CN117946534A - Preparation method of blue dichromatic anthraquinone dye - Google Patents
Preparation method of blue dichromatic anthraquinone dye Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000001000 anthraquinone dye Substances 0.000 title claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- -1 boric acid compound Chemical class 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 238000005859 coupling reaction Methods 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 125000005036 alkoxyphenyl group Chemical group 0.000 claims description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 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 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- VRLDVERQJMEPIF-UHFFFAOYSA-N dbdmh Chemical compound CC1(C)N(Br)C(=O)N(Br)C1=O VRLDVERQJMEPIF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- VBTQNRFWXBXZQR-UHFFFAOYSA-N n-bromoacetamide Chemical compound CC(=O)NBr VBTQNRFWXBXZQR-UHFFFAOYSA-N 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- FXORZKOZOQWVMQ-UHFFFAOYSA-L dichloropalladium;triphenylphosphane Chemical compound Cl[Pd]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FXORZKOZOQWVMQ-UHFFFAOYSA-L 0.000 claims 1
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000012074 organic phase Substances 0.000 description 10
- 239000000975 dye Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UVUZEMDPEFGUPY-UHFFFAOYSA-N 1,8-diamino-4,5-dinitroanthracene-9,10-dione Chemical compound O=C1C2=C([N+]([O-])=O)C=CC(N)=C2C(=O)C2=C1C([N+]([O-])=O)=CC=C2N UVUZEMDPEFGUPY-UHFFFAOYSA-N 0.000 description 2
- NFAACMICJFTIHU-UHFFFAOYSA-N C(CCCC)OC1=CC=C(C=C1)OB(O)O Chemical compound C(CCCC)OC1=CC=C(C=C1)OB(O)O NFAACMICJFTIHU-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000002834 transmittance 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/22—Dyes with unsubstituted amino groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a blue dichromatic anthraquinone dye, wherein the blue dichromatic anthraquinone dye is a compound with a structure of a general formula I-1 or I-2, and the general formula I-1 isThe general formula I-2 is
Description
Technical Field
The invention relates to a preparation method of a dye compound, in particular to a preparation method of a blue dichromatic anthraquinone dye.
Background
The dye liquid crystal material is a guest-host liquid crystal material in which a small amount of a dichroic dye is doped in a host liquid crystal. Due to the existence of the guest-host effect, under the drive of an externally applied electric field, the dichroic dye molecules serving as objects rotate along with the host liquid crystal, the dichroic dye molecules are generally in a long rod shape, the absorption capacity of the long axis and the short axis of the dichroic dye molecules to light are different, and when the dichroic dye molecules rotate, the absorption capacity of the guest-host liquid crystal as a whole also changes, so that the color and the light transmittance are changed, and the purpose of color display is achieved.
The common dichroic dye molecules are azo and anthraquinone, and the azo dye has strong optical performance and excellent solubility, but has poor light and heat stability and limited prospect in commercial application. Anthraquinone dyes are well photostable and thermally stable and can produce vivid colors, and although there is a problem of solubility compared with azo dyes, in practical commercial applications, more anthraquinone dyes are selected.
The color of anthraquinone dye depends on the position and structure of substituent on the mother ring, so that the positioning of substituent is the most critical step in the preparation process of anthraquinone dye, heavy metals are often used in the common preparation method, which can bring pollution problems, in addition, the raw materials of anthraquinone dye have poor solubility, strong acid is often needed to be used as a solvent of a reaction system, and the superposition of the two problems leads to the problems of complex operation, high cost, high pollution, difficult purification and the like of the preparation method of anthraquinone dye.
Disclosure of Invention
The invention aims to provide a preparation method of a blue dichromatic anthraquinone dye, which is simple and convenient to operate, has small pollution and high yield and is easy to purify.
The technical scheme is as follows: in order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a blue dichroic anthraquinone dye.
The dye compound synthesized by the invention is a compound with a general formula I-1 or I-2, wherein the compounds with the general formulas I-1 and I-2 are respectively:
Wherein X is selected from one of alkylphenyl, alkoxyphenyl, cycloalkylphenyl, alkyl-substituted cycloalkylphenyl, alkylphenylethynyl, alkoxyphenylethynyl, cycloalkylphenylethynyl, alkyl-substituted cycloalkylphenylethynyl,
The preparation method comprises the following steps:
(1) Fully dissolving a compound with a formula I-1-1 or I-2-1 and a brominating reagent in an organic solvent, and reacting for 8-24 hours at a temperature controlled within a range of 10-100 ℃ under the protection of inert gas to obtain a compound with a formula I-1-2 or I-2-2, wherein the compounds with the formulas I-1-1 and I-2-1 are respectively:
the compounds of the formula I-1-2 and the formula I-2-2 are respectively:
(2) Fully dissolving the compound of the formula I-1-2 or the formula I-2-2 and a boric acid compound with an X-B (OH) 2 structure in an organic solvent, then adding a weak base reagent and a coupling catalyst, and carrying out a coupling reaction at 20-100 ℃ to obtain a compound of the formula I-1-3 or the formula I-2-3, wherein the compounds of the formula I-1-3 and the formula I-2-3 are respectively:
(3) Fully dissolving the compound of the formula I-1-3 or the formula I-2-3 in an organic solvent, adding a reducing agent, regulating the pH to be weak acid, controlling the temperature to be within the range of 20-100 ℃, and reacting for 2-10 h to obtain the compound of the formula I-1-4 or the formula I-2-4, wherein the compounds of the formula I-1-4 and the formula I-2-4 are respectively:
advantageous effects
Compared with the prior art, the invention has the following advantages:
1. Step 1, positioning substituent groups by using a bromination reagent, and heavy metals are not needed, so that pollution is reduced;
2. the whole reaction system does not use strong acid solvent, and has simple operation and high safety;
3. the final product is convenient to purify, and the yield can reach more than 90%.
Detailed description of the preferred embodiments
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The advantageous effects of the present application will be further described below with reference to examples.
The invention provides a preparation method of a blue dichromatic anthraquinone dye, which is characterized in that the blue dichromatic anthraquinone dye compound prepared by the method has a compound with a general formula I-1 or I-2, and the compounds with the general formulas I-1 and I-2 are respectively as follows:
Wherein X is selected from one of alkylphenyl, alkoxyphenyl, cycloalkylphenyl, alkyl-substituted cycloalkylphenyl, alkylphenylethynyl, alkoxyphenylethynyl, cycloalkylphenylethynyl, alkyl-substituted cycloalkylphenylethynyl.
The total process route diagram of the preparation method is as follows:
The preparation method comprises the following steps:
(1) Will have the formula The compound and a brominating reagent are fully dissolved in an organic solvent, the brominating reagent is selected from one or more of 1, 3-dibromo-5, 5-dimethyl hydantoin, N-bromoacetamide and N-bromosuccinimide, the organic solvent is selected from one or more of N, N-dimethylformamide, acetonitrile and tetrahydrofuran, and the formula/>The mol ratio of the compound to the bromination reagent is 1:2-1:5; then under the protection of inert gas, controlling the temperature to be within the range of 10-100 ℃ and reacting for 8-24 h to obtain the formula/>The crude compound of (2) is pulped, filtered and dried by deionized water and organic solvent respectively to obtain the formula Fine compounds of (3).
(2) The said methodThe compound of (C) and boric acid compound with X-B (OH) 2 structure are fully dissolved in organic solvent, wherein the organic solvent is selected from one or more of toluene, tetrahydrofuran, ethanol and N, N-dimethylformamide, and the formula/> The molar ratio of the compound of (C) to the boric acid compound with the structure of X-B (OH) 2 is 1:2-1:5; then adding a small amount of pure water serving as a weak base reagent and a coupling catalyst, wherein the weak base reagent is selected from one or more of sodium carbonate, potassium carbonate, triethylamine and cesium carbonate, and the coupling catalyst is selected from one or more of bis (triphenylphosphine) palladium dichloride, tetra (triphenylphosphine) palladium, pd132, palladium acetate and palladium chloride. The coupling reaction is carried out at 20-100 ℃, and the reaction is stopped after TLC monitoring until no raw materials exist. Cooling the reaction liquid, adding an organic solvent into the reaction liquid for dilution, standing for layering, extracting an aqueous phase by the organic solvent, merging the aqueous phase into an organic phase, washing the organic phase until the organic phase is neutral, and concentrating the organic phase after drying. Diluting with organic solvent, and collecting product with chromatographic column to obtain formula/>Is a compound of (a).
(3) The said methodThe compound of (2) is fully dissolved in an organic solvent, wherein the organic solvent is selected from one or more of N-methylpyrrolidone, nitrobenzene, N-dimethylformamide, dimethylacetamide and tetrahydrofuran; then adding a reducing agent, wherein the reducing agent is one or more selected from a palladium catalyst, a zinc catalyst, an iron catalyst and a sodium catalyst; and (3) regulating the pH value to be 5-6, controlling the temperature to be 20-100 ℃, performing catalytic hydrogenation reaction for 2-10 h, and stopping the reaction after the hydrogen is not absorbed and no raw material is monitored by sampling TLC. Filtering the reducing agent, stirring the filtrate at room temperature (20-30deg.C) for 2h, concentrating the filtrate, and crystallizing with n-hexane to obtain the final product of formula/>Is a compound of (a).
The advantageous effects of the present invention will be further described below with reference to examples.
Example 1 preparation of 1,4,5, 8-tetramino-2, 6-bis (4' - (pentyloxy) phenyl) -9, 10-anthracenedione
Step 1, preparation of 1, 8-diamino-4, 5-dinitro-2, 7-dibromo-9, 10-anthracenedione
14.9G of 1, 8-diamino-4, 5-dinitroanthraquinone and 34.3g of N-bromosuccinimide are fully dissolved in 300ml of N, N-dimethylformamide and reacted for 12 hours under the protection of nitrogen at room temperature by stirring. Pulping with 1L water, filtering, drying to obtain crude product, and pulping with acetonitrile again. After filtration and drying, 15.5g of 1, 8-diamino-4, 5-dinitro-2, 7-dibromo-9, 10-anthracenedione are obtained, and the yield is 70%.
Step 2, preparation of 1, 8-diamino-4, 5-dinitro-2, 7-bis (4' - (pentyloxy) phenyl) -9, 10-anthracenedione
4.9G of 1, 8-diamino-4, 5-dinitro-2, 7-dibromo-9, 10-anthracene dione and 6.2g of 4-pentoxyphenylboric acid are fully dissolved in 150ml of tetrahydrofuran, then 2.8g of potassium carbonate and 10ml of pure water are added into the system, the temperature is raised for reaction, 0.1g of tetraphenylphosphine palladium is added into the system, the temperature is continuously raised to reflux, and the reaction is stopped after TLC monitoring until no raw materials exist. Cooling the reaction liquid, adding dichloromethane into the reaction liquid for dilution, standing for layering, extracting aqueous phase by using dichloromethane, merging the aqueous phase into an organic phase, washing the organic phase to be neutral, and concentrating the organic phase after drying. The product was collected by chromatography column after dilution with methylene chloride to give 3.53g of 1, 8-diamino-4, 5-dinitro-2, 7-bis (4' - (pentoxy) phenyl) -9, 10-anthracenedione in 54% yield.
Step 3,1, 4,5, 8-tetramino-2, 7-bis (4' - (pentyloxy) phenyl) -9, 10-anthracenedione preparation
Taking 3.3g of the refined product obtained in the previous step, adding 0.17g of 5% palladium-carbon and 70ml of tetrahydrofuran for catalytic hydrogenation, and stopping the reaction after sampling TLC monitors no raw material after hydrogen is not absorbed. Palladium-carbon is filtered, the filtrate is stirred at room temperature (20-30 ℃) for reaction for 2 hours, then concentrated, and n-hexane is added for crystallization, thus obtaining 3g of 1,4,5, 8-tetramino-2, 7-bis (4' - (pentoxy) phenyl) -9, 10-anthracene dione with the yield of 91 percent.
Example 2 preparation of 1,4,5, 8-tetramino-2, 6-bis (4' - (pentyloxy) phenyl) -9, 10-anthracenedione
Step 1, preparation of 1, 8-diamino-4, 5-dinitro-2, 6-dibromo-9, 10-anthracenedione
14.9G of 1, 8-diamino-4, 5-dinitroanthraquinone and 34.3g of N-bromosuccinimide are fully dissolved in 300ml of N, N-dimethylformamide and reacted for 12h under nitrogen protection at room temperature with stirring. Pulping with 1L water, filtering, drying to obtain crude product, and pulping with acetonitrile again. After filtration and drying, 22g of 1, 8-diamino-4, 5-dinitro-2, 6-dibromo-9, 10-anthracenedione are obtained, and the yield is 90%.
Step 2, preparation of 1, 8-diamino-4, 5-dinitro-2, 6-bis (4' - (pentyloxy) phenyl) -9, 10-anthracenedione
4.9G of 1, 8-diamino-4, 5-dinitro-2, 6-dibromo-9, 10-anthracene dione and 6.2g of 4-pentoxyphenylboric acid are fully dissolved in 150ml of tetrahydrofuran, then 2.8g of potassium carbonate and 10ml of pure water are added into the system, the temperature is raised for reaction, 0.1g of tetraphenylphosphine palladium is added into the system, the temperature is continuously raised to reflux, and the reaction is stopped after TLC monitoring until no raw materials exist. Cooling the reaction liquid, adding dichloromethane into the reaction liquid for dilution, standing for layering, extracting aqueous phase by using dichloromethane, merging the aqueous phase into an organic phase, washing the organic phase to be neutral, and concentrating the organic phase after drying. The product was collected by chromatography column after dilution with methylene chloride to give 3.53g of 1, 8-diamino-4, 5-dinitro-2, 6-bis (4' - (pentoxy) phenyl) -9, 10-anthracenedione in 54% yield.
Step 3, preparation of 1,4,5, 8-tetramino-2, 6-bis (4' - (pentyloxy) phenyl) -9, 10-anthracenedione
Taking 3.3g of the refined product obtained in the previous step, adding 0.17g of 5% palladium-carbon and 70ml of tetrahydrofuran for catalytic hydrogenation, and stopping the reaction after sampling TLC monitors no raw material after hydrogen is not absorbed. Palladium-carbon is filtered, the filtrate is stirred at room temperature (20-30 ℃) for reaction for 2 hours, then concentrated, and n-hexane is added for crystallization, thus obtaining 3g of 1,4,5, 8-tetramino-2, 6-bis (4' - (pentoxy) phenyl) -9, 10-anthracene dione with the yield of 91 percent.
By combining the above examples 1-2, the method provided by the invention can achieve the aim of preparing the blue dichroic anthraquinone dye compound by using a simpler operation method, easily-achieved reaction conditions and common organic reagents.
The following liquid crystal compounds can be conveniently prepared with reference to the similar preparation methods using examples 1, 2:
In addition, although the preparation method of the blue anthraquinone dye is not exhaustive, it is anticipated that one skilled in the art will be able to prepare other similar compounds without any inventive effort by combining only his own expertise based on the disclosed examples. Only representative embodiments are listed herein.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing a blue dichroic anthraquinone dye, which is a compound having a general formula I-1 or I-2, wherein the compounds of the general formulas I-1 and I-2 are respectively:
Wherein X is selected from one of alkylphenyl, alkoxyphenyl, cycloalkylphenyl, alkyl-substituted cycloalkylphenyl, alkylphenylethynyl, alkoxyphenylethynyl, cycloalkylphenylethynyl, alkyl-substituted cycloalkylphenylethynyl,
The preparation method comprises the following steps:
(1) Fully dissolving a compound with a formula I-1-1 or I-2-1 and a brominating reagent in an organic solvent, and reacting for 8-24 hours at a temperature controlled within a range of 10-100 ℃ under the protection of inert gas to obtain a compound with a formula I-1-2 or I-2-2, wherein the compounds with the formulas I-1-1 and I-2-1 are respectively:
the compounds of the formula I-1-2 and the formula I-2-2 are respectively:
(2) Fully dissolving the compound of the formula I-1-2 or I-2-2 and a boric acid compound with an X-B (OH) 2 structure in an organic solvent, then adding a weak base reagent dissolved by a small amount of pure water and a coupling catalyst, and carrying out a coupling reaction at 20-100 ℃ to obtain a compound of the formula I-1-3 or I-2-3, wherein the compounds of the formula I-1-3 and I-2-3 are respectively:
(3) Fully dissolving the compound of the formula I-1-3 or the formula I-2-3 in an organic solvent, adding a reducing agent, regulating the pH to be weak acid, controlling the temperature to be within the range of 20-100 ℃, and reacting for 2-10 h to obtain the compound of the formula I-1-4 or the formula I-2-4, wherein the compounds of the formula I-1-4 and the formula I-2-4 are respectively:
2. the method for preparing a blue dichroic anthraquinone dye according to claim 1, wherein said brominating agent in step 1 is selected from one or more of 1, 3-dibromo-5, 5-dimethylhydantoin, N-bromoacetamide, N-bromosuccinimide.
3. The process 1 of the preparation method of blue dichroic anthraquinone dye according to claim 1, wherein the organic solvent in the process 1 is one or more selected from N, N-dimethylformamide, acetonitrile and tetrahydrofuran.
4. The process for preparing a blue dichroic anthraquinone dye according to claim 1, wherein the molar ratio of the compound of formula I-1-1 or I-2-1 to the brominating agent in step 1 is 1:2-1:5.
5. The process 2 of the preparation method of blue dichroic anthraquinone dye according to claim 1, wherein the organic solvent in the process 2 is selected from one or more of toluene, tetrahydrofuran, ethanol, and N, N-dimethylformamide.
6. The method for preparing a blue dichroic anthraquinone dye according to claim 1, wherein said weak base reagent in step 2 is selected from one or more of sodium carbonate, potassium carbonate, triethylamine, cesium carbonate.
7. The process 2 of the preparation method of blue dichroic anthraquinone dye according to claim 1, wherein the coupling catalyst in the process 2 is one or more selected from the group consisting of bis triphenylphosphine palladium dichloride, tetra triphenylphosphine palladium, pd132, palladium acetate and palladium chloride.
8. The process for preparing a blue dichroic anthraquinone dye according to claim 1, wherein the molar ratio of the compound of formula I-1-2 or I-2-2 to the boric acid compound having the structure X-B (OH) 2 in step 2 is 1:2 to 1:5.
9. The process for preparing a blue dichroic anthraquinone dye according to claim 1, wherein said organic solvent in step 3 is selected from one or more of N-methylpyrrolidone, nitrobenzene, N-dimethylformamide, dimethylacetamide.
10. The method for preparing a blue dichroic anthraquinone dye according to claim 1, wherein said reducing agent in step 3 is selected from one or more of palladium catalyst, zinc catalyst, iron catalyst, sodium catalyst.
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