CN103044389A - Compound used as active layer of ultraviolet detector - Google Patents

Compound used as active layer of ultraviolet detector Download PDF

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Publication number
CN103044389A
CN103044389A CN2012104725699A CN201210472569A CN103044389A CN 103044389 A CN103044389 A CN 103044389A CN 2012104725699 A CN2012104725699 A CN 2012104725699A CN 201210472569 A CN201210472569 A CN 201210472569A CN 103044389 A CN103044389 A CN 103044389A
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thionaphthene
group
ethoxycarbonyl
acetyl
acryloyl
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张俊
丛国芳
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LIYANG PRODUCTIVITY PROMOTION CENTER
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LIYANG PRODUCTIVITY PROMOTION CENTER
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Abstract

The invention discloses a compound; an ultraviolet detector which is manufactured by using the compound as an active layer is transparent, soft and light in weight, the application range of the ultraviolet detector is enlarged, and requirements of people are met. The compound which is used as the active layer of the ultraviolet detector is a benzo-pentabasic unsaturated heterocyclic compound and has the structure shown in a formula I.

Description

A kind of compound as the ultraviolet detector active coating
Technical field
The present invention relates to a kind of compound, relate in particular to a kind of compound for the manufacture of photoelectric device.
Background technology
UV-light refer to wavelength at 200nm to the hertzian wave between the 400nm, it extensively exists in nature and people's life.The ultraviolet detection technology is the another novel Detection Techniques that grow up after infrared acquisition, laser acquisition, is widely used in environmental monitoring, uranology, national defense and military and the horizon field such as communicate by letter.
The ultraviolet detection device of comparative maturity is take vacuum photomultiplier and ultraviolet enhancement silicon photoelectric diode as main in the prior art, and the former volume is large, operating voltage is high; The latter needs expensive spectral filter to reduce the impact of visible light and infrared light, brings difficulty to practical application.Development along with semiconductor technology, people have also carried out large quantity research to wide bandgap semiconductor materials, and utilize wide bandgap semiconductor materials, materials such as ZnO and GaN has prepared the ultraviolet detection device, because the advantages such as the semiconductor materials such as ZnO and GaN have the exciton bind energy height, growth temperature is low and capability of resistance to radiation is strong can prepare high performance ultraviolet detection device.But opaque, the inflexibility of this class device, and preparation process needs heat treated, complex process, and preparation cost is higher.
And along with the aggravation of Atmospheric Ozone Layer Depletion, irradiation is more and more stronger to the UV-light of earth surface, and people begin to pay close attention to uv-radiation to the impact of HUMAN HEALTH.Detect timely and accurately external environment ultraviolet radiation intensity, just can take effective safeguard procedures, reduce the generation of pathology, so the Portable ultraviolet detector becomes the focus of people's research.Simultaneously, along with the development of information technology and electronic technology, people are increasing to the demand of low cost, flexibility, low weight, portable electronic product.Along with the development of biological interdisciplinary science, people also have more demand to various transparent or semitransparent devices.And traditional sensitive detection parts based on inorganic semiconductor material are difficult to satisfy these requirements in the prior art, and the electron device based on organic semiconductor material that therefore can realize these characteristics has obtained people and more and more paid close attention to.
Summary of the invention
The invention discloses a kind of compound, the ultraviolet detector that adopts this compound to make as active coating is transparent, flexible, weight is little, can improve the range of application of ultraviolet detector, satisfies people's demand.
Compound as the ultraviolet detector active coating of the present invention is the benzo five-membered unsaturated heterocycle compound, and it has structure shown in general formula I,
Figure BDA0000243653521
In the formula, X represents O, S or NR 7, R wherein 7Represent H, alkyl, halo alkyl, carbonyl alkyl, hydroxy alkylene, hydrocarbyl amino or-oxyl;
Y represents CO or CR 1' OH; R 1' representative following group: H, OH, the alkyl that contains 1-18 carbon, carboxyl, acyl group, alkoxyl group, sulfonic group;
R 1Represent following group: H, OH, the alkyl that contains 1-18 carbon, carboxyl, acyl group, alkoxyl group, sulfonic group, CH 2S (O) nR 8, R 9The substituted benzene propenyl; R wherein 8Represent H, contain alkyl, halo alkyl, hydroxy alkylene or the-oxyl of 1-18 carbon, n=1-2; R 9The amino that represents H, alkyl, alkoxyl group, halogen, carboxyl, amino or replace; And R 1Can with R 1' identical, also can with R 1' difference;
R 2Amino, sulfonic group, itrile group or the acyl group-oxyl etc. that represent following group: H, the alkyl that contains 1-18 carbon, halogen, acyl group, carboxyl, amino or replace;
R 3Amino, acyl group, amide group, ester group or the sulfonic group etc. that represent following group: H, alkyl, alkoxyl group, halogen or haloalkyl, carboxyl, amino or replace;
R 4Represent following group: H, alkyl, alkoxyl group, halogen or haloalkyl, carboxyl, amino or amino, amide group, acyl group, ester group or the sulfonic group etc. that replace;
R 5Amino, acyl group, amide group, ester group or the sulfonic group etc. that represent following group: H, alkyl, alkoxyl group, halogen or haloalkyl, carboxyl, amino or replace;
R 6Amino, acyl group, amide group, ester group or the sulfonic group etc. that represent following group: H, alkyl, alkoxyl group, halogen or haloalkyl, carboxyl, amino or replace; Perhaps,
R 4With R 5Be joined together to form the 5-7 ring structure or with substituent R by carbon, oxygen or nitrogen 10The 5-7 ring structure, R wherein 10Represent H, alkyl, halo alkyl, carbonyl alkyl, hydroxy alkylene, hydrocarbyl amino or-oxyl.
Described in more than defining:
" alkyl " can refer to that carbonatoms is at the alkyl or cycloalkyl of the straight or branched of 1-18, for example, methyl, ethyl, sec.-propyl, n-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, n-hexyl, isohexyl etc. or its corresponding cycloalkyl.
" alkoxyl group " can be that carbonatoms is at the alkoxyl group of 1-18, for example, methoxyl group, oxyethyl group, isopropoxy, positive propoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, isopentyloxy, positive hexyloxy, different hexyloxy etc.
" acyl group " can be hydrocarbon substituted acyl or the aryl-acyl with 1-18 carbon, such as formyl radical, ethanoyl, sec.-propyl acyl group, n-propyl acyl group, allyl group acyl group, cyclopropyl acyl group, normal-butyl acyl group, isobutyl-acyl group, sec-butyl acyl group, tertiary butyl acyl group, n-pentyl acyl group, isopentyl acyl group, n-hexyl acyl group, isohexyl acyl group, phenyl acyl group, tolyl acyl group etc.
" ester group " can be hydrocarbon ester appended (alkyl acyloxy) or the aryl ester group with 1-18 carbon, such as methanoyl, acetoxyl group, sec.-propyl acyloxy, n-propyl acyloxy, allyl group acyloxy, cyclopropyl acyloxy, normal-butyl acyloxy, isobutyl-acyloxy, sec-butyl acyloxy, tertiary butyl acyloxy, n-pentyl acyloxy, isopentyl acyloxy, n-hexyl acyloxy, isohexyl acyloxy, phenyl acyloxy, tolyl acyloxy etc.
" amido " can be that the hydrocarbon with 1-18 carbon replaces amido or aryl amido, such as methyl amido, ethyl amido, sec.-propyl amido, n-propyl amido, allyl group amido, cyclopropyl amido, normal-butyl amido, isobutyl-amido, sec-butyl amido, tertiary butyl amido, n-pentyl amido, isopentyl amido, n-hexyl amido, isohexyl amido, phenyl amido, tolyl amido etc.
Of the present invention as in the compound of ultraviolet detector active coating, when substituted radical is arranged, typically refer to the low alkyl group, lower alkoxy, halogen, amino of C1-C6 etc., especially, the substituting group of the amino of replacement can be the alkyl of C2-C6.
Of the present invention as in the substituting group in the compound of ultraviolet detector active coating, the alkyl in described halo alkyl, carbonyl alkyl, hydroxy alkylene, the hydrocarbyl amino is the alkyl of C1-C6.
Preferably, described compound as the ultraviolet detector active coating comprises that 2-substituted benzene acryloyl-thionaphthene, 2-substituted benzene acryloyl-cumarone or phenyl ring partly pass through R 4, R 5Form the compound that obtains after the adjacent phenyl ether structure with formaldehyde condensation.
The present invention preferably includes as the compound of ultraviolet detector active coating, and 2 substituting group is thionaphthene or the benzofuran compound of 2--oxyl formyl radical or 2-alkyl acyl group.
The present invention preferably includes as the compound of ultraviolet detector active coating, and 2 substituting group is thionaphthene, cumarone or the benzazolyl compounds of 2-(2 '-MSM or methyl sulfoxide ethanoyl) or 2-(2 '-MSM or methyl sulfoxide replace-1 '-hydroxyl) ethyl.
As the indefiniteness example, the present invention can be selected from following particular compound as the compound of ultraviolet detector active coating:
2-ethoxycarbonyl-thionaphthene
2-(2 '-methyl sulfoxide base)-phenyl methyl ketone thiophthene
2-(2 '-methylsulfonyl) acetyl-thionaphthene
2-ethoxycarbonyl-5,6-methylene radical dioxy-thionaphthene
2-(2 '-methyl sulfoxide base) acetyl-5,6-methylene radical dioxy-thionaphthene
2-(2 '-methylsulfonyl) acetyl-5,6-methylene radical dioxy-thionaphthene
2-ethoxycarbonyl-cumarone
2-(2 '-methyl sulfoxide base)-acetyl cumarone
2-ethoxycarbonyl-4-chloro-thionaphthene
2-(1 '-hydroxyl-2 '-methyl sulfoxide base)-ethyl-thionaphthene
2-ethoxycarbonyl-4-methoxyl group-cumarone
2-ethoxycarbonyl-5-methoxyl group-cumarone
2-ethoxycarbonyl-6-methoxyl group-cumarone
2-ethoxycarbonyl-7-methoxyl group-cumarone
2-ethoxycarbonyl-5,6-dimethoxy-thionaphthene
2-ethoxycarbonyl-7-fluoro-cumarone
2-ethoxycarbonyl-5,7-two chloro-cumarones
2-ethoxycarbonyl-5-methoxycarbonyl-thionaphthene
2-acetyl-5-methoxycarbonyl-thionaphthene
2-ethoxycarbonyl-6-methoxycarbonyl-thionaphthene
2-acetyl-5-carboxyl-thionaphthene
2-acetyl-6-methoxycarbonyl-thionaphthene
2-acetyl-6-carboxyl-thionaphthene
2-(2 '-methyl sulfoxide base) acetyl-4-chloro-thionaphthene
2-(2 '-methyl sulfoxide base) acetyl-4-methoxyl group-cumarone
2-(2 '-methyl sulfoxide base) acetyl-5-methoxyl group-cumarone
2-(2 '-methyl sulfoxide base) acetyl-5,6-dimethoxy-thionaphthene
2-(2 '-methyl sulfoxide base) acetyl-6-methoxyl group-cumarone
2-(2 '-methyl sulfoxide base) acetyl-7-methoxyl group-cumarone
2-ethoxycarbonyl-6-diethylin-cumarone
(E)-2-[3 '-(4 "-anisole) acryloyl]-6-ethoxycarbonyl-thionaphthene
(E)-2-[3 '-(4 "-anisole) acryloyl]-5-ethoxycarbonyl-thionaphthene
2-(1 '-hydroxyl-2 '-methyl sulfoxide base) ethyl-5,6-methylene radical dioxy-thionaphthene
2-(1 '-hydroxyl) ethyl-5-methoxycarbonyl-thionaphthene
2-(1 '-hydroxyl) ethyl-6-methoxycarbonyl-thionaphthene
(E)-2-cinnyl-6-ethoxycarbonyl-thionaphthene
(E)-2-[3 '-(2 ", 3 ", 4 "-trimethoxy-benzene) acryloyl]-5-ethoxycarbonyl-thionaphthene
(E)-2-[3 '-(2 ", 3 ", 4 "-trimethoxy-benzene) acryloyl]-6-ethoxycarbonyl-thionaphthene (E)-2-cinnyl-5-ethoxycarbonyl-thionaphthene
(E)-2-[3 '-(2 "-chloro-phenyl-) acryloyl]-5-ethoxycarbonyl-thionaphthene (E)-2-[3 '-(2 "-chloro-phenyl-) acryloyl]-5-methoxycarbonyl-thionaphthene
(E)-2-[3 '-(2 "-chloro-phenyl-) acryloyl]-6-ethoxycarbonyl-thionaphthene
(E)-2-[3 '-(3 ", 4 "-dimethoxy benzene) acryloyl]-6-ethoxycarbonyl-thionaphthene
(E)-2-[3 '-(3 ", 4 "-dimethoxy benzene) acryloyl]-5-ethoxycarbonyl-thionaphthene
2-(2 '-methylsulfonyl) acetyl-5-methoxyl group-cumarone
2-(1 '-hydroxyl-2 '-methyl sulfoxide) ethyl-5-methoxyl group-cumarone
(E)-2-[3 '-(4 "-anisole) acryloyl]-5,6-dimethoxy-indoles
(E)-1-methyl-2-[3 '-(4 "-anisole) acryloyl]-5,6-dimethoxy-indoles
(E)-1-chloroethyl-2-[3 '-(4 "-anisole) acryloyl]-5,6-dimethoxy-indoles
(E)-1-ethanoyl-2-[3 '-(4 "-fluorobenzene) acryloyl]-5,6-dimethoxy-indoles
(E)-1-(2 '-hydroxyethyl)-2-[3 '-(4 "-fluorobenzene) acryloyl]-5-acetoxyl group-indoles
(E)-1-(2 '-amino-ethyl)-2-[3 '-(4 "-fluorobenzene) acryloyl]-5-acetoxyl group-indoles
(E)-1-(2 '-methoxy ethyl)-2-[3 '-(4 "-fluorobenzene) acryloyl]-5-acetoxyl group-indoles
2-ethoxycarbonyl-4-methyl-thionaphthene
2-oenanthyl-5,6-dimethyl-thionaphthene
2-penta oxygen formyl-5,6-diaminobenzene thiophthene
2-ketone acid-thionaphthene
2-(1 ', 2 '-dicarbapentaborane) amylbenzene thiophthene
2-(butyl sulfoxide group) acetyl-5,6-diamino-thionaphthene
2-(4 '-chlorine oxygen in heptan formyl)-5,6-dimethoxy-thionaphthene
2-(4 '-chlorine hexyl sulfoxide group) acetyl-5,6-dimethoxy-thionaphthene
2-(6 '-hydroxyl hexyl) oxygen formyl-5,6-dimethoxy-thionaphthene
2-(6 '-hydroxyl, penta sulfoxide group) acetyl-5,6-dimethoxy-thionaphthene
2-(6 '-methoxyl group hexyl) oxygen formyl-5,6-dimethoxy-thionaphthene
2-(6 '-methoxyl group amyl group sulfoxide group) acetyl-5,6-dimethoxy-thionaphthene
2-ethoxycarbonyl-5,6-ethyl methylene radical dioxy-thionaphthene
2-ethoxycarbonyl-5,6-(2 '-chloroethyl) methylene radical dioxy-thionaphthene
2-ethoxycarbonyl-5,6-(1 '-hydroxyethyl) methylene radical dioxy-thionaphthene
2-ethoxycarbonyl-5,6-(1 '-aminoethyl) methylene radical dioxy-thionaphthene
2-ethoxycarbonyl-5,6-(1 '-methoxy ethyl) methylene radical dioxy-thionaphthene
2-phenyl methyl ketone thiophthene
(E)-2-(3 '-(4 "-anisole) acryloyl)-thionaphthene or
2-acetyl-cumarone.
Four kinds as described below of the manufacture method of compound of the present invention:
A, the X in formula (I) are S, and Y represents CO or CR 1' OH, R 1Be CH 2S (O) nR 8Or R 9During substituted benzene propenyl structure, method at first obtains intermediate (IV) shown in employing route 1 or the route 2, wherein, and R 2, R 3, R 4, R 5, R 6, R 8, R 9, n, R 1' described as defined above, R 11Represent H, OH, contain alkyl, carboxyl, acyl group, alkoxyl group or the sulfonic group of 1-18 carbon;
Route 1:
Figure BDA0000243653522
Synthetic method is: take the Ortho Nitro Benzaldehyde (II) that replaces as starting raw material, under alkaline reagents catalysis, use mercaptoethanol to carry out fragrant nucleophilic substitution reaction, the NO of raw material 2Replaced by ethylmercapto group, generate intermediate (III); Under alkaline reagents catalysis, halogenating agent
Figure BDA0000243653523
(Z represents leavings group) with intermediate (III) reaction, obtains the derivative (IV) of 2-substituted acyl thionaphthene;
Route 2:
Figure BDA0000243653524
Synthetic method is: take the Ortho Nitro Benzaldehyde (II) that replaces as starting raw material, under alkaline reagents catalysis, with sulfhydryl reagent
Figure BDA0000243653525
Directly react to get the derivative (IV) of 2-substituted acyl thionaphthene;
Further, described intermediate (IV) can carry out respectively following reaction and obtains corresponding compound of Formula I:
A. work as R 3, R 4, R 5, R 6In one or more when being ester group, intermediate (IV) is hydrolyzed under alkaline condition and obtains carboxylic acid derivative (V), wherein R 3', R 4', R 5', R 6' respectively corresponding to R 3, R 4, R 5, R 6Group after the hydrolysis
B. intermediate (IV) obtains corresponding hydroxy derivatives (VI) through reduction
Figure BDA0000243653527
C. work as R 11During for methyl, intermediate (IV) and R 9The phenyl formaldehyde intermediate (VII) that replaces carries out aldol condensation, obtains 2 and is R 9The compound of substituted benzene acryloyl (VIII)
D. work as R 11During for alkoxyl group, intermediate (IV) can carry out following reaction and obtain corresponding compound of Formula I:
Figure BDA0000243653529
Intermediate (IV) is under highly basic and heating, obtain compound 2-(2 '-substituent methyl sulfoxide) acyl group benzothiophene derivative (IX) with the reaction of sulfinyl methyl-derivatives, proceed oxidation and reduction and obtain respectively compound 2-(2 '-replacement MSM ethanoyl) benzothiophene derivative (X) and 2-(2 '-replacement MSM or methyl sulfoxide-1 '-hydroxyl) ethylbenzene thiophthene derivative (XI);
B, the X in formula (I) are O, and Y represents CO or CR 1' OH, R 1Be CH 2S (O) nR 8The time, method obtains intermediate (XIII) shown in its synthetic employing route 3, wherein, and R 2, R 3, R 4, R 5, R 6, R 8, n, R 1' described as defined above, R 12Represent following group: H, OH, the alkyl that contains 1-18 carbon, carboxyl, acyl group, alkoxyl group, sulfonic group
Route 3:
Figure BDA00002436535210
Synthetic method is: take the salicylaldhyde (XII) that replaces as starting raw material, under alkaline reagents catalysis, with halogenating agent
Figure BDA00002436535211
(Z represents leavings group) reacts, and generates 2-carbonyl class (XIII) compound;
Wherein, work as R 12During for alkoxyl group, intermediate (XIII) can carry out following reaction and obtain corresponding compound of Formula I:
Figure BDA00002436535212
Intermediate (XIII) is again under highly basic and heating, obtain 2-(2 '-substituent methyl sulfoxide) acyl group benzofuran derivative (XIV) with the reaction of sulfinyl methyl-derivatives, (XIV) proceed oxidation and reduction and obtain respectively compound 2-(2 '-replacement sulfuryl) phenyl methyl ketone benzofuran derivs (XV) and 2-(2 '-replacement MSM or methyl sulfoxide-1 '-hydroxyl) ethyl benzofuran derivative (XVI);
C, X is NR in formula (I) 7, Y represents CO, R 1Be R 9During substituted benzene propenyl structure, method shown in its synthetic employing route 4, wherein, R 2, R 3, R 4, R 5, R 6, R 7, R 9Described as defined above;
Route 4:
Figure BDA00002436535213
Synthetic method is: with the N-R that replaces 7-2-acetyl indole (XVII) is starting raw material, under alkaline reagents catalysis, carries out aldol condensation with the phenyl formaldehyde intermediate (VII) that replaces, and obtains 2 and is R 9The benzene acryloyl target compound (XVIII) that replaces.
Adopt compound of the present invention to deposit the active coating that organic materials is made in transparent flexible substrate, then in the transparent interdigital electrode of this active coating preparation, realize transparence, the flexibility of ultraviolet detector, can be applied in information, electronics, biology or its crossing domain.Because this device has soft characteristic, the corresponding variation can occur along with the outer surface profile of object, and its transparent characteristic can not affect ultraviolet detector to the impact of object outward appearance, the scope of application is wider.
Embodiment
The below describes the specific embodiment of the manufacture method of compound of the present invention in detail.
Embodiment 1:2-ethoxycarbonyl-thionaphthene (3b)
Be cooled to ice bath under 0 ℃, contain Ortho Nitro Benzaldehyde (4.5g, 30mmol) and anhydrous K 2CO 3Among the DMF of (5.0g, 36.2mmol) (60ml), slowly drip ethyl thioglycolate (3.29ml, 30mmol).Dropwise, 0 ℃ is stirred 30min, then reacts 12h in 60 ℃ of oil baths.Reaction solution is poured in the frozen water into solid collected by filtration, chloroform dissolved solids, anhydrous Na 2SO 4Drying is filtered, and is spin-dried for behind the solvent to obtain yellow solid 5.80g (94%) after separating with silica gel column chromatography.
1HNMR(CDCl 3)δ：1.42(t，J＝7.0Hz，3H)，4.42(q，J＝7.0Hz，2H)，7.39-7.47(m，2H)，7.86-7.89(m，2H)，8.06(s，1H).MS(EI +)m/z：206[M] +.HRMS(EI +)：found 206.0397[M] +，(Calcd for C 11H 10O 2S：206.0397)。
Embodiment 2:2-(2 '-methyl sulfoxide base)-phenyl methyl ketone thiophthene (3c)
Under the nitrogen protection, 60% sodium hydride (280mg) is put into three-necked bottle, sherwood oil is washed the grease of three flush away embedding sodium hydrides.Add the constant pressure funnel that fills DMSO (8ml), the remaining a small amount of sherwood oil of decompressing and extracting.DMSO is added in the sodium hydride, in constant pressure funnel, add rapidly the THF (8ml) that is dissolved with 2-ethoxycarbonyl-thionaphthene (3b) (200mg, 0.97mmol).Take out rapidly most air, put into nitrogen, three times repeatedly.Above-mentioned reaction system is heated to 70-75 ℃, and solution is emitted a large amount of hydrogen.Discharge bubble, be chilled to and add the ice bath cooling after the room temperature, slowly drip the THF solution in the dropping funnel.Finish stirring at room 30min.In 3 times of volumes of reaction solution impouring (60ml) frozen water.Transfer PH to 3～4 with 2N hydrochloric acid.With chloroform (80ml * 2) extractive reaction liquid, amalgamation liquid is washed with distilled water (160ml * 3).The chloroform anhydrous Na 2SO 4Dry.Filtering Na 2SO 4, the evaporate to dryness chloroform gets yellow solid 202mg (87%) mutually.
1HNMR(CDCl 3)δ：2.79(s，3H)，AB system(4.33，4.41，J＝13.2Hz，2H)，7.43(t，J＝7Hz，1H)，7.51(t，J＝7.0Hz，1H)，7.88(d，J＝7.0Hz，1H)，7.94(d，J＝7.0Hz，1H)，8.09(s，1H).MS(EI +)m/z：238[M] +.HRMS(EI +)：found238.0102[M] +，(Calcd for C 11H 10O 2S 2：238.0122)。
Embodiment 3:2-(2 '-methylsulfonyl) acetyl-thionaphthene (3d)
2-(2 '-methyl sulfoxide base) acetyl-thionaphthene (3c) (50mg, 0.21mmol) is dissolved in (2ml) in the Glacial acetic acid, the lower 30%H that slowly adds of ice bath cooling 2O 2(1ml).Finish stirring at room reaction 5-6h.Add methylene dichloride (3ml * 2) and extract product, be spin-dried for and obtain white solid 2-(2 '-methylsulfonyl) acetyl-thionaphthene 24mg (45%) after silica gel column chromatography separates behind the solvent.
1HNMR(CDCl 3)δ：3.17(s，3H)，4.60(s，2H)，7.45(t，J＝7.0Hz，1H)，7.53(t，J＝7.0Hz，1H)，7.89(d，J＝8.0Hz，1H)，7.96(d，J＝8.0Hz，1H)，8.11(s，1H).HRMS(EI +)：found 254.0074[M] +，(Calcd for C 11H 10O 3S 2：254.0071)。
Embodiment 4:2-ethoxycarbonyl-5,6-methylene radical dioxy-thionaphthene (8b)
Be raw material with 3,4-methylene radical dioxy-6 nitrobenzaldehyde and ethyl thioglycolate, according to the synthetic orange/yellow solid 2-ethoxycarbonyl-5,6-methylene radical dioxy-thionaphthene (68.5%) of obtaining of the method for embodiment 1.
1HNMR(CDCl 3)δ：1.39(t，J＝7.2Hz，3H)，4.37(q，J＝7.2Hz，2H)，6.04(s，1H)，7.19(s，1H)，7.20(s，1H)，7.89(s，1H).MS(EI +)m/z：250[M] +.HRMS(EI +)：found 250.0305[M] +，(Calcd for C 12H 10O 4S：282.0002)。
Embodiment 5:2-(2 '-methyl sulfoxide base) acetyl-5,6-methylene radical dioxy-thionaphthene (8c)
Take compound 8b as raw material, according to the synthetic faint yellow solid powder (90%) that obtains of the method for embodiment 2.
1HNMR(CDCl 3)δ：2.77(s，3H)，AB system(4.26，4.33，J＝13.2Hz，2H)，6.08(s，1H)，7.22(s，1H)，7.24(s，1H)，7.91(s，1H)。HRMS(EI +)：found282.0002[M] +，(Calcd for C 12H 10O 4S 2：282.0021)。
Embodiment 6:2-(2 '-methylsulfonyl) acetyl-5,6-methylene radical dioxy-thionaphthene (8d)
Take compound 8c as raw material, according to the synthetic faint yellow solid powder (80.0%) that obtains of the method for embodiment 3.
1HNMR(CDCl 3)δ：3.15(s，3H)，4.53(s，2H)，6.09(s，2H)，7.22(s，1H)，7.24(s，1H)，7.94(s，1H)。MS(EI +)m/z：298[M] +.HRMS(EI +)：found297.9967[M] +，(Calcd for C 12H 10O 5S 2：297.9970)。
Embodiment 7:2-ethoxycarbonyl-4-chloro-thionaphthene (4b)
In the sodium hydroxide (100mg, 2.5mmol) water-soluble (0.2ml), slowly add ethyl thioglycolate (0.28ml, 2.5mmol), stirring at room 0.5h under the ice bath.Add 2-chloro-6-fluoro-phenyl aldehyde (200mg, 1.26mmol) and dioxane (2ml), 70 ℃ of oil bath reaction 7h.Filter chloroform filter wash cake.Obtaining the light butter product after the full-automatic combiflash companion instrument chromatographic separation, is yellow solid after the cooling.
1HNMR(CDCl 3)δ：1.43(t，J＝7.0Hz，3H)，4.43(q，J＝7.0Hz，2H)，7.35-7.41(m，2H)，7.73-7.75(m，1H)。MS(EI)：240. 1CNMR(CDCl 3)δ：14.30(C-2”)，61.83(C-1”)，121.25(C-3)，124.81(C-7)，127.46(C-6)，128.35(C-5)，130.46(C-4)，134.76(C-4a)，137.27(C-2)，143.10(C-7a)，162.39(C-1’).MS(EI +)m/z：240[M] +，242[M+2] +.HRMS(EI +)：found240.0014[M] +，(Calcd for C 11H 9O 2SCl：240.0012)。
Embodiment 8:2-(1 '-hydroxyl-2 '-methyl sulfoxide base)-ethyl-thionaphthene (3e)
2-(2 '-methyl sulfoxide base)-phenyl methyl ketone thiophthene (3c) (100mg, 0.42mmol) joins in the mixed solution of THF (2ml) and distilled water (2ml), stirring and dissolving.Add sodium borohydride (20mg, 0.53mmol) under the ice bath, stirring at room reaction 0.5h in batches.Filter, filtrate is used chloroform extraction.Be spin-dried for that silica gel column chromatography obtains faint yellow solid 2-(1 '-hydroxyl-2 '-methyl sulfoxide base)-ethyl-thionaphthene 46mg (54.2%) after separating behind the solvent.
1HNMR(CDCl 3)δ：2.74(s，3H)，3.06-3.32(m，2H)，5.73-5.77(m，1H)，7.29(s，1H)，7.32-7.36(m，2H)，7.73-7.83(m，2H)。MS(ESI +)m/z：263.0[M+Na] +.HRMS(ESI +)：found 263.01885[M+Na] +，(Calcd forC 11H 12O 2S 2Na：263.01764)。
Embodiment 9:2-ethoxycarbonyl-5,6-dimethoxy-thionaphthene (7b)
Add 2-nitro-4 in 25ml DMF, the NaOH of 5-dimethoxy benzaldehyde (2.0g, 9.5mmol) and catalytic amount, ice bath are cooled under 0 ℃, slowly drip ethyl thioglycolate (1.25ml, 11.4mmol).Dropwise 0 ℃ of stirring reaction 30min, then 100 ℃ of oil bath reaction 2h.Reaction solution is poured in the frozen water into solid collected by filtration, chloroform dissolved solids, anhydrous Na 2SO 4Dried overnight.Be spin-dried for that silica gel column chromatography obtains white solid 2-ethoxycarbonyl-5,6-dimethoxy-thionaphthene 1.58g (62.6%) after separating behind the solvent.
1HNMR(CDCl 3)δ：1.405(t，J＝7.2Hz，3H)，3.95(s，3H)，3.98(s，3H)，4.38(q，J＝7.2Hz，2H)，7.24(s，1H)，7.25(s，1H)，7.93(s，1H).MS(EI +)m/z：266[M] +.HRMS(EI +)：found 266.0613[M] +，(Calcd for C 13H 14O 4S：266.0631)。
Embodiment 10:2-ethoxycarbonyl-5-methoxycarbonyl-thionaphthene (5b)
Take 2-nitro-5-methoxycarbonyl phenyl aldehyde and ethyl thioglycolate as raw material, obtain white solid 2-ethoxycarbonyl-5-methoxycarbonyl-thionaphthene (5b) (97%) according to the method reaction of embodiment 1.
1HNMR(CDCl 3)δ：1.43(t，J＝7.2Hz，3H)，3.97(s，3H)，4.43(q，J＝7.2Hz，2H)，7.91(d，J＝8.4Hz，1H)，8.10(d，J＝8.4Hz，1H)，8.12(s，1H)，8.58(s，1H).HRMS(EI +)：found 264.0452[M] +，(Calcd for C 13H 12O 4S：264.0456)。
Embodiment 11:2-acetyl-5-methoxycarbonyl-thionaphthene (1c)
Under the ice bath, in 60ml DMF, add successively 3-aldehyde radical-4-nitro-methyl benzoate (1.95g, 9.3mmol), anhydrous K 2CO 3(1.55g, 11.2mmol) and sulfur alcohol (0.70mg, 11.3mmol).After stirring 10min, stirring at room 1h.Elimination K 2CO 3, evaporate to dryness DMF, chloroform dissolving crude product, washing chloroform phase, chloroform is used anhydrous sodium sulfate drying mutually.Be spin-dried for that silica gel column chromatography obtains white solid 3-aldehyde radical 4-ethylmercapto group-methyl benzoate (1-b) 1.81g (86.5%) after separating behind the solvent.
1HNMR(CDCl 3)δ：1.44(t，J＝7.6Hz，3H)，3.05(q，J＝7.6Hz，2H)，3.94(s，3H)，7.42(d，J＝8.4Hz，1H)，8.12(dd，J＝8.6Hz，1.6Hz，1H)，8.44(d，J＝1.6Hz，1H)，10.25(s，1H)。
In 20ml DMF, add successively 3-aldehyde radical 4-ethylmercapto group-methyl benzoate (1-b) (1.0g, 4.5mmol), calcium oxide (125mg, 2.2mmol), acetone dichloride (825mg, 8.9mmol).90 ℃ of oil bath reaction 10h.Filter the filtrate evaporate to dryness.Chloroform dissolving crude product, washing chloroform phase, chloroform is used anhydrous sodium sulfate drying mutually.Be spin-dried for that silica gel column chromatography obtains yellowish solid 2-acetyl-5-methoxycarbonyl-thionaphthene 0.929g (88.9%) after separating behind the solvent.
1HNMR(CDCl 3)δ：2.69(s，3H)，3.98(s，3H)，7.93(d，J＝8.4Hz，1H)，8.00(s，1H)，8.11(d，J＝8.4Hz，1H)，8.61(s，1H).HRMS(EI +)：found234.0339[M] +，(Calcd for C 12H 10O 3S：234.0351)。
Embodiment 12:2-ethoxycarbonyl-6-methoxycarbonyl-thionaphthene (6b)
Take 2-nitro-4-methoxycarbonyl phenyl aldehyde and ethyl thioglycolate as raw material, obtain white solid 2-ethoxycarbonyl-6-methoxycarbonyl-thionaphthene (6b) (97%) according to the method reaction of embodiment 1.
1HNMR(CDCl 3)δ：1.43(t，J＝7.2Hz，3H)，3.97(s，3H)，4.43(q，J＝7.2Hz，2H)，7.91(d，J＝8.4Hz，1H)，8.04(d，J＝8.4Hz，1H)，8.07(s，1H)，8.58(s，1H).HRMS(EI +)：found 264.0449[M] +，(Calcd for C 13H 12O 4S：264.0456)。
Embodiment 13:2-acetyl-5-carboxyl-thionaphthene (1e)
2-ethanoyl-5-methoxycarbonyl-thionaphthene (1c) (133mg, 0.57mmol) is added in the 5ml dioxane stirring and dissolving.The 2ml water that is dissolved with NaOH (34mg, 0.85mmol) is added in the dioxane stirring at room 2h.The evaporate to dryness reaction solution is used the water dissolution crude product, and 5% hydrochloric acid is transferred PH to 2, separates out solid.Filter, filter cake washes with water, dries to get 36mg brown solid product 2-acetyl-5-carboxyl-thionaphthene (29%).
1HNMR(CDCl 3)δ：2.66(s，3H)，8.01(dd，J＝8.4Hz，1.6Hz，1H)，8.15(d，J＝8.4Hz，1H)，8.48(s，1H)，8.61(s，1H)，13.1(s，1H).MS(ESI -)m/z：219[M-H] -.HRMS(ESI -)：found 219.01148[M-H] -，(Calcd for C 11H 7O 3S：219.01159)。
Embodiment 14:2-acetyl-6-methoxycarbonyl-thionaphthene (2c)
Take 3-aldehyde radical-4-nitro-methyl benzoate and sulfur alcohol as raw material, obtain yellow solid 2-ethylmercapto group-3-aldehyde radical-methyl benzoate (2-b) (101.2%) according to the method reaction of embodiment 19.
1HNMR(CDCl 3)δ：1.39(t，J＝7.6Hz，3H)，3.06(q，J＝7.6Hz，2H)，3.96(s，1H)，7.90(s，1H)，7.90(s，1H)，8.08(s，1H)，10.44(s，1H).
Take compound 2-b and acetone dichloride as raw material, obtain yellow solid (73%) according to the method reaction of embodiment 19. 1HNMR(CDCl 3)δ：2.69(s，3H)，3.97(s，3H)，7.94(d，J＝8.4Hz，1H)，7.96(s，1H)，8.05(d，J＝8.4Hz，1H)，8.59(s，1H).HRMS(EI +)：found 234.0343[M] +，(Calcd for C 12H 10O 3S：234.0351)。
Embodiment 15:2-acetyl-6-carboxyl-thionaphthene (2e)
Take compound 2c as raw material, obtain brown solid product 2-acetyl-6-carboxyl-thionaphthene (59%) according to the reaction of the method for embodiment 21.
1HNMR(CDCl 3)δ：2.67(s，3H)，7.97(dd，J＝8.4Hz，1.2Hz，1H)，8.10(d， J＝8.4Hz，1H)，8.40(s，1H)，8.65(s，1H)，13.2(s，1H).HRMS(ESI -)：found219.01326[M-H] -，(Calcd for C 11H 7O 3S：219.01159)。
Embodiment 16:2-(2 '-methyl sulfoxide base) acetyl-4-chloro-thionaphthene (4c)
Take compound 4b as raw material, obtain faint yellow solid 2-(2 '-methyl sulfoxide base) acetyl-4-chloro-thionaphthene (4c) (59%) according to the reaction of the method for embodiment 2.
1HNMR(CDCl 3)δ：2.83(s，3H)，AB system(4.38，4.45，J＝13.Hz，2H)，7.46(d，J＝4.5Hz，2H)，7.79(t，J＝4.5Hz，1H)，8.24(s，1H).HRMS(EI +)：found 271.9733[M] +，(Calcd for C 11H 9O 2S 2Cl：271.9733)。
Embodiment 17:2-(2 '-methyl sulfoxide base) acetyl-5,6-dimethoxy-thionaphthene (7c)
Take compound 7b as raw material, obtain yellow solid 2-(2 '-methyl sulfoxide base) acetyl-5,6-dimethoxy-thionaphthene (7c) (96%) according to the reaction of the method for embodiment 2.
1HNMR(CDCl 3)δ：2.78(s，3H)，3.96(s，3H)，3.99(s，3H)，AB system(4.28， 4.35，J＝13.6Hz，2H)，7.25(s，1H)，7.28(s，1H)，7.96(s，1H).HRMS(EI +)：found 298.0306[M] +，(Calcd for C 13H 14O 4S 2：298.0334)。
Embodiment 18:(E)-2-[3 '-(4 "-anisole) acryloyl]-6-ethoxycarbonyl-thionaphthene (2dC)
In the 10ml dehydrated alcohol, add according to this 2-ethanoyl-6-methoxycarbonyl-thionaphthene (2c) (100 mg, 0.43mmol), the sodium ethylate of catalytic amount, aubepine (87.2mg, 0.64mmol).Stirring at room 1.5h, evaporate to dryness ethanol, chloroform dissolving crude product filters.Washing chloroform phase, anhydrous sodium sulfate drying chloroform phase.Be spin-dried for that silica gel column chromatography obtains yellow-green colour solid 78mg (52%) after separating behind the solvent.
1HNMR(CDCl 3)δ：1.45(t，J＝7.2Hz，3H)，3.88(s，3H)，4.44(q，J＝7.2Hz，2H)，6.69(d，J＝8.4Hz，2H)，7.42(d，J＝15.2Hz，1H)，7.65(d，J＝8.4Hz，2H)，7.90(d，J＝15.2Hz，1H)，7.96(d，J＝8.4Hz，1H)，8.07(d，J＝8.4Hz，1H)，8.11(s，1H)，8.62(s，1H).HRMS(EI +)：found 366.0920[M] +，(Calcdfor C 21H 18O 4S：366.0926)。
Embodiment 19:(E)-2-[3 '-(4 "-anisole) acryloyl]-5-ethoxycarbonyl-thionaphthene (1dC)
Take compound 1c and aubepine as raw material, obtain yellow-green colour solid E according to the method reaction of embodiment 31)-2-[3 '-(4 "-anisole) acryloyl]-5-ethoxycarbonyl-thionaphthene (1dC) (34%).
1HNMR(CDCl 3)δ：1.45(t，J＝7.2Hz，3H)，3.88(s，3H)，4.44(q，J＝7.2Hz，2H)，6.97(d，J＝8.4Hz，2H)，7.42(d，J＝15.2Hz，1H)，7.65(d，J＝8.4Hz，2H)，7.89(d，J＝15.2Hz，1H)，7.94(d，J＝8.4Hz，1H)，8.12(d，J＝8.4Hz，1H)，8.15(s，1H)，8.64(s，1H).HRMS(EI +)：found 366.0916[M] +，(Calcd for C 21H 18O 4S：366.0926)。
Embodiment 20:2-(1 '-hydroxyl-2 '-methyl sulfoxide base) ethyl-5,6-methylene radical dioxy-thionaphthene (8e)
Take compound 8c as raw material, obtain white solid 2-(1 '-hydroxyl-2 '-methyl sulfoxide base) ethyl-5,6-methylene radical dioxy-thionaphthene (8e) (96%) according to the reaction of the method for embodiment 10.
1HNMR(CDCl 3)δ：2.74(s，3H)，2.03-3.30(m，2H)，5.68(d×d，J＝9.2Hz，2.8Hz)，6.01(s，1H)，7.12(s，1H)，7.13(s，1H)，7.20(s，1H).MS(ESI +)m/z：307[M+Na] +.HRMS(ESI +)：found 307.00916[M+Na] +，(Calcd forC 12H 12O 4S 2Na：307.00747)。
Embodiment 21:2-(1 '-hydroxyl) ethyl-5-methoxycarbonyl-thionaphthene (1f)
Take compound 1c as raw material, obtain pale pink solid 2-(1 '-hydroxyl) ethyl-5-methoxycarbonyl-thionaphthene (1f) (92%) according to the reaction of the method for embodiment 10.
1HNMR(CDCl 3)δ：1.67(d，J＝6.4Hz)，2.18(s，1H)，3.95(s，3H)，5.22(q，J＝6.4Hz，2H)，7.25(s，1H)，7.84(d，J＝8.4Hz，1H)，7.95(d，J＝8.4Hz，1H)，7.95(d，J＝8.4Hz，1H)，8.41(s，1H).MS(EI +)m/z：236[M] +.HRMS(EI +)：found 236.0498[M] +，(Calcd for C 12H 12O 3S：236.0507)。
Embodiment 22:2-(1 '-hydroxyl) ethyl-6-methoxycarbonyl-thionaphthene (2f)
Take compound 2c as raw material, obtain white solid 2-(1 '-hydroxyl) ethyl-6-methoxycarbonyl-thionaphthene (2f) (92%) according to the reaction of the method for embodiment 10.
1HNMR(CDCl 3)δ：1.67(d，J＝6.4Hz)，1.80(s，1H)，3.95(s，3H)，5.23(q，J＝6.4Hz，2H)，7.24(s，1H)，7.74(d，J＝8.4Hz，1H)，7.99(d，J＝8.4Hz，1H)，7.95(d，J＝8.4Hz，1H)，8.53(s，1H).MS(EI +)m/z：236[M] +.HRMS(EI +)：found 236.0507[M] +，(Calcd for C 12H 12O 3S：236.0507)。
Embodiment 23:(E)-2-cinnyl-6-ethoxycarbonyl-thionaphthene (2dA)
Take compound 2c and phenyl aldehyde as raw material, obtain faint yellow solid (E)-2-cinnyl-6-ethoxycarbonyl-thionaphthene (2dA) (17%) according to the method reaction of embodiment 31.
1HNMR(CDCl 3)δ：1.45(t，J＝7.2Hz，3H)，4.44(q，J＝7.2Hz，2H)，7.45-7.47(m，3H)，7.54(d，J＝15.6Hz，1H)，7.69-7.71(m，2H)，7.93(d，J＝15.6Hz，1H)，7.97(d，J＝8.4Hz，1H)，8.08(d，J＝8.4Hz，1H)，8.14(s，1H)，8.63(s，1H).MS(EI +)m/z：336[M] +.HRMS(EI +)：found 336.0793[M] +，(Calcd for C 20H 16O 3S：336.0820)。
Embodiment 24:(E)-2-[3 '-(2 ", 3 ", 4 "-trimethoxy-benzene) acryloyl]-5-ethoxycarbonyl-thionaphthene (1dE)
With compound 1c and 2,3, the 4-TMB is raw material, according to the reaction of the method for embodiment 31 obtain yellow solid (E)-2-[3 '-(2 ", 3 " 4 "-trimethoxy-benzene) acryloyl]-5-ethoxycarbonyl-thionaphthene (1dE) (30%).
1HNMR(CDCl 3)δ：1.44(t，J＝7.2Hz，3H)，3.91(s，3H)，3.94(s，3H)，3.99(s，3H)，4.44(q，J＝7.2Hz，2H)，6.75(d，J＝8.8Hz，1H)，7.42(d，J＝8.8Hz，1H)，7.59(d，J＝15.6Hz，1H)，7.94(d，J＝8.4Hz，1H)，8.08(d，J＝15.6Hz，1H)，8.11-8.14(m，2H)，8.64(s，1H).HRMS(EI +)：found 426.1147[M] +，(Calcd for C 23H 22O 6S：426.1137)。
Embodiment 25:(E)-2-[3 '-(2 ", 3 ", 4 "-trimethoxy-benzene) acryloyl]-6-ethoxycarbonyl-thionaphthene (2dE)
Be raw material with compound 2c and 2,3,4-TMB, according to the reaction of the method for embodiment 31 obtain yellow-green colour oily matter (E)-2-[3 '-(2 ", 3 ", 4 "-trimethoxy-benzene) acryloyl]-6-ethoxycarbonyl-thionaphthene (2dE) (32%).
1HNMR(CDCl 3)δ：1.44(t，J＝7.2Hz，3H)，3.91(s，3H)，3.94(s，3H)，3.99(s，3H)，4.44(q，J＝7.2Hz，2H)，6.75(d，J＝8.8Hz，1H)，7.42(d，J＝8.8Hz，1H)，7.59(d，J＝15.6Hz，1H)，7.96(d，J＝8.4Hz，1H)，8.09(d，J＝15.6Hz，1H)，8.09(s，1H)，8.10(d，J＝8.4Hz，1H)，8.63(s，1H).HRMS(EI +)：found 426.1125[M] +，(Calcd for C 23H 22O 6S：426.1137)。
Embodiment 26:(E)-2-cinnyl-5-ethoxycarbonyl-thionaphthene (1dA)
Take compound 1c and phenyl aldehyde as raw material,, obtain yellow solid (E)-2-cinnyl-5-ethoxycarbonyl-thionaphthene (1dA) (62%) according to the method reaction of embodiment 31.
1HNMR(CDCl 3)δ：1.44(t，J＝7.2Hz，3H)，4.44(q，J＝7.2Hz，2H)，7.54(s，3H)，7.59(d，J＝15.2Hz，1H)，7.68-7.69(m，2H)，7.91(d，J＝15.2Hz，1H)，7.94(d，J＝8.0Hz，1H)，8.10(d，J＝8.0Hz，1H)，8.15(s，1H)，8.64(s，1H).MS(EI +)m/z：336[M] +.HRMS(EI +)：found 336.0796[M] +，(Calcd forC 20H 16O 3S：336.0820)。
Embodiment 27:(E)-2-[3 '-(2 "-chloro-phenyl-) acryloyl]-5-ethoxycarbonyl-thionaphthene (1dB1)
Take compound 1c and o-chlorobenzaldehyde as raw material, obtain yellow solid (E)-2-[3 '-(2 "-chloro-phenyl-) acryloyl according to the method reaction of embodiment 31]-5-ethoxycarbonyl-thionaphthene (1dB1) (62%).
1HNMR(CDCl 3)δ：1.44(t，J＝7.2Hz，3H)，4.44(q，J＝7.2Hz，2H)， 7.35-7.37(m，2H)，7.47(d，J＝8.8Hz，1H)，7.50(d，J＝15.6Hz，1H)，7.79(d×d，J＝8.0Hz，2.4Hz，1H)，7.95(d，J＝8.4Hz，1H)，8.13(d，J＝8.4Hz，1H)，8.17(s，1H)，8.30(d，J＝15.6Hz，1H)，8.65(s，1H).MS(EI +)m/z：370[M] +，372[M+2] +.HRMS(EI +)：found 370.0418[M] +，(Calcd forC 20H 15O 3SCl：370.0430)。
Embodiment 28:(E)-2-[3 '-(2 "-chloro-phenyl-) acryloyl]-5-methoxycarbonyl-thionaphthene (1dB2)
Take compound 1c and o-chlorobenzaldehyde as raw material, obtain pale brown solid (E)-2-[3 '-(2 "-chloro-phenyl-) acryloyl according to the method reaction of embodiment 31]-5-methoxycarbonyl-thionaphthene (1dB2) (25%):
1HNMR(CDCl 3)δ：3.97(s，3H)，7.34-7.39(m，2H)，7.47(d，J＝8.8Hz，1H)，7.50(d，J＝15.6Hz，1H)，7.79(d×d，J＝8.0Hz，2.4Hz，1H)，7.95(d，J＝8.4Hz，1H)，8.13(d，J＝8.4Hz，1H)，8.16(s，1H)，8.30(d，J＝15.6Hz，1H)，8.64(s，1H).MS(EI +)m/z：356[M] +，358[M+2] +.HRMS(EI +)：found356.0254[M] +，(Calcd for C 19H 13O 3SCl：356.0274)。
Embodiment 29:(E)-2-[3 '-(2 "-chloro-phenyl-) acryloyl]-6-ethoxycarbonyl-thionaphthene (2dB)
Take compound 2c and o-chlorobenzaldehyde as raw material, react according to the method for embodiment 31 obtain brown color solid (E)-2-[3 '-(2 "-chloro-phenyl-) acryloyl]-6-ethoxycarbonyl-thionaphthene (2dB) (20%).
1HNMR(CDCl 3)δ：1.44(t，J＝7.2Hz，3H)，4.44(q，J＝7.2Hz，2H)，7.35-7.37(m，2H)，7.47(d，J＝8.8Hz，1H)，7.51(d，J＝15.6Hz，1H)，7.79(d×d，J＝8.0Hz，2.0Hz，1H)，7.97(d，J＝8.4Hz，1H)，8.08(d，J＝8.4Hz，1H)，8.13(s，1H)，8.30(d，J＝15.6Hz，1H)，8.63(s，1H).MS(EI +)m/z：370[M] +.HRMS(EI +)：found 370.0420[M] +，(Calcd for C 20H 15O 3SCl：370.0430)。
Embodiment 30:(E)-2-[3 '-(3 ", 4 "-dimethoxy benzene) acryloyl]-6-ethoxycarbonyl-thionaphthene (2dD)
With compound 2c and 3, the 4-dimethoxy benzaldehyde is raw material, according to the reaction of the method for embodiment 31 obtain brown oil (E)-2-[3 '-(3 ", 4 "-dimethoxy benzene) acryloyl]-6-ethoxycarbonyl-thionaphthene (2dD) (10%).
1HNMR(CDCl 3)δ：1.45(t，J＝7.2Hz，3H)，3.96(s，3H)，3.98(s，3H)，4.44(q，J＝7.2Hz，2H)，6.93(d，J＝8.4Hz，1H)，7.20(s，1H)，7.29(d，J＝8.4Hz，1H)，7.39(d，J＝15.6Hz，1H)，7.88(d，J＝15.6Hz，1H)，7.96(d，J＝8.4Hz，1H)，8.08(d，J＝8.4Hz，1H)，8.12(s，1H)，8.63(s，1H).MS(EI +)m/z：396[M] +.HRMS(EI +)：found 396.1015[M] +，(Calcd for C 22H 20O 5S：396.1031)。
Embodiment 31:(E)-2-[3 '-(3 ", 4 "-dimethoxy benzene) acryloyl]-5-ethoxycarbonyl-thionaphthene (1dD)
With compound 1c and 3, the 4-dimethoxy benzaldehyde is raw material, according to the reaction of the method for embodiment 31 obtain yellow oil (E)-2-[3 '-(3 ", 4 "-dimethoxy benzene) acryloyl]-5-ethoxycarbonyl-thionaphthene (1dD) (10%).
1HNMR(CDCl 3)δ：1.44(t，J＝7.2Hz，3H)，3.94(s，3H)，3.98(s，3H)，4.45(q，J＝7.2Hz，2H)，6.93(d，J＝8.4Hz，1H)，7.20(s，1H)，7.29(d，J＝8.4Hz，1H)，7.40(d，J＝15.2Hz，1H)，7.88(d，J＝15.2Hz，1H)，7.95(d，J＝8.8Hz，1H)，8.12(d，J＝8.8Hz，1H)，8.17(s，1H)，8.65(s，1H).MS(EI +)m/z：396[M] +.HRMS(EI +)：found 396.1032[M] +，(Calcd for C 22H 20O 5S：396.1031)。
Embodiment 32:2-ethoxycarbonyl-4-methyl-thionaphthene (1g)
Take 6-methyl 2-nitrobenzaldehyde and ethyl thioglycolate as raw material, operate according to the method for embodiment 1, get solid particulate 2-ethoxycarbonyl-4-methyl-thionaphthene (69.3%).
1HNMR(CDCl3)δ：1.45(t，J＝7.2Hz，3H)，2.35(s，3H)，4.46(q，J＝7.2Hz，2H)，7.38(m，2H)，7.74(m，1H)，7.98(s，1H)。MS(EI +)m/z：220[M] +.
Embodiment 33:2-oenanthyl-5,6-dimethyl-thionaphthene (17)
Be raw material with 4,5-dimethyl-2-nitro-phenyl aldehyde, sulfur alcohol and 1-chloro octane-2-ketone, obtain solid 2-oenanthyl-5,6-dimethyl-thionaphthene (17) (50%) according to the method reaction of embodiment 19.
1HNMR(CDCl 3)δ：0.96(t，J＝7.2Hz，，3H)，1.30(m，6H)，1.48(m，2H)，2.35(s，6H)，2.89(m，2H)，7.54(s，2H)，7.86(s，1H).MS(EI +)m/z：274[M] +.
Embodiment 34:2-penta oxygen formyl-5,6-diaminobenzene thiophthene (18b)
Be raw material with 5,6-diamino-6 nitrobenzaldehyde and Thiovanic acid pentyl ester, according to synthetic solid 2-penta oxygen formyl-5, the 6-diaminobenzene thiophthene (61%) of obtaining of the method for embodiment 1.
1HNMR(CDCl 3)δ：0.90(t，J＝7.2Hz，，3H)，1.30(m，4H)，1.75(m，2H)，4.35(m，2H)，5.80(s，4H)，6.73(s，1H)，6.80(s，1H)，8.22(s，1H).MS(EI +)m/z：278[M] +.
Embodiment 35:2-ketone acid-thionaphthene (19)
Take 2-nitrobenzaldehyde and sulfydryl 2-carbonyl propionic acid as raw material, according to the synthetic solid 2-ketone acid-thionaphthene (51.5%) that obtains of the method for embodiment 1.
1HNMR(CDCl 3) 1HNMR(CDCl 3)δ：7.32(t，J＝7.0Hz，1H)，7.49(t，J＝7.0Hz，1H)，7.76(d，J＝7.0Hz，1H)，7.79(d，J＝7.0Hz，1H)，7.94(s，1H)，12.6(s，1H).MS(EI +)m/z：206[M] +.
Embodiment 36:2-(1 ', 2 '-dicarbapentaborane) amylbenzene thiophthene (20)
With 2-nitrobenzaldehyde and 1-mercapto hexyl-2, the 3-diketone is raw material, according to synthetic solid 2-(1 ', 2 '-dicarbapentaborane) the amylbenzene thiophthene (40.2%) that obtains of the method for embodiment 1.
1HNMR(CDCl 3) 1HNMR(CDCl 3)δ：0.96(t，J＝7.2Hz，，3H)，1.65(m，2H)，2.40(m，2H)，7.33(t，J＝7.0Hz，1H)，7.46(t，J＝8.0Hz，1H)，7.70(d，J＝7.0Hz，1H)，7.82(d，J＝8.0Hz，1H)，8.05(s，1H).MS(EI +)m/z：232[M] +.
Embodiment 37:2-(butyl sulfoxide group) acetyl-5,6-diamino-thionaphthene (18c)
Be raw material with compound 18b (2-penta oxygen formyl-5,6-diaminobenzene thiophthene), obtain solid 2-(butyl sulfoxide group) acetyl-5,6-diamino-thionaphthene (18c) (80%) according to the method reaction of embodiment 2.
1HNMR(CDCl 3)δ：0.90(t，J＝7.2Hz，3H)，1.33(m，4H)，1.78(m，2H)，AB system(4.28，4.36，J＝13.2Hz，2H)，5.80(s，4H)，6.72(s，1H)，6.78(s，1H)，7.88(s，1H).MS(EI +)m/z：306[M] +.
Embodiment 38:2-(4 '-chlorine oxygen in heptan formyl)-5,6-dimethoxy-thionaphthene (21b)
With compound 2-nitro-4,5-dimethoxy benzaldehyde and Thiovanic acid-4 '-chlorine heptyl ester is raw material, reacts according to the method for embodiment 15 to obtain solid 2-(4 '-chlorine oxygen in heptan formyl)-5,6-dimethoxy-thionaphthene (21b) (55%).
1HNMR(CDCl 3)δ：0.96(t，J＝7.2Hz，3H)，1.33(m，2H)，1.60(m，6H)，3.46(m，1H)，3.73(s，3H)，3.96(s，3H)，4.28(m，2H)，7.18(s，1H)，7.25(s，1H)，8.30(s，1H).MS(EI +)m/z：370[M] +.
Embodiment 39:2-(4 '-chlorine hexyl sulfoxide group) acetyl-5,6-dimethoxy-thionaphthene (21c)
Take compound 21b as raw material, obtain solid 2-(4 '-chlorine hexyl sulfoxide group) acetyl-5,6-dimethoxy-thionaphthene (21c) (85%) according to the reaction of the method for embodiment 2
1HNMR(CDCl 3)δ：0.96(t，J＝7.2Hz，3H)，1.33(m，4H)，1.56(m，4H)，3.46(m，1H)，3.73(s，3H)，3.95(s，3H)，AB system(4.30，4.39，J＝13.2Hz，2H)，7.19(s，1H)，7.26(s，1H)，8.25(s，1H).MS(EI +)m/z：398[M] +.
Embodiment 40:2-(6 '-hydroxyl hexyl) oxygen formyl-5,6-dimethoxy-thionaphthene (22b)
With compound 2-nitro-4, the own ester of 5-dimethoxy benzaldehyde and Thiovanic acid-6 '-hydroxyl is raw material, method reaction according to embodiment 15 obtains solid 2-(6 '-hydroxyl hexyl) oxygen formyl-5,6-dimethoxy-thionaphthene (22b) (50%).
1HNMR(CDCl 3)δ：1.28(m，4H)，1.48(m，2H)，1.76(m，2H)，3.52(m，2H)，3.73(s，3H)，3.95(s，3H)，4.26(m，2H)，5.02(s，1H)，7.21(s，1H)，7.30(s，1H)，8.09(s，1H).MS(EI +)m/z：338[M] +.
Embodiment 41:2-(6 '-hydroxyl amyl group sulfoxide group) acetyl-5,6-dimethoxy-thionaphthene (22c)
Take compound 22b as raw material, obtain solid 2-(6 '-hydroxyl amyl group sulfoxide group) acetyl-5,6-dimethoxy-thionaphthene (22c) (81%) according to the reaction of the method for embodiment 2
1HNMR(CDCl 3)δ：1.29(m，4H)，1.50(m，2H)，1.76(m，2H)，3.53(m，2H)，3.73(s，3H)，3.96(s，3H)，AB system(4.30，4.39，J＝13.2Hz，2H)，5.16(s，1H)，7.29(s，1H)，7.32(s，1H)，8.16(s，1H).MS(EI +)m/z：366[M] +.
Embodiment 42:2-(6 '-methoxyl group hexyl) oxygen formyl-5,6-dimethoxy-thionaphthene (23b)
With compound 2-nitro-4,5-dimethoxy benzaldehyde and Thiovanic acid-6 '-methoxyl group polyhexamethylene is raw material, method reaction according to embodiment 15 obtains solid 2-(6 '-methoxyl group hexyl) oxygen formyl-5,6-dimethoxy-thionaphthene (23b) (63%).
1HNMR(CDCl 3)δ：1.29(m，4H)，1.46(m，2H)，1.75(m，2H)，3.24(s，3H)，3.37(m，2H)，3.72(s，3H)，3.93(s，3H)，4.25(m，2H)，7.19(s，1H)，7.28(s，1H)，8.19(s，1H).MS(EI +)m/z：352[M] +.
Embodiment 43:2-(6 '-methoxyl group amyl group sulfoxide group) acetyl-5,6-dimethoxy-thionaphthene (23c)
Take compound 23b as raw material, obtain solid 2-(6 '-methoxyl group amyl group sulfoxide group) acetyl-5,6-dimethoxy-thionaphthene (23c) (86%) according to the reaction of the method for embodiment 2
1HNMR(CDCl 3)δ：1.31(m，4H)，1.48(m，2H)，1.76(m，2H)，3.24(s，3H)，3.38(m，2H)，3.73(s，3H)，3.92(s，3H)，AB system(4.30，4.39，J＝13.2Hz，2H)，7.18(s，1H)，7.26(s，1H)，7.91(s，1H).MS(EI +)m/z：380[M] +.
Embodiment 44:2-ethoxycarbonyl-5,6-ethyl methylene radical dioxy-thionaphthene (24b)
Be raw material with 3,4-ethyl methylene radical dioxy-6 nitrobenzaldehyde and ethyl thioglycolate, according to the synthetic solid 2-ethoxycarbonyl-5,6-ethyl methylene radical dioxy-thionaphthene (68.5%) of obtaining of the method for embodiment 1.
1HNMR(CDCl 3)δ：0.96(m，3H)，1.42(t，J＝7.2Hz，3H)，2.13(m，2H)，4.37(q，J＝7.2Hz，2H)，6.04(m，1H)，7.21(s，1H)，7.26(s，1H)，7.91(s，1H).MS(EI +)m/z：278[M] +.
Embodiment 45:2-ethoxycarbonyl-5,6-(2 '-chloroethyl) methylene radical dioxy-thionaphthene (25b)
With 3,4-(2 '-chloroethyl) methylene radical dioxy-6 nitrobenzaldehyde and ethyl thioglycolate are raw material, according to the synthetic solid 2-ethoxycarbonyl-5,6-(2 '-chloroethyl) methylene radical dioxy-thionaphthene (25b) (62.0%) of obtaining of the method for embodiment 1.
1HNMR(CDCl 3)δ：1.43(t，J＝7.2Hz，3H)，1.59(d，J＝5.0Hz，3H)，4.38(q，J＝7.2Hz，2H)，4.63(m，1H)，6.23(m，1H)，7.18(s，1H)，7.23(s，1H)，7.96(s，1H).MS(EI +)m/z：312[M] +.
Embodiment 46:2-ethoxycarbonyl-5,6-(1 '-hydroxyethyl) methylene radical dioxy-thionaphthene (26b)
With 3,4-(1 '-hydroxyethyl) methylene radical dioxy-6 nitrobenzaldehyde and ethyl thioglycolate are raw material, according to the synthetic solid 2-ethoxycarbonyl-5,6-(1 '-hydroxyethyl) methylene radical dioxy-thionaphthene (26b) (68.0%) of obtaining of the method for embodiment 1.
1HNMR(CDCl 3)δ：1.42(t，J＝7.2Hz，3H)，2.28(m，2H)，3.53(m，2H)，4.38(q，J＝7.2Hz，2H)，5.16(s，1H)，5.96(m，1H)，7.18(s，1H)，7.25(s，1H)，7.98(s，1H).MS(EI +)m/z：294[M] +.
Embodiment 47:2-ethoxycarbonyl-5,6-(1 '-aminoethyl) methylene radical dioxy-thionaphthene (27b)
With 3,4-(1 '-aminoethyl) methylene radical dioxy-6 nitrobenzaldehyde and ethyl thioglycolate are raw material, according to the synthetic solid 2-ethoxycarbonyl-5,6-(1 '-aminoethyl) methylene radical dioxy-thionaphthene (26b) (68.0%) of obtaining of the method for embodiment 1.
1HNMR(CDCl 3)δ：1.42(t，J＝7.2Hz，3H)，2.35(m，2H)，2.65(m，2H)，4.12(s，1H)，4.38(q，J＝7.2Hz，2H)，5.98(m，1H)，7.16(s，1H)，7.27(s，1H)，8.02(s，1H).MS(EI +)m/z：293[M] +.
Embodiment 48:2-ethoxycarbonyl-5,6-(1 '-methoxy ethyl) methylene radical dioxy-thionaphthene (28b)
With 3,4-(1 '-methoxy ethyl) methylene radical dioxy-6 nitrobenzaldehyde and ethyl thioglycolate are raw material, according to the synthetic solid 2-ethoxycarbonyl-5,6-(1 '-methoxy ethyl) methylene radical dioxy-thionaphthene (26b) (68.0%) of obtaining of the method for embodiment 1.
1HNMR(CDCl 3)δ：1.42(t，J＝7.2Hz，3H)，2.26(m，2H)，3.24(s，3H)，3.37(m，2H)，4.38(q，J＝7.2Hz，2H)，5.98(m，1H)，7.18(s，1H)，7.25(s，1H)，8.03(s，1H).MS(EI +)m/z：308[M] +.
Embodiment 49:2-ethoxycarbonyl-cumarone (9b)
In reaction flask, add successively DMF (5ml), bromoethyl acetate (118mg, 0.71mmol), salicylic aldehyde (146.6mg, 1.2mmol), Anhydrous potassium carbonate (166mg, 1.2mmol).100 ℃ of oil baths reaction 4h, return to room temperature after, steam except DMF first.With the chloroform dissolving, wash the chloroform phase again.During layering, a lot of insolubless appear in chloroform mutually.Suction filtration filtering insolubles, with chloroform filter wash cake repeatedly.Be spin-dried for that silica gel column chromatography obtains the faint yellow oily thing of 57mg (55.9%) after separating behind the solvent.
1HNMR(CDCl 3)δ：1.35(t，J＝7.2Hz，3H)，4.37(q，J＝7.2Hz，2H)，7.22(t，J＝7.6Hz，1H)，7.36(t，J＝7.6Hz，1H)，7.45(s，1H)，7.51(d，J＝8.0Hz，1H)，7.60(d，J＝8.0Hz，1H)。MS(ESI +)m/z：191.4[M+H] +.HRMS(EI +)：found297.9967[M] +，(Calcd for C 11H 10O 3：190.0630)。
Embodiment 50:2-(2 '-methyl sulfoxide base) acetyl cumarone (9c)
Take 9b as raw material, according to synthetic yellow solid 2-(the 2 '-methyl sulfoxide base) acetyl-cumarone (29.6%) that obtains of the method for embodiment 2.
1HNMR(CDCl 3)δ：2.85(s，3H)，AB system(4.30，4.39，J＝13.2Hz，2H)，7.35(t，J＝7.2Hz，1H)，7.54(t，J＝7.2Hz，1H)，7.61(d，J＝8.0Hz，1H)，7.68(s，1H)，7.75(d，J＝8.0Hz，1H)。MS(EI +)m/z：222[M] +.HRMS(EI +)：found222.0350[M] +，(Calcd for C 11H 10O 3S：222.0351)。
Embodiment 51:2-ethoxycarbonyl-4-methoxyl group-cumarone (10b)
Take 2-methoxyl group-6-hydroxy benzaldehyde and bromoethyl acetate as raw material, according to the synthetic yellowish solid 2-ethoxycarbonyl-4-methoxyl group-cumarone (100%) that obtains of the method for embodiment 7.
1HNMR(CDCl 3)δ：1.42(t，J＝7.2Hz，3H)，3.95(s，3H)，4.43(q，J＝7.2Hz，2H)，6.68(d，J＝8.0Hz，1H)，7.19(d，J＝8.0Hz，1H)，7.36(t，J＝7.2Hz，1H)，7.62(s，1H).MS(EI +)m/z：220[M] +.HRMS(EI +)：found 220.0732[M] +，(Calcd for C 12H 12O 4：220.0736)。
Embodiment 52:2-ethoxycarbonyl-5-methoxyl group-cumarone (11b)
Take 3-methoxyl group-6-hydroxy benzaldehyde and bromoethyl acetate as raw material, according to the synthetic white solid 2-ethoxycarbonyl-5-methoxyl group-cumarone (82%) that obtains of the method for embodiment 7.
1HNMR(CDCl3)δ：1.43(t，J＝7.2Hz，3H)，3.85(s，3H)，4.44(q，J＝7.2Hz，2H)，7.05(d，J＝2.4Hz，1H)，7.06(d×d，J＝8.2Hz，2.4Hz，1H)，7.46-7.49(m，2H).MS(EI+)m/z：220[M]+.HRMS(EI+)：found 220.0733[M]+，(Calcd for C12H12O4：220.0736)。
Embodiment 53:2-ethoxycarbonyl-6-methoxyl group-cumarone (12b)
Take 4-methoxyl group-Benzaldehyde,2-hydroxy and bromoethyl acetate as raw material, according to the synthetic white solid 2-ethoxycarbonyl-6-methoxyl group-cumarone (68%) that obtains of the method for embodiment 7.
1HNMR(CDCl 3)δ：1.42(t，J＝7.2Hz，3H)，3.87(s，3H)，4.42(q，J＝7.2Hz，2H)，6.94(d×d，J＝8.8Hz，2.0Hz，1H)，7.07(d，J＝2.0Hz，1H)，7.47(s，1H)，7.53(d，J＝8.8Hz，1H).MS(EI +)m/z：220[M] +.HRMS(EI +)：found220.0739[M] +，(Calcd for C 12H 12O 4：220.0736)。
Embodiment 54:2-ethoxycarbonyl-7-methoxyl group-cumarone (13b)
Take 3-methoxyl group-Benzaldehyde,2-hydroxy and bromoethyl acetate as raw material, according to the synthetic white solid 2-ethoxycarbonyl-7-methoxyl group-cumarone (58%) that obtains of the method for embodiment 7.
1HNMR(CDCl 3)δ：1.42(t，J＝7.2Hz，3H)，4.02(s，3H)，4.44(q，J＝7.2Hz，2H)，6.92(d，J＝7.6Hz，1H)，7.21(d，J＝7.6Hz，1H)，7.22(d×d，J＝7.6Hz，3.2Hz，1H)，7.52(s，1H).MS(EI +)m/z：220[M] +.HRMS(EI +)：found 220.0733[M] +，(Calcd for C 12H 12O 4：220.0736)。
Embodiment 55:2-ethoxycarbonyl-7-fluoro-cumarone (14b)
Take 3-fluoro-Benzaldehyde,2-hydroxy and bromoethyl acetate as raw material, obtain yellow oily 2-ethoxycarbonyl-7-fluoro-cumarone (47%) according to the method reaction of embodiment 7.
1HNMR(CDCl 3)δ：1.43(t，J＝7.2Hz，3H)，4.45(q，J＝7.2Hz，2H)，7.14-7.25(m，2H)，7.43(d，J＝8.0Hz，1H)，7.54(d，J＝2.8Hz，1H).MS(EI +)m/z：208[M] +.HRMS(EI +)：found 208.0531[M] +，(Calcd for C 11H 9O 3F：208.0536)。
Embodiment 56:2-ethoxycarbonyl-5,7-two chloro-cumarones (15b)
Be raw material with 3,5-, two chloro-Benzaldehyde,2-hydroxies and bromoethyl acetate, obtain white solid 2-ethoxycarbonyl-5,7-two chloro-cumarones (65%) according to the method reaction of embodiment 7.
1HNMR(CDCl 3)δ：1.44(t，J＝7.2Hz，3H)，4.46(q，J＝7.2Hz，2H)，7.46(d，J＝1.6Hz，1H)，7.48(s，1H)，7.57(d，J＝1.6Hz，1H).MS(EI +)m/z：258[M] +，260[M+2] +，262[M+4] +.HRMS(EI +)：found 257.9840[M] +，(Calcd for C 11H 8O 3Cl 2：257.9850)。
Embodiment 57:2-(2 '-methyl sulfoxide base) acetyl-4-methoxyl group-cumarone (10c)
Take compound 10b as raw material, obtain yellow solid 2-(2 '-methyl sulfoxide base) acetyl-4-methoxyl group-cumarone (10c) (76%) according to the reaction of the method for embodiment 2.
1HNMR(CDCl 3)δ：2.80(s，3H)，3.98(s，3H)，AB system(4.26，4.39，J＝13.5Hz，2H)，6.71(d，J＝8.0Hz，1H)，7.19(d，J＝8.0Hz，1H)，7.47(t，J＝8.0Hz，1H)，7.79(s，1H).HRMS(EI +)：found 252.0437[M] +，(Calcd forC 12H 12O 4S：252.0456)。
Embodiment 58:2-(2 '-methyl sulfoxide base) acetyl-5-methoxyl group-cumarone (11c)
Take compound 11b as raw material, obtain yellow solid 2-(2 '-methyl sulfoxide base) acetyl-5-methoxyl group-cumarone (11c) (83%) according to the reaction of the method for embodiment 2.
1HNMR(CDCl 3)δ：2.79(s，3H)，3.86(s，3H)，AB system(4.27，4.37，J＝13.2Hz，2H)，7.10(d，J＝2.0Hz，1H)，7.15(d×d，J＝8.8Hz，2.0Hz，1H)，7.48(d，J＝8.8Hz，1H)，7.60(s，1H).HRMS(EI +)：found 252.0439[M] +，(Calcdfor C 12H 12O 4S：252.0456)。
Embodiment 59:2-(2 '-methyl sulfoxide base) acetyl-6-methoxyl group-cumarone (12c)
With compound 12b raw material, obtain yellow solid 2-(2 '-methyl sulfoxide base) acetyl-6-methoxyl group-cumarone (12c) (51%) according to the reaction of the method for embodiment 2.
1HNMR(CDCl 3)δ：2.79(s，3H)，3.89(s，3H)，AB system(4.23，4.33，J＝13.2Hz，2H)，6.97(d×d，J＝8.8Hz，2.0Hz，1H)，7.04(s，1H)，7.60(d，J＝8.8Hz，1H)，7.62(s，1H).HRMS(EI +)：found 252.0443[M] +，(Calcd forC 12H 12O 4S：252.0456)。
Embodiment 60:2-(2 '-methyl sulfoxide base) acetyl-7-methoxyl group-cumarone (13c)
Take compound 13b as raw material, obtain yellow solid 2-(2 '-methyl sulfoxide base) acetyl-7-methoxyl group-cumarone (13c) (66%) according to the reaction of the method for embodiment 2.
1HNMR(d6-DMSO)δ：2.73(s，3H)，3.97(s，3H)，AB system(4.46，4.57，J＝14.0Hz，2H)，7.17(d，J＝7.6Hz，1H)，7.30(t，J＝7.6Hz，1H)，7.41(d，J＝7.6Hz，1H)，8.08(s，1H).HRMS(EI +)：found 252.0459[M] +，(Calcd forC 12H 12O 4S：252.0456)。
Embodiment 61:2-ethoxycarbonyl-6-diethylin-cumarone (16b)
Take 4-diethylin salicylic aldehyde as raw material, obtain yellow oily 2-ethoxycarbonyl-6-diethylin-cumarone (16b) (36%) according to the reaction of the method for embodiment 7.
1HNMR(CDCl 3)δ：1.20(t，J＝6.8Hz，6H)，1.41(t，J＝7.2Hz，3H)，3.41(q，J＝6.8Hz，4H)，4.41(q，J＝7.2Hz，2H)，6.73(d，J＝8.8Hz，1H)，6.76(s，1H)，7.40(s，1H)，7.43(d，J＝8.8Hz，1H).MS(EI +)m/z：261[M] +.HRMS(EI +)：found 261.1365[M] +，(Calcd for C 15H 19NO 3：261.1365)。
Embodiment 62:2-(2 '-methylsulfonyl) acetyl-5-methoxyl group-cumarone (11d)
Take compound 11c as raw material, according to synthetic faint yellow solid 2-(2 '-methylsulfonyl) acetyl-5-methoxyl group-cumarone (57.0%) that obtains of the method for embodiment 3.
1HNMR(CDCl 3)δ：3.16(s，3H)，3.86(s，3H)，4.58(s，2H)，7.10(d，J＝2.4Hz，1H)，7.17(d×d，J＝9.0Hz，2.4Hz，1H)，7.49(d，J＝9.0Hz，1H)，7.65(s，1H)。MS(EI +)m/z：268[M] +.HRMS(EI +)：found 268.0416[M] +，(Calcd for
C 12H 10O 5S：268.0405)。
Embodiment 63:2-(1 '-hydroxyl-2 '-methyl sulfoxide) ethyl-5-methoxyl group-cumarone (11e)
Take compound 11c as raw material, obtain yellowish solid 2-(1 '-hydroxyl-2 '-methyl sulfoxide) ethyl-5-methoxyl group-cumarone (11e) (89%) according to the reaction of the method for embodiment 10.
1HNMR(CDCl 3)δ：2.75(s，3H)，3.12-3.37(m，2H)，3.84(s，3H)，5.50-5.56(m 1H)，6.71(d，J＝5.2Hz，1H)，6.88(d×d，J＝8.8Hz，2.4Hz，1H)，7.01(d，J＝2.4Hz，1H)，7.33(d，J＝8.8Hz，1H)。MS(ESI +)m/z：277.3[M+Na] +.HRMS(ESI +)：found 277.05280[M+Na] +，(Calcd for C 12H 14O 4SNa：277.05105)。
Embodiment 64:(E)-2-[3 '-(4 "-anisole) acryloyl]-5,6-dimethoxy-indoles (G33-1)
With 2-acetyl-5,6-dimethoxy indoles and aubepine are raw material, obtain solid (E)-2-[3 '-(4 "-anisole) acryloyl with the reaction of the method for embodiment 31]-5,6-dimethoxy-indoles (74.5%).
1H NMR(CDCl 3)δ：3.73(s，3H)，3.85(s，3H)，3.92(s，3H)，6.67(d，J＝15.2Hz，1H)，6.80(s，1H)，6.95(s，1H)，7.09(s，2H)，7.38(s，1H)，7.54(d，J＝15.2Hz，1H)，7.68(s，2H)，11.63(br，1H).MS(EI +)m/z：337[M] +.
Embodiment 65:(E)-1-methyl-2-[3 '-(4 "-anisole) acryloyl]-5,6-dimethoxy-indoles (G33-2)
With 1-methyl-2-acetyl-5,6-dimethoxy indoles and aubepine are raw material, obtain solid (E)-1-methyl-2-[3 '-(4 "-anisole) acryloyl with the reaction of the method for embodiment 31]-5,6-dimethoxy-indoles (77.1%).
1H NMR(CDCl 3)δ：3.60(s，3H)，3.73(s，3H)，3.85(s，3H)，3.92(s，3H)，6.67(d，J＝15.2Hz，1H)，6.57(s，2H)，7.09(s，2H)，7.41(s，1H)，7.54(d，J＝15.2Hz，1H)，7.68(s，2H).MS(EI +)m/z：351[M] +.
Embodiment 66:(E)-1-chloroethyl-2-[3 '-(4 "-anisole) acryloyl]-5,6-dimethoxy-indoles (G33-3)
With 1-chloroethyl-2-acetyl-5,6-dimethoxy indoles and aubepine are raw material, obtain solid (E)-1-chloroethyl-2-[3 '-(4 "-anisole) acryloyl with the reaction of the method for embodiment 31]-5,6-dimethoxy-indoles (70.2%).
1H NMR(CDCl 3)δ：2.14(m，3H)，3.70(s，3H)，3.82(s，3H)，3.92(s，3H)， 5.80(m，1H)，6.66(d，J＝15.2Hz，1H)，6.59(s，2H)，7.11(s，2H)，7.38(s，1H)，7.53(d，J＝15.2Hz，1H)，7.71(s，2H).MS(EI +)m/z：399[M] +.
Embodiment 67:(E)-1-ethanoyl-2-[3 '-(4 "-fluorobenzene) acryloyl]-5,6-dimethoxy-indoles (G33-4)
With 1,2-diacetyl-5,6-dimethoxy indoles and p-Fluorobenzenecarboxaldehyde are raw material, obtain solid (E)-1-ethanoyl-2-[3 '-(4 "-fluorobenzene) acryloyl with the reaction of the method for embodiment 31]-5,6-dimethoxy-indoles (72.6%).
1H NMR(CDCl 3)δ：2.19(m，3H)，3.73(s，3H)，3.94(s，3H)，6.68(d，J＝15.2Hz，1H)，6.81(s，2H)，7.11(s，2H)，7.43(s，1H)，7.53(d，J＝15.2Hz，1H)，7.69(s，2H).MS(EI +)m/z：367[M] +.
Embodiment 68:(E)-1-(2 '-hydroxyethyl)-2-[3 '-(4 "-fluorophenyl) acryloyl]-5-acetoxyl group-indoles (G33-5)
Take 1-(2 '-hydroxyethyl)-2-acetyl-5-acetoxy-indole and p-Fluorobenzenecarboxaldehyde as raw material, obtain solid (E)-1-(2 '-hydroxyethyl)-2-[3 '-(4 "-fluorophenyl) acryloyl with the method reaction of embodiment 31]-5-acetoxyl group-indoles (70.5%).
1H NMR(CDCl 3)δ：2.33(s，3H)，4.08(m，4H)，4.30(s，1H)，6.70(d，J＝15.2Hz，1H)，7.02(m，2H)，7.35(m，4H)，7.42(s，1H)，7.53(d，J＝15.2Hz，1H)，7.80(m，1H).MS(EI +)m/z：367[M] +.
Embodiment 69:(E)-1-(2 '-amino-ethyl)-2-[3 '-(4 "-fluorophenyl) acryloyl]-5-acetoxyl group-indoles (G33-6)
Take 1-(2 '-amino-ethyl)-2-acetyl-5-acetoxy-indole and p-Fluorobenzenecarboxaldehyde as raw material, obtain solid (E)-1-(2 '-amino-ethyl)-2-[3 '-(4 "-fluorophenyl) acryloyl with the method reaction of embodiment 31]-5-acetoxyl group-indoles (58.0%).
1H NMR(CDCl 3)δ：2.33(s，3H)，3.12(m，2H)，4.11(m，2H)，5.80(s，2H)，6.68(d，J＝15.2Hz，1H)，6.98(m，2H)，7.02(m，2H)，7.36(m，4H)，7.42(s，1H)，7.53(d，J＝15.2Hz，1H)，7.84(m，1H).MS(EI +)m/z：366[M] +.
Embodiment 70:E) 1-(2 '-methoxy ethyl)-2-[3 '-(4 "-fluorophenyl) acryloyl]-5-acetoxyl group-indoles (G33-7)
Take 1-(2 '-methoxy ethyl)-2-acetyl-5-acetoxy-indole and p-Fluorobenzenecarboxaldehyde as raw material, obtain solid E with the method reaction of embodiment 31)-1-(2 '-methoxy ethyl)-2-[3 '-(4 "-fluorophenyl) acryloyl]-5-acetoxyl group-indoles (70.5%).
1H NMR(CDCl 3)δ：2.32(s，3H)，3.24(s，3H)，3.85(m，2H)，4.08(m，2H)，6.68(d，J＝15.2Hz，1H)，7.02(m，2H)，7.36(m，4H)，7.41(s，1H)，7.53(d，J＝15.2Hz，1H)，7.82(m，1H).MS(EI +)m/z：381[M] +.
Certainly; the present invention also can have other various embodiments; in the situation that does not deviate from spirit of the present invention and essence thereof; those of ordinary skill in the art work as can make according to the present invention various corresponding changes and distortion, but these corresponding changes and distortion all should belong to the protection domain of the appended claim of the present invention.

Claims (2)

1. the compound as the ultraviolet detector active coating is characterized in that described compound is the benzo five-membered unsaturated heterocycle compound, and it has structure shown in general formula I,
Figure FDA0000243653511
In the formula, X represents O, S or NR 7, R wherein 7Represent H, alkyl, halo alkyl, carbonyl alkyl, hydroxy alkylene, hydrocarbyl amino or-oxyl;
Y represents CO or CR 1' OH; R 1' representative following group: H, OH, the alkyl that contains 1-18 carbon, carboxyl, acyl group, alkoxyl group, sulfonic group;
R 1Represent following group: H, OH, the alkyl that contains 1-18 carbon, carboxyl, acyl group, alkoxyl group, sulfonic group, CH 2S (O) nR 8, R 9The substituted benzene propenyl; R wherein 8Represent H, contain alkyl, halo alkyl, hydroxy alkylene or the-oxyl of 1-18 carbon, n=1-2; R 9The amino that represents H, alkyl, alkoxyl group, halogen, carboxyl, amino or replace; And R 1Can with R 1' identical, also can with R 1' difference;
R 2Amino, sulfonic group, itrile group or the acyl group-oxyl etc. that represent following group: H, the alkyl that contains 1-18 carbon, halogen, acyl group, carboxyl, amino or replace;
R 3Amino, acyl group, amide group, ester group or the sulfonic group etc. that represent following group: H, alkyl, alkoxyl group, halogen or haloalkyl, carboxyl, amino or replace;
R 4Represent following group: H, alkyl, alkoxyl group, halogen or haloalkyl, carboxyl, amino or amino, amide group, acyl group, ester group or the sulfonic group etc. that replace;
R 5Amino, acyl group, amide group, ester group or the sulfonic group etc. that represent following group: H, alkyl, alkoxyl group, halogen or haloalkyl, carboxyl, amino or replace;
R 6Amino, acyl group, amide group, ester group or the sulfonic group etc. that represent following group: H, alkyl, alkoxyl group, halogen or haloalkyl, carboxyl, amino or replace; Perhaps,
R 4With R 5Be joined together to form the 5-7 ring structure or with substituent R by carbon, oxygen or nitrogen 10The 5-7 ring structure, R wherein 10Represent H, alkyl, halo alkyl, carbonyl alkyl, hydroxy alkylene, hydrocarbyl amino or-oxyl.
2. the compound as the ultraviolet detector active coating as claimed in claim 1 is characterized in that described compound is:
2-ethoxycarbonyl-thionaphthene
2-(2 '-methyl sulfoxide base)-phenyl methyl ketone thiophthene
2-(2 '-methylsulfonyl) acetyl-thionaphthene
2-ethoxycarbonyl-5,6-methylene radical dioxy-thionaphthene
2-(2 '-methyl sulfoxide base) acetyl-5,6-methylene radical dioxy-thionaphthene
2-(2 '-methylsulfonyl) acetyl-5,6-methylene radical dioxy-thionaphthene
2-ethoxycarbonyl-cumarone
2-(2 '-methyl sulfoxide base)-acetyl cumarone
2-ethoxycarbonyl-4-chloro-thionaphthene
2-(1 '-hydroxyl-2 '-methyl sulfoxide base)-ethyl-thionaphthene
2-ethoxycarbonyl-4-methoxyl group-cumarone
2-ethoxycarbonyl-5-methoxyl group-cumarone
2-ethoxycarbonyl-6-methoxyl group-cumarone
2-ethoxycarbonyl-7-methoxyl group-cumarone
2-ethoxycarbonyl-5,6-dimethoxy-thionaphthene
2-ethoxycarbonyl-7-fluoro-cumarone
2-ethoxycarbonyl-5,7-two chloro-cumarones
2-ethoxycarbonyl-5-methoxycarbonyl-thionaphthene
2-acetyl-5-methoxycarbonyl-thionaphthene
2-ethoxycarbonyl-6-methoxycarbonyl-thionaphthene
2-acetyl-5-carboxyl-thionaphthene
2-acetyl-6-methoxycarbonyl-thionaphthene
2-acetyl-6-carboxyl-thionaphthene
2-(2 '-methyl sulfoxide base) acetyl-4-chloro-thionaphthene
2-(2 '-methyl sulfoxide base) acetyl-4-methoxyl group-cumarone
2-(2 '-methyl sulfoxide base) acetyl-5-methoxyl group-cumarone
2-(2 '-methyl sulfoxide base) acetyl-5,6-dimethoxy-thionaphthene
2-(2 '-methyl sulfoxide base) acetyl-6-methoxyl group-cumarone
2-(2 '-methyl sulfoxide base) acetyl-7-methoxyl group-cumarone
2-ethoxycarbonyl-6-diethylin-cumarone
(E)-2-[3 '-(4 "-anisole) acryloyl]-6-ethoxycarbonyl-thionaphthene
(E)-2-[3 '-(4 "-anisole) acryloyl]-5-ethoxycarbonyl-thionaphthene
2-(1 '-hydroxyl-2 '-methyl sulfoxide base) ethyl-5,6-methylene radical dioxy-thionaphthene
2-(1 '-hydroxyl) ethyl-5-methoxycarbonyl-thionaphthene
2-(1 '-hydroxyl) ethyl-6-methoxycarbonyl-thionaphthene
(E)-2-cinnyl-6-ethoxycarbonyl-thionaphthene
(E)-2-[3 '-(2 ", 3 ", 4 "-trimethoxy-benzene) acryloyl]-5-ethoxycarbonyl-thionaphthene
(E)-2-[3 '-(2 ", 3 ", 4 "-trimethoxy-benzene) acryloyl]-6-ethoxycarbonyl-thionaphthene (E)-2-cinnyl-5-ethoxycarbonyl-thionaphthene
(E)-2-[3 '-(2 "-chloro-phenyl-) acryloyl]-5-ethoxycarbonyl-thionaphthene (E)-2-[3 '-(2 "-chloro-phenyl-) acryloyl]-5-methoxycarbonyl-thionaphthene
(E)-2-[3 '-(2 "-chloro-phenyl-) acryloyl]-6-ethoxycarbonyl-thionaphthene
(E)-2-[3 '-(3 ", 4 "-dimethoxy benzene) acryloyl]-6-ethoxycarbonyl-thionaphthene
(E)-2-[3 '-(3 ", 4 "-dimethoxy benzene) acryloyl]-5-ethoxycarbonyl-thionaphthene
2-(2 '-methylsulfonyl) acetyl-5-methoxyl group-cumarone
2-(1 '-hydroxyl-2 '-methyl sulfoxide) ethyl-5-methoxyl group-cumarone
(E)-2-[3 '-(4 "-anisole) acryloyl]-5,6-dimethoxy-indoles
(E)-1-methyl-2-[3 '-(4 "-anisole) acryloyl]-5,6-dimethoxy-indoles
(E)-1-chloroethyl-2-[3 '-(4 "-anisole) acryloyl]-5,6-dimethoxy-indoles
(E)-1-ethanoyl-2-[3 '-(4 "-fluorobenzene) acryloyl]-5,6-dimethoxy-indoles
(E)-1-(2 '-hydroxyethyl)-2-[3 '-(4 "-fluorobenzene) acryloyl]-5-acetoxyl group-indoles
(E)-1-(2 '-amino-ethyl)-2-[3 '-(4 "-fluorobenzene) acryloyl]-5-acetoxyl group-indoles
(E)-1-(2 '-methoxy ethyl)-2-[3 '-(4 "-fluorobenzene) acryloyl]-5-acetoxyl group-indoles
2-ethoxycarbonyl-4-methyl-thionaphthene
2-oenanthyl-5,6-dimethyl-thionaphthene
2-penta oxygen formyl-5,6-diaminobenzene thiophthene
2-ketone acid-thionaphthene
2-(1 ', 2 '-dicarbapentaborane) amylbenzene thiophthene
2-(butyl sulfoxide group) acetyl-5,6-diamino-thionaphthene
2-(4 '-chlorine oxygen in heptan formyl)-5,6-dimethoxy-thionaphthene
2-(4 '-chlorine hexyl sulfoxide group) acetyl-5,6-dimethoxy-thionaphthene
2-(6 '-hydroxyl hexyl) oxygen formyl-5,6-dimethoxy-thionaphthene
2-(6 '-hydroxyl, penta sulfoxide group) acetyl-5,6-dimethoxy-thionaphthene
2-(6 '-methoxyl group hexyl) oxygen formyl-5,6-dimethoxy-thionaphthene
2-(6 '-methoxyl group amyl group sulfoxide group) acetyl-5,6-dimethoxy-thionaphthene
2-ethoxycarbonyl-5,6-ethyl methylene radical dioxy-thionaphthene
2-ethoxycarbonyl-5,6-(2 '-chloroethyl) methylene radical dioxy-thionaphthene
2-ethoxycarbonyl-5,6-(1 '-hydroxyethyl) methylene radical dioxy-thionaphthene
2-ethoxycarbonyl-5,6-(1 '-aminoethyl) methylene radical dioxy-thionaphthene
2-ethoxycarbonyl-5,6-(1 '-methoxy ethyl) methylene radical dioxy-thionaphthene
2-phenyl methyl ketone thiophthene
(E)-2-(3 '-(4 "-anisole) acryloyl)-thionaphthene or
2-acetyl-cumarone.
CN2012104725699A 2012-11-20 2012-11-20 Compound used as active layer of ultraviolet detector Pending CN103044389A (en)

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Publication number Priority date Publication date Assignee Title
CN101906093A (en) * 2009-06-05 2010-12-08 中国医学科学院医药生物技术研究所 Benzo five-membered unsaturated heterocycle compound and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101906093A (en) * 2009-06-05 2010-12-08 中国医学科学院医药生物技术研究所 Benzo five-membered unsaturated heterocycle compound and preparation method thereof

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