CN103145581B - A kind of aromatic diamine compound containing imide structure and its preparation method and application - Google Patents
A kind of aromatic diamine compound containing imide structure and its preparation method and application Download PDFInfo
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Abstract
Disclosed by the invention is a kind of aromatic diamine compound containing imide structure and its preparation method and application.Aromatic diamine compound containing imide structure of the present invention, utilize the twist structured intermediate of rigid non-planar that the high reaction activity of acyl chlorides and reactive hydrogen first obtains containing imide structure, then to be reacted from the Suzuki of boric acid ester by haloid element and introduce different chemical groups, again by p-fluoronitrobenzene and the amino product being obtained by reacting dinitrobenzene, obtain a kind of novel aromatic diamine compound containing imide structure through reduction.Synthetic method craft of the present invention is simple, purifying is easy, productive rate is higher, synthesized compound has unique fluorescent characteristic, excellent thermal characteristics and solubilized performance, both can be used as photoelectric material, also can be used as monomer for the synthesis of the contour performance polymkeric substance of novel polymeric amide, polyimide, polyamidoimide and polyester-imide simultaneously.
Description
Technical field
The present invention relates to polymer material science field, particularly a kind of aromatic diamine compound containing imide structure and its preparation method and application, this diamine compound both can be used as photoelectric material, also can be used as monomer for the synthesis of the contour performance polymkeric substance of novel polymeric amide, polyimide, polyamidoimide and polyester-imide simultaneously.
Background technology
Polyimide as a class high-performance polymer, because it has excellent thermotolerance, thermostability, high physical strength, excellent dielectric properties, good chemical-resistant, radioresistance, and there is outstanding toughness and flexibility etc., can be used as mould material, coating, jointing material, foam, fiber and advanced composite material matrix etc. are in space flight, aviation, microelectronics and military industry field are widely used application.From the sixties, E.I.Du Pont Company produces PMMI film and plastics, and the application in succession in tackiness agent, coating, foam and fiber, the research for it more and more receives publicity.
Polyimide generally first forms polyamic acid presoma by diamines and dianhydride in polar aprotic solvent, is then prepared by chemical imide method or hot imide method.But most of polyimide not only infusibility melts but also indissoluble solution, make them be difficult to processing and shaping, thus affect its using value.In addition, along with the development of microelectronics industry, the resistance toheat and dielectric properties etc. of associated materials are had higher requirement.Modern microelectronic industry is in order to reach higher integrated level, and require that chip size is more and more less, this is that the application of polyimide material in microelectronic serves great pushing effect.And the diamine monomer due to synthesis of polyimides has excellent structure designability, by introducing the functional group of difference in functionality, give the functional performance that polyimide is certain, therefore, exploitation has the novel high-performance of excellent machinability, and the polyimide of solubility becomes the important directions of polyimide research.
At present, the research for polyimide mainly concentrates on melting, the solubility property of design different structure, thermal characteristics, the synthesis of electrical property and functional new diamine or dianhydride monomer.Research for these performances also mainly concentrates on introduces fluorine element, large volume side base and cast structural and fat chain structure etc. in monomer structure.But perfect still not in the relation of systematically carrying out between Structure and Properties and its mechanism, and widen in its application yet not enough far away, therefore, be necessary to carry out research deep further in the design and synthesis diamine monomer of system.
Summary of the invention
For solving the problem, the object of this invention is to provide a kind of aromatic diamine compound containing imide structure, this diamine compound both can be used as photoelectric material, also can be used as monomer for the synthesis of the contour performance polymkeric substance of novel polymeric amide, polyimide, polyamidoimide and polyester-imide simultaneously.
Another object of the present invention is to provide the synthetic method of the above-mentioned aromatic diamine compound containing imide structure.
The present invention is achieved in that a kind of aromatic diamine compound containing imide structure, and the general structure of this compound is such as formula shown in (A), formula (B):
Wherein Ar1, Ar2 and Ar3 are hydrogen, halogen family substituting group, carbonatoms be the alkyl of 1 ~ 12, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group, nitro or aromatic substituent group, and Ar1 and Ar2 may be the same or different.
The synthetic method of the diamine compound containing imide structure of structure shown in above-mentioned formula (A), is characterized in that comprising the following steps: (1) is containing the synthesis of the imide compound of nitro structure; (2) imide compound containing nitro structure of step (1) gained is reduced to the imide compound containing amino structure; (3) by step (2) gained containing the imide compound of amino structure by the reaction with halogenated nitrobenzene, obtain the imide compound containing dinitrobenzene; (4) imide compound containing dinitrobenzene of step (3) gained is reduced to the diamine compound containing imide structure such as formula structure (A) Suo Shi.
The synthetic method of the diamine compound containing imide structure of structure shown in above-mentioned formula (B), is characterized in that comprising the following steps: (1) is containing the synthesis of the dihalo compound of imide structure; (2) by the diamine compound being reacted the amide containing structure obtained such as formula structure (B) Suo Shi containing imide structure dihalo compound and p-aminophenyl boric acid by Suzuki of step (1) gained.
Diamine compound containing imide structure of the present invention, synthetic method craft is simple, be applicable to suitability for industrialized production, the diamine compound of gained is owing to having fragrant rigid non-planar twist structure, and containing the good imide bond of thermal characteristics, therefore, there is unique fluorescent characteristic, and there is good thermostability and solubility property.This compound both can be used as photoelectric material and had used, and also can be used as monomer for the preparation of polymkeric substance such as novel high-performance poly acid amides, polyimide, polyamidoimide and polyester-imides.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the aromatic diamine compound containing imide structure of gained in embodiment of the present invention 1-3.
3450-3330cm is seen from infrared spectrogram
-1scope in there is-NH
2charateristic avsorption band, at 3020cm
-1there is the characteristic absorbance frequency of Ar-H in place, 1600cm
-1, 1530cm
-1and 1500cm
-1there is the phenyl ring stretching vibration absorption peak of feature in place, 1275cm
-1neighbouring absorption peak is the distortion shock absorption peak of Ar-H, 817cm
-1place is the characteristic absorbance frequency that contraposition two replaces Ar-H, 697cm
-1and 758cm
-1the absorption peak that place occurs is but the characteristic absorbance frequency of monosubstituted Ar-H that these all illustrate that synthesized product all has the feature structure of aromatic diamines.Wherein 1668cm
-1for C=O stretching vibration peak, 1329cm
-1near be the stretching vibration peak of phenyl ring C-N, 1230-1150cm
-1for aliphatic chain C-N stretching vibration peak, this illustrate synthesized by compound all containing imide bond.
A.1273-1326cm
-1there is the charateristic avsorption band of triphenylamine in place;
B.1173cm
-1there is stronger-CF in place
3charateristic avsorption band;
C.1336cm
-1and 1522cm
-1there is stronger nitro absorption peak in place.
Embodiment
The present invention is a kind of aromatic diamine compound containing imide structure, and the general structure of this compound is such as formula shown in (A), formula (B):
Wherein Ar1, Ar2 and Ar3 are hydrogen, halogen family substituting group, carbonatoms be the alkyl of 1 ~ 12, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group, nitro or aromatic substituent group, and Ar1 and Ar2 may be the same or different.Preferably, any one preferably in following structural of described aromatic substituent:
For the diamine compound containing imide structure shown in general structure (A), utilize reactive behavior higher between acyl chlorides and reactive hydrogen, paranitrobenzoyl chloride and pentanoic are obtained by reacting the imide compound intermediate containing nitro structure in the basic conditions; Further nitroreduction is become amido; Recycling halogenated nitrobenzene and the amino imide compound be obtained by reacting containing dinitrobenzene; Dinitrobenzene reduce further finally obtain as shown in general formula (A) containing the diamine compound of imide structure.
Wherein, the structural formula containing the imide compound of nitro structure is:
Wherein Ar1, Ar2 are hydrogen, halogen family substituting group, carbonatoms be the alkyl of 1 ~ 12, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group, nitro or aromatic substituent group, and Ar1 and Ar2 may be the same or different.
Structural formula containing the imide compound of dinitrobenzene is:
For general structure (B), utilize acyl chlorides and the high reactive behavior of reactive hydrogen, the halogenobenzoylchlorides of para-orientation and pentanoic are obtained by reacting the dihalo compound containing imide structure in the basic conditions; Above-mentioned dihalo compound reacts with p-aminophenyl boric acid the diamine compound containing imide structure obtained as shown in general formula (B) further by Suzuki.Structural formula wherein containing the dihalo compound of imide structure is:
Wherein X is chlorine, bromine or iodine; Ar3 is hydrogen, halogen family substituting group, carbonatoms are the alkyl of 1 ~ 12, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group, nitro or aromatic substituent group, and Ar1 and Ar2 may be the same or different.
Any one preferably in following structural of above-mentioned aromatic substituent:
the last obtained aromatic diamine compound containing imide structure can as the application of photoelectric material, also can as polymeric amide, polyimide, polyamidoimide or polyester-imide etc. the high-performance polymer of monomer applications in synthesizing new.
Provide example to be below described in more detail the present invention; it is important to point out that following examples can not be interpreted as the restriction to invention protection domain; some nonessential improvement and adjustment that the person skilled in the art in this field makes the present invention according to foregoing invention content, must belong to protection scope of the present invention.
The synthesis of embodiment 1:4-(Bis (4-aminophenyl) amino)-N, N-diphenylbenzamide, its structural formula is as follows:
(1) synthesis of intermediate 4-Nitro-N, N-diphenylbenzamide
Take 3.3846g(20mmol) pentanoic add in 100ml there-necked flask, add 40ml tetrahydrofuran (THF) and 2.0123ml(25mmol) pyrido pass into argon gas, 30min is stirred under cryosel bath condition, the paranitrobenzoyl chloride taking equimolar amount joins in there-necked flask in batches, stirring reaction, until temperature arrives room temperature, is warmed up to 60 DEG C of reaction more than 6h.Question response terminates rear Rotary Evaporators and solvents tetrahydrofurane is spin-dried for, and dissolves and column chromatography purification, obtain light green product 3.8g, productive rate 61% at 60 DEG C of dried in vacuo overnight with methylene dichloride.The chemical formula of this intermediate is C19H14O3N2, and molecular weight is 318.33, and its structure is as follows:
(2) synthesis of intermediate 4-Amino-N, N-diphenylbenzamide
3.8g(12mmol is added in 100ml there-necked flask) 4-Nitro-N, palladium carbon (the 10%wt of N-diphenylbenzamide and catalytic amount, Pd/C), add 50ml dehydrated alcohol and form solution, magnetic agitation also passes into argon gas, oil bath is heated to 80 DEG C, slowly be added dropwise to 4.8ml hydrazine hydrate, after back flow reaction 8h, by reaction solution suction filtration and column chromatography purify, 3.08g product is obtained, productive rate 89% at 60 DEG C of dried in vacuo overnight.The chemical formula of this intermediate is C19H14O3N2, and molecular weight is 288.34, and its structure is as follows:
（3）4-(Bis(4-nitrophenyl)amino)-N,N-diphenylbenzamide
3.08g(10.6mmol is added in 100ml there-necked flask) 4-Amino-N, N-diphenylbenzamide, 40ml screens out the dimethyl formamide (DMF) of water as solvent through 4A level molecule, add 6.49g(42.4mmol) cesium fluoride (CsF), argon gas is passed under magnetic agitation, oil bath is heated to 150 DEG C, add 4.5ml(42.4mmol again) p-fluoronitrobenzene, after back flow reaction 24h, poured into by reaction solution in icy salt solution, firmly stir and separate out yellow solid, suction filtration column chromatography are purified, 4.1g product is obtained, productive rate 73% at 60 DEG C of dried in vacuo overnight.The chemical formula of this intermediate is C31H22O5N4, and molecular weight is 530.53, and its structure is as follows:
(4) synthesis of 4-(Bis (4-aminophenyl) amino)-N, N-diphenylbenzamide
4.1g(7.73mmol is added in 100ml there-necked flask) 4-(Bis (4-nitrophenyl) amino)-N, palladium carbon (the 10%wt of N-diphenylbenzamide and catalytic amount, Pd/C), add 50ml dehydrated alcohol and form solution, magnetic agitation also passes into argon gas, oil bath is heated to 80 DEG C, slowly be added dropwise to 6.4ml hydrazine hydrate, after back flow reaction 8h, by reaction solution suction filtration and column chromatography purify, 3.31g product is obtained, productive rate 91% at 60 DEG C of dried in vacuo overnight.The fusing point of this compound is 230.5 DEG C, and 5% heat decomposition temperature is 400 DEG C, and have effect and the compacting discolouration of aggregation-induced emission, can send out two kinds of different wave length fluorescence, fluorescence emission wavelengths is respectively as 468nm and 537nm.This compound being soluble solution is in general organic solvent, and as methylene dichloride, ethyl acetate, chloroform, glycol dimethyl ether, dimethyl sulfoxide (DMSO), DMF, N,N-dimethylacetamide etc., the infrared spectrogram of compound is as shown in Fig. 1 curve a.
Embodiment 2:4-(Bis (4-aminophenyl) amino)-N, N-bis (4'-(trifluoromethyl)-[1,1'-biphenyl]-4-yl) synthesis of-benzamide, its structural formula is as follows:
(1) intermediate 4, the synthesis of 4 '-BisbromophenylAmine
Take 5g(29.6mmol) pentanoic add in 250ml there-necked flask, 50ml dimethyl formamide (DMF) is as solvent, magnetic agitation also passes into argon gas, 30min is stirred under cryosel bath condition, take 59.2mmol(10.53g) N-bromo-succinimide (NBS) be dissolved in 50mlDMF, to be added dropwise in there-necked flask and to dropwise in 30min, under cryosel bath condition, reacting 6h.To be poured into by reaction solution after question response terminates in icy salt solution firmly to stir and separate out gray solid, suction filtration also with saturated sodium bicarbonate (NaHCO3) solution washing three times, obtains 8.8g product at 60 DEG C of dried in vacuo overnight, productive rate 91%.The chemical formula of this intermediate is C12H9NBr2, and molecular weight is 327.01, and its structure is as follows:
(2) synthesis of intermediate N, N-bis (4-bromophenyl)-4-nitrobenzamide
Get 8.8g(26.9mmol) N, N-bis (4-bromophenyl)-4-nitrobenzamide adds in 250ml there-necked flask, add 50ml tetrahydrofuran (THF) and 3.1ml(40mmol) pyrido pass into argon gas, 30min is stirred under cryosel bath condition, the paranitrobenzoyl chloride taking equimolar amount joins in there-necked flask in batches, stirring reaction, until temperature arrives room temperature, is warmed up to 60 DEG C of reaction more than 6h.Question response terminates rear Rotary Evaporators and solvents tetrahydrofurane is spin-dried for, and dissolves and column chromatography purification, obtain Off-white product 8.54g, productive rate 67% at 60 DEG C of dried in vacuo overnight with methylene dichloride.The chemical formula of this intermediate is C19H12O3N2Br2, and molecular weight is 476.12, and its structure is as follows:
(3) synthesis of intermediate 4-Nitro-N, N-bis (4'-(trifluoromethyl)-[1,1'-biphenyl]-4-yl) benzamide
By 17.9mmol(8.54g) 4, 4 '-BisbromophenylAmine and 35.8mmol(6.8g) 4-(Trifluoro-methyl) phenylboronicAcid joins in 250ml there-necked flask, add 100ml tetrahydrofuran (THF) as solvent, add the solution of potassium carbonate 53.7ml of 2M again, magnetic agitation also passes into argon gas, after oil bath temperature is heated to 70 DEG C, add the tetra-triphenylphosphine palladium of catalytic amount, after back flow reaction 24h, reaction solution is spin-dried for and column chromatography purification, collect product point and obtain light green solid, product 9.8g is obtained at 60 DEG C of dried in vacuo overnight, productive rate 91%.The chemical formula of this intermediate is C33H20O3N2F6, and molecular weight is 606.51, and its structure is as follows:
(4) synthesis of intermediate 4-Amino-N, N-bis (4'-(trifluoromethyl)-[1,1'-biphenyl]-4-yl) benzamide
9.8g(16.2mmol is added in 100ml there-necked flask) 4-Nitro-N, N-bis (4'-(trifluoromethyl)-[1,1'-biphenyl]-4-yl) the palladium carbon (10%wt of benzamide and catalytic amount, Pd/C), add 50ml dehydrated alcohol and form solution, magnetic agitation also passes into argon gas, oil bath is heated to 80 DEG C, slowly be added dropwise to 6.4ml hydrazine hydrate, after back flow reaction 8h, by reaction solution suction filtration and column chromatography purify, obtain 8.1g product at 60 DEG C of dried in vacuo overnight, productive rate 87%.The chemical formula of this intermediate is C33H22ON2F6, and molecular weight is 576.53, and its structure is as follows:
(5) synthesis of intermediate 4-(Bis (4-nitrophenyl) amino)-N, N-bis (4'-(trifluoromethyl)-1,1'-biphenyl]-4-yl) benzamide
8.1g(14mmol is added in 100ml there-necked flask) 4-Amino-N, N-bis (4'-(trifluoromethyl)-[1, 1'-biphenyl]-4-yl) benzamide, 40ml screens out the dimethyl formamide (DMF) of water as solvent through 4A level molecule, add 6.38g(42mmol) cesium fluoride (CsF), argon gas is passed under magnetic agitation, oil bath is heated to 150 DEG C, add 5.9ml(56mmol again) p-fluoronitrobenzene, after back flow reaction 24h, reaction solution is poured in icy salt solution, firmly stir and separate out yellow solid, suction filtration column chromatography are purified, 8.37g product is obtained at 60 DEG C of dried in vacuo overnight, productive rate 76%.The chemical formula of this intermediate is C45H28O3N4F6, and molecular weight is 786.72, and its structure is as follows:
(6) synthesis of 4-(Bis (4-aminophenyl) amino)-N, N-bis (4'-(trifluoromethyl)-[1,1'-biphenyl]-4-yl) benz-amide
8.37g(10.6mmol is added in 100ml there-necked flask) 4-(Bis (4-nitrophenyl) amino)-N, N-bis (4 '-(trifluoromethyl)-[1,1 '-biphenyl]-4-yl) the palladium carbon (10%wt of benzamide and catalytic amount, Pd/C), add 70ml dehydrated alcohol and form solution, magnetic agitation also passes into argon gas, oil bath is heated to 80 DEG C, slowly be added dropwise to 8.6ml hydrazine hydrate, after back flow reaction 8h, by reaction solution suction filtration and column chromatography purify, obtain 6.59g product at 60 DEG C of dried in vacuo overnight, productive rate 82%.The chemical formula of this compound is C45H32ON4F6, and molecular weight is 758.75.The fusing point of this compound is 238 DEG C, and 5% heat decomposition temperature is 423 DEG C, has the effect of aggregation-induced emission, and maximum emission wavelength is 437nm.This compound being soluble solution and general organic solvent, as methylene dichloride, ethyl acetate, chloroform, glycol dimethyl ether, dimethyl sulfoxide (DMSO), DMF, N,N-dimethylacetamide etc., the infrared spectrogram of compound is as shown in Fig. 1 curve b.
The synthesis of embodiment 3:N, N-bis (4'-amino-[1,1'-biphenyl]-4-yl)-4-nitrobenzamide, its structural formula is as follows:
(1) intermediate 4, the synthesis of 4 '-BisbromophenylAmine
(2) synthesis of intermediate N, N-bis (4-bromophenyl)-4-nitrobenzamide
By the above two kinds of intermediates of method synthesis of embodiment 2.
(3) synthesis of diamine monomer N, N-bis (4'-amino-[1,1'-biphenyl]-4-yl)-4-nitrobenzamide
By 11.9g(25mmol) 4,4 '-BisbromophenylAmine and 7.53g(55mmol) p-aminophenyl borate hydrochlorate joins in 250ml there-necked flask, add 100ml tetrahydrofuran (THF) as solvent, add the solution of potassium carbonate 82.5ml of 2M again, magnetic agitation also passes into argon gas, after oil bath temperature is heated to 70 DEG C, add the tetra-triphenylphosphine palladium of catalytic amount, after back flow reaction 24h, reaction solution is spin-dried for and column chromatography purification, collect product point and obtain safran solid, obtain product 11.43g at 60 DEG C of dried in vacuo overnight, productive rate 91%.The chemical formula of this compound is C31H24N4O3, and molecular weight is 500.55.The fusing point of this compound is 233 DEG C, and 5% heat decomposition temperature is 401.56 DEG C, this compound being soluble solution and general organic solvent, as methylene dichloride, ethyl acetate, chloroform, glycol dimethyl ether, dimethyl sulfoxide (DMSO), DMF, N, N-N,N-DIMETHYLACETAMIDEs etc., the infrared spectrogram of compound is as shown in Fig. 1 curve c.
The synthesis of embodiment 4:4-(Bis (4-aminophenyl) amino)-N, N-bis (4'-(2,2-diphenylvinyl)-[1,1'-biphenyl]-4-yl) benzamide, its structural formula is as follows:
(1) intermediate 4, the synthesis of 4 '-BisbromophenylAmine
(2) synthesis of intermediate N, N-bis (4-bromophenyl)-4-nitrobenzamide
By the above two kinds of intermediates of method synthesis of embodiment 2
(3) synthesis of intermediate N, N-bis (4'-(2,2-diphenylvinyl)-[1,1'-biphenyl]-4-yl)-4-nitrobenzamide
By 20mmol(9.54g) 4,4 '-dibromo pentanoic and 40mmol(15.29g) triphenylethylene boric acid fat joins in 250ml there-necked flask, add 100ml tetrahydrofuran (THF) as solvent, add the solution of potassium carbonate 60ml of 2M again, magnetic agitation also passes into argon gas, after oil bath temperature is heated to 70 DEG C, add the tetra-triphenylphosphine palladium of catalytic amount, after back flow reaction 24h, reaction solution is spin-dried for and column chromatography purification, collect product point and obtain light yellow solid, obtain product 15.38g at 60 DEG C of dried in vacuo overnight, productive rate 93%.The chemical formula of this intermediate is C59H42O3N2, and molecular weight is 826.98, and its structure is as follows:
(4) synthesis of intermediate 4-Amino-N, N-bis (4'-(2,2-diphenylvinyl)-[1,1'-biphenyl]-4-yl) benzamide
15.38g(18.6mmol is added in 100ml there-necked flask) N, N-bis (4'-(2,2-diphenylvinyl)-[1,1'-biphenyl]-4-yl) the palladium carbon (10%wt of-4-nitrobenzamide and catalytic amount, Pd/C), add 100ml dehydrated alcohol and form solution, magnetic agitation also passes into argon gas, oil bath is heated to 80 DEG C, slowly be added dropwise to 7.44ml hydrazine hydrate, after back flow reaction 8h, by reaction solution suction filtration and column chromatography purify, 12g product is obtained, productive rate 81% at 60 DEG C of dried in vacuo overnight.The chemical formula of this intermediate is C59H44ON2, and molecular weight is 796.99, and its structure is as follows:
(5) synthesis of 4-(Bis (4-nitrophenyl) amino)-N, N-bis (4'-(2,2-diphenylvinyl)-[1,1'-biphenyl]-4-yl) benz-amide
12g(15mmol is added in 100ml there-necked flask) 4-Amino-N, N-bis (4'-(2, 2-diphenylvinyl)-[1, 1'-biphenyl]-4-yl) benzamide, 60ml screens out the dimethyl formamide (DMF) of water as solvent through 4A level molecule, add 9.144g(60mmol) cesium fluoride (CsF), argon gas is passed under magnetic agitation, oil bath is heated to 150 DEG C, add 6.4ml(60mmol again) p-fluoronitrobenzene, after back flow reaction 24h, reaction solution is poured in icy salt solution, firmly stir and separate out yellow solid, suction filtration column chromatography are purified, 11.22g product is obtained at 60 DEG C of dried in vacuo overnight, productive rate 72%.The chemical formula of this intermediate is C71H50O5N4, and molecular weight is 1039.18, and its structure is as follows:
(6) synthesis of 4-(Bis (4-aminophenyl) amino)-N, N-bis (4'-(2,2-diphenylvinyl)-[1,1'-biphenyl]-4-yl) benz-amide
11.22g(10.8mmol is added in 250ml there-necked flask) 4-(Bis (4-nitrophenyl) amino)-N, N-bis (4'-(2,2-diphenylvinyl)-[1,1'-biphenyl]-4-yl) the palladium carbon (10%wt of benzamide and catalytic amount, Pd/C), add 150ml dehydrated alcohol and form solution, magnetic agitation also passes into argon gas, oil bath is heated to 80 DEG C, slowly be added dropwise to 8.2ml hydrazine hydrate, after back flow reaction 8h, by reaction solution suction filtration and column chromatography purify, 8.35g product is obtained, productive rate 79% at 60 DEG C of dried in vacuo overnight.The chemical formula of this compound is C71H54ON4, and molecular weight is 979.21.
The synthesis of embodiment 5:4-(Bis (4-aminophenyl) amino)-N, N-bis (4'-tetraphenylvinyl) benzamide, its structural formula is as follows:
(1) intermediate 4, the synthesis of 4 '-BisbromophenylAmine
(2) synthesis of intermediate N, N-bis (4-bromophenyl)-4-nitrobenzamide
By the above two kinds of intermediates of method synthesis of embodiment 2.
(3) synthesis of intermediate 4-Nitro-N, N-bis (4'-(1,2,2-triphenylvinyl)-[1,1'-biphenyl]-4-yl) benzamide
By 9.54g(20mmol) 4,4 '-BisbromophenylAmine and 40mmol(18.34g) tetraphenyl ethylene boric acid fat joins in 500ml there-necked flask, add 200ml tetrahydrofuran (THF) as solvent, add the solution of potassium carbonate 60ml of 2M again, magnetic agitation also passes into argon gas, after oil bath temperature is heated to 70 DEG C, add the tetra-triphenylphosphine palladium of catalytic amount, after back flow reaction 24h, reaction solution is spin-dried for and column chromatography purification, collect product point and obtain light yellow solid, obtain product 17.43g at 60 DEG C of dried in vacuo overnight, productive rate 89%.The chemical formula of this intermediate is C71H50O3N2, and molecular weight is 979.17, and its structure is as follows:
(4) synthesis of intermediate 4-Amino-N, N-bis (4'-(1,2,2-triphenylvinyl)-[1,1'-biphenyl]-4-yl) benzamide
17.43g(17.8mmol is added in 250ml there-necked flask) 4-Nitro-N, N-bis (4'-(1,2,2-triphenylvinyl)-[1,1'-biphenyl]-4-yl) the palladium carbon (10%wt of benzamide and catalytic amount, Pd/C), add 150ml dehydrated alcohol and form solution, magnetic agitation also passes into argon gas, and oil bath is heated to 80 DEG C, is slowly added dropwise to 7.12ml hydrazine hydrate, after back flow reaction 8h, by reaction solution suction filtration and column chromatography purify, obtain 13g product at 60 DEG C of dried in vacuo overnight, productive rate 77%.The chemical formula of this intermediate is C71H52ON2, and molecular weight is 949.19, and its structure is as follows:
(5) 4-(Bis (4-aminophenyl) amino)-N, N-bis (4'-(1,2,2-triphenylvinyl)-[1,1'-biphenyl]-4-yl)-benzamide synthesizes
13g(13.7mmol is added in 100ml there-necked flask) 4-(Bis (4-nitrophenyl) amino)-N, N-bis (4'-(1, 2, 2-triphenylvinyl)-[1, 1'-biphenyl]-4-yl) benzamide, 70ml screens out the dimethyl formamide (DMF) of water as solvent through 4A level molecule, add 9.144g(41.1mmol) cesium fluoride (CsF), argon gas is passed under magnetic agitation, oil bath is heated to 150 DEG C, add 6.24ml(60mmol again) p-fluoronitrobenzene, after back flow reaction 24h, reaction solution is poured in icy salt solution, firmly stir and separate out yellow solid, suction filtration column chromatography are purified, 11.425g product is obtained at 60 DEG C of dried in vacuo overnight, productive rate 70%.The chemical formula of this intermediate is C83H58O5N4, and molecular weight is 1191.37, and its structure is as follows:
（6）4-(Bis(4-aminophenyl)amino)-N,N-bis(4'-(1,2,2-triphenylvinyl)-[1,1'-biphenyl]-4-yl)-benzamide
11.425g(9.6mmol is added in 250ml there-necked flask) 4-(Bis (4-nitrophenyl) amino)-N, N-bis (4'-(1,2,2-triphenylvinyl)-[1,1'-biphenyl]-4-yl) the palladium carbon (10%wt of benzamide and catalytic amount, Pd/C), add 150ml dehydrated alcohol and form solution, magnetic agitation also passes into argon gas, and oil bath is heated to 80 DEG C, is slowly added dropwise to 8ml hydrazine hydrate, after back flow reaction 8h, by reaction solution suction filtration and column chromatography purify, obtain 8.9g product at 60 DEG C of dried in vacuo overnight, productive rate 82%.The chemical formula of this compound is C83H62ON4, and molecular weight is 1131.41.
The synthesis of embodiment 6:N, N-bis (4'-amino-[1,1'-biphenyl]-4-yl)-Triphenylethylenebenzamide, its structural formula is as follows:
(1) intermediate 4, the synthesis of 4 '-BisbromophenylAmine
By synthetic method synthesis (1) monomer in embodiment 2.
(2) synthesis of intermediate 4-(Bromomethyl)-N, N-bis (4-bromophenyl) benzamide
Get 9.81g(30mmol) 4,4 '-BisbromophenylAmine adds in 250ml there-necked flask, add 50ml tetrahydrofuran (THF) and 40mmol(3.2ml) pyrido pass into argon gas, 30min is stirred under cryosel bath condition, the paranitrobenzoyl chloride taking equimolar amount joins in there-necked flask in batches, stirring reaction, until temperature arrives room temperature, is warmed up to 60 DEG C of reaction more than 6h.Question response terminates rear Rotary Evaporators and solvents tetrahydrofurane is spin-dried for, and dissolves and column chromatography purification, obtain oyster product 9.59g, productive rate 61% at 60 DEG C of dried in vacuo overnight with methylene dichloride.The chemical formula of this intermediate is C20H14Br3ON, and molecular weight is 524.04, and its structure is as follows:
(3) synthesis of intermediate N, N-bis (4-bromophenyl)-Triphenylethylenebenzamide
Get 4-(the Bromomethyl)-N of 9.59g (18.3mmol), N-bis (4-bromophenyl) benzamide adds in 250ml there-necked flask, add 54.9mmol(9.5ml) triethyl-phosphite, pass into argon gas and whipping temp be heated to 150 DEG C reaction 24h, room temperature is down to after reaction terminates, add 2.9g (16mmol) benzophenone and tetrahydrofuran (THF) 50ml, 18h is reacted under room temperature, question response terminates rear Rotary Evaporators and solvents tetrahydrofurane is spin-dried for, dissolve with methylene dichloride and column chromatography purification, light green product 8.38g is obtained at 60 DEG C of dried in vacuo overnight, productive rate 86%.The chemical formula of this intermediate is C33H23Br2ON, and molecular weight is 609.35, and its structure is as follows:
(4) synthesis of N, N-bis (4'-amino-[1,1'-biphenyl]-4-yl)-Triphenylethylenebenzamide
By 8.38g(13.76mmol) N, N-bis (4-bromophenyl)-Triphenylethylenebenzamide and 4.1g(30mmol) p-aminophenyl borate hydrochlorate joins in 250ml there-necked flask, add 100ml tetrahydrofuran (THF) as solvent, add the solution of potassium carbonate 15ml of 2M again, magnetic agitation also passes into argon gas, after oil bath temperature is heated to 70 DEG C, add the tetra-triphenylphosphine palladium of catalytic amount, after back flow reaction 24h, reaction solution is spin-dried for and column chromatography purification, collect product point and obtain light green solid, product 7.9g is obtained at 60 DEG C of dried in vacuo overnight, productive rate 91%.The chemical formula of this compound is C45H35ON3, and molecular weight is 633.78.
Claims (6)
1., containing an aromatic diamine compound for imide structure, the general structure of this compound is such as formula shown in (A):
Wherein Ar1, Ar2 are hydrogen or aromatic substituent group, and Ar1 and Ar2 may be the same or different, this aromatic substituent group be selected from following structural any one:
2. contain the synthetic method of the aromatic diamine compound of imide structure described in claim 1, it is characterized in that comprising the following steps:
(1) containing the synthesis of the imide compound of nitro structure;
(2) imide compound containing nitro structure of step (1) gained is reduced to the imide compound containing amino structure;
(3) by step (2) gained containing the imide compound of amino structure by the reaction with halogenated nitrobenzene, obtain the imide compound containing dinitrobenzene;
(4) imide compound containing dinitrobenzene of step (3) gained is reduced to the diamine compound containing imide structure such as formula structure (A) Suo Shi.
3. the synthetic method of the aromatic diamine compound containing imide structure according to claim 2, is characterized in that the structural formula of the imide compound containing nitro structure in described step (1) is:
Wherein Ar1, Ar2 are hydrogen or aromatic substituent group, and Ar1 and Ar2 may be the same or different, aromatic substituent group be selected from following structural any one:
4. the synthetic method of the aromatic diamine compound containing imide structure according to claim 2, is characterized in that the structural formula of the imide compound containing dinitrobenzene in described step (3) is:
5. described in claim 1, contain the application of aromatic diamine compound as photoelectric material of imide structure.
6. described in claim 1 containing the aromatic diamine compound of imide structure as monomer applications in synthesizing polyamides, polyimide, polyamidoimide or polyester-imide.
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| Musubu Ichikawa等.Solution-processable dendric triphenylamine nonamers as hole-transporting and hole-injection materials for organic light-emitting devices.《synthetic mttals》.2006,第156卷(第21-24期), * |
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