CN103408445B - Arylamine derivatives and preparation method thereof - Google Patents
Arylamine derivatives and preparation method thereof Download PDFInfo
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- CN103408445B CN103408445B CN201310308674.3A CN201310308674A CN103408445B CN 103408445 B CN103408445 B CN 103408445B CN 201310308674 A CN201310308674 A CN 201310308674A CN 103408445 B CN103408445 B CN 103408445B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 150000004982 aromatic amines Chemical class 0.000 title abstract description 7
- -1 arylamine compounds Chemical class 0.000 claims abstract description 65
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229940125904 compound 1 Drugs 0.000 claims description 11
- QEPPHIJQCNEGDG-UHFFFAOYSA-N bromine;ethynylbenzene Chemical compound [Br].C#CC1=CC=CC=C1 QEPPHIJQCNEGDG-UHFFFAOYSA-N 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004440 column chromatography Methods 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 229940125782 compound 2 Drugs 0.000 claims description 8
- 230000006837 decompression Effects 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 7
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 150000001345 alkine derivatives Chemical class 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002304 perfume Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910017489 Cu I Inorganic materials 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 125000005266 diarylamine group Chemical group 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 125000005264 aryl amine group Chemical group 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 125000005259 triarylamine group Chemical group 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to arylamine derivatives and a preparation method thereof. The preparation method comprises (a.) a step of synthesizing a precursor, (b.) a step of catalyzing by palladium and (c.) a step of purifying. Compared to common arylamine compounds, the arylamine compounds prepared by the preparation method contain acetylenic bonds. Alkynes take an important position whether from a production point of view or a theoretical point of view. Many alkynes, some of which are perfume or important products, are important industrial raw materials and are produced in a very large amount. Accordingly, the arylamine derivatives prepared by the preparation method have certain applications in real life.
Description
Technical field
The present invention relates to a kind of aromatic amino-derivative and preparation method thereof, belong to especially for the synthesis of arylamine skeleton.
Background technology
Arylamine and derivative thereof are widely used in chemical industry, medicine, agrochemicals, Chemicals for Photograph, additive, tensio-active agent and polymer production etc., are important organic raw material, and most arylamine is all from corresponding nitro-compound.Arylamine, will along with China's Economic development as important Chemicals, and the particularly development of medicine, agricultural chemicals, dyestuff etc., demand presents the trend of increasing rapidly.The operational path that arylamine is produced in aromatic nitro compound reduction is many, and principal synthetic routes has: (1) uses iron reduction in the dielectric; (2) with sodium sulfide reducing; (3) catalytic hydrogenating reduction method; (4) electrolytic reduction; (5) CO/H
2o reduction system method; (6) hydrazine hydrate method.Diaryl-amine is the important chemical of a class, has purposes very widely.The early stage main stablizer etc. being used as dyestuff, spices and agricultural chemicals, the intermediate of medicine synthesis, rubber antioxygen and explosive, fiber, plastics and rubber.In recent years along with the development of organic light guide drum and electroluminescent organic material, triarylamine analog hole transport materials becomes the emphasis of people's research day by day, and the application of diaryl-amine in synthesis triarylamine analog hole transport materials is more and more important.The synthetic method of diaryl-amine mainly contains the condensation of aryl primary amine self-condensation, aryl primary amine and fragrant halogen compound, aryl primary amine and four kinds of methods such as the reaction of aromatic series phenolic compound and the reaction of aryl primary amine an alkali metal salt and aromatic sulfonic acid salt.As follows:
1. the self-condensation reaction of aryl primary amine
2. the reaction of aryl primary amine and fragrant halogen compound
3. the reaction of aryl primary amine and aromatic series phenolic compound
4. the reaction of aryl primary amine an alkali metal salt and aromatic sulfonic acid salt
Summary of the invention
The object of the present invention is to provide a kind of aromatic amino-derivative and preparation method thereof.
Concrete technical scheme is as follows:
A kind of aromatic amino-derivative, its structural formula is:
Wherein, R
1, R
2, R
3can be hydrogen, straight chained alkyl, branched-chain alkyl, cyano group, amino, phenyl etc. and its corresponding derivative, Z can be carbon or nitrogen.
Further, it is polysubstituted aromatic amino-derivative.
Further, it is the benzocyclobutane ketone derivatives of efficient synthesis containing tetra-atomic ring.
The preparation method of above-mentioned aromatic amino-derivative, comprises the steps:
A, precursor synthesize;
B, palladium chtalyst;
C, purifying.
Further, step a specifically comprises: with Pd (PPh
3)
2cl
2for catalyzer, CuI is promotor, and 1,6-diine and phenylacetylene bromine are joined successively in appropriate acetonitrile, and add a certain amount of triethylamine, stirring at room temperature reacts 24 hours, prepares compound 1.
Further, step a carries out under anhydrous and oxygen-free condition, and/or 1,6-diine and phenylacetylene bromine mol ratio are 1: 2.4.
Further, step b specifically comprises: compound 1 for catalyst system, reacts 12 or 24 hours with tri-n-butylamine with palladium, triphenyl phosphorus in DMF DMF.
Further, step b carries out under the condition of 100 DEG C, and/or compound 1 adopts 5mmol, and palladium adopts 0.25mmol, and triphenyl phosphorus adopts 0.5mmol, and tri-n-butylamine adopts 2.5ml, DMF DMF to adopt 7ml.
Further, react 12 hours, after reactant adds water washing, be extracted with ethyl acetate, isolated organic phase successively uses 5% hydrochloric acid soln, 5% solution of potassium carbonate, saturated common salt water washing, decompression is spin-dried for, and can obtain the compound 2 needed through column chromatography for separation, i.e. aromatic amino-derivative, wherein the mol ratio of triphenyl phosphorus and palladium is 2: 1; Or reaction obtains the crude product of aromatic amino-derivative for 24 hours.
Further, step c specifically comprises: after the crude product of aromatic amino-derivative adds water washing, be extracted with ethyl acetate, isolated organic phase successively uses 5% hydrochloric acid soln, 5% solution of potassium carbonate, saturated common salt water washing, decompression selects dry chromatography to be separated the compound 2 that can obtain needs, i.e. aromatic amino-derivative, column chromatography productive rate is about 88%.
Compared with currently available technology, the invention provides a kind of synthetic method of brand-new arylamine skeleton, generate a series of new aromatic amino-derivative.Relative to common aromatic amine compound, aromatic amine compounds prepared by present method has the existence of acetylene bond, and no matter from producing or the angle of theory, alkynes class all occupies extremely important status, many alkynes classes are important industrial raw material, produce with very huge quantity, some is spices or important product, and the aromatic amino-derivative therefore synthesized by the present invention still has certain purposes in real life.
Chemically in performance and at various synthetic use, alkynes class all occupies special critical positions, and often they are beginning raw materials of synthesis.Synthetic work person has a kind of like this understanding, be exactly had multiple acetylene bond in the molecule, this molecule just becomes has lived, molecule is just provided with easily by the position of attack, starting point is made with this position, carry out next step reaction, the aromatic amino-derivative therefore synthesized by the present invention also has certain value in theoretical investigation.
The application prospect of aromatic amino-derivative in organic synthesis field still very widely thus.
Accompanying drawing explanation
Fig. 1 (a), Fig. 1 (b) are the chemical formula of aromatic amino-derivative of the present invention.
Fig. 2 (a), Fig. 2 (b), the proton nmr spectra of Fig. 2 (c) embodiment of the present invention.
Embodiment
Describe the present invention with reference to the accompanying drawings below, it is a kind of preferred embodiment in numerous embodiments of the present invention.
Embodiment one:
The synthesis of aromatic amino-derivative: shown in synthetic route.
A, precursor synthesize:
Under anhydrous and oxygen-free condition, with Pd (PPh
3)
2cl
2for Catalysts Cu I is promotor, 1,6-diine and phenylacetylene bromine are joined successively in appropriate acetonitrile, and add a certain amount of triethylamine, stirring at room temperature reacts 24 hours, prepares compound 1; Wherein 1,6-diine and phenylacetylene bromine mol ratio are 1: 2.4.
B, palladium chtalyst:
At 100 DEG C, compound 1(5mmol) with palladium (0.25mmol) and triphenyl phosphorus (0.5mmol) for catalyst system, with tri-n-butylamine (2.5ml) for reactant, in DMF DMF (7ml), reaction obtains the crude product of aromatic amino-derivative for 24 hours.
C, purifying:
After the crude product of aromatic amino-derivative adds water washing, be extracted with ethyl acetate, isolated organic phase successively uses 5% hydrochloric acid soln, 5% solution of potassium carbonate, saturated common salt water washing, decompression selects dry chromatography to be separated the compound 2 that can obtain our needs, i.e. aromatic amino-derivative, column chromatography productive rate is about 88%.
The structure of aromatic amino-derivative is passed through;
1h NMR;
13c NMR; HRMS; IR measures.
Aromatic amino-derivative:
1H NMR(300MHz,CDCl
3):δ7.65,7.63(d,J=6.0Hz,2H),7.45-7.25(m,8H),6.78(s,1H),4.27-4.20(q,J=6.0Hz,4H),3.79(s,2H),3.60(s,2H),3,15-3.10(q,J=6.0Hz,4H),1.50-1.44(m,4H),1.30-1.25(m,10H),0.91-0.87(t,J=6.0Hz,6H);
13C NMR(75MHz,CDCl
3):171.8,147.7,145.2,143.5,141.1,141.1,131.1,130.7,129.4,128.2,127.8,127.6,127.2,124.1,118.9,109.8,94.3,88.0,61.8,59.9,53.3,51.8,41.0,40.5,29.6,20.7,20.3,14.1,14.0ppm.
HRMS (APCI) calculated value C
39h
47nO
6[M+H]
+626.3476, measured value 626.3474.
FT-IR(neat):max3456,2957,1734,1589,1466,1244,1180,1157,1070,862,756,700,527cm
-1.
Embodiment two:
A kind of aromatic amino-derivative, its structural formula of described aromatic amino-derivative is:
Described R
1, R
2, R
3can be hydrogen, straight chained alkyl, branched-chain alkyl, cyano group, amino, phenyl etc. and its corresponding derivative, Z can be carbon and nitrogen.
Preparation method is: the synthesis of a, precursor, b, palladium chtalyst, c, purifying.
Described a, precursor synthesize:
Under anhydrous and oxygen-free condition, with Pd (PPh
3)
2cl
2for Catalysts Cu I is promotor, 1,6-diine and phenylacetylene bromine are joined successively in appropriate acetonitrile, and add a certain amount of triethylamine, stirring at room temperature reacts 24 hours, prepares compound 1; Wherein 1,6-diine and phenylacetylene bromine mol ratio are 1: 2.4.
Described b, palladium chtalyst are:
Under the condition of 100 DEG C, compound 1 with palladium, triphenyl phosphorus for catalyst system, with tri-n-butylamine at N, reaction 12 hours in dinethylformamide (DMF), after reactant adds water washing, be extracted with ethyl acetate, isolated organic phase successively uses 5% hydrochloric acid soln, 5% solution of potassium carbonate, saturated common salt water washing, decompression is spin-dried for, and can obtain the compound 2 of our needs through column chromatography for separation, i.e. aromatic amino-derivative, wherein the mol ratio of triphenyl phosphorus and palladium is 2: 1.
Described c, purifying are:
After the crude product of aromatic amino-derivative adds water washing, be extracted with ethyl acetate, isolated organic phase successively uses 5% hydrochloric acid soln, 5% solution of potassium carbonate, saturated common salt water washing, decompression selects dry chromatography to be separated the compound 2 that can obtain our needs, i.e. aromatic amino-derivative, column chromatography productive rate is about 88%.
Embodiment three:
Aromatic amino-derivative is polysubstituted aromatic amino-derivative, and its structural formula of described aromatic amino-derivative is:
Described R
1, R
2, R
3can be hydrogen, straight chained alkyl, branched-chain alkyl, cyano group, amino, phenyl etc. and its corresponding derivative, Z can be carbon and nitrogen.
Preparation method comprises following operation: the synthesis of a, precursor, b, palladium chtalyst, c, purifying.
Described aromatic amino-derivative is simply to work as R
1hydrogen, R
2, R
3be normal-butyl be example: under anhydrous and oxygen-free condition, with Pd (PPh
3)
2cl
2for Catalysts Cu I is promotor, 1,6-diine and phenylacetylene bromine are joined successively in appropriate acetonitrile, and add a certain amount of triethylamine, stirring at room temperature reacts 24 hours, prepares compound 1; Wherein 1,6-diine and phenylacetylene bromine mol ratio are 1: 2.4.Then compound 1 under the condition of 100 DEG C with palladium, triphenyl phosphorus for catalyst system, with tri-n-butylamine at N, in dinethylformamide (DMF), reaction 12 hours, after reactant adds water washing, is extracted with ethyl acetate, isolated organic phase successively uses 5% hydrochloric acid soln, 5% solution of potassium carbonate, saturated common salt water washing, decompression is spin-dried for, the compound 2 of our needs can be obtained, i.e. aromatic amino-derivative through column chromatography for separation.
Aromatic amino-derivative can as the precursor in pharmaceutical synthesis and exploitation; And due to the singularity of its structure, it may be made also to have certain utility value in organic synthesis field.
Above by reference to the accompanying drawings to invention has been exemplary description; obvious specific implementation of the present invention is not subject to the restrictions described above; as long as have employed the various improvement that method of the present invention is conceived and technical scheme is carried out; or directly apply to other occasion, all within protection scope of the present invention without improving.
Claims (5)
1. an aromatic amino-derivative, is characterized in that, its structural formula is:
。
2. the preparation method of aromatic amino-derivative as claimed in claim 1, is characterized in that, comprise the steps:
A, precursor synthesize: with Pd (PPh
3)
2cl
2for catalyzer, CuI is promotor, and 1,6-diine and phenylacetylene bromine are joined successively in appropriate acetonitrile, and add a certain amount of triethylamine, stirring at room temperature reacts 24 hours, prepares compound 1, and structural formula is
;
B, palladium chtalyst: compound 1 for catalyst system, reacts 12 or 24 hours with tri-n-butylamine with palladium, triphenyl phosphorus in DMF DMF;
C, purifying: after the crude product of aromatic amino-derivative adds water washing, be extracted with ethyl acetate, isolated organic phase successively uses 5% hydrochloric acid soln, 5% solution of potassium carbonate, saturated common salt water washing, decompression is spin-dried for the compound 2 that column chromatography for separation can obtain needing, i.e. aromatic amino-derivative, column chromatography productive rate is 88%.
3. the preparation method of aromatic amino-derivative as claimed in claim 2, it is characterized in that, step a carries out under anhydrous and oxygen-free condition, and 1,6-diine and phenylacetylene bromine mol ratio are 1:2.4.
4. the preparation method of aromatic amino-derivative as claimed in claim 2, it is characterized in that, step b is 100
ocarry out under the condition of C, compound 1 adopts 5mmol, and palladium adopts 0.25mmol, and triphenyl phosphorus adopts 0.5mmol, and tri-n-butylamine adopts 2.5ml, DMF DMF to adopt 7ml.
5. the preparation method of aromatic amino-derivative as claimed in claim 2, it is characterized in that, react 12 hours, after reactant adds water washing, be extracted with ethyl acetate, isolated organic phase successively uses 5% hydrochloric acid soln, 5% solution of potassium carbonate, saturated common salt water washing, decompression is spin-dried for, can obtain the compound 2 needed through column chromatography for separation, i.e. aromatic amino-derivative, wherein the mol ratio of triphenyl phosphorus and palladium is 2:1; Or reaction obtains the crude product of aromatic amino-derivative for 24 hours.
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| CN106588694B (en) * | 2016-12-01 | 2018-05-04 | 安徽师范大学 | A kind of aromatic nitriles derivative and preparation method thereof |
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| CN107043342A (en) * | 2017-04-06 | 2017-08-15 | 盐城工学院 | Arylalkyl thioethers analog derivative and preparation method thereof |
| CN107043341A (en) * | 2017-04-06 | 2017-08-15 | 盐城工学院 | Diaryl sulfide analog derivative and preparation method thereof |
| CN106966937A (en) * | 2017-04-06 | 2017-07-21 | 盐城工学院 | Diaryl selenide analog derivative and preparation method thereof |
| CN107641080B (en) * | 2017-09-29 | 2018-12-14 | 安徽师范大学 | A kind of dihydronaphthalene ketones derivant and preparation method thereof containing spirane structure |
| CN114014779A (en) * | 2021-12-14 | 2022-02-08 | 安徽师范大学 | Bisaryl oxime ether compound and preparation method thereof |
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| CN102718643A (en) * | 2012-04-11 | 2012-10-10 | 安徽师范大学 | Benzocyclobutanone derivative and synthesis method thereof |
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| CN102718643A (en) * | 2012-04-11 | 2012-10-10 | 安徽师范大学 | Benzocyclobutanone derivative and synthesis method thereof |
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| Title |
|---|
| Rhodium-catalyzed enantioselective [2+2+2] cycloaddition of diynes with unfunctionalized alkenes;Takanori Shibata et al;《Tetrahedron》;20071231;第63卷;12853-12859 * |
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