CN117003605B - Preparation method of deuterated naphthyl anthracene compound - Google Patents
Preparation method of deuterated naphthyl anthracene compound Download PDFInfo
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- CN117003605B CN117003605B CN202310982404.4A CN202310982404A CN117003605B CN 117003605 B CN117003605 B CN 117003605B CN 202310982404 A CN202310982404 A CN 202310982404A CN 117003605 B CN117003605 B CN 117003605B
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- -1 deuterated naphthyl anthracene compound Chemical class 0.000 title claims abstract description 60
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims abstract description 15
- 229910052805 deuterium Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000012043 crude product Substances 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 38
- 239000003960 organic solvent Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 28
- 239000012074 organic phase Substances 0.000 claims description 23
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 238000000746 purification Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical group [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000011403 purification operation Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003377 acid catalyst Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000000859 sublimation Methods 0.000 claims description 6
- 230000008022 sublimation Effects 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- VOIVTTPPKHORBL-UHFFFAOYSA-N 1-naphthalen-1-ylanthracene Chemical compound C1=CC=C2C(C=3C4=CC5=CC=CC=C5C=C4C=CC=3)=CC=CC2=C1 VOIVTTPPKHORBL-UHFFFAOYSA-N 0.000 claims description 3
- GWNJZSGBZMLRBW-UHFFFAOYSA-N 9,10-dinaphthalen-1-ylanthracene Chemical compound C12=CC=CC=C2C(C=2C3=CC=CC=C3C=CC=2)=C(C=CC=C2)C2=C1C1=CC=CC2=CC=CC=C12 GWNJZSGBZMLRBW-UHFFFAOYSA-N 0.000 claims description 3
- VIZUPBYFLORCRA-UHFFFAOYSA-N 9,10-dinaphthalen-2-ylanthracene Chemical compound C12=CC=CC=C2C(C2=CC3=CC=CC=C3C=C2)=C(C=CC=C2)C2=C1C1=CC=C(C=CC=C2)C2=C1 VIZUPBYFLORCRA-UHFFFAOYSA-N 0.000 claims description 3
- HICWKUFWPIBTCN-UHFFFAOYSA-N 9-naphthalen-1-yl-10-phenylanthracene Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=CC2=CC=CC=C12 HICWKUFWPIBTCN-UHFFFAOYSA-N 0.000 claims description 3
- RAGVQHQWLQWIKP-UHFFFAOYSA-N 9-naphthalen-2-yl-10-phenylanthracene Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=C(C=CC=C2)C2=C1 RAGVQHQWLQWIKP-UHFFFAOYSA-N 0.000 claims description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims description 3
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 3
- 238000004537 pulping Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims 1
- 229940011051 isopropyl acetate Drugs 0.000 claims 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical class C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical class C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- SYACRXBYRNYMLN-UHFFFAOYSA-N 9-bromo-10-naphthalen-1-ylanthracene Chemical class C12=CC=CC=C2C(Br)=C(C=CC=C2)C2=C1C1=CC=CC2=CC=CC=C12 SYACRXBYRNYMLN-UHFFFAOYSA-N 0.000 description 1
- ZIRVQSRSPDUEOJ-UHFFFAOYSA-N 9-bromoanthracene Chemical class C1=CC=C2C(Br)=C(C=CC=C3)C3=CC2=C1 ZIRVQSRSPDUEOJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MFFWLPUTVHVELN-UHFFFAOYSA-N dichloromethane;propan-2-yl acetate Chemical compound ClCCl.CC(C)OC(C)=O MFFWLPUTVHVELN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
- C07B59/001—Acyclic or carbocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/10—Purification; Separation; Use of additives by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/05—Isotopically modified compounds, e.g. labelled
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of deuterated naphthlene anthracene compound, which comprises the steps of mixing naphthlene anthracene compound, a preparation catalyst and a deuterium source, and then carrying out deuteration reaction for 1-60 h at 30-150 ℃ in inert atmosphere to obtain a deuterated naphthlene anthracene compound crude product. The invention has simple and easy process, low cost, high deuterium source utilization rate, high reaction yield and high deuteration degree.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of deuterated naphthyl anthracene compounds.
Background
Currently, the OLED display technology has been applied to the fields of smart phones, tablet computers, vehicle screens and the like, and further will expand to the large-size application fields of televisions and the like. However, compared with the actual product application requirements, the performance of the OLED device such as luminous efficiency, service life and the like needs to be further improved.
The organic photoelectric material is an organic material with photoelectric activity, has the advantages of definite relative molecular mass, strong chemical modification, wide selection range, capability of generating various lights such as red, green and blue, and the like, and is widely applied to the fields of Organic Light Emitting Diodes (OLED), organic transistors, organic solar cells, organic memories and the like.
The characteristic of fast decay rate of the OLED blue light material becomes a key material for influencing the display effect and the service life of the OLED. In the OLED matrix material, the hydrogen/deuterium exchange of the unstable heterocyclic carbon hydrogen bond can prolong the service life of the device, and the replacement of the unstable C-H bond in the main structure by the C-D bond can increase the service life of the device by 5 times without losing the luminous efficiency. Therefore, the deuterated photoelectric material not only can improve the luminous efficiency of the OLED device and can flexibly display, but also has the characteristics of improving the brightness, having long half-life and the like.
Wherein, deuterated naphthlene and derivatives thereof are intermediates for preparing various organic photoelectric materials, such as the prior deuterated naphthlene and derivatives thereof have the following preparation steps: firstly, brominating deuterated naphthalene to synthesize deuterated 1-bromonaphthalene and obtaining deuterated 1-naphthalene boric acid through coupling, secondly, brominating deuterated anthracene to obtain deuterated 9-bromoanthracene and obtaining 9- (1-naphthyl) anthracene-D16 with deuterated 1-naphthalene boric acid through Suzuki, and coupling deuterated anthracene and deuterated naphthalene to obtain 9- (1-naphthyl) anthracene-D16 through Suzuki as deuterated main bodies.
In addition, since the prepared deuterated naphthlene and the derivative thereof are basically crude products, subsequent purification is needed to improve the purity, otherwise, the color purity of the device can be greatly influenced, and the service life of the device can be particularly reduced, so that the obtained deuterated naphthlene and the derivative thereof with high purity are very important for preparing the organic photoelectric material.
Disclosure of Invention
The invention aims to provide a preparation method of deuterated naphthyl anthracene compounds, which has the advantages of simple and feasible process, low cost, high deuterium source utilization rate, high reaction yield and high deuteration degree.
The technical scheme adopted for solving the technical problems is as follows:
the preparation process of deuterated naphthalene anthracene compound includes mixing naphthalene anthracene compound, catalyst and deuterium source, and deuterating at 30-150 deg.c in inert atmosphere for 1-60 hr to obtain coarse deuterated naphthalene anthracene compound;
the preparation catalyst is a mixture of an acid catalyst and heavy water; the deuterium source is deuterated benzene;
The mass ratio of the naphthyl anthracene compound to the acid catalyst to the heavy water to the deuterated benzene is 1:0.01 to 0.5:0.001 to 0.1:0.01 to 100.
The invention realizes direct deuteration of the target product by a one-step method, has short synthesis steps, high deuterium utilization efficiency and low cost, and accords with the basic idea of green chemistry. However, in this production method, the addition amount of each substance and the reaction conditions are controlled as the process key points, otherwise, it is difficult to maintain the stability of the naphthalene group anthracene compound (naphthalene group anthracene/naphthalene group anthracene derivative), and intramolecular polymerization is likely to occur, resulting in a low yield.
In the preparation process of deuterated products, a metal catalyst, an acid catalyst, a base catalyst and near-critical or supercritical heavy water are used as catalysts, and the selection of the catalysts not only affects the deuteration degree of the naphtyl anthracene compound, but also can not even cause deuteration, so that the selection of the catalysts is very critical, and the catalysts need to be selected according to the specific preparation method of specific deuterated products.
Aiming at the specificity of a reaction system of the naphthalene anthracene compound, deuterated benzene is adopted as a deuterium source, a catalyst prepared by heavy water is adopted for catalysis, the addition amount of the heavy water in the system is small, the heavy water is not used as the deuterium source, the heavy water is used for adjusting the acidity of the system, the stability of the naphthalene anthracene compound is maintained, the polymerization in molecules of the naphthalene anthracene compound is avoided, the reaction yield is improved, but if the heavy water is used as the deuterium source, the addition amount is excessively high, and the final deuteration degree and the reaction yield are reduced.
The inventors found that if the water modulation is not emphasized in the catalyst, the naphthalene anthracene compound is easy to undergo intramolecular polymerization, greatly reduces the reaction yield, and affects the deuteration degree and purity of the product.
Therefore, the mass addition ratio of the naphthalene anthracene compound, the catalyst, the heavy water and the deuterated benzene is controlled to be 1:0.01 to 0.5:0.001 to 0.1: 0.01-100, high reaction yield and high deuteration degree when deuteration is realized.
The reaction of the invention needs a certain temperature, the temperature is lower than 30 ℃, the deuteration rate is slow, the reaction sites are uneven, the temperature is higher than 150 ℃, the decomposition of the naphthyl anthracene compound is accelerated, and the yield is low.
In order to provide a stable reaction environment and avoid the influence of external moisture on the reaction, the reaction is carried out under an inert atmosphere.
The deuteration degree of the deuterated naphthyl anthracene compound is more than 95 percent.
The method also comprises a purification step of the crude deuterated naphthyl anthracene compound, wherein the purification step comprises one purification operation, and the one purification operation is as follows: mixing the crude deuterated naphthlene compound with dichloromethane, adding saturated sodium bicarbonate aqueous solution for washing, removing the saturated sodium bicarbonate aqueous solution, and drying an organic phase at 20-40 ℃ to obtain the once purified deuterated naphthlene compound; wherein, the adding amount of the crude deuterated naphthlene anthracene compound, methylene dichloride and saturated sodium bicarbonate aqueous solution is 1g: 2-10 mL: 4-20 mL.
The primary purification operation also comprises water washing, and the water washing scheme is as follows:
Mixing the crude deuterated naphthlene compound with dichloromethane, adding water for washing, separating liquid to keep an organic phase, adding the organic phase into a saturated sodium bicarbonate aqueous solution for washing, removing the saturated sodium bicarbonate aqueous solution, and drying the organic phase at 20-40 ℃;
Or mixing the crude deuterated naphthlene anthracene compound with dichloromethane, adding saturated sodium bicarbonate aqueous solution for washing, removing the saturated sodium bicarbonate aqueous solution, adding water for washing, separating liquid, retaining an organic phase, and drying the organic phase at 20-40 ℃;
Or mixing the crude deuterated naphthlene compound with dichloromethane, adding water to wash, separating liquid to keep an organic phase, adding the organic phase to wash with saturated sodium bicarbonate aqueous solution, removing the saturated sodium bicarbonate aqueous solution, adding water to wash, separating liquid to keep the organic phase, and drying the organic phase at 20-40 ℃.
The water consumption for each water washing is 2-10 mL for each g of crude deuterated naphthlene compound.
The purification step further comprises a secondary purification operation, the secondary purification operation being: mixing the once purified deuterated naphtyl anthracene compound with an organic solvent A, refluxing and pulping for 0.5-10 h at 80-100 ℃, cooling to 5-20 ℃, filtering to obtain a filter cake, and leaching with a mixed solution of the organic solvent A and the organic solvent B to obtain purified deuterated naphtyl anthracene and derivatives thereof; the organic solvent A is selected from one of ethyl acetate, isopropyl acetate dichloromethane and chloroform; the organic solvent B is selected from one of ethanol, isopropanol, tertiary butanol and methanol.
The dosage ratio of the deuterated naphthyl anthracene compound after primary purification to the organic solvent A is 1g: 1-2 mL; the dosage ratio of the organic solvent A to the organic solvent B in the mixed solution of the organic solvent A and the organic solvent B is 1mL: 0.5-2 mL.
The purification step further comprises a secondary purification operation, the secondary purification operation being: transferring the once purified deuterated naphthlene anthracene compound into a sublimator, wherein the sublimation temperature is 100-400 ℃, the vacuum degree is 10-100 Pa, the sublimation time is 2-20 h, and the temperature is reduced to 20-30 ℃ to obtain the purified deuterated naphthlene anthracene compound.
After two purifications, the purity of the deuterated naphtyl anthracene compound is more than 99 percent.
The naphthyl anthracene compound is selected from one of 1- (naphthalene-1-yl) anthracene, 9, 10-di (naphthalene-1-yl) anthracene, 9-naphthalene-1-yl-10-naphthalene-2-anthracene, 9, 10-di (naphthalene-2-yl) anthracene, 9- (2-naphthyl) -10-phenyl anthracene and 9- (1-naphthyl) -10-phenyl anthracene.
The acid catalyst is one of molybdenum pentachloride, titanium tetrachloride, trifluoromethanesulfonic acid, aluminum trichloride, tungsten hexachloride and niobium pentachloride.
The deuterated naphthlene anthracene compound prepared by the preparation method of the deuterated naphthlene anthracene compound is applied to the preparation of organic electroluminescent devices.
The beneficial effects of the invention are as follows: the invention realizes direct deuteration of the target product by a one-step method, has short synthesis steps, high deuterium utilization efficiency and low cost, and accords with the basic idea of green chemistry.
Drawings
FIG. 1 is a synthetic scheme of deuterated 1- (naphthalen-1-yl) anthracene according to example 1 of the invention.
FIG. 2 is a synthetic scheme for deuterated 9, 10-bis (naphthalen-1-yl) anthracene according to example 4 of the invention.
FIG. 3 is a synthetic scheme for deuterated 9-naphthalen-1-yl-10-naphthalen-2-anthracene according to example 7 of the invention.
FIG. 4 is a synthetic scheme for deuterated 9, 10-bis (naphthalen-2-yl) anthracene according to example 10 of the present invention.
FIG. 5 is a synthetic scheme for deuterated 9- (2-naphthyl) -10-phenylanthracene in example 13 of the present invention.
FIG. 6 is a synthetic scheme for deuterated 9- (1-naphthyl) -10-phenylanthracene in example 16 of the present invention.
FIG. 7 is a nuclear magnetic resonance spectrum of deuteration degree according to example 1 of the present invention.
FIG. 8 shows GC detection data of example 1 of the present invention.
Fig. 9 is a synthetic scheme of deuterated naphthylanthracene of comparative example 1.
Detailed Description
The technical scheme of the invention is further specifically described by the following specific examples.
In the present invention, the materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
Examples:
The following 18 examples are provided, and the preparation method of the invention is adopted for preparation, and the specific preparation method is as follows:
Mixing a naphthyl anthracene compound, a preparation catalyst and a deuterium source, and then carrying out deuteration reaction for 1-60 h at 30-150 ℃ in an inert atmosphere to obtain a deuterated naphthyl anthracene compound crude product;
the preparation catalyst is a mixture of an acid catalyst and heavy water; the deuterium source is deuterated benzene;
The mass ratio of the naphthyl anthracene compound to the acid catalyst to the heavy water to the deuterated benzene is 1:0.01 to 0.5:0.001 to 0.1:0.01 to 100. The catalyst is one of molybdenum pentachloride, titanium tetrachloride, trifluoromethanesulfonic acid, aluminum trichloride, tungsten hexachloride and niobium pentachloride. The parameter control is shown in Table 1.
Wherein, examples 1-12 use the following purification methods to purify the crude product of deuterated naphthyl anthracene compound, the specific purification method is: primary purification: mixing the crude product of the deuterated naphtyl anthracene compound with dichloromethane, adding water to wash the separated solution, then keeping an organic phase, adding the organic phase to wash the mixture with saturated sodium bicarbonate aqueous solution, removing the saturated sodium bicarbonate aqueous solution, adding water to wash the mixture, keeping the organic phase, and drying the mixture at 20-40 ℃ to obtain the once purified deuterated naphtyl anthracene compound, wherein the addition amount of the obtained product of the step 1), the dichloromethane and the saturated sodium bicarbonate aqueous solution is 1g: 2-10 mL: 4-20 mL; the obtained product and the addition amount of water each time satisfy the following conditions: 1g: 2-10 mL.
And (3) secondary purification: mixing the once purified deuterated naphtyl anthracene compound with an organic solvent A, refluxing and pulping for 0.5-10 h at 80-100 ℃, cooling to 5-15 ℃, filtering to obtain a filter cake, and leaching with a mixed solution of the organic solvent A and the organic solvent B to obtain the purified deuterated naphtyl anthracene compound; wherein, the adding amount of the deuterated naphthyl anthracene compound after primary purification and the organic solvent A is 1g: 1-2 mL; the addition amount of the mixed solution of the organic solvent A and the organic solvent B is 1mL: 0.5-2 mL. The parameter control is shown in Table 2. In this embodiment, the organic solvent a is ethyl acetate and the organic solvent B is ethanol.
The adding amount of the crude product of deuterated naphthlene anthracene compound, methylene dichloride and saturated sodium bicarbonate aqueous solution is A;
And (3) recording the addition amount of the deuterated naphtyl anthracene compound and the organic solvent A after primary purification to meet the requirement of B.
Wherein examples 13-18 differ from the purification methods of examples 1-12 in that: transferring the once purified deuterated naphthlene anthracene compound into a sublimator, wherein the sublimation temperature is 100-400 ℃, the vacuum degree is 10-100 Pa, the sublimation time is 2-20 h, and the temperature is reduced to 20-30 ℃ to obtain the purified deuterated naphthlene anthracene compound. The key parameter control is shown in table 2.
Comparative example 1 is a prior art deuterated 9-bromo-10- (1-naphthyl) anthracene (fig. 9) prepared using the preparation method described in the background.
Comparative example 2 differs from example 3 in that heavy water was not added to the raw material, and the other is the same as example 3.
The synthetic route diagrams of examples 1,4, 7, 10, 13 and 16 are shown in fig. 1-6.
The following measurements were carried out on the examples and comparative examples obtained by means of nuclear magnetic resonance hydrogen spectrometry:
1) Deuteration degree detection is calculated by adopting the following formula:
Wherein A is the hydrogen peak area of the deuterated sample, D is the deuteration degree, M1 is the added mass of the deuterated sample, the unit is g, n is the number of H atoms to be deuterated in the deuterated sample, M is the relative molecular mass of the deuterated sample, the unit is g, and M2 is the added mass of the internal standard, and the unit is g.
2) And (3) purity detection: and detecting by adopting a gas chromatograph.
3) And (3) yield detection: the calculation formula is that the weight of the deuterated naphthlene anthracene compound is obtained in actual practice/the weight of the deuterated naphthlene anthracene compound is obtained in physical theory.
Fig. 7-8 are test data for the product of example 1.
The specific detection results are shown in Table 3.
TABLE 1 Key parameter control for the preparation of the examples of the invention
TABLE 2 critical parameter control for purification of the examples of the invention
TABLE 3 deuteration of examples of the present invention
The above-described embodiment is only a preferred embodiment of the present invention, and is not limited in any way, and other variations and modifications may be made without departing from the technical aspects set forth in the claims.
Claims (4)
1. A preparation method of deuterated naphthyl anthracene compound is characterized in that: mixing a naphthyl anthracene compound, a preparation catalyst and a deuterium source, and then carrying out deuteration reaction for 1-60 h at 30-150 ℃ in an inert atmosphere to obtain a deuterated naphthyl anthracene compound crude product;
the preparation catalyst is a mixture of an acid catalyst and heavy water; the deuterium source is deuterated benzene;
The mass ratio of the naphthyl anthracene compound to the acid catalyst to the heavy water to the deuterated benzene is 1:0.01 to 0.5:0.001 to 0.1: 5-100;
The method also comprises a purification step of the crude deuterated naphthyl anthracene compound, wherein the purification step comprises one purification operation, and the one purification operation is as follows: mixing the crude deuterated naphthlene compound with dichloromethane, adding saturated sodium bicarbonate aqueous solution for washing, removing the saturated sodium bicarbonate aqueous solution, and drying an organic phase at 20-40 ℃ to obtain the once purified deuterated naphthlene compound; wherein, the adding amount of the crude deuterated naphthlene anthracene compound, methylene dichloride and saturated sodium bicarbonate aqueous solution is 1g: 2-10 mL: 4-20 mL;
The purification step further comprises a secondary purification operation, the secondary purification operation being: mixing the once purified deuterated naphtyl anthracene compound with an organic solvent A, refluxing and pulping for 0.5-10 h at 80-100 ℃, cooling to 5-20 ℃, filtering to obtain a filter cake, and leaching with a mixed solution of the organic solvent A and the organic solvent B to obtain the purified deuterated naphtyl anthracene compound; the organic solvent A is selected from one of ethyl acetate, isopropyl acetate, methylene dichloride and chloroform; the organic solvent B is selected from one of ethanol, isopropanol, tertiary butanol and methanol; or the purification step further comprises a secondary purification operation, wherein the secondary purification operation is as follows: transferring the once purified deuterated naphthlene anthracene compound into a sublimator, wherein the sublimation temperature is 100-400 ℃, the vacuum degree is 10-100 Pa, the sublimation time is 2-20 h, and the temperature is reduced to 20-30 ℃ to obtain the purified deuterated naphthlene anthracene compound;
The naphthyl anthracene compound is selected from one of 1- (naphthalene-1-yl) anthracene, 9, 10-di (naphthalene-1-yl) anthracene, 9-naphthalene-1-yl-10-naphthalene-2-anthracene, 9, 10-di (naphthalene-2-yl) anthracene, 9- (2-naphthyl) -10-phenyl anthracene and 9- (1-naphthyl) -10-phenyl anthracene;
The acid catalyst is one of molybdenum pentachloride, titanium tetrachloride, trifluoromethanesulfonic acid, aluminum trichloride, tungsten hexachloride and niobium pentachloride.
2. The method of manufacturing according to claim 1, characterized in that: the primary purification operation also comprises water washing, and the water washing scheme is as follows:
Mixing the crude deuterated naphthlene compound with dichloromethane, adding water for washing, separating liquid to keep an organic phase, adding the organic phase into a saturated sodium bicarbonate aqueous solution for washing, removing the saturated sodium bicarbonate aqueous solution, and drying the organic phase at 20-40 ℃;
Or mixing the crude deuterated naphthlene anthracene compound with dichloromethane, adding saturated sodium bicarbonate aqueous solution for washing, removing the saturated sodium bicarbonate aqueous solution, adding water for washing, separating liquid, retaining an organic phase, and drying the organic phase at 20-40 ℃;
Or mixing the crude deuterated naphthlene compound with dichloromethane, adding water to wash, separating liquid to keep an organic phase, adding the organic phase to wash with saturated sodium bicarbonate aqueous solution, removing the saturated sodium bicarbonate aqueous solution, adding water to wash, separating liquid to keep the organic phase, and drying the organic phase at 20-40 ℃.
3. The preparation method according to claim 2, characterized in that: the water consumption for each water washing is 2-10 mL for each g of crude deuterated naphthlene compound.
4. The method of manufacturing according to claim 1, characterized in that: the dosage ratio of the deuterated naphthyl anthracene compound after primary purification to the organic solvent A is 1g: 1-2 mL; the dosage ratio of the organic solvent A to the organic solvent B in the mixed solution of the organic solvent A and the organic solvent B is 1 mL: 0.5-2 mL.
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