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Preparation method of compound containing C (sp2)-N bonds

A compound, C3-C6 technology, used in the production of bulk chemicals, electrolysis processes, electrolysis components, etc., can solve problems such as poor selectivity and the use of large oxidants

Active Publication Date: 2019-01-04
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The technical problem to be solved by the present invention is to overcome the C(sp 2 )-H bond into C(sp 2 )-N bonds have poor selectivity, use a large number of oxidants and other defects, and provide a C(sp 2 The preparation method of )-N bond compound; This preparation method can obtain by C(sp 2 )-H bond compound is transformed into C(sp 2 )-N bond product; the method has mild reaction conditions, environmental friendliness, high yield, good purity, and is suitable for industrialized production

Method used

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  • Preparation method of compound containing C (sp2)-N bonds
  • Preparation method of compound containing C (sp2)-N bonds
  • Preparation method of compound containing C (sp2)-N bonds

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Experimental program
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Effect test

Embodiment 1-1

[0100]

[0101] Pyridinamide substrate 1a (39.6mg, 0.2mmol), morpholine (69.7mg, 0.8mmol), copper trifluoromethanesulfonate (7.3mg, 0.02mmol), potassium pivalate ( 56 mg, 0.4 mmol), tetrabutylammonium iodide (36.9 mg, 0.1 mmol) and acetonitrile (2 mL). Then add platinum sheets (1.5×1.0cm) to the cathode and anode respectively 2 ) electrode, pass a current of 3.0mA, and continue electrolysis at 27°C for 24h. After the reaction was completed, the solvent was suspended to dryness under reduced pressure, and then separated and purified by silica gel column chromatography to obtain a colorless solid 3a (48.7 mg, 0.172 mol, yield 86%, purity greater than 95%). 1 H NMR (400MHz, CDCl 3 ):δ11.06(s,1H),8.57-8.54(m,2H),8.21(d,J=7.6Hz,1H),7.79(td,J=7.6,1.6Hz,1H),7.37(ddd, J=7.6,4.8,0.8Hz,1H),7.13-6.99(m,3H),3.89(t,J=4.4Hz,4H),2.85(t,J=4.4Hz,4H). 13 C NMR (100MHz, CDCl 3 ): δ161.7, 150.3, 148.2, 141.8, 137.58, 132.9, 126.3, 125.1, 124.0, 122.2, 120.0, 119.4, 67.5, 52.3.

Embodiment 1-2

[0103]

[0104] With the above reaction conditions, starting from 1e (0.2 mmol), a colorless solid 3e (55.9 mg, yield 84%, purity greater than 95%) could be obtained. 1 H NMR (400MHz, CDCl 3 ): δ11.34(s,1H),9.27(s,1H),8.70(s,1H),8.67(dd,J=8.0,0.8Hz,1H),8.59(d,J=8.0Hz,1H) ,8.00(d,J=8.4Hz,1H),7.79-7.69(m,2H),7.24-7.09(m,3H),4.03(t,J=4.4Hz,4H),2.98(t,J=4.4 Hz,4H). 13 C NMR (100MHz, CDCl 3 ): δ162.4, 151.2, 144.2, 141.8, 136.1, 133.2, 131.1, 129.7, 129.0, 128.2, 127.7, 125.3, 123.9, 120.6, 120.0, 119.7, 67.7, 52.4.

Embodiment 1-3

[0106]

[0107] With the same reaction conditions as above, starting from 1f (0.2 mmol), a white solid 3f (48.3 mg, yield 85%, purity greater than 95%) can be obtained. 1 H NMR (400MHz, CDCl 3 ):δ10.91(s,1H),9.51(s,1H),8.80(d,J=2.4Hz,1H),8.64-8.63(m,1H),8.56(d,J=8.0Hz,1H) ,7.23-7.11(m,3H),3.95(t,J=4.4Hz,4H),2.94(t,J=4.0Hz,4H). 13 C NMR (100MHz, CDCl 3 ): δ160.5, 147.4, 145.1, 144.7, 142.7, 141.8, 132.6, 125.5, 124.6, 120.4, 119.6, 67.6, 52.5.

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Abstract

The invention discloses a preparation method of a compound containing C (sp2)-N bonds as shown in a formula I. The preparation method includes the step: performing constant-current electrolysis reaction on a compound as shown in a formula II and a compound as shown in a formula III in the presence of copper catalysts, oxidation reduction catalysts and alkali reagents in organic solvents in a non-separation electrolytic tank to obtain the compound containing the C (sp2)-N bonds as shown in the formula I, wherein the oxidation reduction catalysts are iodized salt. According to the preparation method, conventional expensive oxidants can be omitted, the compound containing the C (sp2)-N bonds can be selectively transformed into a C (sp2)-N bond product, and the compound is high in yield, goodin purity and more suitable for industrial production.

Description

technical field [0001] The present invention relates to a kind of containing C (sp 2 )-N bond compound preparation method. Background technique [0002] Under catalytic conditions, aromatic C(sp 2 )-H into C(sp 2 )-N bond has always been one of the very important challenges in synthetic chemistry. Over the past decade, transition-metal-catalyzed regioselective C–H functionalization has emerged as an effective method for constructing C–C bonds and C–X (heteroatom) bonds. Especially under the catalysis conditions of cheap metal Cu(II), the research on the reaction of C-H bond conversion into C-N bond has received a lot of attention, as reported in the following non-patent literature: (a) Shang, M.; Sun, S.-Z.; Wang, H.-L. Wang, M.-M.; Dai, H.-X. Synthesis 2016, 48, 4381. (b) Rao, W.-H.; Shi B.-F. Org. Chem. Front.2016,3,1028.(c)Chen,X.;Hao,X.-S.;Goodhue,C.E.;Yu,J.-Q.J.Am.Chem.Soc.2006,128,6790.(d)Uemura , T.; Imoto, S.; Chatani, N. Chem. Lett. 2006, 35, 842. (e) Li, G.; ...

Claims

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Application Information

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IPC IPC(8): C25B3/10C25B3/29
CPCC25B3/29Y02P20/55
Inventor 梅天胜杨启亮
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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