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2-phenoxyl tetrahydrofuran (tetrahydropyrane) derivatives and application thereof in synthesis of penoxsulam

A technology of phenoxytetrahydrofuran and tetrahydrofuran, which is applied in the direction of organic chemistry, can solve the problems of difficult preparation, high price, and low yield, and achieves cheap and easy-to-obtain synthetic raw materials, less by-products, and improved product quality. Yield effect

Active Publication Date: 2015-04-29
CHANGZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0012] This synthetic route seems brief, but the diazotization reaction process wherein can produce a large amount of waste water, makes its pollution control cost very high, and starting material 2-fluoro-6-trifluoromethylaniline is expensive in addition, and self-preparation is difficult ( Many steps, low yield), therefore, prepare penoxsulam with this route, industrial application value is very low

Method used

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  • 2-phenoxyl tetrahydrofuran (tetrahydropyrane) derivatives and application thereof in synthesis of penoxsulam
  • 2-phenoxyl tetrahydrofuran (tetrahydropyrane) derivatives and application thereof in synthesis of penoxsulam
  • 2-phenoxyl tetrahydrofuran (tetrahydropyrane) derivatives and application thereof in synthesis of penoxsulam

Examples

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Effect test

Embodiment 1

[0026] Example 1: 2-(2-(methylthio)-3-(trifluoromethyl)phenoxy)tetrahydrofuran (I-1)

[0027] At room temperature, slowly drop 10 g m-trifluoromethylphenol (61.69 mmol) into 1,4-dioxane (30 mL) dissolved in 2,3-dihydrofuran (14 mL) and anhydrous hydrogen chloride (0.15 g) , stirred overnight, the reaction solution was evaporated to dryness, ethyl acetate (30mL) and saturated sodium bicarbonate solution (30mL) were added to the obtained raffinate, the organic layer was dried over anhydrous sodium sulfate for 2h, then filtered and evaporated to dryness, reduced pressure Distillation gave 13.31 g of the compound 2-(3-(trifluoromethyl)phenoxy)tetrahydrofuran, with a yield of 93%. 1 H NMR (400MH z, CDCl 3 )δ7.41-7.22(m, 4H, Ar-H), 5.49(t, J=3.2Hz, 1H, furan ring hydrogen), 3.82-3.74(m, 2H, furan ring hydrogen), 2.37-2.30(m ,1H,furan ring hydrogen),2.41-2.32(m,1H,furan ring hydrogen),1.92-1.80(m,2H,furan ring hydrogen);ESI-MS:233[M+H + ].

[0028] N 2 Under protection, 2-(3-(tr...

Embodiment 2

[0029]Example 2: 2-(2-(ethylthio)-3-(trifluoromethyl)phenoxy)tetrahydrofuran (I-2)

[0030] With 2-(3-(trifluoromethyl)phenoxy)tetrahydrofuran as raw material, with reference to the method of Example 1, under the action of n-butyllithium, diethyl disulfide is used to react (other raw materials are the same), The target product I-2 was obtained with a yield of 89%, 1 H NMR (400MHz, CDCl 3 )δ7.20(d, 1H, J=8.0Hz, Ar-H), 7.13-7.02(m, 2H, Ar-H), 5.58(t, J=3.2Hz, 1H, furan ring hydrogen), 3.84- 3.72(m, 1H, furan ring hydrogen), 3.64-3.51(m, 1H, furan ring hydrogen), 2.85(q, 2H, CH 2 ,J=6.4Hz),2.42-2.36(m,1H,furan ring hydrogen),2.25-2.17(m,1H,furan ring hydrogen),1.94-1.84(m,2H,furan ring hydrogen),1.30(t, 3H,CH 3 , J=6.4Hz); ESI-MS: 293[M+H + ].

Embodiment 3

[0031] Example 3: 2-(2-(propylthio)-3-(trifluoromethyl)phenoxy)tetrahydrofuran (I-3)

[0032] With 2-(3-(trifluoromethyl)phenoxy)tetrahydrofuran as raw material, with reference to the method of Example 1, under the action of n-butyllithium, dipropyl disulfide is used to react (other raw materials are the same), The target product I-3 was obtained with a yield of 91%, 1 H NMR (400MHz, CDCl 3 )δ7.20(d, 1H, J=8.0Hz, Ar-H), 7.13-7.02(m, 2H, Ar-H), 5.56(t, J=3.2Hz, 1H, furan ring hydrogen), 3.85- 3.73(m, 1H, furan ring hydrogen), 3.63-3.51(m, 1H, furan ring hydrogen), 2.83(t, 2H, CH 2 ,J=6.4Hz), 1.63(m,2H,CH 2 ),1.01(t,3H,CH 3 , J=6.4Hz), 2.41-2.32 (m, 1H, furan ring hydrogen), 2.22-2.16 (m, 1H, furan ring hydrogen), 1.94-1.83 (m, 2H, furan ring hydrogen); ESI-MS: 307[M+H + ].

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Abstract

The invention discloses 2-phenoxyl tetrahydrofuran (tetrahydropyrane) derivatives and the application thereof in synthesis of penoxsulam, and belongs to the field of pesticide synthesis. A new intermediate of a penoxsulam pesticide is synthesized by the derivatives of the design of the invention. A high-toxicity raw material is not required to be used in the preparation of the intermediate; a product is convenient to purify and high in yield; a synthesizing process is environment-friendly; the synthesis cost is low. The penoxsulam pesticide can be prepared conveniently by utilizing the intermediate; the intermediate has a good application prospect. The series of derivatives are easy and convenient to synthesize; compared with the reported penoxsulam intermediate, a low-boiling-point raw material with high toxicity, namely, chloromethyl methyl ether, is not required to be used in the synthesizing process; the safety of the synthesizing process is improved; the derivatives are favorable to industrialized production and application.

Description

technical field [0001] The invention relates to a series of 2-phenoxytetrahydrofuran (pyr)an derivatives, a preparation method and application thereof, and belongs to the field of pesticide synthesis. Background technique [0002] Penoxsulam, chemical name: 2-(2,2-difluoroethoxy)-6-trifluoromethyl-N-(5,8-dimethoxy-[1,2,4] Triazolo[1,5-c]pyrimidin-2-yl)benzenesulfonamide, common name: Penoxsulam, trade name: Daojie, CAS registration number: 219714-96-2, its structural formula is as follows: [0003] [0004] Penoxsulam (Peoxsulam) is an outstanding representative of sulfonylurea (amine) herbicides. It is a post-emergence herbicide successfully developed by Dow Agro Sciences in the United States. It inhibits the synthesis of acetolactate Enzyme (ALS) activity. It was officially registered with the U.S. Environmental Protection Agency in September 2004, and then promoted and applied in the rice-growing areas of the southern United States, and entered my country in 2008. P...

Claims

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Application Information

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IPC IPC(8): C07D307/20C07D309/12C07D487/04
CPCC07D307/20C07D309/12C07D487/04
Inventor 张跃辜顺林严生虎刘建武徐思田沈介发马晓明陈代祥叶志文
Owner CHANGZHOU UNIV
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