CN109422717A - A kind of synthetic method of heterochromatic compound - Google Patents

A kind of synthetic method of heterochromatic compound Download PDF

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CN109422717A
CN109422717A CN201710740922.XA CN201710740922A CN109422717A CN 109422717 A CN109422717 A CN 109422717A CN 201710740922 A CN201710740922 A CN 201710740922A CN 109422717 A CN109422717 A CN 109422717A
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formula
synthetic method
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刘运奎
杨欢
郑立孟
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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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
    • C07D311/76—Benzo[c]pyrans

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The present invention provides a kind of preparation methods of heterochromatic compound.The synthetic method is using neighbour's alkynyl compound of benzaldehyde category shown in formula (I) as starting material, under the catalysis of palladium acetate, using tertbutanol peroxide as nucleopilic reagent, sodium ethoxide or sodium carbonate are alkali, in organic solvent, it is reacted 6-18 hours at 20-100 DEG C, reaction solution is isolated and purified chroman compound shown in obtained formula (II)；The features such as synthetic method of the invention has small to environmental hazard, and reaction condition is relatively mild, saves energy consumption, and selectivity of product is high, easy to operate.

Description

A kind of synthetic method of heterochromatic compound
Technical field
The present invention relates to a kind of synthetic method of organic compound, the system with a kind of chroman compound is related in particular to Preparation Method.
Background technique
Heterochromatic compound is widely distributed in nature, is the precursor structure of many natural products, some are heterochromatic full Class compound has active compound for anti tumor, is a kind of important natural products.Its structural unit is widely present in many tools Have in the molecular structure of bioactivity, for example, the drug for hypertension of vitamin E and many beta-receptor antagonists.It is different simultaneously Chroman compound is one of the key intermediate of many important drugs, be widely used in medicine, pesticide, etc. industries.It is different The synthetic method of chroman compound has one-step method, two-step method and three-step approach.In recent years, organic chemists new development is a variety of The method for synthesizing heterochromatic compound.Such as Butin et al. constructed by the method that furans open loop-heterochromatic alkene ring closes it is heterochromatic The skeleton structure of full compound (see Tetrahedron Letters, 2006,37 (11): 8439-8441.).Abdel-Ghany Et al. by cyclohexylmethylene cyanogen and active nitrile, active halogenated compound, carbon disulfide, aldehyde, isothiocyanates and isocyanic acid Ester reaction has synthesized a series of new heterochromatic ene derivatives.(see Cheminform, 2010,32 (11))
Currently, generating a large amount of spent acid and the acidity containing organic matter during traditional industrially prepared heterochromatic compound Waste water and lead to environmental pollution, increase control expense.Therefore, in view of heterochromatic compound in pharmaceutical chemistry and organic fine Important application in terms of Chemical Manufacture, the synthetic method for exploring a kind of easy, efficient indanone compounds is to be of great significance 's.
Summary of the invention
In view of the deficienciess of the prior art, the present invention is intended to provide a kind of method for preparing chroman compound, overcomes The shortcomings that prior art, realizes that the cyclisation of adjacent alkynyl benzaldehyde is anti-using palladium acetate as catalyst in tert-Butanol peroxide presence It answers.
In order to achieve the above object of the invention, the technical solution adopted by the present invention is that:
One kind is at Pd (OAC)2/ TBHP system acts on the synthetic method of heterochromatic compound shown in following formula (II), described Method are as follows: using neighbour's alkynyl compound of benzaldehyde category shown in formula (I) as starting material, under the catalysis of palladium acetate, with peroxidating uncle Butanol is nucleopilic reagent, and sodium ethoxide or sodium carbonate are alkaline matter, in organic solvent, it is small that 6-18 is reacted at 20-100 DEG C When, reaction solution is isolated and purified chroman compound shown in obtained formula (II)；
In formula (I) or formula (II), R1For H, R2For H, methyl, chlorine ,-COOCH3。
Reaction equation is as follows:
The raw material that the present invention uses is neighbour's alkynyl compound of benzaldehyde category shown in formula (I), and those skilled in the art can be with The method according to disclosed in existing literature is voluntarily prepared.
Reaction of the present invention is in the presence of palladium acetate, its main feature is that low toxicity is efficiently, and auxiliary without extra ligand It helps.The amount of the substance of the palladium acetate be formula (I) shown in neighbour's alkynyl compound of benzaldehyde category substance amount 5%~ 20%, preferably 10%.
Reaction of the present invention, the nucleopilic reagent are tert-Butanol peroxide, the substance of the tertbutanol peroxide Amount be formula (I) shown in neighbour's alkynyl compound of benzaldehyde category substance amount 100%~200%, preferably 120%.
Reaction of the present invention, the alkaline matter be sodium ethoxide or sodium carbonate, the substance of the alkaline matter Amount be formula (I) shown in neighbour's alkynyl compound of benzaldehyde category substance amount 100%~200%, preferably 120%.
Organic solvent of the present invention is acetonitrile, tetrahydrofuran, toluene or methylene chloride, preferably uses acetonitrile.It is described to have The volume of solvent is calculated as 10~30mL/mmol with the amount of the substance of neighbour's alkynyl compound of benzaldehyde category shown in formula (I).
Reaction of the present invention preferably carries out under the conditions of 30 DEG C, and the reaction time is preferably 12 hours.
The present invention specifically recommends the synthetic method of the chroman compound to include the following steps: adjacent alkynyl benzene first Aldehyde, palladium acetate, tert-Butanol peroxide, sodium ethoxide, acetonitrile are added in voltage-resistant reactor, are stirred to react under the conditions of 30 DEG C 12 hours, institute Reaction solution is obtained through isolating and purifying to obtain target product.Further, following method can be used in described isolate and purify: into reaction solution Column chromatography silica gel is added, and solvent is removed by vacuum distillation, then by pillar layer separation, with petroleum ether and ethyl acetate volume Than the mixed liquor for 40:1 as eluent, the eluent containing target product is collected, solvent is evaporated off and obtains formula (II) institute Show chroman compound.
Further, the column chromatography silica gel is 100~200 mesh, and the quality of the column chromatography silica gel is with formula (I) shownization The amount for closing the substance of object is calculated as 0.5g/mmol.
Further, heterochromatic compound shown in formula (II) is preferably one of following compounds:
The present invention passes through adjacent alkynyl benzaldehyde at Pd (OAC)2Under the effect of/TBHP system, participated in by tertbutanol peroxide Nucleophilic addition/cyclisation be made chroman class metaplasia object, the utility model has the advantages that temperature is lower compared with existing preparation method, to environment It endangers small；Reaction condition is relatively mild, saves energy consumption；Selectivity of product is high；In addition, also have substrate universality strong, behaviour Make the features such as easy.
Specific embodiment
Invention is further described in detail combined with specific embodiments below, and the scope of protection of the present invention is not limited to this.
Embodiment 1
By 0.3mmol neighbour's alkynyl benzaldehyde, 10%mol palladium acetate, 0.3mmol tertbutanol peroxide, 0.36mmol ethyl alcohol Sodium is added in 10mL voltage-resistant reactor, adds 3mL acetonitrile as solvents.Then, the magnetic agitation 6h under the conditions of 50 DEG C.So Afterwards, it is added in reaction solution two spoon column chromatography silica gels (100-200 mesh), and solvent is removed by vacuum distillation, then pass through column Chromatographic isolation obtains pure product (using petrol ether/ethyl acetate=200:1 as eluant, eluent).Obtain the mesh as shown in structural formula Mark product 1- (t-butylperoxy) different chromene of -3- phenyl -1H- is colourless oil liquid, yield 72%.
Characterize data:1H NMR(CDCl3,500MHz):δ7.90-7.88(m,2H),7.45-7.36 (m,5H),7.31- 7.28 (m, 1H), 7.25 (d, J=7.5Hz, 1H), 6.71 (s, 1H), 6.59 (s, 1H), 1.26 (s, 9H)；13C NMR (125MHz,CDCl3):δ150.4,134.6,131.7,130.1,128.8, 128.3,127.0,126.5,125.4,124.5, 123.5,110.5,110.1,81.0,26.5.
Embodiment 2
By 0.3mmol neighbour's alkynyl benzaldehyde, 10%mol palladium acetate, 0.36mmol tertbutanol peroxide, 0.36mmol ethyl alcohol Sodium is added in 10mL voltage-resistant reactor, is added 3.5mL tetrahydrofuran and is made solvent.Then, the magnetic agitation under the conditions of 50 DEG C 6h.Then, it is added in reaction solution two spoon column chromatography silica gels (100-200 mesh), and solvent is removed by vacuum distillation, then lead to It crosses pillar layer separation and obtains the different chromene of pure product 1- (t-butylperoxy) -3- phenyl -1H- (with petroleum ether/acetic acid second Ester=200:1 is as eluant, eluent).Obtain the target product as shown in structural formula, yield 68%.
Characterize data:1H NMR(CDCl3,500MHz):δ7.90-7.88(m,2H),7.45-7.36 (m,5H),7.31- 7.28 (m, 1H), 7.25 (d, J=7.5Hz, 1H), 6.71 (s, 1H), 6.59 (s, 1H), 1.26 (s, 9H)；13C NMR (125MHz,CDCl3):δ150.4,134.6,131.7,130.1,128.8, 128.3,127.0,126.5,125.4,124.5, 123.5,110.5,110.1,81.0,26.5.
Embodiment 3
By 0.3mmol 2-((4- chlorphenyl) acetenyl) benzaldehyde, 10%mol palladium acetate, the 0.6 tertiary fourth of mmol peroxidating Alcohol, 0.6mmol sodium ethoxide are added in 10mL voltage-resistant reactor, are added 6mL tetrahydrofuran and are made solvent.Then, in 80 DEG C of items Magnetic agitation 18h under part.Then, two spoon column chromatography silica gels (100-200 mesh) is added in reaction solution, and passes through vacuum distillation Solvent is removed, then pure product 1- (t-butylperoxy) -3- (the 4- chlorobenzene as shown in structural formula is obtained by pillar layer separation Base) the different chromene of -1H- (using petrol ether/ethyl acetate=200:1 as eluant, eluent).Obtaining target product is white solid, Yield is 78%.
Characterize data:1H NMR(CDCl3,500MHz):δ7.82-7.79(m,2H),7.43-7.35 (m,4H),7.31- (7.28 m, 1H), 7.23 (d, J=7.5Hz, 1H), 6.68 (s, 1H), 6.56 (s, 1H), 1.25 (s, 9H)；13C NMR (125MHz,CDCl3):δ149.3,134.6,133.2,131.4,130.1, 128.6,127.0,126.8,126.7,124.6, 123.5,100.49,100.47,81.1,26.5.
Embodiment 4
By 0.3mmol 2-((4- chlorphenyl) acetenyl) benzaldehyde, 5%mol palladium acetate, the tertiary fourth of 0.36mmol peroxidating Alcohol, 0.3mmol sodium carbonate are added in 10mL voltage-resistant reactor, add 3.5mL acetonitrile as solvents.Then, in 100 DEG C of items Magnetic agitation 12h under part.Then, two spoon column chromatography silica gels (100-200 mesh) is added in reaction solution, and passes through vacuum distillation Solvent is removed, then pure product 1- (t-butylperoxy) -3- (the 4- chlorobenzene as shown in structural formula is obtained by pillar layer separation Base) the different chromene of -1H- (using petrol ether/ethyl acetate=200:1 as eluant, eluent).It is solid for white to obtain target product Body, yield 81%
Characterize data:1H NMR(CDCl3,500MHz):δ7.82-7.79(m,2H),7.43-7.35 (m,4H),7.31- 7.28 (m, 1H), 7.23 (d, J=7.5Hz, 1H), 6.68 (s, 1H), 6.56 (s, 1H), 1.25 (s, 9H)；13C NMR (125MHz,CDCl3):δ149.3,134.6,133.2,131.4,130.1, 128.6,127.0,126.8,126.7,124.6, 123.5,100.49,100.47,81.1,26.5.
Embodiment 5
By 0.3mmol 2-((4- chlorphenyl) acetenyl) benzaldehyde, 20%mol palladium acetate, 0.36 mmol peroxidating uncle Butanol, 0.36mmol sodium carbonate are added in 10mL voltage-resistant reactor, add 3.5mL acetonitrile as solvents.Then, in 20 DEG C of items Magnetic agitation 12h under part.Then, two spoon column chromatography silica gels (100-200 mesh) is added in reaction solution, and passes through vacuum distillation Solvent is removed, then the different benzo of pure product 1- (t-butylperoxy) -3- (4- chlorphenyl) -1H- is obtained by pillar layer separation Pyrans (using petrol ether/ethyl acetate=200:1 as eluant, eluent).It is solid for white to obtain the target product as shown in structural formula Body, yield 54%
Characterize data:1H NMR(CDCl3,500MHz):δ7.82-7.79(m,2H),7.43-7.35 (m,4H),7.31- 7.28 (m, 1H), 7.23 (d, J=7.5Hz, 1H), 6.68 (s, 1H), 6.56 (s, 1H), 1.25 (s, 9H)；13C NMR (125MHz,CDCl3):δ149.3,134.6,133.2,131.4,130.1, 128.6,127.0,126.8,126.7,124.6, 123.5,100.49,100.47,81.1,26.5.
Embodiment 6
By 0.3mmol 2-((4- chlorphenyl) acetenyl) benzaldehyde, 10%mol palladium acetate, 0.36 mmol peroxidating uncle Butanol, 0.36mmol sodium ethoxide are added in 10mL voltage-resistant reactor, add 3.5mL acetonitrile as solvents.Then, in 50 DEG C of items Magnetic agitation 12h under part.Then, two spoon column chromatography silica gels (100-200 mesh) is added in reaction solution, and passes through vacuum distillation Solvent is removed, then pure product 2- (the heterochromatic alkene -3- base of 1- (t-butylperoxy) -1H-) benzene first is obtained by pillar layer separation Sour methyl esters (using petrol ether/ethyl acetate=100:1 as eluant, eluent).It is solid for white to obtain the target product as shown in structural formula Body, yield 67%
Characterize data:1H NMR(CDCl3,500MHz):δ7.73-7.69(m,2H),7.53-7.49 (m,1H),7.43- 7.35 (m, 3H), 7.30-7.27 (m, 1H), 7.17 (d, J=7.5Hz, 1H), 6.69 (s, 1H), 6.20 (s, 1H), 3.85 (s, 3H),1.26(s,9H)；13C NMR(125MHz,CDCl3):δ 169.3,150.7,134.9,131.3,131.2,130.0, 129.3,129.0,128.5,126.8,126.7, 124.3,123.0,102.9,101.2,81.1,52.3,26.4.
Embodiment 7
By 0.3mmol 2-((4- chlorphenyl) acetenyl) benzaldehyde, 10%mol palladium chloride, 0.36 mmol peroxidating The tert-butyl alcohol, 0.3mmol sodium ethoxide are added in 10mL voltage-resistant reactor, add 3.5mL acetonitrile as solvents.Then, in 50 DEG C Under the conditions of magnetic agitation 12h.Then, it is added in reaction solution two spoon column chromatography silica gels (100-200 mesh), and is steamed by decompression Solvent is removed in distillation, then obtains pure product 2- (the heterochromatic alkene -3- base of 1- (t-butylperoxy) -1H-) benzene by pillar layer separation Methyl formate (using petrol ether/ethyl acetate=100:1 as eluant, eluent).The target product as shown in structural formula is obtained as white Solid, yield 55%
Characterize data:1H NMR(CDCl3,500MHz):δ7.73-7.69(m,2H),7.53-7.49 (m,1H),7.43- 7.35 (m, 3H), 7.30-7.27 (m, 1H), 7.17 (d, J=7.5Hz, 1H), 6.69 (s, 1H), 6.20 (s, 1H), 3.85 (s, 3H),1.26(s,9H)；13C NMR(125MHz,CDCl3):δ 169.3,150.7,134.9,131.3,131.2,130.0, 129.3,129.0,128.5,126.8,126.7, 124.3,123.0,102.9,101.2,81.1,52.3,26.4.
Embodiment 8
By 0.3mmol 2-((4- chlorphenyl) acetenyl) benzaldehyde, 10%mol palladium acetate, 0.36 mmol peroxidating uncle Butanol, 0.6mmol sodium ethoxide are added in 10mL voltage-resistant reactor, are added 3.5mL toluene and are made solvent.Then, in 50 DEG C of items Magnetic agitation 12h under part.Then, two spoon column chromatography silica gels (100-200 mesh) is added in reaction solution, and passes through vacuum distillation Solvent is removed, then pure product 2- (the heterochromatic alkene -3- base of 1- (t-butylperoxy) -1H-) benzene first is obtained by pillar layer separation Sour methyl esters (using petrol ether/ethyl acetate=100:1 as eluant, eluent).It is solid for white to obtain the target product as shown in structural formula Body, yield 53%
Characterize data:1H NMR(CDCl3,500MHz):δ7.73-7.69(m,2H),7.53-7.49 (m,1H),7.43- 7.35 (m, 3H), 7.30-7.27 (m, 1H), 7.17 (d, J=7.5Hz, 1H), 6.69 (s, 1H), 6.20 (s, 1H), 3.85 (s, 3H),1.26(s,9H)；13C NMR(125MHz,CDCl3):δ 169.3,150.7,134.9,131.3,131.2,130.0, 129.3,129.0,128.5,126.8,126.7, 124.3,123.0,102.9,101.2,81.1,52.3,26.4.
Embodiment 9
By 0.3mmol 2- (o-tolyl acetenyl) benzaldehyde, 10%mol palladium acetate, the tertiary fourth of 0.36mmol peroxidating Alcohol, 0.36mmol sodium ethoxide are added in 10mL voltage-resistant reactor, add 3.5mL acetonitrile as solvents.Then, in 50 DEG C of items Magnetic agitation 12h under part.Then, two spoon column chromatography silica gels (100-200 mesh) is added in reaction solution, and passes through vacuum distillation Solvent is removed, then pure product 1- (t-butylperoxy) -3- (the adjacent toluene as shown in structural formula is obtained by pillar layer separation Base) the different chromene of -1H- (using petrol ether/ethyl acetate=200:1 as eluant, eluent).It is solid for white to obtain target product Body, yield 73%
Characterize data:1H NMR(CDCl3, 500MHz): δ 7.61 (d, J=7.5Hz, 1H), 7.45- 7.42 (m, 1H), 7.38 (d, J=7.0Hz, 1H), 7.34-7.31 (m, 2H), 7.29 (m, 2H), 7.23 (d, J=7.5Hz, 1H), 6.72 (s, 1H),6.18(s,1H),2.62(s,3H),1.32(s,9H)；13C NMR (125MHz,CDCl3):δ152.2,136.9, 135.2,131.5,130.7,130.0,129.4,129.0, 128.7,127.0,126.5,125.5,124.3,122.9, 103.7,101.1,81.0,26.5,20.7.
Embodiment 10
By 0.3mmol 2- (o-tolyl acetenyl) benzaldehyde, 10%mol palladium acetate, the tertiary fourth of 0.36mmol peroxidating Alcohol, 0.6mmol sodium carbonate are added in 10mL voltage-resistant reactor, are added 3.5mL tetrahydrofuran and are made solvent.Then, in 50 DEG C Under the conditions of magnetic agitation 12h.Then, it is added in reaction solution two spoon column chromatography silica gels (100-200 mesh), and is steamed by decompression Solvent is removed in distillation, then obtains pure product 1- (t-butylperoxy) -3- (the adjacent first as shown in structural formula by pillar layer separation Phenyl) the different chromene of -1H- (using petrol ether/ethyl acetate=200:1 as eluant, eluent).It is solid for white to obtain target product Body, yield 56%
Characterize data:1H NMR(CDCl3, 500MHz): δ 7.61 (d, J=7.5Hz, 1H), 7.45- 7.42 (m, 1H), (7.38 d, J=7.0Hz, 1H), 7.34-7.31 (m, 2H), 7.29 (m, 2H), 7.23 (d, J=7.5Hz, 1H), 6.72 (s, 1H),6.18(s,1H),2.62(s,3H),1.32(s,9H)；13C NMR (125MHz,CDCl3):δ152.2,136.9, 135.2,131.5,130.7,130.0,129.4,129.0, 128.7,127.0,126.5,125.5,124.3,122.9, 103.7,101.1,81.0,26.5,20.7.
Embodiment 11
By 0.3mmol 2- (o-tolyl acetenyl) benzaldehyde, 10%mol palladium acetate, the tertiary fourth of 0.36mmol peroxidating Alcohol, 0.36mmol sodium ethoxide are added in 10mL voltage-resistant reactor, are added 3.5mL methylene chloride and are made solvent.Then, in 50 Magnetic agitation 12h under the conditions of DEG C.Then, two spoon column chromatography silica gels (100-200 mesh) is added in reaction solution, and passes through decompression Solvent is distilled off, then (the neighbour of pure product 1- (t-butylperoxy) -3- as shown in structural formula is obtained by pillar layer separation Tolyl) the different chromene of -1H- (using petrol ether/ethyl acetate=200:1 as eluant, eluent).Target product is obtained as white Solid, yield 57%
Characterize data:1H NMR(CDCl3, 500MHz): δ 7.61 (d, J=7.5Hz, 1H), 7.45-7.42 (m, 1H), 7.38 (d, J=7.0Hz, 1H), 7.34-7.31 (m, 2H), 7.29 (m, 2H), 7.23 (d, J=7.5Hz, 1H), 6.72 (s, 1H),6.18(s,1H),2.62(s,3H),1.32(s,9H)；13C NMR (125MHz,CDCl3):δ152.2,136.9, 135.2,131.5,130.7,130.0,129.4,129.0, 128.7,127.0,126.5,125.5,124.3,122.9, 103.7,101.1,81.0,26.5,20.7.。

Claims (10)

1. one kind is at Pd (OAC)2/ TBHP system acts on the synthetic method of heterochromatic compound shown in following formula (II), and feature exists In the method are as follows: using neighbour's alkynyl compound of benzaldehyde category shown in formula (I) as starting material, under the catalysis of palladium acetate, with mistake The oxidation tert-butyl alcohol is nucleopilic reagent, and sodium ethoxide or sodium carbonate are that alkaline matter reacts 6- at 20-100 DEG C in organic solvent 18 hours, reaction solution was isolated and purified chroman compound shown in obtained formula (II)；
In formula (I) or formula (II), R1For H, R2For H, methyl, chlorine ,-COOCH3。
2. synthetic method as described in claim 1, it is characterised in that: the amount of the substance of the palladium acetate is shown in formula (I) The 5%~20% of the amount of the substance of adjacent alkynyl compound of benzaldehyde category.
3. synthetic method as described in claim 1, it is characterised in that: the amount of the substance of the tertbutanol peroxide is formula (I) Shown in neighbour's alkynyl compound of benzaldehyde category substance amount 100%~200%.
4. synthetic method as described in claim 1, it is characterised in that: the amount of the substance of the alkaline matter is shown in formula (I) Adjacent alkynyl compound of benzaldehyde category substance amount 100%~200%.
5. synthetic method as described in claim 1, it is characterised in that: the organic solvent be acetonitrile, tetrahydrofuran, toluene or Methylene chloride.
6. synthetic method as described in claim 1, it is characterised in that: the volume of the organic solvent is with neighbour shown in formula (I) The amount of the substance of alkynyl compound of benzaldehyde category is calculated as 10~30mL/mmol.
7. synthetic method as described in claim 1, it is characterised in that: the reaction temperature of the reaction is 50 DEG C.
8. synthetic method as described in claim 1, it is characterised in that: the reaction time of the reaction is 12h.
9. the synthetic method as described in one of claim 1~8, it is characterised in that described to isolate and purify are as follows: add into reaction solution Enter column chromatography silica gel, and solvent is removed by vacuum distillation, then by pillar layer separation, with petroleum ether and ethyl acetate volume ratio For 40:1 mixed liquor as eluent, collect the eluent containing target product, solvent be evaporated off and obtains color shown in formula (II) Full class compound.
10. synthetic method as described in claim 1, it is characterised in that: the column chromatography silica gel is 100~200 mesh, described The quality of column chromatography silica gel is calculated as 0.5g/mmol with the amount of the substance of compound shown in formula (I).
CN201710740922.XA 2017-08-25 2017-08-25 A kind of synthetic method of heterochromatic compound Pending CN109422717A (en)

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