KR101737001B1 - Diketopyrrolopyrrole derivatives, diketopyrrolopyrrole derivatives dye and method thereof - Google Patents
Diketopyrrolopyrrole derivatives, diketopyrrolopyrrole derivatives dye and method thereof Download PDFInfo
- Publication number
- KR101737001B1 KR101737001B1 KR1020150075031A KR20150075031A KR101737001B1 KR 101737001 B1 KR101737001 B1 KR 101737001B1 KR 1020150075031 A KR1020150075031 A KR 1020150075031A KR 20150075031 A KR20150075031 A KR 20150075031A KR 101737001 B1 KR101737001 B1 KR 101737001B1
- Authority
- KR
- South Korea
- Prior art keywords
- formula
- derivative
- diketopyrrolopyrrole
- dye
- triple bond
- Prior art date
Links
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical class C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- -1 benzonitrile derivative compound Chemical class 0.000 claims description 3
- 101150003085 Pdcl gene Proteins 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 2
- 239000002184 metal Substances 0.000 claims 2
- 239000000049 pigment Substances 0.000 abstract description 24
- 239000011347 resin Substances 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 6
- 238000002834 transmittance Methods 0.000 abstract description 3
- 230000003595 spectral effect Effects 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- AHUQRGHAKJSUKU-UHFFFAOYSA-N 1,4-bis[5-(1-benzofuran-2-yl)thiophen-2-yl]-2,5-bis(2-ethylhexyl)pyrrolo[3,4-c]pyrrole-3,6-dione Chemical compound C1=CC=C2OC(C3=CC=C(S3)C3=C4C(=O)N(C(=C4C(=O)N3CC(CC)CCCC)C=3SC(=CC=3)C=3OC4=CC=CC=C4C=3)CC(CC)CCCC)=CC2=C1 AHUQRGHAKJSUKU-UHFFFAOYSA-N 0.000 description 3
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000008359 benzonitriles Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- YPLYFEUBZLLLIY-UHFFFAOYSA-N dipropan-2-yl butanedioate Chemical compound CC(C)OC(=O)CCC(=O)OC(C)C YPLYFEUBZLLLIY-UHFFFAOYSA-N 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ACJSMQZKXAMMRA-UHFFFAOYSA-N 1h-pyrrolo[3,2-b]pyrrol-5-one Chemical class N1C=CC2=NC(=O)C=C21 ACJSMQZKXAMMRA-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- RQGPLDBZHMVWCH-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole Chemical compound C1=NC2=CC=NC2=C1 RQGPLDBZHMVWCH-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/004—Diketopyrrolopyrrole dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The present invention relates to a diketopyrrolopyrrole derivative containing a novel triple bond, wherein the diketopyrrolopyrrole derivative is a dye for a salt-pigment hybrid type red color resist for an LCD color filter, a color filter photosensitive resin having a high transmittance, Can be used as a diketopyrrolopyrrole derivative dye including a triple bond which has excellent properties and improved spectral characteristics of a conventional pigment (CIPigment Red 254).
Description
The present invention relates to a ketopyrrolopyrrole derivative containing a triple bond having excellent solubility and heat resistance, which is used for producing a colored photosensitive resin for a color filter substrate, a dye containing the derivative, and a process for producing the dye.
The LCD color filter is mainly manufactured by a photolithography method using a pigment of red (CI Pigment Red 254), green (CI Pigment Green 58), and blue (CI Pigment Blue 15: 6) together with a colored photosensitive resin composition .
More specifically, the mill base for an LCD color photoresist refers to a pigment prepared by dispersing pigments, dispersants, monomers, and solvents in a particle size of 100 nm or less in terms of particle size of a pigment present as macromolecular macromolecules.
However, if the pigment for the LCD color filter substrate is strong in cohesion, the fineness does not proceed, and the pigment in each sub-pixel causes light transmission decay due to the presence of the re-aggregated insoluble pigment particles Causing light reflection and light scattering, and ultimately causing a decrease in the contrast ratio
Currently LCD color filter Red of the three primary colors PIGMENT RED 254 Pigment is a pigment with excellent physical properties and high color strength as a chromophore of 1,4-diketopyrrollo (3,4c) pyrrole (DPP) It is widely used as a resist material.
However, with such pigments only, the size of the display screen is getting larger and there are many restrictions to satisfy the high C / R contrast ratio and brightness demanded by consumers.
In order to overcome such disadvantages, a dye type or dye type hybrid type color filter material capable of minimizing scattering of backlight due to the particle size of pigments and dramatically improving the transmittance through hybridization of existing pigments and dyes Is required.
However, since the stability of the dye is lower than that of the pigment, it is difficult to maintain the inherent color in the liquid crystal alignment film process and the durability thereof is weak.
In terms of the fabrication of color filters, pigment-based photoresists can be used in a number of ways to introduce a method of using ink-jet printing in the manufacture of color filter substrates to reduce the cost of manufacturing color filters by preventing prolonged and repetitive processes in conventional photolithography Patents are being introduced.
This inkjet printing method has an advantage of having a manufacturing step of about one-third of that of the photolithography method. For this reason, soluble dyes for primary colors tend to be preferred to non-soluble pigments.
(CI Pigment Red 254) based on diketo pyrrolo-pyrrole (DPP), which was originally synthesized by Shiva Guyi in the case of red, has excellent thermal stability and bright red tint It is usefully used.
However, according to the single crystal X-ray measurement, the DPP has excellent thermal stability due to hydrogen bonding between the planarity of the molecular structure itself and oxygen of one mole of
Bull. Korean Chem. Soc. 2010, Vol. 31, No. 4, DPP-based dyes, which not only increase the solubility and color purity of the DPP-based dyestuffs and prevent the decrease of brightness, but also have excellent thermal stability, have been introduced. However, these dyes have a drawback in that they have poor solubility in solvents and poor compatibility with photosensitive resins.
At present, it is considered that the optimal technical method for developing a high transmittance color filter is the development of a salt-pigment hybrid type color resist which is compatible with a photosensitive resin. In order to realize a wide color reproducibility and to improve the light transmission efficiency of a color filter, Heat resistance and high melting property, which are excellent in the spectroscopic characteristics such as a high heat resistance and a high heat resistance.
The present invention provides a diketopyrrolopyrrole derivative dye containing a novel triple bond which is excellent in solubility and thermal stability and applicable to a salt-pigment hybrid type color resist. .
A first preferred embodiment according to the present invention relates to a diketopyrrolopyrrole derivative comprising a triple bond represented by the following general formula
[Chemical Formula 1]
In Formula 1,
R 1 is an alkyl group having a carbon number of 1-15, each independently, or -CH 2 OH, - (CH 2 ) 2 OH, - (CH 2) 3 OH, - (CH 2) 4 OH, - (CH 2) 5 OH, - (CH 2) 6 OH, - (CH 2) 7 OH, - (CH 2) 8 OH, - (CH 2) 9 OH, - (CH 2) 10 OH, - (CH 2) 11 OH, - ( CH 2 ) 12 OH or
Wherein A 1, A 2, A 3 are each independently an alkyl group or -CH 2 OH, with a carbon number of 1-15 - (CH 2) 2 OH , - (CH 2) 3 OH, - (CH 2) 4 OH, - (CH 2) 5 OH, - (CH 2) 6 OH, - (CH 2) 7 OH, - (CH 2) 8 OH, - (CH 2) 9 OH, - (CH 2) 10 OH, - (CH 2 ) 11 OH, - (CH 2 ) 12 OH.
A second preferred embodiment of the present invention relates to a diketopyrrolopyrrole derivative dye comprising a diketopyrrolopyrrole derivative containing a triple bond represented by the general formula (1).
A third preferred embodiment according to the present invention relates to a process for preparing a diketopyrrolopyrrole derivative comprising a triple bond represented by formula (1), comprising the steps of:
a) reacting a compound of formula (2) with a reactant of formula (3) to synthesize a benzonitol derivative of formula (4); And
b) reacting the benzonitrile derivative compound with a reactant of formula (5) to produce a diketopyrrolopyrrole derivative of formula (1).
The diketopyrrolopyrrole (DPP) red dye containing the triple bond represented by the formula (1) according to the present invention is excellent in the thermal stability because of its excellent molecular structure flatness and intermolecular crystallinity of diketopyrrolopyrrole It is a dye that complements the problem of poor solubility and compatibility with solvents and binders.
The present invention relates to a dyestuff pyrrolopyrrole (DPP) derivative containing a triple bond, thereby satisfying both compatibility with a photosensitive resin as a binder while maintaining thermal stability when used in a salt-pigment hybrid type color resist, It is a dye that has color reproduction rate implementation and light transmission efficiency of color filter.
1 is a graph showing NMR analysis results of 3,6-bis [4- (2- (triisopropylsily) ethyl] phenyl] pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H) -dione.
2 is a graph showing the UV spectrum of 3,6-bis [4- (2- (triisopropylsily) ethyl] phenyl] pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H) -dione.
FIG. 3 is a TGA graph showing the heat resistance of 3,6-bis [4- (2- (triisopropylsily) ethyl] phenyl] pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H) -dione.
In order to accomplish the above object, the present invention is a diketopyrrolopyrrole derivative dye containing a triple bond of the following formula (1).
The diketopyrrolopyrrole derivative of the present invention represented by the following formula (1) is obtained by synthesizing a compound of the formula (2) and a reaction product of the formula (3), synthesizing the benzonitol derivative compound of the formula (4) The cyclization reaction of formula (6) is carried out.
[Chemical Formula 1]
(2)
(3)
(x is any one of Cl, Br and I)
[Chemical Formula 4]
[Chemical Formula 5]
[Chemical Formula 6]
That is, the compound of formula (2) and the reactant of formula (3) are synthesized in the form of a benzonitol derivative having a triple bond in a THF solvent and a palladium catalyst, and the compound of formula (4) And then the compound of formula (6) and the benzonitol derivative containing the triple bond of formula (4) are cyclized to obtain a diketopyrrolopyrrole derivative containing the triple bond of formula (1).
[Chemical Formula 1]
The synthesis according to the above formula (1)
Reacting a compound of formula (2) with a compound of formula (3) to synthesize a compound of formula (4) including the triple bond; And
And reacting the compound of formula (4) with a compound of formula (5) to synthesize a compound of formula (1) including a final triple bond.
Hereinafter, the present invention will be described in more detail.
The diketopyrrolopyrrole derivative containing a triple bond as shown in the above formula (1) has excellent solubility and heat resistance for use in the production of a colored photosensitive resin for a color filter substrate, and a method for producing the dye. The dye has excellent solubility and thermal stability, And to DPP (diketopyrrolopyrrole) dyes usable in RED colors applicable to hybrid type color resists.
Reacting the starting materials (2) and (3) to synthesize the derivative (4)
That is, the compound of formula (2) and the reaction product of formula (3) are dissolved in a palladium catalyst and THF as a solvent under an argon atmosphere, followed by stirring to obtain a benzonitrile derivative of formula (IV) including a novel triple bond.
Formula 2 R 1 are each independently an alkyl group or -CH 2 OH with a carbon number of 1-15, a - (CH 2) 2 OH, - (CH 2) 3 OH, - (CH 2) 4 OH, - (CH 2) 5 OH, - (CH 2) 6 OH, - (CH 2) 7 OH, - (CH 2) 8 OH, - (CH 2) 9 OH, - (CH 2) 10 OH, - (CH 2) 11 OH , - (CH 2 ) 12 OH or
More detail, the A 1, A 2, A 3 are each independently an alkyl group having a carbon number of 1-15 or -CH 2 OH, - (CH 2 ) 2 OH, - (CH 2) 3 OH, - (CH 2) 4 OH, - (CH 2) 5 OH, - (CH 2) 6 OH, - (CH 2) 7 OH, - (CH 2) 8 OH, - (CH 2) 9 OH, - (CH 2) 10 OH, - (CH 2 ) 11 OH, - (CH 2 ) 12 OH.
The following benzonitrile intermediates containing the triple bonds: EMI10.1 to synthesize the
The benzonitol derivative represented by the formula (4) can be reacted with a compound of the formula (5) in a basic atmosphere to obtain an intermediate of the formula (6). The compound of the formula (6) and the benzonitol derivative of the formula Lt; RTI ID = 0.0 > triple bond < / RTI >
More specifically, the diketopyrrolopyrrole derivative containing the triple bond of the
Example
Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are for the purpose of illustrating the present invention more specifically, and the present invention is not limited thereto.
[ Example ]
In this embodiment, a benzonitol derivative having the following general formula (5) and a triple bond of the following general formula (4) is subjected to a cyclization reaction under a base to give a diketopyrrolopyrrole (DPP) ≪ / RTI >
[Chemical Formula 1]
The preparation method of a diketopyrrolopyrrole (DPP) derivative including a triple bond includes a dissolution step of dissolving and stirring the compound of formula (4) as a fifth step; (5); Neutralizing after completion of the reaction; Product (1) recovery step; And a product washing and drying step.
Example One. Diketopyrrolopyrrole-based Synthesis of derivatives
In Example 1, the starting material, the compound of Formula 2, and the compound of
[Reaction Scheme 1]
(13.6 g, 0.075 mol) of 4-bromobenzonenitrile was added to 700 ml of THF (10 times the amount of triethylamine) and 0.082 eq. Of palladium catalyst PdCl 2 (pph 3 ) 2 containing ligand (4.4 g, 0.006 mol ) And 0.1 equivalent of copper iodide (1.4 g, 0.0075 mol) were added, and the mixture was stirred at room temperature for 1 hour. Then, 69.4 g of triethylamine (16 times of the catalyst) was added to the solution, and the mixture was continuously stirred for 30 minutes. And kept at room temperature.
After the argon gas was strongly blown into the reactor, the temperature was raised to 60 ° C to 80 ° C, and 1 equivalent of TIPS acethylene substrate was slowly added dropwise with stirring for about 1 hour. The reaction was confirmed by TLC (solvent condition: n-hexane: EtOAc = 9: 1) and the mixture was stirred for 6 hours while maintaining the same temperature.
After completion of the reaction, the reaction mixture was cooled to room temperature, and vacuum filtration was carried out to remove the solid component. Then, ethyl acetate (300 ml) and distilled water (100 ml) were added to separate the organic layer and the receiving layer. The same operation was repeated three times for washing.
The recovered organic layer was washed with 10 g of anhydrous magnesium sulfate and then filtered under reduced pressure to recover only the organic layer. The desired 4- [2- (triisopropylsily) ethyl] benzonitrile (Formula 4) was obtained by distillation under reduced pressure.
Example 2. Diketopyrrolopyrrole-based Synthesis of derivatives
The step of synthesizing a diketopyrrolopyrrole (DPP) derivative containing a triple bond, which is a
[Reaction Scheme 2]
Sodium tert-butoxide (22.11 g, 0.23 mol) was slowly added to 340 ml of 2-methyl-2-buthanol in a nitrogen atmosphere at room temperature, and the mixture was stirred for 30 minutes at 80 ° C (65.2 g, 0.23 mol), which was prepared in Example 1 and contained the triple bond as shown in Chemical Formula 4, was added, and the mixture was stirred for 20 minutes while being heated to 100 ° C to be completely melted.
Succinic acid diisopropyl ester (16.1 g, 0.08 mol) represented by Chemical Formula 5 was dissolved in 20 mL of 2-methyl-2-buthanol. The thus-obtained compound (5) was gradually added dropwise to the mixture containing the base of formula (4) while stirring at a temperature of 100 ° C in the above-mentioned manner to induce the reaction (the presence or absence of the reaction influences the time and amount of reduction ).
The mixture was gradually added dropwise for 1 hour and then allowed to react at 100 ° C for 15 hours to 18 hours.
The reaction temperature and dropping time are determined by the molecular size. There is a weak dispersing power between molecules, and sufficient energy is provided to overcome the dispersing power. It is preferable that the dispersing power increases as the size of the molecule increases. That is, it is preferable that the greater the number of carbon atoms, the greater energy is provided. For example, in the case of the benzonitrile derivative containing the triple bond, Lt; / RTI >
After the reaction, the reaction mixture was cooled to 20 to 25 ° C and neutralized to pH = 7 with 2N HCl. Distilled water was added to the reaction mixture for 30 minutes.
After completion of the neutralization step, the reaction product was filtered under reduced pressure to recover the solid component (1).
The solid content was further added to the distilled water as the reaction solvent, stirred for 20 minutes, and filtered under reduced pressure. The washed solid was washed three times repeatedly, sufficiently washed, and then dried under vacuum to obtain a novel diketopyrrolopyrrole (DPP) -based dyestuff including a triple bond according to the formula (1) in a yield of 45%.
NMR and UV spectra were confirmed for structure confirmation, and it was confirmed that diketopyrrolopyrrole derivatives containing triple bonds were well prepared (FIGS. 1 and 2).
As a result of TGA (heat resistance measurement) measurement, it was confirmed that sufficient stability was shown up to 350 ° C (FIG. 3).
Claims (5)
[Chemical Formula 1]
In Formula 1, R 1 is each independently an alkyl group or -CH 2 OH, with a carbon number of 1-15 - (CH 2) 2 OH , - (CH 2) 3 OH, - (CH 2) 4 OH, - (CH 2) 5 OH, - (CH 2) 6 OH, - (CH 2) 7 OH, - (CH 2) 8 OH, - (CH 2) 9 OH, - (CH 2) 10 OH, - (CH 2) 11 OH, - (CH 2 ) 12 OH or
Wherein A 1, A 2, A 3 are each independently an alkyl group or -CH 2 OH, with a carbon number of 1-15 - (CH 2) 2 OH , - (CH 2) 3 OH, - (CH 2) 4 OH, - (CH 2) 5 OH, - (CH 2) 6 OH, - (CH 2) 7 OH, - (CH 2) 8 OH, - (CH 2) 9 OH, - (CH 2) 10 OH, - (CH 2 ) 11 OH, - (CH 2 ) 12 OH.
[Chemical Formula 1]
In Formula 1, R 1 is each independently an alkyl group or -CH 2 OH, with a carbon number of 1-15 - (CH 2) 2 OH , - (CH 2) 3 OH, - (CH 2) 4 OH, - (CH 2) 5 OH, - (CH 2) 6 OH, - (CH 2) 7 OH, - (CH 2) 8 OH, - (CH 2) 9 OH, - (CH 2) 10 OH, - (CH 2) 11 OH, - (CH 2 ) 12 OH or
Wherein A 1, A 2, A 3 are each independently an alkyl group or -CH 2 OH, with a carbon number of 1-15 - (CH 2) 2 OH , - (CH 2) 3 OH, - (CH 2) 4 OH, - (CH 2) 5 OH, - (CH 2) 6 OH, - (CH 2) 7 OH, - (CH 2) 8 OH, - (CH 2) 9 OH, - (CH 2) 10 OH, - (CH 2 ) 11 OH, - (CH 2 ) 12 OH.
a) adding a compound of the formula (2), a reactant of the formula (3), and a metal catalyst, and then reacting to synthesize a benzonitrile derivative compound of the formula (4); And
b) reacting the benzonitrile derivative compound with a compound of formula (5) to produce a diketopyrrolopyrrole derivative of formula (1).
[Chemical Formula 1]
(2)
In Formula 1 and 2, R 1 are each independently an alkyl group having 1-15 or -CH 2 OH, - (CH 2 ) 2 OH, - (CH 2) 3 OH, - (CH 2) 4 OH, - (CH 2) 5 OH, - (CH 2) 6 OH, - (CH 2) 7 OH, - (CH 2) 8 OH, - (CH 2) 9 OH, - (CH 2) 10 OH, - (CH 2 ) 11 OH, - (CH 2 ) 12 OH or
Wherein A 1, A 2, A 3 are each independently an alkyl group or -CH 2 OH, with a carbon number of 1-15 - (CH 2) 2 OH , - (CH 2) 3 OH, - (CH 2) 4 OH, - (CH 2) 5 OH, - (CH 2) 6 OH, - (CH 2) 7 OH, - (CH 2) 8 OH, - (CH 2) 9 OH, - (CH 2) 10 OH, - (CH 2 ) 11 OH, - (CH 2 ) 12 OH.
(3)
(X is any one of Cl, Br, and I)
[Chemical Formula 4]
In Formula 4, R 1 is each independently an alkyl group or -CH 2 OH, with a carbon number of 1-15 - (CH 2) 2 OH , - (CH 2) 3 OH, - (CH 2) 4 OH, - (CH 2) 5 OH, - (CH 2) 6 OH, - (CH 2) 7 OH, - (CH 2) 8 OH, - (CH 2) 9 OH, - (CH 2) 10 OH, - (CH 2) 11 OH, - (CH 2 ) 12 OH or
Wherein A 1, A 2, A 3 are each independently an alkyl group or -CH 2 OH, with a carbon number of 1-15 - (CH 2) 2 OH , - (CH 2) 3 OH, - (CH 2) 4 OH, - (CH 2) 5 OH, - (CH 2) 6 OH, - (CH 2) 7 OH, - (CH 2) 8 OH, - (CH 2) 9 OH, - (CH 2) 10 OH, - (CH 2 ) 11 OH, - (CH 2 ) 12 OH.
[Chemical Formula 5]
Wherein the metal catalyst of step a) is a palladium catalyst (PdCl 2 (pph 3 ) 2 ).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150075031A KR101737001B1 (en) | 2015-05-28 | 2015-05-28 | Diketopyrrolopyrrole derivatives, diketopyrrolopyrrole derivatives dye and method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150075031A KR101737001B1 (en) | 2015-05-28 | 2015-05-28 | Diketopyrrolopyrrole derivatives, diketopyrrolopyrrole derivatives dye and method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20160141139A KR20160141139A (en) | 2016-12-08 |
| KR101737001B1 true KR101737001B1 (en) | 2017-05-18 |
Family
ID=57576914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150075031A KR101737001B1 (en) | 2015-05-28 | 2015-05-28 | Diketopyrrolopyrrole derivatives, diketopyrrolopyrrole derivatives dye and method thereof |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101737001B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200024023A (en) | 2018-08-27 | 2020-03-06 | 동우 화인켐 주식회사 | Diketopyrrolopyrrole Derivatives and Dye Comprising the Same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100032657A1 (en) | 2006-10-12 | 2010-02-11 | Toyo Ink Mfg Co., Ltd | Organic transistor |
-
2015
- 2015-05-28 KR KR1020150075031A patent/KR101737001B1/en active IP Right Grant
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100032657A1 (en) | 2006-10-12 | 2010-02-11 | Toyo Ink Mfg Co., Ltd | Organic transistor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200024023A (en) | 2018-08-27 | 2020-03-06 | 동우 화인켐 주식회사 | Diketopyrrolopyrrole Derivatives and Dye Comprising the Same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20160141139A (en) | 2016-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101955690B (en) | Method for manufacturing the pigment dispersed solution | |
| KR102166216B1 (en) | Green pigment composition for color filter, and color filter | |
| US7888398B2 (en) | Pigment | |
| US20060152570A1 (en) | Intermediate chemical substance in the production of pigment crystals, method for manufacturing pigment crystals using the same, and pigment crystal | |
| KR101988047B1 (en) | High transmissional green dye for lcd and synthetic method thereof | |
| TWI741152B (en) | Quinoline Yellow Compound | |
| JP7047679B2 (en) | Pigment composition, coloring composition and color filter | |
| TWI388632B (en) | Color filter composition and color filter | |
| TW202020061A (en) | Pigment composition, coloring composition and color filter | |
| JP5268230B2 (en) | Novel dye compound and blue resist composition for color filter containing the dye compound | |
| KR101737001B1 (en) | Diketopyrrolopyrrole derivatives, diketopyrrolopyrrole derivatives dye and method thereof | |
| JP7354669B2 (en) | display device | |
| KR102051911B1 (en) | High transmissional yellow dye for lcd and synthetic method thereof | |
| TW200531994A (en) | Color filter for electrical display device | |
| CN112638882A (en) | Alkylene compounds, quinophthalone compounds and quinophthalone mixtures | |
| KR102697047B1 (en) | Diketopyrrolopyrrole compound, manufacturing method thereof, colored photosensitive resin composition comprising same, and color filter employing same | |
| WO2006088171A1 (en) | Novel colorant compound and method of manufacturing the same as well as blue resist composition for use in color filter containing the same | |
| KR101222552B1 (en) | Diketo―pyrrolo―pyrrole Dye Having Good Thermal Resistance For Color Filters And Process Of Processing Thereof | |
| JP7527925B2 (en) | Method for producing xanthene dyes | |
| TWI812745B (en) | quinophthalone compounds | |
| CN112424651B (en) | Color filter | |
| CN110563691B (en) | Dibenzopyran compound, pigment composition, color resist, color filter, and ink composition for inkjet | |
| KR101177633B1 (en) | Process Of Processing Diketo-pyrrolo-pyrrole Dye Having High Transmittance For Color Filters | |
| JP4735793B2 (en) | Colored resist composition and color filter using phthalocyanine pigment | |
| KR101753754B1 (en) | dipyrromethene-type compound, colorant compositions comprising the same, quencher for improving of contrast ratio comprising the same and color filter comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |