CN103073397B - Preparation method of 2,3,6,7,10,11-hexahydroxy triphenylene - Google Patents
Preparation method of 2,3,6,7,10,11-hexahydroxy triphenylene Download PDFInfo
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- CN103073397B CN103073397B CN201310031520.4A CN201310031520A CN103073397B CN 103073397 B CN103073397 B CN 103073397B CN 201310031520 A CN201310031520 A CN 201310031520A CN 103073397 B CN103073397 B CN 103073397B
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- dimethoxy benzene
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- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- QMLILIIMKSKLES-UHFFFAOYSA-N triphenylene-2,3,6,7,10,11-hexol Chemical group C12=CC(O)=C(O)C=C2C2=CC(O)=C(O)C=C2C2=C1C=C(O)C(O)=C2 QMLILIIMKSKLES-UHFFFAOYSA-N 0.000 title claims abstract description 31
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 110
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 claims abstract description 102
- 238000003756 stirring Methods 0.000 claims abstract description 83
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 55
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000007787 solid Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 46
- 238000005829 trimerization reaction Methods 0.000 claims description 45
- 235000010265 sodium sulphite Nutrition 0.000 claims description 23
- 238000001291 vacuum drying Methods 0.000 claims description 19
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims 1
- 230000008676 import Effects 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 38
- 238000001035 drying Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract 2
- 239000002244 precipitate Substances 0.000 abstract 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 229910052979 sodium sulfide Inorganic materials 0.000 abstract 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 30
- 230000001105 regulatory effect Effects 0.000 description 16
- SLGBZMMZGDRARJ-UHFFFAOYSA-N triphenylene Chemical compound C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
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- Fats And Perfumes (AREA)
- Cosmetics (AREA)
Abstract
The invention relates to a preparation method of 2,3,6,7,10,11-hexahydroxy triphenylene, which comprises the following steps of: Step 1, preparing tripoly o-dimethoxybenzene, Step 2, adding tripoly o-dimethoxybenzene into N-methyl pyrrolidone, Step 3, adding a certain amount of sodium sulfide while stirring, Step 4, heating to certain temperature, Step 5,stirring at the constant temperature, Step 6, cooling, Step 7, adding a certain amount of deionized water, Step 8, using hydrochloric acid to adjust a pH (potential of hydrogen) value, separating a precipitate out, filtering, Step 9, dissolving a filter residue in a certain amount of tetrahydrofuran, dropwise adding methylene chloride at a certain proportion, separating a precipitate out, filtering, and Step 10, obtaining a white solid, and drying to obtain 2,3,6,7,10,11-hexahydroxy triphenylene. 2,3,6,7,10,11-hexahydroxy triphenylene prepared by the preparation method is the white solid, the appearance is attractive, and the purity is greater than 99%.
Description
Technical field
The present invention relates to a kind of preparation method of 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene.
Background technology
The compound being made up of three phenyl ring is to separate from the lysate of benzene the earliest, and be first referred to as benzophenanthrene (triphenybene) by Schultz, benzophenanthrene is due to its special structure, make it have good optics and electric property, at present, along with organic, polymer is in the breakthrough of optoelectronic areas, benzophenanthrene and derivative thereof more and more receive publicity.
2,3,6,7,10,11-hexahydroxy-benzo phenanthrene is a kind of important intermediate in synthetic triphenylene, traditionally, can pyrocatechol be made or reduce quinone to form (NO.1993/118642 as open in the patent of Japanese unexamined) by transistion metal compound (as iron trichloride), but the product purity obtaining be not high, color is black, and outward appearance is very poor.
Therefore, invent a kind of newly 2,3,6,7,10, the preparation method of 11-hexahydroxy-benzo phenanthrene improves purity and the outward appearance of product, and real is the task of top priority.
Summary of the invention
The technical problem to be solved in the present invention is: overcome that traditional preparation method makes 2,3,6, the defect that 7,10,11-hexahydroxy-benzo phenanthrene is black, appearance poor, purity is low, preparation method of the present invention make 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene, it is white solid, purity >99%, the product purity making than traditional method is higher, and outward appearance is also attractive in appearance.
In order to solve the problems of the technologies described above, the present invention proposes following technical scheme: a kind of preparation method of 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene, it comprises the steps:
Step 1: prepare trimerization 1,2-dimethoxy benzene;
Step 2: trimerization 1,2-dimethoxy benzene is joined in N-Methyl pyrrolidone;
Step 3: under stirring, add a certain amount of sodium sulphite;
Step 4: be heated to certain temperature;
Step 5: constant temperature stirs;
Step 6: cooling;
Step 7: add a certain amount of deionized water;
Step 8: regulate pH value with hydrochloric acid, separate out precipitation, filter;
Step 9: filter residue is dissolved in a certain amount of tetrahydrofuran (THF), drips a certain proportion of methylene dichloride, separates out precipitation, filters;
Step 10: obtain white solid, be dried and can obtain 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene.
The further restriction of technique scheme is, in above-mentioned steps 1, the method for preparing trimerization 1,2-dimethoxy benzene is as follows: in ethylene dichloride, add Vanadium Pentoxide in FLAKES, the vitriol oil, iron trichloride, stir; Ice bath, under nitrogen protection, drips 1,2-dimethoxy benzene, dropwises stirring at room temperature 24 hours; Be poured into water, separate ethylene dichloride layer, dry, evaporate to dryness, the solid obtaining is trimerization 1,2-dimethoxy benzene.
The further restriction of technique scheme is, in above-mentioned steps 2, the part by weight of trimerization 1,2-dimethoxy benzene and N-Methyl pyrrolidone is 1:3～1:20, preferably 1:8～1:12.
The further restriction of technique scheme is, in above-mentioned steps 3, the part by weight of trimerization 1,2-dimethoxy benzene and sodium sulphite is 1:3～1:10, preferably 1:5.
The further restriction of technique scheme is, in above-mentioned steps 4, temperature is 100-160 DEG C, preferably 120～140 DEG C.
The further restriction of technique scheme is, in above-mentioned steps 5, and 5～30 hours time that constant temperature stirs, preferably 10～15 hours.
The further restriction of technique scheme is, in above-mentioned steps 7, the part by weight of trimerization 1,2-dimethoxy benzene and deionized water is 1:50～1:300, preferably 1:90～1:110.
The further restriction of technique scheme is, in above-mentioned steps 8, regulates pH value to reach 2～6, preferably 3～5.
The further restriction of technique scheme is, in above-mentioned steps 9, the part by weight of trimerization 1,2-dimethoxy benzene and tetrahydrofuran (THF) is 1:5～1:30, preferably 1:8～1:12, the part by weight of tetrahydrofuran (THF) and methylene dichloride is 1:5～1:20, preferably 1:10～1:12.
The further restriction of technique scheme is, in above-mentioned steps 10, drying mode is vacuum-drying.
Compared with prior art, the present invention has following beneficial effect: preparation method of the present invention make 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene is white solid, purity >99%, the product purity making than traditional method is higher, and outward appearance is also attractive in appearance.
Embodiment
The present invention proposes a kind of preparation method of 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene, comprises the steps:
Step 1: prepare trimerization 1,2-dimethoxy benzene;
In above-mentioned steps 1, the method for preparing trimerization 1,2-dimethoxy benzene is as follows: in ethylene dichloride, add Vanadium Pentoxide in FLAKES, the vitriol oil, iron trichloride, stir; Ice bath, under nitrogen protection, drips 1,2-dimethoxy benzene, dropwises stirring at room temperature 24 hours; Be poured into water, separate ethylene dichloride layer, dry, evaporate to dryness, the solid obtaining is trimerization 1,2-dimethoxy benzene;
Step 2: trimerization 1,2-dimethoxy benzene is joined in N-Methyl pyrrolidone;
In above-mentioned steps 2, the part by weight of trimerization 1,2-dimethoxy benzene and N-Methyl pyrrolidone is 1:3～1:20, preferably 1:8～1:12;
Step 3: under stirring, add a certain amount of sodium sulphite;
In above-mentioned steps 3, the part by weight of trimerization 1,2-dimethoxy benzene and sodium sulphite is 1:3～1:10, preferably 1:5;
Step 4: be heated to certain temperature;
In above-mentioned steps 4, temperature is 100-160 DEG C, preferably 120～140 DEG C;
Step 5: constant temperature stirs;
In above-mentioned steps 5,5～30 hours time that constant temperature stirs, preferably 10～15 hours;
Step 6: cool to room temperature;
Step 7: add a certain amount of deionized water;
In above-mentioned steps 7, the part by weight of trimerization 1,2-dimethoxy benzene and deionized water is 1:50～1:300, preferably 1:90～1:110;
Step 8: regulate pH value with hydrochloric acid, separate out precipitation, filter;
In above-mentioned steps 8, regulate pH value to reach 2～6, preferably 3～5;
Step 9: filter residue is dissolved in a certain amount of tetrahydrofuran (THF), the methylene dichloride of dropping certainweight ratio, separates out precipitation, filters;
In above-mentioned steps 9, the part by weight of trimerization 1,2-dimethoxy benzene and tetrahydrofuran (THF) is 1:5～1:30, preferably 1:8～1:12, and the part by weight of tetrahydrofuran (THF) and methylene dichloride is 1:5～1:20, preferably 1:10～1:12;
Step 10: obtain white solid, be dried and can obtain 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene;
In above-mentioned steps 10, drying mode is vacuum-drying.
The preparation of trimerization 1,2-dimethoxy benzene
In 500ml ethylene dichloride, add that 10g Vanadium Pentoxide in FLAKES, the 10g vitriol oil are slow, 440g iron trichloride, stir.Ice bath, under nitrogen protection, drips 70g 1,2-dimethoxy benzene, dropwises stirring at room temperature 24 hours.Pour in 3000ml water, separate ethylene dichloride layer, dry, evaporate to dryness, obtains 50g solid, is trimerization 1,2-dimethoxy benzene.
preparation Example 1
Synthetic according to the method described above intermediate trimerization 1,2-dimethoxy benzene 10g is incorporated in the N-Methyl pyrrolidone of 100ml, under stirring, add sodium sulphite 60g, be heated to 130 DEG C, constant temperature stirs 15 hours, is cooled to room temperature, adds deionized water 1000ml to stir, regulating pH value with hydrochloric acid is 4, separates out solid.Filter, take out filter residue.Filter residue adds 100ml tetrahydrofuran (THF), and stirring and dissolving drips 1000ml methylene dichloride, and crystallize out filters.Filter residue vacuum drying, obtains white solid 6.3g, is 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene, purity >99%.
preparation Example 2
Synthetic according to the method described above intermediate trimerization 1,2-dimethoxy benzene 10g is incorporated in the N-Methyl pyrrolidone of 200ml, under stirring, add sodium sulphite 60g, be heated to 130 DEG C, constant temperature stirs 15 hours, is cooled to room temperature, adds deionized water 1000ml to stir, regulating pH value with hydrochloric acid is 4, separates out solid.Filter, take out filter residue.Filter residue adds 100ml tetrahydrofuran (THF), and stirring and dissolving drips 1000ml methylene dichloride, and crystallize out filters.Filter residue vacuum drying, obtains white solid 5.0g, is 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene, purity >99%.
preparation Example 3
Synthetic according to the method described above intermediate trimerization 1,2-dimethoxy benzene 10g is incorporated in the N-Methyl pyrrolidone of 100ml, under stirring, add sodium sulphite 30g, be heated to 130 DEG C, constant temperature stirs 15 hours, is cooled to room temperature, adds deionized water 1000ml to stir, regulating pH value with hydrochloric acid is 4, separates out solid.Filter, take out filter residue.Filter residue adds 100ml tetrahydrofuran (THF), and stirring and dissolving drips 1000ml methylene dichloride, and crystallize out filters.Filter residue vacuum drying, obtains white solid 6.1g, is 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene, purity >99%.
preparation Example 4
Synthetic according to the method described above intermediate trimerization 1,2-dimethoxy benzene 10g is incorporated in the N-Methyl pyrrolidone of 100ml, under stirring, add sodium sulphite 100g, be heated to 130 DEG C, constant temperature stirs 15 hours, is cooled to room temperature, adds deionized water 1000ml to stir, regulating pH value with hydrochloric acid is 4, separates out solid.Filter, take out filter residue.Filter residue adds 100ml tetrahydrofuran (THF), and stirring and dissolving drips 1000ml methylene dichloride, and crystallize out filters.Filter residue vacuum drying, obtains white solid 6.0g, is 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene, purity >99%.
preparation Example 5
Synthetic according to the method described above intermediate trimerization 1,2-dimethoxy benzene 10g is incorporated in the N-Methyl pyrrolidone of 100ml, under stirring, add sodium sulphite 60g, be heated to 130 DEG C, constant temperature stirs 15 hours, is cooled to room temperature, adds deionized water 500ml to stir, regulating pH value with hydrochloric acid is 4, separates out solid.Filter, take out filter residue.Filter residue adds 100ml tetrahydrofuran (THF), and stirring and dissolving drips 1000ml methylene dichloride, and crystallize out filters.Filter residue vacuum drying, obtains white solid 6.2g, is 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene, purity >99%.
preparation Example 6
Synthetic according to the method described above intermediate trimerization 1,2-dimethoxy benzene 10g is incorporated in the N-Methyl pyrrolidone of 100ml, under stirring, add sodium sulphite 60g, be heated to 130 DEG C, constant temperature stirs 15 hours, is cooled to room temperature, adds deionized water 3000ml to stir, regulating pH value with hydrochloric acid is 4, separates out solid.Filter, take out filter residue.Filter residue adds 100ml tetrahydrofuran (THF), and stirring and dissolving drips 1000ml methylene dichloride, and crystallize out filters.Filter residue vacuum drying, obtains white solid 6.3g, is 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene, purity >99%.
preparation Example 7
Synthetic according to the method described above intermediate trimerization 1,2-dimethoxy benzene 10g is incorporated in the N-Methyl pyrrolidone of 100ml, under stirring, add sodium sulphite 60g, be heated to 130 DEG C, constant temperature stirs 15 hours, is cooled to room temperature, adds deionized water 1000ml to stir, regulating pH value with hydrochloric acid is 4, separates out solid.Filter, take out filter residue.Filter residue adds 50ml tetrahydrofuran (THF), and stirring and dissolving drips 1000ml methylene dichloride, and crystallize out filters.Filter residue vacuum drying, obtains white solid 6.0g, is 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene, purity >99%.
preparation Example 8
Synthetic according to the method described above intermediate trimerization 1,2-dimethoxy benzene 10g is incorporated in the N-Methyl pyrrolidone of 100ml, under stirring, add sodium sulphite 60g, be heated to 130 DEG C, constant temperature stirs 15 hours, is cooled to room temperature, adds deionized water 1000ml to stir, regulating pH value with hydrochloric acid is 4, separates out solid.Filter, take out filter residue.Filter residue adds 300ml tetrahydrofuran (THF), and stirring and dissolving drips 3000ml methylene dichloride, and crystallize out filters.Filter residue vacuum drying, obtains white solid 5.0g, is 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene, purity >99%.
preparation Example 9
Synthetic according to the method described above intermediate trimerization 1,2-dimethoxy benzene 10g is incorporated in the N-Methyl pyrrolidone of 100ml, under stirring, add sodium sulphite 60g, be heated to 130 DEG C, constant temperature stirs 15 hours, is cooled to room temperature, adds deionized water 1000ml to stir, regulating pH value with hydrochloric acid is 4, separates out solid.Filter, take out filter residue.Filter residue adds 100ml tetrahydrofuran (THF), and stirring and dissolving drips 500ml methylene dichloride, and crystallize out filters.Filter residue vacuum drying, obtains white solid 6.1g, is 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene, purity >99%.
preparation Example 10
Synthetic according to the method described above intermediate trimerization 1,2-dimethoxy benzene 10g is incorporated in the N-Methyl pyrrolidone of 100ml, under stirring, add sodium sulphite 60g, be heated to 130 DEG C, constant temperature stirs 15 hours, is cooled to room temperature, adds deionized water 1000ml to stir, regulating pH value with hydrochloric acid is 4, separates out solid.Filter, take out filter residue.Filter residue adds 100ml tetrahydrofuran (THF), and stirring and dissolving drips 2000ml methylene dichloride, and crystallize out filters.Filter residue vacuum drying, obtains white solid 5.6g, is 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene, purity >99%.
preparation Example 11
Synthetic according to the method described above intermediate trimerization 1,2-dimethoxy benzene 10g is incorporated in 50ml N-Methyl pyrrolidone, under stirring, add sodium sulphite 50g, be heated to 160 DEG C, constant temperature stirs 15 hours, is cooled to room temperature, adds deionized water 1000ml to stir, regulating pH value with hydrochloric acid is 4, separates out solid.Filter, take out filter residue.Filter residue adds 100ml tetrahydrofuran (THF), and stirring and dissolving drips 1000 ml methylene dichloride, and crystallize out filters.Filter residue vacuum drying, obtains white solid 6.0g, is 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene, purity >99%.
preparation Example 12
Synthetic according to the method described above intermediate trimerization 1,2-dimethoxy benzene 10g is incorporated in 100ml N-Methyl pyrrolidone, under stirring, add sodium sulphite 50g, be heated to 100 DEG C, constant temperature stirs 15 hours, is cooled to room temperature, adds deionized water 1000ml to stir, regulating pH value with hydrochloric acid is 4, separates out solid.Filter, take out filter residue.Filter residue adds 100ml tetrahydrofuran (THF), and stirring and dissolving drips 1000 ml methylene dichloride, and crystallize out filters.Filter residue vacuum drying, obtains white solid 5.9g, is 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene, purity >99%.
preparation Example 13
Synthetic according to the method described above intermediate trimerization 1,2-dimethoxy benzene 10g is incorporated in 100ml N-Methyl pyrrolidone, under stirring, add sodium sulphite 50g, be heated to 130 DEG C, constant temperature stirs 15 hours, is cooled to room temperature, adds deionized water 500ml to stir, regulating pH value with hydrochloric acid is 6, separates out solid.Filter, take out filter residue.Filter residue adds 100ml tetrahydrofuran (THF), and stirring and dissolving drips 1000 ml methylene dichloride, and crystallize out filters.Filter residue vacuum drying, obtains white solid 5.8g, is 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene, purity >99%.
preparation Example 14
Synthetic according to the method described above intermediate trimerization 1,2-dimethoxy benzene 10g is incorporated in 100ml N-Methyl pyrrolidone, under stirring, add sodium sulphite 50g, be heated to 130 DEG C, constant temperature stirs 15 hours, is cooled to room temperature, adds deionized water 1000ml to stir, regulating pH value with hydrochloric acid is 2, separates out solid.Filter, take out filter residue.Filter residue adds 50ml tetrahydrofuran (THF), and stirring and dissolving drips 500 ml methylene dichloride, and crystallize out filters.Filter residue vacuum drying, obtains white solid 6.0g, is 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene, purity >99%.
preparation Example 15
Synthetic according to the method described above intermediate trimerization 1,2-dimethoxy benzene 10g is incorporated in the N-Methyl pyrrolidone of 100ml, under stirring, add sodium sulphite 60g, be heated to 130 DEG C, constant temperature stirs 5 hours, is cooled to room temperature, adds deionized water 1000ml to stir, regulating pH value with hydrochloric acid is 4, separates out solid.Filter, take out filter residue.Filter residue adds 100ml tetrahydrofuran (THF), and stirring and dissolving drips 2000ml methylene dichloride, and crystallize out filters.Filter residue vacuum drying, obtains white solid 5.0g, is 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene, purity >99%.
preparation Example 16
Synthetic according to the method described above intermediate trimerization 1,2-dimethoxy benzene 10g is incorporated in the N-Methyl pyrrolidone of 100ml, under stirring, add sodium sulphite 60g, be heated to 130 DEG C, constant temperature stirs 30 hours, is cooled to room temperature, adds deionized water 1000ml to stir, regulating pH value with hydrochloric acid is 4, separates out solid.Filter, take out filter residue.Filter residue adds 100ml tetrahydrofuran (THF), and stirring and dissolving drips 2000ml methylene dichloride, and crystallize out filters.Filter residue vacuum drying, obtains white solid 6.3g, is 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene, purity >99%.
The present invention has following beneficial effect: preparation method of the present invention make 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene, is white solid, purity >99%, the product purity making than the method for tradition side is higher, outward appearance is also attractive in appearance.
Claims (8)
1. one kind 2,3,6,7,10, the preparation method of 11-hexahydroxy-benzo phenanthrene, is characterized in that, it comprises the steps:
Step 1: prepare trimerization 1,2-dimethoxy benzene;
In ethylene dichloride, add Vanadium Pentoxide in FLAKES, the vitriol oil, iron trichloride, stir; Ice bath, under nitrogen protection, drips 1,2-dimethoxy benzene, dropwises stirring at room temperature 24 hours; Import in water, separate ethylene dichloride layer, dry, evaporate to dryness, the solid obtaining is trimerization 1,2-dimethoxy benzene;
Step 2: trimerization 1,2-dimethoxy benzene is joined in N-Methyl pyrrolidone; And the part by weight of trimerization 1,2-dimethoxy benzene and N-Methyl pyrrolidone is 1:3～1:20;
Step 3: under stirring, add a certain amount of sodium sulphite; And the part by weight of trimerization 1,2-dimethoxy benzene and sodium sulphite is 1:3～1:10;
Step 4: be heated to 100-160 DEG C;
Step 5: constant temperature stirs 5～30 hours;
Step 6: cooling;
Step 7: add deionized water; And the part by weight of trimerization 1,2-dimethoxy benzene and deionized water is 1:50～1:300;
Step 8: reach 2～6 with salt acid for adjusting pH value, separate out precipitation, filter;
Step 9: filter residue is dissolved in a certain amount of tetrahydrofuran (THF), drips a certain proportion of methylene dichloride, separates out precipitation, filters; And the part by weight of trimerization 1,2-dimethoxy benzene and tetrahydrofuran (THF) is 1:5～1:30, the part by weight of tetrahydrofuran (THF) and methylene dichloride is 1:5～1:20;
Step 10: obtain white solid, vacuum-drying can obtain 2,3,6,7,10,11-hexahydroxy-benzo phenanthrene.
2. according to claim 1 a kind of 2,3,6,7,10, the preparation method of 11-hexahydroxy-benzo phenanthrene, is characterized in that, in above-mentioned steps 2, the part by weight of trimerization 1,2-dimethoxy benzene and N-Methyl pyrrolidone is 1:8～1:12.
3. according to claim 1 a kind of 2,3,6,7,10, the preparation method of 11-hexahydroxy-benzo phenanthrene, is characterized in that, in above-mentioned steps 3, the part by weight of trimerization 1,2-dimethoxy benzene and sodium sulphite is 1:5.
4. according to claim 1 a kind of 2,3,6,7,10, the preparation method of 11-hexahydroxy-benzo phenanthrene, is characterized in that, in above-mentioned steps 4, temperature is 120-140 DEG C.
5. according to claim 1 a kind of 2,3,6,7,10, the preparation method of 11-hexahydroxy-benzo phenanthrene, is characterized in that, in above-mentioned steps 5, and 10～15 hours time that constant temperature stirs.
6. according to claim 1 a kind of 2,3,6,7,10, the preparation method of 11-hexahydroxy-benzo phenanthrene, is characterized in that, in above-mentioned steps 7, the part by weight of trimerization 1,2-dimethoxy benzene and deionized water is 1:90～1:110.
7. according to claim 1 a kind of 2,3,6,7,10, the preparation method of 11-hexahydroxy-benzo phenanthrene, is characterized in that, in above-mentioned steps 8, regulates pH value to reach 3～5.
8. according to claim 1 a kind of 2,3,6,7, the preparation method of 10,11-hexahydroxy-benzo phenanthrene, is characterized in that, in above-mentioned steps 9, the part by weight of trimerization 1,2-dimethoxy benzene and tetrahydrofuran (THF) is 1:8～1:12, and the part by weight of tetrahydrofuran (THF) and methylene dichloride is 1:10～1:12.
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