Synthesis method of 3, 4-dicarboxylic acid diethyl ester furoxan

A technology of diethyl diformate and furoxan oxide is applied in 3 fields, can solve the problems of no reported purity, low purity, and high risk of experimental operation, achieves safe and reliable synthesis process, simple and easy-to-obtain raw materials, and improved reaction yield. rate effect

Inactive Publication Date: 2013-10-16
XIAN MODERN CHEM RES INST
View PDF1 Cites 4 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The first method is based on EtO 2 CC (NO 2 )=NO 2 K raw material, in N 2 o 4 It is an oxidant synthesis, and the disadvantage of this method is that the cost of raw materials is high and the risk of experimental operation is high, and the product yield obtained by this method is the highest 90%, and the purity is 95% (the yield in the literature is 94%, and there is no purity report); the second The method uses ethyl nitroacetate (EtOOCCH=N(OH)O) as the raw material and copper acetate as the oxidant to synthesize. Compared with the first method, this method adopts a milder oxidant for reaction and overcomes the first method. Unsafe in method operation, but shortcoming is raw material cost height, reaction time is long and yield is low, and data report is only 43%, and there is no purity report; The third method is raw material with ethyl acetoacetate, with nitrous acid Sodium and dilute HNO 3 It is obtained by oxidizing an oxidant into a ring, such as "Synthesis and Characterization of Diaminoazodioxyfuroxan" (Energetic Materials, 2008, 16(1), 53-55), which discloses a 3,4-dicarboxylic acid The synthesis method of diethyl ester oxidized furoxan, the specific operation process is: slowly drop the aqueous solution of sodium nitrite into the mixed solution of ethyl acetoacetate and glacial acetic acid at -10°C, and control the temperature at -5°C. After the dropwise additio...

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Synthesis method of 3, 4-dicarboxylic acid diethyl ester furoxan
  • Synthesis method of 3, 4-dicarboxylic acid diethyl ester furoxan
  • Synthesis method of 3, 4-dicarboxylic acid diethyl ester furoxan

Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0025] Preparation of Monoethyl Malonate Potassium Salt:

[0026] Add 50g (0.3mol) of diethyl malonate and 120mL of ethanol into the three-necked flask, heat to reflux temperature, add potassium hydroxide ethanol solution (17.5gKOH dissolved in 80ml of ethanol) dropwise, The reaction was continued for 2 hours. After cooling, a large amount of solids were precipitated, filtered, washed with alcohol, and dried to obtain 41.9 g of monoethyl malonate potassium salt, with a yield of 82.3% and a purity of 98.5%.

Embodiment 1

[0029] Add 22.1g (0.13mol) of monoethyl malonate potassium salt and 65mL of carbon tetrachloride into the three-necked flask, and dropwise add 189g (3.0mol) of industrial nitric acid with a mass concentration of 98% at 0-5°C, dropwise After the addition, 31g (0.45mol) of sodium nitrite was added in batches, the reaction temperature was controlled at 7-9°C and kept warm for 4h, the mixture was poured into ice water, the organic phase was separated, extracted with carbon tetrachloride, the organic phase was combined, and the Anhydrous MgSO 4 After drying and filtering, the filtrate was heated to reflux for 5 hours, and then the solvent was distilled off under reduced pressure to obtain a light yellow transparent liquid, 3,4-diethyl dicarboxylate furoxan, with a yield of 94.2% and a purity of 98.7% (HPLC).

[0030] Product structure identification:

[0031] IR (KBr, ν / cm-1): 1751 (C=O), 1626 (C-N), 1479 (O-N-O), 1335, 1302, 1250 (N-O), 1202 (furoxan ring), 1026, 856, 758;

[00...

Embodiment 2

[0037] Add 22.1g (0.13mol) of monoethyl malonate potassium salt and 65mL of carbon tetrachloride into the three-necked flask, and dropwise add 122.8g (1.95mol) of industrial nitric acid with a mass concentration of 98% at -5 to 0°C After the dropwise addition, 17.9 g (0.26 mol) of sodium nitrite was added, the reaction temperature was controlled at 3-6° C. and kept for 3 h, the mixture was poured into ice water, the organic phase was separated, extracted with carbon tetrachloride, and the organic phases were combined. with anhydrous MgSO 4 After drying and filtering, the filtrate was heated to reflux for 2 hours, and then the solvent was distilled off under reduced pressure to obtain a light yellow transparent liquid, 3,4-diethyl dicarboxylate furoxan, with a yield of 94% and a purity of 98.2% (HPLC).

[0038] The structure identification result of the product obtained in this embodiment is the same as that in Example 1.

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

PUM

No PUM Login to view more

Abstract

The invention relates to a furoxan ring, and provides a synthesis method of 3, 4-dicarboxylic acid diethyl ester furoxan. The method adopts a monoethyl malonate potassium salt as a raw material and takes sodium nitrate/nitrite as an oxidizing agent. The substances are subjected to oxidation nitration and a ring formation reaction in a carbon tetrachloride solution, thus obtaining the target compound 3, 4-dicarboxylic acid diethyl ester furoxan with purity up to 98.7% and yield up to 94.2%. The synthesis method provided in the invention has the advantages of high purity and high yield.

Description

technical field [0001] The invention relates to an oxidized furoxan ring, in particular to a synthesis method of 3,4-diethyl dicarboxylate oxidized furoxan. Background technique [0002] Furoxan ring (Furoxan) is a nitrogen-oxygen five-membered ring with a coordinated oxygen atom. Because the ring contains a "potential nitro group", it becomes an explosive group. Furazan and furoxan derivatives have always been regarded as very useful. Hopeful energetic materials, because of their high nitrogen content, active oxygen and positive standard enthalpy of formation, and high density, are important structural units for the construction of new high-energy compounds. The energetic derivatives with oxyfurazanyl as the explosive group have the following characteristics (1) the oxyfurazanyl can provide a relatively higher energy density; Additives can improve the oxygen balance of the system; (3) Furazanyl oxide can endow its derivatives with ring tension and high standard enthalpy of...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

Application Information

Patent Timeline
no application Login to view more
IPC IPC(8): C07D271/08
Inventor 刘敏郭涛邱少君李普瑞葛忠学姜俊唐望郑晓东秦明娜石强张彦吕英迪陈志强李洪丽
Owner XIAN MODERN CHEM RES INST
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Try Eureka
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap