CN107325017A - A kind of synthetic method of 1,4 phenylenediamines of quaternary carboxylic acid N, N, N ', N ' four (4 ' carboxyl biphenyl base) - Google Patents
A kind of synthetic method of 1,4 phenylenediamines of quaternary carboxylic acid N, N, N ', N ' four (4 ' carboxyl biphenyl base) Download PDFInfo
- Publication number
- CN107325017A CN107325017A CN201710629064.1A CN201710629064A CN107325017A CN 107325017 A CN107325017 A CN 107325017A CN 201710629064 A CN201710629064 A CN 201710629064A CN 107325017 A CN107325017 A CN 107325017A
- Authority
- CN
- China
- Prior art keywords
- phenylenediamines
- isosorbide
- nitrae
- carboxylic acid
- solvent
- 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
- 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
- C07C227/20—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 by hydrolysis of N-acylated amino-acids or derivatives thereof, e.g. hydrolysis of carbamates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
Abstract
A kind of quaternary carboxylic acidN,N,N′,NThe synthetic method of ' tetra- (4 ' carboxyl biphenyl base) 1,4 phenylenediamines;1,4 dibromobenzenes react with diphenylamines through aryl amination to be generatedN,N,N′,N' tetraphenyl Isosorbide-5-Nitrae phenylenediamine (A), A and NBS, which reacts, to be generatedN,N,N′,N' tetra- (4 bromophenyl) 1,4 phenylenediamines (B).Compound B and 4 methoxycarbonyl group phenyl boric acids add catalyst reaction generation under the conditions of inert gas shieldingN,N,N′,N' tetra- (4 ' methoxycarbonyl group xenyl) 1,4 phenylenediamines (C).Compound C generates target compound D through hydrolysis:N,N,N′,N' tetra- (4 ' carboxyl biphenyl base) 1,4 phenylenediamines.The present invention synthesis one there is no literature reported on many phenyl ring fragrant four carboxylic acid compounds;Synthetic method is simple, cost is low, yield is high and mentions the high advantage of purity.Target compound D such as following formulas:
Description
Technical field
The present invention relates to the technical field of organic chemistry, especially a kind of quaternary carboxylic acidN,N,N′,N'-four (4 '-carboxyl biphenyls
Base) -1,4- phenylenediamines synthetic method.
Background technology
The rigid tetracarboxylic acid acids part of extension is widely used in the synthesis of MOFs materials, and this kind of material generally has good
Pore passage structure, big specific surface area, make this kind of material in gas separation with storage, chemical sensitisation, catalysis and medicament slow release etc.
Different field has potential application.Because the fragrant four carboxylic acid of fragrant four carboxylic acid's particularly long-chain has following characteristic and turns into system
The preferable selection of standby higher-dimension metal organic frame:First, can the carboxyl of all or part of deprotonation the part can be made to have more
Flexile coordination mode;2nd, the carboxyl at two ortho positions is closer to the distance, it is easy to form intramolecular hydrogen bond;3rd, because itself is big
Steric hindrance, have certain angle between phenyl ring and phenyl ring, part carboxyl can also have certain angle with phenyl ring, can be never
Equidirectional and metallic ion coordination;4th, the higher symmetry of molecule is conducive to the growth of crystal and the design of structure.Such as 2009
Year Lin(Ma L., Jin A., Xie Z., et al. Angew. Chem. Int. Ed., 2009, 48: 9905-
9908)Two metal organic frames are successfully synthesized under the conditions of solvent heat Deng using two tetrabasic carboxylic acid parts and mantoquita, author makes
The specific surface area of compound is effectively increased with freeze-drying, while also increasing the adsorbance of hydrogen.Use freeze-drying
Hydrogen adsorptive capacity of the method than vacuum drying many one times.Stylianou etc.(Stylianou K. C., Heck R., Chong S.
Y., et al. J. Am. Chem. Soc., 2010, 132: 4119-4130)Report uses the tetrabasic carboxylic acid part based on pyrene
The metal organic frame 1,1 that (1,3,6,8- tetra- (4 benzoic acid) pyrene (TBAPy)) and indium nitrate synthesize a hyperfluorescence is presented
Good heat endurance.Experiment shows that 1 has strong fluorescence at 471 and 529 nm.The fluorescence lifetime of compound 1 reaches 0.110
Ms, quantum yield is 6.7%.The rigid corner Carboxylic acid ligand of extension usually leads to many micropores that structure is novel, specific surface area is big
MOFs materials, and microcellular structure can be changed, make electronic environment in its micropore obtain optimization 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 the structure novelty involved by the present inventionN,N,N′,N'-four (4 '-carboxyl biphenyl base) -1,4- phenylenediamines are a kind of parts with huge potential using value.At present still
Without the document report compound.
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
The synthetic method of (4 '-carboxyl biphenyl base) -1,4- phenylenediamines.
The present invention'sN,N,N′,NThe synthetic method of '-four (4 '-carboxyl biphenyl base)-Isosorbide-5-Nitrae-phenylenediamines, 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 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, plus 20 ~ 40 mL water dilutions, 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, reacts 2 ~ 10 hours at 0 ~ 30 DEG C, after reaction terminates plus 10.0 ~ 20.0 milliliters of saturated sodium bisulfite solution, adds water 10 ~ 30
Milliliter dilution, collects 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, 4- methoxycarbonyl groups phenyl boric acid, potassium carbonate and a certain amount of dioxane, mol ratioN,N,N′,N'-four (4- bromobenzenes
Base) -1,4- phenylenediamines:4- methoxycarbonyl phenyl methyl borates:Potassium carbonate is 1:4.5~5.0:10.0 ~ 15.0,N,N,N′,N'-four
The ratio of (4- bromophenyls) -1,4- phenylenediamines and solvent is 1 mmoles:10.0 ~ 15.0 milliliters.A certain amount of palladium salt is added as catalysis
Agent, 90 DEG C react 20 ~ 30 hours, reaction end steam Isosorbide-5-Nitrae-dioxane, plus 20 ~ 30 mL water dilution, dichloromethane extraction
(40 ~ 70 mL × 3), collect organic phase and it are carried out with anhydrous sodium sulfite to remove water process, filter, steam dichloromethane molten
Agent obtains crude product, finally with petroleum ether and dichloromethane by volume for 4:0.8 ~ 1.2 mixed solvent is eluant, eluent post color
Spectrometry separating-purifying obtains compound C:N,N,N′,N'-four (4 '-methoxycarbonyl group xenyl) -1,4- phenylenediamines;
(IV) willN,N,N′,N'-four (4 '-methoxycarbonyl group xenyl) -1,4- phenylenediamines and NaOH in molar ratio 1:30 ~ 50 add
The in the mixed solvent of Isosorbide-5-Nitrae-dioxane and water, volume ratio is 3 ~ 5:1,95 DEG C is flowed back 8 ~ 12 hours, and excessive Isosorbide-5-Nitrae-two is evaporated off
The ring of oxygen six, is diluted with water, and adds excessive dilute HNO3Progress is acidified to pH=2, separates out yellow solid, is dried in vacuo to obtain finalization
Compound D:N,N,N′,N'-four (4 '-carboxyl biphenyl base) -1,4- phenylenediamines.
A kind of described quaternary carboxylic acidN,N,N′,NThe synthetic method of '-four (4 '-carboxyl biphenyl base)-Isosorbide-5-Nitrae-phenylenediamines, system
During standby A, 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.
A kind of described quaternary carboxylic acidN,N,N′,NThe synthetic method of '-four (4 '-carboxyl biphenyl base)-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, plus 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。
A kind of described quaternary carboxylic acidN,N,N′,NThe synthetic method of '-four (4 '-carboxyl biphenyl base)-Isosorbide-5-Nitrae-phenylenediamines, its
It is characterised by:The catalyst that prepare compound A is used is double (dibenzalacetone) palladiums, and consumption is Isosorbide-5-Nitrae-dibromobenzene molal quantity
0.5~1.2%。
A kind of described quaternary carboxylic acidN,N,N′,NThe synthetic method of '-four (4 '-carboxyl biphenyl base)-Isosorbide-5-Nitrae-phenylenediamines, system
During standby compound B, A and NBS mol ratio are 1:3.5 ~ 5.5, it need to add 50 ~ 80mL dichloromethane makees solvent.
A kind of described quaternary carboxylic acidN,N,N′,NThe synthetic method of '-four (4 '-carboxyl biphenyl base)-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.
A kind of described quaternary carboxylic acidN,N,N′,NThe synthetic method of '-four (4 '-carboxyl biphenyl base)-Isosorbide-5-Nitrae-phenylenediamines, system
During standby compound C, mol ratio B:4- methoxycarbonyl group phenyl boric acids:Potassium carbonate is 1:4.5~5.0:10.0~15.0.It need to add 80 ~ 120mL
Dioxane makees solvent.It is 4 by volume to purify B petroleum ethers and dichloromethane:0.8 ~ 1.2 mixed solvent is eluant, eluent.
A kind of described quaternary carboxylic acidN,N,N′,NThe synthetic method of '-four (4 '-carboxyl biphenyl base)-Isosorbide-5-Nitrae-phenylenediamines, system
The catalyst that standby compound C is used is tetrakis triphenylphosphine palladium, and consumption is the 1 ~ 2.5% of the amount of B material.
A kind of described quaternary carboxylic acidN,N,N′,NThe synthetic method of '-four (4 '-carboxyl biphenyl base)-Isosorbide-5-Nitrae-phenylenediamines,N,N,N′,N'-four (4 '-methoxycarbonyl group xenyl) -1,4- phenylenediamines and NaOH in molar ratio 1:30 ~ 50, solvent Isosorbide-5-Nitrae-dioxy six
The in the mixed solvent of ring and water, volume ratio is 3 ~ 5:1, it is acidified to pH=2.
With this method composite structure noveltyN,N,N′,NThe beneficial effect of '-four (4 '-carboxyl biphenyl base) -1,4- phenylenediamines
It is really: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. no
Same domain has potential application.The rigid tetrabasic carboxylic acid part of extension usually leads to many micropores that structure is novel, specific surface area is big
MOFs materials, and microcellular structure can be changed, make electronic environment in its stomata obtain optimization 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 '-carboxyl biphenyl base) -1,4- phenylenediamines are a kind of quaternary Carboxylic acid ligands with huge potential using value.
Brief description of the drawings
Target compound D structural formula schematic diagram in Fig. 1 present invention.
Compound A and B synthesis schematic diagram 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 '-carboxyl biphenyl base)-Isosorbide-5-Nitrae-phenylenediamines, synthesis step is:
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 are generatedN,N,N',N'- four(4- bromophenyls)- 1,4- phenylenediamines(B), synthesis
Route is as shown in Figure 2.B to methoxycarbonyl group phenyl boric acid through Suzuki coupling reactions with generatingN,N,N',N'- four(4'- methoxycarbonyl groups
Xenyl)- 1,4- phenylenediamines(C), finally hydrolysis obtains target compound to CN,N,N',N'- four (4'- carboxyl biphenyls base) -1,4-
Phenylenediamine(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, is passed through after the min of argon gas 15 and is rapidly added the phosphines of 3.5 mL tri--(2- tolyls), argon gas protection lower 90
12 h are reacted in DEG C oil bath, and reaction end steams toluene, plus the dilution of 30 mL water, dichloromethane extraction (30 mL × 3), collected organic
Layer, anhydrous Na2SO3Dry, filter, 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, NBS (6.9 g, 38.8 mmol) are added, room temperature is stirred
4 h are mixed, stop reaction, saturation Na is added2SO3Solution, separates organic phase, anhydrous MgSO4Dry, filter, steaming chloroform must react
Crude product, absolute ethyl alcohol is recrystallized 3 times, distillation water washing precipitation, obtains 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- bromophenyls)- 1,4- benzene
Diamines (5.5 g, 7.6 mmol), 4- methoxycarbonyl groups phenyl boric acid (6.6 g, 4.8 eq), K2CO3 (13.8g, 100.32
Mmol) and 100 mL Isosorbide-5-Nitraes-dioxane, it is passed through N2After 10 min, plus 2% tetrakis triphenylphosphine palladium, 90 DEG C of 24 h of reaction,
Reaction end steams Isosorbide-5-Nitrae-dioxane, plus the dilution of 30 mL water, dichloromethane extraction (60 mL × 3), and collected organic layer is anhydrous
Na2SO3Dry, filter, steam dichloromethane and obtain reacting coarse product, through silica gel column chromatography (eluant, eluent after drying:Petroleum ether/dichloro
Methane=4:1) purify, obtain pale yellow powderN,N,N',N'- four(4'- methoxycarbonyl group xenyls)- 1,4- phenylenediamines (5.2 g,
5.5 mmol), yield 72%.Fusing point:345-347 ℃.
Compound C nuclear-magnetisms1H NMR、13C NMR and high resolution mass spectrum data:1H NMR (400 MHz, CDCl3) δ
8.09 (d, J = 8.4 Hz, 8H), 7.99 (d, J = 8.2 Hz, 8H), 7.66 (d, J = 8.4 Hz, 9H),
7.51 (d, J = 2.1 Hz, 4H), 7.35 (d, J = 8.2 Hz, 9H), 3.96 (s, 12H). 13C NMR
(101 MHz, CDCl3) δ166.97, 144.59, 142.97, 139.63, 133.07, 131.58, 130.15,
129.33, 129.06, 127.69, 126.31, 117.85, 52.27。HRMS(ESI), C62H48N2O8, measured value (meter
Calculation value),m/z: 959.0536[M+H]+(950.0531)。
(IV) is as shown in Figure 3:Sequentially added in 250 mL round-bottomed flaskN,N,N',N'- four(4'- methoxycarbonyl groups join
Phenyl)- 1,4- phenylenediamines (3.5 g, 3.7 mmol), NaOH (5 g, 125 mmol), H2O (20 mL) and 60 mL 1,4-
Dioxane, 95 DEG C of 12 h of reaction, steams Isosorbide-5-Nitrae-dioxane, adds in appropriate water dissolving carboxylic acid sodium salt, filtering, filtrate
Plus dilute HNO3PH is acidified to for 2, precipitation is separated out, stood, supernatant liquor is toppled over, suction filtration, dry target compound yellow mercury oxide D
(3.23 g, 3.6 mmol), yield 98%.Fusing point:More than 350 DEG C.
Compound D nuclear-magnetisms1H NMR、13C NMR and high resolution mass spectrum data:1H NMR (400 MHz, DMSO ) δ
12.96 (s, 4H), 8.11-7.91 (m, 9H), 7.85 (m, 2H), 7.75 (m, 10H), 7.56 (m, 9H),
7.21-6.95 (m, 6H). 13C NMR (101 MHz, DMSO) δ167.61, 131.97, 130.42, 129.51,
129.26, 129.14, 128.58, 127.59, 126.62, 126.53, 124.01.HRMS (ESI), C58H40N2O8[M-
H]+, measured value (calculated value), m/z: 891.2805(891.2813).
The above described is only a preferred embodiment of the present invention, not making any formal limitation to the present invention, appoint
What is without departing from technical solution of the present invention content, and what the technical spirit according to the present invention was made to above example any simply repaiies
Change, equivalent variations and modification, in the range of still falling within technical solution of the present invention.
Claims (9)
1. a kind of quaternary carboxylic acidN,N,N′,NThe synthetic method of '-four (4 '-carboxyl biphenyl base)-Isosorbide-5-Nitrae-phenylenediamines, its feature exists
In 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, rapidly joins three-(2- tolyls) phosphines, mol ratio Isosorbide-5-Nitrae-dibromobenzene 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,
Reaction end steam toluene, plus 20 ~ 40 mL water dilution, dichloromethane extract 20 ~ 40 mL × 3, collect organic phase be used in combination
Anhydrous sodium sulfite carries out removing water process to it, filters, and is concentrated in vacuo, is by volume with petroleum ether and ethyl acetate finally
20:0.8 ~ 1.2 mixed solvent is that eluant, eluent obtains compound A with column chromatography separating-purifying:N,N,N′,N'-tetraphenyl -1,
4- phenylenediamines;
(ⅱ) N,N,N′,N'-tetraphenyl -1,4- phenylenediamines and NBSN- bromo-succinimide in molar ratio 1:3.5 ~ 5.5 mix
It is dissolved in after conjunction in certain solvent,N,N,N′,NThe amount ratio of '-tetraphenyl -1,4- phenylenediamines and solvent is 1 mmoles:6.0 ~ 8.0 millis
Rise, reacted 2 ~ 10 hours at 0 ~ 30 DEG C, reaction adds 10.0 ~ 20.0 milliliters of saturated sodium bisulfite solution after terminating, add water 10 ~ 30 millis
Dilution is risen, organic phase is collected 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 alcohol 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, 4- methoxycarbonyl groups phenyl boric acid, potassium carbonate and a certain amount of dioxane, mol ratioN,N,N′,N'-four (4- bromobenzenes
Base) -1,4- phenylenediamines:4- methoxycarbonyl group phenyl boric acids:Potassium carbonate is 1:4.5~5.0:10.0 ~ 15.0,N,N,N′,N'-four (4- bromines
Phenyl) ratio of -1,4- phenylenediamines and solvent is 1 mmoles:10.0 ~ 15.0 milliliters, add a certain amount of palladium salt and be used as catalyst, 90
DEG C reaction 20 ~ 30 hours, reaction end steams Isosorbide-5-Nitrae-dioxane, plus 20 ~ 30 mL water dilutions, the dichloromethane of 40 ~ 70 mL × 3
Alkane is extracted, and is collected organic phase and simultaneously it is carried out with anhydrous sodium sulfite to remove water process, filter, steams dichloromethane solvent and obtain and slightly produce
Thing, finally with petroleum ether and dichloromethane by volume for 4:0.8 ~ 1.2 mixed solvent is that eluant, eluent is separated with column chromatography
Purification obtains compound C:N,N,N′,N'-four (4 '-methoxycarbonyl group xenyl) -1,4- phenylenediamines;
(IV) willN,N,N′,N'-four (4 '-methoxycarbonyl group xenyl) -1,4- phenylenediamines and NaOH in molar ratio 1:30 ~ 50 add
The in the mixed solvent of Isosorbide-5-Nitrae-dioxane and water, volume ratio is 3 ~ 5:1,95 DEG C is flowed back 8 ~ 12 hours, and excessive Isosorbide-5-Nitrae-dioxy is evaporated off
Six rings, are diluted with water, and add excessive dilute HNO3PH=2 are acidified to, yellow solid is separated out, is dried in vacuo to obtain final compound D:N,N,N′,N'-four (4 '-carboxyl biphenyl base)-Isosorbide-5-Nitrae-phenylenediamines, its chemical structural formula is:
。
2. quaternary carboxylic acid according to claim 1N,N,N′,NThe synthesis of '-four (4 '-carboxyl biphenyl base) -1,4- phenylenediamines
Method, it is characterised in that:When preparing A, three-(2- tolyls) phosphines are rapidly joined under nitrogen or argon, mol ratio Isosorbide-5-Nitrae-
Dibromobenzene: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.
3. quaternary carboxylic acid according to claim 1N,N,N′,NThe synthesis of '-four (4 '-carboxyl biphenyl base) -1,4- phenylenediamines
Method, it is characterised in that:A is prepared using toluene as solvent, is reacted 10 ~ 16 hours in 85 ~ 100 DEG C of oil bath heatings, reaction terminates
Toluene is steamed, plus 20 ~ 40 mL water dilutions, is extracted with the dichloromethane of 20 ~ 40 mL × 3, column chromatography purifies A with petroleum ether and acetic acid
Ethyl ester is 20 by volume:0.8~1.2.
4. quaternary carboxylic acid according to claim 1N,N,N′,NThe synthesis of '-four (4 '-carboxyl biphenyl base) -1,4- phenylenediamines
Method, it is characterised in that:The catalyst that prepare compound A is used is double (dibenzalacetone) palladiums, and consumption is Isosorbide-5-Nitrae-dibromobenzene
The 0.5 ~ 1.2% of molal quantity.
5. quaternary carboxylic acid according to claim 1N,N,N′,NThe synthesis of '-four (4 '-carboxyl biphenyl base) -1,4- phenylenediamines
Method, it is characterised in that:During prepare compound B, A and NBS mol ratio are 1:3.5 ~ 5.5, it need to add 50 ~ 80mL dichloromethane work
Solvent.
6. quaternary carboxylic acid according to claim 1N,N,N′,NThe synthesis of '-four (4 '-carboxyl biphenyl base) -1,4- phenylenediamines
Method, it is characterised in that:During prepare compound B, purifying B is recrystallized 3 times with 10 ~ 30 mL absolute ethyl alcohols.
7. quaternary carboxylic acid according to claim 1N,N,N′,NThe synthesis of '-four (4 '-carboxyl biphenyl base) -1,4- phenylenediamines
Method, it is characterised in that:During prepare compound C, mol ratio B:4- methoxycarbonyl group phenyl boric acids:Potassium carbonate is 1:4.5~5.0:10.0
~15.0;It need to add 80 ~ 120mL dioxane makees solvent, and purifying B petroleum ethers and dichloromethane are 4 by volume:0.8 ~ 1.2
Mixed solvent is eluant, eluent.
8. quaternary carboxylic acid according to claim 1N,N,N′,NThe synthesis of '-four (4 '-carboxyl biphenyl base) -1,4- phenylenediamines
Method, it is characterised in that:The catalyst that prepare compound C is used be tetrakis triphenylphosphine palladium, consumption for B material amount 1 ~
2.5%。
9. quaternary carboxylic acid according to claim 1N,N,N′,NThe synthesis of '-four (4 '-carboxyl biphenyl base) -1,4- phenylenediamines
Method, it is characterised in that:N,N,N′,N'-four (4 '-methoxycarbonyl group xenyl) -1,4- phenylenediamines and NaOH in molar ratio 1:30~
50, the in the mixed solvent of solvent Isosorbide-5-Nitrae-dioxane and water, volume ratio is 3 ~ 5:1, it is acidified to pH=2.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710629064.1A CN107325017A (en) | 2017-07-28 | 2017-07-28 | A kind of synthetic method of 1,4 phenylenediamines of quaternary carboxylic acid N, N, N ', N ' four (4 ' carboxyl biphenyl base) |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710629064.1A CN107325017A (en) | 2017-07-28 | 2017-07-28 | A kind of synthetic method of 1,4 phenylenediamines of quaternary carboxylic acid N, N, N ', N ' four (4 ' carboxyl biphenyl base) |
Publications (1)
Publication Number | Publication Date |
---|---|
CN107325017A true CN107325017A (en) | 2017-11-07 |
Family
ID=60227994
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710629064.1A Pending CN107325017A (en) | 2017-07-28 | 2017-07-28 | A kind of synthetic method of 1,4 phenylenediamines of quaternary carboxylic acid N, N, N ', N ' four (4 ' carboxyl biphenyl base) |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107325017A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107868018A (en) * | 2017-11-22 | 2018-04-03 | 遵义医学院 | N, N, N ', N ' four [4 (4 ' carboxyl) xenyls)] 9,10 anthradiamine synthetic methods |
CN113201144A (en) * | 2021-04-30 | 2021-08-03 | 北京科技大学 | Rigid tetracarboxyl hydrogen bond organic framework material and preparation and application thereof |
CN114163776A (en) * | 2022-01-24 | 2022-03-11 | 西南石油大学 | Epoxy resin with pressure-bearing and leakage-stopping functions and preparation method thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012001452A (en) * | 2010-06-15 | 2012-01-05 | Kyushu Univ | Organic semiconductor material |
-
2017
- 2017-07-28 CN CN201710629064.1A patent/CN107325017A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012001452A (en) * | 2010-06-15 | 2012-01-05 | Kyushu Univ | Organic semiconductor material |
Non-Patent Citations (4)
Title |
---|
BRYAN E. KOENE等: "Study of Energy Transfer and Triplet Exciton Diffusion in Hole-Transporting Host Materials", 《ADV. FUNCT. MATE.》 * |
JUN Y. KIM等: "Horizontal Orientation of Disk-like Hole Transport Molecules and Their Application for Organic Light-Emitting Diodes Requiring a Lower Driving Voltage", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
KYRIAKOS C. STYLIANOU等: "A Guest-Responsive Fluorescent 3D Microporous Metal-Organic Framework Derived from a Long-Lifetime Pyrene Core", 《J. AM. CHEM. SOC.》 * |
LIQING MA等: "Freeze Drying Significantly Increases Permanent Porosity and Hydrogen Uptake in 4,4-Connected Metal–Organic Frameworks", 《ANGEW. CHEM. INT. ED.》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107868018A (en) * | 2017-11-22 | 2018-04-03 | 遵义医学院 | N, N, N ', N ' four [4 (4 ' carboxyl) xenyls)] 9,10 anthradiamine synthetic methods |
CN113201144A (en) * | 2021-04-30 | 2021-08-03 | 北京科技大学 | Rigid tetracarboxyl hydrogen bond organic framework material and preparation and application thereof |
CN114163776A (en) * | 2022-01-24 | 2022-03-11 | 西南石油大学 | Epoxy resin with pressure-bearing and leakage-stopping functions and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107325017A (en) | A kind of synthetic method of 1,4 phenylenediamines of quaternary carboxylic acid N, N, N ', N ' four (4 ' carboxyl biphenyl base) | |
CN103086838A (en) | Preparation method of tetramethyl biphenyl | |
CN111454286B (en) | Synthesis method of difluoro alkenyl boron compound | |
CN108786922B (en) | Preparation method of nickel and palladium modified nano silicon dioxide for coupling reaction | |
CN108558916B (en) | Synthesis process of p-phenylbutoxy benzoic acid | |
CN103193808A (en) | Chirality zinc complex | |
CN105601472B (en) | The preparation method of new 5 [4 (1 carboxyl naphthyl)] M-phthalic acid | |
Fan et al. | Salen-type nickel (II), palladium (II) and copper (II) complexes having chiral and racemic camphoric diamine components | |
CN108947754B (en) | Use of bidentate phosphite ligands in C-F bond building reactions | |
CN105237337B (en) | The synthetic method of new 5 [10 (9 carboxyl anthryl)] M-phthalic acid | |
CN113024611B (en) | N-heterocyclic carbene cyclic palladium compound and preparation method and application thereof | |
Bai et al. | Highly regio-and stereoselective palladium-catalyzed allene bifunctionalization cascade via π-allyl intermediate | |
CN107868018A (en) | N, N, N ', N ' four [4 (4 ' carboxyl) xenyls)] 9,10 anthradiamine synthetic methods | |
JP5407332B2 (en) | Method for producing quarterpyridine derivative and its intermediate | |
CN107382756A (en) | Quaternary carboxylic acid N, N, N ', the synthetic method of N ' four (4 carboxy vinyl phenyl) 1,4 phenylenediamines | |
CN110483333A (en) | A kind of preparation method for the polycarboxylic acid organic ligand that dicyanogen methyl isophorone replaces | |
CN112441920B (en) | Method for copper photocatalytic synthesis of 9-acetoxyl-9, 10-dihydrophenanthrene compound | |
CN108484451A (en) | A kind of method that one kettle way prepares 1,2- alkamine compounds | |
CN108101831B (en) | Aromatic amine compound containing tetramethyl isoindoline or oxide structure thereof and preparation method thereof | |
CN113563270B (en) | Synthesis method of 2-bromopyrimidine | |
CN114854033B (en) | Preparation and application of Eu metal-organic framework material based on non-planar porphyrin ligand | |
CN111039849B (en) | Preparation method of carbazole ring-containing compound | |
CN113087640B (en) | Chiral ONO tridentate Schiff base carboxylic acid ligand and preparation method and application thereof | |
CN116082268B (en) | Chiral benzomorpholine compound and preparation method thereof | |
CN106946916A (en) | A kind of new method for preparing asymmetric borane reagent Bpin Bdan |
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 | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20171107 |