CN113215599B - Synthesis method of O-phosphinyl substituted phenol and alcohol derivatives - Google Patents
Synthesis method of O-phosphinyl substituted phenol and alcohol derivatives Download PDFInfo
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Abstract
The invention discloses a method for preparing O-phosphinyl-substituted phenol and alcohol derivatives through dehydrogenation under the condition of electrooxidation 'one-pot' method. Under the condition of electrochemical oxidation, phenol and alcohol derivatives and a diphenylphosphine compound are used as raw materials, tetrabutylammonium iodide (TBAI) is used as an electrolyte, and cesium carbonate is used as a base to prepare the O-phosphinyloxy substituted phenol and alcohol derivatives in one step. Compared with the reported preparation methods of O-phosphinyl substituted phenol and alcohol compounds, the method disclosed by the invention is green and environment-friendly, the raw materials are easy to obtain, a metal catalyst and a chemical oxidant are not required, the reaction condition is mild, the application range is wide, the operation is simple, the atom economy is high, and only hydrogen is generated as a byproduct after the reaction.
Description
Technical Field
The invention relates to a synthetic method of O-phosphinyl substituted phenol and alcohol derivatives. Under the condition of electrochemical oxidation, phenol and alcohol derivatives and diphenylphosphine compounds are used as raw materials to prepare the O-phosphinyl-substituted phenol and alcohol derivatives by a one-pot method. Compared with the reported preparation method of O-phosphinyl-substituted phenol and alcohol compounds, the method disclosed by the invention is green and environment-friendly, has the advantages of readily available raw materials, no need of a metal catalyst or an oxidation-reduction agent, mild reaction conditions, wide application range, simplicity in operation and high atom economy, and only generates hydrogen as a byproduct after the reaction.
Background
Organophosphorus compounds are important intermediates in organic synthesis. They are used as structural components in medicinal chemistry, and as intermediates for the preparation of polymers, optoelectronic materials, flame retardants, lubricants and phosphine ligands, and have a wide range of biological properties and biological activities. (Bock, t.;
h; mulhaupt, r.macromol.chem.phys.2007,208,1324; kirumakki, s.; huang, j.; abbiah, a.; yao, j.; rowland, A.; smith, b.; mukherjee, a.; samarajeewa, s.; clearfield, a.j.mater.chem.2009,19,2593; kim, d.; salman, s.; corocepanu, v.; padmaperuma, a.b.; sapochak, l.s.; kahn, a.; bredas, j.l.chem.mater.2010,22, 247). Conventional O-phosphonooxy extractionThe substituted phenols and alcohol derivatives are prepared by a process of phosphorylating reaction using a metal catalyst such as iron, manganese, copper, palladium, silver and the like as a catalyst (b.xiong, g.wang, c.zhou, y.liu, C, -a, yang, P, zhang, k.tang, q.zhou, j.organomet.chem.2019,885,21-31, m.ariawa, m.yamaguchi, tetrahedron lett.2010,51,4840-4842 c.li, t.chen, l.b.han, danon trans.2016,45,14893-14897, arisawa, m.; yamaguchi, M.J.am.chem.Soc.2000,122,2387, arisawa, M.J.am.chem.Soc.2000,122,2387, B.Xiong, Q.Cheng, C.Hu, P.Zhang, Y.Liu and K.Tang, chemistry select,2017,2,6891, (f) B.Xiong, X.Feng, L.Zhu, T.Chen, Y.Zhou, C.T.Au and S.Yi, ACS.Cat., 2014,5, 537); with the development of scientific technology, in addition to the conventional metal catalyst method, methods using various chemical oxidizing agents have been reported, for example, 2, 3-dichloro-5, 6-dicyan-p-benzoquinone (DDQ), dicumyl peroxide (DCP), hydrogen peroxide (H) 2 O 2 ) Oxygen, etc. (Shin, c.h.; kim, g.g.; chun, m.s.; kwon, h.j.; kim, d.h.kr 2014128892 a, nov 6,2014b.xiong, x.feng, l.zhu, t.chen, y.zhou, c. -t.au, s. -f.yin, ACS catal.2015,5,537-543; liu, l. -l.mao, b.yang, s. -d.yang, chem.commun.2014,50,10879-10882; h.huang, j.ash, j.y.kang, org.lett.2018,20,4938-4941; t.yuan, s.huang, c.cai, g. -p.lu, org.biomol.chem.2018,16,30-33; j.eljo, g.k.murphy, tetrahedron lett.2018,59,2965-2969; l.duan, k.zhao, z.wang, f. -l.zhang, z.gu, ACS catal.2019,9, 9852-9858). Reacting phenol and alcohol derivatives with phosphorus compounds. The process requires the use of inert gas shielding, ligands and strong bases, the Phosphorus oxychloride starting material needs to be prepared beforehand, the Phosphorus oxychloride and phosphoric acid themselves are sensitive to water and humid air, have a strong pungent odor, are complicated to handle and work up, and have high reaction temperatures (n.p. kenny, k.v. rajuntran, d.g. gilheany, chem.commu.2015, 51,16561-16564 h. -j.hong, a.r.bae, i. -h.um, bull.korean chem.soc.2013,34,2251-2255 c) s.bergec, s.alaas, a.lic kit, phosphorus, sulfur, and silicon, 2011,186, 1531-1537).
However, the above methods generally have the disadvantages of raw materials requiring pre-functionalization, harsh reaction conditions, addition of an oxidant and a metal catalyst, low atom economy, and the like. Under the condition of electrooxidation, phenol and alcohol derivatives and diphenylphosphine compounds are used as raw materials to prepare a series of O-phosphinyl-substituted phenol and alcohol derivatives (1) with different structures in a one-pot method efficiently. The method has the advantages of environmental protection, easily obtained raw materials, no need of metal catalysts and redox agents, mild reaction conditions, wide application range, simple operation and high atom economy, and only generates hydrogen as a byproduct after the reaction.
Disclosure of Invention
The invention aims to provide a method for preparing O-phosphinyl-substituted phenol and alcohol derivatives, which is green and environment-friendly, has easily obtained raw materials, does not need a metal catalyst or an oxidation reducing agent, has mild reaction conditions, wide application range, simple operation and high atom economy.
In order to achieve the purpose, the technical scheme of the invention is as follows:
performing electrochemical oxidation, wherein in an air atmosphere, the phenol and alcohol derivative (2) and the diphenylphosphine compound (3) undergo a cross dehydrogenation coupling reaction (reaction formula 1). And after the reaction is finished, performing product separation and characterization according to a conventional separation and purification method to obtain the corresponding O-phosphinyl-substituted phenol and alcohol derivative (1).
The specific technical scheme is as follows:
1. phenol, alcohol derivatives and diphenylphosphine compounds are used as raw materials, and the substituent groups are as follows:
1) The substituent R is one or more of phenyl, naphthyl, substituted aryl (the substituent in the substituted aryl is one or more of F, cl, br, alkyl with 1-4 carbon atoms and alkoxy with 1-4 carbon atoms), and heterocyclic aryl; heterocyclic aryl (heterocyclic aryl is thienyl).
2) The substituent R is alkyl (C1-C4 alkyl) or substituted alkyl (aryl or anisoyl as substituent of substituted alkyl).
2. The reaction solvent is one or more than one organic solvents of methanol, ethanol, dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone and acetonitrile; among them, the most effective is in acetonitrile.
3. When the phenol and the alcohol derivative (2) are reacted with the diphenylphosphine compound (3), the optimum molar ratio is 1; the molar concentration of the phenol and the alcohol derivative (2) is 0.1 to 1.5M, preferably 0.05M.
4. The reaction time is 1-24 hours. Wherein the optimal reaction time is 3-4 hours.
5. The optimum reaction temperature is 25-40 ℃.
6. The reaction is carried out under constant current, the current intensity is 1-10mA, and the optimal reaction current is 6mA.
7. The alkali used in the reaction is cesium carbonate, sodium carbonate, potassium phosphate, wherein Cs is used 2 CO 3 The reaction effect is best when the cesium carbonate is used as alkali, and the concentration of the cesium carbonate is optimal to be 0.05M.
8. The electrode used in the anode in the reaction is graphite, nickel, platinum or reticular glassy carbon electrode, wherein graphite is used as the anode as the best.
9. The cathode used in the reaction is graphite, nickel, platinum or reticular glassy carbon electrode, wherein nickel is the best cathode.
10. The electrolyte used in the reaction is tetrabutylammonium iodide, 1, 3-dimethylimidazole iodide, tetrabutylammonium hexafluorophosphate, tetraethylammonium bromide, potassium bromide, ammonium iodide or tetrabutylammonium tetrafluoroborate, and the most preferred electrolyte is tetrabutylammonium iodide.
The invention has the following advantages:
1) Electrochemical oxidation, as an environmentally friendly strategy, can replace traditional chemical oxidants and use electrons as clean, renewable reagents.
2) The electrochemical oxidation reaction is carried out at normal temperature and normal pressure, and the method is safe and reliable and is simple and convenient to operate and post-treat.
3) Phenol and alcohol derivatives can be converted into oxygen radicals by an electrochemical oxidation method without using a metal catalyst, an oxidant, a photo-redox reagent or the like, and only hydrogen is generated as a byproduct after the reaction.
4) The raw materials of the synthon phenol and the alcohol derivative (2) and the diphenylphosphine compound (3) are cheap and easy to obtain.
5) The synthesis reaction conditions of the O-phosphino-substituted phenol and the alcohol derivative (1) are mild, the operation is simple, the product can be scaled up, and the yield is high.
In conclusion, the method realizes the cross dehydrogenation coupling reaction of phenol and alcohol derivatives and diphenylphosphine compounds under the condition of electro-oxidation and mild condition, synthesizes a series of O-phosphinyloxy substituted phenol and alcohol derivatives with diverse structures in high yield, and has the advantages of green and environment-friendly reaction, easily obtained raw materials, no need of metal catalysts and oxidation and reduction agents, mild reaction condition, wide application range, simple operation and high atom economy.
Detailed Description
The following examples are provided to aid in the understanding of the present invention, but the invention is not limited thereto.
Example 1
To a 10mL septum-free reaction tube were added phenol 2a (18. Mu.L, 0.2 mmol), diphenylphosphine 3a (52. Mu.L, 0.3 mmol), tetrabutylphosphonium iodide (TBAI) (74mg, 0.2 mmol), cesium carbonate (65mg, 0.2 mmol) and 4mL of CH in this order at normal temperature and pressure under an air atmosphere 3 CN, graphite is used as an anode (8 mm in length, 2mm in width, 50mm in height), nickel is used as a cathode (8 mm in length, 2mm in width, 50mm in height), the depth of the lower ends of the anode and the cathode inserted below the liquid level is 8mm, the distance between the two electrodes is 5mm, the planes of the length and the height of the two electrodes (the anode and the cathode) are arranged in parallel with each other (the area of the opposite surfaces of the anode and the cathode placed in the reaction solution is 64 mm) 2 ) The reaction was carried out at a constant current of 6mA for 4 hours. After completion of the reaction, extraction was carried out with ethyl acetate (3X 10 mL), the organic layers were combined, dried over anhydrous sodium sulfate, filtered, the volatile components were removed under reduced pressure, and then silica gel was usedSeparating by column chromatography (petroleum ether as eluent)
Ethyl acetate, v/v = 12) to give the desired product 1a as a white solid (57.2 mg, 97% yield). The target product was confirmed by nuclear magnetic resonance spectroscopy.
Example 2
The reaction procedure and operation conditions were the same as in example 1, except that the reaction was carried out in the absence of electric current, as in example 1. The reaction was stopped and the target product 1a was not obtained by the same post-treatment as above. Indicating that current is not necessarily absent.
Example 3
The reaction procedure and operation conditions were the same as in example 1, except that the reaction was carried out without adding electrolyte tetrabutyl iodide, as in example 1. The reaction was stopped, and the target product 1a was obtained by the same post-treatment as described above. Indicating that no electrolyte addition reaction occurred.
Example 4
The reaction procedure and operation conditions were the same as in example 1, except that the reaction was carried out in the presence of iodine instead of tetrabutylammonium iodide, as in example 1. The reaction was stopped, and the desired product 1a was not obtained by the same post-treatment as described above. Indicating that iodine cannot be recycled.
Example 5
The reaction procedure and operation conditions were the same as in example 1, except that potassium hydroxide was added in the reaction instead of cesium carbonate, in example 1. The reaction was stopped, and the desired product 1a was not obtained by the same post-treatment as described above. Indicating that potassium hydroxide does not increase the yield of the desired product.
Example 6
The reaction procedure and operating conditions were the same as in example 1, except that p-methylphenol 2b (21. Mu.l, 0.2 mmol) was added to the reaction. The reaction was stopped and worked up to give the desired product 1b as a white solid (51mg, 83%). The target product was confirmed by nuclear magnetic resonance spectroscopy.
Example 7
The reaction procedure and operating conditions were the same as in example 1, except that m-methylphenol 2c (21. Mu.l, 0.2 mmol) was added to the reaction. The reaction was stopped and worked up to give the title product 1c as a white solid (44.5 mg, 72% yield). The target product was confirmed by nuclear magnetic resonance spectroscopy.
Example 8
The reaction procedure and operation conditions were the same as in example 1, except that p-methoxyphenol 2d (25mg, 0.2mmol) was added. The reaction was stopped and worked up to give the desired product 1d as a yellow solid (30.5 mg, 47% yield). The target product was confirmed by nuclear magnetic resonance spectroscopy.
Example 9
The reaction procedure and operating conditions were the same as in example 1, except that 3-methoxyphenol 2e (22. Mu.l, 0.2 mmol) was added to the reaction. The reaction was stopped and worked up to give the title product 1e as a white solid (49 mg, 76% yield). The target product is confirmed by nuclear magnetic resonance spectroscopy.
Example 10
The reaction procedure and operating conditions were the same as in example 1, except that 2-allylphenol 2f (26. Mu.l, 0.2 mmol) was added to the reaction. The reaction was stopped, and worked up to give the objective product 1f (47.5 mg, 71% yield) as a colorless oily liquid. The target product is confirmed by nuclear magnetic resonance and high resolution mass spectrometry.
Example 11
The reaction procedure and operation conditions were the same as in example 1, except that 2g (25mg, 0.2mmol) of 2, 5-dimethylphenol was added to the reaction. The reaction was stopped and worked up to give the title product as a white solid, 1g (53.7 mg,83% yield). The target product is confirmed by nuclear magnetic resonance spectroscopy.
Example 12
The reaction procedure and operating conditions were the same as in example 1, except that 3, 5-dimethylphenol was added for 2h (25mg, 0.2mmol) during the reaction. The reaction was stopped and worked up to give the title product as a white solid for 1h (54.4 mg,83% yield). The target product is confirmed by nuclear magnetic resonance and high-resolution mass spectrometry.
Example 13
The reaction procedure and operating conditions were the same as in example 1, except that 4-methyl-2-methoxyphenol 2i (26. Mu.l, 0.2 mmol) was added to the reaction. The reaction was stopped and worked up to give the desired product 1i as a white solid (53.8 mg, 80% yield). The target product was confirmed by nuclear magnetic resonance spectroscopy.
Example 14
The reaction procedure and operating conditions were the same as in example 1, except that p-fluorophenol 2j (23mg, 0.2mmol) was added in the reaction. The reaction was stopped and worked up to give the desired product 1j (30.5 mg, 49% yield) as a yellow solid. The target product was confirmed by nuclear magnetic resonance spectroscopy.
Example 15
The reaction procedure and operating conditions were the same as in example 1, except that p-chlorophenol 2k (26mg, 0.2mmol) was added to the reaction. The reaction was stopped and worked up to give the desired product 1k as a white solid (49.5 mg, 75% yield). The target product is confirmed by nuclear magnetic resonance spectroscopy.
Example 16
The reaction procedure and operation conditions were the same as in example 1, except that 2l (35mg, 0.2mmol) of p-bromophenol was added to the reaction. The reaction was stopped and worked up to give the desired product 1l as a white solid (50.3 mg, 67% yield). The target product is confirmed by nuclear magnetic resonance spectroscopy.
Example 17
The reaction procedure and operating conditions were the same as in example 1, except that p-phenylphenol 2m (34mg, 0.2mmol) was added to the reaction. The reaction was stopped and worked up to give the desired product as a white solid, 1m (64.8 mg, 87% yield). The target product was confirmed by nuclear magnetic resonance spectroscopy.
Example 18
The reaction procedure and operation conditions were the same as in example 1 except that 4-acetylphenol 2n (27mg, 0.2mmol) was added to the reaction. The reaction was stopped and worked up to give the desired product 1n as a white solid (41.7 mg, 62% yield). The target product is confirmed by nuclear magnetic resonance spectroscopy.
Example 19
The reaction procedure and operation conditions were the same as in example 1 except that p-hydroxyacetophenone 2o (30mg, 0.2mmol) was used in the reaction. The reaction was stopped and worked up to give the title product 1o as a white solid (32.6 mg, 47% yield). The target product is confirmed by the measurement of nuclear magnetic resonance spectrum and high-resolution mass spectrum.
Example 20
The reaction procedure and operating conditions were the same as in example 1, except that 4-acetylphenol 2p (30mg, 0.2mmol) was added to the reaction. The reaction was stopped and worked up to give the desired product 1p as a yellow solid (34.1 mg, 48% yield). The target product was confirmed by nuclear magnetic resonance spectroscopy.
Example 21
The reaction procedure and operating conditions were the same as in example 1 except that 2, 4-dihydroxyacetophenone 2q (30mg, 0.2mmol) was added to the reaction. The reaction was stopped and worked up to give the title product 1q as a white solid (27.7 mg, 39% yield). The target product is confirmed by nuclear magnetic resonance and high resolution mass spectrometry.
Example 22
The reaction procedure and operating conditions were the same as in example 1, except that 2-naphthol 2r (29mg, 0.2mmol) was added to the reaction. The reaction was stopped and worked up to give the title product 1r as a white solid (61 mg, 89% yield). The target product is confirmed by nuclear magnetic resonance spectroscopy.
Example 23
The reaction procedure and operating conditions were the same as in example 1, except that 6-bromo-2-naphthol 2s (45mg, 0.2mmol) was added to the reaction. The reaction was stopped and worked up to give the desired product as a white solid, 1s (52.9 mg, 62% yield). The target product was confirmed by nuclear magnetic resonance spectroscopy.
Example 24
The reaction procedure and operation conditions were the same as in example 1, except that 6 t (30mg, 0.2mmol) of hydroxybenzothiazole was added to the reaction. The reaction was stopped and worked up to give the desired product 1t as a white solid (49.3 mg, 70% yield). The target product was confirmed by nuclear magnetic resonance spectroscopy.
Example 25
Example 26
The reaction procedure and operation conditions were the same as in example 1, except that 2-phenoxy-1-phenylethyl alcohol 2v (43mg, 0.2mmol) was added to the reaction. The reaction was stopped and worked up to give the title product 1v as a white solid (67.2 mg, 81% yield). The target product is confirmed by the measurement of nuclear magnetic resonance spectrum and high-resolution mass spectrum.
Typical Compound characterization data
Diphenylphosphine-substituted phenol and alcohol derivatives 1a-1e,1i-1n,1p,1r-1s,1u are known compounds whose nuclear magnetic resonance spectra 1 H、 13 The C NMR and melting point data are consistent with literature reports (Yujun Li, qi Yang, liquan Yang, ning Lei and Ke Zheng. Chem. Commun.,2019,55,4981, Y.Ou, Y.Huang, Z.He, G.Yu, Y.Huo, Y.Gao, X.Li and Q.chen. Chem. Commun.,2020,56, 1357-1360).
2-Allylphenyldiphenylphosphinate (1 f) as a colorless oil. 1 H NMR(CDCl 3 ,400MHz)δ7.88(dd,J＝12.5and 7.3Hz,4H),7.56-7.52(m,2H),7.48-7.44(m,4H),7.29(d,J＝7.6Hz,1H),7.17-7.15(m,1H),7.07-7.00(m,2H),6.00-5.89(m,1H),5.09-4.98(m,2H),3.45(d,J＝6.4Hz,2H)； 13 C NMR(CDCl 3 ,100MHz)δ149.3(d,J＝8.1Hz),136.2,132.5(d,J＝2.8Hz),131.8(d,J＝10.4Hz),131.3(d,J＝137.5Hz),130.8(d,J＝5.9Hz),130.7,128.7(d,J＝13.4Hz),127.6,124.6,120.1(d,J＝3.9Hz),116.4,34.5； 31 P NMR(CDCl 3 ,160MHz)δ30.7.C 21 H 19 O 2 HRMS theoretical value of P [ M + Na ]] + 337.1015; the measurement value was 337.1011.
2,5-dimethylphenyl diphenylphosphinate (1 g) as a white solid; the melting point is 114.0-115.8 ℃; 1 H NMR(CDCl 3 ,400MHz)δ7.91-7.86(m,4H),7.54-7.50(m,2H),7.47-7.43(m,4H),7.11(s,1H),7.00(d,J＝7.6Hz,1H),6.78(d,J＝7.6Hz,1H),2.24(s,3H),2.18(s,3H)； 13 C NMR(CDCl 3 ,100MHz)δ149.4(d,J＝8.3Hz),137.0,132.4(d,J＝2.8Hz),131.7(d,J＝10.3Hz),131.5(d,J＝137.7Hz),131.0,128.6(d,J＝13.3Hz),125.7(d,J＝5.7Hz),125.2,120.9(d,J＝3.6Hz),21.0,16.5； 31 P NMR(CDCl 3 ,160MHz)δ30.2.C 21 H 13 O 2 HRMS theoretical value of P [ M + H] + :3231196; the measurement value was 323.1196.
3,5-dimethyl diphenyl phosphine (1 h) white solid with melting point of 108.8-110.6 ℃; 1 H NMR(CDCl 3 ,400MHz)δ7.92–7.85(m,4H),7.55–7.50(m,2H),7.48–7.42(m,4H),6.83(s,2H),6.70(s,1H),2.21(s,6H). 13 C NMR(CDCl 3 ,100MHz)δ150.85(d,J＝8.3Hz),139.45,132.38(d,J＝2.8Hz),132.02,131.83(d,J＝10.3Hz),130.64,128.59(d,J＝13.4Hz),126.37,118.29(d,J＝4.8Hz),21.26. 31 P NMR(CDCl 3 ,160MHz)δ29.8.C 20 H 19 O 2 HRMS theoretical value of P [ M + H] + 323.1196; the measurement value was 323.1196.
4-Propioniylphenyldiphosphinate (1 o) white solid, melting point: 93.7-94.2 ℃. 1 H NMR(CDCl 3 ,400MHz)δ7.92-7.85(m,6H),7.58-7.53(m,2H),7.47(tdd,J＝6.7,3.7,1.3Hz,4H),7.32-7.27(m,2H),2.91(q,J＝7.3Hz,2H),1.18(t,J＝7.2Hz,3H)； 13 C NMR(CDCl3,100MHz)δ199.6,154.8(d,J＝8.1Hz),133.5,132.9(d,J＝2.7Hz),131.9(d,J＝10.6Hz),131.3,130.1,129.9,128.9(d,J＝13.4Hz),120.8(d,J＝5.1Hz),31.8,8.3； 31 P NMR(CDCl3,160MHz)31.4.C 21 H 20 O 3 HRMS theoretical value of P [ M + H] + 351.1150; measurement value 351.1142.
2-acetyl-4-hydroxyphenyl diphenylphosphinate (1 q) as a white solid having a melting point of 147.9-148.5 ℃; 1 H NMR(CDCl3,400MHz)δ12.41(s,1H),7.92–7.85(m,4H),7.62(d,J＝8.9Hz,1H),7.59–7.53(m,2H),7.51–7.45(m,4H),6.88(dd,J＝8.9,1.0Hz,1H),6.78(dd,J＝2.4,1.1Hz,1H),2.54(s,3H). 13 C NMR(CDCl3,100MHz)δ203.46,164.31,157.27(d,J＝7.9Hz),132.91(d,J＝2.9Hz),132.57,131.85(d,J＝10.5Hz),131.24,129.86,128.90(d,J＝13.6Hz),117.03,112.09(d,J＝4.9Hz),109.74(d,J＝5.9Hz),26.68. 31 P NMR(CDCl3,160MHz)δ31.4.C 20 H 17 O 4 HRMS theoretical value of P [ M + H] + 353.0938; the measurement value was 353.0933.
Benzo[d]1t, white solid with melting point of 113.1-115.1 ℃; 1 H NMR(CDCl3,400MHz)δ8.89(s,1H),7.98(d,J＝8.8Hz,1H),7.94-7.88(m,5H),7.56-7.52(m,2H),7.49-7.44(m,4H),7.34-7.31(m,1H)； 13 CNMR(CDCl3,100MHz)δ153.9,148.8(d,J＝8.2Hz),132.8(d,J＝2.8Hz),131.9(d,J＝10.4Hz),130.6(d,J＝137.3Hz),128.8(d,J＝13.4Hz),124.3,120.1(d,J＝5.0Hz),113.6(d,J＝4.7Hz)； 31 P NMR(CDCl3,160MHz)δ32.3.C 19 H 14 NO 2 HRMS theoretical value of PS [ M + Na ]] + 374.0375; found 374.0367.
2-phenoxy-1-phenylethynyl diphosphinate (1 v.) white solid with melting point of 58.4-59.0 ℃; 1 H NMR(CDCl3,400MHz)δ7.92–7.85(m,2H),7.74–7.67(m,2H),7.55–7.38(m,6H),7.3–7.28(m,5H),7.23(dd,J＝8.6,7.4Hz,2H),6.93(t,J＝7.4Hz,1H),6.82–6.75(m,2H),5.72(dd,J＝9.3,4.7Hz,1H),4.41(dd,J＝10.2,7.0Hz,1H),4.19(dd,J＝10.2,4.6Hz,1H). 13 C NMR(CDCl3,100MHz)δ158.30,137.71(d,J＝3.2Hz),132.47(d,J＝7.2Hz),132.15(dd,J＝10.2,2.6Hz),131.98,131.85(d,J＝5.7Hz),131.72,131.10(d,J＝6.4Hz),129.46,128.61,128.55,128.42(d,J＝3.3Hz),128.30,126.88,121.11,114.65,75.79(d,J＝5.8Hz),71.42(d,J＝4.8Hz). 31 P NMR(CDCl3,160MHz)δ32.5.C 26 H 23 O 3 HRMS theoretical value of P [ M + Na ]] + 437.1277; the measurement value was 437.1276.
Claims (10)
1. A method for synthesizing O-phosphinyl-substituted phenol and alcohol derivatives, wherein the structural formula of the O-phosphinyl-substituted phenol and alcohol derivative (1) is as follows:
in the structural formula, a substituent R is one or more than two of the following,
the substituent R is one or more than two of phenyl, naphthyl, substituted aryl and heterocyclic aryl;
or the substituent R is alkyl or substituted alkyl;
the method is characterized in that:
the synthetic route is shown as the following reaction formula, in the air atmosphere, one or more than two of phenol and alcohol derivatives (2) are used as raw materials, and the raw materials and a diphenylphosphine compound (3) are subjected to dehydrogenation coupling reaction under the action of electrochemical oxidation to generate one or more than two of O-phosphinoxy substituted phenol and alcohol derivatives (1);
wherein the substituent R is the same as the above formula (1); after the reaction is finished, separating products to obtain O-phosphinyl substituted phenol and alcohol derivatives (1);
the synthesis method is characterized by comprising the following steps: carrying out a reaction in a reaction solvent in the presence of a base;
when the phenol and alcohol derivative (2) reacts with the diphenylphosphine compound (3), the alkali is one or more of cesium carbonate, sodium carbonate, potassium carbonate or potassium phosphate; the concentration of the alkali in the reaction solvent is 0.05-1.0M;
the synthesis method is characterized by comprising the following steps: carrying out a reaction in a reaction solvent in the presence of an electrolyte;
when the phenol and alcohol derivative (2) reacts with the diphenylphosphine compound (3), the electrolyte is one or more of tetrabutylammonium iodide, 1, 3-dimethyl imidazole iodide, tetrabutylammonium hexafluorophosphate, tetraethylammonium bromide, potassium bromide, ammonium iodide or tetrabutylammonium tetrafluoroborate; the concentration of the electrolyte in the reaction solvent is 0.05-1.0M.
2. A method of synthesis according to claim 1, characterized in that: when reacting phenol and alcohol derivatives (2) with a diphenylphosphine compound (3), wherein: the reaction solvent is one or more than two of methanol, ethanol, dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone and acetonitrile; when the phenol and alcohol derivative (2) is reacted with the diphenylphosphine compound (3), the molar ratio of the phenol and alcohol derivative (2) to the diphenylphosphine compound (3) is 1-1; the molar concentration of phenol and alcohol derivative (2) in the reaction solvent is 0.1-1.5M.
3. A method of synthesis according to claim 1, characterized in that: the reaction is carried out in a reaction vessel provided with a cathode and an anode, the anode and the cathode are oppositely arranged at a distance of 3-10mm, part or all of the cathode and the anode are arranged in a reaction solution of a reaction system, and the area of the opposite surfaces of the anode and the cathode arranged in the reaction solution is 25-100mm 2 (ii) a And applying current between a cathode and an anode in the reaction system, wherein the current introduced into the reaction system is 1-10mA.
4. A synthesis method according to claim 1 or 3, characterized in that: when the phenol and alcohol derivative (2) are reacted with the diphenylphosphine compound (3), the reaction time is 1 to 24 hours.
5. A method of synthesis according to claim 1, characterized in that: when the phenol and alcohol derivative (2) are reacted with the diphenylphosphine compound (3), the reaction temperature is from room temperature to 80 ℃.
6. A synthesis method according to claim 1 or 3, characterized in that: when the phenol and alcohol derivative (2) reacts with the diphenylphosphine compound (3), the cathode and the anode are one or two of graphite, nickel, platinum or reticular glassy carbon electrodes.
7. A method of synthesis according to claim 1, characterized in that: the substituent of the substituted aryl is one or more of F, cl, br, alkyl with 1-4 carbon atoms and alkoxy with 1-4 carbon atoms.
8. A method of synthesis according to claim 1, characterized in that: the substituent R is alkyl or substituted alkyl;
wherein the carbon atom number of the alkyl is 1-4;
the substituent in the substituted alkyl is one or more of aryl and benzyl ether, the aryl is phenyl or substituted aryl, and the substituent in the substituted aryl is one or more of F, cl, br, alkyl with 1-4 carbon atoms and alkoxy with 1-4 carbon atoms.
9. A method of synthesis according to claim 3, characterized in that: the area of the opposite surfaces of the anode and the cathode placed in the reaction solution is 64-100mm 2 。
10. The method of synthesis according to claim 4, wherein: when the phenol and alcohol derivative (2) are reacted with the diphenylphosphine compound (3), the reaction time is 3 to 4 hours.
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Citations (2)
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| WO2015030440A1 (en) * | 2013-09-02 | 2015-03-05 | 고려대학교 산학협력단 | Thermal dehydroboration of hydroxy arene boronic acid compound, and method for preparing hydroxy arene compound in which functional group is introduced to ortho or meta position of phenolic compound, using thermal dehydroboration |
| CN111206262A (en) * | 2020-02-25 | 2020-05-29 | 新疆大学 | Synthesis method of N-phosphino-substituted carbazole and indole derivatives |
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| WO2015030440A1 (en) * | 2013-09-02 | 2015-03-05 | 고려대학교 산학협력단 | Thermal dehydroboration of hydroxy arene boronic acid compound, and method for preparing hydroxy arene compound in which functional group is introduced to ortho or meta position of phenolic compound, using thermal dehydroboration |
| CN111206262A (en) * | 2020-02-25 | 2020-05-29 | 新疆大学 | Synthesis method of N-phosphino-substituted carbazole and indole derivatives |
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| "Electrochemical Dehydrogenative Phosphorylation of Alcohols for the";Deng, Lingling等;《 Journal of Organic Chemistry》;20191231;第949-956页 * |
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