CN110172054A - A kind of synthetic method of 9H- oxygen/thia anthracene compound - Google Patents
A kind of synthetic method of 9H- oxygen/thia anthracene compound Download PDFInfo
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- CN110172054A CN110172054A CN201910403546.4A CN201910403546A CN110172054A CN 110172054 A CN110172054 A CN 110172054A CN 201910403546 A CN201910403546 A CN 201910403546A CN 110172054 A CN110172054 A CN 110172054A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
- C07D311/82—Xanthenes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
- C07D335/12—Thioxanthenes
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of synthetic methods of 9H- oxygen/thia anthracene compound, the benzene that the 9H- oxygen/thioxanthene formula (I) compound and electron-donating group replace reacts to obtain after solvent dissolves under deicer, catalyst action, and the 9H- oxygen/thia anthracene compound has molecular structure shown in formula (III)；Wherein, Z is oxygen atom or sulphur atom；R is the aryl that electron-donating group replaces.Synthetic method provided by the invention does not need metal catalytic, does not need addition halogen, can not add peroxide, without pyroreaction condition, reaction condition is simple, yield is high, waste discharge is few, it is environmentally friendly method, it is beneficial to energy conservation environmental protection, consersion unit is simple, easy to industrialized production.
Description
Technical field
The present invention relates to heterocyclic compound technical fields, more particularly, to a kind of conjunction of 9H- oxygen/thia anthracene compound
At method.
Background technique
Because of oxygen/extensive use of the thia anthracene derivant in biology, organic pigment and fluorescent material, so having attracted very
More concerns, meanwhile, 9H- oxygen/thia anthracene compound be widely used in again medicine intermediate (Nucleic Acids Res.1989,
17,8135.；Tetrahedron Lett., 1988,29,577.), therefore, introducing the group has great research significance.
But usually 9H- oxygen/thia anthracene compound arylation will first pass through the pre- function dough of halogen
(Org.Lett.2015,17,5096-5099；J.Am.Chem.Soc.2014,136,6276-6287), or use transition gold
Belong to reagent (RSC Adv., 2016,6,84748-84751) and peroxide (Angew.Chem.Int.Ed.2013,52,
13228-13232), and higher reaction temperatures are needed.This kind of reaction is unfavorable for energy conservation and environmental protection, is also unfavorable for industrialized production.
Therefore, it is necessary to develop energy conservation and environmental protection, synthesis 9H- oxygen/thia anthracene compound synthesis easy to industrialized production
Method.
Summary of the invention
The present invention is to overcome the defect for being unfavorable for energy conservation and environmental protection described in the above-mentioned prior art, being difficult to industrialized production, is mentioned
For a kind of synthetic method of 9H- oxygen/thia anthracene compound, the synthetic method provided does not need metal catalytic, does not need peroxidating
Object, without pyroreaction condition, reaction condition is simple, yield is high, waste discharge is few, is beneficial to energy conservation environmental protection, and reaction is set
It is standby simple, it is easy to industrialized production.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of synthetic method of 9H- oxygen/thia anthracene compound, the 9H- oxygen/thioxanthene formula (I) compound
It under deicer, catalyst action reacts to obtain after solvent dissolves with the benzene that electron-donating group replaces, the 9H- oxygen/thia
Anthracene compound has molecular structure shown in formula (III)；
Wherein, Z is oxygen atom or sulphur atom；R is the aryl that electron-donating group replaces.
Shown in the molecular structural formula such as formula (II) for the benzene that electron-donating group replaces.
The reaction carries out in the atmosphere containing oxygen.For example, the reaction carries out in air atmosphere.
The reaction carries out under normal pressure.Temperature can be room temperature.In this field, room temperature refers to 20~30 DEG C.
Preferably, the catalyst is dichlorocyanobenzoquinone, potassium peroxydisulfate, tert-butyl hydroperoxide, iodobenzene diacetate
Or the combination of one or more of di-t-butyl peroxide.In the application, dichlorocyanobenzoquinone abbreviation DDQ.
It is highly preferred that the catalyst is dichlorocyanobenzoquinone.
Shown in 9H- oxygen/thia anthracene compound synthesis mechanism such as reaction equation (1) of the invention, said by taking catalyst DDQ as an example
Bright, oxygen/thioxanthene (1 in reaction equation (1)) generates single electron transfer in the effect of DDQ and generates oxygen/thioxanthene radical ion pair
Shown in (2 in reaction equation (1)), then extract to form benzyl radicals (reaction equation (1) by the proton of DDQ free radical anion
In 3).Benzyl cation (4 in reaction equation (1)) is generated by second of single electron transfer process, as nucleopilic reagent with confession
Benzene (5 in reaction equation (1)) the attack benzyl cation of electronics, then protonation sloughs a proton and generates 9-H oxygen/thioxanthene
(6 in reaction equation (1)).
Particularly, it is catalyst that the present invention uses DDQ for the first time, makes xanthene or sulphur under the air and temperate condition of normal pressure
Miscellaneous anthracene is reacted with the benzene that electron-donating group replaces generates 9H- oxygen/thia anthracene compound.
Synthetic method provided by the invention does not need metal catalytic, does not need addition halogen, can not add peroxide,
Without pyroreaction condition, reaction condition is simple, yield is high, waste discharge is few, and yield can reach 58%~99%, is
Environmentally friendly method is beneficial to energy conservation environmental protection, and consersion unit is simple, easy to industrialized production.
Preferably, the molar ratio of formula (I) compound and catalyst is 1: (1~1.5).
Preferably, the molar ratio of formula (I) compound and catalyst is 1: 1.
Preferably, the deicer is molecular sieve.
Preferably, the electron-donating group is the combination of one or more of alkyl, hydroxyl or alkoxy.
Preferably, the electron-donating group is the combination of one or more of methyl, hydroxyl or methoxyl group.
Preferably, the total number of carbon atoms of the electron-donating group is 1~10.
Preferably, the number of carbon atom is more than or equal to 6 in R, is less than or equal to 10.
Preferably, the number of the electron-donating group is 1~3.
It is highly preferred that the number of the electron-donating group is 2~3.At this point, reactant benzene is disubstituted or trisubstituted
Benzene.
Preferably, the benzene that the electron-donating group replaces is 1,3- dimethoxy benzene and/or 1,3,5- trimethoxy-benzenes.
Preferably, the molar ratio for the benzene that formula (I) compound and electron-donating group replace is 1: (1~3).
It is highly preferred that the molar ratio for the benzene that formula (I) compound and electron-donating group replace is 1: 3.
Preferably, the solvent is n,N-Dimethylformamide, acetonitrile, Isosorbide-5-Nitrae-dioxane, 1,2- dichloroethanes, tetrahydro
The combination of one or more of furans, nitromethane or dimethyl sulfoxide.
It is highly preferred that the solvent is acetonitrile.
Preferably, the temperature of the reaction is 10~70 DEG C, and the air pressure of the reaction is 1~3atm.
It is highly preferred that the temperature of the reaction is 25 DEG C, the air pressure of the reaction is 1atm.
Compared with prior art, the beneficial effects of the present invention are:
Synthetic method provided by the invention does not need metal catalytic, does not need addition halogen, can not add peroxide,
Without pyroreaction condition, reaction condition is simple, yield is high, waste discharge is few, is environmentally friendly method, is conducive to
Energy conservation and environmental protection, consersion unit is simple, easy to industrialized production.
Detailed description of the invention
Fig. 1 is the nuclear-magnetism H spectrum of 9- (2,4- Dimethoxyphenyl) -9H- xanthene of embodiment 1.
Fig. 2 is the nuclear-magnetism C spectrum of 9- (2,4- Dimethoxyphenyl) -9H- xanthene of embodiment 1.
Fig. 3 is the nuclear-magnetism H spectrum of 9- (2,4- Dimethoxyphenyl) -9H- thioxanthene of embodiment 3.
Fig. 4 is the nuclear-magnetism C spectrum of 9- (2,4- Dimethoxyphenyl) -9H- thioxanthene of embodiment 3.
Specific embodiment
The present invention is further illustrated With reference to embodiment.
Raw material in embodiment can be by being commercially available；
Unless stated otherwise, the present invention uses reagent, method and apparatus for the art conventional reagent, method and are set
It is standby.
Embodiment 1
The synthetic method of 9- (2,4- Dimethoxyphenyl) -9H- xanthene.
It takes 15mL pressure resistance reaction tube, is added DDQ 45mg, xanthene 36mg, 1,3- dimethoxy benzene 83mg, molecular sieve
100mg, acetonitrile 2mL, opening reaction, stir 12h at room temperature.Ethyl acetate 10mL quenching reaction is added after reaction, adds
Salt water 10mL washing, separate organic phase, water phase is extracted with ethyl acetate 3 times, merge organic phase, column chromatography for separation obtain 9- (2,
4- Dimethoxyphenyl) -9H- xanthene sterling 50mg, yield 83%, gained 9- (2,4- Dimethoxyphenyl) -9H- xanthene
Molecular structural formula be
Fig. 1 and Fig. 2 be respectively 9- made from the present embodiment (2,4- Dimethoxyphenyl) -9H- xanthene nuclear-magnetism H spectrum and
Nuclear-magnetism C spectrum.Chemical shift 1H NMR (400MHz, Chloroform-d) the δ 7.22-7.15 (m, 2H) of spectral peak in Fig. 1 hydrogen spectrum,
7.14-7.08 (m, 4H), 6.99-6.93 (m, 2H), 6.86 (d, J=8.4Hz, 1H), 6.49 (d, J=2.4Hz, 1H), 6.37
(dd, J=8.4,2.5Hz, 1H), 5.73 (s, 1H), 3.84 (s, 3H), 3.75 (s, 3H)；The chemical shift of spectral peak in Fig. 2 carbon spectrum
13C NMR (101MHz, Chloroform-d) δ 159.34,157.20,151.44,130.68,129.39,128.03,
127.41,125.05,122.98,116.15,104.80,98.70,55.55,55.24,36.39, it was demonstrated that obtained material 9-
(2,4- Dimethoxyphenyl) -9H- xanthene.
Embodiment 2
9- (2,4,6- trimethoxyphenyl) -9H- oxygen/thioxanthene synthetic method.
15mL pressure resistance reaction tube is taken, DDQ 45mg, oxygen/thioxanthene 36mg, 1,3,5- trimethoxy-benzene 101mg is added, point
12h is stirred in son sieve 100mg, acetonitrile 2mL, opening reaction at room temperature.Ethyl acetate 10mL is added after reaction to be quenched instead
It answers, adds salt water 10mL to wash, separate organic phase, water phase is extracted with ethyl acetate 3 times, merges organic phase, and column chromatography for separation obtains
9- (2,4,6- trimethoxyphenyl) -9H- oxygen/thioxanthene sterling 65mg, yield 99%.
Embodiment 3
The synthetic method of 9- (2,4- Dimethoxyphenyl) -9H- thioxanthene.
It takes 15mL pressure resistance reaction tube, is added DDQ 45mg, thioxanthene 39mg, 1,3- dimethoxy benzene 83mg, molecular sieve
100mg, acetonitrile 2mL, opening reaction, stir 12h at room temperature.Ethyl acetate 10mL quenching reaction is added after reaction, adds
Salt water 10mL washing, separate organic phase, water phase is extracted with ethyl acetate 3 times, merge organic phase, column chromatography for separation obtain 9- (2,
4- Dimethoxyphenyl) -9H- thioxanthene sterling 42mg, divides yield 70%.Gained 9- (2,4- Dimethoxyphenyl) -9H- thia
The molecular structural formula of anthracene is
Fig. 3 and Fig. 4 be respectively 9- made from the present embodiment (2,4- Dimethoxyphenyl) -9H- thioxanthene nuclear-magnetism H spectrum and
Nuclear-magnetism C spectrum.Chemical shift 1H NMR (400MHz, Chloroform-d) δ 7.43-7.39 (m, 2H) of spectral peak in Fig. 3 hydrogen spectrum,
7.38-7.34 (m, 2H), 7.20-7.14 (m, 4H), 6.98 (d, J=8.5Hz, 1H), 6.48 (d, J=2.5Hz, 1H), 6.35
(dd, J=8.5,2.5Hz, 1H), 5.65 (s, 1H), 3.86 (s, 3H), 3.75 (s, 3H)；The chemical shift of spectral peak in Fig. 4 carbon spectrum
13C NMR(101MHz,Chloroform-d)δ159.63,157.48,137.57,132.92,130.16,129.50,
126.63,126.40,126.32,122.20,103.97,98.78,55.28,55.24,45.66, it was demonstrated that obtained material 9-
(2,4- Dimethoxyphenyl) -9H- thioxanthene.
Embodiment 4
The synthetic method of 9- (2,4,6- trimethoxyphenyl) -9H- thioxanthene.
It takes 15mL pressure resistance reaction tube, is added DDQ 45mg, thioxanthene 39mg, 1,3,5- trimethoxy-benzene 101mg, molecular sieve
100mg, acetonitrile 2mL, opening reaction, stir 12h at room temperature.Ethyl acetate 10mL quenching reaction is added after reaction, adds
Salt water 10mL washing, separate organic phase, water phase is extracted with ethyl acetate 3 times, merge organic phase, column chromatography for separation obtain 9- (2,
4,6- trimethoxyphenyls) -9H- thioxanthene sterling 65mg, yield 79%.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all this
Made any modifications, equivalent replacements, and improvements etc., should be included in the claims in the present invention within the spirit and principle of invention
Protection scope within.
Claims (10)
1. a kind of synthetic method of 9H- oxygen/thia anthracene compound, which is characterized in that the 9H- oxygen/thioxanthene formula
(I) benzene that compound and electron-donating group replace reacts to obtain after solvent dissolves under deicer, catalyst action, described
9H- oxygen/thia anthracene compound has molecular structure shown in formula (III)；
Wherein, Z is oxygen atom or sulphur atom；R is the aryl that electron-donating group replaces.
2. synthetic method according to claim 1, which is characterized in that the catalyst is dichlorocyanobenzoquinone, over cure
The combination of one or more of sour potassium, tert-butyl hydroperoxide, iodobenzene diacetate or di-t-butyl peroxide.
3. synthetic method according to claim 1, which is characterized in that the molar ratio of formula (I) compound and catalyst is 1:
(1~1.5).
4. synthetic method according to claim 1, which is characterized in that the deicer is molecular sieve.
5. synthetic method according to claim 1, which is characterized in that the electron-donating group is alkyl, hydroxyl or alcoxyl
The combination of one or more of base.
6. synthetic method according to claim 5, which is characterized in that the number of the electron-donating group is 1~3.
7. synthetic method according to claim 6, which is characterized in that the benzene that the electron-donating group replaces is 1,3- diformazan
Oxygroup benzene and/or 1,3,5- trimethoxy-benzene.
8. synthetic method according to claim 1, which is characterized in that the benzene that formula (I) compound and electron-donating group replace
Molar ratio be 1: (1~3).
9. synthetic method according to claim 1, which is characterized in that the solvent be n,N-Dimethylformamide, acetonitrile,
The group of one or more of Isosorbide-5-Nitrae-dioxane, 1,2- dichloroethanes, tetrahydrofuran, nitromethane or dimethyl sulfoxide
It closes.
10. synthetic method according to claim 1, which is characterized in that the temperature of the reaction is 10~70 DEG C, described anti-
The air pressure answered is 1~3atm.
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| CN109232525A (en) * | 2018-09-27 | 2019-01-18 | 浙江工业大学 | A kind of photochemical catalytic oxidation synthetic method of thioxanthones compound |
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| CN109232525A (en) * | 2018-09-27 | 2019-01-18 | 浙江工业大学 | A kind of photochemical catalytic oxidation synthetic method of thioxanthones compound |
Non-Patent Citations (4)
| Title |
|---|
| BERTRAND SCHWEITZER-CHAPUT, ET AL: "Synergistic Effect of Ketone and Hydroperoxide in Brønsted Acid Catalyzed Oxidative Coupling Reactions", 《ANGEWANDTE CHEMIE, INTERNATIONAL EDITION》 * |
| GUODONG SHEN, ET AL: "Palladium-copper catalyzed C(sp3)-C(sp2) bond C-H activation cross-coupling reaction: selective arylation to synthesize 9-aryl-9H-xanthene and 9,9-diaryl-xanthene derivatives", 《RSC ADVANCES》 * |
| HONGRU WU, ET AL: "Graphene-Oxide-Catalyzed Direct CH CH-Type Cross-Coupling: The Intrinsic Catalytic Activities of Zigzag Edges", 《ANGEWANDTE CHEMIE, INTERNATIONAL EDITION》 * |
| ZHIHUA PENG, ET AL: "Direct Arylation of Benzyl Ethers with Organozinc Reagents", 《J. ORG. CHEM.》 * |
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