CN104725399B - Method for using ionic liquid to promote intramolecular cross dehydrogenation coupling so as to synthesize benzothieno[3,2-b]chromone compounds - Google Patents
Method for using ionic liquid to promote intramolecular cross dehydrogenation coupling so as to synthesize benzothieno[3,2-b]chromone compounds Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
Abstract
The invention discloses a method for using ionic liquid to promote intramolecular cross dehydrogenation coupling so as to synthesize benzothieno[3,2-b]chromone compounds. The method is characterized in that under a metal-free condition, water is used as solvent, the ionic liquid promotes the cross dehydrogenation coupling reaction of 3-aryloxybenzothiophene-2-aldehyde to effectively synthesize the benzothieno[3,2-b]chromone compounds, the reaction can be well performed under a gram-grade scale, and the activity of accelerator has no obvious declination after the accelerator is recycled for 5 times.
Description
Technical field
The invention belongs to organic compound technique applied technical field, it is related to benzothiophene simultaneously [3,2-b] chromone class chemical combination
The green syt of thing.
Background technology
Chromone and its derivative are the critically important heterocyclic compounds of a class, and there are such compound many biological and medicines to live
Property, including：Antibacterial, antimycotic and algae-resistant activity.In numerous chromone derivatives, 11H- benzothiophene simultaneously [3,2-b] chromone
Class compound due to relatively low molecular weight and logP calculated values, with good medicine and bioactivity, by medicine and
Synthesize the concern of chemistry.Miller groups（US20020183310A1）Report salicylic acid or thiosalicylic acid and adjacent fluorine α-bromobenzene
Ethyl ketone has synthesized a series of benzothiophenes simultaneously [3,2- under cesium carbonate effectb] chromone compounds and such compound is carried out
Active testing, it is found that such compound is the β ERs of a series of novel（Estrogen Receptor beta, ER
β）Selective ligands.But the synthetic method has used alkali and halogen-containing substrate, Atom economy is poor, reacts not green.
C h bond is most commonly seen chemical bond in organic compound, and c h bond catalytic activation is due to avoiding the pre- of reactant
Function dough, greatly improves Atom economy and reduces the discharge of waste, and current organic synthesis is turned into its unique advantage
One of study hotspot of methodology；On the basis of the direct function dough reaction of c h bond for developing in recent years, Canadian McGill
University's professor's Li Chaojun group（J. Am. Chem. Soc., 2005, 127, 3672）Propose a kind of more green more efficient
C h bond activating method, and be referred to as to intersect dehydrogenation coupling（Cross-Dehydrogenative Coupling）, i.e. CDC is anti-
Should.Intersect dehydrogenation coupling reaction and have become the study hotspot that c h bond in recent years activates field.
Ionic liquid, because having the advantages that low volatility, good dissolubility energy and can be recycled, is to study in the world
One of hot fields.Green Chemistry is more conformed to when ionic liquid is as solvent or catalyst and realizes height between organic compound
The requirement of effect, high selectivity and mild condition conversion, is applied to organic synthesis, biomass conversion and other various fields.Closely
Nian Lai, ionic liquid is also used in transition metal-catalyzed c h bond priming reaction as solvent, but there is not yet heterocycle from
Sub- liquid is independently used for being catalyzed the research report of c h bond priming reaction.Based on the basis of our previous research works, present invention hair
One kind is opened up with ionic liquid as accelerator, TBHP is oxidant, the 3- aryloxy group benzothiophene -2- aldehyde compounds in water phase
There is the CDC reactions of intramolecular, a series of benzothiophenes simultaneously [3,2- have been synthesized in simple, green, efficient methodb] chromone class
Compound.
The content of the invention
Instant invention overcomes synthesis benzothiophene simultaneously [3,2-b] chromone compounds conventional method Atom economy difference and
Not green enough shortcoming, there is provided a kind of is accelerator with the ionic liquid that can be recycled, and water is solvent, through intersecting dehydrogenation idol
The synthesis such as formula of the method efficient green of connection（II）Shown benzothiophene simultaneously [3,2-b] chromone compounds, wherein, it is described anti-
Process is answered as shown in formulas below.
Ar is phenyl ring, substituted benzene ring, naphthalene nucleus.Preferably, Ar is phenyl ring, substituted benzene ring, naphthalene nucleus.
X is O or S.
In the present invention, Ar and X includes but are not limited to above-mentioned group.
Such as above reaction equation, the present invention utilizes formula（I）Shown 3- aryloxy group benzothiophene -2- aldehyde compounds are bottom
Thing, with different ionic liquid as accelerator, with different oxidizing, is reacted in reaction dissolvent, is synthesized such as formula
（II）Shown benzothiophene simultaneously [3,2-b] chromone compounds.
In the present invention, the ionic liquid accelerator is：1- butyl -3- methylimidazole villaumites（[Bmim]Cl）；1- butyl-
3- methylimidazole bromides（[Bmim]Br）；1- butyl -3- methylimidazole salt compounded of iodine（[Bmim]I）；1- butyl -3- methylimidazole tetrafluoros
Borate（[Bmim]BF4）；1- butyl -3- methylimidazole hexafluorophosphates（[Bmim]PF6）；Anion is halogen ion, cation
It is the ionic liquid of imidazoles, benzimidazole, benzotriazole, pyridines, morpholine class, pyrrolidinone compounds and quaternary ammonium salt
Deng.Preferably, the ionic liquid accelerator is 1- butyl -3- methylimidazole bromides（[Bmim]Br）.Wherein, the accelerator
Consumption be such as formula（I）The 25-100 mol% of shown substrate.Preferably, the consumption of the accelerator is such as formula（I）Shown
50 mol% of substrate.
In the present invention, the oxidant is：The aqueous solution of TBHP 70%（TBHP）, di-tert-butyl peroxide
（DTBP）, benzoyl peroxide（BPO）, ammonium persulfate-sodium bisulfate（Oxone）, metachloroperbenzoic acid（m-CPBA）, acetic acid
Iodobenzene（PhI(OAc)2）, the aqueous solution of hydrogen peroxide 30%（H2O2）.Preferably, the oxidant is TBHP（0.2 mL）.
In the present invention, the reaction dissolvent is water, 1,2- dichloroethanes, acetonitrile, tetrahydrofuran, toluene.Preferably, it is described
Solvent is water.Wherein, the consumption of the solvent is 0.02-0.2 mL.Preferably, the solvent load is 0.05 mL.
The present invention synthesizes benzothiophene simultaneously [3,2-b] reaction of chromone compounds comprises the following steps：In reaction tube
Add ionic liquid accelerator, formula（I）Shown 3- aryloxy group benzothiophene -2- aldehyde, then sequentially adds oxidant and solvent,
12-36 h are reacted under magnetic agitation at 80-120 DEG C, water is added after having reacted, be then extracted with ethyl acetate, organic phase
Anhydrous sodium sulfate drying is used after merging, filtering, concentration is obtained such as formula through column chromatography for separation（II）Shown target product benzothiophene
And [3,2-b] chromone, water mutually revolve remove water and be vacuum dried ionic liquid be used for promote next secondary response, realize ionic liquid promote
Enter the recycling of agent.
The invention allows for being prepared according to above-mentioned synthetic method of the invention such as formula（II）Shown benzothiophene
And [3,2-b] chromone compounds.
Wherein, formula（II）It is 11H- benzo [4,5] thieno [3,2-b] chromone, 2- fluoro- 11H- benzo [4,5] thieno
[3,2-b] chromone, 2- chloro- 11H- benzo [4,5] thieno [3,2-b] chromone, 2- bromo- 11H- benzo [4,5] thieno [3,2-b] chromone, 11- oxos -11H- benzo [4,5] thieno [3,2-b] chromene -2- nitriles, 2- methoxyl groups -11H- benzo [4,5] thiophene
And [3,2-b] chromone, 2- methyl isophthalic acids 1H- benzo [4,5] thieno [3,2-b] chromone, the 2- tert-butyl groups -11H- benzo [4,5] thiophene
Fen simultaneously [3,2-b] chromone, 4- Trifluoromethyl-1s 1H- benzo [4,5] thieno [3,2-b] chromone.
The present invention is synthesizing 11H- benzo [4,5] thieno [3,2-b] as a example by chromone, by reactant 3- phenoxy group benzo thiophenes
The amount of fen -2- aldehyde is extended to a gram level（Expand 40 times）, yield is basically unchanged.
The present invention is synthesizing 11H- benzo [4,5] thieno [3,2-b] as a example by chromone, to ionic liquid accelerator [Bmim]
Br is reclaimed and reused, and the yield for recycling 5 times is 75%-82%.
The present invention synthesizes benzothiophene simultaneously [3,2-b] innovative point of method of chromone compounds has：（1）Reaction of atomic is passed through
Ji property is high, and condition is easy to be gentle, simple to operate；（2）Reaction has wide substrate；（3）Reaction is carried out in green solvent water,
It is environmentally friendly；（4）Yield is basically unchanged after reaction amplification quantity, is adapted to large-scale industrial production；（5）Reactive ion liquid promotees
Entering agent can realize recycling, and after recycling 5 times activity without being decreased obviously.
Brief description of the drawings
Fig. 1,3,5 ... ... 15 represent synthesized target product 2-10's respectively1The phenogram of HNMR.Fig. 2,4,6 ... ...
16 represent synthesized target product 2-10 respectively13The phenogram of C NMR, it may be determined that product structure.
Specific embodiment
With reference to specific examples below, the present invention is described in further detail, the data given by following examples
Including concrete operations and reaction condition and product.Product structure is confirmed through NMR, HRMS.
Benzothiophene as shown in table 1 simultaneously [3,2-b] chromone compounds are to be synthesized by the inventive method and obtained
Product, there is not yet open source literature discloses these compounds.
The new benzothiophene of the invention of table 1 simultaneously [3,2-b] chromone compounds
Embodiment 1
11H- benzo [4,5] thieno [3,2-b] chromone synthesis
Ionic liquid accelerator [Bmim] Br is added in reaction tube（0.1 mmol）, 3- phenoxy group benzothiophene -2- aldehyde
（0.2 mmol）, then sequentially add TBHP（0.2 mL）And water（0.05 mL）, 100oUnder C during magnetic agitation reaction 24
Between, room temperature is cooled to after having reacted, 2 mL water are added, then it is extracted with ethyl acetate（3 × 10 mL）, organic phase merging
Anhydrous sodium sulfate drying is used afterwards, and filtering is removed under reduced pressure ethyl acetate, product 1 is obtained through column chromatography for separation（Eluant, eluent polarity：Oil
Ether/ethyl acetate 8: 1）.Yield：82%.
Embodiment 2
11H- benzo [4,5] thieno [3,2-b] chromone the synthesis of gram level
Ionic liquid accelerator [Bmim] Br is added in reaction tube（4 mmol）, 3- aryloxy group benzothiophene -2- aldehyde（8
mmol）, then sequentially add TBHP（8 mL）And water（2 mL）, 100oReacted for 24 times under C under magnetic agitation, reacted
After be cooled to room temperature, the solid suction filtration for obtaining, crude by column chromatography separates to obtain product 1（Eluant, eluent polarity：Petroleum ether/acetic acid
Ethyl ester 8: 1）.Yield：80%.
Embodiment 3
2- fluoro- 11H- benzo [4,5] thieno [3,2-b] chromone synthesis
Ionic liquid accelerator [Bmim] Br is added in reaction tube（0.1 mmol）, 3- (4- fluorophenoxies) benzo thiophene
Fen -2- aldehyde（0.2 mmol）, then sequentially add TBHP（0.2 mL）And water（0.05 mL）, 100oMagnetic agitation is anti-under C
Answered for 24 times, room temperature is cooled to after having reacted, add 2 mL water, be then extracted with ethyl acetate（3 × 10 mL）, it is organic
Anhydrous sodium sulfate drying is used after mutually merging, filtering is removed under reduced pressure ethyl acetate, product 2 is obtained through column chromatography for separation（Eluant, eluent pole
Property：Petrol ether/ethyl acetate 12: 1）.Yield：77%；1H NMR (400 MHz, CDCl3): δ 8.20 (d, J =
8.0 Hz,1 H), 8.03 (dd, J = 8.4, 3.2 Hz, 1 H), 7.93 (d, J = 8.4 Hz, 1 H), 7.70
(dd, J = 9.2, 4.0 Hz, 1 H), 7.65-7.61 (m, 1 H), 7.56 (td, J = 7.2, 0.8 Hz,1
H), 7.50 (ddd, J = 9.2, 7.6, 3.2 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ 172.6
(d, J CF = 2.2 Hz), 159.4 (d, J CF = 245.2 Hz), 154.1, 152.3(d, J CF = 1.5 Hz),
140.1, 129.6, 129.2, 125.3, 123.9, 123.8, 122.6, 121.9 (d, J CF = 25.1 Hz),
120.3, 120.1 (d, J CF = 8.3 Hz), 111.0 (d, J CF = 24.2 Hz). ESI HRMS calcd. for
C15H7FO2S [M+H]+ 271.0224, found 271.0223.
Embodiment 4
2- chloro- 11H- benzo [4,5] thieno [3,2-b] chromone synthesis
Ionic liquid accelerator [Bmim] Br is added in reaction tube（0.1 mmol）, 3- (4- chlorophenoxies) benzo thiophene
Fen -2- aldehyde（0.2 mmol）, then sequentially add TBHP（0.2 mL）And water（0.05 mL）, 100oMagnetic agitation is anti-under C
24 h are answered, room temperature is cooled to after having reacted, add 2 mL water, be then extracted with ethyl acetate（3 × 10 mL）, organic phase
Anhydrous sodium sulfate drying is used after merging, filtering is removed under reduced pressure ethyl acetate, product 3 is obtained through column chromatography for separation（Eluant, eluent polarity：
Petrol ether/ethyl acetate 12: 1）.Yield：81%；1H NMR (400 MHz, CDCl3): δ 8.35 (d, J = 2.4
Hz, 1 H), 8.19 (ddd, J = 8.0, 1.2, 0.8 Hz, 1 H), 7.93 (dt, J = 8.0, 0.8 Hz, 1
H), 7.71 (dd, J = 8.8, 2.4 Hz, 1 H), 7.66-7.54 (m, 3 H). 13C NMR (100 MHz,
CDCl3): δ 172.1, 154.4, 153.9, 140.2, 134.0, 130.9, 129.6, 129.1, 125.4,
125.3, 123.9, 123.7, 122.6, 120.7, 119.8. ESI HRMS calcd. for C15H7ClO2S [M+H]+
286.9928, found 286.9928.
Embodiment 5
2- bromo- 11H- benzo [4,5] thieno [3,2-b] chromone synthesis
Ionic liquid accelerator [Bmim] Br is added in reaction tube（0.1 mmol）, 3- (4- bromobenzenes epoxide) benzo thiophene
Fen -2- aldehyde（0.2 mmol）, then sequentially add TBHP（0.2 mL）And water（0.05 mL）, 100oMagnetic agitation is anti-under C
24 h are answered, room temperature is cooled to after having reacted, add 2 mL water, be then extracted with ethyl acetate（3 × 10 mL）, organic phase
Anhydrous sodium sulfate drying is used after merging, filtering is removed under reduced pressure ethyl acetate, product 4 is obtained through column chromatography for separation（Eluant, eluent polarity：
Petrol ether/ethyl acetate 12: 1）.Yield：88%；1H NMR (400 MHz, CDCl3): δ 8.51 (d, J = 2.4
Hz, 1 H), 8.19 (ddd, J = 8.4, 1.2, 0.8 Hz, 1 H), 7.93 (dt, J = 8.4, 0.8 Hz, 1
H), 7.84 (dd, J = 8.8, 2.4 Hz, 1 H),7.65-7.54 (m, 3 H). 13C NMR (100 MHz,
CDCl3): δ 172.0, 154.8, 153.9, 140.2, 136.7, 129.6, 129.1, 128.6, 125.3,
124.0, 123.9, 122.6, 120.8, 120.0, 118.3. ESI HRMS calcd. for C15H7BrO2S [M+H]+
330.9423, found 330.9424.
Embodiment 6
11- oxos -11H- benzo [4,5] thieno [3,2-b] chromene -2- nitriles synthesis
Ionic liquid accelerator [Bmim] Br is added in reaction tube（0.1 mmol）, 3- (4- cyano-benzene oxygens) benzo thiophene
Fen -2- aldehyde（0.2 mmol）, then sequentially add TBHP（0.2 mL）And water（0.05 mL）, 100oMagnetic agitation is anti-under C
24 h are answered, room temperature is cooled to after having reacted, add 2 mL water, be then extracted with ethyl acetate（3 × 10 mL）, organic phase
Anhydrous sodium sulfate drying is used after merging, filtering is removed under reduced pressure ethyl acetate, product 5 is obtained through column chromatography for separation（Eluant, eluent polarity：
Petrol ether/ethyl acetate 6: 1）.Yield：75%；1H NMR (400 MHz, CDCl3): δ 8.70 (d, J = 2.4
Hz, 1 H), 8.19 (d, J = 8.0 Hz, 1 H), 7.98 (dd, J = 8.8, 2.4 Hz, 1 H), 7.94
(d, J = 8.0 Hz, 1 H), 7.79 (d, J = 8.8 Hz, 1 H), 7.68-7.64 (m, 1 H), 7.60-
7.56 (m, 1 H). 13C NMR (100 MHz, CDCl3): δ 171.3, 157.7, 153.7, 140.3, 136.0,
131.7, 130.0, 128.7, 125.6, 124.0, 123.1, 122.6, 121.2, 119.8, 117.5, 109.3.
ESI HRMS calcd. for C16H7NO2S [M+H]+ 278.0270, found 278.0271.
Embodiment 7
2- methoxyl groups -11H- benzo [4,5] thieno [3,2-b] chromone synthesis
Ionic liquid accelerator [Bmim] Br is added in reaction tube（0.1 mmol）, 3- (4- methoxyphenoxies) benzo
Thiophene -2- aldehyde（0.2 mmol）, then sequentially add TBHP（0.2 mL）And water（0.05 mL）, 100oMagnetic agitation under C
24 h are reacted, room temperature is cooled to after having reacted, add 2 mL water, be then extracted with ethyl acetate（3 × 10 mL）, it is organic
Anhydrous sodium sulfate drying is used after mutually merging, filtering is removed under reduced pressure ethyl acetate, product 6 is obtained through column chromatography for separation（Eluant, eluent pole
Property：Petrol ether/ethyl acetate 16: 1）.Yield：65%；1H NMR (400 MHz, CDCl3): δ 8.19 (ddd, J =
8.0, 1.6, 0.8 Hz, 1 H), 7.92 (dt, J = 8.0, 0.8 Hz, 1 H),7.75 (d, J = 3.2 Hz,
1 H), 7.63-7.52 (m, 3 H), 7.35 (dd, J = 9.2, 3.2 Hz, 1 H), 3.95 (s, 3 H). 13C
NMR (100 MHz, CDCl3): δ 173.2, 156.8, 153.8, 150.9, 139.9, 129.4, 129.3,
125.1, 123.9, 123.7, 123.3, 122.5, 120.3, 119.4, 105.2, 56.0. ESI HRMS calcd.
for C16H10O3S [M+H]+ 283.0423, found 283.0423.
Embodiment 8
2- methyl isophthalic acids 1H- benzo [4,5] thieno [3,2-b] chromone synthesis
Ionic liquid accelerator [Bmim] Br is added in reaction tube（0.1 mmol）, 3- (4- methylphenoxies) benzo thiophene
Fen -2- aldehyde（0.2 mmol）, then sequentially add TBHP（0.2 mL）And water（0.05 mL）, 100oMagnetic agitation is anti-under C
24 h are answered, room temperature is cooled to after having reacted, add 2 mL water, be then extracted with ethyl acetate（3 × 10 mL）, organic phase
Anhydrous sodium sulfate drying is used after merging, filtering is removed under reduced pressure ethyl acetate, product 7 is obtained through column chromatography for separation（Eluant, eluent polarity：
Petrol ether/ethyl acetate 14: 1）.Yield：57%；1H NMR (400 MHz, CDCl3): δ 8.20-8.18 (m, 2
H), 7.92 (dd, J = 8.0, 0.4 Hz, 1 H), 7.63-7.52 (m, 4 H), 2.51 (s, 3 H). 13C
NMR (100 MHz, CDCl3): δ 173.5, 154.4, 153.8, 140.0, 135.1, 135.0, 129.5,
129.2, 125.4, 125.1, 123.9, 122.5, 122.4, 120.7, 117.8, 21.0. ESI HRMS calcd.
for C16H10O2S [M+H]+ 267.0474, found 267.0472.
Embodiment 9
The 2- tert-butyl groups -11H- benzo [4,5] thieno [3,2-b] chromone synthesis
Ionic liquid accelerator [Bmim] Br is added in reaction tube（0.1 mmol）, 3- (4- tert-butyl benzenes epoxide) benzo
Thiophene -2- aldehyde（0.2 mmol）, then sequentially add TBHP（0.2 mL）And water（0.05 mL）, 100oMagnetic agitation under C
24 h are reacted, room temperature is cooled to after having reacted, add 2 mL water, be then extracted with ethyl acetate（3 × 10 mL）, it is organic
Anhydrous sodium sulfate drying is used after mutually merging, filtering is removed under reduced pressure ethyl acetate, product 8 is obtained through column chromatography for separation（Eluant, eluent pole
Property：Petrol ether/ethyl acetate 16: 1）.Yield：63%；1H NMR (400 MHz, CDCl3): δ 8.38 (d, J =
2.8 Hz, 1 H), 8.20 (ddd, J = 8.0, 1.2, 0.8 Hz, 1H), 7.93-7.91 (m, 1 H), 7.83
(dd, J = 9.2, 2.8 Hz, 1 H), 7.64-7.52 (m, 3 H), 1.43 (s, 9 H). 13C NMR (100
MHz, CDCl3): δ 173.7, 154.3, 153.7, 148.3, 140.0, 131.7, 129.5, 129.2, 125.1,
123.9, 122.5, 122.1, 121.8, 120.8, 117.7, 34.9, 31.4. ESI HRMS calcd. for
C19H16O2S [M+H]+ 309.0944, found 309.0945.
Embodiment 10
4- Trifluoromethyl-1s 1H- benzo [4,5] thieno [3,2-b] chromone synthesis
Ionic liquid accelerator [Bmim] Br is added in reaction tube（0.1 mmol）, 3- (2- 4-trifluoromethylphenopendants) benzene
Bithiophene -2- aldehyde（0.2 mmol）, then sequentially add TBHP（0.2 mL）And water（0.05 mL）, 120oMagnetic force is stirred under C
24 h of reaction are mixed, room temperature is cooled to after having reacted, add 2 mL water, be then extracted with ethyl acetate（3 × 10 mL）, have
Machine is removed under reduced pressure ethyl acetate, product 9 is obtained through column chromatography for separation after mutually merging with anhydrous sodium sulfate drying, filtering（Eluant, eluent pole
Property：Petrol ether/ethyl acetate 15: 1）.Yield：53%；1H NMR (400 MHz, CDCl3): δ 8.62 (ddd, J =
2.4, 1.2, 0.8 Hz, 1 H), 8.21 (ddd, J = 8.0, 1.6, 0.8 Hz, 1 H ), 8.07 (ddd, J
= 7.6, 2.0, 0.8 Hz, 1 H), 7.94 (dt, J = 7.6, 1.2 Hz, 1 H), 7.66-7.55 (m, 3
H). 13C NMR (100 MHz, CDCl3): δ 172.1, 153.4, 152.8, 140.2, 131.3(q, J CF = 4.7
Hz), 130.5, 129.9, 129.0, 125.5, 124.3, 123.8, 123.7, 122.7, 121.5, 120.9,
119.9 (q, J CF = 32.7 Hz). ESI HRMS calcd. for C16H7F3O2S [M+H]+ 321.0192, found
321.0191.
Claims (9)
1. a kind of ionic liquid promotes intramolecular to intersect the side of dehydrogenation coupling synthesis benzothiophene simultaneously [3,2-b] chromone compounds
Method, it is characterised in that with 3- aryloxy group benzothiophene -2- aldehyde compounds as substrate, with different ionic liquid as accelerator, with
Different is oxidizing, is reacted in reaction dissolvent, synthesizes benzothiophene as shown in formula (II) simultaneously [3,2-b] chromone
Class compound, wherein, R is phenyl ring, substituted benzene ring, naphthalene nucleus；When R is phenyl ring, R ' is H；When R is substituted benzene ring or naphthalene nucleus, R '
It is R except remaining group after phenyl ring；X is O or S
2. the synthetic method of benzothiophene as claimed in claim 1 simultaneously [3,2-b] chromone compounds, it is characterised in that described
Ionic liquid accelerator is：Anion is halogen ion；Cation is imidazoles, benzimidazole, pyridines, m orphine, pyrroles
The ionic liquid of alkanone class and quaternary ammonium salt, the consumption of the accelerator is the 25-100mol% of the substrate as shown in formula (I).
3. the synthetic method of benzothiophene as claimed in claim 2 simultaneously [3,2-b] chromone compounds, it is characterised in that described
Ionic liquid accelerator is:1- butyl -3- methylimidazole villaumites ([Bmim] Cl)；1- butyl -3- methylimidazoles bromide ([Bmim]
Br)；1- butyl -3- methylimidazoles salt compounded of iodine ([Bmim] I).
4. the synthetic method of benzothiophene as claimed in claim 1 simultaneously [3,2-b] chromone compounds, it is characterised in that described
Oxidant be：The aqueous solution of TBHP 70%, di-tert-butyl peroxide, benzoyl peroxide, potassium hydrogen persulfate
Complex salt, metachloroperbenzoic acid, iodobenzene acetate, the aqueous solution of hydrogen peroxide 30%, the consumption of the oxidant is as shown in formula (I)
Substrate 2.5 equivalents.
5. the synthetic method of benzothiophene as claimed in claim 1 simultaneously [3,2-b] chromone compounds, it is characterised in that described
Reaction dissolvent is water, 1,2- dichloroethanes, acetonitrile, tetrahydrofuran, toluene, and the consumption of the solvent is 0.02-0.2mL.
6. the synthetic method of benzothiophene as claimed in claim 1 simultaneously [3,2-b] chromone compounds, it is characterised in that described
Reaction is comprised the following steps：Ionic liquid accelerator, the 3- aryloxy group benzothiophenes -2- shown in formula (I) are added in reaction tube
Aldehyde, then sequentially adds oxidant and solvent, is reacted 12-36 hours under magnetic agitation at 80-120 DEG C, adds again after having reacted
Enter water, be then extracted with ethyl acetate, organic phase uses anhydrous sodium sulfate drying after merging, filtering, concentration is obtained through column chromatography for separation
To simultaneously [3, the 2-b] chromone of the target product benzothiophene as shown in formula (II), water mutually revolves water removal and vacuum drying ionic liquid is used
In next secondary response, the recycling of ionic liquid accelerator is realized.
7. the synthetic method of benzothiophene as claimed in claim 1 simultaneously [3,2-b] chromone compounds, it is characterised in that its knot
Shown in structure such as formula (II)：
Wherein, formula (II) be benzo [4,5] thieno [3,2-b] chromone, 2- fluoro- benzo [4,5] thieno [3,2-b] chromone,
2- chlorobenzenes simultaneously [4,5] thieno [3,2-b] chromone, 2- bromobenzenes simultaneously [4,5] thieno [3,2-b] chromone, 11- oxos benzo [4,
5] thieno [3,2-b] chromene -2- nitriles, 2- methoxyl groups benzo [4,5] thieno [3,2-b] chromone, 2- methyl benzo [4,5] thiophene
Fen simultaneously [3,2-b] chromone, the 2- tert-butyl groups benzo [4,5] thieno [3,2-b] chromone, 4- trifluoromethyls benzo [4,5] thieno
[3,2-b] chromone.
8. the synthetic method of benzothiophene as claimed in claim 1 simultaneously [3,2-b] chromone compounds, it is characterised in that closing
Into benzothiophene simultaneously [3,2-b] chromone when, the amount of reactant 3- phenoxy group benzothiophene -2- aldehyde is expanded 40 times to gram levels, produce
Produce rate is constant.
9. the synthetic method of benzothiophene as claimed in claim 1 simultaneously [3,2-b] chromone compounds, it is characterised in that closing
Into benzothiophene simultaneously [3,2-b] chromone when, ionic liquid accelerator [Bmim] Br is reclaimed and reused, circulation makes
It is 75%-82% with the yield of 5 times.
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