CN105038292B - Solubility carbazoles diazine violet pigment - Google Patents
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- 0 CCCCCCc1cccc2c1c(cc1N=C3C(Cl)=C4Oc(cc5[n](*)c6cccc(*)c6c5c5)c5N=C4C(Cl)=C3Oc1c1)c1[n]2C Chemical compound CCCCCCc1cccc2c1c(cc1N=C3C(Cl)=C4Oc(cc5[n](*)c6cccc(*)c6c5c5)c5N=C4C(Cl)=C3Oc1c1)c1[n]2C 0.000 description 1
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Abstract
The present invention relates to formula（1）A shown class solubility carbazoles diazine violet pigment, belongs to organic synthesis field.This pigment, with 3 aminocarbazole derivants and halo benzoquinone as raw material, is obtained through coupling, condensation reaction.Compared with original similar violet pigment, this pigment has preferable dissolubility, substantially increases the dispersibility of violet pigment, simplifies pigmentation technique, and this for the production efficiency improving pigment and ensures that end product quality etc. has preferable effect；And this pigment is heterocycle conjugated system, molecule is plane symmetry structure, and heat stability is good, and hole mobility is up to 1E10‑7cm2V‑1s‑1More than, there is preferable charge transport ability, can be applicable to the fields such as Organic Light Emitting Diode, organic semiconductor.（1）Wherein：R1For C12 50 alkyl；R2、R3For H, C1 C20 alkyl of any position, phenyl；X is halogen；Whole molecule is centrosymmetric structure.
Description
Technical field
The present invention relates to a class solubility carbazoles diazine violet pigment, belong to organic synthesis field.
Background technology
Diazines pigment is a kind of excellent Heterocyclics Pigments of application performance, and its parent chemical constitution is triphendioaxazine,
Wherein carbazole dioxazine purple (Pigment Violet 23) be a kind of high-grade purple pigment of function admirable, China exploitation and
Produce relatively early, there are the various features such as bright in luster, strong coloring force and resistance to migration, but because this pigment-dispersing is not good, face
Typically by dispersant during materialization, production efficiency is caused to reduce it is difficult to high-quality pigment is obtained, the gloss of impact finished product
Degree and tinting strength, tinting power.For this reason, the dispersibility improving carbazoles diazines pigment further is particularly important.
It is known that the heterocyclic molecular with the pi-conjugated greatly structure of plane has preferable stability, and its pi-conjugated greatly and
The pi-conjugated track of p- can undertake electric charge transformation task, be often used as the hole transport with high thermal stability in electroluminescent field
Material.Such as phthalocyanine-like compound and phenylpropyl alcohol azoles disazo pigment all have good photoelectric properties, can be used as solar-electricity
Charge-conduction material in photosensitizer in pond and photoelectric device.But preferable dissolubility and excellent film property are such
Compound makes the important prerequisite of photoelectricity and organic semiconductor device.Therefore, with photoelectric device and organic semiconducting materials
Develop further, the requirement to molecular structure improves constantly, and develops the heterocycle conjugated structure that dissolubility is good, filming performance is excellent
Compound, and study its application in fields such as photoelectricity, organic field effect tubes further and more and more paid attention to, one
It is directly the focus of researcher concern in recent ten years.
Have good dispersion concurrently and the carbazoles diazine violet pigment of Electroluminescence yet there are no pertinent literature report
Road.
Content of the invention
For the problems referred to above, the present invention provides that a class solubility is good, good stability have the carbazoles two of photoelectric properties
Piperazine violet pigment.
Solubility diazines violet pigment of the present invention, its structural formula is：
Wherein：R1For C12-50 alkyl；R2、R3For H, C1-C20 alkyl of any position, phenyl；X is halogen；Whole point
Son is centrosymmetric structure.
Preferably：R1Contain the alkyl of side chain for C12-42；R2、R3H, C1-C10 alkyl of any position；X is chlorine, bromine；Entirely
Molecule is centrosymmetric structure.
Preferably：R1Contain the alkyl of side chain for C16-42；R2、R3H, C1-C10 alkyl for any position；X is chlorine or bromine；Whole
Individual molecule is centrosymmetric structure.
The invention provides the preparation method of this solubility carbazoles diazine violet pigment, specific as follows：
By 3- aminocarbazole derivant, alkalescence salt, halo benzoquinone, high boiling organic solvent, (boiling point is 170 DEG C～220
Between DEG C) put in reaction bulb, add oxidant after completion of the reaction at 25 DEG C～80 DEG C, at 130 DEG C～220 DEG C, continue reaction,
Remove high boiling organic solvent after completion of the reaction, add low boiling point organic solvent (boiling point is between 40 DEG C～120 DEG C), through molten
Solution filters, filtrate concentrates, after recrystallization solubility carbazoles diazine purple pigment product.Reaction equation is as follows：
Above-mentioned alkalescence salt is one of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, preferably sodium carbonate, carbonic acid
Potassium.
Above-mentioned high boiling organic solvent is one of halogeno-benzene, solvent naphtha, nitro-aromatic, preferably o-dichlorohenzene, nitro
Benzene；Low boiling point organic solvent is one of alkyl halide, esters, ketone, ether solvent, preferably dichloromethane, ethyl acetate.
Above-mentioned oxidant is one of paratoluensulfonyl chloride, Benzenecarbonyl chloride., trifluoromethanesulfanhydride anhydride, trifluoromethanesulfonic acid, excellent
Select toluene sulfochloride, Benzenecarbonyl chloride..
Beneficial effects of the present invention are：(1) this pigment has dissolubility in common solvents, has both maintained carbazole dioxazine
The advantages of bright in luster, strong coloring force of purple dye, make it have good dissolubility again, substantially increase violet pigment
Dispersibility, simplifies pigmentation technique, and this for the production efficiency improving pigment and ensures that end product quality etc. has preferable effect
Really；(2) the preparation method process is simple that the present invention provides, is easy to operation it is easy to promote；(3) the carbazoles diazine of the present invention
Class violet pigment is heterocycle conjugated system, and molecule is plane symmetry structure, and heat stability is good, and hole mobility is up to 1E10- 7cm2V-1s-1More than, there is preferable charge transport ability, can be applicable to Organic Light Emitting Diode, organic semiconductor field.
Raw material 3- aminocarbazole derivant synthesizes according to the method for list of references 1,2：[1]Karen S.MacMillan,
Jacinth Naidoo,Jue Liang,etl.Development of Proneurogenic,Neuroprotective
Small Molecules, Journal of the American Chemical Society, 133 (5), 1428-1437,
2011；
[2]David Cantillo,Mojtaba Mirhosseini Moghaddam,and C.Oliver
Kappe.Hydrazine-mediated Reduction of Nitro and Azide
FunctionalitiesCatalyzed by Highly Active and Reusable Magnetic Iron Oxide
Nanocrystals, Journal of Organic Chemistry, 78 (9), 4530-45422013.
Specific implementation method
It is that the present invention is better illustrated, as follows for embodiment：
Embodiment 1：
2.7g N- dodecyl -3- aminocarbazole, 1g sodium carbonate, 1g tetrachloroquinone, 27mL o-dichlorohenzene are put into reaction
In bottle, at 40 DEG C, after reaction 6h, add 2g paratoluensulfonyl chloride, at 165 DEG C, continue reaction 6h, remove most of after completion of the reaction
O-dichlorohenzene, adds ethyl acetate, dissolution filter, filtrate concentrate, after recrystallization solubility carbazoles diazine violet pigment
Product 1.6g, yield 76%.
1H NMR(400MHz,CDCl3):δ(ppm)8.34-8.21(m,2H),8.14–8.11(m,2H),7.83-7.81
(m,2H),7.53-7.49(m,2H),7.31-7.28(m,2H),7.09-7.05(m,2H),4.19-4.15(t,4H),1.79-
1.72(m,4H),1.31-1.29(m,36H),0.91-0.85(t,6H)；13C NMR(400MHz,CDCl3):δ(ppm)164.6,
141.3,135.7,135.3,130.7,128.4,125.8,124.3,121.7,121.4,119.8,109.6,99.6,99.4,
99.2,58.331.9,28.1,22.7,11.4.MS(EI,m/z)519.
Embodiment 2：
By 4.2g N- (2- butyl octyl) -3- aminocarbazole, 1.5g sodium carbonate, 1.5g tetrachloroquinone, 40mL neighbour's dichloro
Benzene is put in reaction bulb, adds 2.6g paratoluensulfonyl chloride at 40 DEG C after reaction 6h, continues reaction 6h at 165 DEG C, and reaction finishes
Remove most of o-dichlorohenzene afterwards, add dichloromethane, dissolution filter, filtrate concentrate, after recrystallization solubility carbazoles two
Piperazine violet pigment product 4.3g, yield 81%.
1H NMR(400MHz,CDCl3):δ(ppm)8.34-8.21(m,2H),8.14–8.11(m,2H),7.83-7.81
(m,2H),7.53-7.49(m,2H),7.31-7.28(m,2H),7.09-7.05(m,2H),3.97-3.95(m,4H),1.51-
1.49(m,2H),1.31-1.29(m,32H),0.91-0.85(t,12H)；13C NMR(400MHz,CDCl3):δ(ppm)
164.6,141.3,135.7,135.3,130.7,128.4,125.8,124.3,121.7,121.4,119.8,109.6,99.6,
99.4,99.2,62.5,34.4,32.9,28.1,22.7,14.1.
Embodiment 3：
By 5g N- (2- hexyl certain herbaceous plants with big flowers alkyl) -3- aminocarbazole, 1.5g sodium carbonate, 1.5g tetrachloroquinone, 40mL o-dichlorohenzene
Put in reaction bulb, at 40 DEG C, after reaction 6h, add 3g paratoluensulfonyl chloride, continue reaction 6h at 165 DEG C, remove after completion of the reaction
Remove most of o-dichlorohenzene, add ethyl acetate, dissolution filter, filtrate concentrate, after recrystallization solubility carbazoles diazine
Violet pigment product 5.1g, yield 85%.
1H NMR(400MHz,CDCl3):δ(ppm)8.34-8.21(m,2H),8.14–8.11(m,2H),7.83-7.81
(m,2H),7.53-7.49(m,2H),7.31-7.28(m,2H),7.09-7.05(m,2H),3.97-3.95(m,4H),1.51-
1.49(m,2H),1.31-1.29(m,48H),0.91-0.85(t,12H)；13C NMR(400MHz,CDCl3):δ(ppm)
164.6,141.3,135.7,135.3,130.7,128.4,125.8,124.3,121.7,121.4,119.8,109.6,99.6,
99.4,99.2,62.5,34.4,32.9,28.1,22.7,14.1.
Embodiment 4：
4g N- (2- octyldodecyl) -3- aminocarbazole, 1g sodium bicarbonate, 1g tetrachloroquinone, 37mL Nitrobenzol are put
Enter in reaction bulb, at 40 DEG C, after reaction 6h, add 2g trifluoromethanesulfonic acid, at 165 DEG C, continue reaction 6h, remove big after completion of the reaction
Part o-dichlorohenzene, adds ethyl acetate, dissolution filter, filtrate concentrate, after recrystallization solubility carbazoles diazine purple
Pigment product 3.7g, yield 83%.
1H NMR(400MHz,CDCl3):δ(ppm)8.34-8.21(m,2H),8.14–8.11(m,2H),7.83-7.81
(m,2H),7.53-7.49(m,2H),7.31-7.28(m,2H),7.09-7.05(m,2H),3.97-3.95(m,4H),1.51-
1.49(m,2H),1.31-1.29(m,64H),0.91-0.85(t,12H)；13C NMR(400MHz,CDCl3):δ(ppm)
164.6,141.3,135.7,135.3,130.7,128.4,125.8,124.3,121.7,121.4,119.8,109.6,99.6,
99.4,99.2,62.5,34.4,32.9,28.1,22.7,14.1.
Embodiment 5
By 7g N- (2- eicosyl docosane) base -3- amino -4- methyl -8- amyl group carbazole, 1g sodium carbonate, 1.7g
Tetrabromo-quinone, 40mL o-dichlorohenzene are put in reaction bulb, add 1.5g Benzenecarbonyl chloride., continue at 165 DEG C at 25 DEG C after reaction 7h
Reaction 6h, removes most of o-dichlorohenzene after completion of the reaction, adds dichloromethane, and dissolution filter, filtrate concentrate, after recrystallization
Solubility carbazoles diazine purple pigment product 7.9g, yield 82%.
1H NMR(400MHz,CDCl3):δ(ppm)7.97-7.93(m,2H),7.46–7.44(m,2H),7.26-7.23
(m,2H),6.89-6.86(m,2H),4.08-4.05(m,4H),2.64-2.61(m,4H),2.34(s,6H),1.61-1.58
(m,4H),1.52-1.49(m,2H),1.31-1.29(m,152H),1.26-1.24(m,8H),0.91-0.88(t,18H)；13CNMR(400MHz,CDCl3):δ(ppm)164.6,141.2,140.5,135.6,131.4,125.1,124.0,123.9,
123.4,122.1,118.6,103.3,96.4,86.9,85.7,62.8,34.4,32.9,31.7,31.2,30.9,29.9,
29.5,22.7,14.4,14.1.
Embodiment 6
By 6.4g N- cetyl -1- octyl group -3- amino -7- eicosyl carbazole, 1g sodium carbonate, 1g tetrachloroquinone,
27mL o-dichlorohenzene is put in reaction bulb, adds 2g paratoluensulfonyl chloride at 60 DEG C after reaction 6h, continues reaction 7h at 135 DEG C,
Remove most of o-dichlorohenzene after completion of the reaction, add dichloromethane, dissolution filter, filtrate concentrate, after recrystallization solubility
Carbazoles diazine purple pigment product 5.7g, yield 79%.
1H NMR(400MHz,CDCl3):δ(ppm)8.07-8.06(m,4H),7.38–7.34(m,2H),7.26-7.23
(m,2H),4.18-4.15(m,4H),2.64-2.61(m,8H),1.75-1.73(m,4H),1.61-1.58(m,8H),1.31-
1.29(m,140H),0.91-0.88(t,18H)；13C NMR(400MHz,CDCl3):δ(ppm)164.4,141.1,135.3,
130.5,127.1,125.1,124.1,123.0,120.7,120.4,110.3,107.4,99.6,99.2,96.1,58.6,
35.7,31.5,29.6,22.7,14.1.
Embodiment 7
By 6g N- dotriacontyl -3- amino -4- ethyl -6- phenyl carbazole, 1.3g potassium carbonate, 2.5g iodanil,
27mL Nitrobenzol is put in reaction bulb, adds 2g paratoluensulfonyl chloride at 70 DEG C after reaction 5h, continues reaction 4h, instead at 200 DEG C
Most of Nitrobenzol should be removed after finishing, add ethyl acetate, dissolution filter, filtrate concentrate, after recrystallization solubility carbazole
Class diazine purple pigment product 6.6g, yield 80%.
1H NMR(400MHz,CDCl3):δ(ppm)7.87-7.85(m,2H),7.78–7.76(m,2H),7.71-7.68
(m,2H),7.53-7.50(m,8H),7.43–7.39(m,2H),6.91-6.87(m,2H),4.18-4.15(m,4H),2.61-
2.59(m,4H),1.75-1.73(m,4H),1.31-1.26(m,116H),1.25-1.23(m,6H),0.91-0.88(t,6H)
；13C NMR(400MHz,CDCl3):δ(ppm)164.6,148.4,141.2,135.6,130.1,129.2,128.4,127.9,
127.6,126.4,122.7,119.4,116.8,111.6,103.3,96.6,58.3,50.8,29.6,22.7,21.3,14.8,
14.1.
Embodiment 8
By 4g N- cetyl -3- amino -5- hexyl carbazole, 1.3g potassium carbonate, 1g tetrachloroquinone, 27mL o-dichlorohenzene
Put in reaction bulb, at 30 DEG C, after reaction 6h, add 2g paratoluensulfonyl chloride, continue reaction 5h at 210 DEG C, remove after completion of the reaction
Remove most of o-dichlorohenzene, add dichloromethane, dissolution filter, filtrate concentrate, after recrystallization solubility carbazoles diazine
Violet pigment product 4g, yield 86%.
1H NMR(400MHz,CDCl3):δ(ppm)8.26-8.24(m,2H),7.61–7.58(m,2H),7.39-7.36
(m,2H),7.33-7.32(m,2H),7.09–7.06(m,2H),4.18-4.15(m,4H),2.61-2.59(m,4H),1.75-
1.73(m,4H),1.61-1.58(m,4H)1.31-1.26(m,64H),,0.91-0.88(t,6H)；13C NMR(400MHz,
CDCl3):δ(ppm)164.6,141.3,139.7,139.6,135.3,131.9,130.7,125.8,124.3,122.4,
114.0,106.8,102.3,99.4,99.2,58.3,33.1,29.7,22.7,14.1.
Above-described embodiment compound is tested through solubility test and hole mobility, the results are shown in Table 1,2.
Table 1. solubility test result
As can be seen from Table 1：The embodiment of the present invention 1～8 all has preferable dissolubility in different organic solvents.
Table 2. hole mobility test result
(making of organic thin film transistor device and measuring and calculation method reference literature：Organic film FET
(OTFT) preparation of device and research [D], Shanghai University 2008 M Sc thesis)
As can be seen from Table 2：Hole mobility in organic thin film transistor device for the embodiment of the present invention 1～8 all exists
1E10-7cm2V-1s-1More than, it is typical p-type semiconductor material, illustrate that the present invention can be used for Organic Light Emitting Diode and organic
Semi-conducting material.
Claims (2)
1. a class solubility carbazoles diazine violet pigment is it is characterised in that structural formula is：
R1Contain the alkyl of side chain for C12-42； R2、R3H, C1-C10 alkyl for any position；X is chlorine or bromine；Whole point
Son is centrosymmetric structure.
2. solubility carbazoles diazine violet pigment as claimed in claim 1 is it is characterised in that R1Contain for C16-42 and prop up
The alkyl of chain； R2、R3H, C1-C10 alkyl for any position；X is chlorine or bromine；Whole molecule is centrosymmetric structure.
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62185088A (en) * | 1986-02-12 | 1987-08-13 | Nippon Kayaku Co Ltd | Carbazole dioxazine compound and use thereof |
| DE102004001883A1 (en) * | 2004-01-14 | 2005-08-11 | Clariant Gmbh | triphendioxazine |
| TW201105750A (en) * | 2009-03-31 | 2011-02-16 | Solvay | Process for the preparation of easily dispersible violet pigment |
| CN101864188A (en) * | 2009-04-17 | 2010-10-20 | 上海汇友精密化学品有限公司 | Sunproof water-soluble dye, method for preparing same and application thereof |
| KR20110098638A (en) * | 2010-02-26 | 2011-09-01 | 후지필름 가부시키가이샤 | Colored curable composition, color filter and method of producing color filter, solid-state image sensor and liquid crystal display device |
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