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Method for directly synthesizing furoxan from methyl ketone

A technology of furoxan and methyl ketone, which is applied in the direction of organic chemistry, can solve the problems that raw materials cannot be purchased through commercial channels, limit the application prospects of synthetic methods, and reduce atom economy, so as to reduce the difficulty of post-processing of products and improve the quality of products. Universal applicability and effect of saving workload

Inactive Publication Date: 2019-12-27
QINGDAO INST OF BIOENERGY & BIOPROCESS TECH CHINESE ACADEMY OF SCI
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Problems solved by technology

[0005] However, there are still many problems in the above method: (1) the reaction requires the participation of metal catalysts and acid and alkali reagents, which leads to difficulties in post-processing, and does not conform to the concept of "green chemistry"; (2) the reaction requires the introduction of dimethyl methylene Positioning groups such as sulfone or pre-nitration pretreatment of raw materials greatly reduce the atom economy of the reaction; (3) raw materials can only be prepared in advance and cannot be purchased through commercial channels, which greatly limits the application prospects of synthetic methods

Method used

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  • Method for directly synthesizing furoxan from methyl ketone
  • Method for directly synthesizing furoxan from methyl ketone
  • Method for directly synthesizing furoxan from methyl ketone

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specific Embodiment approach 1

[0019] Specific embodiment 1: methyl ketone is acetophenone

[0020] Add 1 mmol of acetophenone into the reaction flask, and dissolve it in 1,4-dioxane (1 mL), add 528 μL of tert-butyl nitrite dropwise under stirring at room temperature, then raise the temperature to 60°C, and under air atmosphere, React for 24 hours. After the reaction, the organic solvent was removed with a rotary evaporator, purified by column chromatography or recrystallization to obtain 139 mg of furoxan product, and the reaction yield was 95%. Structure Identification: 1 H NMR (400MHz, Chloroform-d) δ8.20 (dd, J = 8.4, 1.2Hz, 2H), 7.86 (dd, J = 8.4, 1.2Hz, 2H), 7.70 (dt, J = 13.7, 7.5Hz, 2H), 7.54 (dt, J=13.8, 7.9Hz, 4H). 13 C NMR (100MHz, Chloroform-d) δ181.8, 180.5, 154.3, 135.5, 135.3, 133.87, 133.85, 130.6, 129.7, 129.3, 129.0, 111.6. HRMS (ESI): calcd for C 16 h 10 N 2 o 4 Na(M+Na) + :317.0533.Found:317.0529. The structural formula of furoxan is:

[0021]

specific Embodiment approach 2

[0022] Specific embodiment 2: methyl ketone is p-methyl acetophenone

[0023] Add 1mmol of p-methylacetophenone into the reaction flask and dissolve it in 1,4-dioxane (1mL). With stirring at room temperature, add 528μL of tert-butyl nitrite dropwise, then raise the temperature to 60°C and air Under atmosphere, react for 24 hours. After the reaction, the organic solvent was removed with a rotary evaporator, purified by column chromatography or recrystallization to obtain 155.5 mg of furoxan product, and the reaction yield was 97%. Structure Identification: 1 H NMR (400MHz, Chloroform-d) δ8.10(d, J=7.8Hz, 2H), 7.75(d, J=7.8Hz, 2H), 7.34(d, J=8.0Hz, 2H), 7.31(d ,J=8.1Hz,2H),2.46(s,3H),2.44(s,3H). 13 CNMR (100MHz, Chloroform-d) δ181.3, 180.0, 154.6, 147.0, 146.8, 131.49, 131.46, 130.7, 130.0, 129.84, 129.76, 111.9, 22.01, 21.97. HRMS (ESI): calcd for C 18 h 14 N 2 o 4 Na(M+Na) + :345.0846.Found:345.0839. The structural formula of furoxan is:

[0024]

specific Embodiment approach 3

[0025] Specific embodiment 3: methyl ketone is p-phenylacetophenone

[0026] Add 1 mmol of p-phenylacetophenone into the reaction flask, and dissolve it in 1,4-dioxane (1 mL), add 528 μL of tert-butyl nitrite dropwise under stirring at room temperature, then raise the temperature to 60 °C, and air Under atmosphere, react for 24 hours. After the reaction, the organic solvent was removed with a rotary evaporator, purified by column chromatography or recrystallization to obtain 215 mg of furoxan product, and the reaction yield was 96%. Structure Identification: 1 H NMR (400MHz, Chloroform-d) δ8.31 (d, J = 8.6Hz, 2H), 7.96 (d, J = 8.4Hz, 2H), 7.77 (dd, J = 14.4, 8.4Hz, 4H), 7.69 –7.60(m,4H),7.55–7.40(m,6H). 13 C NMR (100MHz, Chloroform-d)δ181.3,180.0,154.6,148.3,148.1,139.3,132.6,132.5,131.3,130.4,129.14,129.11,128.8,127.9,127.7,127.44,127.43.I11) calcd for C 28 h 18 N 2 o 4 H(M+H) + :447.1339.Found:447.1348. The structural formula of furoxan is:

[0027]

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Abstract

The invention discloses a method for directly synthesizing furoxan from methyl ketone, and belongs to the technical field of organic chemical synthesis. According to the method, methyl ketone is usedas a raw material, methyl ketone and a green nitration reagent tert-butyl nitrite (TBN) are subjected to a free radical reaction in an air or oxygen atmosphere with acetonitrile, toluene or 1, 4-dioxane as a reaction solvent to directly synthesize the furoxan. According to the method, a metal catalyst is not used in the synthesis process, acid and alkali are avoided, tert-butyl nitrite directly participates in the reaction, the tert-butyl nitrite is low in price and good in functional group compatibility, and the nitration reagent is very green. The methyl ketone can be directly purchased commercially, so that the reaction path is shortened and the workload of raw material preparation is saved compared with the traditional synthesis method. And meanwhile, the method only generates the target product furoxan, so that the environmental pollution and the difficulty of product post-treatment are reduced.

Description

technical field [0001] The invention relates to a method for directly synthesizing furoxan from methyl ketone, belonging to the technical field of organic chemical synthesis. Background technique [0002] Furazan oxide is an important five-membered nitrogen-oxygen heterocycle, which is not only a key component of high-energy materials and functional materials, but also the core structure of many drugs and biologically active natural products with anti-tumor, anti-coagulation and anti-tumor effects , such as 3,4-dinitrofurazanylfuroxan (DNTF) is a high energy density energetic material, 4,4'-dimethyl-dibenzoylfurazan is a potential NO releasing prodrugs and more. The traditional method for synthesizing furoxan from methyl ketone needs three steps: (a) aldehyde is converted into corresponding oxime by oximation; (b) gained oxime is converted into corresponding oxime acid chloride through dehydrohalogenation; (c ) Oxime acid chloride 22 undergoes dehydrodehalogenation to form...

Claims

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Application Information

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IPC IPC(8): C07D271/08C07D413/14
CPCC07D271/08C07D413/14
Inventor 王庆刚徐广强郭泫华
Owner QINGDAO INST OF BIOENERGY & BIOPROCESS TECH CHINESE ACADEMY OF SCI
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