CN104262122A - Method for synthesizing 1,4-butene diketone compound - Google Patents

Method for synthesizing 1,4-butene diketone compound Download PDF

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CN104262122A
CN104262122A CN201410438153.4A CN201410438153A CN104262122A CN 104262122 A CN104262122 A CN 104262122A CN 201410438153 A CN201410438153 A CN 201410438153A CN 104262122 A CN104262122 A CN 104262122A
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butenyldione
compounds
synthetic method
nitrae
isosorbide
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CN104262122B (en
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刘运奎
吴德贵
张剑
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Shandong Borod Biotechnology Co Ltd
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Zhejiang University of Technology ZJUT
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties

Abstract

The invention belongs to the technical field of organic compound synthesis, provides a method for synthesizing a 1,4-butene diketone compound and aims to solve the problems that metal participates, materials are complex and the conditions are harsh in the method for synthesizing the 1,4-butene diketone compound at present. The synthesizing method comprises the step of reacting for 12-48h at 25-80 DEG C by using substituted aryne and phenol as initial materials, using 1-chloromethyl-4-fluoro-1,4-diazabicyclo[2.2.2] octane bi(tetrafluoroboric acid) salt (selectfluor) as an oxidant and using CH3CN as a solvent to prepare the 1,4-butene diketone compound. The invention provides a method for synthesizing the 1,4-butene diketone compound, which has the advantages that materials can be easily obtained, no metal participates and the reaction condition is moderate. The reaction formula is shown in the specification.

Description

The synthetic method of a kind of Isosorbide-5-Nitrae-butenyldione compounds
Technical field
The present invention relates to organic compound synthesis technical field, be specifically related to the synthetic method of a kind of Isosorbide-5-Nitrae-butenyldione compounds.
Background technology
In recent years, Isosorbide-5-Nitrae-butenyldione compounds has attracted the extensive concern of people, because it is the key components of steroid drugs, antitumor and some natural products.Meanwhile, Isosorbide-5-Nitrae-butenyldione compounds is the important organic intermediate of a class, can be used for cycloaddition reaction, Michael addition and some other reaction.
The method of this compounds of conventional synthesis has the following disadvantages: (1) needs metal as catalyzer (see people .Catal Lett (2010) 137:8-15 such as L.Keith Woo; The people .Chem.Eur.J.2014 such as Rai-Shung Liu, 20,1-6; The people .Org.Lett.2013 such as Zhiyong Wang, 15,2148-2151.Because metal generally has certain toxicity, the finished product can be polluted.Therefore this method is subject to larger restriction for pharmaceutical industry.(2) raw material is complicated, not easily obtains (see people .Eur.J.Org.Chem.2012,3647-3657 such as Arasambattu K.Mohanakrishnan.(3) operational condition harshness (as needed high temperature), selectivity is low.In view of above Problems existing, develop by without metal superlattice, the method Worth Expecting that efficiently synthesizes Isosorbide-5-Nitrae-butenyldione compounds by simple raw material.
Summary of the invention
For solving synthesis 1 at present, metal superlattice, raw material is complicated, condition is harsh problem is there is in the method for 4-butenyldione compounds, the present invention proposes a kind of 1, the synthetic method of 4-butenyldione compounds, the invention provides a kind of raw material simple and easy to get, without the method for the synthesis Isosorbide-5-Nitrae-butenyldione compounds of metal superlattice, reaction conditions gentleness.
The present invention is achieved by the following technical solutions: a kind of 1, the synthetic method of 4-butenyldione compounds, described synthetic method is to replace aryne and phenol for starting raw material, with 1-chloromethyl-4-fluoro-1,4-diazabicyclo [2.2.2] octane two (Tetrafluoroboric acid) salt (Selectfluor) as oxygenant, with CH 3cN is solvent, reacts 12 ~ 48 hours, prepare Isosorbide-5-Nitrae-butenyldione compounds under 25 ~ 80 DEG C of conditions; Reaction formula is as follows:
In reaction formula, R is selected from H, methyl, ethyl, propyl group, sec.-propyl, fluorine, chlorine, bromine a kind of.
Wherein, in described starting raw material phenol consumption with replace aryne mol ratio be 1 ~ 4: 1, preferred molar ratio is 2: 1.
The mol ratio of described oxygenant (Selectfluor) 1-chloromethyl-4-fluoro-Isosorbide-5-Nitrae-diazabicyclo [2.2.2] octane two (Tetrafluoroboric acid) salt and starting raw material is 1 ~ 4: 1, and preferred molar ratio is 2: 1.
Described solvent is selected from acetonitrile, and consumption is the amount making solute dissolves.
Described synthetic method step specific as follows: under 25 ~ 80 DEG C of conditions, first replacement aryne is dissolved in acetonitrile reaction bottle, then dividing 1 ~ 2 time by phenol and oxygenant adds in reaction flask, every minor tick 1 ~ 2 hour, after phenol and oxygenant add, stirring reaction 12-48 hour, gained reaction solution obtains Isosorbide-5-Nitrae-butenyldione compounds through separation and purification.
Further, described separation and purification can be adopted with the following method: add column chromatography silica gel in gained reaction solution, and by underpressure distillation except desolventizing, then obtain pure products by TLC (be 10: 1 as eluent using petrol ether/ethyl acetate volume ratio) separation.
The present invention, by replacing aryne under phenol/Selectfluor catalyst system effect, by the oxygen in activating air, realizes by aryne through oxidative dimerization one-step synthesis Isosorbide-5-Nitrae-butenyldione compounds.
Compared with prior art, the invention has the beneficial effects as follows: have that raw material is simple and easy to get, without metal superlattice, reaction conditions is gentle, selectivity is high and activated the advantages such as oxygen in air.
Embodiment
Below by specific embodiment, the present invention is described in further detail.
Embodiment 1
By 0.5mmol phenylacetylene, 10ml CH 3cN adds in 50ml reaction flask, and 1mmol Selectfluor and 1mmol phenol are secondary at twice to add in reaction flask, and interval time is 2 hours, after adding, and continues stirring 20 hours at being placed in 30 DEG C.Then, two spoon column chromatography silica gels (100-200 order) are added in reaction solution, and by underpressure distillation except desolventizing, then obtain pure product (be 10: 1 as eluent using petrol ether/ethyl acetate volume ratio) by pillar layer separation.This material is yellow solid, productive rate 53%.
Characterization data: R f=0.48 (petroleum ether-EtOAc, 6: 1); Mp108-111 DEG C; IR (neat, cm -1) v:1660 (C=O), 1620 (C=C); E: Z=12: 1; 1hNMR (CDCl 3, 500MHz) and δ: 8.07-8.05 (m, 2H), 8.07 (s, 1H), 7.65-7.61 (m, 2H), 7.54-7.51 (t, J=8Hz, 2H); 13c NMR (CDCl 3, 125MHz) and δ: 189.8,136.9,135.1,133.8,128.86,128.85; MS (EI, 70eV): m/z (%)=236 (36), 105 (100) [M +].
Embodiment 2
By 0.5mmol phenylacetylene, 10ml CH 3cN adds in 50ml reaction flask, then adds 1mmolSelectfluor and 1mmol phenol, after adding, stirs 24 hours at being placed in 30 DEG C.Then, two spoon column chromatography silica gels (100-200 order) are added in reaction solution, and by underpressure distillation except desolventizing, then obtain pure product (be 10: 1 as eluent using petrol ether/ethyl acetate volume ratio) by pillar layer separation.This material is yellow solid, productive rate 35%.
Embodiment 3
By 0.5mmol phenylacetylene, 10ml CH 3cN adds in 50ml reaction flask, and 1mmol Selectfluor and 1mmol phenol are secondary at twice to add in reaction flask, and interval time is 2 hours, after adding, and continues stirring 20 hours at being placed in 25 DEG C.Then, two spoon column chromatography silica gels (100-200 order) are added in reaction solution, and by underpressure distillation except desolventizing, then obtain pure product (be 10: 1 as eluent using petrol ether/ethyl acetate volume ratio) by pillar layer separation.This material is yellow solid, productive rate 48%.
Embodiment 4
By 0.5mmol phenylacetylene, 10ml CH 3cN adds in 50ml reaction flask, and 1mmol Selectfluor and 1mmol phenol are secondary at twice to add in reaction flask, and interval time is 2 hours, after adding, and continues stirring 20 hours at being placed in 80 DEG C.Then, two spoon column chromatography silica gels (100-200 order) are added in reaction solution, and by underpressure distillation except desolventizing, then obtain pure product (be 10: 1 as eluent using petrol ether/ethyl acetate volume ratio) by pillar layer separation.This material is yellow solid, productive rate 40%.
Embodiment 5
By 0.5mmol phenylacetylene, 10ml CH 3cN adds in 50ml reaction flask, and 0.5mmol Selectfluor and 0.5mmol phenol are secondary at twice to add in reaction flask, and interval time is 2 hours, after adding, and continues stirring 20 hours at being placed in 30 DEG C.Then, two spoon column chromatography silica gels (100-200 order) are added in reaction solution, and by underpressure distillation except desolventizing, then obtain pure product (be 10: 1 as eluent using petrol ether/ethyl acetate volume ratio) by pillar layer separation.This material is yellow solid, productive rate 42%.
Embodiment 6
By 0.5mmol phenylacetylene, 10ml CH 3cN adds in 50ml reaction flask, and 2mmol Selectfluor and 2mmol phenol are secondary at twice to add in reaction flask, and interval time is 2 hours, after adding, and continues stirring 20 hours at being placed in 30 DEG C.Then, two spoon column chromatography silica gels (100-200 order) are added in reaction solution, and by underpressure distillation except desolventizing, then obtain pure product (be 10: 1 as eluent using petrol ether/ethyl acetate volume ratio) by pillar layer separation.This material is yellow solid, productive rate 45%.
Embodiment 7
By 0.5mmol phenylacetylene, 10ml CH 3cN adds in 50ml reaction flask, and 1mmol Selectfluor and 1mmol phenol are secondary at twice to add in reaction flask, and interval time is 2 hours, after adding, and continues stirring 40 hours at being placed in 30 DEG C.Then, two spoon column chromatography silica gels (100-200 order) are added in reaction solution, and by underpressure distillation except desolventizing, then obtain pure product (be 10: 1 as eluent using petrol ether/ethyl acetate volume ratio) by pillar layer separation.This material is yellow solid, productive rate 35%.
Embodiment 8
By 0.5mmol phenylacetylene, 10ml CH 3cN adds in 50ml reaction flask, and 1mmol Selectfluor and 1mmol phenol are secondary at twice to add in reaction flask, and interval time is 2 hours, after adding, and continues stirring 48 hours at being placed in 30 DEG C.Then, two spoon column chromatography silica gels (100-200 order) are added in reaction solution, and by underpressure distillation except desolventizing, then obtain pure product (be 10: 1 as eluent using petrol ether/ethyl acetate volume ratio) by pillar layer separation.This material is yellow solid, productive rate 50%.
Embodiment 9
By 0.5mmol4-methylbenzene acetylene, 10ml CH 3cN adds in 50ml reaction flask, 1mmolSelectfluor and 1mmol phenol adds in reaction flask at twice, and interval time is 2 hours, after adding, and continues stirring 20 hours at being placed in 30 DEG C.Then, two spoon column chromatography silica gels (100-200 order) are added in reaction solution, and by underpressure distillation except desolventizing, then obtain pure product (be 10: 1 as eluent using petrol ether/ethyl acetate volume ratio) by pillar layer separation.This material is yellow solid, productive rate 51%.
Characterization data: R f=0.45 (petroleumether-EtOAc, 6: 1); Mp142-144 DEG C; IR (neat, c -): v:1646 (C=O), 1620 (C=C); 1hNMR (CDCl 3, 500MHz) and δ: 8.01 (s, 1H), 7.99 (d, J=8Hz, 2H), 7.34 (d, J=7.5Hz, 2H), 2.46 (s, 3H); 13cNMR (CDCl 3, 125MHz) and δ: 189.4 (s), 144.9,135.0,134.5,129.6,129.0,21.7; MS (EI, 70eV): m/z (%)=264 (60) 119 (100) [M +].
Embodiment 10
By 0.5mmol2-methylbenzene acetylene, 10ml CH 3cN adds in 50ml reaction flask, 1mmolSelectfluor and 1mmol phenol adds in reaction flask at twice, and interval time is 2 hours, after adding, and continues stirring 20 hours at being placed in 30 DEG C.Then, two spoon column chromatography silica gels (100-200 order) are added in reaction solution, and by underpressure distillation except desolventizing, then obtain pure product (be 10: 1 as eluent using petrol ether/ethyl acetate volume ratio) by pillar layer separation.This material is yellow solid, productive rate 47%.
Characterization data: R f=0.55 (petroleumether-EtOAc, 6: 1); Mp151-153 DEG C; IR (neat, c -): v:1645 (C=O), 1601 (C=C); 1hNMR (CDCl 3, 500MHz) and δ: 7.62 (dd, J=7.9,1.3Hz, 2H), 7.46 (s, 2H), 7.44 (td, J=7.6,1.4Hz, 2H), 7.33-7.29 (m, 4H), 2.53 (s, 6H); 13cNMR (CDCl 3, 125MHz) and δ: 194.4,138.6,138.5,137.1,131.9 (d, J=4.8Hz), 129.2,125.7,20.8; MS (EI, 70eV): m/z (%)=264 (8), 145 (100) [M +].
Embodiment 11
By 0.5mmol3-methylbenzene acetylene, 10ml CH 3cN adds in 50ml reaction flask, 1mmolSelectfluor and 1mmol phenol adds in reaction flask at twice, and interval time is 2 hours, after adding, and continues stirring 20 hours at being placed in 30 DEG C.Then, two spoon column chromatography silica gels (100-200 order) are added in reaction solution, and by underpressure distillation except desolventizing, then obtain pure product (be 10: 1 as eluent using petrol ether/ethyl acetate volume ratio) by pillar layer separation.This material is yellow solid, productive rate 48%.
Characterization data: R f=0.53 (petroleumether-EtOAc, 6: 1); Mp114-115 DEG C; IR (neat, c -): v1646 (C=O), 1596 (C=C); 1hNMR (CDCl 3, 500MHz) and δ: 8.01 (s, 2H), 7.88 (d, J=10.9Hz, 4H), 7.44 (m, 4H), 2.46 (s, 3H); 13c NMR (CDCl 3, 125MHz) and δ: 190.0,138.8,136.9,135.1,134.6,129.3,128.7,126.1,21.3; MS (EI, 70eV): m/z (%)=264 (7), 119 (100) [M +].
Embodiment 12
By 0.5mmol4-Liquid Crystal Compounds Intermediate p-Ethyl-phenylacetylene, 10ml CH 3cN adds in 50ml reaction flask, 1mmolSelectfluor and 1mmol phenol adds in reaction flask at twice, and interval time is 2 hours, after adding, and continues stirring 20 hours at being placed in 30 DEG C.Then, two spoon column chromatography silica gels (100-200 order) are added in reaction solution, and by underpressure distillation except desolventizing, then obtain pure product (be 10: 1 as eluent using petrol ether/ethyl acetate volume ratio) by pillar layer separation.This material is yellow solid, productive rate 43%.
Characterization data: R f=0.53 (petroleumether-EtOAc, 6: 1); Mp113-115 DEG C; R (neat, c -): v1666 (C=O), 1605 (C=C); 1hNMR (CDCl 3, 500MHz) and δ: 8.05-7.98 (m, 6H), 7.36 (d, J=8.3Hz, 4H), 2.75 (q, J=7.6Hz, 4H), 1.29 (t, J=7.6Hz, 6H); 13c NMR (CDCl 3, 125MHz) and δ: 189.4,151.0,134.9,134.7,129.1,128.4,29.0,15.0; MS (EI, 70eV): m/z (%)=292 (33), 133 (100) [M +].
Embodiment 13
By 0.5mmol4-propylbenzene acetylene, 10ml CH 3cN adds in 50ml reaction flask, 1mmolSelectfluor and 1mmol phenol adds in reaction flask at twice, and interval time is 2 hours, after adding, and continues stirring 20 hours at being placed in 30 DEG C.Then, two spoon column chromatography silica gels (100-200 order) are added in reaction solution, and by underpressure distillation except desolventizing, then obtain pure product (be 10: 1 as eluent using petrol ether/ethyl acetate volume ratio) by pillar layer separation.This material is yellow solid, productive rate 38%.
Characterization data: R f=0.63 (petroleumether-EtOAc, 6: 1); Mp96-98 DEG C; IR (neat, c -): v1651 (C=O), 1604 (C=C); 1hNMR (CDCl 3, 500MHz) and δ: 8.02 (s, 2H), 8.00 (d, J=8.3Hz, 4H), 7.33 (d, J=8.3Hz, 4H), 2.71-2.66 (m, 4H), 1.73-1.65 (m, 4H), 0.97 (t, J=7.3Hz, 6H); 13c NMR (CDCl 3, 125MHz) and δ: 189.4,149.5,134.9,134.7,129.0 (d, J=7.4Hz), 77.3,38.1,24.1,13.7; MS (EI, 70eV): m/z (%)=320 (33), 147 (100) [M +].
Embodiment 14
By 0.5mmol4-isopropyl benzene acetylene, 10ml CH 3cN adds in 50ml reaction flask, 1mmolSelectfluor and 1mmol phenol adds in reaction flask at twice, and interval time is 2 hours, after adding, and continues stirring 20 hours at being placed in 30 DEG C.Then, two spoon column chromatography silica gels (100-200 order) are added in reaction solution, and by underpressure distillation except desolventizing, then obtain pure product (be 10: 1 as eluent using petrol ether/ethyl acetate volume ratio) by pillar layer separation.This material is yellow solid, productive rate 36%.
Characterization data: R f=0.6 (petroleum ether-EtOAc, 6: 1); Mp78-80 DEG C; IR (neat, cm -1): v1652 (C=O), 1605 (C=C); 1hNMR (CDCl 3, 500MHz) and δ: 8.02 (t, 3H), 7.39 (d, J=8.2Hz, 2H), 3.05-2.98 (m, 1H), 1.30 (d, J=6.9Hz, 6H); 13c NMR (CDCl 3, 125MHz) and δ: 189.4,155.5,134.9 (d, J=16.0Hz), 129.2,127.0,34.3,23.6; MS (EI, 70eV): m/z (%)=320 (17), 147 (100) [M +].
Embodiment 15
By 0.5mmol2-naphthalene acetylene, 10ml CH 3cN adds in 50ml reaction flask, and 1mmol Selectfluor and 1mmol phenol add in reaction flask at twice, and interval time is 2 hours, after adding, and continues stirring 20 hours at being placed in 30 DEG C.Then, two spoon column chromatography silica gels (100-200 order) are added in reaction solution, and by underpressure distillation except desolventizing, then obtain pure product (be 10: 1 as eluent using petrol ether/ethyl acetate volume ratio) by pillar layer separation.This material is yellow solid, productive rate 45%.
Characterization data: R f=0.43 (petroleum ether-EtOAc, 6: 1); Mp125-127 DEG C; IR (neat, cm -1): v1662 (C=O), 1625 (C=C); 1hNMR (CDCl 3, 500MHz) and δ: 8.67 (d, J=1.1Hz, 2H), 8.30 (s, 2H), 8.18 (dd, J=8.6,1.8Hz, 2H), 8.05 (d, J=7.7Hz, 2H), 8.00 (d, J=8.7Hz, 2H), 7.94 (d, J=8.2Hz, 2H), 7.69-7.66 (m, 2H), 7.64-7.60 (m, 2H); 13cNMR (CDCl 3, 125MHz) and δ: 189.7,136.0,135.1,134.4,132.5,131.2,129.8,129.0 (d, J=11.8Hz), 127.9,127.1,124.1; MS (EI, 70eV): m/z (%)=336 (100) [M +].
Embodiment 16
By 0.5mmol4-fluorobenzene acetylene, 10ml CH 3cN adds in 50ml reaction flask, lmmolSelectfluor and 1mmol phenol adds in reaction flask at twice, and interval time is 2 hours, after adding, and continues stirring 20 hours at being placed in 30 DEG C.Then, two spoon column chromatography silica gels (100-200 order) are added in reaction solution, and by underpressure distillation except desolventizing, then obtain pure product (be 10: 1 as eluent using petrol ether/ethyl acetate volume ratio) by pillar layer separation.This material is yellow solid, productive rate 46%.
Characterization data: R f=0.5 (petroleum ether-EtOAc, 6: 1); Mp136-138 DEG C; IR (neat, cm -1): v1653 (C=O), 1594 (C=C); 1hNMR (CDCl 3, 500MHz) and δ: 8.14-8.10 (m, 4H), 8.01 (s, 2H), 7.2-7.20 (m, 4H); 13cNMR (CDCl 3, 125MHz) and δ: 188.1,166.3 (d, J=255Hz), 134.90,131.7,131.6,116.2 (d, J=21Hz); MS (EI, 70eV): m/z (%)=272 (28), 123 (100) [M +].
Embodiment 17
By 0.5mmol3-fluorobenzene acetylene, 10ml CH 3cN adds in 50ml reaction flask, and 1mmol Selectfluor and 1mmol phenol add in reaction flask at twice, and interval time is 2 hours, after adding, and continues stirring 20 hours at being placed in 30 DEG C.Then, two spoon column chromatography silica gels (100-200 order) are added in reaction solution, and by underpressure distillation except desolventizing, then obtain pure product (be 10: 1 as eluent using petrol ether/ethyl acetate volume ratio) by pillar layer separation.This material is yellow solid, productive rate 43%.
Characterization data: R f=0.48 (petroleum ether-EtOAc, 6: 1); Mp106-108 DEG C; IR (neat, cm -1): v1656 (C=O), 1621 (C=C); E: Z=1.08: 1; 1hNMR (CDCl 3, 500MHz) and δ: 7.74-7.72 (m, 2H), 7.64-7.61 (m, 2H), 7.48-7.44 (m, 2H), 7.32-7.28 (m, 2H), 7.16 (S, 2H); 13cNMR (CDCl 3, 125MHz) and δ: 190.9 (d, J=2.5Hz), 163.0 (d, J=247.5Hz), 138.8 (d, J=6.25Hz), 135.6,130.6 (d, J=7.5Hz), 124.6 (d, J=3.75Hz); 121.1 (d, J=22.5Hz), 115.5 (d, J=22.5Hz); MS (EI, 70eV): m/z (%)=272 (10), 123 (100) [M +].
Embodiment 18
By 0.5mmol2-fluorobenzene acetylene, 10ml CH 3cN adds in 50ml reaction flask, and 1mmol Selectfluor and 1mmol phenol add in reaction flask at twice, and interval time is 2 hours, after adding, and continues stirring 20 hours at being placed in 30 DEG C.Then, two spoon column chromatography silica gels (100-200 order) are added in reaction solution, and by underpressure distillation except desolventizing, then obtain pure product (be 10: 1 as eluent using petrol ether/ethyl acetate volume ratio) by pillar layer separation.This material is yellow solid, productive rate 45%.
Characterization data: R f=0.46 (petroleum ether-EtOAc, 6: 1); Mp DEG C; IR (neat, cm -1): v1656 (C=O), 1609 (C=C); 1hNMR (CDCl 3, 500MHz) and δ: 7.88-7.85 (m, 2H), 7.75 (t, J=2Hz, 2H), 7.61-7.57 (m, 2H), 7.31-7.28 (m, 2H), 7.21-7.17 (m, 2H); 13cNMR (CDCl 3, 125MHz) and δ: 188.5 (d, J=2.5Hz), 161.8 (d, J=255Hz), 137.7 (d, J=7.5Hz), 135.1 (d, J=8.8Hz), 131.0 (d, J=2.5Hz), 125.8 (d, J=11.3Hz); 124.6 (d, J=3.8Hz), 116.7 (d, J=22.5Hz); MS (EI, 70eV): m/z (%)=272 (22), 123 (100) [M +].
Embodiment 19
By 0.5mmol4-bromobenzene acetylene, 10ml CH 3cN adds in 50ml reaction flask, and 1mmol Selectfluor and 1mmol phenol add in reaction flask at twice, and interval time is 2 hours, after adding, and continues stirring 20 hours at being placed in 30 DEG C.Then, two spoon column chromatography silica gels (100-200 order) are added in reaction solution, and by underpressure distillation except desolventizing, then obtain pure product (be 10: 1 as eluent using petrol ether/ethyl acetate volume ratio) by pillar layer separation.This material is yellow solid, productive rate 34%.
Characterization data: R f=0.58 (petroleum ether-EtOAc, 6: 1); Mp177-178 DEG C; IR (neat, cm -1): v1666 (C=O), 1610 (C=C); 1hNMR (CDCl 3, 500MHz) and δ: 7.99 (s, 2H), 7.94 (d, J=8.5Hz, 4H), 7.70 (d, J=8.5Hz, 4H); 13cNMR (CDCl 3, 125MHz) and δ: 188.6,135.5,134.8,132.3,130.3,129.4; MS (EI, 70eV): m/z (%)=394 (100) [M +].

Claims (6)

1. the synthetic method of a 4-butenyldione compounds, it is characterized in that, described synthetic method is to replace aryne and phenol for starting raw material, with 1-chloromethyl-4-fluoro-1,4-diazabicyclo [2.2.2] octane two (Tetrafluoroboric acid) salt as oxygenant, with CH 3cN is solvent, reacts 12 ~ 48 hours, prepare Isosorbide-5-Nitrae-butenyldione compounds under 25 ~ 80 DEG C of conditions; Reaction formula is as follows:
2. the synthetic method of a kind of Isosorbide-5-Nitrae-butenyldione compounds according to claim 1, is characterized in that: in reaction formula, R is selected from H, methyl, ethyl, propyl group, sec.-propyl, fluorine, chlorine, bromine a kind of.
3. the synthetic method of a kind of Isosorbide-5-Nitrae-butenyldione compounds according to claim 1, is characterized in that: in described starting raw material phenol consumption with replace aryne mol ratio be 1 ~ 4: 1.
4. according to claim 1 a kind of 1, the synthetic method of 4-butenyldione compounds, it is characterized in that: the mol ratio of described oxygenant 1-chloromethyl-4-fluoro-Isosorbide-5-Nitrae-diazabicyclo [2.2.2] octane two (Tetrafluoroboric acid) salt and starting raw material is 1 ~ 4: 1.
5. the synthetic method of a kind of Isosorbide-5-Nitrae-butenyldione compounds according to claim 1, is characterized in that: described solvent is selected from acetonitrile, and consumption is the amount making solute dissolves.
6. according to any one of claim 1 to 5 a kind of 1, the synthetic method of 4-butenyldione compounds, it is characterized in that: described synthetic method step specific as follows: under 25 ~ 80 DEG C of conditions, first replacement aryne is dissolved in acetonitrile reaction bottle, then phenol and oxygenant are divided 1 ~ 2 time and add in reaction flask, every minor tick 1 ~ 2 hour, after phenol and oxygenant add, stirring reaction 12 ~ 48 hours, gained reaction solution obtains Isosorbide-5-Nitrae-butenyldione compounds through separation and purification.
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CN104926628A (en) * 2015-06-02 2015-09-23 浙江工业大学 Method for synthesizing benzil derivative
CN105753668A (en) * 2016-03-11 2016-07-13 江南大学 Oxygen-participative alkyne green oxidative carbonylation reaction under promotion effects of visible light
CN107641085A (en) * 2016-07-29 2018-01-30 浙江工业大学 A kind of synthetic method of hexichol ketenes and its derivative

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104926628A (en) * 2015-06-02 2015-09-23 浙江工业大学 Method for synthesizing benzil derivative
CN105753668A (en) * 2016-03-11 2016-07-13 江南大学 Oxygen-participative alkyne green oxidative carbonylation reaction under promotion effects of visible light
CN107641085A (en) * 2016-07-29 2018-01-30 浙江工业大学 A kind of synthetic method of hexichol ketenes and its derivative
CN107641085B (en) * 2016-07-29 2019-12-24 浙江工业大学 Synthesis method of diphenylenone and derivatives thereof

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