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A palladium-catalyzed o-tolylamide γ-c-(sp 3 ) The synthetic method of h sulfur/selenoethers

A technology for o-toluidine amide and tolylamide, which is applied in the field of palladium-catalyzed synthesis of o-toluidine amide γ-C-H sulfur/selenide compounds, can solve problems such as poor atom economy, and achieve high selectivity and product yield High and wide substrate applicability

Active Publication Date: 2021-07-27
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] C-H functionalization is an important means to construct thioether compounds, but the research direction of this method mainly focuses on the ortho C(sp 2 )-H activation and C(sp 2 )-S bond construction, C(sp3)-H often has a large reaction inertness in organic research due to its stable bond energy, and requires multi-step reactions to achieve its functionalization and poor atom economy. Direct functionalization reaction has always been the focus and difficulty of research

Method used

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  • A palladium-catalyzed o-tolylamide γ-c-(sp <sup>3</sup> ) The synthetic method of h sulfur/selenoethers
  • A palladium-catalyzed o-tolylamide γ-c-(sp <sup>3</sup> ) The synthetic method of h sulfur/selenoethers
  • A palladium-catalyzed o-tolylamide γ-c-(sp <sup>3</sup> ) The synthetic method of h sulfur/selenoethers

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030]

[0031] Add N-(o-tolyl) pyridine amide (4.24 grams, 20.0mmol), diphenyl disulfide (2.61 grams, 0.6eq), palladium acetate (449.0 milligrams, 10mol%), potassium acetate ( 3.92 g, 2.0 eq) and tert-butyl hydroperoxide (5.84 g, 2.0 eq), toluene (200.0 mL). Stir at 120 °C for 16.0 h under air atmosphere. Then the mixture was cooled to room temperature, filtered after cooling and concentrated under reduced pressure. Purified by silica gel column chromatography (developing solvent: petroleum ether: ethyl acetate = 40:1) to obtain 4.54 g of the target product as a colorless transparent oil, with a yield of 71%.

[0032] 1 H NMR (400MHz, CDCl 3 )δ10.68(s,1H),8.58(d,J=4.6Hz,1H),8.33(d,J=7.8Hz,1H),8.26(d,J=8.1Hz,1H),7.93(td, J=7.7,1.2Hz,1H),7.53–7.47(m,3H),7.38(t,J=7.4Hz,1H),7.32(t,J=7.1Hz,2H),7.26(d,J=7.2 Hz,1H),7.20 (d,J=7.3Hz,1H),7.09(t,J=7.5Hz,1H),4.24(s,2H). 13 C NMR (101MHz, CDCl 3 )δ162.36, 150.00, 148.13, 137.58, 136.12, 135.14, 131.80, 130.47, 128.90, 128.66, 12...

Embodiment 2

[0034]

[0035] Add N-(o-tolyl) pyridine amide (4.24 grams, 20.0mmol), p-toluene disulfide (2.95 grams, 0.6eq), palladium acetate (359.2 mg, 8mol%), potassium acetate ( 3.92 g, 2.0 eq) and tert-butyl hydroperoxide (5.84 g, 2.0 eq), p-xylene (100.0 mL). Stirred at 120°C for 12.0h under air atmosphere. Then the mixture was cooled to room temperature, filtered after cooling and concentrated under reduced pressure. Purified by silica gel column chromatography (developing solvent: petroleum ether: ethyl acetate = 40:1) to obtain 4.56 g of the target product as a colorless transparent oil, with a yield of 68%.

[0036] 1 H NMR (400MHz, CDCl 3)δ10.68(s,1H),8.65(d,J=4.4Hz,1H),8.35(d,J=7.8Hz,1H),8.27(d,J=8.1Hz,1H),7.95(t, J=7.2Hz, 1H), 7.53(dd, J=7.1, 4.8 Hz, 1H), 7.43(d, J=7.9Hz, 2H), 7.38(d, J=7.6Hz, 1H), 7.19(d, J=7.2Hz,1H), 7.15–7.09(m,3H),4.20(s,2H),2.36(s,3H). 13 C NMR (101MHz, CDCl 3 )δ162.35, 150.08, 148.13, 137.59, 137.54, 136.10, 132.57, 131.27, 130.48, 129.66, 128....

Embodiment 3

[0038]

[0039] Add N-(o-tolyl)pyridine amide (4.24 grams, 20.0mmol), 4,4'-dimethoxydiphenyl disulfide (3.90 grams, 0.7eq), palladium acetate (538.8 mg, 12mol%), potassium acetate (3.92g, 2.0eq) and tert-butyl hydroperoxide (5.84g, 2.0eq), toluene (80.0ml). Stirred at 110°C for 18.0h under air atmosphere. Then the mixture was cooled to room temperature, filtered after cooling and concentrated under reduced pressure. Purified by silica gel column chromatography (developing solvent: petroleum ether: ethyl acetate = 40:1) to obtain 5.4 g of the target product as a colorless transparent oil, with a yield of 77%.

[0040] 1 H NMR (400MHz, CDCl 3 )δ10.65(s,1H),8.69(d,J=4.3Hz,1H),8.36(d,J=7.8Hz,1H),8.27(d,J=8.0Hz,1H),7.99–7.93( m,1H),7.54(dd,J=6.9,5.2Hz,1H),7.46(d,J=8.6Hz,2H),7.41–7.35(m,1H),7.09(t,J=7.1Hz,2H ),6.84(d,J=8.6Hz,2H),4.14(s,2H),3.83(s,3H). 13 C NMR (101MHz, CDCl 3 )δ162.35, 159.72,150.11,148.13,137.56,136.01,135.34,130.53,128.85,128.46,127.29, 126.42,124.59,122...

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Abstract

The invention discloses a palladium-catalyzed synthesis method of o-tolylamide γ-C-(sp3)H sulfur / selenoether compounds. The method comprises: combining the compound represented by formula (I) with formula (III) The compound shown is dissolved in an organic solvent, and under the action of a catalyst, an oxidant, and an alkaline substance, reacts at a temperature of 100 to 130° C. for 8-24 hours. After the reaction, the resulting reaction solution is post-processed to obtain the formula (II ) shown in γ‑C(sp 3 )‑H sulfur / selenide compounds. The present invention successfully realizes γ-C(sp for the first time) 3 The direct synthesis of )-H sulfur / selenoether compounds avoids the use of high-risk and high-toxic compounds such as benzyl bromide and thiophenol in traditional methods, and has few side reactions. At the same time, the product can be synthesized into sulfone compounds and corresponding hydrolyzed products with high application value through simple oxidation and hydrolysis. Therefore, the invention has the advantages of simple operation, mild reaction conditions, high selectivity, high product yield and wide substrate applicability, and is an efficient organic synthesis means.

Description

technical field [0001] The invention relates to a palladium-catalyzed synthesis method of o-tolylamide gamma-C-(sp3)H sulfur / selenoether compounds, belonging to the field of organic synthesis. Background technique [0002] Thioether compounds have a wide range of biological activities, and are the key components of many drugs and active intermediates, such as the dibenzoxazepine atypical antipsychotic quetiapine. At the same time, thioethers are also key intermediates for the construction of sulfone drugs or active substances, and the oxidation of thioethers is one of the common methods for synthesizing sulfone compounds. Therefore, obtaining thioether compounds quickly and efficiently has always been a hot spot of concern. [0003] The traditional method is to use the nucleophilic substitution reaction between thiophenol and benzyl bromide to synthesize thioether compounds, but there are many by-products, difficult preparation of raw materials and high toxicity. In modern...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D213/81C07D215/48C07D217/26C07D231/56
CPCC07D213/81C07D215/48C07D217/26C07D231/56
Inventor 谢媛媛侯加浩王凯程科
Owner ZHEJIANG UNIV OF TECH
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