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Preparation method of 1,1,3-tri-substituted divinyl dimethyl phosphate compound

A technology for dimethyl allenyl phosphate and compounds, which is applied in the field of preparation of 1,1,3-trisubstituted allenyl dimethyl phosphate compounds, and can solve complex synthesis of substrates, difficulty in obtaining raw materials, and limitations Problems such as the scope of application, to achieve the effect of low reaction cost, high reaction efficiency and good atom economy

Inactive Publication Date: 2016-04-27
PEKING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The shortcoming of these methods is: (1) first kind of method raw material is difficult to obtain, has limited scope of application
(2) The second method requires complex ligands, and the substrate synthesis is more complicated, so it is not suitable for application

Method used

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  • Preparation method of 1,1,3-tri-substituted divinyl dimethyl phosphate compound
  • Preparation method of 1,1,3-tri-substituted divinyl dimethyl phosphate compound
  • Preparation method of 1,1,3-tri-substituted divinyl dimethyl phosphate compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] Synthesis of Dimethyl 1,3-Diphenyldienyl Phosphate

[0042] Add 59mg (ie 0.26mmol) phenyl phosphodiester diazonium, 20mg (ie 0.2mmol) diisopropylamine, 7.6mg (ie 0.04mmol) cuprous iodide, 1mL1, 4-dioxane. After the reaction tube is sealed, replace the system with a nitrogen atmosphere, add 20mg of phenylacetylene (ie 0.2mmol), and react at 80°C for 3 hours. After the reaction, the solid insolubles in the system are filtered off with suction, and concentrated under reduced pressure using a rotary evaporator. 1,3-Diphenyldienyl dimethyl phosphate can be obtained by column chromatography purification using petroleum ether:ethyl acetate 1:1 as eluent with a yield of 85%. Its structure is shown in the following formula:

[0043]

[0044] Keeping other reaction conditions unchanged, reacting at 50°C for 5 hours, the yield was 83%; reacting at 40°C for 30 hours, the yield was 75%;

[0045] Keeping other reaction conditions unchanged, increase the amount of phenyl phospho...

Embodiment 2

[0054] Synthesis of Dimethyl 1-(4-Chlorophenyl)-3-Phenyldienyl Phosphate

[0055] Add 45mg (ie 0.26mmol) dimethyl diazonium phenylphosphate, 20mg (ie 0.2mmol) diisopropylamine, 7.6mg (ie 0.04mmol) cuprous iodide, 1mL1 to a 25mL long tubular reaction tube ,4-dioxane. After the reaction tube is sealed, replace the system with a nitrogen atmosphere, add 27mg of p-chlorophenylacetylene (0.2mmol), and react at 80°C for 3 hours. Concentrate, use petroleum ether: ethyl acetate 1:1 as eluent column chromatography to obtain 1-(4-chlorophenyl)-3-phenyldienyl phosphate dimethyl ester, its structure is as follows Shown:

[0056]

[0057] The compound is a colorless liquid with a yield of 86%, and its NMR data are as follows:

[0058] 1 HNMR (400MHz, CDCl 3 )δ7.61(d, J=8.0Hz, 2H), 7.27-7.38(m, 7H), 6.73(d, J=12.8Hz, 1H), 3.81(d, J=11.2Hz, 3H), 3.78( d,J=10.8Hz,3H); 13 CNMR (100MHz, CDCl 3 )δ212.66(d, J=2.7Hz), 133.77(d, J=2.0Hz), 130.75(d, J=76Hz), 129.95(d, J=8.1Hz), 129.16(d, ...

Embodiment 3

[0060] Synthesis of Dimethyl 1-(4-Bromophenyl)-3-Phenyldienyl Phosphate

[0061] Add 59mg (ie 0.26mmol) dimethyl diazonium phenylphosphate, 20mg (ie 0.2mmol) diisopropylamine, 7.6mg (ie 0.04mmol) cuprous iodide to a 25mL long tubular reaction tube, 1mL1 ,4-dioxane. After the reaction tube is sealed, replace the system with a nitrogen atmosphere, add 36mg of p-bromophenylacetylene (0.2mmol), and react at 80°C for 3 hours. After the reaction, filter out the solid insoluble matter in the system, and use a rotary evaporator to reduce the pressure Concentrate, and use petroleum ether: ethyl acetate 1:1 as eluent column chromatography to obtain 1-(4-bromophenyl)-3-phenyldienyl phosphate dimethyl ester, its structure is as follows Shown:

[0062]

[0063] The compound is a colorless liquid with a yield of 80%, and its NMR data are as follows:

[0064] 1 HNMR (400MHz, CDCl 3 )δ7.61(d,J=8.0Hz,2H),7.47(d,J=8.0Hz,2H),7.30-7.38(m,3H),7.21-7.23(m,2H),6.71(d,J =12.2Hz,1H),3.80(d,J=...

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Abstract

The invention discloses a preparation method of a 1,1,3-tri-substituted divinyl dimethyl phosphate compound. The preparation method comprises the steps of enabling aryl diazonium phosphatide / alkyl tosylhydrazone phosphatide and terminal alkyne to react in an organic solvent under the action of a copper catalyst and alkali to obtain the 1,1,3-tri-substituted divinyl dimethyl phosphate compound. According to the method, coupling the aryl diazonium phosphatide / alkyl tosylhydrazone phosphatide and the terminal alkyne to obtain the 1,1,3-tri-substituted divinyl dimethyl phosphate compound is realized for the first time, the reaction efficiency is high, and the reaction cost is low. The aryl diazonium phosphatide is prepared through a known method; the alkyl tosylhydrazone phosphatide can be prepared by generating hydrazone through dimethyl benzoylphosphonate and p-toluenesulfonyl hydrazide, and then processing through potassium carbonate. The involved reaction operations are convenient and simple, and the preparation method has excellent tolerance and universality to functional groups, and can be widely used for preparing the 1,1,3-tri-substituted divinyl dimethyl phosphate compound.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a preparation method of 1,1,3-trisubstituted dienyl dimethyl phosphate compound. Background technique [0002] 1,1,3-Trisubstituted allienyl phosphate dimethyl compounds play an important role in organic synthesis and are widely used in scientific research. 1,1,3-Trisubstituted Dienyl Phosphate Dimethyl Ester compounds are mainly used in organic synthesis, they can be used as molecular building blocks to participate in a wide variety of organic chemical reactions to construct more complex target compounds; Axial chirality of carbon atoms is involved in catalytically induced asymmetric synthesis; Dimethyl Dienyl Phosphate is a structural unit in many drug molecules and natural products. For a long time, people have continuously improved and perfected the synthesis method of 1,1,3-trisubstituted dienyl phosphate dimethyl ester compound. In the currently known syntheti...

Claims

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Application Information

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IPC IPC(8): C07F9/40C07F9/6553
CPCC07F9/4003C07F9/655345
Inventor 王剑波吴承贵叶飞吴国骄徐帅邓桂胜张艳
Owner PEKING UNIV
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