CN106243125B - A kind of Molecular orbit compound and its synthetic method - Google Patents
A kind of Molecular orbit compound and its synthetic method Download PDFInfo
- Publication number
- CN106243125B CN106243125B CN201610618687.4A CN201610618687A CN106243125B CN 106243125 B CN106243125 B CN 106243125B CN 201610618687 A CN201610618687 A CN 201610618687A CN 106243125 B CN106243125 B CN 106243125B
- Authority
- CN
- China
- Prior art keywords
- alkyl
- benzene amine
- bromo
- alkyl benzene
- quinone
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of Molecular orbit compound and its synthetic methods shown in formula (1), belong to organic synthesis field.The dyestuff wants raw material based on iodo aniline, reacts and is made with four halobenzene quinones again after alkylation, bromination.Compared with original similar Molecular orbit dyestuff, it is at room temperature liquid that not only bright in colour and stability is good for the dyestuff, superior solubility, this guarantees there is better effects for the application effect and final product quality that improve dyestuff；Meanwhile the dyestuff is stable heterocycle conjugated system, planes of molecules is symmetrical, and thermal stability is good, and hole mobility is up to 1E10‑6cm2V‑1s‑1More than, there is preferable charge transport ability, can be applied to the fields such as Organic Light Emitting Diode, organic semiconductor.
Description
Technical field
The present invention relates to a kind of Molecular orbit compound and its synthetic methods, belong to organic synthesis field.
Background technique
Molecular orbit compound is linear five yuan of a symmetrical plane be made of three phenyl ring and two oxazines heterocycles
Heterocyclic system structure, parent are dioxygen acridine structure, are containing 4 heteroatomic donor-acceptor chromogen systems, electronics
Probability from ground state transition to excitation state is more much larger than the heterocycle for containing only single oxygen acridine, thus contains in visible light region
Stronger n- π absorption band, can be used as the chromogen of reactive dye, fluorescent dye, laser dye, photoelectric conversion dyestuff etc..
It is well known that the heterocyclic molecular with plane structure pi-conjugated greatly has preferable stability, and its it is big pi-conjugated and
The pi-conjugated track of p- can undertake charge transformation task, and the hole transport with high thermal stability is often used as in electroluminescent field
Material can be used as the charge-conduction material in the photosensitizer and photoelectric device in solar battery, with photoelectric device and
The further development of organic semiconducting materials, requirement to molecular structure are continuously improved, and develop that dissolubility is good, filming performance is excellent
Different new type heterocycle conjugated structure compound, and it is further studied in the application in the fields such as photoelectricity, organic field effect tube
More and more paid attention to, is also always the hot spot of researcher concern in recent ten years.Molecular orbit class at present
The research for closing object is only limited to have the powder product of aqueous substituent group, in organic solvent without dissolubility, film forming official post its nothing
Method is for making photoelectricity and organic semiconductor device.
Research of the Molecular orbit compound in electroluminescent material field yet there are no pertinent literature report.
Summary of the invention
In view of the above-mentioned problems, it is an object of that present invention to provide one kind, dissolubility is good in organic solvent, stability is high, and can
It is used to prepare the Molecular orbit compound of electroluminescent material.
Molecular orbit compound of the present invention, structural formula are as follows:
Wherein: the halogens such as X Cl, Br, I；R is any position C12-50 alkyl；Entire molecule is centrosymmetric structure.
It is preferred that: X Cl；R is alkyl of any position C12-42 containing branch；Entire molecule is centrosymmetric structure.
It is preferred that: X Cl；R is alkyl of any position C16-42 containing branch；Entire molecule is centrosymmetric structure.
It is preferred that compound specific as follows: A:X Cl；R is the C12 alkyl of 2 substitutions；
B:X is Cl；R is the C16 alkyl of 2 substitutions；
C:X is Br；R is the C16 alkyl of 3 substitutions；
D:X is Cl；R is the C24 alkyl of 2 substitutions；
E:X is Cl；R is the C41 alkyl of 2 substitutions.
The preparation method of the Molecular orbit compound is specific as follows:
(1) preparation of Grignard Reagent: brominated alkanes are diluted with anhydrous tetrahydro furan and stand-by after mixing.At three mouthfuls
Magnesium chips, anhydrous tetrahydro furan and iodine are added in flask, the anhydrous tetrahydro of brominated alkanes is added dropwise under nitrogen protection and magnetic agitation
Tetrahydrofuran solution is added dropwise, then system is warming up to 78 DEG C -80 DEG C and is heated to reflux obtained Grignard Reagent, and Grignard Reagent is down to
It is stand-by after room temperature.
(2) synthesis of alkyl benzene amine: iodo aniline is dissolved in anhydrous tetrahydro furan, adds [1,1'- bis- (diphenyl
Phosphino-) ferrocene] palladium chloride, it is passed through nitrogen and system is cooled to -78 DEG C--80 DEG C, step (1) is added under stirring
Grignard Reagent obtained is reacted, then system is warmed to room temperature, and the reaction was continued, aqueous hydrochloric acid solution quenching reaction is added, through extracting
Take, wash, drying, obtaining intermediate product after purification through silica gel chromatographic column --- alkyl benzene amine.
(3) synthesis of bromo alkyl benzene amine: by alkyl benzene amine, bromo-succinimide, NaHSO4/SiO2Immobilized acid, dispersion
In CH3OH/CH3In the solvent of CN (v/v=1:3).React at room temperature, TLC monitor end of reaction, through extraction, washing, drying,
Intermediate product is obtained after purification through silica gel chromatographic column --- bromo alkyl benzene amine.
(4) synthesis of Molecular orbit compound: being added bromo alkyl benzene amine, four halobenzene quinones and sodium carbonate in reaction flask,
Then o-dichlorohenzene is added, be uniformly mixed and is reacted at 40 DEG C -50 DEG C, TLC monitoring is added after completion of the reaction to toluene sulphur
Acyl chlorides reacts at 165 DEG C -170 DEG C, system is placed under oil bath removes solvent after reaction, after purification through silica gel chromatographic column
Molecular orbit compound can be obtained.
The invention has the benefit that (1) Molecular orbit compound is planar rigidity symmetrical structure, thermal stability is good,
Dissolubility is good, good film-forming property；(2) compound has preferable charge transport ability, and hole mobility is up to 1E10-6cm2V- 1s-1, can be applied to Organic Light Emitting Diode, organic semiconductor field, and can be used as polymer semiconductor after further polymerizeing
Material has broad application prospects；(3) preparation method is simple, convenient for operation, is easy to industrialize.
The preparation of immobilized acid is synthesized referring to the method for bibliography 1 in step (3): [1] Gary
W.Breton.Selective Monoacetylation of Unsymmetrical Diols Catalysed by Silica
Gel-Supported Sodium Hydrogen Sulfate[J].J.Org.Chem.1997,62,8952-8954。
Specific implementation method
It is as follows for embodiment to be better illustrated to the present invention:
Embodiment 1
(1) preparation of bromododecane Grignard Reagent: by 49.348g, the bromododecane 50mL anhydrous four of 198mmol
The dilution of hydrogen furans is simultaneously stand-by after mixing.5.703g, the anhydrous tetrahydro furan of 238mmol magnesium chips, 100mL are added in three-necked flask
It mutters and three iodine, the anhydrous tetrahydrofuran solution of bromododecane, about 30~40min is added dropwise under nitrogen protection and magnetic agitation
Be added dropwise, then system is warming up to 78 DEG C is heated to reflux after 1~2h and Grignard Reagent is made, by Grignard Reagent be cooled to room temperature to
With.
(2) synthesis of 2- dodecyl polyaniline: by 13.142g, 60mmol2- Iodoaniline is dissolved in 60mL anhydrous tetrahydro furan
In, 0.439g is added, 0.6mmol [1,1'- bis- (diphenylphosphino) ferrocene] palladium chloride is passed through nitrogen and drops system
54.161g is added to -78 DEG C in temperature under stirring, 198mmol bromododecane Grignard Reagent, again will after reacting 1h at -78 DEG C
System is warmed to room temperature, the reaction was continued for 24 hours be added mass percent 5% aqueous hydrochloric acid solution quench reaction, through extraction, washing, do
It is dry, obtain intermediate product after purification through silica gel chromatographic column --- 2- dodecyl polyaniline (7.87g, yield 50%).
Light yellow liquid；1H NMR(400MHz,CDCl3)δ:0.92-0.89(t,3H,-CH 3),1.29(m,
18H),1.67-1.60(m,2H),2.53-2.49(t,2H),3.62(s,2H,-NH), 6.71-6.69 (d, J=1.6Hz, J=
7.6Hz, 1H), 6.77-6.74 (t, J=14.8Hz, 1H), 7.07-7.04 (d, J=15.6Hz, 2H)13C NMR(100MHz,
CDCl3)δ:14.15,22.72,28.78,29.39,29.60,29.66,29.71,29.75,31.34,31.96,115.52,
118.73,126.82,126.99,129.43,144.05.
(3) synthesis of 4- bromododecane alkyl benzene amine: by 5.24g, 20mmol2- dodecane alkyl benzene amine, 3.738g,
21mmol bromo-succinimide, 360mg, 2mmol NaHSO4/SiO2Immobilized acid be dissolved in 40mL CH3OH/CH3CN (v/v=
In solvent 1:3), at room temperature react 12~14h, TLC monitor end of reaction, through extraction, washing, drying, through silica gel chromatograph
Intermediate product is obtained after column purification --- 4- bromo 2- dodecyl polyaniline (4.272g, yield 63%).
Light yellow liquid；1H NMR(400MHz,CDCl3) δ: 0.92-0.89 (t, J=7.2Hz, 14.6Hz,
3H), 1.31 (s, 18H), 1.66-1.58 (m, 2H), 2.47-2.43 (t, J=8.0Hz, 16.0Hz, 2H), 3.63 (s, 2H ,-
), NH 6.57-6.55 (d, J=8.4Hz, J=7.6Hz, 1H), 7.15-7.12 (dd, J=2.0Hz, 8.4Hz, 1H), 7.18-
7.17 (d, J=2.0Hz, 1H)13C NMR(100MHz,CDCl3)δ:14.17,22.74,28.49,29.40,29.55,
29.62,29.64,29.68,29.70,29.71,31.14,31.96,110.39,116.94,129.10,129.43,131.84,
143.14.
(4) 3.404g, 10.0mmol 4- bromo 2- dodecane the synthesis of Molecular orbit compound: are added in reaction flask
Then 30mL o-dichlorohenzene, mixing is added in base aniline, the tetrachloroquinone of 1.23g, 5.0mmol, 1.272g, 12mmol sodium carbonate
2h is reacted uniformly and at 40 DEG C, TLC is monitored adds 2.292g after completion of the reaction, 12mmol paratoluensulfonyl chloride, at 165 DEG C
Molecular orbit is can be obtained into through silica gel chromatographic column as solvent is removed under 110 DEG C of oil baths in system after purification after reaction 3h
Composition powder (0.679g, yield 16%).
Purple solid；1H NMR(400MHz,CDCl3) δ: 0.85-0.81 (t, J=8.0Hz, 14.6Hz, 6H),
1.25-1.09 (m, 36H), 1.65-1.56 (m, 4H), 2.46-2.40 (t, J=8.0Hz, 16.0Hz, 4H), 6.71-6.65 (d,
J=8.4Hz, J=7.6Hz, 2H), 7.16-7.14 (d, J=2.0Hz, 8.4Hz, 2H)13C NMR(100MHz,CDCl3)δ:
14.15,22.70,28.44,29.39,29.50,29.60,29.60,29.65,29.70,29.71,31.14,31.96,
109.31,119.02,122.34,128.47,132.38,135.32,136.39,140.73,164.16.
Embodiment 2
(1) preparation of bromohexadecane Grignard Reagent: by 57.463g, the bromohexadecane 50mL anhydrous four of 198mmol
The dilution of hydrogen furans is simultaneously stand-by after mixing.5.703g, the anhydrous tetrahydro furan of 238mmol magnesium chips, 100mL are added in three-necked flask
It mutters and three iodine, the anhydrous tetrahydrofuran solution of bromohexadecane, about 30~40min is added dropwise under nitrogen protection and magnetic agitation
Be added dropwise, then system is warming up to 78 DEG C is heated to reflux after 1~2h and Grignard Reagent is made, by Grignard Reagent be cooled to room temperature to
With.
(2) synthesis of hexadecane aniline: by 13.142g, 60mmol 2- Iodoaniline is dissolved in 60mL anhydrous tetrahydro furan,
0.439g is added, 0.6mmol [1,1'- bis- (diphenylphosphino) ferrocene] palladium chloride is passed through nitrogen and system cools down
To -78 DEG C, it is added 62.276g under stirring, 198mmol bromohexadecane Grignard Reagent is reacted at -78 DEG C after 1h again by body
System is warmed to room temperature, the reaction was continued for 24 hours be added mass percent 5% aqueous hydrochloric acid solution quench reaction, through extraction, washing, drying,
Intermediate product is obtained after purification through silica gel chromatographic column --- 2- hexadecylaniline (9.42g, yield 49%).
Light yellow liquid；1H NMR(400MHz,CDCl3)δ:0.91-0.89(t,3H,-CH 3),1.27(m,
26H,-(CH 2)13CH3),1.66-1.60(m,2H,-CH2CH2 (CH2)9CH3), 2.52-2.49 (t, J=15.6Hz, 2H ,-
CH 2CH 2 (CH2)9CH3),3.62(s,2H,-NH), 6.71-6.68 (d, J=1.6Hz, J=7.6Hz, 1H), 6.76-6.74 (t, J
=14.8Hz, 1H), 7.06-7.04 (d, J=15.6Hz, 2H)13C NMR(100MHz,CDCl3)δ:14.14,22.70,
23.14,26.62,27.15,28.75,29.36,29.60,29.62,29.70,29.71,31.32,31.93,115.51,
118.72,126.80,126.97,129.40,144.04.
(3) synthesis of 4- bromohexadecane base aniline: by 6.4g, 20mmol2- hexadecane alkyl benzene amine, 3.738g,
21mmol bromo-succinimide, 360mg 2mmol NaHSO4/SiO2Immobilized acid be dissolved in 100mL CH3OH/CH3CN(v/v
=1:3) solvent in, at room temperature react 12~14h, TLC monitor end of reaction, through extraction, washing, drying, through silica gel color
Intermediate product is obtained after spectrum column purification --- 4- bromo -2- hexadecylaniline (4.87g, yield 61%).
Light yellow liquid；1H NMR(400MHz,CDCl3) δ: 0.90-0.89 (t, J=7.2Hz, 14.6Hz,
3H,-CH 3),1.31(s,26H,-(CH 2)9CH3),1.64-1.58(m,2H,-CH2CH 2(CH2)9CH3), 2.45-2.41 (t, J=
8.0Hz,16.0Hz,2H),-CH 2CH2(CH2)9CH3), 3.63 (s, 2H ,-NH), 6.57-6.54 (d, J=8.4Hz, J=
7.6Hz, 1H), 7.13-7.10 (dd, J=2.0Hz, 8.4Hz, 1H), 7.16-7.15 (d, J=2.0Hz, 1H)13C NMR
(100MHz,CDCl3)δ:14.14,22.69,23.14,26.62,27.14,28.72,29.36,29.61,29.63,29.70,
29.71,31.35,31.97,115.51,118.72,126.80,126.97,129.40,144.04.
(4) 3.995g, 10.0mmol4- bromo -2- hexadecane the synthesis of Molecular orbit compound: are added in reaction flask
Base aniline, the tetrachloroquinone of 1.23g, 5.0mmol, 1.272g, 12mmol sodium carbonate, 30mL o-dichlorohenzene are added separately to
In the round-bottomed flask of 100mL, it is uniformly mixed and reacts at 40 DEG C 2h, TLC monitoring adds 2.292g after completion of the reaction,
12mmol paratoluensulfonyl chloride reacts system at 165 DEG C after 3h as solvent is removed under 110 DEG C of oil baths, through silica gel chromatographic column
Molecular orbit compound products (0.577g, yield 12%) can be obtained after purification.
Purple solid；1H NMR(400MHz,CDCl3) δ: 0.84-0.81 (t, J=8.0Hz, 14.6Hz, 6H ,-
CH 3),1.25-1.09(m,52H),1.65-1.54(m,4H,-CH2CH 2(CH2)9CH3), 2.44-2.40 (t, J=8.0Hz,
16.0Hz,4H,-CH 2CH2(CH2)9CH3), 6.72-6.65 (d, J=8.4Hz, J=7.6Hz, 2H), 7.15-7.14 (d, J=
2.0Hz,8.4Hz,2H).13C NMR(100MHz,CDCl3)δ:14.15,22.67,23.14,26.59,27.13,28.74,
29.33,29.61,29.65,29.71,29.76,31.38,31.97,109.11,119.08,122.54,128.46,132.28,
135.34,136.31,140.76,164.15.
Embodiment 3
(1) preparation of 4- bromohexadecane Grignard Reagent: by 30.229g, the 4- bromohexadecane of 99mmol with 30mL without
The dilution of water tetrahydrofuran is simultaneously stand-by after mixing.2.856g, 119mmol magnesium chips, 60mL anhydrous four are added in three-necked flask
Hydrogen furans and three iodine, the anhydrous tetrahydrofuran solution of dropwise addition 4- bromohexadecane under nitrogen protection and magnetic agitation, about 30
~40min is added dropwise, then system is warming up to 78 DEG C is heated to reflux after 1~2h and Grignard Reagent is made, and Grignard Reagent is down to
It is stand-by after room temperature.
(2) synthesis of 3- (4- cetyl) aniline: by 6.56g, 30mmol3- Iodoaniline is dissolved in the anhydrous tetrahydro furan of 60mL
In muttering, 0.220g is added, 0.3mmol [1,1'- bis- (diphenylphosphino) ferrocene] palladium chloride is passed through nitrogen and by system
- 78 DEG C are cooled to, is added 32.635g under stirring, 99mmol 4- bromohexadecane Grignard Reagent, after reacting 1h at -78 DEG C
System is warmed to room temperature again, the reaction was continued for 24 hours be added mass percent 5% aqueous hydrochloric acid solution quench reaction, extracted, washed
Wash, dry, obtaining intermediate product after purification through silica gel chromatographic column --- 3- (4- cetyl) aniline (4.876g, yield
41%).
Light yellow liquid；1H NMR(400MHz,CDCl3)δ:0.91-0.88(t,6H),1.25-1.31(m,
22H),1.60-1.58(m,4H),2.76-2.65(m,1H),3.61(s,2H,-NH), 6.72-6.68 (d, J=1.6Hz, J=
7.6Hz, 1H), 6.73-6.69 (t, J=14.8Hz, 1H), 7.02-7.16 (d, J=15.6Hz, 2H)13C NMR(100MHz,
CDCl3)δ:14.14,14.42,20.15,22.70,27.10,29.32,29.60,29.92,31.93,36.35,39.77,
116.51,118.52,126.70,127.97,128.40,145.04.
(3) synthesis of the bromo- 3- of 4- (4- cetyl) aniline: by 3.176g, 10mmol 3- (4- cetyl) aniline,
1.869g, 10.5mmol bromo-succinimide, 180mg, 1mmol NaHSO4/SiO2Immobilized acid be dissolved in 60mL CH3OH/
CH3In the solvent of CN (v/v=1:3), at room temperature react 12~14h, TLC monitor end of reaction, through extraction, washing, drying,
Intermediate product is obtained after purification through silica gel chromatographic column --- the bromo- 3- of 4- (4- cetyl) aniline (2.34g, yield 59%).
Light yellow liquid；1H NMR(400MHz,CDCl3)δ:0.90-0.88(t,6H),1.25-1.33(m,
22H),1.60-1.58(m,4H,),2.76-2.70(m,1H),3.62(s,2H,-NH), 6.46-6.41 (d, J=1.6Hz, J=
7.6Hz, 1H), 7.17-7.14 (t, J=14.8Hz, 1H), 7.20-7.16 (d, J=15.6Hz, 1H)13C NMR(100MHz,
CDCl3)δ:14.15,14.41,20.16,22.71,27.08,29.32,29.60,29.93,31.93,36.35,39.77,
106.51,118.32,129.20,129.67,131.40,144.54.
(4) 1.982g, 5.0mmol 4- bromo- 3- (4- hexadecane the synthesis of Molecular orbit compound: are added in reaction flask
Base) aniline, the tetrabromo-quinone of 0.62g, 2.5mmol, 0.636g, 6.0mmol sodium carbonate, 20mL o-dichlorohenzene is added separately to
In the round-bottomed flask of 100mL, it is uniformly mixed and reacts at 40 DEG C 2h, TLC monitoring adds 1.146g after completion of the reaction,
6.0mmol paratoluensulfonyl chloride reacts system at 165 DEG C after 3h as solvent is removed under 110 DEG C of oil baths, through silica gel chromatographic column
Molecular orbit compound products (0.475g, yield 18%) can be obtained after purification.
Purple solid；1H NMR(400MHz,CDCl3)δ:0.91-0.88(t,12H),1.25-1.33(m,44H),
1.60-1.58(m,8H,),2.76-2.70(m,2H),7.04(s,2H),7.0 6(s,2H).13C NMR(100MHz,CDCl3)
δ:14.15,14.41,20.16,22.71,27.08,29.32,29.60,29.93,31.93,36.35,39.77,109.15,
119.02,122.64,128.47,132.18,135.31,136.37,140.77,164.16
Embodiment 4
(1) preparation of 6- bromo lignocerane Grignard Reagent: the 6- bromo lignocerane of 41.283g, 99mmol are used
The dilution of 30mL anhydrous tetrahydro furan is simultaneously stand-by after mixing.2.856g, 119mmol magnesium chips, 80mL are added in three-necked flask
Anhydrous tetrahydro furan and three iodine, the anhydrous tetrahydro furan that 6- bromo lignocerane is added dropwise under nitrogen protection and magnetic agitation are molten
Liquid, about 30~40min are added dropwise, then system is warming up to 78 DEG C is heated to reflux after 1~2h and Grignard Reagent is made, and grignard is tried
Agent is cooled to room temperature for use.
(2) synthesis of 2- (6- tetracosyl) aniline: by 6.56g, 30mmol 2- Iodoaniline is dissolved in 100mL anhydrous four
In hydrogen furans, 0.220g is added, 0.3mmol [1,1'- bis- (diphenylphosphino) ferrocene] palladium chloride is passed through nitrogen and incites somebody to action
System is cooled to -78 DEG C, addition 43.744g 99mmol 6- bromo lignocerane Grignard Reagent under stirring, anti-at -78 DEG C
System is warmed to room temperature again after answering 1h, the reaction was continued for 24 hours be added mass percent 5% aqueous hydrochloric acid solution quench reaction, through extracting
Take, wash, drying, obtaining intermediate product after purification through silica gel chromatographic column --- (4.641g is received 2- (6- tetracosyl) aniline
Rate 36%).
Light yellow liquid；1H NMR(400MHz,CDCl3)δ:0.91-0.88(t,6H,-CH 3),1.29-
1.24(m,38H),1.60-1.58(m,4H,),2.76-2.65(m,1H),3.63(s,2H,-NH), 6.72-6.70 (d, J=
1.6Hz, J=7.6Hz, 1H), 6.73-6.68 (t, J=14.8Hz, 1H), 7.02-7.16 (d, J=15.6Hz, 2H)13C NMR
(100MHz,CDCl3)δ:14.14,22.70,27.10,29.32,29.60,29.92,31.93,32.15,36.35,39.77,
116.51,118.52,126.70,127.97,128.40,145.04.
(3) synthesis of the bromo- 2- of 3- (6- tetracosyl) aniline: by 4.298g, 10mmol 2- (6- tetracosyl) benzene
Amine, 1.869g, 10.5mmol bromo-succinimide, 180mg, 1mmol NaHSO4/SiO2Immobilized acid be dissolved in 60mL
CH3OH/CH3In the solvent of CN (v/v=1:3), at room temperature react 12~14h, TLC monitor end of reaction, through extraction, washing,
Drying obtains intermediate product through silica gel chromatographic column after purification --- the bromo- 2- of 3- (6- tetracosyl) aniline (2.594g, yield
51%).
Light yellow liquid；1H NMR(400MHz,CDCl3)δ:0.89-0.88(t,6H),1.29-1.25(m,
38H),1.61-1.59(m,4H,),2.75-2.73(m,1H),3.65(s,2H,-NH), 6.44-6.26 (d, J=1.6Hz, J=
7.6Hz, 1H), 7.17-7.10 (t, J=14.8Hz, 1H), 7.20-7.18 (d, J=15.6Hz, 1H)13C NMR(100MHz,
CDCl3)δ:14.14,22.70,27.13,29.31,29.62,29.92,31.93,32.15,36.32,39.37,107.91,
118.62,129.20,129.67,131.40,145.04.
(4) 2.543g, the bromo- 2- of 5.0mmol 3- (6- 24 synthesis of Molecular orbit compound: are added in reaction flask
Alkyl) aniline, the tetrachloroquinone of 0.62g, 2.5mmol, 0.636g, 6.0mmol sodium carbonate, 20mL o-dichlorohenzene is added separately to
In the round-bottomed flask of 100mL, it is uniformly mixed and reacts at 40 DEG C 2h, TLC monitoring adds 1.146g after completion of the reaction,
6.0mmol paratoluensulfonyl chloride reacts system at 165 DEG C after 3h as solvent is removed under 110 DEG C of oil baths, through silica gel chromatographic column
Molecular orbit compound products (0.444g, yield 15%) can be obtained after purification.
Purple solid；1H NMR(400MHz,CDCl3)δ:0.91-0.88(t,12H),1.33-1.25(m,76H),
1.60-1.58(m,8H,),2.76-2.70(m,2H),7.04(s,2H),7.06(s,2H).13C NMR(100MHz,CDCl3)δ:
14.15,14.43,20.15,22.70,27.09,29.32,29.60,29.94,31.96,36.38,39.75,109.13,
119.07,122.68,128.45,132.19,135.36,136.39,140.78,164.15
Embodiment 5
(1) preparation of 16- bromo hentetracontane Grignard Reagent: the 16- bromo hentetracontane of 39.362g, 60mmol are used
The dilution of 30mL anhydrous tetrahydro furan is simultaneously stand-by after mixing.Be added 1.728g in three-necked flask, 72mmol magnesium chips, 80mL without
Water tetrahydrofuran and three iodine, the anhydrous tetrahydro furan that 16- bromo hentetracontane is added dropwise under nitrogen protection and magnetic agitation are molten
Liquid, about 30~40min are added dropwise, then system is warming up to 80 DEG C is heated to reflux after 1~2h and Grignard Reagent is made, by grignard
Reagent is cooled to room temperature for use.
(2) synthesis of 2- (16- hentetracontane base) aniline: by 4.38g, 20mmol 2- Iodoaniline is dissolved in 100mL anhydrous four
In hydrogen furans, 0.220g is added, 0.3mmol [1,1'- bis- (diphenylphosphino) ferrocene] palladium chloride is passed through nitrogen and incites somebody to action
System is cooled to -80 DEG C, is added 40.818g under stirring, 60mmol16- bromo lignocerane Grignard Reagent, anti-at -78 DEG C
System is warmed to room temperature again after answering 1h, the reaction was continued for 24 hours be added mass percent 5% aqueous hydrochloric acid solution quench reaction, through extracting
Take, wash, drying, obtaining intermediate product after purification through silica gel chromatographic column --- 2- (16- hentetracontane base) aniline (2.672g,
Yield 20%).
Light yellow liquid；1H NMR(400MHz,CDCl3)δ:0.90-0.88(t,6H,-CH 3),1.29-
1.23(m,72H),1.58-1.56(m,4H,),2.75-2.71(m,1H),3.65(s,2H,-NH), 6.72-6.71 (d, J=
1.6Hz, J=7.6Hz, 1H), 6.73-6.70 (t, J=14.8Hz, 1H), 7.02-7.00 (d, J=15.6Hz, 2H)13C NMR
(100MHz,CDCl3)δ:14.14,22.70,27.09,29.32,29.60,29.92,31.90,36.35,40.07,116.11,
118.50,126.69,127.07,128.79,145.42.
(3) synthesis of the bromo- 2- of 3- (16- hentetracontane base) aniline: by 2.656g, 4mmol 2- (16- hentetracontane base)
Aniline, 0.748g, 4.2mmol bromo-succinimide, 44mg, 0.4mmol NaHSO4/SiO2Immobilized acid be dissolved in 60mL
CH3OH/CH3In the solvent of CN (v/v=1:3), at room temperature react 12~14h, TLC monitor end of reaction, through extraction, washing,
Drying obtains intermediate product through silica gel chromatographic column after purification --- the bromo- 2- of 3- (16- hentetracontane base) aniline (1.375g, yield
46%).
Light yellow liquid；1H NMR(400MHz,CDCl3)δ:0.89-0.88(t,6H,-CH 3),1.29-
1.23(m,72H),1.58-1.57(m,4H,),2.73-2.71(m,1H),3.67(s,2H,-NH), 6.72-6.71 (d, J=
1.6Hz, J=7.6Hz, 1H), 6.73-6.72 (t, J=14.8Hz, 1H), 7.05-7.01 (d, J=15.6Hz, 1H)13C NMR
(100MHz,CDCl3)δ:14.15,22.72,27.10,29.30,29.63,29.92,31.90,36.35,40.07,107.78,
118.60,129.21,129.65,131.37,145.45.
(4) 0.748g, the bromo- 2- of 1.0mmol3- (16- 41 synthesis of Molecular orbit compound: are added in reaction flask
Alkyl) aniline, the tetrachloroquinone of 0.124g, 0.5mmol, 0.127g, 1.2mmol sodium carbonate, 20mL o-dichlorohenzene is separately added into
Into the round-bottomed flask of 100mL, it is uniformly mixed and reacts at 40 DEG C 2h, TLC monitoring adds 0.229g after completion of the reaction,
1.2mmol paratoluensulfonyl chloride reacts system at 165 DEG C after 3h as solvent is removed under 110 DEG C of oil baths, through silica gel chromatographic column
Molecular orbit compound products (0.084g, yield 10%) can be obtained after purification.
Purple solid；Light yellow liquid；1H NMR(400MHz,CDCl3)δ:0.90-0.89(t,
12H,-CH 3),1.29-1.23(m,144H),1.58-1.57(m,8H,),2.72-2.71(m,2H),7.12(s,2H),7.10
(s,2H).13C NMR(100MHz,CDCl3)δ:14.13,22.70,27.15,29.32,29.68,29.96,31.92,36.37,
40.09,109.15,119.10,122.69,128.50,132.21,135.39,136.38,140.79,164.25
Above-described embodiment compound is tested through dissolubility, thermal stability and carrier mobility, the results are shown in Table 1,2.
The dye dissolubility test result of 1. Examples 1 to 5 of table
(the test method reference literature of thermal stability: design, synthesis and the photoelectric properties research of Optical Properties of Novel Conjugated
[D], 2012 doctoral thesis of Shanghai Communications University, page 54)
The dissolubility of the embodiment of the present invention 1~5 in organic solvent is good as can be seen from Table 1, in air and nitrogen
With preferable thermal stability.
2. hole mobility test result of table
(production of organic thin film transistor device and measuring and calculation method reference literature: organic film FET
(OTFT) preparation and research [D] of device, 2008 M Sc thesis of Shanghai University)
As can be seen from Table 2: hole mobility of the embodiment of the present invention 1~5 in organic thin film transistor device exists
1E10-6cm2V-1s-1More than, it is typical p-type semiconductor material, illustrates that the present invention can be used for Organic Light Emitting Diode and organic
Semiconductor material.
Claims (2)
1. a kind of Molecular orbit compound, which is characterized in that structural formula are as follows:
Entire molecule is centrosymmetric structure；Specially following compound:
A:X is Cl；R is the C12 alkyl of 2 substitutions；
B:X is Cl；R is the C16 alkyl of 2 substitutions；
C:X is Br；R is the C16 alkyl of 3 substitutions；
D:X is Cl；R is the C24 alkyl of 2 substitutions；
Or E:X is Cl；R is the C41 alkyl of 2 substitutions.
2. the method for preparing Molecular orbit compound as described in claim 1, which is characterized in that real by the following method
It is existing:
(1) preparation of Grignard Reagent: brominated alkanes are diluted with anhydrous tetrahydro furan and stand-by after mixing；In three-necked flask
The anhydrous tetrahydro furan of brominated alkanes is added dropwise in middle addition magnesium chips, anhydrous tetrahydro furan and iodine under nitrogen protection and magnetic agitation
Solution is added dropwise, then system is warming up to 78 DEG C -80 DEG C and is heated to reflux obtained Grignard Reagent, and Grignard Reagent is down to room temperature
It is stand-by afterwards；
(2) synthesis of alkyl benzene amine: iodo aniline is dissolved in anhydrous tetrahydro furan, adds [1,1'- bis- (diphenylphosphinos)
Ferrocene] palladium chloride, it is passed through nitrogen and system is cooled to -78 DEG C -80 DEG C, it is obtained that step (1) is added under stirring
Grignard Reagent is reacted, then system is warmed to room temperature, and the reaction was continued, and aqueous hydrochloric acid solution quenching reaction is added, extracted, washed
It washs, dry, obtaining intermediate product-alkyl benzene amine after purification through silica gel chromatographic column；
(3) synthesis of bromo alkyl benzene amine: by alkyl benzene amine, bromo-succinimide, the immobilized acid of NaHSO4/SiO2 is dispersed in
In the solvent of CH3OH/CH3CN；React at room temperature, TLC monitor end of reaction, through extraction, washing, drying, through silica gel chromatograph
Intermediate product-bromo alkyl benzene amine is obtained after column purification；
(4) synthesis of Molecular orbit compound: bromo alkyl benzene amine, four halobenzene quinones and sodium carbonate are added in reaction flask, then
O-dichlorohenzene is added, be uniformly mixed and is reacted at 40 DEG C -50 DEG C, TLC monitoring adds paratoluensulfonyl chloride after completion of the reaction,
It is reacted at 165 DEG C -170 DEG C, system is placed under oil bath removes solvent after reaction, obtained after purification through silica gel chromatographic column
Molecular orbit compound；
Alkyl in the brominated alkanes, alkyl benzene amine and bromo alkyl benzene amine is C12 alkyl, and the four halobenzenes quinone is tetrachlorobenzene
Quinone；Alternatively,
Alkyl in the brominated alkanes, alkyl benzene amine and bromo alkyl benzene amine is C16 alkyl, and the four halobenzenes quinone is tetrachlorobenzene
Quinone；Alternatively,
Alkyl in the brominated alkanes, alkyl benzene amine and bromo alkyl benzene amine is C16 alkyl, and the four halobenzenes quinone is tetrabromo-benzene
Quinone；Alternatively,
Alkyl in the brominated alkanes, alkyl benzene amine and bromo alkyl benzene amine is C24 alkyl, and the four halobenzenes quinone is tetrachlorobenzene
Quinone；Alternatively,
Alkyl in the brominated alkanes, alkyl benzene amine and bromo alkyl benzene amine is C41 alkyl, and the four halobenzenes quinone is tetrachlorobenzene
Quinone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610618687.4A CN106243125B (en) | 2016-08-01 | 2016-08-01 | A kind of Molecular orbit compound and its synthetic method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610618687.4A CN106243125B (en) | 2016-08-01 | 2016-08-01 | A kind of Molecular orbit compound and its synthetic method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106243125A CN106243125A (en) | 2016-12-21 |
| CN106243125B true CN106243125B (en) | 2018-12-21 |
Family
ID=57607317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610618687.4A Expired - Fee Related CN106243125B (en) | 2016-08-01 | 2016-08-01 | A kind of Molecular orbit compound and its synthetic method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106243125B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114907259A (en) * | 2022-04-28 | 2022-08-16 | 常州中氪生命科学技术有限公司 | Synthetic method of Sotolira intermediate |
| CN115010606B (en) * | 2022-06-09 | 2024-01-23 | 中国农业大学 | Synthesis method and application of 2-sec-butyl-6-ethylaniline |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008098222A (en) * | 2006-10-06 | 2008-04-24 | Toyo Ink Mfg Co Ltd | Organic transistor |
| JP2012206989A (en) * | 2011-03-30 | 2012-10-25 | Sumitomo Chemical Co Ltd | Soluble heteroacene compound, thin film containing the same, and organic transistor |
-
2016
- 2016-08-01 CN CN201610618687.4A patent/CN106243125B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN106243125A (en) | 2016-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kumar et al. | Oxidative trimerization of o-dialkoxybenzenes to hexaalkoxytriphenylenes: molybdenum (v) chloride as a novel reagent | |
| CN105985266B (en) | Trifluoromethylthio reagent, preparation method and applications | |
| CN106243125B (en) | A kind of Molecular orbit compound and its synthetic method | |
| CN105419958B (en) | It is a kind of for the anti-staining soaping agent of acid dyes, preparation method and application | |
| CN105566941A (en) | Amphiphilic aza-BODIPY fluorescent dye and preparation method thereof | |
| CN104557856A (en) | Preparation method for 9,9-diaryl thiophene xanthene-10,10-dioxide | |
| CN106512848A (en) | Cyclic quaternary ammonium salt gemini surfactant and preparation method thereof | |
| CN107098834A (en) | A kind of preparation method of aromatic sulfinic acids class compound | |
| CN101270049B (en) | Method of preparing cydia molesta sex pheromone | |
| CN105504860A (en) | Synthesis and applications of pyranoquinoline fluorescent dye | |
| CN102020579B (en) | Method for synthesizing diamide compound (R1R2NCO) 2CH2OCH2 | |
| Xu et al. | Phase-transfer catalysis of a new cationic gemini surfactant with ester groups for nucleophilic substitution reaction | |
| CN105505379A (en) | Long-wavelength BODIPY fluorescent dye derivative and preparation method thereof | |
| CN110423217A (en) | A kind of preparation method of conjugated enynes compound | |
| CN109593062A (en) | Double aziridinyl intermediates of a kind of Pseudolarix acid B photoaffinity probe and preparation method thereof | |
| CN105859718B (en) | A kind of preparation method of the nitrogenous poly-heterocyclic compounds of copper catalysis | |
| CN109574906A (en) | A kind of preparation method of 3,3 '-two Indoleacetic esters | |
| CN101402629A (en) | Synthesis and uses of terthienyl and derivatives thereof | |
| CN107033175B (en) | The connected fluorine boron fluorescent dye oligomer and its preparation method and application of diacetylene | |
| CN102659688B (en) | Novel spirobifluorene compound 2-methyl-7-benzimidazolyl spirobifluorene, and method and application thereof | |
| CN114920756A (en) | Preparation method of glabridin | |
| CN108410202A (en) | A kind of preparation method of seven methine cyanine dyes of quinoline | |
| Lu et al. | Synthesis and photochromism of dithienylethene-based isocyanide and gold (I) complexes with various alkyl chains | |
| CN108558595B (en) | P-phenylene ethylene bridged trimer indene derivative and preparation method thereof | |
| CN113072470A (en) | N-acetonitrile bis-benzenesulfonylimine derivative and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181221 Termination date: 20210801 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |