CN109824725B - Preparation method of 4-phosphate-2H-chromene derivative - Google Patents
Preparation method of 4-phosphate-2H-chromene derivative Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000010898 silica gel chromatography Methods 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000002024 ethyl acetate extract Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000035484 reaction time Effects 0.000 abstract description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- -1 phosphate ester compounds Chemical class 0.000 description 9
- 150000008371 chromenes Chemical class 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000004679 31P NMR spectroscopy Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZHDGEEPULWOWON-UHFFFAOYSA-N 2-prop-2-ynylphenol Chemical compound OC1=CC=CC=C1CC#C ZHDGEEPULWOWON-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001344 alkene derivatives Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- HDFFVHSMHLDSLO-UHFFFAOYSA-M dibenzyl phosphate Chemical compound C=1C=CC=CC=1COP(=O)([O-])OCC1=CC=CC=C1 HDFFVHSMHLDSLO-UHFFFAOYSA-M 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses 4-phosphate-2HThe preparation method of the-chromene derivative comprises the steps of taking o-propargyl alcohol phenol as a raw material, adding an organic solvent to fully dissolve the o-propargyl alcohol phenol at room temperature, adding a compound containing P (O) -OH, reacting at 80 ℃ for 3-6 hours, and after the reaction is finished, separating and purifying the reaction product by silica gel column chromatography to obtain 4-phosphate-2H-chromene derivatives. The method has the characteristics of simple and easily obtained raw materials, mild reaction conditions, simple and convenient operation, short reaction time, less pollution and the like, and is a chemical synthesis method with better popularization and application prospects.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to 4-phosphate-2HA process for the preparation of chromene derivatives.
Background
Organic phosphate ester compounds are very important organic compounds and organic intermediate building blocks in organic synthesis, and the compounds have good catalytic activity, optical activity and biological activity, so that the organic phosphate ester compounds have wide application in the fields of biology, optical active materials, medicine and the like. Meanwhile, the organic phosphorus compound is also indispensable in the living body, such as ADP, ATP, RNA, organic phospholipid bilayer and the like in the human body. However, it is difficult to find out natural organophosphate compounds in nature, and most of phosphorus exists in nature in the form of inorganic salts, and most of organophosphate compounds known at present are synthesized by chemical means.
Further, 2HThe-chromene skeleton compound is a very important compound, has certain pharmacological properties, is an important intermediate for synthesizing a plurality of natural compounds and pharmaceutically active molecules at present, and has certain health care effect. Thus, pair 2HThe functional group synthesis of the chromene skeleton compound has very important application prospect and theoretical guidance, and is concerned by organic synthesizers. Although the 4-position functionalization 2 is currently constructedHThere are many methods for the construction of chromene derivatives, but for the construction of 4-phosphate-2H-colorThe literature on alkene derivatives has not been reported to date.
Based on organic phosphates and 2HThe extensive application of chromene derivatives in the fields of organic synthesis, medicinal chemistry, material science and the like develops an atom economic, efficient and green synthesis strategy to construct 4-phosphate-2HParticularly important are chromene derivatives.
Disclosure of Invention
The invention aims to provide 4-phosphate-2 with cheap and easily obtained reagents, mild reaction conditions, simple process operation, short reaction time and less pollutionHA process for the preparation of chromene derivatives.
4-phosphate-2 of the inventionHProcess for the preparation of chromene derivatives from o-propargyl alcohol phenol (C)
) Adding an organic solvent into the raw materials at room temperature to fully dissolve the raw materials, then adding a compound containing P (O) -OH, reacting for 3 to 6 hours at the temperature of 80 ℃, and after the reaction is finished, separating and purifying the reaction product by silica gel column chromatography to obtain the compound shown in the formula (A)
) 4-phosphoric acid ester-2 as shownH-a chromene derivative;
wherein the formula (A) is
) Or formula (A)
) R in (1)1～R4Each independently is H, CH3、X（F、Cl、Br）、OCH3Any one of the above; r5And R6Each independently is any one of aryl, alkoxy, aryloxy and alkyl; ar (Ar)1And Ar2All are aryl groups substituted by different substituents.
The reaction is represented by the following formula:
wherein the mass of the organic solvent is 10-30 times of that of the o-propargyl alcohol phenol compound, and the organic solvent is any one of 1, 2-dichloroethane, 1, 2-dichloromethane, tetrahydrofuran, dioxane, acetonitrile and nitromethane.
In the present invention, the ratio of the amounts of the o-propargylphenol and the p- (o) -OH group-containing compound is preferably 1:1.5 to 2.5, more preferably 1: 2.0.
in the reaction process of the invention, TCL is used for tracking the reaction progress time, and the reaction time is recommended to be 4-8 hours, preferably 8 hours.
The reaction temperature of the method is controlled to be 60-80 ℃, and preferably 80 ℃.
The method provided by the invention comprises the following steps: o-propargyl alcohol phenol (C)
) Dissolving the mixture in an organic solvent at room temperature, adding a compound containing P (O) -OH, reacting at 80 ℃ for 3-6 hours, and separating and purifying a reaction product after the reaction is finished to obtain 4-phosphate-2H-chromene derivatives.
The separation and purification of the invention can adopt the following steps: adding the reaction solution into a saturated sodium bicarbonate solution, adding ethyl acetate, fully stirring, standing and layering; the separated aqueous layer was extracted with ethyl acetateCombining the ethyl acetate extract and the separated organic layer, washing with saturated saline solution and drying with anhydrous sodium sulfate; evaporating to remove ethyl acetate solvent, and separating and purifying by silica gel column chromatography to obtain 4-phosphate-2H-chromene derivatives.
Compared with the prior art, the invention has the beneficial effects that: 1. providing a new synthesis strategy to construct; 2. the reaction of the invention does not need a catalyst, and the condition is mild; 3. the method has simple and convenient operation and wide substrate applicability, and can obtain 4-phosphate-2 with different substituentsH-a chromene derivative; 4. the invention has the advantages of simple and easily obtained raw materials, short reaction time and less pollution.
Detailed Description
Example 1: diphenyl- (2, 2-diphenyl-2)HPreparation of (E) -chromen-4-yl) -phosphinic acid esters
Representative implementation procedure: sequentially adding o-propargyl alcohol phenol into a reaction bottle at room temperature
-1 (300 mg, 1 mmol) and 5 ml of dry 1, 2-dichloroethane, then diphenylphosphoric acid (436 mg, 2 mmol) was added to the reaction flask, and then the reaction was left to react at 80 ℃ for 3 hours. Tracking the reaction progress by TLC, after the reaction is finished, adding a saturated sodium bicarbonate solution into the reaction solution, adding ethyl acetate, fully stirring, and standing for layering; extracting the separated water layer with ethyl acetate, mixing the ethyl acetate extract and the separated organic layer, washing with saturated saline solution, and drying with anhydrous sodium sulfate; evaporating to remove ethyl acetate solvent, and separating and purifying by silica gel column chromatography to obtain diphenyl- (2, 2-diphenyl-2)HChromen-4-yl hypophosphite 410 mg, reaction yield 82%.1H NMR (400 MHz, CDCl3): δ 6.13 (d, J = 1.2 Hz, 1 H), 6.90 – 6.93 (m, 3 H), 7.09 – 7.21 (m, 11 H), 7.43 – 7.53 (m, 5 H), 7.55 – 7.61 (m, 2 H), 7.90 – 7.95 (m, 4 H). 13C NMR (100 MHz, CDCl3): δ 83.9, 111.9, 112.0, 116.7, 118.3, 118.4, 121.1, 121.8, 126.9, 127.5, 127.9, 128.7, 128.9, 129.8, 130.7, 131.1, 131.7, 131.8, 132.6, 132.7, 142.2, 142.3, 144.4, 153.6. 31P NMR (160 MHz, CDCl3): δ 31.3. HRMS (ESI, m/z): calcd for C33H25O3P: [M+H]+ = 501.1614; found: 501.1616。
Example 2: dibenzyl- (2, 2-diphenyl-2)HPreparation of (E) -chromen-4-yl) phosphates
Sequentially adding o-propargyl alcohol phenol into a reaction bottle at room temperature
-2 (300 mg, 1 mmol) and 5 ml of dry 1, 2-dichloroethane, then dibenzyl phosphate (556 mg, 2 mmol) was added to the reaction flask, the reaction was then left to react at 80 ℃ for 3 hours, and the progress of the reaction was followed by TLC. The separation and purification steps are the same as in example 1 to obtain diphenyl- (2, 2-diphenyl-2)HChromen-4-yl) phosphate 476 mg, reaction yield 85%.1H NMR (400 MHz, CDCl3): δ 5.11 (s, 2 H), 5.13 (s, 2 H), 6.06 (s, 1 H), 6.82 (t, J = 7.6 Hz, 1 H), 6.92 (d, J = 8.0 Hz, 1 H), 7.15 – 7.29 (m, 17 H), 7.35 – 7.37 (m, 5 H). 13C NMR (100 MHz, CDCl3): δ 70.1, 83.8, 111.6, 111.7, 116.5, 117.8, 117.9, 121.0, 121.9, 126.9, 127.6, 128.0, 128.1, 128.6, 128.7, 130.7, 135.1, 135.2, 141.8, 141.9, 144.5, 153.4. 31P NMR (160 MHz, CDCl3): δ -6.1. HRMS (ESI, m/z): calcd for C35H29O5P: [M+H]+ = 561.1825; found: 561.1825。
Example 3: diphenyl- (2, 2-di (p-methylphenyl) -2HPreparation of (4-chromen-yl) -phosphinic acid esters
Sequentially adding o-propargyl alcohol phenol into a reaction bottle at room temperature
-3 (328 mg, 1 mmol) and 5 ml of dry 1, 2-dichloroethane, then diphenyl phosphate (436 mg, 2 mmol) was added to the reaction flask, the reaction was left at 80 ℃ for 4 hours, and the progress of the reaction was followed by TLC. The separation and purification steps are the same as in example 1 to obtain diphenyl- (2, 2-di (p-methylphenyl) -2HChromen-4-yl phosphinate 423 mg, reaction yield 80%.1H NMR (400 MHz, CDCl3): δ 2.26 (s, 6 H), 6.10 (d, J = 1.2 Hz, 1 H), 6.86 – 6.90 (m, 2 H), 6.95 – 7.00 (m, 8 H), 7.14 – 7.18 (m, 1 H), 7.41 – 7.49 (m, 5 H), 7.55 – 7.59 (m, 2 H), 7.89 – 7.94 (m, 4 H). 13C NMR (100 MHz, CDCl3): δ 20.9, 83.8, 112.2, 112.3, 116.6, 118.3, 118.4, 120.9, 121.7, 126.8, 128.5, 128.6, 128.8, 129.9, 130.5, 131.2, 131.6, 131.7, 132.5, 132.6, 137.0, 141.6, 142.0, 142.1, 153.6. 31P NMR (160 MHz, CDCl3): δ 31.0. HRMS (ESI, m/z): calcd for C35H29O3P: [M+H]+ = 529.1927; found: 529.1925。
Example 4: diphenyl- (2, 2-di (p-methoxyphenyl) -2HPreparation of (4-chromen-yl) -phosphinic acid esters
Sequentially adding o-propargyl alcohol phenol into a reaction bottle at room temperature
-4 (360 mg, 1 mmol) and 5 ml of dry 1, 2-dichloroethane, then diphenyl phosphate (436 mg, 2 mmol) was added to the reaction flask, the reaction was left at 80 ℃ for 3 hours, and the progress of the reaction was followed by TLC. Separation and purification procedure as in example1 to obtain diphenyl- (2, 2-di (p-methoxyphenyl) -2HChromen-4-yl phosphinate 364 mg, reaction yield 65%.1H NMR (400 MHz, CDCl3): δ 3.74 (s, 6 H), 6.08 (d, J = 1.2 Hz, 1 H), 6.68 (d, J = 8.8 Hz, 4 H), 6.86 – 6.92 (m, 2 H), 7.01 (d, J = 8.8 Hz, 4 H), 7.15 – 7.19 (m, 1 H), 7.42 – 7.50 (m, 5 H), 7.56 – 7.60 (m, 2 H), 7.89 – 7.94 (m, 4 H). 13C NMR (100 MHz, CDCl3): δ 55.1, 83.5, 112.4, 112.5, 113.1, 116.6, 118.3, 118.4, 120.9, 121.7, 128.2, 128.6, 128.8, 129.9, 130.5, 131.2, 131.6, 131.7, 132.5, 132.6, 136.8, 142.0, 142.1, 153.6, 158.7. 31P NMR (160 MHz, CDCl3): δ 31.1. HRMS (ESI, m/z): calcd for C35H29O5P: [M+H]+ = 561.1825; found: 561.1824。
Claims (3)
1. A method for synthesizing 4-phosphate-2H-chromene derivatives is characterized by comprising the following steps: the method comprises the steps of taking o-propargyl alcohol phenol (I) as a raw material, adding an organic solvent to dissolve at room temperature, then adding a compound containing P (O) -OH, reacting at 80 ℃ for 3-6 hours, and after the reaction is finished, separating and purifying a reaction product by silica gel column chromatography to obtain a 4-phosphate-2H-chromene derivative shown as a formula (II);
wherein R1-R4 in the formula (I) and the formula (II) are respectively and independently any one of H, CH3, F, Cl, Br and OCH 3; r5 and R6 are independently any one of aryl, alkoxy, aryloxy and alkyl; ar1 and Ar2 are aryl groups substituted by different substituents; the organic solvent is one of 1, 2-dichloroethane and nitromethane.
2. The method of claim 1, wherein the method comprises the steps of: the amount ratio of the raw material feeding substances is that the o-propargyl alcohol phenol: the compound containing P (O) -OH is 1:1.5 to 2.5.
3. The method of claim 1, wherein the method comprises the steps of: the separation and purification method comprises the following steps: adding the reaction solution into a saturated sodium bicarbonate solution, adding ethyl acetate, fully stirring, and standing for layering; extracting the separated water layer with ethyl acetate, mixing the ethyl acetate extract and the separated organic layer, washing with saturated saline solution, and drying with anhydrous sodium sulfate; the ethyl acetate solvent is removed by evaporation, and then the 4-phosphate-2H-chromene derivative is obtained by silica gel column chromatography separation and purification.
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