kind of material generally has good
Good pore passage structure, big specific surface area, make this kind of material energy gas storage with separating, being catalyzed, chemical sensitisation and medicine
The different fields such as sustained release have potential application.For example, MOFs can under specific temperature and pressure absorbing carbon dioxide, and
The temperature of desorption only needs higher than adsorption temp 50 DEG C.The result of spectrum analysis, diffraction analysis and theoretical calculation shows
Show, the MOFs is to CO2Strong absorption be a kind of unprecedented collaborative processes.If the MOFs of size as sugar is shakeout, it
Area can have football pitch so big.Because it has very big specific surface area and high porosity, also just have very strong
CO2Storage capacity.Such as Long seminars (Angew. Chem. Int. Ed., 2009,48 (1) in 2009: 128-132)
In the solvent of DMF and alcohol, 6 MOFs materials M using solvent structure2(dobpdc)（dobpdc4-= 4,4’-
Dioxidobiphenyl-3,3 '-dicarboxylate, M=Mg, Mn, Fe, Co, Ni, Zn）, higher than dependent on metal
Threshold pressure under, CO2Molecule is inserted into metal-amine key, and induction amino recombinates the aminoquinoxaline point to form ordered arrangement
Subchain；It is clear that a large amount of CO are separated under small range of temperature2Ability be accomplished, if it is possible to complete, will very
Existing CO is reduced in big degree2Capture and the difficulty of Plugging Technology Applied.
2016, Qu seminars (Chirality. 2016,28 (4):340-346) useN, N’,N”- three (4- carboxylics
Base phenyl) amine is part, it is a kind of relatively stable in aqueous that La (III) is that metal ion has been built under conditions of solvent heat
Fluorescence coordination polymer { [La (HNTB)2(HPY)](H2O)6}n (1, H3NTB = N,N’,N”- three (4- carboxyl phenyls) amine,
PY=pyridine).One side La3+Metal cluster combined with Carboxylic acid ligand and improve the stability of coordination polymer in aqueous,
The H of another aspect functionalization3NTB parts produce stronger transmitting light under ultraviolet light, can be using it as spy based on this 2 points
Survey Fe3+In the presence of and monitoring nitro benzene vapour foundation.Wherein being quenched for fluorescence shows to Fe in aqueous3+Selected with height
The selectivity selected, while it also can a large amount of nitro benzene vapours of quick response.In order to probe into this fluorescence probe under various concentrations
Aqueous solution Fe3+Sensitiveness intensity, choose 0 μM ~ 1000 μM Fe3+Solution is tested, and at 0 μM, fluorescence is most strong, and
The fluorescent quenching at 1000 μM.Presence for detecting nitro benzene vapour, employs membrane equipment and is placed on homemade device
In complete nitro benzene vapour it is solid in real time-gas monitoring.The rigid corner Carboxylic acid ligand of extension usually leads to structure novelty, ratio
The big more micropore MOFs materials of surface area, and microcellular structure can be changed, make electronic environment in its micropore obtain optimizing so as to improve
Above-mentioned application performance, therefore, design composite structure it is novel extend polycarboxylic acid part and applied to MOFs materials synthesis into
For one of focus for studying now.However, large-sized rigid multi-carboxylic acid compounds' synthesis is relatively difficult.Therefore institute in the present invention
The structure novelty being related toN,N,N′,N'-four (4- carboxy vinyls phenyl) -1,4- phenylenediamines be it is a kind of have it is huge it is potential should
With the part of value.There is no literature reported on the compound at present.
The content of the invention
To synthesize that cost is low, yield is high, product purity is high new it is an object of the invention to provide a kind ofN,N,N′,N'-four
(4- carboxy vinyls phenyl) -1,4- phenylenediamine synthetic methods.
The present invention'sN,N,N′,NThe synthetic method of '-four (4- carboxy vinyls phenyl)-Isosorbide-5-Nitrae-phenylenediamines, synthesis step
For：
(I) adds a certain amount of sodium tert-butoxide and proper catalyst using Isosorbide-5-Nitrae-dibromobenzene and diphenylamines as raw material, adds toluene and makees
For solvent, three-(2- tolyls) phosphines, mol ratio Isosorbide-5-Nitrae-dibromobenzene are rapidly joined under nitrogen or argon:Diphenylamines:Tertiary fourth
Sodium alkoxide is 1:2.1~2.3:2.1 ~ 2.5, the amount ratio of Isosorbide-5-Nitrae-dibromobenzene and toluene is 1 mmoles:3.0 ~ 4.5 milliliters.After adding
85 ~ 100 DEG C of oil bath heatings are reacted 10 ~ 16 hours, and reaction end steams toluene, adds 20 ~ 40 mL water to dilute, dichloromethane extraction
(20 ~ 40 mL × 3), collect organic phase simultaneously it is carried out with anhydrous sodium sulfite to remove water process, filter, be concentrated in vacuo, finally with
Petroleum ether and ethyl acetate are 20 by volume:0.8 ~ 1.2 mixed solvent is that eluant, eluent is obtained with column chromatography separating-purifying
Compound A：N,N, N′,N'-tetraphenyl -1,4- phenylenediamines；
(ⅱ) N,N,N′,N'-tetraphenyl -1,4- phenylenediamines and NBS（N- bromo-succinimide）In molar ratio 1:3.5~5.5
It is dissolved in after mixing in certain solvent,N,N,N′,NThe amount ratio of '-tetraphenyl -1,4- phenylenediamines and solvent is 1 mmoles:6.0~8.0
Milliliter, reacted 2 ~ 10 hours at 0 ~ 30 DEG C, reaction adds 10.0 ~ 20.0 milliliters of saturated sodium bisulfite solution after terminating, and adds water 10 ~ 30
Milliliter dilution, collect organic phase and it is carried out with anhydrous magnesium sulfate to remove water process, filter, be concentrated in vacuo, finally with 10 ~ 30
ML absolute ethyl alcohols recrystallization purifying 3 times, filtering, dry compound B：N,N,N′,N'-four (4- bromophenyls) -1,4- phenylenediamines；
(III) is separately added under argon gas or nitrogen protection in 250 mL there-necked flasksN,N,N′,N'-four (4- bromophenyls) -1,
4- phenylenediamines, methyl acrylate, potassium carbonate, triphenylphosphine, TBAB and a certain amount of molten DMF, mol ratioN,N,N′,N'-four (4- bromophenyls) -1,4- phenylenediamines：Methyl acrylate：Potassium carbonate：Triphenylphosphine：TBAB is 1: 5.0~
7.0：2.0~4.0：0.1~0.3：4 ~ 6,N,N,N′,NThe ratio of '-four (4- bromophenyls) -1,4- phenylenediamines and solvent is 1 mmoles：
10.0 ~ 15.0 milliliters.A certain amount of palladium salt is added as catalyst, 90 DEG C are reacted 30 ~ 50 hours, and reaction pours into 50 after terminating
Precipitation is separated out in mL frozen water, adds a small amount of hydrochloric acid catalyst, suction filtration obtains a large amount of yellow solids, adds 20 ~ 40 mL water dilute
Release, dichloromethane extraction (40 ~ 70 mL × 3), collect organic phase and it is carried out with anhydrous sodium sulfite to remove water process, filter,
Steam dichloromethane solvent and obtain crude product, finally with dichloromethane and petroleum ether by volume for 10:0.8 ~ 1.2 mixed solvent
For eluant, eluent compound C is obtained with column chromatography separating-purifying：N, N, N′, N′-Four (4- methoxycarbonylvinyls phenyl)-
1,4- phenylenediamines；
(IV) willN, N, N′, N′-Four (4- methoxycarbonylvinyls phenyl) -1,4- phenylenediamines and LiOH in molar ratio 1:50~
70 add the in the mixed solvent of Isosorbide-5-Nitrae-dioxane and water, and volume ratio is 2 ~ 4:1,95 DEG C is flowed back 8 ~ 14 hours, is evaporated off excessive 1,
4- dioxane, is diluted with water, and adds excessive dilute HNO3PH=2 are acidified to, yellow solid is separated out, is dried in vacuo to obtain finalization
Compound D：N,N,N′,N'-four (4- carboxy vinyls phenyl) -1,4- phenylenediamines.
A kind of described quaternary carboxylic acidN,N,N′,NThe synthesis side of '-four (4- carboxy vinyls phenyl) -1,4- phenylenediamines
Method, when preparing A, three-(2- tolyls) phosphines, mol ratio Isosorbide-5-Nitrae-dibromobenzene are rapidly joined under nitrogen or argon：Diphenylamines：
Sodium tert-butoxide is 1:2.1~2.3:2.1 ~ 2.5, the amount ratio of Isosorbide-5-Nitrae-dibromobenzene and toluene is 1 mmoles：3.0 ~ 4.5 milliliters.
Described quaternary carboxylic acidN,N,N′,NThe synthetic method of '-four (4- carboxy vinyls phenyl)-Isosorbide-5-Nitrae-phenylenediamines, system
Standby A is reacted 10 ~ 16 hours using toluene as solvent in 85 ~ 100 DEG C of oil bath heatings, and reaction end steams toluene, adds 20 ~ 40 mL
Water dilutes, dichloromethane extraction (20 ~ 40 mL × 3), and column chromatography purifies A with petroleum ether and ethyl acetate by volume for 20:
0.8~1.2。
Described quaternary carboxylic acidN,N,N′,NThe synthetic method of '-four (4- carboxy vinyls phenyl)-Isosorbide-5-Nitrae-phenylenediamines, its
It is characterised by：The catalyst that prepare compound A is used is double (dibenzalacetone) palladiums, and dosage is Isosorbide-5-Nitrae-dibromobenzene molal quantity
0.5~1.2%。
A kind of described quaternary carboxylic acidN,N,N′,NThe synthesis side of '-four (4- carboxy vinyls phenyl) -1,4- phenylenediamines
Method, during prepare compound B, A and NBS mol ratio are 1:3.5 ~ 5.5,50 ~ 80mL dichloromethane need to be added to make solvent.
Described quaternary carboxylic acidN,N,N′,NThe synthetic method of '-four (4- carboxy vinyls phenyl)-Isosorbide-5-Nitrae-phenylenediamines, its
It is characterised by：During prepare compound B, purifying B is recrystallized 3 times with 10 ~ 30 mL absolute ethyl alcohols.
Described quaternary carboxylic acidN,N,N′,NThe synthetic method of '-four (4- carboxy vinyls phenyl)-Isosorbide-5-Nitrae-phenylenediamines, system
During standby compound C, mol ratio B：Methyl acrylate：Potassium carbonate：Triphenylphosphine：TBAB is 1: 5.0~7.0：2.0~
4.0：0.1~0.3：4~6.50mL DMF need to be added to make solvent.It is 10 by volume to purify C dichloromethane and petroleum ether:0.8~
1.2 mixed solvent is eluant, eluent.
A kind of described quaternary carboxylic acidN,N,N′,NThe synthesis side of '-four (4- carboxy vinyls phenyl) -1,4- phenylenediamines
Method, the catalyst that prepare compound C is used are palladium, and dosage is the 3 ~ 7% of the amount of B material.
Described quaternary carboxylic acidN,N,N′,NThe synthetic method of '-four (4- carboxy vinyls phenyl)-Isosorbide-5-Nitrae-phenylenediamines,N,N,N′,N′-Four (4- methoxycarbonylvinyls phenyl) -1,4- phenylenediamines and LiOH in molar ratio 1:50 ~ 70, solvent Isosorbide-5-Nitrae-dioxy
The in the mixed solvent of six rings and water, volume ratio are 2 ~ 4:1, it is acidified to pH=2.
With this method composite structure noveltyN,N,N′,N'-four (4- carboxy vinyls phenyl) -1,4- phenylenediamines it is beneficial
Effect is：The rigid tetracarboxylic acid acids part of extension is widely used in the synthesis of MOFs materials, and this kind of material generally has orderly
Pore passage structure, big specific surface area, make this kind of material gaseous storage with separating, chemical sensitisation, catalysis and medicament slow release etc.
Different field has potential application.It is more micro- that the rigid tetrabasic carboxylic acid part of extension usually leads to that structure is novel, specific surface area is big
Hole MOFs materials, and microcellular structure can be changed, make electronic environment in its duct obtain optimizing so as to improve above-mentioned application performance, because
This, the novel extension polycarboxylic acid part of design composite structure simultaneously turns into the focus studied now applied to synthesizing for MOFs materials
One of.However, large-sized rigid multi-carboxylic acid compounds' synthesis is relatively difficult.Therefore, with this method composite structure noveltyN,N,N′,N'-four (4- carboxy vinyls phenyl) -1,4- phenylenediamines are a kind of quaternary carboxylate ligands with huge potential using value
Body.
Brief description of the drawings
Target compound D structural formula schematic diagram in Fig. 1 present invention.
Compound A and the synthesis schematic diagram of B structure formula in Fig. 2 present invention.
Compound C and D synthesis schematic diagram in Fig. 3 present invention.
Embodiment
The present invention'sN,N,N′,NThe synthetic method of '-four (4- carboxy vinyls phenyl)-Isosorbide-5-Nitrae-phenylenediamines, synthesis step
For：
With Isosorbide-5-Nitrae-dibromobenzene, diphenylamines is that raw material reacts generation through Buchwald-Hartwig aryl aminationsN,N,N',N'- four benzene
Base -1,4- phenylenediamines（A）, A and NBS bromination reactions generateN,N,N',N'- four（4- bromophenyls）- 1,4- phenylenediamines（B）, synthesis
Route is as shown in Figure 2.B reacts with methyl acrylate through Heck to be generatedN,N,N',N'- four（4- methoxycarbonylvinyl phenyl）-
1,4- phenylenediamines（C）, finally hydrolysis obtains target compound to CN,N,N',N'- four (4- carboxy vinyls phenyl) -1,4- benzene two
Amine（D）, synthetic route is as shown in Figure 3.
Specific embodiment is as follows：
(I) is as shown in Figure 2：Weigh Isosorbide-5-Nitrae-dibromobenzene (2.9 g, 12.3 mmol), diphenylamines (5.0 g, 29.6 mmol),
Double (dibenzylidene ketone) palladiums (0.04 g, 0.07 mmol), sodium tert-butoxide (2.9 g, 30.2 mmol) is in 250 mL there-necked flasks
In, 50 mL toluene are added, the phosphines of 3.5 mL tri--(2- tolyls), argon gas protection lower 90 are rapidly added after being passed through the min of argon gas 15
12 h are reacted in DEG C oil bath, and reaction end steams toluene, adds 30 mL water to dilute, dichloromethane extraction (30 mL × 3), collects organic
Layer, anhydrous Na2SO3Dry, filtering, steam solvent and obtain reacting coarse product, through silica gel column chromatography (eluant, eluent after drying：Petroleum ether/
Ethyl acetate=20:1) purify, obtain white powder A (3.04 g, 7.4 mmol), yield 60%.Fusing point：197~198 ℃.
Compound A nuclear-magnetisms1H NMR、13C NMR and high resolution mass spectrum data：1H NMR (400 MHz, CDCl3) δ
7.28 ~7.22 (m, 8H), 7.11 (m, 8H), 6.98 (m, 8H). 13C NMR (101 MHz,CDCl3) δ
142.82, 132.12, 129.15, 125.42, 123.70, 122.38。HRMS(ESI), C30H24N2, measured value (calculating
Value),m/z: 413. 5245[M+H] +(413.5250)。
(II) is as shown in Figure 2：WeighN,N,N',N'- tetraphenyl -1,4- phenylenediamines (4.0 g, 9.7 mmol) are in 250
In mL there-necked flasks, 60 mL dichloromethane are slowly added into there-necked flask, add NBS (6.9 g, 38.8 mmol), room temperature is stirred
4 h are mixed, stop reaction, add saturation Na2SO3Solution, separate organic phase, anhydrous MgSO4Dry, filtering, steaming chloroform must react
Crude product, absolute ethyl alcohol recrystallize 3 times, distillation water washing precipitation, obtain white powder B (6.9 g, 9.5 mmol), yield,
98%.Fusing point：99~101 ℃.
Compound B nuclear-magnetisms1H NMR、13C NMR and high resolution mass spectrum data：1H NMR (400 MHz, CDCl3) δ
7.34 (m, 4H), 7.26 (m, 4H), 7.08 (d, J = 7.4 Hz, 4H), 6.95 (m, 8H). 13C NMR
(101 MHz, CDCl3) δ:132.31, 132.17, 131.90, 129.40, 125.46, 125.08。HRMS(ESI),
C30H20Br4N2, measured value (calculated value),m/z: 729. 1084[M+H]+ (729.1092)。
(III) is as shown in Figure 3：It is separately added into 250 mL there-necked flasksN,N,N′,N′- four (4- phenyl-bromides) -1,4- benzene
Diamines (3.0 g, 4.1 mmol), methyl acrylate (2.1 g, 6.0 eq), K2CO3(1.5 g, 10.9 mmol)、PPh3
(0.13 g, 0.5 mmol) and TBAB (6.3g, 20.5 mmol), sequentially adds in 250 mL three-necked flasks, adds
Enter 50 mL DMF as solvent, after being passed through the min of Ar 10, add Pd (OAc)2(0.02 g, 5.0 mmol%), 120 DEG C of reactions
48 h, reaction is poured into after terminating separates out precipitation in 50 mL frozen water, add a small amount of hydrochloric acid catalyst, and suction filtration obtains a large amount of Huangs
Color solid, 30 mL water are added to dilute, dichloromethane extraction (60 mL × 3) collected organic layer, anhydrous Na2SO3Dry, filtering, steam
Dichloromethane solvent obtains crude product, through silica gel column chromatography (eluant, eluent after drying:Dichloromethane/petroleum ether=10:1) purify, obtain light
Yellow powder C (2.8 g, 3.7mmol), yield 90.3%.Fusing point：335-340℃.
Compound C nuclear-magnetisms1H NMR、13C NMR and high resolution mass spectrum data：1H NMR (400 MHz, CDCl3 ) δ
8.12-8.00 (m, 8H), 7.48 (d, J = 30.2 Hz, 4H),7.37-7.31(m, 8H), 7.14 (s, 4H),
6.31(d, J = 30.2 Hz, 4H), 3.77(s, 12H). 13C NMR (101 MHz, CDCl3) δ 168.23,
145.50, 144.27, 137.71, 132.81, 132.03, 128.19,123.50, 116.07, 52.01. HRMS
(ESI), C46H40N2O8[M+Na]+, measured value (calculated value), m/z:771.8172(771.8184).
(IV) is as shown in Figure 3：Sequentially added in 250 mL round-bottomed flaskN, N, N′, N′-Four (4- methoxycarbonyl groups
Ethenylphenyl) -1,4- phenylenediamines（2.0 g, 3.7 mmol）, LiOH (5. 0 g, 208.3 mmol) is added to 250 mL
In round-bottomed flask, 60 mL Isosorbide-5-Nitraes-dioxane and 20 mL water are added, 95 DEG C of 12 h of reaction, Isosorbide-5-Nitrae-dioxane is steamed, adds
Appropriate water dissolving carboxylic acid sodium salt, filters, dilute HNO is added in filtrate3It is 2 to be acidified to PH, separates out precipitation, stands, it is clear to topple over upper strata
Liquid, the target compound yellow mercury oxide D (3.26 g, 3.65 mml) for filtering, drying, yield 98.8%.Fusing point is more than 350 DEG C.
Compound D nuclear-magnetisms1H NMR、13C NMR and high resolution mass spectrum data：1H NMR (400 MHz, DMSO-d 6) δ
8.11-8.01 (m, 8H), 7.45 (d, J = 30.2 Hz, 4H), 7.38-7.30 (m, 8H), 7.14 (d, J =
2.1 Hz, 4H), 6.27 (d, J = 30.2 Hz, 4H)。13C NMR (101MHz, DMSO-d 6) δ 170.46,
145.50,143.73,137.72,132.81,132.03,128.19,123.50,115.05 HRMS (EI),
C42H32N2O8[M+Na]+, measured value (calculated value), m/z:715.7116(715.7121).
The above described is only a preferred embodiment of the present invention, not making any formal limitation to the present invention, appoint
Without departing from technical solution of the present invention content, what the technical spirit according to the present invention was made to above example any simply repaiies for what
Change, equivalent variations and modification, in the range of still falling within technical solution of the present invention.
Claims (9)
1. quaternary carboxylic acidN,N,N′,NThe synthetic method of '-four (4- carboxy vinyls phenyl)-Isosorbide-5-Nitrae-phenylenediamines, it is characterised in that
Synthesis step is：
(I) adds a certain amount of sodium tert-butoxide and proper catalyst using Isosorbide-5-Nitrae-dibromobenzene and diphenylamines as raw material, adds toluene conduct
Solvent, three-(2- tolyls) phosphines, mol ratio Isosorbide-5-Nitrae-dibromobenzene are rapidly joined under nitrogen or argon：Diphenylamines：The tert-butyl alcohol
Sodium is 1:2.1~2.3:2.1 ~ 2.5, the amount ratio of Isosorbide-5-Nitrae-dibromobenzene and toluene is 1 mmoles：3.0 ~ 4.5 milliliters, after adding 85 ~
100 DEG C of oil bath heatings are reacted 10 ~ 16 hours, and reaction end steams toluene, adds 20 ~ 40 mL water to dilute（20~40 mL×3）Dichloro
Methane extracts, and collects organic phase and it is carried out with anhydrous sodium sulfite to remove water process, filter, be concentrated in vacuo, finally with oil
Ether and ethyl acetate are 20 by volume:0.8 ~ 1.2 mixed solvent is that eluant, eluent obtains chemical combination with column chromatography separating-purifying
Thing A：N,N,N′,N'-tetraphenyl -1,4- phenylenediamines；
(ⅱ) N,N,N′,N'-tetraphenyl -1,4- phenylenediamines and NBS（N- bromo-succinimide）, in molar ratio 1:3.5~5.5
It is dissolved in after mixing in certain solvent,N,N,N′,NThe amount ratio of '-tetraphenyl -1,4- phenylenediamines and solvent is 1 mmoles：6.0~8.0
Milliliter, reacted 2 ~ 10 hours at 0 ~ 30 DEG C, reaction adds 10.0 ~ 20.0 milliliters of saturated sodium bisulfite solution after terminating, and adds water 10 ~ 30
Milliliter dilution, collect organic phase and it is carried out with anhydrous magnesium sulfate to remove water process, filter, be concentrated in vacuo, finally with 10 ~ 30
ML absolute ethyl alcohols recrystallization purifying 3 times, filtering, dry compound B：N,N,N′,N'-four (4- bromophenyls) -1,4- phenylenediamines；
(III) is separately added under argon gas or nitrogen protection in 250 mL there-necked flasksN,N,N′,N'-four (4- bromophenyls) -1,
4- phenylenediamines, methyl acrylate, potassium carbonate, triphenylphosphine, TBAB and a certain amount of solvent DMF, mol ratioN,N,N′,N'-four (4- bromophenyls) -1,4- phenylenediamines：Methyl acrylate：Potassium carbonate：Triphenylphosphine：TBAB is 1:
5.0~7.0：2.0~4.0：0.1~0.3：4 ~ 6,N,N,N′,NThe ratio of '-four (4- bromophenyls) -1,4- phenylenediamines and solvent is 1 milli
Rub：10.0 ~ 15.0 milliliters, a certain amount of palladium salt is added as catalyst, and 90 DEG C are reacted 30 ~ 50 hours, and reaction is fallen after terminating
Enter and precipitation is separated out in 50 mL frozen water, add a small amount of hydrochloric acid catalyst, suction filtration obtains a large amount of yellow solids, adds 20 ~ 40 mL
Water dilutes, and the extraction of (40 ~ 70 mL × 3) dichloromethane, collects organic phase and it is carried out with anhydrous sodium sulfite to remove water process,
Filtering, steams dichloromethane solvent and obtains crude product, finally with dichloromethane and petroleum ether by volume for 10:0.8 ~ 1.2 it is mixed
Bonding solvent is that eluant, eluent obtains compound C with column chromatography separating-purifying：N, N, N′, N′-Four (4- methoxycarbonylvinyls
Phenyl) -1,4- phenylenediamines；
(IV) willN, N, N′, N′-Four (4- methoxycarbonylvinyls phenyl) -1,4- phenylenediamines and LiOH in molar ratio 1:50~
70 add the in the mixed solvent of Isosorbide-5-Nitrae-dioxane and water, and volume ratio is 2 ~ 4:1,95 DEG C is flowed back 8 ~ 14 hours, is evaporated off excessive 1,
4- dioxane, is diluted with water, and adds excessive dilute HNO3PH=2 are acidified to, yellow solid is separated out, is dried in vacuo to obtain finalization
Compound D：N,N,N′,N'-four (4- carboxy vinyls phenyl)-Isosorbide-5-Nitrae-phenylenediamines, its chemical structural formula are：
。
It is 2. according to claim 1N,N,N′,NThe synthetic method of '-four (4- carboxy vinyls phenyl)-Isosorbide-5-Nitrae-phenylenediamines,
It is characterized in that：When preparing A, three-(2- tolyls) phosphines, mol ratio Isosorbide-5-Nitrae-dibromo are rapidly joined under nitrogen or argon
Benzene：Diphenylamines：Sodium tert-butoxide is 1:2.1~2.3:2.1 ~ 2.5, the amount ratio of Isosorbide-5-Nitrae-dibromobenzene and toluene is 1 mmoles：3.0~4.5
Milliliter.
It is 3. according to claim 1N,N,N′,NThe synthetic method of '-four (4- carboxy vinyls phenyl)-Isosorbide-5-Nitrae-phenylenediamines,
It is characterized in that：A is prepared using toluene as solvent, is reacted 10 ~ 16 hours in 85 ~ 100 DEG C of oil bath heatings, reaction end steams first
Benzene, 20 ~ 40 mL water are added to dilute, dichloromethane extraction (20 ~ 40 mL × 3), column chromatography purifying A is pressed with petroleum ether and ethyl acetate
Volume ratio is 20:0.8~1.2.
It is 4. according to claim 1N,N,N′,NThe synthetic method of '-four (4- carboxy vinyls phenyl)-Isosorbide-5-Nitrae-phenylenediamines,
It is characterized in that：The catalyst that prepare compound A is used is double (dibenzalacetone) palladiums, and dosage is Isosorbide-5-Nitrae-dibromobenzene molal quantity
0.5 ~ 1.2%.
It is 5. according to claim 1N,N,N′,NThe synthetic method of '-four (4- carboxy vinyls phenyl)-Isosorbide-5-Nitrae-phenylenediamines,
It is characterized in that：During prepare compound B, A and NBS mol ratio are 1:3.5 ~ 5.5,50 ~ 80mL dichloromethane need to be added to make solvent.
It is 6. according to claim 1N,N,N′,NThe synthetic method of '-four (4- carboxy vinyls phenyl)-Isosorbide-5-Nitrae-phenylenediamines,
It is characterized in that：During prepare compound B, purifying B is recrystallized 3 times with 10 ~ 30 mL absolute ethyl alcohols.
It is 7. according to claim 1N,N,N′,NThe synthetic method of '-four (4- carboxy vinyls phenyl)-Isosorbide-5-Nitrae-phenylenediamines,
It is characterized in that：During prepare compound C, mol ratio B：Methyl acrylate：Potassium carbonate：Triphenylphosphine：TBAB is 1:
5.0~7.0：2.0~4.0：0.1~0.3：4 ~ 6,50mL DMF need to be added to make solvent, C dichloromethane is purified and petroleum ether presses volume
Than for 10:0.8 ~ 1.2 mixed solvent is eluant, eluent.
It is 8. according to claim 1N,N,N′,NThe synthetic method of '-four (4- carboxy vinyls phenyl)-Isosorbide-5-Nitrae-phenylenediamines,
It is characterized in that：The catalyst that prepare compound C is used is palladium, and dosage is the 3 ~ 7% of the amount of B material.
It is 9. according to claim 1N,N,N′,NThe synthetic method of '-four (4- carboxy vinyls phenyl)-Isosorbide-5-Nitrae-phenylenediamines,
It is characterized in that：N,N,N′,N′-Four (4- methoxycarbonylvinyls phenyl) -1,4- phenylenediamines and LiOH in molar ratio 1:50~
70, the in the mixed solvent of solvent Isosorbide-5-Nitrae-dioxane and water, volume ratio is 2 ~ 4:1, it is acidified to pH=2.
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| JP2011114322A (en) * | 2009-11-30 | 2011-06-09 | Fujifilm Corp | Charge transporting compound, charge transporting film using the same, organic electroluminescent element, electrophotographic photosensitive member, method for producing charge transporting film, and novel charge transporting compound |
| US20110269994A1 (en) * | 2010-04-28 | 2011-11-03 | Fujifilm Corporation | Method of producing a triarylamine compound |
| CN105037691A (en) * | 2014-04-24 | 2015-11-11 | 浙江工业大学 | Poly[1,4-bis(diphenylamino)benzene], application thereof and lithium ion battery prepared therefrom |
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2017
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011114322A (en) * | 2009-11-30 | 2011-06-09 | Fujifilm Corp | Charge transporting compound, charge transporting film using the same, organic electroluminescent element, electrophotographic photosensitive member, method for producing charge transporting film, and novel charge transporting compound |
| US20110269994A1 (en) * | 2010-04-28 | 2011-11-03 | Fujifilm Corporation | Method of producing a triarylamine compound |
| CN105037691A (en) * | 2014-04-24 | 2015-11-11 | 浙江工业大学 | Poly[1,4-bis(diphenylamino)benzene], application thereof and lithium ion battery prepared therefrom |
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