CN101514153A - Synthesis method for high-purity substituted anthraquinones - Google Patents
Synthesis method for high-purity substituted anthraquinones Download PDFInfo
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- CN101514153A CN101514153A CNA2009100818457A CN200910081845A CN101514153A CN 101514153 A CN101514153 A CN 101514153A CN A2009100818457 A CNA2009100818457 A CN A2009100818457A CN 200910081845 A CN200910081845 A CN 200910081845A CN 101514153 A CN101514153 A CN 101514153A
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- 150000004056 anthraquinones Chemical class 0.000 title abstract description 21
- 238000001308 synthesis method Methods 0.000 title abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 8
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical class CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000010189 synthetic method Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000012024 dehydrating agents Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 16
- 230000005669 field effect Effects 0.000 abstract description 8
- 238000007086 side reaction Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- 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 17
- 230000005311 nuclear magnetism Effects 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 235000001018 Hibiscus sabdariffa Nutrition 0.000 description 5
- 235000005291 Rumex acetosa Nutrition 0.000 description 5
- 240000007001 Rumex acetosella Species 0.000 description 5
- 235000003513 sheep sorrel Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- -1 4-bromobenzene acid anhydride Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001454 anthracenes Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WQOWBWVMZPPPGX-UHFFFAOYSA-N 2,6-diaminoanthracene-9,10-dione Chemical compound NC1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 WQOWBWVMZPPPGX-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- XOGPDSATLSAZEK-UHFFFAOYSA-N 2-Aminoanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 XOGPDSATLSAZEK-UHFFFAOYSA-N 0.000 description 2
- UJDXSZLTIXIGGN-UHFFFAOYSA-N 2-bromo-6-chloroanthracene-9,10-dione Chemical compound BrC1=CC=C2C(=O)C3=CC(Cl)=CC=C3C(=O)C2=C1 UJDXSZLTIXIGGN-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JUFYHUWBLXKCJM-UHFFFAOYSA-N 2,6-dibromoanthracene-9,10-dione Chemical compound BrC1=CC=C2C(=O)C3=CC(Br)=CC=C3C(=O)C2=C1 JUFYHUWBLXKCJM-UHFFFAOYSA-N 0.000 description 1
- VTSDGYDTWADUJQ-UHFFFAOYSA-N 2-bromoanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(Br)=CC=C3C(=O)C2=C1 VTSDGYDTWADUJQ-UHFFFAOYSA-N 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000004768 bromobenzenes Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/24—Quinones containing halogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention relates to a synthesis method for high-purity substituted anthraquinones, belonging to the technical field of the preparation of an intermediate that synthesizes organic light emitting materials and field effect transistor materials. The synthesis method for a compound I comprises that the compound is obtained by losing a molecule of water under the action of a shrinking agent by means of a product II of the Friedel-Crafts reaction of 2-X1 substituted phthalic anhydride and X2 substituted benzene. The inventor comes up with the inventive course and optimizes document course on the basis of reading a great deal of documents, which avoids the generation of side reaction and facilitates industrial production. The product, which is obtained by the inventive method, is relatively soluble and has white color, thus facilitating the synthesis of the organic light emitting material and the field effect transistor material.
Description
Technical field
The invention belongs to the intermediate preparation technical field of synthetic luminous organic material and field effect transistor tube material, particularly relate to high purity 2-replacement and 2, the synthetic method of 6-two substituted anthraquinones.
Background technology
Anthraquinone derivative is anthraquinone series compound dyestuff, organic dye and other Chemicals important material, wherein β-anthraquinone use value maximum.Along with various countries the going deep into of research and development aspect OLED and the field-effect transistor, the anthraquinone analog compound demand is also increased (people such as Seung Kyu Lee, organic letters, 05,7:323-326, people such as Wang Xinhua, organicletters, 08,10:641-644, people such as J.-H.Park, organic letters, 07,9:2573-2576).The synthetic method of anthraquinone has a lot: direct oxidation method, substitution method, Firedel-Crafts etc., the anthraquinone derivative that these synthetic methods obtain can satisfy dyestuffs industries to be used, but be difficult to meet the demands as electronic product, mainly exist purity not high, be difficult to problems such as purifying.In the organic semiconductor industry, the anthracene class as blue light material and field effect transistor tube material be extensive use of (LG chemistry CN1898355, the US7326371 of Kodak, EP1156536, people such as Wang Fosong, organic letters, 06,8:785-788); Wherein the β substituted anthraquinone (mainly is 2-replacement and 2,6-two replaces) can introduce various groups, obtain having the anthracene class material of different performance, these materials are used on the luminescent device, can improve device lifetime, reduce trigger voltage, so the countries in the world scientist researches and develops at input great effort aspect the anthracene class material.β substituted anthraquinone derivative (mainly be 2-replacement and 2,6-two replaces) is intermediate (masahiro kamamura, the US20070200490 of synthetic these anthracene classes, people such as Kaname Ito, Angew.Chem.Int.Ed., 2003,42, No.10:1159-1162, people such as J.-H.Park, organicletters, 07,9:2573-2576), it is significant therefore to develop β substituted anthraquinone derivative; Because trace impurity has a strong impact on the performance of device, so key is the highly purified β substituted anthraquinone derivative of exploitation.The β substituted anthraquinone synthetic method of bibliographical information is mainly based on groups converted at present, as people such as world patent WO02053545, WO03095445, Seung Kyu Lee, organicletters, 05, the synthetic method that 7:323-326 mentions, these methods are raw material with the product of dyestuffs industries, and the synthetic compound is not mentioned the sign of purity yet; The more important thing is that anthraquinone analog compound aromatic ring hydrogen is very active, have a lot of side reactions, be difficult to purify with common method of purification.Domestic also have a bibliographical information, and as applied chemistry, 2006,23 (7), 812 methods of mentioning can only be used difficult industrialization in the laboratory; The method of proposition such as Lin Li usefulness Firedel-Crafts method processing 2-methylanthraquinone (dyestuff and dyeing, 04,41:289-283), but cyclization in the end will be used a large amount of low boiling point organic solvents, and reaction process also will steam solvent, and is wayward at course of industrialization.
The present inventor has summed up at present synthetic β substituted anthraquinone document, find: there is certain defective in method at present, and raw material is impure on the one hand, and synthesis technique is easy to generate side reaction on the other hand, the by product that produces is difficult to purifying, causes synthetic photoelectric material to use.The β substituted anthraquinone is the intermediate of synthetic luminous organic material and field effect transistor tube material, and the synthetic of high purity anthraquinone is the key of these materials of exploitation.Obtain the employed anthraquinone derivative of electronic material, need to seek good synthetic method, and can realize industrialization.
Summary of the invention
The present invention finds quick, efficient, an easy synthetic route, and intermediate that obtains and last product do not need loaded down with trivial details purifying, can directly use.
The synthetic method of Compound I,
X wherein
1=H, halogen, C
1-4Alkyl, X
2=halogen, C
1-4Alkyl.
Comprise the steps: (1) 2-X
1Replace phthalic anhydride and X
2Friedel-crafts reaction takes place and obtains Compound I I in substituted benzene under the catalysis of aluminum trichloride (anhydrous), (2) Compound I I dehydration a part water under the effect of dehydrating agent closes ring and obtains Compound I.
Described step (2) dehydrating agent is the vitriol oil, strong phosphoric acid, concentrated hydrochloric acid or acetate, and temperature of reaction is 100-200 ℃.
Preferred 100-160 ℃.
Described step (2) is that Compound I I is joined in the dehydrating agent in batches, is warmed up to 100-200 ℃ again and reacts 4-5 hour down.
The terminal point of described step (2) reaction is designated as and obtains uniform reaction soln.
The reaction product that the middle compound used therefor II of described step (2) is a step (1) is poured the solid of separating out in the frozen water into, the filtration drying gained.
In the described step (1), the consumption of aluminum chloride is 2-X
1The 2-3 that replaces the phthalic anhydride molar weight doubly, temperature of reaction is 30-100 ℃.
Preferred 40-70 ℃.
Wherein, X1=H, X2=Br or X1=Br, X2=Br, I, Cl, methyl, ethyl, the tertiary butyl, sec.-propyl.
The present invention makes raw material with phthalic anhydride and derivative, bromobenzene (chlorobenzene, toluene, ethylbenzene, propylbenzene) industrial raw material, and is cheap, be easy to get, do not need special purifying.Aluminum chloride adds in batches, reaction at a certain temperature, and obtaining solution just can stopped reaction, does not need to detect to follow the tracks of, and this is typical paying-the Ke addition reaction.Reaction solution is poured into and is obtained white solid II in a certain amount of ice-water, do not have tar and not exclusively phenomenon existence, can directly drop into next step after the separation drying, product separates very method, and product does not need further purifying can be directly used in the next step, more helps suitability for industrialized production.White solid II only need be elevated under the certain temperature and react under the dehydrating agent effect, obtains homogeneous solution and finishes with regard to proved response, pour into again and just can obtain 99% above white products in ice-water, do not need the purifying decolouring, also do not have carbonization phenomenon, product is soluble in THF, CHCl
3Etc. common organic solvent.Need low-temp reaction different fully with general Firedel-Crafts.We are according to document (masahirokamamura, US20070200490, people such as Kaname Ito, Angew.Chem.Int.Ed., 2003,42, No.10:1159-1162, people such as J.-H.Park, organic letters, 07, method 9:2573-2576) has been done Comparative Examples, with 2-aminoanthraquinone and 2,6-diamino-anthraquinone and cupric bromide, the nitrite tert-butyl reaction removes amino and is substituted, also obtain polysubstituted product, through recrystallization, cross silicagel column etc. and repeatedly handle and also can't obtain pure compound, product is very little in THF equal solvent solvability, is unfavorable for further reaction.It is more molten to obtain product with method of the present invention, and color is a white, is convenient to synthetic luminous organic material and field effect transistor tube material like this.
The contriver has proposed route of the present invention, and has optimized the document route reading on the lot of documents basis, has avoided the generation of side reaction, is convenient to industrialization and produces.
Compare with the bibliographical information method, the present invention has following advantage:
1, synthesizing efficient, quick, environmental protection, industrialization easily.
2, do not have by product to exist in the building-up process, avoid loaded down with trivial details purifying.
3, remove the compound that relates among the present invention, present method can also be extrapolated to analogue compounds, and use range is wide.
4, the product I solvability that obtains of the inventive method is good, can participate in reaction at low temperatures, as luminous organic material and field-effect transistor material intermediate.
Description of drawings
Fig. 1 is the nuclear-magnetism figure of embodiment 1.
Fig. 2 is the nuclear-magnetism figure of embodiment 2.
Fig. 3 is the nuclear-magnetism figure of embodiment 3.
Fig. 4 is the nuclear-magnetism figure of embodiment 4.
Fig. 5 is the nuclear-magnetism figure of embodiment 5.
Fig. 6 is the nuclear-magnetism figure of embodiment 7.
Fig. 7 is the nuclear-magnetism figure of embodiment 8.
Embodiment
According to following preparation embodiment and the embodiment that is used to illustrate, can obtain better understanding of the present invention, but can not be interpreted as limitation of the present invention.
2-bromo anthraquinone synthetic route:
1-1：
785G bromobenzene, 148G phthalic anhydride add the 500ML four-hole bottle, add aluminum chloride 355G under the room temperature in batches, and solution becomes light yellow look.Elevated temperature, 50-60 ℃ was reacted 5 hours, obtained homogeneous solution, poured in the ice; Filter, with 200ML water washing solid, obtain white products, 70 degree oven dry obtain 250G, productive rate 80%.
HNMR(400MHz，d6-DMSO，TMS)δ(ppm)：7.96(d，1H)，7.67(m，3H)，7.61(m，1H)，7.50(d，2H)，7.34(d，1H)。See Fig. 1
1-2：
Add the 1000G vitriol oil, on go on foot product 209G and add in batches and be sorrel, elevated temperature is to 150-160 ℃, color becomes sorrel, react 4 hours, pours into during 500ML water and 500G ice, and separates out a large amount of white solids, agitation and filtration.With 400ML water washing 2 times, 200ML washing with alcohol; Drying obtains 157G, productive rate 80%.
HNMR(400MHz，CDCl
3，TMS)δ(ppm)：8.44(s，1H)，8.32(s，2H)，8.17(d，1H)，7.94(d，1H)，7.84(d，2H)。See Fig. 2.It is very good that nuclear-magnetism detects purity.
Comparative Examples 1:
90 gram 2-aminoanthraquinone (95%), 108 gram cupric bromides, acetonitrile 1L add 2L four-hole bottle inflated with nitrogen and stirred 30 minutes.Temperature rising 65 degree reactions begin to drip nitrite tert-butyl, drip end in 2 hours, and a large amount of khaki color solids generations are arranged, and the some plate does not have raw material and exists, and stopped reaction is handled with dilute hydrochloric acid.Methyl alcohol purifying 3 times is crossed post and is handled, and obtains 61.5g, productive rate 66%, and nuclear-magnetism detects still a lot of impurity.See Fig. 3
2,6-dibromo-anthraquinone synthetic route:
The 2-1:4-phthalate bromine is synthetic
101G sodium hydroxide, 800ML water add, and add the 176G phthalic anhydride in batches, stir molten entirely.Drip bromine 64ML, add the 90 degree reactions 6 hours that raise.Filter, solid stirs with 400ML water, filters and obtains white solid.Add the 2L four-hole bottle, the heating of 1000ML water is molten entirely, and solid 134.8G, productive rate 45.7% are separated out in cooling.
HNMR (400MHz, acetone, TMS) δ (ppm): 8.16 (s, 1H), 8.03 (d, 2H), 7.89 (d, 1H).See Fig. 4
2-2:4-bromobenzene acid anhydride is synthetic
90G raw material, 300ML diacetyl oxide add the 1L four-hole bottle, and stirring heating refluxed 4 hours, then till the basic absence of liquid of solvent distillation.Cooling has a large amount of solids to separate out, and the 150ML petroleum ether and stirring is filtered, 200ML petroleum ether and stirring washing 2 times, 73.6g, productive rate 88%.
HNMR(400MHz，CDCl
3，TMS)δ(ppm)：8.16(s，1H)，8.03(d，2H)，7.89(d，1H)。See Fig. 5
2-3：
176 bromobenzenes, on go on foot product 47G and add the 500ML four-hole bottle, add aluminum chloride 75G in batches, reaction solution becomes sorrel.Elevated temperature 50-60 degree, reaction solution becomes light brown, reacts 5 hours, pours in the 150ML ice-water; Wash solid again with dilute hydrochloric acid solution, obtain the white products suction filtration, obtain product 70 degree oven dry, 73.4G, productive rate 85%
2-4：
Add the 240G vitriol oil, the 3rd step product 47.4G adds in batches and is sorrel, elevated temperature 150-160 degree, and color becomes sorrel, reacts 4 hours, pours in the 100ML water, separates out a large amount of solids, agitation and filtration.With 400ML water washing 2 times, 200ML washing with alcohol; Drying obtains 41G, 90% (HPLC 99.4%).
HNMR(400MHz，CDCl
3，TMS)δ(ppm)：8.44(s，1H)，8.2(d，1H)，7.9(d，1H)。See Fig. 6.
Comparative Examples 2:
70 grams 2,6-diamino-anthraquinone (95%), 160 gram cupric bromides, acetonitrile 800ML add 2L four-hole bottle inflated with nitrogen and stirred 30 minutes.Temperature rising 65 degree reactions begin to drip nitrite tert-butyl, drip end in 2 hours, and a large amount of khaki color solids generations are arranged, and the some plate does not have raw material and exists, and stopped reaction is handled with 20% dilute hydrochloric acid.Washing with alcohol 2 times, 1,4-dioxane purifying 4 times, post processing excessively, obtaining the detection of product nuclear-magnetism still has impurity (tetrabromo is for anthraquinone).
HNMR (400MHz, CDCl
3, TMS) δ (ppm): 8.44 (s, 1H), 8.2 (d, 1H), 7.9 (d, 1H), 8.5 (tetrabromo is for anthraquinones).See Fig. 7.
Embodiment 3:
The vitriol oil among the embodiment 1 is changed to strong phosphoric acid, comes to the same thing, easier operation.
Embodiment 4:
The vitriol oil among the embodiment 1 is changed to acetate, comes to the same thing.
Embodiment 5:
The vitriol oil among the embodiment 2 is changed to strong phosphoric acid, concentrated hydrochloric acid, acetate, comes to the same thing.
Embodiment 6:
2-bromo-6-chloroanthraquinone:
Adopt identical method, use raw material 4-bromobenzene acid anhydride, chlorobenzene can Synthetic 2-bromo-6-chloroanthraquinone.MS(FD)：317.6
Embodiment 7:
2-bromo-6-tectoquinone:
Adopt identical method, use raw material 4-bromobenzene acid anhydride, toluene can Synthetic 2-bromo-6-toluene anthraquinone.MS(FD)：297.189
Claims (9)
1, the synthetic method of Compound I,
X wherein
1=H, halogen or C
1-4Alkyl, X
2=halogen or C
1-4Alkyl.
Comprise the steps: (1) 2-X
1Replace phthalic anhydride and X
2Friedel-crafts reaction takes place and obtains Compound I I in substituted benzene under the catalysis of aluminum trichloride (anhydrous), (2) Compound I I dehydration a part water under the effect of dehydrating agent closes ring and obtains Compound I.
2, synthetic method according to claim 1, described step (2) dehydrating agent is the vitriol oil, strong phosphoric acid, concentrated hydrochloric acid or acetate, temperature of reaction is 100-200 ℃.
3, synthetic method according to claim 2, described temperature of reaction are 100-160 ℃.
4, synthetic method according to claim 2, described step (2) are that Compound I I is joined in the dehydrating agent in batches, are warmed up to 100-200 ℃ again and react 4-5 hour down.
5, synthetic method according to claim 1, the terminal point of described step (2) reaction is designated as and obtains uniform reaction soln.
6, synthetic method according to claim 1, the reaction product that the middle compound used therefor II of described step (2) is a step (1) is poured the solid of separating out in the frozen water into, the filtration drying gained.
7, synthetic method according to claim 1, in the described step (1), the consumption of aluminum chloride is 2-X
1The 2-3 that replaces the phthalic anhydride molar weight doubly, temperature of reaction is 30-100 ℃.
8, synthetic method according to claim 7, described temperature of reaction are 40-70 ℃.
9, according to the arbitrary described synthetic method of claim 1-8, wherein, X1=H, X2=Br, perhaps X1=Br, X2=Br, I, Cl, methyl, ethyl, the tertiary butyl or sec.-propyl.
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| PCT/CN2010/071403 WO2010118660A1 (en) | 2009-04-13 | 2010-03-30 | Method for synthesizing substituted anthraquinone with high purity |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010118660A1 (en) * | 2009-04-13 | 2010-10-21 | 北京阿格蕾雅科技发展有限公司 | Method for synthesizing substituted anthraquinone with high purity |
| CN102190641A (en) * | 2011-03-23 | 2011-09-21 | 四川科伦药物研究有限公司 | Method for preparing citalopram and key intermediate of escitalopram |
| CN102659551A (en) * | 2012-04-23 | 2012-09-12 | 张晗 | Preparation method of synthetic anthraquinone |
| CN103787970A (en) * | 2014-01-14 | 2014-05-14 | 北京万全德众医药生物技术有限公司 | Technology for preparing 6,9-difluoro benzisothiazol-5,10-diketone employing one-pot method |
| CN114906818A (en) * | 2021-02-08 | 2022-08-16 | 中国石油化工股份有限公司 | Alkyl anthraquinone working solution, preparation method thereof and production method of hydrogen peroxide |
| CN115490703A (en) * | 2021-06-17 | 2022-12-20 | 广东阿格蕾雅光电材料有限公司 | Synthetic method of BTBF |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4404140A (en) * | 1981-10-26 | 1983-09-13 | E. I. Du Pont De Nemours And Company | Manufacture of alkylanthraquinones |
| CN1321631A (en) * | 2000-04-28 | 2001-11-14 | 葛秀龙 | Processing technology of 2-amyl anthraquinone |
| CN101514153B (en) * | 2009-04-13 | 2012-07-04 | 广东阿格蕾雅光电材料有限公司 | Synthesis method for high-purity substituted anthraquinones |
-
2009
- 2009-04-13 CN CN2009100818457A patent/CN101514153B/en not_active Expired - Fee Related
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010118660A1 (en) * | 2009-04-13 | 2010-10-21 | 北京阿格蕾雅科技发展有限公司 | Method for synthesizing substituted anthraquinone with high purity |
| CN102190641A (en) * | 2011-03-23 | 2011-09-21 | 四川科伦药物研究有限公司 | Method for preparing citalopram and key intermediate of escitalopram |
| CN102659551A (en) * | 2012-04-23 | 2012-09-12 | 张晗 | Preparation method of synthetic anthraquinone |
| CN103787970A (en) * | 2014-01-14 | 2014-05-14 | 北京万全德众医药生物技术有限公司 | Technology for preparing 6,9-difluoro benzisothiazol-5,10-diketone employing one-pot method |
| CN114906818A (en) * | 2021-02-08 | 2022-08-16 | 中国石油化工股份有限公司 | Alkyl anthraquinone working solution, preparation method thereof and production method of hydrogen peroxide |
| CN114906818B (en) * | 2021-02-08 | 2024-05-17 | 中国石油化工股份有限公司 | Alkyl anthraquinone working solution, preparation method thereof and hydrogen peroxide production method |
| CN115490703A (en) * | 2021-06-17 | 2022-12-20 | 广东阿格蕾雅光电材料有限公司 | Synthetic method of BTBF |
| CN115490703B (en) * | 2021-06-17 | 2024-05-31 | 广东阿格蕾雅光电材料有限公司 | BTBF synthesis method |
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| WO2010118660A1 (en) | 2010-10-21 |
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