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Method for preparing 1, 2-diketone by catalyzing and oxidizing alkynes

A technology for catalytic oxidation and alkynes, which is used in the preparation of carbonyl compounds by oxidation, chemical instruments and methods, preparation of organic compounds, etc., to achieve the effects of wide range of use, excellent yield, and mild reaction conditions

Inactive Publication Date: 2010-01-13
SUZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] However, in actual research, it is found that it is difficult to solve the above problems simply by replacing the oxidizing agent, and it is necessary to find an efficient catalytic system that can cooperate with the corresponding oxidizing agent to make the reaction mild and economical.

Method used

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  • Method for preparing 1, 2-diketone by catalyzing and oxidizing alkynes
  • Method for preparing 1, 2-diketone by catalyzing and oxidizing alkynes
  • Method for preparing 1, 2-diketone by catalyzing and oxidizing alkynes

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Experimental program
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Effect test

Embodiment 1

[0022]

[0023] Ru(PPh 3 ) 3 Cl 2 (0.001% mmol), tert-butanol peroxide (7.3 mmol), compound 1a (2 mmol, 356 mg), 1,4-dioxane (10 mL). Then the system was heated in an oil bath at 80°C in the air for about 12 hours, extracted with ethyl acetate (40mL×3), and the oxidation product 2a could be obtained by simple column chromatography. When the cocatalyst was selected as 10mol% I 2 (condition a), the yield is 96.5%; when using 10mol% ICl (condition b), the yield is 76.3%; when using 10mol% IBr (condition c), the yield is 72.4%; when using 10mol% KI (condition d), the yield is 52.6%; when using 10mol% KBr (condition e), the yield is 44.7%; when using 10mol%Bu 4 NI (condition f), yield 83.4%.

[0024] mp: 94-95°C; 1 H NMR (CDCl 3 , 400MHz): δ7.48-7.51(m, 4H), 7.62-7.66(m, 2H), 7.96-7.98(m, 4H); 13 C NMR (CDCl 3 , 100MHz): δ128.9, 129.8, 132.8, 134.9, 194.5; MS (C 14 h 10 o 2 ): 210; IR (KBr, cm -1 ): v1660.

Embodiment 2

[0026]

[0027] Ru(PPh 3 ) 3 Cl 2 (0.001% mmol), iodine (0.2 mmol, 51.0 mg), compound 1b (2 mmol, 417 mg), tert-butanol peroxide (7.3 mmol), 1,4-dioxane (10 mL). Then the system was heated in an oil bath at 100° C. in air for about 10 hours, extracted with ethyl acetate (40 mL×3), and the oxidation product 2b was obtained by simple column chromatography with a yield of 93.5%. Yellow solid; mp: 53-54°C; Yield: 96%; 1H NMR (CDCl 3 , 400MHz): δ3.86(s, 3H), 6.95-6.99(m, 2H), 7.46-7.51(m, 2H), 7.61-7.63(m, 1H), 7.92-7.98(m, 4H); 13C NMR (CDCl 3 , 100MHz): δ55.5, 114.3, 125.8, 128.9, 129.7, 132.2, 133.0, 134.7, 164.9, 193.1, 194.8; MS(C 15 h 12 o 3 ): 240. IR (KBr, cm-1): v 1677.

Embodiment 3

[0029]

[0030] Ru 2 (OAc) 4 (0.001% mmol), iodine (0.2 mmol, 51 mg), compound 1c (2 mmol, 316 mg), tert-butanol peroxide (7.3 mmol), 1,4-dioxane (10 mL). Then the system was heated in an oil bath at 80°C in air for about 12 hours, extracted with ethyl acetate (40 mL×3), and the oxidation product 2c was obtained by simple column chromatography with a yield of 68.8%. 1 HNMR (CDCl 3 , 300MHz): δ0.94(t, 3H, J=7.2Hz), 1.37-1.45(m, 2H), 1.64-1.71(m, 2H), 2.86-2.91(m, 2H), 7.50(t, 2H , J=7.2Hz), 7.63(d, 1H, J=9Hz), 7.98(d, 2H, J=7.2Hz); 13 C NMR (CDCl 3 , 300MHz): δ13.79, 22.30, 24.88, 38.49, 128.84, 130.11, 131.96, 134.56, 182.60, 203.55; MS(C 12 h 14 o 2 ): 190.0994; IR (KBr, cm -1 ): v 1712.

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Abstract

The invention belongs to the field of catalysis and oxidization, and particularly discloses a method for preparing 1, 2-diketone by catalyzing and oxidizing alkynes. The method comprises the following steps: taking alkynes R1-C-C-R2 (acetylenic link exists between C and C) as a reaction substrate, taking one of TBHP, m-chloroperoxybenzoic acid and p-benzoquinone as a oxidant, taking one of dichloro (p-cymene) ruthenium (II) dimer, tri (triphenylphosphine) ruthenous chloride, ruthenium acetate, ruthenium dichlorophenyl (II) dimer, ruthenium trichloride, BINAP ruthenous chloride, dodecacarbonyltriruthenium and tricarbonyldichlororuthenium (II) dimer as a catalyst, taking one of iodine, iodine chloride, iodine bromide, potassium iodide, tetrabutyl ammonium iodide and potassium bromide as a cocatalyst, and taking 1, 4-dioxane as a solvent to react under 40 DEG C to 100 DEG C for 4 to 24 h to prepare the 1, 2-diketone. The method is economic, environmental-friendly and mild.

Description

technical field [0001] The invention relates to the field of catalytic oxidation, in particular to a method for catalytically oxidizing alkyne and its derivatives into 1,2-diketone. Background technique [0002] One of the oxidation products of alkynes is 1,2-diketone, which is a very important class of organic compounds. It is not only included in a variety of natural products with physiological activities, but also widely used in the synthesis of other heterocycles. compound. At present, the commonly used oxidants for the oxidation of alkynes mainly include the following types: high-valent metal oxidants (such as potassium permanganate, potassium dichromate), DMSO, osmium tetroxide, peroxides (such as hydrogen peroxide, potassium persulfate), etc. When the above oxidants are used to catalyze the oxidation of alkynes to prepare 1,2-diketones, the reaction conditions are harsh, the selectivity is low, and the substrate usage range is narrow. [0003] For economic and envir...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B41/06C07C45/28C07C49/784C07C49/84C07C49/76C07C49/813C07C49/792C07C49/12C07C255/56C07C253/30C07C205/45C07C201/12C07D333/22C07D213/50B01J31/22B01J31/26B01J27/13B01J31/20
Inventor 贾俊任伟万小兵
Owner SUZHOU UNIV
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