Preparation method of oxalate

A technology of oxalate and -br, applied in the field of preparing oxalate, can solve the problem of no green method for synthesizing oxalate, and achieve the effects of easy functionalization, wide substrate versatility, and easy availability of raw materials

Active Publication Date: 2018-11-23
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] (3) Transition metal catalyzed CO and CH 3 The oxidative coupling reaction of OH can only be used to synthesize dimethyl oxalate, and the reaction requires an additional oxidant
[0007] In summary, there is no green method for synthesizing oxalate

Method used

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  • Preparation method of oxalate
  • Preparation method of oxalate
  • Preparation method of oxalate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034]

[0035] Add compound 1a (0.5 mmol, 101.6 mg), compound 2a (2 mmol, 224vL), Eosin Y (0.00 5mol, 3.6 mg), N,N-dimethylformamide into a 25mL Schlenk tube (2 mL); then react for 36 hours in oxygen under the irradiation of a 12W green LED lamp; after the reaction is complete, extract with ethyl acetate (10 mL × 3), dry with anhydrous magnesium sulfate, and remove the solvent with a rotary evaporator. The product 3a can be obtained by silica gel adsorption and simple column chromatography with a yield of 85%. The main test data of the prepared product are as follows. Through analysis, it can be known that the actual synthesized product is consistent with the theoretical analysis.

[0036] 1 H NMR (400 MHz, CDCl 3 ) δ 7.94 – 7.89 (m, 2H), 7.63 (t, J =7.4 Hz, 1H),7.50 (t, J =7.7 Hz, 2H), 5.55 (s, 2H), 4.40 (q, J =7.1 Hz, 2H), 1.40 (t, J =7.2Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 189.79, 156.91, 156.88, 134,10, 133.48,128.84, 127.65, 67.59, 63.35, 13.75; HRMS (ESI-TOF): Anal. ...

Embodiment 2

[0038]

[0039] Add compound 1b (0.5 mmol, 114.2 mg), compound 2a (2 mmol, 224vL), Eosin Y (0.005 mol, 3.6 mg), N,N-dimethylformamide into a 25mL Schlenk tube (2 mL). Then the system was reacted for 36 hours under the irradiation of a 12 W green LED lamp in oxygen. After the reaction, it was extracted with ethyl acetate (10 mL × 3), dried with anhydrous magnesium sulfate, and the solvent was removed with a rotary evaporator and silica gel was adsorbed. The product 3b was obtained by simple column chromatography with a yield of 73%. The main test data of the prepared product are as follows. Through analysis, it can be known that the actual synthesized product is consistent with the theoretical analysis.

[0040] 1 H NMR (400 MHz, CDCl 3 ) δ 8.03-7.97 (m, 1H), 7.66-7.59 (m, 1H), 7.33 --7.27 (m, 1H), 7.24-7.17 (m, 1H), 5.43 (d, J =3.7 Hz, 2H), 4.42 (q, J =7.1 Hz,2H), 1.42 (t, J =7.2 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 188.00, 187.97, 163.65, 161.12, 157.04, 156.91, 136.10, 13...

Embodiment 3

[0042]

[0043] Add compound 1c (0.5 mmol, 119.5 mg), compound 2a (2 mmol, 224vL), Eosin Y (0.005 mol, 3.6 mg), N,N-dimethylformamide to a 25mL Schlenk tube (2 mL). Then the system was reacted for 36 hours under the irradiation of a 12 W green LED lamp in oxygen. After the reaction is complete, extract with ethyl acetate (10 mL × 3), dry with anhydrous magnesium sulfate, remove the solvent with a rotary evaporator, and adsorb on silica gel. The product 3c can be obtained by simple column chromatography with a yield of 90%. The main test data of the prepared product are as follows. Through analysis, it can be known that the actual synthesized product is consistent with the theoretical analysis.

[0044] 1 H NMR (400 MHz, CDCl 3 ) δ 7.50-7.36 (m, 3H), 7.18-7.13 (m, 1H), 5.52(s, 2H), 4.40 (q, J =7.1 Hz, 2H), 3.84 (s, 3H), 1.40 (s, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 189.64, 159.82, 156.88, 134.69, 129.82, 120.47, 119.98, 111.95, 67.63, 63.29, 55.27, 13.71; HRMS (ESI-TOF): Anal. ...

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Abstract

The invention discloses a preparation method of oxalate. The preparation method comprises the following steps of using a diazo compound and alpha-Br ketone compound as reaction primers, using O2 (oxygen) as an oxygen source and an oxidant, using visible light as an energy source, using organic dye as a photocatalyst, and performing the free radical process in an organic solvent, so as to obtain the oxalate. The preparation method has the advantages that the reaction is more green, environment-friendly and economic; the generality of the primer is broad, the later functionalization is easier, the reaction conditions are moderate, and the reaction can be performed in air; the usage amount of the photocatalyst is small, and the post-treatment is simple and convenient; the used raw materials of reaction matter, photocatalyst and the like are low in prices and are easy to obtain, the reaction composition is reasonable, the ligand is not required, the atom economy is high, and the number ofreaction steps is fewer; the higher yield rate can be obtained by one-step reaction, the current green chemical and sustained development requirements and orientation are met, and the preparation method is suitable for synthesizing the asymmetric substituted oxalate which is difficult to synthesize by the traditional method.

Description

Technical field [0001] The invention relates to a method for preparing oxalate, and belongs to the technical field of organic synthesis. Background technique [0002] Oxalate is widely present in natural products and drug molecules, and is also a common structural unit in organic synthesis. At present, there are many methods for preparing oxalates, but each method has some shortcomings. E.g: [0003] (1) The traditional use of oxalyl chloride or oxalyl monochloride to react with alcohol or ether requires alkali catalysis. Among them, oxalyl chloride is not only sensitive to air, afraid of moisture, but also highly toxic and corrosive. The synthesized oxalate can only be For symmetrically substituted oxalates, if oxalyl monochloride is used as the raw material, oxalyl monochloride needs to be prepared first, and this step is difficult to control and the synthesis is more troublesome; [0004] (2) Transesterification of oxalate to synthesize new oxalate; [0005] (3) CO and CH cataly...

Claims

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Application Information

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IPC IPC(8): C07C67/00C07C67/18C07C69/36
CPCC07C67/00C07C67/18C07D307/42C07C69/36
Inventor 万小兵马美华郝伟伟马亮郑永高廉鹏程
Owner SUZHOU UNIV
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