CN102167701A - Fluorine-containing diphenyl-pyrrolo-pyrrolidinedione (DPP) pigments and preparation method thereof - Google Patents
Fluorine-containing diphenyl-pyrrolo-pyrrolidinedione (DPP) pigments and preparation method thereof Download PDFInfo
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 40
- 239000011737 fluorine Substances 0.000 title claims abstract description 39
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000000049 pigment Substances 0.000 title abstract description 11
- 238000002360 preparation method Methods 0.000 title description 4
- AQDXOENJKIIKFC-UHFFFAOYSA-N 2,3-diphenyl-1,4-dihydropyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound O=C1C(=O)NC2=C1NC(C=1C=CC=CC=1)=C2C1=CC=CC=C1 AQDXOENJKIIKFC-UHFFFAOYSA-N 0.000 title 1
- 150000003233 pyrroles Chemical class 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 4
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 9
- -1 xenyl Chemical group 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract 6
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 abstract 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000007787 solid Substances 0.000 description 18
- 238000010992 reflux Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 4
- 239000005695 Ammonium acetate Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 4
- 235000019257 ammonium acetate Nutrition 0.000 description 4
- 229940043376 ammonium acetate Drugs 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 239000012230 colorless oil Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 0 *c(c(F)cc(C(C(C1C(c(c(F)c(c(F)c2F)F)c2F)N2)C2=O)NC1=O)c1)c1F Chemical compound *c(c(F)cc(C(C(C1C(c(c(F)c(c(F)c2F)F)c2F)N2)C2=O)NC1=O)c1)c1F 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YXWJGZQOGXGSSC-UHFFFAOYSA-N 2,3,4,5,6-pentafluorobenzonitrile Chemical compound FC1=C(F)C(F)=C(C#N)C(F)=C1F YXWJGZQOGXGSSC-UHFFFAOYSA-N 0.000 description 1
- RAAGZOYMEQDCTD-UHFFFAOYSA-N 2-fluorobenzoyl chloride Chemical compound FC1=CC=CC=C1C(Cl)=O RAAGZOYMEQDCTD-UHFFFAOYSA-N 0.000 description 1
- WLPATYNQCGVFFH-UHFFFAOYSA-N 2-phenylbenzonitrile Chemical compound N#CC1=CC=CC=C1C1=CC=CC=C1 WLPATYNQCGVFFH-UHFFFAOYSA-N 0.000 description 1
- AENWELNMNRFMBH-UHFFFAOYSA-N CCOC(C(C1)C(C2=CCCC=C2)NC1=O)=O Chemical compound CCOC(C(C1)C(C2=CCCC=C2)NC1=O)=O AENWELNMNRFMBH-UHFFFAOYSA-N 0.000 description 1
- KSOOPPHQQIUBOV-UHFFFAOYSA-N O=C(C(C12)C(c(cc3)ccc3F)NC1=O)NC2c1cc(F)cc(F)c1 Chemical compound O=C(C(C12)C(c(cc3)ccc3F)NC1=O)NC2c1cc(F)cc(F)c1 KSOOPPHQQIUBOV-UHFFFAOYSA-N 0.000 description 1
- PMBWYDCSOSTTDK-UHFFFAOYSA-N [Br].CCOC(C)=O Chemical compound [Br].CCOC(C)=O PMBWYDCSOSTTDK-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- RQGPLDBZHMVWCH-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole Chemical class C1=NC2=CC=NC2=C1 RQGPLDBZHMVWCH-UHFFFAOYSA-N 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
Classifications
-
- 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)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
本发明涉及一种含氟1，4-二酮吡咯[3，4-C]并吡咯衍生物，其结构如式I所示。本发明所揭示的含氟1，4-二酮吡咯[3，4-C]并吡咯衍生物可用作颜料，其丰富了现有DPP类颜料的色谱。式I中，A和B分别独立选自：芳环基、杂环基、含氟芳环基或含氟杂环基杂环基中一种，且A和B中至少有一个为含氟芳环基或含氟杂环基杂环基；其中，所说的杂环基或含氟芳环基的杂原子选自：N、O或S中一种或二种以上，杂原子的个数为1～3的整数。The invention relates to a fluorine-containing 1,4-diketopyrrole[3,4-C]pyrrole derivative, the structure of which is shown in formula I. The fluorine-containing 1,4-diketopyrrole[3,4-C]pyrrole derivative disclosed in the present invention can be used as a pigment, which enriches the color spectrum of existing DPP pigments.
In formula I, A and B are independently selected from one of: aromatic ring group, heterocyclic group, fluorine-containing aromatic ring group or fluorine-containing heterocyclic group heterocyclic group, and at least one of A and B is a fluorine-containing aromatic ring group. Cyclic group or fluorine-containing heterocyclic heterocyclic group; wherein, the heteroatoms of said heterocyclic group or fluorine-containing aromatic ring group are selected from one or more of N, O or S, and the number of heteroatoms It is an integer of 1 to 3.
Description
Technical field
The present invention relates to a kind of fluorine-containing Pyrrolopyrrole derivatives, specifically, relate to a kind of fluorine-containing 1,4-diketone pyrroles [3,4-C] and pyrrole derivative.
Background technology
1,4-diketone pyrroles [3,4-C] and azoles are a kind of high performance pigments (being called for short DPP class pigment).DPP class pigment has high tinctorial strength, good flowability, dispersiveness and acidproof/alkalescence and solvent resistance, is highly suitable for automobile finish, plastics and high-grade industrial coating.
Yet the chromatogram of existing DPP class pigment is essentially ruddiness, and chromatogram is narrower, and is still unsatisfactory.
Summary of the invention
The present inventor introduces fluorine atom having 1 now in 4-diketone pyrroles [3,4-C] and the azoles, obtain the fluorine-containing 1 of a kind of novelty, 4-diketone pyrroles [3,4-C] and pyrrole derivative, find that its coloured light is the gold-tinted redness, enriched the chromatogram of existing DPP class pigment.
Of the present invention fluorine-containing 1,4-diketone pyrroles [3,4-C] and pyrrole derivative, its structure is suc as formula shown in the I:
Among the formula I, A and B independently are selected from respectively: a kind of in aromatic ring yl, heterocyclic radical, fluorine-containing aromatic ring yl or the fluorine-containing heterocyclic radical heterocyclic radical, and have at least one to be fluorine-containing aromatic ring yl or fluorine-containing heterocyclic radical heterocyclic radical among A and the B;
Wherein, the heteroatoms of said heterocyclic radical or fluorine-containing aromatic ring yl is selected from: among N, O or the S one or two or more kinds (containing two kinds), heteroatomic number is 1～3 integer.
The present invention also provides the method for compound shown in a kind of preparation formula I, and its key step is: by lactam analog compound (its structure is suc as formula shown in the II) and corresponding nitrile (BCN) reaction, make target compound (compound shown in the formula I).
Among the formula II, R is that (preferred R is C to alkyl or virtue (perfume (or spice)) base
1～C
6The straight or branched alkyl, preferred R is C
1～C
3The straight or branched alkyl); The definition of A is described identical with preamble.
Embodiment
In optimized technical scheme of the present invention, A and B independently are selected from respectively: C
6～C
20Aromatic ring yl or fluorine-containing C
6～C
20Aromatic ring yl is a kind of, and has at least one to be fluorine-containing C among A and the B
6～C
20Aromatic ring yl;
Preferred technical scheme is that A and B independently are selected from respectively: C
6～C
12Aromatic ring yl or fluorine-containing C
6～C
12Aromatic ring yl is a kind of, and has at least one to be fluorine-containing C among A and the B
6～C
12Aromatic ring yl;
Best technical scheme is, A and B independently are selected from respectively: a kind of in the group shown in group shown in group, the formula V shown in group, the formula IV or the formula VI shown in phenyl, xenyl, naphthyl, the formula III, and have at least one to be group shown in formula III, IV, V or the VI among A and the B:
Wherein: m is 1～7 integer; N is 1～5 integer; P is that 0～5 integer, q are 0～4 integer, and p and q are not zero simultaneously; The curve place of marking is the position of substitution.
The method of compound shown in the preparation formula I provided by the present invention (target compound), its synthetic route is as follows:
Specifically comprise the steps:
(1) under 0 ℃, (mass concentration is 10%～20% in the NaOH solution of compound shown in the formula VIII (specifically as methyl aceto acetate etc.),) drip compound shown in the formula VII, dropwise, kept at least 1 hour at room temperature (20 ℃～30 ℃) state, add ammonium chloride again, stir after at least 0.5 hour, obtain compound shown in the formula IX through extraction, drying and underpressure distillation successively;
(2) under alkaline condition, dripping bromine ethyl acetate in the ethanolic soln of compound shown in the formula IX refluxes after 24 hours at least, filters out solid inorganic alkali or salt, and with washing with alcohol inorganic salt salt, filtrate steaming removal solvent, underpressure distillation obtains compound shown in the formula X;
(3) compound shown in the formula X and ammonium acetate were refluxed 20 hours in acetate at least, reaction solution is poured in the frozen water, filters, and washing leaching cake, filter cake obtain compound shown in the formula II after with the methylene dichloride recrystallization;
(4) having under rare gas element (as nitrogen etc.) existence condition, with compound shown in the formula II and nitrile compounds (BCN, wherein the definition of B is described identical with preamble) in the tertiary amyl alcohol solution of sodium tert-amyl alcohol, refluxed at least 6 hours, then the gained reaction solution is joined (protonated) in the mixing solutions of forming by methyl alcohol, water and acetate, filter and washing leaching cake, obtain target compound (compound shown in the formula I) after the drying.
Disclosed fluorine-containing 1,4-diketone pyrroles [3,4-C] and pyrrole derivative can be used as pigment, and it has enriched the chromatogram of existing DPP class pigment.
The present invention is further elaborated below by embodiment, and listed embodiment does not limit protection scope of the present invention.
In the following example.Said room temperature is 20 ℃～30 ℃
Embodiment 1
(1) mass concentration is that 15% aqueous sodium hydroxide solution 150ml is cooled to 0 ℃ under ice bath, add methyl aceto acetate (13.00g then, 0.1mol), under the mechanical stirring, slowly drip Benzoyl chloride (15.47g, 0.11mol) in above mixed solution, drip off finish after, be warming up to room temperature, TLC follows the tracks of reaction, and (reaction times is about 1 hour, silica-gel plate, developping agent ethyl acetate: sherwood oil=1: 1 (v/v)) to terminal, add ammonium chloride (5.30g, 0.1mol), behind the stirring 0.5h, petroleum ether extraction (30ml * 3) water, merge organic phase, behind the anhydrous magnesium sulfate drying, underpressure distillation obtains colorless oil 15.99g, structure is suc as formula shown in the IX-1, productive rate 83.2%;
1H-NMR(400Hz，CDCl
3)：δ＝1.23-1.27(t，3H)，3.99(s，2H)，4.19-4.28(m，2H)，7.46-7.50(t，2H，)，7.56-7.61(t，1H)，7.93-7.97(t，2H，)；
13C-NMR：δ＝14.1，48.2，61.5，128.4，128.7，133.5，133.9，170.1，190.5；MS：M
+＝192.1。
(2) compound shown in the formula IX-1 (10.19g, 0.053mol), K
2CO
3(7.62g, 0.055mol) (9.02g 0.054mol) is suspended in the 100ml ethanolic soln reflux 24h with ethyl bromoacetate.Cool to room temperature filters out solid matter then, and uses the washing with alcohol solid, merges ethanolic soln, and underpressure distillation obtains colorless oil 11.73g, and structure is suc as formula shown in the X-1, productive rate 79.5%.
1H-NMR(400Hz，CDCl
3)：δ＝1.15-1.19(t，3H)，1.22-1.26(t，3H)，3.00-3.14(m，2H)，4.12-4.18(m4H)，4.86-4.90(t，1H)，7.49-7.53(t，2H)，7.60-7.63(t，1H)，8.04-8.06(t，2H)；
13C-NMR：14.1，35.2，49.1，61.3，128.6，128.8，133.5，135.5，169.9，173.3，195.1；MS：M
+＝278.3。
(3) compound shown in the formula X-1 (11.13g, 0.04mol) and ammonium acetate (TLC controls reaction end for 12.31g, the 0.16mol) 20h that refluxes in 50ml acetate.Reactant is poured in the 200ml frozen water then, has a large amount of light yellow solids to separate out at once, filters, and uses the frozen water washing leaching cake, after the drying, uses the methylene dichloride recrystallization, obtains 7.56 white solids, and structure is suc as formula shown in the II-1, productive rate 81.7%;
1H-NMR(400Hz，CDCl
3)：δ＝1.03-1.07(t，3H)，3.33-3.35(d，2H)，3.92-3.98(m，2H)，7.40-7.47(m，3H)，7.54-7.58(m，2H)，10.64(br?s，1H)；
13C-NMR：δ＝14.4，48.2，61.1，127.8，128.5，132.3，133.9，168.8，192.7；MS：M
+＝231.1；mp：180-182℃。
(4) under nitrogen protection, (0.92g 0.04mol) joins in the 30ml tertiary amyl alcohol, adds the FeCl of catalytic amount then with sodium Metal 99.5
3, reflux, the sodium reaction finishes behind the 2h, and (2.06g, 0.02mol), (4.62g 0.02mol) is dissolved in the 20ml tertiary amyl alcohol compound shown in the formula II-1, slowly is added drop-wise in the above-mentioned solution, and 2h dropwises to add the benzene nitrile.Under reflux state, keep 5h then.Reaction solution is cooled to 60 ℃, adds the mixing solutions 50ml that is made up of methyl alcohol, water and acetate, and behind the stirring at room 2h, backflow 2h filters, and methyl alcohol and water washing filter cake with hot obtain gold-tinted red solid 4.58g, and structure is suc as formula shown in the I-1, productive rate 79.9%.
Embodiment 2
Under nitrogen protection, (0.92g 0.04mol) joins in the 30ml tertiary amyl alcohol, adds the FeCl of catalytic amount then with sodium Metal 99.5
3, reflux, the sodium reaction finishes behind the 2h, and (3.58g, 0.02mol), (4.62g 0.02mol) is dissolved in the 20ml tertiary amyl alcohol compound shown in the formula II-1, slowly is added drop-wise in the above-mentioned solution, and 2h dropwises to phenyl benzene nitrile in adding.Under reflux state, continue reaction 5h then.Reaction solution is cooled to 60 ℃, adds the mixing solutions 50ml of methyl alcohol, water and acetate, and behind the stirring at room 2h, backflow 2h filters, and methyl alcohol and water washing filter cake with heat obtain purple light red solid 5.88g, and structure is suc as formula shown in the I-2, productive rate 80.7%;
Embodiment 3
Under nitrogen protection, (0.92g 0.04mol) joins in the 30ml tertiary amyl alcohol, adds the FeCl of catalytic amount then with sodium Metal 99.5
3, reflux, the sodium reaction finishes behind the 2h, and (2.18g, 0.02mol), (4.62g 0.02mol) is dissolved in the 20ml tertiary amyl alcohol compound shown in the formula II-1, slowly is added drop-wise in the above-mentioned solution, and 2h dropwises to add nitrilthiophene.Under reflux state, continue reaction 5h then.Reaction solution is cooled to 60 ℃, adds the mixing solutions 50ml of methyl alcohol, water and acetate, and behind the stirring at room 2h, backflow 2h filters, and methyl alcohol and water washing filter cake with heat obtain red solid 4.54g, and structure is suc as formula shown in the I-3, productive rate 77.2%.
Embodiment 4
(1) the aqueous sodium hydroxide solution 150ml of mass concentration 15% is cooled to 0 ℃ under ice bath, add then methyl aceto acetate (13.00g, 0.1mol), under the mechanical stirring, drip slowly that (15.90g is 0.11mol) in above mixed solution, after dropwising to fluorobenzoyl chloride, be warming up to room temperature, TLC follows the tracks of reaction, and (reaction times is about 1 hour, silica-gel plate, ethyl acetate: sherwood oil=1: 1 (v/v)) to terminal, add ammonium chloride (5.30g, 0.1mol), behind the stirring 0.5h, petroleum ether extraction (30ml * 3) water, merge organic phase, behind the anhydrous magnesium sulfate drying, underpressure distillation obtains light yellow oil 17.02g, shown in the structural formula IX-2, productive rate 81.0%;
1H-NMR(400Hz，CDCl
3)：δ＝1.21-1.25(t，3H)，3.97(s，2H)，4.15-4.21(m，2H)，7.10-7.14(t，2H，)，7.96-7.98(d，2H)；
13C-NMR：δ＝14.09，45.96，61.55，115.86.131.39，167.39，164.44，167.38，191.03，191.07；MS：M
+＝210.1。
(2) compound shown in the formula IX-2 (11.11g, 0.053mol), K
2CO
3(7.62g, 0.055mol) with ethyl bromoacetate (9.02g 0.054mol) is suspended in the 100ml ethanolic soln, reflux 24h, TLC controls reaction end.Cool to room temperature filters out solid matter then, and uses the washing with alcohol solid, merges ethanolic soln, and underpressure distillation obtains colorless oil 12.02g, and structure is suc as formula shown in the X-2, productive rate 76.4%;
1H-NMR(400Hz，CDCl
3)：δ＝1.19-1.25(m，6H)，3.10-3.15(m，2H)，4.11-4.17(m，4H)，4.83-4.87(t，1H)，7.56-7.62(m，2H)，8.59-8.65(m，2H)；
13C-NMR：δ＝13.7，13.9，33.1，49.4，60.8，61.6，128.5，128.7，133.5，135.8，168.5，171.0；MS：M
+＝296.1。
(3) compound (11.92g shown in the formula X-2,0.04mol) and ammonium acetate (reactant is poured in the 200ml frozen water then for 12.31g, the 0.16mol) 20h that refluxes in 50ml acetate, there are a large amount of light yellow solids to separate out at once, filter, use the frozen water washing leaching cake, after the drying, use the methylene dichloride recrystallization, obtain the 7.92g white solid, structure is suc as formula shown in the II-2, productive rate 80.2%.
1H-NMR(400Hz，CDCl
3)：δ＝1.17-1.21(t，3H)，3.49(s，2H)，4.10-4.14(m，2H)，7.41-7.49(m，2H)，7.58-7.62(m，2H)，9.12(br?s，1H)；
13C-NMR：δ＝14.5，39.1，60.4，105.0，128.6，129.1，130.0，130.9，151.6，163.6，177.5；MS：M
+＝249.1；mp：190-192℃；
(4) under nitrogen protection, (0.92g 0.04mol) joins in the 30ml tertiary amyl alcohol, adds the FeCl of catalytic amount then with sodium Metal 99.5
3, reflux, the sodium reaction finishes behind the 2h, adds 3, and (2.78g, 0.02mol), (5.00g 0.02mol) is dissolved in the 20ml tertiary amyl alcohol compound shown in the formula II-2 5-difluorobenzonilyile, slowly is added drop-wise in the above-mentioned solution, and 2h dropwises.Under reflux state, keep 5h then.Reaction solution is cooled to 60 ℃, adds the mixing solutions 50ml that is made up of methyl alcohol, water and acetate, and behind the stirring at room 2h, backflow 2h filters, and methyl alcohol and water washing filter cake with hot obtain gold-tinted red solid 5.11g, and structure is suc as formula shown in the I-4, productive rate 75.0%.
Embodiment 5
(1) mass concentration is that 150ml is cooled to 0 ℃ in 15% the aqueous sodium hydroxide solution under ice bath, add then methyl aceto acetate (13.00g, 0.1mol), under the mechanical stirring, slowly drip 3,4, the 5-trifluorobenzoyl chloride (21.40g, 0.11mol), after dropwising, be warming up to room temperature, TLC follows the tracks of reaction, and (reaction times is about 1 hour, silica-gel plate, ethyl acetate: sherwood oil=1: 1 (v/v)) to terminal, add ammonium chloride (5.30g, 0.1mol), behind the stirring 0.5h, petroleum ether extraction (30ml * 3), merge organic phase, behind the anhydrous magnesium sulfate drying, underpressure distillation obtains light yellow oil 20.37g, structure is suc as formula shown in the IX-3, productive rate 82.8%;
1H-NMR(400Hz，CDCl
3)：δ＝1.25-1.29(t，3H)，3.51(s，2H)，4.07-4.13(m，2H)，7.25-7.27(d，2H)；
13C-NMR：δ＝14.1，48.2，61.0，110.8，134.5，144.7，160.4，168.9，190.1；MS：M
+＝246.2。
(2) compound shown in the formula IX-3 (13.00g, 0.053mol), K
2CO
3(7.61g, 0.055mol) (9.00g 0.054mol) is suspended in the 100ml ethanolic soln reflux 24h with ethyl bromoacetate, cool to room temperature then, filter out solid matter, and use the washing with alcohol solid, merge ethanolic soln, underpressure distillation, obtain colorless oil 13.91g, structure is suc as formula shown in the X-3, productive rate 79.5%.
1H-NMR(400Hz，CDCl
3)：δ＝1.21-1.27(m，6H)，3.11-3.17(m，2H)，4.08-4.14(m，4H)，4.43-4.47(t，1H)，7.28-7.34(m，2H)；
13C-NMR：δ＝14.1.35.2，49.1，61.3，110.8，135.5，144.5，159.5，169.9，173.1，195.2；MS：M
+＝332.1。
(3) compound (13.31g shown in the formula X-3,0.04mol) and ammonium acetate (reactant is poured in the 200ml frozen water then for 12.32g, the 0.16mol) 20h that refluxes in 50ml acetate, a large amount of again at once solids are separated out, filter, use the frozen water washing leaching cake, after the drying, use the methylene dichloride recrystallization, obtain the 9.12g solid, structure is suc as formula shown in the II-3, productive rate 80.5%.
1H-NMR(400Hz，CDCl
3)：δ＝1.22-1.26(t，3H)，2.87(s，2H)，4.11-4.17(m，2H)，7.17-7.23(m，2H)，9.21(br?s，1H)；
13C-NMR：δ＝14.7，61.7，42.7，101.2，108.4，133.8，139.4，144.8，167.7，180.1；MS：M
+＝285.1；mp：216-218℃。
(4) under nitrogen protection, (0.92g 0.04mol) joins in the 30ml tertiary amyl alcohol, adds the FeCl of catalytic amount then with sodium Metal 99.5
3, reflux, the sodium reaction finishes behind the 2h, and (3.86g, 0.02mol), (5.71g 0.02mol) is dissolved in the 20ml tertiary amyl alcohol compound shown in the formula II-3, slowly is added drop-wise in the above-mentioned solution, and 2h dropwises to add the penta fluoro benzene nitrile.Under reflux state, keep 5h then.Reaction solution is cooled to 60 ℃, adds the mixing solutions 50ml that is made up of methyl alcohol, water and acetate, and behind the stirring at room 2h, backflow 2h filters, and methyl alcohol and water washing filter cake with hot obtain gold-tinted red solid 6.40g, and structure is suc as formula shown in the I-5, productive rate 73.9%.
Claims (6)
- One kind fluorine-containing 1,4-diketone pyrroles [3,4-C] and pyrrole derivative, its structure is suc as formula shown in the I:
Among the formula I, A and B independently are selected from respectively: a kind of in aromatic ring yl, heterocyclic radical, fluorine-containing aromatic ring yl or the fluorine-containing heterocyclic radical heterocyclic radical, and have at least one to be fluorine-containing aromatic ring yl or fluorine-containing heterocyclic radical heterocyclic radical among A and the B;Wherein, the heteroatoms of said heterocyclic radical or fluorine-containing aromatic ring yl is selected from: N, 0 or S in one or two or more kinds, heteroatomic number is 1～3 integer. - 2. as claimed in claim 1 fluorine-containing 1,4-diketone pyrroles [3,4-C] and pyrrole derivative is characterized in that wherein A and B independently are selected from respectively: C 6～C 20Aromatic ring yl or fluorine-containing C 6～C 20Aromatic ring yl is a kind of, and has at least one to be fluorine-containing C among A and the B 6～C 20Aromatic ring yl.
- 3. as claimed in claim 2 fluorine-containing 1,4-diketone pyrroles [3,4-C] and pyrrole derivative is characterized in that wherein A and B independently are selected from respectively: C 6～C 12Aromatic ring yl or fluorine-containing C 6～C 12Aromatic ring yl is a kind of, and has at least one to be fluorine-containing C among A and the B 6～C 12Aromatic ring yl.
- 4. as claimed in claim 3 fluorine-containing 1,4-diketone pyrroles [3,4-C] and pyrrole derivative, it is characterized in that, wherein A and B independently are selected from respectively: a kind of in the group shown in group shown in group, the formula V shown in group, the formula IV or the formula VI shown in phenyl, xenyl, naphthyl, the formula III, and have at least one to be group shown in formula III, IV, V or the VI among A and the B:
Wherein: m is 1～7 integer; N is 1～5 integer; P is that 0～5 integer, q are 0～4 integer, and p and q are not zero simultaneously; The curve place of marking is the position of substitution. - 5. as claimed in claim 4 fluorine-containing 1,4-diketone pyrroles [3,4-C] and pyrrole derivative is characterized in that, described fluorine-containing 1,4-diketone pyrroles [3,4-C] and pyrrole derivative are compound shown in formula I-4 or the formula I-5:
- 6. one kind prepares as described in the claim 1～5 any one fluorine-containing 1,4-diketone pyrroles [3,4-C] and the method for pyrrole derivative, it is characterized in that, the key step of described method is: having under the rare gas element existence condition, refluxed at least 6 hours in the tertiary amyl alcohol solution of sodium tert-amyl alcohol by compound shown in the formula II and BCN, after protonated, filtration, washing leaching cake and drying, obtain target compound successively then;Among the formula II, R is C 1～C 6The straight or branched alkyl, the definition of A and B with as identical as described in the claim 1～5 any one.
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| JP2015168725A (en) * | 2014-03-05 | 2015-09-28 | 東洋インキＳｃホールディングス株式会社 | Pigment additive, pigment composition using the same, coloring composition, and color filter |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1231167A (en) * | 1998-03-27 | 1999-10-13 | 莱雅公司 | Cosmitis compositions containing novel pigment |
| CN1297450A (en) * | 1998-04-22 | 2001-05-30 | 西巴特殊化学品控股有限公司 | Preparation of alkylthio- and/or arylthio-substd. diketo-diaryl-pyrrolopyrroles |
| WO2004007604A1 (en) * | 2002-07-17 | 2004-01-22 | Ciba Specialty Chemicals Holding Inc. | High-molecular-weight polymeric material comprising diketopyrrolopyrrole pigments |
| CN1749327A (en) * | 2005-09-28 | 2006-03-22 | 华东理工大学 | A kind of preparation method of DPP pigment |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1231167A (en) * | 1998-03-27 | 1999-10-13 | 莱雅公司 | Cosmitis compositions containing novel pigment |
| CN1297450A (en) * | 1998-04-22 | 2001-05-30 | 西巴特殊化学品控股有限公司 | Preparation of alkylthio- and/or arylthio-substd. diketo-diaryl-pyrrolopyrroles |
| WO2004007604A1 (en) * | 2002-07-17 | 2004-01-22 | Ciba Specialty Chemicals Holding Inc. | High-molecular-weight polymeric material comprising diketopyrrolopyrrole pigments |
| CN1749327A (en) * | 2005-09-28 | 2006-03-22 | 华东理工大学 | A kind of preparation method of DPP pigment |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2015168725A (en) * | 2014-03-05 | 2015-09-28 | 東洋インキＳｃホールディングス株式会社 | Pigment additive, pigment composition using the same, coloring composition, and color filter |
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