CN114524797B - Synthetic method of benzothiophene - Google Patents
Synthetic method of benzothiophene Download PDFInfo
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- CN114524797B CN114524797B CN202210156577.6A CN202210156577A CN114524797B CN 114524797 B CN114524797 B CN 114524797B CN 202210156577 A CN202210156577 A CN 202210156577A CN 114524797 B CN114524797 B CN 114524797B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
- B01J31/0291—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/72—Benzo[c]thiophenes; Hydrogenated benzo[c]thiophenes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention belongs to the technical field of fine chemical preparation, and discloses a method for synthesizing benzothiophene, which takes ionic liquid as a catalyst, and mixes the ionic liquid, thiophene and 2, 5-dimethoxy tetrahydrofuran under the condition of protective atmosphere and then carries out stirring reaction, thereby synthesizing the benzothiophene; wherein the ionic liquid has a chemical structure shown as a formula IL I, IL II or IL III. According to the invention, sulfonic acid functionalized ionic liquid is used as a catalyst, the reaction is carried out in an ionic liquid-organic two-phase environment, thiophene and 2, 5-dimethoxytetrahydrofuran are used as raw materials, benzothiophene is prepared through one-step reaction, and the ionic liquid can be repeatedly used. Compared with the traditional benzothiophene preparation method, the synthetic method has the advantages of simple operation, easy catalyst recovery, reusability and the like.
Description
Technical Field
The invention belongs to the technical field of fine chemical preparation, and particularly relates to a synthetic method of benzothiophene.
Background
Benzothiophenes have a special conjugated structure and unique pharmacological and biological activities, and thus are widely used in the fields of pesticides, medicines, materials and the like, and can be industrially used as dyes, organic light-emitting semiconductors and the like. The current industrial synthesis of benzothiophenes comprises mainly the following three methods: (1) At high temperature (475 ℃), with CrO 3 As an oxidizing agent, al 2 O 3 Catalyzing 2-ethyl thiophenol with catalyst to synthesize by intramolecular cyclization; (2) Ethylbenzene and hydrogen sulfide are used as raw materials and are prepared by gas-phase high-temperature reaction; and (3) preparing thiophenol and acetylene at high temperature.
Because benzothiophene has a large market scale and most of the existing synthetic methods have the defects of high energy consumption, poor product selectivity and the like, the synthetic research on benzothiophene at home and abroad is never stopped. For example, greensfelde reports a method for synthesizing benzothiophene by catalyzing hydrogen sulfide and styrene at 600 ℃ by using iron sulfide and aluminum oxide as catalysts, wherein the conversion rate of the styrene is 60%, but the reaction conditions adopted by the method are severe (j.am. The Chinese patent CN 111423409A describes a method for preparing benzothiophene by taking chloroacetaldehyde and thiophenol as raw materials through nucleophilic substitution and intramolecular dehydration cyclization reaction; however, this method requires a multi-step synthesis and the post-treatment of the reaction is complicated. Arasabtu et al, under the protection of nitrogen, in a homogeneous system, using trifluoromethanesulfonic acid as a catalyst, 2, 5-dimethoxytetrahydrofuran and thiophene as raw materials, in a dichloromethane solvent, reacting under the ice bath condition to synthesize benzothiophene with a yield of 82% (org. Lett.2014,16, 2720-2723); the reaction raw materials are cheap and easy to obtain, and because the reaction is carried out under homogeneous conditions, the trifluoromethanesulfonic acid catalyst is dissolved in the reaction mixed liquid, and the reaction is too violent, the temperature of the reaction mixture has to be reduced by using an ice bath. And the trifluoromethanesulfonic acid catalyst cannot be recovered after the reaction is finished. In addition, the price of trifluoromethanesulfonic acid is 4500 yuan/kg (Chemical Book), which is far in excess of the product price. Therefore, the method has no practical condition for application in the industry.
In summary, a method for synthesizing benzothiophene, which is simple in operation, mild in conditions, and suitable for industrial production, is still needed in the industry at present.
Disclosure of Invention
In view of the above drawbacks and needs of the prior art, the present invention provides a method for synthesizing benzothiophene, wherein a sulfonic acid functionalized ionic liquid is used as a catalyst, the reaction is performed in an ionic liquid-organic two-phase environment, thiophene and 2, 5-dimethoxytetrahydrofuran are used as raw materials, benzothiophene is prepared through a one-step reaction, and the ionic liquid catalyst can be reused. Compared with the traditional benzothiophene preparation method, the synthetic method has the advantages of simple operation, easy recovery of the catalyst, reusability and the like. In addition, the present invention can further ensure the yield by further preferably setting the reaction conditions (such as temperature, catalyst ratio, time, etc.).
In order to achieve the above object, the present invention provides a method for synthesizing benzothiophene, which is characterized in that ionic liquid is used as a catalyst, under the condition of protective atmosphere, the ionic liquid, thiophene and 2, 5-dimethoxytetrahydrofuran are mixed and then stirred for reaction, so as to synthesize benzothiophene; wherein the molar ratio of the thiophene to the 2, 5-dimethoxytetrahydrofuran is 1-1.5: 1;
and, the ionic liquid has a chemical structure as shown in formula IL I, formula IL II or IL III:
in the formula IL I, the formula IL II and the formula IL III, n is 1 or 2, Y is one of trifluoromethanesulfonate and p-toluenesulfonate.
As a further preference of the present invention, the ionic liquid is in particular [ PrSO 3 HMIm]OTf (1- (3-sulfopropyl) -3-methylimidazolium trifluoromethanesulfonate), [ BSO 3 HMIm]OTf (1- (4-sulfobutyl) -3-methylimidazolium trifluoromethanesulfonate), [ BSO 3 HPy]OTf (N- (4-sulfobutyl) pyridine trifluoromethanesulfonate), [ BSO 3 HMIm]OTs (1- (4-sulfobutyl) -3-methylimidazolium P-toluenesulfonate), [ P ] 4443 SO 3 H]OTf (1- (3-sulfopropyl) -tributylphosphine trifluoromethanesulfonate), [ P ] 4444 SO 3 H]At least one of OTf (1- (3-sulfobutyl) -tributylphosphine trifluoromethanesulfonate); the chemical structural formulas are respectively shown as follows:
as a further preference of the invention, after the reaction is finished, an extracting agent is further added into the reaction liquid system for extraction and separation, and an upper organic phase and a lower liquid are respectively collected; wherein the extracting agent is at least one of n-hexane or ethyl acetate;
and drying the lower layer liquid to obtain the recovered ionic liquid, wherein the recovered ionic liquid can be used as a catalyst to be recycled for synthesizing benzothiophene.
In a further preferred embodiment of the present invention, the target benzothiophene is obtained by combining and concentrating the upper organic phase, and then distilling and separating the mixture under atmospheric pressure and reduced pressure.
As a further preferred aspect of the present invention, the molar ratio of the ionic liquid to 2, 5-dimethoxytetrahydrofuran is 0.2:1 to 1:1.
as a further preference of the present invention, the stirring reaction is carried out at a temperature of 20 ℃ to 80 ℃ for a reaction time of 4 to 8 hours.
As a further preferred aspect of the present invention, the stirring reaction is carried out at room temperature.
As a further preferred aspect of the present invention, the protective atmosphere is nitrogen or an inert gas.
Compared with the prior art, the invention uses the ionic liquid shown in formula IL I, IL II or IL III to catalyze thiophene and 2, 5-dimethoxy tetrahydrofuran to react under the condition of protective atmosphere, so as to synthesize benzothiophene; after the reaction is finished, the ionic liquid in the reaction system can be recovered by simple separation and extraction and used for the next synthesis reaction.
Compared with the method reported by Arasabottu in the prior art, the preparation method of benzothiophene uses sulfonic acid functionalized ionic liquid to replace trifluoromethane sulfonic acid as a catalyst. Since the mixture of 2, 5-dimethoxytetrahydrofuran and thiophene is immiscible with the ionic liquid, the reaction proceeds under two liquid-liquid phase conditions consisting of the ionic liquid and the organic mixture. By virtue of limited contact of the reaction raw material and the acidic ionic liquid catalyst under the liquid-liquid two-phase condition, the excessively fast reaction rate under the homogeneous condition is inhibited, so that the target product benzothiophene can be generated at high selectivity under the temperature condition of 20-80 ℃ without using an ice bath. The catalytic system can improve the yield of benzothiophene and ensure the repeated use of the ionic liquid catalyst.
Compared with the existing industrial synthesis method of the benzothiophene, the method for preparing the benzothiophene does not need to use a large amount of organic solvent, the reaction is carried out in an ionic liquid-organic two-phase environment, and the method has the advantages of simple reaction process operation, mild conditions, high selectivity of the product benzothiophene, easy separation and purification and the like.
In conclusion, compared with the method for preparing benzothiophene by intramolecular cyclization of ethyl thiophenol or reaction of styrene and hydrogen sulfide which is generally adopted in the current industry, the method takes sulfonic acid functionalized ionic liquid as the catalyst, and has the advantages of cheap and easily obtained raw materials, simple synthesis operation, recyclable catalyst, easy product separation and the like.
Drawings
FIG. 1 is a schematic flow diagram of the preparation of benzothiophenes in an example of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1:
the preparation method of the embodiment of the invention comprises the following steps: under the protection of nitrogen, 1.33g (10.0 mmol) of 2, 5-dimethoxy tetrahydrofuran, 0.84g (10.0 mmol) of thiophene and [ PrSO 3 HMIm]OTf 3.54g (10.0 mmol; available from Lanzhou chemical and physical research institute of Chinese academy of sciences) was mixed and reacted at room temperature (25 ℃) with stirring for 4 hours. After the reaction, the reaction solution was extracted with n-hexane, the organic phase was combined and concentrated, and the mixture was distilled under normal pressure and reduced pressure (1.0 MPa,85 ℃ C.) to obtain 1.00g of benzothiophene (75% overall yield).
Example 2:
the preparation method of the embodiment of the invention comprises the following steps: under the protection of nitrogen, 1.33g (10 mmol) of 2, 5-dimethoxy tetrahydrofuran, 0.84g (10 mmol) of thiophene and [ BSO ] are taken 3 HMIm]OTf 3.68g (10mmol; CAS number: 657414-80-7, available from Lanzhou chemical and physical research institute of Chinese academy of sciences) were mixed and reacted at room temperature (25 ℃) with stirring for 4 hours. After the reaction, the reaction solution was allowed to stand, the organic phase was concentrated by extraction with n-hexane, and then distilled under normal pressure and reduced pressure (1.0 MPa,85 ℃ C.) to obtain 0.94g of benzothiophene (total yield 70%).
Example 3:
the preparation method of the embodiment of the invention comprises the following steps: under the protection of nitrogen, 1.33g (10.0 mmol) of 2, 5-dimethoxy tetrahydrofuran, 0.84g (10.0 mmol) of thiophene and [ BSO ] are taken 3 HPy]OTf 3.64g (10.0 mmol; CAS number: 855785-75-0, available from Lanzhou chemical and physical research institute of Chinese academy of sciences) was mixed and reacted at room temperature (25 ℃) with stirring for 4 hours. After the reaction, the reaction solution was extracted with ethyl acetate. The organic phase was combined and concentrated, and then distilled under reduced pressure at normal pressure (1.0 MPa,85 ℃ C.) to obtain 0.74g of benzothiophene (total yield: 55%).
Example 4:
the preparation method of the embodiment of the invention comprises the following steps: under the protection of nitrogen, 1.33g (10.0 mmol) of 2, 5-dimethoxy tetrahydrofuran, 0.84g (10.0 mmol) of thiophene and [ BSO ] are taken 3 HMIm]3.91g of OTs (10.0 mmol; CAS number: 410522-18-8, available from Lanzhou chemical and physical research institute of Chinese academy of sciences) were mixed and reacted at 60 ℃ with stirring for 8 hours. After the reaction, n-hexane was used for extraction. After the organic phases were combined and concentrated, 0.13g of benzothiophene (10% of total yield) was obtained by atmospheric and vacuum distillation (1.0 MPa,85 ℃).
Example 5:
the preparation method of the embodiment of the invention comprises the following steps: under the protection of nitrogen, 1.99g (15.0 mmol) of 2, 5-dimethoxy tetrahydrofuran, 0.84g (10.0 mmol) of thiophene and [ PrSO 3 HMIm]OTf 3.54g (10.0 mmol; available from Lanzhou chemical and physical research institute of Chinese academy of sciences) was mixed, and the mixture was stirred at room temperature (25 ℃) for 4 hours. After the reaction was completed, extraction was performed with ethyl acetate. After the organic phases were combined, 0.74g of benzothiophene (total yield 55%) was obtained by atmospheric and vacuum distillation (1.0 MPa,85 ℃).
Example 6:
the preparation method of the embodiment of the invention comprises the following steps: under the protection of nitrogen, 1.99g (10.0 mmol) of 2, 5-dimethoxy tetrahydrofuran, 1.26g (15.0 mmol) of thiophene and [ PrSO 3 HMIm]OTf 3.54g (10.0 mmol; available from Lanzhou chemical and physical research institute of Chinese academy of sciences) were mixed, and the reaction mixture was stirred at room temperature (25 ℃ C.) for 4 hours. After the reaction, n-hexane was used for extraction. After the organic phases were combined, 0.87g of benzothiophene (65% total yield) was obtained by atmospheric and vacuum distillation (1.0 MPa,85 ℃).
Examples 7 to 9:
examples 7-9 are similar to example 1 as ionic liquids [ PrSO 3 HMIm]OTf (purchased from Lanzhou chemical and physical research institute of Chinese academy of sciences) is used as a catalyst, synthesis reaction is carried out at different temperatures (the reaction conditions except the temperature are the same as those in example 1), and the synthesis reaction results are shown in Table 1.
TABLE 1 reaction conditions and results of examples 7-9
Examples 10 to 11:
examples 10 to 11 are, analogously to example 1, ionic liquids [ PrSO ] 3 HMIm]OTf (obtained from the institute of chemico-physical, lanzhou, academy of science, china) was used as a catalyst, and the synthesis reaction was carried out using different catalyst addition ratios (the reaction conditions except the catalyst addition ratio were the same as those in example 1), and the synthesis reaction results are shown in table 2.
TABLE 2 reaction conditions and results of examples 10-11
Examples 12 to 13:
examples 12-13 are similar to example 1 in that the ionic liquid [ PrSO 3 HMIm]OTf (purchased from Lanzhou chemical and physical research institute of Chinese academy of sciences) as catalystThe synthesis reactions were carried out with different reaction times (the reaction conditions except for the reaction time were the same as in example 1), and the results of the synthesis reactions are shown in Table 3.
TABLE 3 reaction conditions and results of examples 12-14
Examples 14 to 18
Examples 14-18 were the recovery of dry ionic liquid [ PrSO ] from example 1 3 HMIm]OTf is a catalyst (vacuum drying for 2 h), and the catalyst was recycled to perform a synthesis reaction (the specific reaction conditions were the same as in example 1), thereby examining the catalyst recycling performance. The results are shown in table 4, from which it is clear that the ionic liquid catalyst can be reused at least 5 times without significant loss of product yield.
TABLE 4 reaction conditions and reaction results for examples 15-19
Example 19
The preparation method of the embodiment of the invention comprises the following steps: under the protection of nitrogen, 1.33g (10.0 mmol) of 2, 5-dimethoxy tetrahydrofuran, 0.84g (10.0 mmol) of thiophene and [ P ] 4443 SO 3 H]OTf 4.86g (10.0 mmol; made by the same manner as "Control of phase separation catalysts/products heated synthesis of long-chain wax esters at modulators", chem.Eng.2019,4, 627-633) were mixed and reacted at room temperature (25 ℃) for 4 hours with stirring. After the reaction, the reaction mixture was extracted with n-hexane, the organic phase was combined and concentrated, and distillation was carried out under normal pressure and reduced pressure (1.0MPa, 85 ℃ C.) to obtain 0.60g of benzothiophene (total yield 45%).
Example 20
The preparation method of the embodiment of the invention comprises the following steps: under the protection of nitrogen, 1.33g (10.0 mmol) of 2, 5-dimethoxy tetrahydrofuran, 0.84g (10.0 mmol) of thiophene and [ P ] 4444 SO 3 H]OTf 5.12g (10.0 mmol; made by the same manner as "Control of phase separation catalysts/products heated synthesis of long-chain wax esters at modulators", chem.Eng.2019,4, 627-633) was mixed and reacted at room temperature (25 ℃) for 4 hours with stirring. After the reaction, the reaction mixture was extracted with n-hexane, the organic phase was combined and concentrated, and distillation was carried out under normal pressure and reduced pressure (1.0MPa, 85 ℃ C.) to obtain 0.53g of benzothiophene (total yield 40%).
The above embodiments are merely examples, and for example, other inert gases (e.g., argon) may be used as the shielding gas in addition to nitrogen.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. A method for synthesizing benzothiophene is characterized in that ionic liquid is used as a catalyst, and under the condition of protective atmosphere, the ionic liquid, thiophene and 2, 5-dimethoxy tetrahydrofuran are mixed and then stirred for reaction, so that benzothiophene is synthesized; wherein the molar ratio of the thiophene to the 2, 5-dimethoxytetrahydrofuran is 1-1.5: 1;
and, the ionic liquid has a chemical structure as shown in formula IL I, formula IL II or IL III:
in the formulas IL I, IL II and IL III, n is 1 or 2, Y is one of trifluoromethanesulfonate and p-toluenesulfonate.
2. The process for the synthesis of benzothiophenes as claimed in claim 1, wherein the ionic liquid is in particular [ PrSO 3 HMIm]OTf (1- (3-sulfopropyl) -3-methylimidazolium trifluoromethanesulfonate), [ BSO 3 HMIm]OTf (1- (4-sulfobutyl) -3-methylimidazolium trifluoromethanesulfonate), [ BSO 3 HPy]OTf (N- (4-sulfobutyl) pyridine trifluoromethanesulfonate), [ BSO 3 HMIm]OTs (1- (4-sulfobutyl) -3-methylimidazole P-toluenesulfonate), [ P ] 4443 SO 3 H]OTf (1- (3-sulfopropyl) -tributylphosphine trifluoromethanesulfonate), [ P ] 4444 SO 3 H]At least one of OTf (1- (3-sulfobutyl) -tributylphosphine trifluoromethanesulfonate); the chemical structural formulas are respectively shown as follows:
3. the method for synthesizing benzothiophene of claim 1, wherein an extractant is further added to the reaction liquid system after the reaction is finished, and the upper organic phase and the lower liquid are collected separately; wherein the extracting agent is at least one of n-hexane or ethyl acetate;
and drying the lower layer liquid to obtain the recovered ionic liquid, wherein the recovered ionic liquid can be used as a catalyst to be recycled for synthesizing benzothiophene.
4. The method for synthesizing benzothiophene according to claim 3, wherein the target benzothiophene is obtained by distilling the organic phase at normal pressure and then distilling and separating at reduced pressure after the organic phase at the upper layer is synthesized and concentrated.
5. The method of synthesizing benzothiophene of claim 1, wherein the molar ratio of ionic liquid to 2, 5-dimethoxytetrahydrofuran is 0.2:1 to 1:1.
6. the method for synthesizing benzothiophene of claim 1, wherein the stirring reaction is carried out at a temperature of 20 to 80 ℃ for 4 to 8 hours.
7. The process for the synthesis of benzothiophenes as claimed in claim 6, wherein the stirring reaction is carried out at room temperature.
8. The method of synthesizing benzothiophene of claim 1, wherein the protective atmosphere is nitrogen or an inert gas.
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| CN102952114A (en) * | 2011-08-26 | 2013-03-06 | 中国科学院大连化学物理研究所 | Application of SO3H- functionalized ionic liquid serving as catalyst to synthesis of 2-acetylthiophene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102952114A (en) * | 2011-08-26 | 2013-03-06 | 中国科学院大连化学物理研究所 | Application of SO3H- functionalized ionic liquid serving as catalyst to synthesis of 2-acetylthiophene |
Non-Patent Citations (3)
| Title |
|---|
| "Effects of water and alcohols on the polymerization of furan during its acid-catalyzed conversion into benzofuran";Hu, Xun et al.;《RSC Advances》;第6卷(第46期);第40489-40501页 * |
| "Lewis Acid/Broensted Acid Mediated Benz-Annulation of Thiophenes and Electron-Rich Arenes";Rafiq, Settu Muhamad et al.;《Organic Letters》;第16卷(第10期);第2720-2723页 * |
| "Stable, Crystalline Acenedithiophenes with up to Seven Linearly Fused Rings";Payne, Marcia M.et al.;《Organic Letters》;第6卷(第19期);第3325-3328页 * |
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