CN109897031B - Benzothiazole derivative containing coumarin group and preparation method and application thereof - Google Patents
Benzothiazole derivative containing coumarin group and preparation method and application thereof Download PDFInfo
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- CN109897031B CN109897031B CN201711343507.7A CN201711343507A CN109897031B CN 109897031 B CN109897031 B CN 109897031B CN 201711343507 A CN201711343507 A CN 201711343507A CN 109897031 B CN109897031 B CN 109897031B
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- thiazol
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- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 241000500437 Plutella xylostella Species 0.000 claims abstract description 8
- 125000005605 benzo group Chemical group 0.000 claims description 68
- 125000000437 thiazol-2-yl group Chemical group [H]C1=C([H])N=C(*)S1 0.000 claims description 68
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 44
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 14
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 14
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 claims description 14
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 14
- 241000607479 Yersinia pestis Species 0.000 claims description 12
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- -1 C1-12Alkyl Chemical class 0.000 claims description 6
- 241001425390 Aphis fabae Species 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims 1
- 241000238631 Hexapoda Species 0.000 abstract description 7
- 240000006677 Vicia faba Species 0.000 abstract description 7
- 235000010749 Vicia faba Nutrition 0.000 abstract description 7
- 235000002098 Vicia faba var. major Nutrition 0.000 abstract description 7
- 239000000575 pesticide Substances 0.000 abstract description 7
- 241001124076 Aphididae Species 0.000 abstract description 6
- 230000000607 poisoning effect Effects 0.000 abstract description 6
- 230000002265 prevention Effects 0.000 abstract 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 60
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 60
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 30
- 238000005160 1H NMR spectroscopy Methods 0.000 description 30
- 238000002844 melting Methods 0.000 description 30
- 230000008018 melting Effects 0.000 description 30
- 239000000843 powder Substances 0.000 description 30
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 29
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003814 drug Substances 0.000 description 6
- 229940079593 drug Drugs 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000000749 insecticidal effect Effects 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 241001600408 Aphis gossypii Species 0.000 description 3
- ORHBXUUXSCNDEV-UHFFFAOYSA-N umbelliferone Chemical compound C1=CC(=O)OC2=CC(O)=CC=C21 ORHBXUUXSCNDEV-UHFFFAOYSA-N 0.000 description 3
- ZPSJGADGUYYRKE-UHFFFAOYSA-N 2H-pyran-2-one Chemical compound O=C1C=CC=CO1 ZPSJGADGUYYRKE-UHFFFAOYSA-N 0.000 description 2
- 241000982105 Brevicoryne brassicae Species 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 241001556089 Nilaparvata lugens Species 0.000 description 2
- 241000255969 Pieris brassicae Species 0.000 description 2
- 241001414989 Thysanoptera Species 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
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- 229920000136 polysorbate Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LVFMXQKJUDYAGX-UHFFFAOYSA-N 2-[4-(5-bromopentoxy)phenyl]-1,3-benzothiazole Chemical compound BrCCCCCOC1=CC=C(C=C1)C=1SC2=C(N=1)C=CC=C2 LVFMXQKJUDYAGX-UHFFFAOYSA-N 0.000 description 1
- HSHNITRMYYLLCV-UHFFFAOYSA-N 4-methylumbelliferone Chemical compound C1=C(O)C=CC2=C1OC(=O)C=C2C HSHNITRMYYLLCV-UHFFFAOYSA-N 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- 102000012440 Acetylcholinesterase Human genes 0.000 description 1
- 108010022752 Acetylcholinesterase Proteins 0.000 description 1
- 244000291564 Allium cepa Species 0.000 description 1
- 235000010167 Allium cepa var aggregatum Nutrition 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- 239000005886 Chlorantraniliprole Substances 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000927584 Frankliniella occidentalis Species 0.000 description 1
- 241000258937 Hemiptera Species 0.000 description 1
- 239000005906 Imidacloprid Substances 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- 241000721621 Myzus persicae Species 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- 241000500441 Plutellidae Species 0.000 description 1
- 241000344246 Tetranychus cinnabarinus Species 0.000 description 1
- 241000131345 Tipula <genus> Species 0.000 description 1
- 229940022698 acetylcholinesterase Drugs 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000000078 anti-malarial effect Effects 0.000 description 1
- 230000002155 anti-virotic effect Effects 0.000 description 1
- 239000003430 antimalarial agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- FXRDPPFLWGSMQT-UHFFFAOYSA-N benzo[f]chromen-3-one Chemical compound C1=CC=C2C(C=CC(O3)=O)=C3C=CC2=C1 FXRDPPFLWGSMQT-UHFFFAOYSA-N 0.000 description 1
- 238000004166 bioassay Methods 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- PSOVNZZNOMJUBI-UHFFFAOYSA-N chlorantraniliprole Chemical compound CNC(=O)C1=CC(Cl)=CC(C)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl PSOVNZZNOMJUBI-UHFFFAOYSA-N 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001647 drug administration Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 1
- 229940056881 imidacloprid Drugs 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention belongs to the field of pesticides, and discloses a coumarin group-containing benzothiazole derivative, a preparation method and an application thereof, wherein the derivative has a structure shown in a formula (I):
Description
Technical Field
The invention relates to the field of pesticides, in particular to a benzothiazole derivative containing coumarin groups, a preparation method of the derivative and application of the derivative in preventing and controlling agricultural pests.
Background
Agricultural pests are widely distributed, quickly outbreak, difficult to control, and some kinds of harmful insects also have the characteristics of wide host range, short generation period, quick propagation and the like, seriously affect the yield and quality of agricultural products, and cause huge economic loss to agricultural production. Currently, chemical control still occupies the major position in the comprehensive control of agricultural pests, but some existing agents have high toxicity, relatively single action targets and improper use, so that the problem of drug resistance of insects is increasingly prominent, and the use and development of pesticides are limited. Therefore, the development of a novel high-efficiency, low-toxicity and environment-friendly pesticide has important significance for preventing and treating agricultural pests, ensuring the safety of crops and increasing the yield of grains.
The compounds containing coumarin group have broad-spectrum biological activity such as antivirus, anticancer, antimalarial, antioxidant, insecticidal, bacteriostatic and the like, and are gradually favored by drug manufacturers. Recent researches show that the compounds have acetylcholinesterase inhibitory activity, the enzyme is an important enzyme in the nervous system of insects, and the research on the inhibitory (poisoning) effect of the compounds on the insects has great application prospect. Meanwhile, the benzothiazole compound serving as an important benzo-heterocycle compound has the characteristics of various structures, simplicity and convenience in synthesis and wide activity spectrum, and has wide application in the fields of pesticides and medicines.
According to the invention, an active substructure splicing method is applied, a coumarin group and a benzothiazole group with broad-spectrum activity are organically combined in the same molecular structure through an alkyl chain, a series of benzothiazole derivatives containing the coumarin group are designed and synthesized, and biological assay finds that the derivatives have obvious insecticidal activity.
Disclosure of Invention
The invention aims to provide a benzothiazole derivative containing coumarin groups.
The invention also aims to provide a preparation method of the benzothiazole derivative containing coumarin groups.
The 3 rd object of the present invention is to provide the use of the above derivatives.
The invention provides a benzothiazole derivative containing coumarin group with the structure shown in the general formula (I),
in formula (I), the various groups and symbols have the definitions as set forth below:
R1selected from hydrogen, C1-12Alkyl, halogen;
R2selected from hydrogen, C1-12Alkyl radical, C1-12Alkoxy, halogen;
n is selected from any 1 integer from 1 to 12;
y represents the attachment position of the oxygen atom to which it is attached on the benzene ring, and the position is selected from the ortho-position, meta-position, and para-position of the benzene ring.
In formula (I), the various groups and symbols have the preferred definitions as set out below:
R1selected from hydrogen, C1-6An alkyl group;
R2selected from hydrogen, C1-6An alkoxy group;
n is selected from any 1 integer from 2 to 6;
y represents the attachment position of the oxygen atom to which it is attached to the benzene ring, and the attachment position is selected from the meta-position and the para-position of the benzene ring.
In formula (I), the various groups and symbols have the further preferred definitions as described below:
R1selected from H, CH3；
R2Selected from H, OCH3；
n is selected from any 1 integer from 2 to 6;
y represents the attachment position of the oxygen atom to which it is attached to the benzene ring, and the attachment position is selected from the meta-position and the para-position of the benzene ring. In formula (I), the various groups and symbols have the particularly preferred definitions as set forth in table 1 below:
TABLE 1 numbering of the Compounds (I) and corresponding structures
In a second aspect of the present invention, there is provided a method for preparing a coumarin group-containing benzothiazole derivative of formula (I), which comprises reacting a compound of formula (II) with a compound of formula (III) to prepare a coumarin group-containing benzothiazole derivative of formula (I), wherein the reaction formula is represented by the following general formula (a):
wherein in each of the above structural formulae:
R1、R2n and Y have the definitions of the corresponding groups and codes as described above.
The benzothiazole derivative containing coumarin group in the formula (I) is synthesized by the following steps:
dissolving the compound of the formula (II) and an equivalent amount of the compound of the formula (III) in DMF, adding excessive potassium carbonate, reacting for 4-6h at 60-70 ℃, adding water with the volume of 1.2-1.5 times that of the DMF, extracting for 3 times by using ethyl acetate, washing an extract with saturated saline solution for 3 times, drying, distilling to remove the solvent, and purifying by column chromatography to obtain the coumarin group-containing benzothiazole derivative of the formula (I).
The third aspect of the invention relates to the application of the benzothiazole derivative containing coumarin group in the formula (I), which is characterized in that the benzothiazole derivative is applied to the aspect of controlling agricultural pests and can be applied to the field of pesticides as insecticides.
The derivatives of formula (I) provided by the invention can be used for controlling various agricultural pests, such as thysanoptera, lepidoptera, diptera and homoptera pests, and mites. The composition can be used for preventing and treating Frankliniella occidentalis, Thrips shallot (Prisner), diamondback moth (Pierisrapaeline), cabbage caterpillar (Nilaparvata lugens), root maggot (Tipula praepotenes), Chironomica oryzae Matsumura, cotton aphid (Aphis gossypii), cabbage aphid (Lipophis eryimi), broad bean aphid (Aphis fabae), brown planthopper (Plutella xylostella), Tetranychus cinnabarinus (Tenuis cinnabarinus), and the like.
The invention relates to the use of derivatives of formula (I), which are characterized by being suitable for controlling lepidopteran and homopteran agricultural pests. The composition can be specifically used for preventing and treating plutella xylostella, cabbage caterpillar, cotton aphid, cabbage aphid, broad bean aphid and the like.
The invention relates to the use of derivatives of formula (I), which are characterized by being particularly suitable for controlling diamondback moth and aphis fabae.
Has the advantages that:
1. the benzothiazole derivative containing coumarin group in the formula (I) has a novel molecular structure and a clear structural formula, wherein the structural formula contains two active groups of benzothiazole phenyl and benzopyran-2-one which are connected through 1 dioxy alkylene.
2. The preparation method of the coumarin group-containing benzothiazole derivative of the formula (I) is characterized in that 2- (bromoalkoxyphenyl) benzothiazole (formula II) and 7-hydroxy-2H-benzopyran-2-ketone (formula III) react to prepare the coumarin group-containing benzothiazole derivative, and the reaction raw materials are easy to obtain, short in reaction time, simple and convenient to operate and high in yield.
3. The benzothiazole derivative containing coumarin groups in the formula (I) shows obvious activity of preventing and controlling agricultural pests and has application as a pesticide.
Detailed Description
The essential features of the invention can be seen from the following examples, which should not be construed as limiting the invention in any way.
Preparation examples
Example 1: 7- (2- (3- (benzo [ d ]))]Thiazol-2-yl) phenoxy) ethoxy) -2H-benzopyran-2-one (1) Preparation of
Dissolving 2- (3- (2-bromoethoxy) phenyl) benzothiazole (0.55g, 1.6mmol) and 7-hydroxy-2H-benzopyran-2-one (0.26g, 1.6mmol) in DMF, adding potassium carbonate (0.415g, 3mmol), reacting for 4H, adding water with the volume 1.5 times that of the DMF into the reaction solution, extracting with ethyl acetate for 3 times, washing the extract with saturated saline solution for 3 times, drying, distilling to remove the solvent, and purifying by column chromatography to obtain 7- (2- (3- (benzo [ d ] thiazol-2-yl) phenoxy) ethoxy) -2H-benzopyran-2-one (1).
Example 2: 7- (6- (3- (benzo [ d ]))]Thiazol-2-yl) phenoxy) hexyloxy) -4-methyl-2H-benzopyran-
Preparation of 2-ketone (10)
Dissolving 2- (3- (6-bromohexyloxy) phenyl) benzothiazole (0.48g, 1.2mmol) and 7-hydroxy-4-methyl-2H-benzopyran-2-one (0.21g, 1.2mmol) in DMF, adding potassium carbonate (0.415g, 3mmol), reacting for 6H, adding water with the volume of 1.5 times that of the DMF into the reaction solution, extracting with ethyl acetate for 3 times, washing the extract with saturated saline solution for 3 times, drying, distilling to remove the solvent, and purifying by column chromatography to obtain 7- (6- (3- (benzo [ d ] thiazol-2-yl) phenoxy) hexyloxy) -4-methyl-2H-benzopyran-2-one (10).
Example 3: 7- (5- (4- (benzo [ d ]))]Thiazol-2-yl) phenoxy) pentyloxy) -2H-benzopyran-2-one (14)
Preparation of
Dissolving 2- (4- (5-bromopentyloxy) phenyl) benzothiazole (0.55g, 1.46mmol) and 7-hydroxy-2H-benzopyran-2-one (0.23g, 1.46mmol) in DMF, adding potassium carbonate (0.55g, 4mmol), reacting for 4H, adding water with the volume 1.5 times that of the DMF into the reaction solution, extracting with ethyl acetate for 3 times, washing the extract with saturated saline for 3 times, drying, distilling to remove the solvent, and purifying by column chromatography to obtain 7- (5- (4- (benzo [ d ] thiazol-2-yl) phenoxy) pentyloxy) -2H-benzopyran-2-one (14).
Fruit of Chinese wolfberryExample 4: 7- (4- (4- (benzo [ d ]))]Thiazol-2-yl) -2-methoxyphenoxy) butoxy) -2H-benzopyran Preparation of pyran-2-one (23)
2- (4- (4-bromobutoxy) -3-methoxyphenyl) benzothiazole (0.56g, 1.4mmol) and 7-hydroxy-2H-benzopyran-2-one (0.23g, 1.4mmol) are dissolved in DMF, potassium carbonate (0.55g, 4mmol) is added, reaction is carried out for 6H, water with the volume 1.5 times that of DMF is added to the reaction solution, extraction is carried out for 3 times with ethyl acetate, the extract is washed with saturated brine for 3 times, drying and solvent removal by distillation are carried out, and purification is carried out by column chromatography to obtain 7- (4- (4- (benzo [ d ] thiazol-2-yl) -2-methoxyphenoxy) butoxy) -2H-benzopyran-2-one (23).
Using the procedures of examples 1 to 4 above, coumarin group-containing benzothiazole derivatives of formula (I) 1 to 30 were prepared:
7- (2- (3- (benzo [ d ]))]Thiazol-2-yl) phenoxy) ethoxy) -2H-chromen-2-one (1): a white powder; the yield is 71.2%; melting point 183-185 deg.C;1H NMR(400MHz，DMSO-d6)δ：8.17(d，J＝7.8Hz，1H)，8.08(d，J＝7.8Hz，1H)，8.00(t，J＝14.0Hz，1H)，7.73-7.63(m，3H)，7.61-7.41(m，3H)，7.27-7.19(m，1H)，7.11(d，J＝2.3Hz，1H)，7.03(dt，J＝12.7，4.7Hz，1H)，6.31(d，J＝9.5Hz，1H)，4.50(s，4H)；13C NMR(101MHz，CDCl3)δ：167.68，161.77，161.14，158.95，155.83，154.03，143.35，135.09，135.02，130.21，128.88，126.40，125.34，123.28，121.67，120.85，118.00，113.40，113.04，112.90，112.81，101.66，67.09，66.48；EI-MS，m/z：415[M]+；Anal Calcd.for C24H17NO4S(415.09)。
7- (3- (3- (benzo [ d ]))]Thiazol-2-yl) phenoxyYl) propoxy) -2H-chromen-2-one (2): a white powder; the yield is 56.2%; melting point 176 and 178 ℃;1H NMR(400MHz，DMSO-d6)δ：8.15(d，J＝7.9Hz，1H)，8.08(d，J＝8.0Hz，1H)，7.99(d，J＝9.5Hz，1H)，7.64(t，J＝7.8Hz，3H)，7.56(t，J＝7.5Hz，1H)，7.53-7.43(m，2H)，7.24-7.14(m，1H)，7.09-6.93(m，2H)，6.29(d，J＝9.5Hz，1H)，4.29(dd，J＝14.3，6.3Hz，4H)，2.26(dd，J＝12.1，6.0Hz，2H)；13C NMR(101MHz，CDCl3)δ：167.83，162.07，161.23，159.24，155.87，154.03，143.40，135.08，134.94，130.13，128.79，126.37，125.29，123.25，121.65，120.46，117.77，113.12，112.84，112.65，101.54，64.97，64.33，29.07；EI-MS，m/z：429[M]+；Anal Calcd.for C25H19NO48(429.10)。
7- (4- (3- (benzo [ d ]))]Thiazol-2-yl) phenoxy) butoxy) -2H-chromen-2-one (3): a white powder; the yield is 68.7%; melting point 123-;1H NMR(400MHz，DMSO-d6)δ：8.15(t，J＝7.0Hz，1H)，8.07(d，J＝8.1Hz，1H)，7.99(d，J＝9.5Hz，1H)，7.68-7.59(m，3H)，7.56(t，J＝7.6Hz，1H)，7.49(td，J＝7.6，3.9Hz，2H)，7.17(d，J＝6.0Hz，1H)，7.02(s，1H)，6.97(d，J＝8.6Hz，1H)，6.28(d，J＝9.5Hz，1H)，4.19(s，4H)，1.97(d，J＝17.6Hz，4H)；13C NMR(101MHz，CDCl3)δ：167.90，162.23，161.25，159.39，155.92，154.05，143.41，135.09，134.91，130.09，128.76，126.35，125.28，123.24，121.65，120.27，117.68，113.02，112.92，112.76，112.51，101.40，68.13，67.61，25.90，25.86；EI-MS，m/z：443[M]+.Anal Calcd.for C26H21NO4S(443.12)。
7- (5- (3- (benzo [ d ]))]Thiazol-2-yl) phenoxy) pentyloxy) -2H-benzopyran-2-one (4): a white powder; the yield is 47.5%; melting point 143-145 ℃;1H NMR(400MHz，DMSO-d6)δ：8.16(d，J＝7.9Hz，1H)，8.08(d，J＝8.1Hz，1H)，7.99(d，J＝9.5Hz，1H)，7.69-7.59(m，3H)，7.56(t，J＝7.6Hz，1H)，7.49(dd，J＝10.9，5.0Hz，2H)，7.16(d，J＝8.2Hz，1H)，7.03-6.92(m，2H)，6.28(d，J＝9.5Hz，1H)，4.13(t，J＝6.3Hz，4H)，1.89-1.78(m，4H)，1.67-1.57(m，2H)；13C NMR(101MHz，CDCl3)δ：168.02，162.32，161.28，159.51，155.92，153.93，143.43，135.02，134.80，130.08，128.74，126.38，125.29，123.21，121.64，120.22，117.79，112.97，112.75，112.46，101.37，68.41，67.92，28.97，28.76，22.73；EI-MS，m/z：457[M]+；Anal Calcd.for C27H23NO4S(457.13)。
7- (6- (3- (benzo [ d ]))]Thiazol-2-yl) phenoxy) hexyloxy) -2H-chromen-2-one (5): a white powder; the yield is 47.8%; melting point 134-137 deg.C;1H NMR(400MHz，DMSO-d6)δ：8.14(d，J＝7.9Hz，1H)，8.07(d，J＝8.0Hz，1H)，7.97(d，J＝9.5Hz，1H)，7.59(ddd，J＝21.6，14.1，7.7Hz，4H)，7.47(t，J＝7.7Hz，2H)，7.15(d，J＝8.1Hz，1H)，7.00-6.87(m，2H)，6.27(d，J＝9.5Hz，1H)，4.09(d，J＝5.9Hz，4H)，1.78(d，J＝5.3Hz，4H)，1.51(s，4H)；13C NMR(101MHz，CDCl3)δ：167.97，162.36，161.28，159.56，155.90，154.06，143.45，135.08，134.85，130.05，128.73，126.34，125.25，123.23，121.64，120.11，117.69，112.92，112.77，112.40，101.33，68.46，67.99，29.17，28.94，25.84，25.77；EI-MS，m/z：471[M]+；Anal Calcd.for C28H25NO4S(471.15)。
7- (2- (3- (benzo [ d ]))]Thiazol-2-yl) phenoxy) ethoxy) -4-methyl-2H-chromen-2-one (6): a white powder; the yield is 65.7%; melting point 189-191 deg.C;1H NMR(400MHz，DMSO-d6)δ：8.17(dd，J＝7.5，4.5Hz，1H)，8.09(t，J＝7.2Hz，1H)，7.85-7.61(m，3H)，7.62-7.43(m，3H)，7.33-7.15(m，1H)，7.10(d，J＝2.4Hz，1H)，7.07-7.02(m，1H)，6.23(s，1H)，4.59-4.41(m，4H)，2.41(s，3H)；13C NMR(101MHz，CDCl3)δ：167.69，161.59，161.25，158.96，155.22，154.03，152.51，135.09，135.01，130.21，126.40，125.65，125.34，123.28，121.67，120.84，118.00，112.82，112.73，112.22，101.65，67.04，66.50，18.68；EI-MS，m/z：429[M]+；Anal Calcd.for C25H19NO4S(429.10)。
7- (3- (3- (benzo [ d ]))]Thiazol-2-yl) phenoxy) propoxy) -4-methyl-2H-chromen-2-one (7): a white powder; the yield is 53.5%; melting point 117-;1H NMR(400MHz，DMSO-d6)δ：8.15(d，J＝8.0Hz，1H)，8.08(d，J＝8.1Hz，1H)，7.72-7.60(m，3H)，7.56(t，J＝7.7Hz，1H)，7.52-7.43(m，2H)，7.20(d，J＝9.0Hz，1H)，7.03(dd，J＝9.9，5.2Hz，2H)，6.21(s，1H)，4.29(dd，J＝13.6，6.5Hz，4H)，2.39(s，3H)，2.31-2.21(m，2H)；13C NMR(101MHz，CDCl3)δ：167.85，161.88，161.29，159.26，155.26，153.99，152.51，135.06，134.91，130.13，126.37，125.55，125.30，123.24，121.64，120.46，117.82，113.67，112.65，112.51，112.01，101.56，64.91，64.36，29.10，18.66；EI，MS，m/z：443[M]+；Anal Calcd.for C26H21NO4S(443.12)。
7- (4- (3- (benzo [ d ]))]Thiazol-2-yl) phenoxy) butoxy) -4-methyl-2H-benzopyran-2-one (8): a white powder; the yield is 78.3%; melting point 142-144 ℃;1H NMR(400MHz，DMSO-d6)δ：8.14(t，J＝6.4Hz，1H)，8.07(d，J＝8.0Hz，1H)，7.71-7.61(m，2H)，7.57(dd，J＝15.3，7.2Hz，2H)，7.48(td，J＝7.5，3.8Hz，2H)，7.17(dd，J＝8.2，1.6Hz，1H)，6.98(dd，J＝12.8，4.1Hz，2H)，6.19(s，1H)，4.19(s，4H)，2.38(s，3H)，1.95(s，4H)；13C NMR(101MHz，CDCl3)δ：167.86，162.01，161.31，159.38，155.24，154.04，152.58，135.07，134.86，130.08，126.34，125.52，125.27，123.22，121.65，120.22，117.62，113.50，112.77，112.53，111.84，101.37，68.06，67.62，25.88，18.62；EI-MS，m/z：457[M]+；Anal Calcd.for C27H23NO4S(457.13)。
7- (5- (3- (benzo [ d ]))]Thiazol-2-yl) phenoxyYl) pentyloxy) -4-methyl-2H-chromen-2-one (9): a white powder; the yield is 44.6%; melting point 114-;1H NMR(400MHz，DMSO-d6)δ：8.14(d，J＝7.8Hz，1H)，8.06(d，J＝8.0Hz，1H)，7.66-7.52(m，4H)，7.47(t，J＝7.8Hz，2H)，7.15(dd，J＝8.2，2.1Hz，1H)，6.98-6.91(m，2H)，6.19(t，J＝2.9Hz，1H)，4.11(t，J＝5.8Hz，4H)，2.37(s，3H)，1.89-1.78(m，4H)，1.66-1.50(m，2H)；13C NMR(101MHz，CDCl3)δ：167.98，162.12，161.35，159.50，155.29，153.96，152.58，135.03，134.81，130.07，126.36，125.50，125.28，123.21，121.64，120.19，117.76，113.48，112.75，112.62，111.85，101.37，68.35，67.92，28.97，28.77，22.73，18.66；EI-MS，m/z：471[M]+；Anal Calcd.for C28H25NO4S(471.15)。
7- (6- (3- (benzo [ d ]))]Thiazol-2-yl) phenoxy) hexyloxy) -4-methyl-2H-chromen-2-one (10): a white powder; the yield is 56.6%; melting point 128-;1H NMR(400MHz，DMSO-d6)δ：8.15(d，J＝7.8Hz，1H)，8.07(d，J＝8.1Hz，1H)，7.70-7.59(m，3H)，7.56(t，J＝7.6Hz，1H)，7.48(t，J＝7.6Hz，2H)，7.16(d，J＝8.1Hz，1H)，6.96(d，J＝10.3Hz，2H)，6.20(s，1H)，4.10(t，J＝5.8Hz，4H)，2.38(s，3H)，1.79(d，J＝4.9Hz，4H)，1.52(s，4H)；13C NMR(101MHz，CDCl3)δ：167.97，162.16，161.37，159.56，155.25，154.04，152.63，135.06，134.82，130.04，126.33，125.48，125.25，123.21，121.64，120.09，117.69，113.40，112.76，112.60，111.77，101.33，68.40，67.99，29.16，28.95，25.84，25.77，18.63；EI-MS，m/z：485[M]+；Anal Calcd.for C29H27NO4S(485.17)。
7- (2- (4- (benzo [ d ]))]Thiazol-2-yl) phenoxy) ethoxy) -2H-chromen-2-one (11): a white powder; the yield is 60.3%; melting point 217-219 ℃;1H NMR(400MHz，DMSO-d6)δ：8.11(t，J＝8.1Hz，1H)，8.09-7.95(m，4H)，7.66(d，J＝8.6Hz，1H)，7.53(t，J＝7.5Hz，1H)，7.44(t，J＝7.4Hz，1H)，7.19(d，J＝8.6Hz，2H)，7.10(s，1H)，7.03(d，J＝8.5Hz，1H)，6.32(d，J＝9.5Hz，1H)，4.49(s，4H)；13C NMR(101MHz，CDCl3)δ：167.64，161.71，161.09，160.74，155.83，154.19，143.32，134.88，129.19，128.89，127.03，126.28，124.92，122.89，121.55，116.98，115.04，113.45，113.02，112.94，101.62，66.96，66.37；EI-MS，m/z：415[M]+.Anal Calcd.for C24H17NO4S(415.09)。
7- (3- (4- (benzo [ d ]))]Thiazol-2-yl) phenoxy) propoxy) -2H-chromen-2-one (12): a white powder; the yield is 64.5%; melting point 175-177 ℃;1H NMR(400MHz，DMSO-d6)δ：8.12(d，J＝7.9Hz，1H)，8.07-7.96(m，4H)，7.64(d，J＝8.6Hz，1H)，7.53(t，J＝7.2Hz，1H)，7.43(t，J＝7.6Hz，1H)，7.16(d，J＝8.8Hz，2H)，7.05(d，J＝2.2Hz，1H)，7.00(dd，J＝8.6，2.3Hz，1H)，6.30(d，J＝9.5Hz，1H)，4.27(dd，J＝14.1，6.3Hz，4H)，2.29-2.20(m，2H)；13C NMR(101MHz，CDCl3)δ：167.76，162.02，161.18，161.09，155.88，154.21，143.37，134.87，129.15，128.81，126.63，126.24，124.85，122.84，121.53，114.89，113.18，112.81，112.66，101.53，64.92，64.33，28.99；EI-MS，m/z：429[M]+；Anal Calcd.for C25H19NO4S(429.10)。
7- (4- (4- (benzo [ d ]))]Thiazol-2-yl) phenoxy) butoxy) -2H-chromen-2-one (13): a white powder; the yield is 60.5%; melting point 158-160 ℃;1H NMR(400MHz，DMSO-d6)δ：8.11(d，J＝7.9Hz，1H)，8.02(dd，J＝14.2，9.0Hz，4H)，7.63(d，J＝8.6Hz，1H)，7.53(t，J＝7.4Hz，1H)，7.43(t，J＝7.5Hz，1H)，7.13(d，J＝8.8Hz，2H)，7.02(d，J＝2.0Hz，1H)，6.97(dd，J＝8.6，2.3Hz，1H)，6.29(d，J＝9.5Hz，1H)，4.17(d，J＝4.8Hz，4H)，1.93(s，4H)；13C NMR(101MHz，CDCl3)δ：167.86，162.20，161.27，155.92，154.22，143.42，134.86，129.15，128.78，126.46，126.23，124.83，122.82，121.53，114.86，113.09，112.94，112.55，101.38，68.11，67.59，25.88，25.81；EI-MS，m/z：443[M]+；Anal Calcd.for C26H21NO4S(443.12)。
7- (5- (4- (benzo [ d ]))]Thiazol-2-yl) phenoxy) pentyloxy) -2H-benzopyran-2-one (14): a gray powder; the yield is 68.4%; melting point 149-151 deg.C;1H NMR(400MHz，DMSO-d6)δ：8.11(t，J＝6.5Hz，1H)，8.06-7.96(m，4H)，7.62(d，J＝8.6Hz，1H)，7.52(dd，J＝11.2，4.1Hz，1H)，7.43(t，J＝7.1Hz，1H)，7.12(d，J＝8.8Hz，2H)，7.03-6.90(m，2H)，6.28(d，J＝9.5Hz，1H)，4.11(dd，J＝10.4，6.2Hz，4H)，1.83(dt，J＝13.4，6.5Hz，4H)，1.60(dt，J＝14.8，7.4Hz，2H)；13C NMR(101MHz，CDCl3)δ：167.85，162.26，161.39，161.25，155.86，154.21，143.46，134.83，129.09，128.77，126.27，126.22，124.81，122.78，121.53，114.86，112.88，112.44，101.31，68.34，67.88，28.88，28.74，22.67；EI-MS，m/z：457[M]+；Anal Calcd.for C27H23NO4S(457.13)。
7- (6- (4- (benzo [ d ]))]Thiazol-2-yl) phenoxy) hexyloxy) -2H-chromen-2-one (15): a gray powder; the yield is 57.8%; melting point 143-145 ℃;1H NMR(400MHz，DMSO-d6)δ：8.11(d，J＝7.9Hz，1H)，8.06-7.94(m，4H)，7.62(d，J＝8.6Hz，1H)，7.52(t，J＝7.6Hz，1H)，7.43(t，J＝7.5Hz，1H)，7.11(d，J＝8.7Hz，2H)，6.95(dd，J＝15.1，6.5Hz，2H)，6.28(d，J＝9.5Hz，1H)，4.08(d，J＝3.7Hz，4H)，1.78(s，4H)，1.50(s，4H)；13C NMR(101MHz，CDCl3)δ：167.90，162.35，161.46，161.28，155.91，154.23，143.45，134.85，129.10，128.74，126.27，126.21，124.79，122.79，121.52，114.86，112.94，112.43，101.33，68.45，67.99，29.09，28.92，25.80，25.77；EI-MS，m/z：471[M]+；Anal Calcd.for C28H25NO4S(471.15)。
7- (2- (4- (benzo [ d ]))]Thiazol-2-yl) phenoxy) ethoxy) -4-methylyl-2H-chromen-2-one (16): a white powder; the yield is 62.3%; melting point 227-;1H NMR(400MHz，DMSO-d6)δ：8.13(d，J＝7.8Hz，1H)，8.04(dd，J＝15.4，8.3Hz，3H)，7.72(d，J＝8.7Hz，1H)，7.53(t，J＝7.5Hz，1H)，7.44(t，J＝7.5Hz，1H)，7.21(t，J＝7.2Hz，2H)，7.07(dd，J＝16.9，5.5Hz，2H)，6.24(s，1H)，4.49(s，4H)，2.42(s，3H)；13C NMR(101MHz，CDCl3)δ：167.66，161.53，161.22，160.75，155.19，154.17，152.48，134.87，129.20，127.02，126.28，125.67，124.92，122.88，121.55，116.99，115.05，114.01，112.73，112.27，101.62，66.92，66.40，18.68；EI-MS，m/z：429[M]+；Anal Calcd.for C25H19NO4S(429.10)。
7- (3- (4- (benzo [ d ]))]Thiazol-2-yl) phenoxy) propoxy) -4-methyl-2H-chromen-2-one (17): a white powder; the yield is 66.8%; melting point 129-132 deg.C;1H NMR(400MHz，DMSO-d6)δ：8.11(d，J＝7.8Hz，1H)，8.02(t，J＝8.4Hz，3H)，7.68(d，J＝8.7Hz，1H)，7.52(t，J＝7.2Hz，1H)，7.43(t，J＝7.3Hz，1H)，7.15(d，J＝8.8Hz，2H)，7.05-6.95(m，2H)，6.21(s，1H)，4.27(dd，J＝13.3，6.4Hz，4H)，2.39(s，3H)，2.29-2.17(m，2H)；13C NMR(101MHz，CDCl3)δ：167.75，161.81，161.27，161.10，155.21，154.19，152.56，134.84，129.12，126.56，126.23，125.58，124.85，122.81，121.53，114.88，113.67，112.43，111.97，101.51，64.86，64.37，28.99，18.62；EI-MS，m/z：443[M]+；Anal Calcd.for C26H21NO4S(443.12)。
7- (4- (4- (benzo [ d ]))]Thiazol-2-yl) phenoxy) butoxy) -4-methyl-2H-benzopyran-2-one (18): a white powder; the yield is 67.5%; melting point 175-;1H NMR(400MHz，DMSO-d6)δ：8.12(d，J＝7.9Hz，1H)，8.02(t，J＝7.9Hz，3H)，7.68(d，J＝8.7Hz，1H)，7.52(dd，J＝11.2，4.1Hz，1H)，7.43(t，J＝7.6Hz，1H)，7.13(d，J＝8.8Hz，2H)，7.04-6.93(m，2H)，6.21(d，J＝0.9Hz，1H)，4.16(t，J＝11.0Hz，4H)，2.40(s，3H)，1.93(s，4H)；13C NMR(101MHz，CDCl3)δ：167.83，161.99，161.33，161.28，155.26，154.21，152.60，134.84，129.12，126.40，126.22，125.55，124.82，122.80，121.53，114.85，113.55，112.56，111.89，101.36，68.05，67.61，25.87，25.80，18.64；EI-MS，m/z：457[M]+；Anal Calcd.for C27H23NO4S(457.13)。
7- (5- (4- (benzo [ d ]))]Thiazol-2-yl) phenoxy) pentyloxy) -4-methyl-2H-benzopyran-2-one (19): a gray powder; the yield is 54.5%; melting point 132-;1H NMR(400MHz，DMSO-d6)δ：8.11(d，J＝7.8Hz，1H)，8.02(dd，J＝7.8，4.3Hz，3H)，7.67(d，J＝8.7Hz，1H)，7.52(t，J＝7.4Hz，1H)，7.43(t，J＝7.4Hz，1H)，7.12(d，J＝8.7Hz，2H)，7.02-6.92(m，2H)，6.20(s，1H)，4.19-4.03(m，4H)，2.39(s，3H)，1.92-1.76(m，4H)，1.68-1.54(m，2H)；13C NMR(101MHz，CDCl3)δ：167.83，162.05，161.38，161.32，155.20，154.18，152.64，134.81，129.07，126.24，126.21，125.51，124.80，122.76，121.52，114.84，113.43，112.52，111.76，101.31，68.27，67.88，28.88，28.74，22.66，18.60；EI-MS，m/z：471[M]+；Anal Calcd.for C28H25NO4S(471.15)。
7- (6- (4- (benzo [ d ]))]Thiazol-2-yl) phenoxy) hexyloxy) -4-methyl-2H-chromen-2-one (20): a brown-yellow powder; the yield is 50.2%; melting point 157-;1H NMR(400MHz，DMSO-d6)δ：8.11(d，J＝7.6Hz，1H)，7.99(d，J＝21.0Hz，3H)，7.67(d，J＝8.3Hz，1H)，7.52(d，J＝7.5Hz，1H)，7.44(d，J＝7.4Hz，1H)，7.11(d，J＝8.0Hz，2H)，6.96(d，J＝11.0Hz，2H)，6.20(s，1H)，4.09(s，4H)，2.39(s，3H)，1.72(s，4H)，1.47(s，4H)；13C NMR(101MHz，CDCl3)δ：167.89，162.14，161.46，161.36，155.25，154.21，152.64，134.83，129.08，126.22，126.21，125.50，124.79，122.77，121.52，114.86，113.43，112.60，111.79，101.32，68.38，67.98，29.08，28.93，25.79，25.76，18.63；EI-MS，m/z：485[M]+；Anal Calcd.for C29H27NO4S(485.17)。
7- (2- (4- (benzo [ d ]))]Thiazol-2-yl) -2-methoxyphenoxy) ethoxy) -2H-chromen-2-one (21): a white powder; the yield is 63.7%; melting point 207-;1H NMR(400MHz，DMSO-d6)δ：8.12(d，J＝8.1Hz，1H)，8.03(t，J＝8.1Hz，2H)，7.71-7.60(m，3H)，7.54(t，J＝7.1Hz，1H)，7.44(t，J＝7.6Hz，1H)，7.22(d，J＝8.4Hz，1H)，7.13(d，J＝2.3Hz，1H)，7.03(dd，J＝8.6，2.4Hz，1H)，6.32(d，J＝9.5Hz，1H)，4.50(d，J＝5.1Hz，2H)，4.45(d，J＝4.9Hz，2H)，3.90(s，3H)；13C NMR(101MHz，CDCl3)δ：167.74，161.81，161.15，155.83，154.13，150.45，149.99，143.34，134.95，128.80，127.67，126.30，125.00，122.92，121.55，120.98，113.54，113.42，113.11，112.91，110.49，101.84，67.54，67.09，56.19；EI-MS，m/z：445[M]+；Anal Calcd.for C25H19NO5S(445.10)。
7- (3- (4- (benzo [ d ]))]Thiazol-2-yl) -2-methoxyphenoxy) propoxy) -2H-chromen-2-one (22): a white powder; the yield is 61.9%; melting point 161-163 ℃;1H NMR(400MHz，DMSO-d6)δ：8.11(d，J＝7.8Hz，1H)，8.01(dd，J＝14.6，8.8Hz，2H)，7.62(dd，J＝14.3，11.0Hz，3H)，7.53(t，J＝7.5Hz，1H)，7.43(t，J＝7.4Hz，1H)，7.16(d，J＝8.4Hz，1H)，7.05(s，1H)，6.99(d，J＝8.6Hz，1H)，6.29(d，J＝9.5Hz，1H)，4.32-4.18(m，4H)，3.91(s，3H)，2.30-2.18(m，2H)；13C NMR(101MHz，CDCl3)δ：167.86，162.06，161.20，155.88，154.14，150.79，149.75，143.38，134.92，128.77，127.00，126.26，124.93，122.86，121.53，121.05，113.14，112.88，112.73，112.62，110.25，101.53，65.34，64.99，56.17，28.97.EI-MS，m/z：459[M]+；Anal Calcd.for C26H21NO5S(459.11)。
7- (4- (4- (benzo [ d ]))]Thiazol-2-yl) -2-methoxyphenoxy) butoxy) -2H-chromen-2-one (23): a white powder; the yield is 58.1%; melting point 142-144 ℃;1H NMR(400MHz，DMSO-d6)δ：8.11(d，J＝7.9Hz，1H)，8.01(dd，J＝14.9，8.8Hz，2H)，7.68-7.57(m，3H)，7.53(t，J＝7.7Hz，1H)，7.43(t，J＝7.6Hz，1H)，7.15(d，J＝8.4Hz，1H)，7.01(s，1H)，6.97-6.95(m，1H)，6.29(d，J＝9.5Hz，1H)，4.17(d，J＝15.5Hz，4H)，3.90(s，3H)，1.94(s，4H)；13C NMR(101MHz，CDCl3)δ：167.89，162.22，161.20，155.88，154.14，150.93，149.65，143.42，134.90，128.74，126.70，126.24，124.89，122.82，121.53，121.08，112.96，112.90，112.46，112.38，110.15，101.31，68.55，68.18，56.16，25.94，25.72；EI-MS，m/z：473[M]+；Anal Calcd.for C27H23NO5S(473.10)。
7- (5- (4- (benzo [ d ]))]Thiazol-2-yl) -2-methoxyphenoxy) pentyloxy) -2H-chromen-2-one (24): a white powder; the yield is 66.3%; melting point 116-;1H NMR(400MHz，DMSO-d6)δ：8.10(t，J＝6.5Hz，1H)，8.06-7.98(m，1H)，7.97(d，J＝6.5Hz，1H)，7.61(ddd，J＝10.3，7.4，2.0Hz，3H)，7.53(t，J＝7.7Hz，1H)，7.43(t，J＝7.6Hz，1H)，7.14(d，J＝8.4Hz，1H)，6.99(dd，J＝8.7，3.6Hz，1H)，6.96(dd，J＝8.6，2.4Hz，1H)，6.28(d，J＝9.5Hz，1H)，4.18-3.99(m，4H)，3.90(s，3H)，1.92-1.74(m，4H)，1.60(dt，J＝15.1，7.7Hz，2H)；13C NMR(101MHz，CDCl3)δ：167.98，162.35，161.26，155.92，154.16，151.14，149.66，143.43，134.90，128.72，126.55，126.23，124.87，122.82，121.52，121.12，112.95，112.41，112.38，110.19，101.32，68.85，68.44，56.21，29.00，28.90，25.75；EI-MS，m/z：487[M]+；Anal Calcd.for C28H25NO5S(487.15)。
7- (6- (4- (benzo [ d ]))]Thiazol-2-yl) -2-methoxyphenoxy) hexyloxy) -2H-chromen-2-one (25): a yellow-white powder; the yield is 46.5%; melting point 125-126 ℃;1H NMR(400MHz，DMSO-d6)δ：8.11(d，J＝7.9Hz，1H)，8.01(dd，J＝16.6，8.8Hz，2H)，7.70-7.56(m，3H)，7.53(t，J＝7.3Hz，1H)，7.43(t，J＝7.5Hz，1H)，7.13(d，J＝8.4Hz，1H)，7.01-6.88(m，2H)，6.28(d，J＝9.5Hz，1H)，4.07(dq，J＝12.2，6.8Hz，4H)，3.89(s，3H)，1.79(d，J＝5.2Hz，4H)，1.51(s，4H)；13C NMR(101MHz，CDCl3)δ：167.94，162.56，162.27，161.26，155.84，154.10，151.05，149.63，143.4，134.85，128.76，126.55，126.22，124.87，122.77，121.51，121.10，112.86，112.42，110.17，101.32，68.74，68.31，56.18，36.46，31.41，28.73，22.60；EI-MS，m/z：501[M]+；Anal Calcd.for C29H27NO5S(501.16)。
7- (2- (4- (benzo [ d ]))]Thiazol-2-yl) -2-methoxyphenoxy) ethoxy) -4-methyl-2H-chromen-2-one (26): a white powder; the yield is 68.4%; melting point 218-220 ℃;1H NMR(400MHz，DMSO-d6)δ：8.12(d，J＝7.9Hz，1H)，8.04(d，J＝8.1Hz，1H)，7.74-7.60(m，3H)，7.54(t，J＝7.6Hz，1H)，7.44(t，J＝7.6Hz，1H)，7.23(t，J＝7.8Hz，1H)，7.12(d，J＝2.4Hz，1H)，7.05(dd，J＝8.8，2.4Hz，1H)，6.24(s，1H)，4.53-4.42(m，4H)，3.90(s，3H)，2.42(s，3H)；13C NMR(101MHz，CDCl3)δ：167.74，161.61，161.25，155.20，154.12，152.50，150.48，149.98，134.94，127.62，126.30，125.58，125.00，122.91，121.55，120.99，113.95，113.52，112.77，112.21，110.47，101.82，67.54，67.02，56.19，18.67；EI-MS，m/z：459[M]+；Anal Calcd.for C26H21NO5S(459.11)。
7- (3- (4- (benzo [ d ]))]Thiazol-2-yl) -2-methoxyphenoxy) propoxy) -4-methyl-2H-chromen-2-one (27): a white powder; the yield is 60.2%; melting point 156-;1H NMR(400MHz，DMSO-d6)δ：8.11(d，J＝7.9Hz，1H)，8.03(d，J＝8.1Hz，1H)，7.71-7.63(m，2H)，7.60(d，J＝7.9Hz，1H)，7.53(t，J＝7.5Hz，1H)，7.43(t，J＝7.5Hz，1H)，7.18(d，J＝8.4Hz，1H)，7.04-6.97(m，2H)，6.21(s，1H)，4.32-4.20(m，4H)，3.91(s，3H)，2.39(s，3H)，2.30-2.18(m，2H)；13C NMR(101MHz，CDCl3)δ：167.84，161.85，161.28，155.22，154.12，152.54，150.81，149.73，134.89，126.93，126.25，125.53，124.91，122.83，121.52，121.04，113.63，112.73，112.51，111.95，110.22，101.52，65.35，64.93，56.16，28.98，18.62；EI-MS，m/z：473[M]+；Anal Calcd.for C27H23NO5S(473.10)。
7- (4- (4- (benzo [ d ]))]Thiazol-2-yl) -2-methoxyphenoxy) butoxy) -4-methyl-2H-chromen-2-one (28): a yellow-white powder; the yield is 48.7%; melting point 123-;1H NMR(400MHz，DMSO-d6)δ：8.11(d，J＝7.9Hz，1H)，8.03(d，J＝8.2Hz，1H)，7.71-7.63(m，2H)，7.61(d，J＝8.2Hz，1H)，7.53(t，J＝7.6Hz，1H)，7.44(t，J＝7.5Hz，1H)，7.15(d，J＝8.4Hz，1H)，7.05-6.93(m，2H)，6.21(s，1H)，4.15(t，J＝16.7Hz，4H)，3.90(s，3H)，2.40(s，3H)，1.94(s，4H)；13C NMR(101MHz，CDCl3)δ：167.94，162.05，161.36，155.28，154.14，152.60，150.92，149.67，134.90，126.72，126.25，125.50，124.90，122.83，121.52，121.08，113.51，112.65，112.41，111.88，110.18，101.33，68.57，68.13，56.18，25.94，25.72，18.65；EI-MS，m/z：487[M]+；Anal Calcd.for C28H25NO5S(487.15)。
7- (5- (4- (benzo [ d ]))]Thiazol-2-yl) -2-methoxyphenoxy) pentyloxy) -4-methyl-2H-benzopyran-2-one (29): a white powder; the yield is 56.5%; melting point 126-;1H NMR(400MHz，DMSO-d6)δ：8.11(d，J＝7.9Hz，1H)，8.03(d，J＝8.1Hz，1H)，7.73-7.62(m，2H)，7.58(t，J＝10.1Hz，1H)，7.53(t，J＝7.6Hz，1H)，7.43(t，J＝7.6Hz，1H)，7.13(d，J＝8.3Hz，1H)，6.97(d，J＝13.6Hz，2H)，6.20(s，1H)，4.15-4.06(m，4H)，3.90(s，3H)，2.38(s，3H)，1.89-1.76(m，4H)，1.61(dd，J＝14.5，7.7Hz，2H)；13C NMR(101MHz，CDCl3)δ：167.94，162.09，161.31，155.26，154.12，152.57，151.07，149.66，134.88，126.59，126.23，125.49，124.88，122.80，121.51，121.11，113.46，112.54，112.43，111.83，110.18，101.36，68.77，68.27，56.20，28.78，28.75，22.62，18.63；EI-MS，m/z：501[M]+；Anal Calcd.for C29H27NO5S(501.16)。
7- (6- (4- (benzo [ d ]))]Thiazol-2-yl) -2-methoxyphenoxy) hexyloxy) -4-methyl-2H-chromen-2-one (30): a white powder; the yield is 54.2%; melting point 118-;1H NMR(400MHz，DMSO-d6)δ：8.11(d，J＝7.9Hz，1H)，8.03(d，J＝8.1Hz，1H)，7.70-7.62(m，2H)，7.58(t，J＝9.9Hz，1H)，7.53(t，J＝7.6Hz，1H)，7.43(t，J＝7.6Hz，1H)，7.12(d，J＝8.4Hz，1H)，6.96(d，J＝9.8Hz，2H)，6.20(s，1H)，4.07(dt，J＝18.5，9.2Hz，4H)，3.89(s，3H)，2.38(s，3H)，1.79(d，J＝5.0Hz，4H)，1.51(s，4H)；13C NMR(101MHz，CDCl3)δ：167.97，162.15，161.34，155.27，154.15，152.59，151.14，149.64，134.89，126.52，126.22，125.48，124.86，122.80，121.51，121.11，113.42，112.61，112.37，111.80，110.17，101.31，68.84，68.37，56.20，28.99，28.90，25.75，25.73，18.63；EI-MS，m/z：515[M]+；Anal Calcd.for C30H29NO5S(515.18)。
examples of the use
Example 5: the invention relates to a benzothiazole derivative containing coumarin group and having the formula (I) for killing agricultural pests
Activity assay
The insecticidal activity of the benzothiazole derivative containing coumarin groups in the formula (I) is measured by taking Plutella xylostella and Aphis fabae as target insects, respectively adopting a leaf-soaking disc method and a seedling-soaking method, and taking chlorantraniliprole and imidacloprid as contrast agents.
The specific determination method is as follows:
leaf-soaking dish method: weighing 10mg of original drug, dissolving the original drug in 1mL of DMF, and then adding 0.5 per mill of Tween water to a constant volume of 25mL to prepare 400mg/L mother liquor. Each treatment was repeated 3 times with a blank control. Soaking fresh cabbage leaf dish in the medicinal liquid for 10 s, taking out and naturally drying. 3 leaf discs are placed in each culture dish, 10 third-instar plutella xylostella larvae are inoculated, and the culture dish is placed in a thermostatic chamber at 25 ℃ for culture, and the relative humidity is kept to be about 55 percent. The number of dead and live insects 5 days after the drug administration was investigated and subjected to statistical analysis.
A seedling soaking method: and (3) cultivating broad beans indoors, raising heads when the broad beans emerge, inoculating 5 heads to each broad bean, and removing adult aphids after 24 hours until the adult aphids produce nymphs. If aphid is raised indoors for 3 days, the test is carried out. Weighing 10mg of original drug, dissolving the original drug in 1mL of DMF, and then adding 0.5 per mill of Tween water to a constant volume of 25mL to prepare 400mg/L mother liquor. Each treatment was repeated 3 times with a blank control. Soaking the young broad bean with Myzus persicae in the medicinal liquid for 10 s, taking out, inserting into penicillin bottle filled with clear water, culturing in 25 deg.C thermostatic chamber, and maintaining relative humidity at about 55%. The results were observed 3 days after dosing, and the number of dead and live worms was examined and statistically analyzed.
The results of the insecticidal activity measurement are shown in Table 2, and the coumarin group-containing benzothiazole derivatives of formula (I) show significant insecticidal activity at a concentration of 400 mg/L. The poisoning effect of the compounds 3, 6, 7, 9, 14, 15, 16, 20, 21 and 29 on diamond back moths reaches over 50 percent, wherein the poisoning effect of the compounds 3, 6, 14, 21 and 29 reaches over 80 percent. The poisoning effect of the compounds 1-10, 12-15, 18, 19, 22, 23, 25, 26 and 28-30 on the aphis fabae reaches over 50 percent, wherein the poisoning effect of the compounds 1, 5, 7, 8, 10, 12, 15, 22, 23 and 28-30 reaches over 80 percent.
TABLE 2 insecticidal Activity measurement data of coumarin group-containing benzothiazole derivatives of formula (I)
Table notes (release):a10mg/L，b200mg/L，c400mg/L，d4mg/L
those of ordinary skill in the art will understand that: the invention is not to be considered as limited to the specific embodiments thereof, but is to be understood as being modified in all respects, all changes and equivalents that come within the spirit and scope of the invention.
Claims (8)
1. A benzothiazole derivative containing coumarin group in the formula (I),
wherein,
R1selected from hydrogen, C1-12Alkyl, halogen;
R2selected from hydrogen, C1-12Alkyl radical, C1-12Alkoxy, halogen;
n is selected from any 1 integer from 1 to 12;
the connecting position of the oxygen atom represented by Y is selected from ortho-position, meta-position and para-position of a benzene ring.
2. A coumarin group-containing benzothiazole derivative according to claim 1, wherein:
R1selected from hydrogen, C1-6An alkyl group;
R2selected from hydrogen, C1-6An alkoxy group;
n is selected from any 1 integer from 2 to 6;
the oxygen atom bonding position represented by Y is selected from meta-position and para-position of benzene ring.
3. A coumarin group-containing benzothiazole derivative according to claim 2, characterized in that:
R1selected from H, CH3；
R2Selected from H, OCH3；
n is selected from any 1 integer from 2 to 6;
the oxygen atom bonding position represented by Y is selected from meta-position and para-position of benzene ring.
4. A coumarin group-containing benzothiazole derivative according to claim 3, characterized in that it is one of the following compounds:
7- (2- (3- (benzo [ d ] thiazol-2-yl) phenoxy) ethoxy) -2H-benzopyran-2-one,
7- (3- (3- (benzo [ d ] thiazol-2-yl) phenoxy) propoxy) -2H-benzopyran-2-one,
7- (4- (3- (benzo [ d ] thiazol-2-yl) phenoxy) butoxy) -2H-benzopyran-2-one,
7- (5- (3- (benzo [ d ] thiazol-2-yl) phenoxy) pentyloxy) -2H-benzopyran-2-one,
7- (6- (3- (benzo [ d ] thiazol-2-yl) phenoxy) hexyloxy) -2H-benzopyran-2-one,
7- (2- (3- (benzo [ d ] thiazol-2-yl) phenoxy) ethoxy) -4-methyl-2H-benzopyran-2-one,
7- (3- (3- (benzo [ d ] thiazol-2-yl) phenoxy) propoxy) -4-methyl-2H-benzopyran-2-one,
7- (4- (3- (benzo [ d ] thiazol-2-yl) phenoxy) butoxy) -4-methyl-2H-benzopyran-2-one,
7- (5- (3- (benzo [ d ] thiazol-2-yl) phenoxy) pentyloxy) -4-methyl-2H-benzopyran-2-one,
7- (6- (3- (benzo [ d ] thiazol-2-yl) phenoxy) hexyloxy) -4-methyl-2H-benzopyran-2-one,
7- (2- (4- (benzo [ d ] thiazol-2-yl) phenoxy) ethoxy) -2H-benzopyran-2-one,
7- (3- (4- (benzo [ d ] thiazol-2-yl) phenoxy) propoxy) -2H-benzopyran-2-one,
7- (4- (4- (benzo [ d ] thiazol-2-yl) phenoxy) butoxy) -2H-benzopyran-2-one,
7- (5- (4- (benzo [ d ] thiazol-2-yl) phenoxy) pentyloxy) -2H-benzopyran-2-one,
7- (6- (4- (benzo [ d ] thiazol-2-yl) phenoxy) hexyloxy) -2H-benzopyran-2-one,
7- (2- (4- (benzo [ d ] thiazol-2-yl) phenoxy) ethoxy) -4-methyl-2H-benzopyran-2-one,
7- (3- (4- (benzo [ d ] thiazol-2-yl) phenoxy) propoxy) -4-methyl-2H-benzopyran-2-one,
7- (4- (4- (benzo [ d ] thiazol-2-yl) phenoxy) butoxy) -4-methyl-2H-benzopyran-2-one,
7- (5- (4- (benzo [ d ] thiazol-2-yl) phenoxy) pentyloxy) -4-methyl-2H-benzopyran-2-one,
7- (6- (4- (benzo [ d ] thiazol-2-yl) phenoxy) hexyloxy) -4-methyl-2H-benzopyran-2-one,
7- (2- (4- (benzo [ d ] thiazol-2-yl) -2-methoxyphenoxy) ethoxy) -2H-benzopyran-2-one,
7- (3- (4- (benzo [ d ] thiazol-2-yl) -2-methoxyphenoxy) propoxy) -2H-benzopyran-2-one,
7- (4- (4- (benzo [ d ] thiazol-2-yl) -2-methoxyphenoxy) butoxy) -2H-benzopyran-2-one,
7- (5- (4- (benzo [ d ] thiazol-2-yl) -2-methoxyphenoxy) pentyloxy) -2H-benzopyran-2-one,
7- (6- (4- (benzo [ d ] thiazol-2-yl) -2-methoxyphenoxy) hexyloxy) -2H-benzopyran-2-one,
7- (2- (4- (benzo [ d ] thiazol-2-yl) -2-methoxyphenoxy) ethoxy) -4-methyl-2H-benzopyran-2-one,
7- (3- (4- (benzo [ d ] thiazol-2-yl) -2-methoxyphenoxy) propoxy) -4-methyl-2H-benzopyran-2-one,
7- (4- (4- (benzo [ d ] thiazol-2-yl) -2-methoxyphenoxy) butoxy) -4-methyl-2H-benzopyran-2-one,
7- (5- (4- (benzo [ d ] thiazol-2-yl) -2-methoxyphenoxy) pentyloxy) -4-methyl-2H-benzopyran-2-one,
7- (6- (4- (benzo [ d ] thiazol-2-yl) -2-methoxyphenoxy) hexyloxy) -4-methyl-2H-chromen-2-one.
5. A process for producing a coumarin group-containing benzothiazole derivative according to any one of claims 1 to 4, which comprises the steps of:
wherein in each of the above structural formulae:
R1、R2n, Y each have the meaning as claimed in any of claims 1 to 4.
6. Use of a coumarin group-containing benzothiazole derivative according to any one of claims 1 to 4 for producing an agricultural pest control agent.
7. Use according to claim 6, characterized in that the use of a coumarin group-containing benzothiazole derivative according to any one of claims 1 to 4 for the preparation of a formulation for controlling lepidopteran, homopteran agricultural pests.
8. The use according to claim 7, characterized in that the use of the coumarin group-containing benzothiazole derivatives according to any one of claims 1 to 4 for preparing a preparation for controlling diamondback moth and aphis fabae.
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| CN1616448A (en) * | 2003-11-11 | 2005-05-18 | 沈阳化工研究院 | Benzopyrone compounds with pest killing and sterilizing activity and preparation and use |
| CN1802372A (en) * | 2003-06-11 | 2006-07-12 | 麦克弗罗斯特加拿大有限公司 | 7-[(1,3-thiazol-2-yl)thio]-coumarin derivatives and their use as leukotriene biosynthesis inhibitors |
| CN101747306A (en) * | 2008-11-28 | 2010-06-23 | 中国中化集团公司 | Substituent ether compound and application thereof |
| CN101747276A (en) * | 2008-11-28 | 2010-06-23 | 中国中化集团公司 | Ether compound with nitrogenous quinary alloy and application thereof |
| CN101935291A (en) * | 2010-09-13 | 2011-01-05 | 中化蓝天集团有限公司 | Cyano phthalic diamide compounds, preparation method thereof and use thereof as agricultural chemical pesticide |
| CN105753808A (en) * | 2014-12-18 | 2016-07-13 | 湖南化工研究院有限公司 | Thiazole amide compounds, preparing method thereof and applications of the compounds |
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| CN1802372A (en) * | 2003-06-11 | 2006-07-12 | 麦克弗罗斯特加拿大有限公司 | 7-[(1,3-thiazol-2-yl)thio]-coumarin derivatives and their use as leukotriene biosynthesis inhibitors |
| CN1616448A (en) * | 2003-11-11 | 2005-05-18 | 沈阳化工研究院 | Benzopyrone compounds with pest killing and sterilizing activity and preparation and use |
| CN101747306A (en) * | 2008-11-28 | 2010-06-23 | 中国中化集团公司 | Substituent ether compound and application thereof |
| CN101747276A (en) * | 2008-11-28 | 2010-06-23 | 中国中化集团公司 | Ether compound with nitrogenous quinary alloy and application thereof |
| CN101935291A (en) * | 2010-09-13 | 2011-01-05 | 中化蓝天集团有限公司 | Cyano phthalic diamide compounds, preparation method thereof and use thereof as agricultural chemical pesticide |
| CN105753808A (en) * | 2014-12-18 | 2016-07-13 | 湖南化工研究院有限公司 | Thiazole amide compounds, preparing method thereof and applications of the compounds |
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