CN105037428A - Preparation method for coumarin-3-phosphonate derivative - Google Patents

Preparation method for coumarin-3-phosphonate derivative Download PDF

Info

Publication number
CN105037428A
CN105037428A CN201510406290.4A CN201510406290A CN105037428A CN 105037428 A CN105037428 A CN 105037428A CN 201510406290 A CN201510406290 A CN 201510406290A CN 105037428 A CN105037428 A CN 105037428A
Authority
CN
China
Prior art keywords
coumarin
preparation
phosphonate derivative
derivative
following group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510406290.4A
Other languages
Chinese (zh)
Other versions
CN105037428B (en
Inventor
袁金伟
李远哲
肖咏梅
杨亮茹
游利琴
买文鹏
毛璞
屈凌波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henan University of Technology
Original Assignee
Henan University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henan University of Technology filed Critical Henan University of Technology
Priority to CN201510406290.4A priority Critical patent/CN105037428B/en
Publication of CN105037428A publication Critical patent/CN105037428A/en
Application granted granted Critical
Publication of CN105037428B publication Critical patent/CN105037428B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention discloses a preparation method for a coumarin-3-phosphonate derivative (I) and belongs to the field of organic chemistry. By taking a substituted coumarin derivative and phosphite ester as raw materials, the coumarin-3-phosphonate derivative is synthesized under the joint action of an AgNO3 catalyst and an adjuvant. The raw materials are low in price and are easily available, the reaction condition is wild, the operation is simple and convenient, the synthetic yield is high, and industrial production is facilitated. The derivative has potential application in the field of materials, chemical engineering, medicines and the like. The preparation method disclosed by the invention provides a novel path for synthesizing the coumarin-3-phosphonate derivative. The formula is shown in the description.

Description

A kind of preparation method of coumarin-3-phosphonate derivative
Technical field
The present invention relates to a kind of preparation method of coumarin-3-phosphonate derivative, belong to organic chemistry filed.
Background technology
Tonka bean camphor is the important natural product of a class, and its derivative has biological activity widely, as antimicrobial antiphlogistic, anti-senile dementia, AntiHIV1 RT activity and anti-thymic carcinoma etc.The phosphonylation tonka bean camphor of 3-, as the phosphorous derivant of tonka bean camphor, has good cytotoxicity to the leukemia cell of the mankind, and therefore, the synthesis of the phosphonylation coumarin derivatives of research 3-has important practical significance.
At present, the synthesis of coumarin-3-phosphonate derivative adopts Knoevenagel to react usually or Arbuzov reaction realizes, but these methods need polystep reaction and condition is relatively harsh, lacks economy and practicality.Document " ZhouP, JiangYJ, ZouJP, etal.Mn (OAc) 3-mediatedfreeradicalphosphonylationofflavonesandcoumarins [J] .Synthesis, 2012,44:1043-1050. " and " Zou Jianping, Jiang Yaojia, Pan Xiangqiang. a kind of method [P] .CN101497632A of synthesizing coumarin-3-phosphonate derivative " with Mn (OAc) 3for catalyzer, lipid acid is solvent, and tonka bean camphor and phosphite reactions obtain the phosphonylation coumarin derivatives of 3-.Document " MiX; HuangMM; ZhangJY; etal.Regioselectivepaddadium-catalyzedphosphonationofcou marinswithdialkylH-phosphonatesviaC-Hfunctionalization [J] .OrgLett; 2013,15 (24): 6266-6269. " is catalyzer with metal Pd, 2,2 '-dipyridyls etc. are part, K 2s 2o 8for oxygenant, tonka bean camphor and phosphorous acid ester obtain the phosphonylation coumarin derivatives of 3-by metal activation 3 hydrogen.Document " MiX; WangCY; HuangMM; etal.Silver-catalyzedsynthesisof3-phosphoratedcoumarinsv iaradicalcyclizationofalkynoatesanddialkylH-phosphonates [J] .OrgLett; 2014,16 (12): 3356-3359. " is with Ag 2cO 3for catalyzer, with alkynes ester for raw material, obtain the phosphonylation coumarin derivatives of 3-with phosphorous acid ester by free radical reaction.But these synthetic methods need acid to make solvent, or use precious metal to be catalyzer, or use the shortcomings such as the reacting precursor that is difficult to obtain.Therefore; be badly in need of inquiring into a kind of step simple, mild condition, the synthetic method of the coumarin-3-phosphonate derivative that yield is higher; this will promote the exploitation of coumarin-3-phosphonate derivative, has great importance to the research and development of protection China independent intellectual property right.
Summary of the invention
Based on above-mentioned research background, the object of the present invention is to provide a kind of mild condition, yield high, obtained the new synthetic method of coumarin-3-phosphonate derivative by single step reaction.
For realizing the object of the invention, the present invention with substituted cumarin and phosphorous acid ester for raw material, at catalyst A gNO 3with synthesizing coumarin-3-phosphonate derivative under auxiliary acting in conjunction.Coumarin-3-phosphonate derivative of the present invention has following general formula I.
Wherein R represents following group: C1-5 alkyl, phenyl or benzyl, preferably-CH 3,-C 2h 5,-CH 2cH 2cH 3,-CH (CH 3) 2; R 1represent one of hydrogen base or following group: methyl, ethyl, methoxy or ethoxy, preferably-H ,-CH 3,-OCH 3; R 2represent hydrogen base or following group monosubstituted or two replacement on phenyl ring: methyl, ethyl, methoxyl group, oxyethyl group, nitro, amino, hydroxyl, kharophen, acetoxyl group or halogen, R 2be preferably as follows group monosubstituted on phenyl ring :-F ,-Cl ,-Br ,-CH 3,-C 2h 5,-OCH 3,-OC 2h 5,-OH ,-NH 2,-NHCOCH 3.
Concrete technical scheme realizes as follows: be first dissolved in suitable organic solvent by substituted cumarin A and phosphorous acid ester B, then add catalyst A gNO 3and auxiliary, react at 80-100 DEG C.After reaction terminates, be cooled to room temperature, through washing, extraction, dry, pressure reducing and steaming solvent, obtains general formula (I) coumarin-3-phosphonate derivative crude product.
The preferred 1:2 of mol ratio of substituted cumarin A and phosphorous acid ester B.Catalyst A gNO 3amount be 5% of substituted cumarin molar weight.
Mg (NO selected by auxiliary 3) 26H 2o, Fe (NO 3) 39H 2o, NaNO 3, Cu (NO 3) 23H 2o, Cr (NO 3) 39H 2o, preferred Mg (NO 3) 26H 2o is as auxiliary, and the amount added is 50% of substituted cumarin molar weight.
In organic solvent selection THF, toluene, dioxane, methyl alcohol, chloroform, DMSO and acetonitrile etc., one or more are as solvent, and preferred acetonitrile is solvent.Preferred employing 90 DEG C is best temperature of reaction, and the best reaction times is 5h.
R, R in formula 1, R 2state the same.
Abstraction and purification coumarin-3-phosphonate derivative crude product, such as, is undertaken being separated to obtain coumarin-3-phosphonate derivative (I) by silica gel column chromatography by crude product, makes it obtain better application.In addition, by adding appropriate sherwood oil in the ethyl acetate solution of (I), (I) crystallization can be made.This analog derivative has potential application in material, chemical industry, medicine and other fields.
Agents useful for same of the present invention all commercially.
The principle of the invention is: first phosphorous acid ester reacts with Silver Nitrate and generate intermediate ((CH 3) 2cHO) 2p (O) Ag mixture, sloughs Ag (0) and forms phosphorus free radical afterwards; Then 3 carbon atoms of phosphorus free radical attack tonka bean camphor, form carbon radicals, by Ag (I) effect, obtain an electronics and form Ag (0), thus form a carbonium ion; Target product coumarin-3-phosphonate derivative is obtained finally by cancellation proton.
Beneficial effect of the present invention is: the method cheaper starting materials of synthesizing coumarin-3-phosphonate derivative of the present invention is easy to get, reaction conditions gentle, obtain target compound by single step reaction, easy and simple to handle, synthetic yield is high, reach more than 60%, be very beneficial for suitability for industrialized production, for preparation there is antimicrobial antiphlogistic, the coumarin-3-phosphonate derivative of anticancer isoreactivity provides a new approach.
Embodiment
Below by embodiment, the present invention will be further elaborated, but and do not mean that content limitation of the present invention is in embodiment.
Embodiment 1.R=-CH (CH 3) 2, R 1=R 2during=-H, the preparation of tonka bean camphor-3-di-isopropyl phosphate derivatives
Tonka bean camphor (0.5mmol, 73mg) is added and diisopropyl phosphite (1.0mmol, 166mg) is dissolved in 3.0mLCH in 10mL reaction flask 3in CN, then add AgNO 3(0.025mmol, 4.2mg) and Mg (NO 3) 26H 2o (0.25mmol, 64mg).React under heated and stirred in oil bath, temperature of reaction is 90 DEG C.By TLC tracking reaction process, the reaction times is 5h, after reaction terminates, removes solvent under reduced pressure, adds 10mL ethyl acetate in raffinate, with the NaHCO that 20mL is saturated 3washing secondary, then the brine It using 10mL saturated is once, purifies (eluent: ethyl acetate/petroleum ether=1/5), obtain white solid 0.096g, productive rate 62.0% after solution is concentrated with silica gel column chromatography.
Fusing point 95-96 DEG C. 1hNMR (CDCl 3) δ: 8.49 (d, J p-H=6.9Hz, 1H), 7.62-7.55 (m, 2H), 7.32-7.28 (m, 2H), 4.87-4.79 (m, 2H), 1.34 (dd, J p-H=12.9Hz, J h-H=6.0Hz, 12H). 13cNMR (CDCl 3) δ: 158.1 (d, J p-C=22.9Hz), 155.2,152.9 (d, J p-C=10.7Hz), 134.0,129.3,124.8,119.8,118.0 (d, J p-C=22.7Hz), 116.8,72.2 (d, J p-C=9.8Hz), 24.0 (d, J p-C=6.8Hz), 23.8 (d, J p-C=7.6Hz). 31pNMR (CDCl 3) δ: 8.2.IR (KBr) ν (cm -1): 2981,2935 (-CH 3), 1738 (C=O), 1614,1566 (Ar-), 1450 (P-C), 1248 (P=O), 1105 (P-O) .ESIMS311.3 [M+H] +(calculatedforC 15h 20o 5p +311.1).
Embodiment 2.R=-CH 2cH 2cH 3, R 1=-H, R 2during=-H, the preparation of tonka bean camphor-3-diη-propyl phosphate derivatives
In 10mL reaction flask, add tonka bean camphor (0.5mmol, 73mg) and di-n-propyl phosphite (1.0mmol, 166mg) is dissolved in 3.0mL chloroform, then add AgNO 3(0.025mmol, 4.2mg) and Fe (NO 3) 39H 2o (0.25mmol, 101mg).React under heated and stirred in oil bath, temperature of reaction is 80 DEG C.By TLC tracking reaction process, the reaction times is 5h, after reaction terminates, removes solvent under reduced pressure, adds 10mL ethyl acetate in raffinate, with the NaHCO that 20mL is saturated 3washing secondary, then the brine It using 10mL saturated is once, purifies (eluent: ethyl acetate/petroleum ether=1/5), obtain faint yellow viscous liquid 0.093g, productive rate 60.0% after solution is concentrated with silica gel column chromatography.
1HNMR(CDCl 3)δ:8.50(d,J P-H＝6.9Hz,1H),7.64-7.56(m,2H),7.34-7.29(m,2H),4.20-4.06(m,4H),1.76-1.68(m,4H),0.94(d,J H-H＝7.4Hz,6H). 13CNMR(CDCl 3)δ:158.1(d,J P-C＝23.4Hz),155.2,153.4(d,J P-C＝10.5Hz),134.2,129.3,124.9,118.8,117.9(d,J P-C＝22.7Hz),116.8,68.8(d,J P-C＝10.2Hz),23.8(d,J P-C＝10.4Hz),10.0. 31PNMR(CDCl 3)δ:10.5.IR(KBr)ν(cm -1):2968,2931,2850(-CH 3,-CH 2),1732(C＝O),1610,1564(Ar-),1445(P-C),1248(P＝O),1008(P-O).ESIMS311.2[M+H] +(calculatedforC 15H 20O 5P +311.1).
Embodiment 3.R=-CH (CH 3) 2, R 1=-H, R 2=-OCH 3time, the preparation of ayapanin-3-di-isopropyl phosphate derivatives
In 25mL reaction flask, add ayapanin (1.0mmol, 176mg) and diisopropyl phosphite (2.0mmol, 232mg) is dissolved in 5.0mL methyl alcohol, then add AgNO 3(0.05mmol, 8.4mg) and NaNO 3(0.5mmol, 42.5mg).React under heated and stirred in oil bath, temperature of reaction is 90 DEG C.By TLC tracking reaction process, the reaction times is 5h, after reaction terminates, removes solvent under reduced pressure, adds 10mL ethyl acetate in raffinate, with the NaHCO that 20mL is saturated 3washing secondary, then the brine It using 10mL saturated is once, purifies (eluent: ethyl acetate/petroleum ether=1/3), obtain white solid 0.216g, productive rate 64.0% after solution is concentrated with silica gel column chromatography.
Fusing point 76-77 DEG C. 1hNMR (CDCl 3) δ: 8.37 (d, J p-H=6.8Hz, 1H), 7.42 (d, J h-H=8.7Hz, 1H), 6.82 (dd, J h-H=2.4Hz, J h-H=8.7Hz, 1H), 6.74 (d, J h-H=2.4Hz, 1H), 4.80-4.72 (m, 2H), 1.33 (d, J h-H=6.2Hz, 6H), 1.26 (d, J h-H=6.2Hz, 6H). 13cNMR (CDCl 3) δ: 164.7,158.4 (d, J p-C=23.7Hz), 157.4,152.9 (d, J p-C=11.3Hz), 130.4,113.2 (d, J p-C=16.6Hz), 111.7 (d, J p-C=23.2Hz), 100.5,71.9 (d, J p-C=9.6Hz), 55.9,24.0 (d, J p-C=6.5Hz), 23.8 (d, J p-C=7.5Hz). 31pNMR (CDCl 3) δ: 8.8.IR (KBr) ν (cm -1): 2981,2935 (-CH 3), 1738 (C=O), 1614,1553 (Ar-), 1373 (P-C), 1252 (P=O), 1142 (P-O) .ESIMS341.3 [M+H] +(calculatedforC 16h 22o 6p +341.1).
Embodiment 4.R=-CH (CH 3) 2, R 1=-H, R 2=-NO 2time, the preparation of 6-nitro tonka bean camphor-3-di-isopropyl phosphate derivatives
In 25mL reaction flask, add 6-nitro tonka bean camphor (1.0mmol, 191mg) and diisopropyl phosphite (2.0mmol, 232mg) is dissolved in 5.0mL dioxane, then add AgNO 3(0.05mmol, 8.4mg) and Cr (NO 3) 39H 2o (0.5mmol, 200mg).React under heated and stirred in oil bath, temperature of reaction is 100 DEG C.By TLC tracking reaction process, the reaction times is 5h, after reaction terminates, removes solvent under reduced pressure, adds 10mL ethyl acetate in raffinate, with the NaHCO that 20mL is saturated 3washing secondary, then the brine It using 10mL saturated is once, purifies (eluent: ethyl acetate/petroleum ether=2/1), obtain faint yellow viscous liquid 0.212g, productive rate 60.0% after solution is concentrated with silica gel column chromatography.
1HNMR(CDCl 3)δ:8.56(d,J P-H＝5.9Hz,1H),8.54(s,1H),8.48(dd,J H-H＝2.6Hz,J H-H＝9.0Hz,1H),7.50(d,J H-H＝9.0Hz,1H),4.95-4.87(m,2H),1.43(d,J H-H＝6.2Hz,6H),1.35(d,J H-H＝6.2Hz,6H). 13CNMR(CDCl 3)δ:158.4,156.5(d,J P-C＝22.3Hz),150.9(d,J P-C＝10.5Hz),144.1,128.2,124.9,122.9,121.0,118.1,118.0(d,J P-C＝23.5Hz),72.8(d,J P-C＝10.2Hz),24.0(d,J P-C＝6.5Hz),23.8(d,J P-C＝6.5Hz). 31PNMR(CDCl 3)δ:5.6.IR(KBr)ν(cm -1):3087,2965(-CH 3,),1735(C＝O),1625,1578(Ar-),1376(P-C),1245(P＝O),1134(P-O).ESIMS356.1[M+H] +(calculatedforC 15H 19NO 7P +356.0).
Embodiment 5.R=-CH (CH 3) 2, R 1=-CH 3, R 2during=-OH, the preparation of AP20am16-3-di-isopropyl phosphate derivatives
AP20am16 (1.0mmol, 176mg) is added and diisopropyl phosphite (2.0mmol, 232mg) is dissolved in 5.0mLCH in 25mL reaction flask 3in CN, then add AgNO 3(0.05mmol, 8.4mg) and Cu (NO 3) 23H 2o (0.5mmol, 120.5mg).React under heated and stirred in oil bath, temperature of reaction is 90 DEG C.By TLC tracking reaction process, the reaction times is 5h, after reaction terminates, removes solvent under reduced pressure, adds 10mL ethyl acetate in raffinate, with the NaHCO that 20mL is saturated 3washing secondary, then the brine It using 10mL saturated is once, purifies (eluent: ethyl acetate/petroleum ether=5/1), obtain faint yellow viscous liquid 0.21g, productive rate 62.0% after solution is concentrated with silica gel column chromatography.
1HNMR(CDCl 3)δ:10.1(s,-OH),7.64(d,J H-H＝8.9Hz,1H),6.94(dd,J H-H＝2.4Hz,J H-H＝8.9Hz,1H),6.89(d,J H-H＝2.4Hz,1H),4.89-4.80(m,2H),2.90(d,J P-H＝0.9Hz,3H),1.40(d,J H-H＝6.2Hz,6H),1.33(d,J H-H＝6.2Hz,6H). 13CNMR(CDCl 3)δ:163.4(d,J P-C＝20.8Hz),159.5(d,J P-C＝25.3Hz),155.7,127.5,114.1,112.6(d,J P-C＝25.2Hz),111.1,109.1,102.8,72.4(d,J P-C＝10.0Hz),24.0(d,J P-C＝7.4Hz),23.8(d,J P-C＝7.4Hz),17.1(d,J P-C＝6.2Hz). 31PNMR(CDCl 3)δ:10.0.IR(KBr)ν(cm -1):3105(-OH),2993,2905(-CH 3),1736(C＝O),1599,1482(Ar-),1352(P-C),1198(P＝O),1005(P-O).ESIMS341.2[M+H] +(calculatedforC 16H 22O 6P +341.1).
Embodiment 6.R=-CH (CH 3) 2, R 1=-CH 3, R 2=-OC 2h 5time, the preparation of 4-methyl-CYP1A-3-di-isopropyl phosphate derivatives
In 25mL reaction flask, add 4-methyl-CYP1A (1.0mmol, 204mg) and diisopropyl phosphite (2.0mmol, 232mg) is dissolved in 5.0mL toluene, then add AgNO 3(0.05mmol, 8.4mg) and Mg (NO 3) 26H 2o (0.5mmol, 128mg).React under heated and stirred in oil bath, temperature of reaction is 90 DEG C.By TLC tracking reaction process, the reaction times is 5h, after reaction terminates, removes solvent under reduced pressure, adds 10mL ethyl acetate in raffinate, with the NaHCO that 20mL is saturated 3washing secondary, then the brine It using 10mL saturated is once, purifies (eluent: ethyl acetate/petroleum ether=5/1), obtain clear crystal 0.24g, productive rate 68.0% after solution is concentrated with silica gel column chromatography.
Fusing point 83-84 DEG C. 1hNMR (CDCl 3) δ: 7.70 (dd, J h-H=4.7Hz, J h-H=8.6Hz, 1H), 6.87-6.85 (m, 1H), 6.74 (d, J h-H=2.5Hz, 1H), 4.83-4.80 (m, 2H), 4.12-4.09 (m, 2H), 2.96 (d, J p-H=1.1Hz, 3H), 1.45 (d, J h-H=5.5Hz, 1H), 1.41-1.38 (m, 6H), 1.33-1.30 (m, 6H). 13cNMR (CDCl 3) δ: 163.4,162.6 (d, J p-C=17.1Hz), 158.8 (d, J p-C=23.3Hz), 155.6,127.2,113.5 (d, J p-C=25.8Hz), 113.1,111.2,100.6,71.6 (d, J p-C=9.7Hz), 64.3,24.0 (d, J p-C=7.2Hz), 23.9 (d, J p-C=7.2Hz), 16.8 (d, J p-C=5.7Hz), 14.4. 31pNMR (CDCl 3) δ: 10.2.IR (KBr) ν (cm -1): 3096,2967,2855 (-CH 3,-CH 2), 1735 (C=O), 1562,1480 (Ar-), 1340 (P-C), 1178 (P=O), 1025 (P-O) .ESIMS369.2 [M+H] +(calculatedforC 18h 26o 6p +369.1).
Embodiment 7.R=-CH (CH 3) 2, R 1=-H, R 2=-OCH 3time, the preparation of 6,7-escoparone-3-di-isopropyl phosphate derivatives
6,7-escoparone (1.0mmol, 204mg) is added and diisopropyl phosphite (2.0mmol, 232mg) is dissolved in 5.0mLCH in 25mL reaction flask 3in CN, then add AgNO 3(0.05mmol, 8.4mg) and Mg (NO 3) 26H 2o (0.5mmol, 128mg).React under heated and stirred in oil bath, temperature of reaction is 90 DEG C.By TLC tracking reaction process, the reaction times is 5h, after reaction terminates, removes solvent under reduced pressure, adds 10mL ethyl acetate in raffinate, with the NaHCO that 20mL is saturated 3washing secondary, then the brine It using 10mL saturated is once, purifies (eluent: ethyl acetate/petroleum ether=2/1), obtain white solid 0.277g, productive rate 75.0% after solution is concentrated with silica gel column chromatography.
Fusing point 196-198 DEG C. 1hNMR (CDCl 3) δ: 8.43 (d, J=16.9Hz), 6.9 (s, 1H), 6.84 (s, 1H), 4.87-4.47 (m, 2H), 3.98 (s, 3H, OCH 3), 3.93 (s, 3H, OCH 3), 1.41 (d, J=6.2Hz, 6H), 1.33 (d, J=6.2Hz, 6H). 13cNMR (CDCl 3): δ 158.70 (d, J=14.4Hz), 154.96,152.78 (d, J=7.0Hz), 152.03,146.71,114.67 (d, J=197.2Hz), 110.79 (d, J=14.5Hz), 108.69,99.69,72.02 (d, J=6.0Hz), 56.59,56.41,24.10 (d, J=4.2Hz), 23.89 (d, J=4.7Hz). 31pNMR (CDCl 3) δ: 9.96.IR (KBr) ν (cm -1): 2980,2934 (-CH 3), 1740 (C=O), 1615,1554 (Ar-), 1368 (P-C), 1250 (P=O), 1138 (P-O) .ESIMS:m/z371.1 ([M+H] +, C 17h 24o 7p +calcd.371.1)..

Claims (3)

1. such as formula a preparation method for coumarin-3-phosphonate derivative (I) Suo Shi, it is characterized in that, synthesize as follows: first substituted cumarin derivative A and phosphorous acid ester B is dissolved in organic solvent, then add catalyst A gNO 3and auxiliary, react at 80-100 DEG C; After reaction terminates, be cooled to room temperature, through washing, extraction, dry, pressure reducing and steaming solvent, obtains general formula (I) coumarin-3-phosphonate derivative crude product;
Wherein R represents following group: C1-5 alkyl, phenyl or benzyl; R 1represent following group: hydrogen base, methyl, ethyl, methoxy or ethoxy; R 2represent hydrogen base or monosubstituted or disubstituted following group on phenyl ring: methyl, ethyl, methoxyl group, oxyethyl group, nitro, amino, hydroxyl, kharophen, acetoxyl group or halogen;
Described auxiliary is Mg (NO 3) 26H 2o, Fe (NO 3) 39H 2o, NaNO 3, Cu (NO 3) 23H 2o, Cr (NO 3) 39H 2o;
Described organic solvent is one or more in THF, toluene, dioxane, methyl alcohol, chloroform, DMSO or acetonitrile.
2. the preparation method of coumarin-3-phosphonate derivative according to claim 1, is characterized in that,
R choosing-CH 3,-C 2h 5,-CH 2cH 2cH 3,-CH (CH 3) 2; R 1select following group :-H ,-CH 3,-OCH 3; R 2mono-substituted following group on phenyl ring :-F ,-Cl ,-Br ,-CH 3,-C 2h 5,-OCH 3,-OC 2h 5,-OH ,-NH 2,-NHCOCH 3.
3. the preparation method of coumarin-3-phosphonate derivative according to claim 1 or 2, it is characterized in that, described reaction raw materials substituted cumarin A and the mol ratio of phosphorous acid ester B are 1:2.
CN201510406290.4A 2015-07-10 2015-07-10 Preparation method for coumarin-3-phosphonate derivative Active CN105037428B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510406290.4A CN105037428B (en) 2015-07-10 2015-07-10 Preparation method for coumarin-3-phosphonate derivative

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510406290.4A CN105037428B (en) 2015-07-10 2015-07-10 Preparation method for coumarin-3-phosphonate derivative

Publications (2)

Publication Number Publication Date
CN105037428A true CN105037428A (en) 2015-11-11
CN105037428B CN105037428B (en) 2017-01-25

Family

ID=54444446

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510406290.4A Active CN105037428B (en) 2015-07-10 2015-07-10 Preparation method for coumarin-3-phosphonate derivative

Country Status (1)

Country Link
CN (1) CN105037428B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105566384A (en) * 2016-01-15 2016-05-11 河南工程学院 Method for preparing (E)-2-aryl-alpha, beta-unsaturated carbonyl phosphonate derivative
CN107955037A (en) * 2017-11-21 2018-04-24 哈尔滨工业大学 A kind of preparation method of benzenephosphonic acid ester derivant

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008209361A (en) * 2007-02-28 2008-09-11 Nobuaki So Lipid membrane localized fluorescent probe
CN101497632A (en) * 2009-03-04 2009-08-05 苏州大学 Method for synthesizing coumarin-3-phosphonate derivative
CN103254236A (en) * 2013-05-28 2013-08-21 苏州大学 Preparation method of 4-aryl coumarin-3-phosphonate derivatives

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008209361A (en) * 2007-02-28 2008-09-11 Nobuaki So Lipid membrane localized fluorescent probe
CN101497632A (en) * 2009-03-04 2009-08-05 苏州大学 Method for synthesizing coumarin-3-phosphonate derivative
CN103254236A (en) * 2013-05-28 2013-08-21 苏州大学 Preparation method of 4-aryl coumarin-3-phosphonate derivatives

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
XIA MI ET AL.: "Silver-Catalyzed Synthesis of 3‑Phosphorated Coumarins via Radical Cyclization of Alkynoates and Dialkyl H‑Phosphonates", 《ORGANIC LETTERS》 *
姜耀甲: "醋酸锰引发的膦自由基选择性反应研究及其应用", 《工程科技1辑》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105566384A (en) * 2016-01-15 2016-05-11 河南工程学院 Method for preparing (E)-2-aryl-alpha, beta-unsaturated carbonyl phosphonate derivative
CN107955037A (en) * 2017-11-21 2018-04-24 哈尔滨工业大学 A kind of preparation method of benzenephosphonic acid ester derivant

Also Published As

Publication number Publication date
CN105037428B (en) 2017-01-25

Similar Documents

Publication Publication Date Title
Yam et al. A Novel High‐Nuclearity Luminescent Gold (i)–Sulfido Complex
CN105859774B (en) A kind of preparation method of phosphine benzene-like compounds
US20040259922A1 (en) Epothilone derivatives, a process for their production thereof and their use
US5457219A (en) Phosphorus compounds
US7767825B2 (en) 2,2′,6,6′-tetraoxazolinyl biphenyl ligand and method for preparing the same
DE112011104615B4 (en) Organoboron compound and method of making same
Recsei et al. Synthesis of modified binol-phosphoramidites
Yuan et al. Silver-catalyzed synthesis of 2-arylvinylphosphonates by cross-coupling of β-nitrostyrenes with H-phosphites
KR20130105778A (en) Novel method for preparing 5-acetoxymethylfurfural using alkylammonium acetate salts
CN105037428A (en) Preparation method for coumarin-3-phosphonate derivative
CN105566384A (en) Method for preparing (E)-2-aryl-alpha, beta-unsaturated carbonyl phosphonate derivative
CA2571592C (en) Process for preparing diisopropyl((1-(hydroxymethyl)-cyclopropyl)oxy) methylphosphonate
DE60209810T2 (en) (ARYL) (AMINO) BORANESE AND METHOD FOR THE PRODUCTION THEREOF
Biricik et al. New bis (diphenylphosphino) aniline derivatives: Synthesis and spectroscopic characterization
CN108299486A (en) A method of cyclopropylboronic acid ester compounds are prepared based on iron catalysis
CN105209435A (en) Pyridine- or pyrazine-containing compounds
CN109734667B (en) Polysubstituted imidazole compound and synthesis method and application thereof
Taylor et al. Spontaneous dehydrocoupling in peri-substituted phosphine–borane adducts
CN102977040B (en) Method for synthesizing 2-quinoxalinyl dimethylacetal and 2-quinoxalinyl formaldehyde
CN1465580A (en) Simple method for synthesizing pro-drug of compete A-4
CN108409784B (en) Preparation method of phosphorus chiral important intermediate
Failla et al. SYNTHESIS AND CHARACTERIZATION OF AMINOPYRIDIN-2-YL-METHYL-PHOSPHONIC ACIDS
CN112110800B (en) 3-aryl-2-propyne-1-alcohol derivative and preparation method thereof
CN113773294B (en) Preparation method and application of flavone and isoflavone compounds
Gessner Diphenyl [2-(phenylsulfonyl) propan-2-yl]-λ5-phosphanethione

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant