CN102249969A - Phenyl-(3-aryl-2-allyl)selenide compounds, and preparation method and application thereof - Google Patents
Phenyl-(3-aryl-2-allyl)selenide compounds, and preparation method and application thereof Download PDFInfo
- Publication number
- CN102249969A CN102249969A CN2011102204940A CN201110220494A CN102249969A CN 102249969 A CN102249969 A CN 102249969A CN 2011102204940 A CN2011102204940 A CN 2011102204940A CN 201110220494 A CN201110220494 A CN 201110220494A CN 102249969 A CN102249969 A CN 102249969A
- Authority
- CN
- China
- Prior art keywords
- aryl
- phenyl
- propenyl
- selenide
- selenide compounds
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of organic synthesis, and discloses phenyl-(3-aryl-2-allyl)selenide compounds, and a preparation method and application thereof. The phenyl-(3-aryl-2-allyl)selenide compounds are shown as a formula in the specifications; and in the formula, R1 is selected from alkyl with 1 to 6 carbon atoms, aryl and sulfo-heteroaryl. The invention also provides a preparation method for the phenyl-(3-aryl-2-allyl)selenide compounds. The method comprises the following step of: reacting allyl carbonate compounds 2 with selenophenol sodium salt 1 at the temperature of between -10 and 50DEG C for 6 to 48 hours in an organic solvent by taking an iridium complex generated by reacting [Ir(COD)Cl]2 with a chiral ligand L as a catalyst to obtain the phenyl-(3-aryl-2-allyl)selenide compounds 3. Compared with the prior art, the method has the advantages of mild reaction conditions, simple operation, high yield of the reaction, and high regioselectivity.
Description
Technical field
The invention belongs to technical field of organic synthesis, relate to a kind of phenyl-(3-aryl-2-propenyl) selenide compounds, preparation method and application thereof.
Background technology
Selenium is a kind of very important trace element, can be used as useful nutritive element of essential nutritive element of photochromics, electrolytic manganese industry catalyzer, animal body and plant etc.The allyl group selenide is important organic synthesis intermediate, and the allyl group selenide loses α-hydrogen and generation area alkylated reaction optionally easily.[a) Clive, D L.J.Tetrahedron.1979,34,1049.b) Hiroi, K.; And Sato, H.Chem.Lett.1986,10,1723.c) Rich, H.J.Oxidation in Organic Chernistrl, Part C, Ed.; Trahanovsky, W.S., Acdemic Press, New York, 1978,1-130.d) Organoselenium Chemistry; A Practica Approach, ed.T.G.Back, Oxford, New York, 1990; E) Organoselenium Chemistry:Modern Developments in Organic Synthesis, ed.T.Wirth, Springer, Berlin, 2000.f) Abe, H.; Yamasaki, A.; Koshiba, N.; Takeuchi, Y.; And Harayama, T.; Chem.Pharm.Bull.2001.49,1223.] multiple rearrangement reaction can take place in the allyl group selenide, and these rearrangement reactions extensively have application in organic synthesis.[a) Sharpless, K.B.; And Lauer, R.F.J.Am.Chem.Soc.1972,94,7154.b) Sharpleas, K.B.; Iauer, R.F.J.Am.Chem.Soc.1973,95,2697.c) Reich, H.J.Org.Chem.1975,40,2570.c) J.N.Fitzner, R.G.Shea, J.E.Fankhauser and P.B.Hopkins, J.Org.Chem., 1985,50,419.d) T.Hori and K.B.Sharpless, J.Org.Chem., 1979,44,4208.] seleno in the allyl group selenide also is a reactive group, easily is substituted, and forms various substituents.[a) Fitmer, J.N.; Shea, R.G.; Fankhauser, J.E.; And Hopkin, P.B.J.Org.Chem.1985,50,417.b) Shea, R.G.; Fitzner, J.N.; Fankhauser, J.E.; Spaltenstein, A.; Carpino, P.A.; Peevey, R.M.; Pratt, D.V.; Tenge, B.J.; And Hopkins, P.B.J.Org.Chem.1986,51,5243.c) Shea, R.G.; Fitzner, J.N.; And Hopkins, P.B.J.Org.Chem.1984,49,3647.d) Krief, A.; Colaux, C.; And Dumont, W.Tetrahedron Lett.1997,38,3315.e) Genna, D.T.; Hencken, C.P.; Siegler, M.A.; And Posner, G.H.Org.Lett., 2010,12,4694.] the known organic compound that contains selenium has strong anticancer and antioxygenation.[a)Mugesh，G.；du?Mont，W.-W.；and?Sies，H.Chem.Rev.，2001，101，2125.b)El-Bayoumy，K.；and?Nutr.Cancer，2001，40，4.]
The synthetic method of known allyl group selenide mainly contains following several: one, allyl halide and aryl selenium anion reaction, this method are a kind of methods commonly used of synthesis of allyl selenide, but the reaction times is longer, and yield is not high.[a) Kataev, E.G.; Kataev, L.M.; And Chmutova, G.A.Zh.Org.Khim.1966,2,2242.b] Sharp, K.B.; And Yong, M.W.J.Org.Chem.1975,40,947.c] Nishiyama, H.; Itagaki, K.; Skata, K.; And Itoh, K.Tetrahedron Lett.1982,23,4103.d] Bao, W.; And Zhang, Y.Synlett.1996,3,1187-1188.e] Qian, W.; Bao, W.; And Zhang, Y.Synlett.1997,4,393-394.f] Zheng, Y.; Bao, W.; And Zhang, Y.Synth.Commun.2000,30,1731-1736.h] Zheng, Y.; Bao, W.; And Zhang, Y.Synth.Commun.2000,30,1731-1736.i] Wu, J.Y.; Lu, G.L.; Ma, Z.X.; And Chen, J.Chem.Res.Chinese Univ.2000,16,182-184.] two, acetic acid allyl vinegar and phenylseleno trimethyl silane react under the catalysis of zinc iodide.[a] Miyoshi, N.; Ishii, H.; Murai, S.; And Sonoda, N.Chem.Lett.1979,873.b] Nishiyama, H.; Itagaki, K.; Sakata, K.; And Itoh, K.Tetrahedron lett.1981,22,5285.] three, under the palladium catalyst effect, acetic acid allyl vinegar and diselenide reaction, problem such as this type of reaction suitability is relatively poor, and does not meet Atom economy, and productive rate is lower.[a] Fukuraws, S.I.; Fujinami, T.; And Sakai, S.Chem.Lett.1990.927.b] X.J.Zhao, H.R.Zhao and X.Huang, Chinese Chem.Lett., 2002,13,396.] thus the synthetic method of the allyl group selenide of the easier transition metal-catalyzed highly selective of exploitation have very high value.And form allyl group selenide compound by allylation reaction with metal catalytic.In the research of the bright seminar of organic Zhao Xiao of department of chemistry of Tongji University, having invented metal iridium catalytic is the allyl substitution reaction of nucleophilic reagent with virtue (alkane) basic sodium mercaptides.[a) Zheng, S.; Gao, N.; Liu, W.; Liu, D.; Zhao, X.; Cohen, T.Org.Lett.2010,12,4454-4457.b) Gao, N.; Zheng, S.; Yang, W.; And Zhao, X.Org.Lett.2011,13,1514-1516.c) Zheng, S.; Gao, N.; Cui, R.; Zhang, M.; Zhao, X.Chem.Commun.2011,47,6969.] and utilize the selenophenol sodium salt, and in reaction, have more Atom economy, have more challenge, and the research of iridium catalysis formation allyl group selenide also there is not relevant report at present yet.
Summary of the invention
In order to overcome the defective that above-mentioned prior art exists, the purpose of this invention is to provide a kind of reaction conditions gentleness, easy and simple to handle, reaction yield phenyl-(3-aryl-2-propenyl) selenide compounds preferably.
Another object of the present invention provides the preparation method of a kind of above-mentioned phenyl-(3-aryl-2-propenyl) selenide compounds.
The 3rd purpose of the present invention provides the application of a kind of above-mentioned phenyl-(3-aryl-2-propenyl) selenide compounds.
Technical scheme of the present invention is as follows:
The invention provides a kind of phenyl-(3-aryl-2-propenyl) selenide compounds, such compound structure is shown below:
Wherein:
R
1Be selected from C
1-C
16Alkyl, aryl, the heteroaryl of sulfur-bearing.
Described alkyl is selected from methyl, propyl group or styroyl etc.
Described aryl is selected from Ph, 4-MeOC
6H
4, 4-ClC
6H
4, 3-CF
3C
6H
4, 3-MeOC
6H
4Or 4-MeC
6H
4Deng.
The heteroaryl of described sulfur-bearing is a thienyl group.
The present invention also provides the preparation method of a kind of above-mentioned phenyl-(3-aryl-2-propenyl) selenide compounds, and this method is shown below:
In organic solvent, temperature of reaction is-10 ℃～50 ℃, with [Ir (COD) Cl]
2The iridium complex that generates with chiral ligand L effect is a catalyzer, and allyl carbonate ester compound 2 and 1 reaction of selenophenol sodium salt after reaction is carried out 6-48 hour, make phenyl-(3-aryl-2-propenyl) selenide compounds 3.
In the described allyl carbonate ester compound 2, R
1Be selected from C
1-C
16Alkyl, aryl, the heteroaryl of sulfur-bearing, wherein: alkyl is selected from methyl, propyl group or styroyl etc., and aryl is selected from Ph, 4-MeOC
6H
4, 4-ClC
6H
4, 3-CF
3C
6H
4, 3-MeOC
6H
4Or 4-MeC
6H
4Deng, the heteroaryl of sulfur-bearing is a thienyl group; R
2Be selected from methyl, ethyl or the tertiary butyl.
Described selenophenol sodium salt 1, allyl carbonate ester compound 2, [Ir (COD) Cl]
2, chiral ligand L mol ratio be 1-2: 1.2-3: 0.01-0.04: 0.02-0.08; Preferred mol ratio is 1: 1.2: 0.03: 0.06.
Described chiral ligand is the optically pure part with following structural formula:
Described organic solvent is selected from toluene, methylene dichloride, 1, a kind of in 2-ethylene dichloride or the tetrahydrofuran (THF).
Further, need to add in the amine substance and by product HCl in this method prepares the step of catalyzer, wherein: amine substance is a Tri N-Propyl Amine.
Gained phenyl-(3-aryl-2-propenyl) selenide compounds separates through the method for thin-layer chromatography, column chromatography or underpressure distillation.With the method for thin-layer chromatography, column chromatography, used developping agent is the mixed solvent of non-polar solvent and polar solvent; Recommend solvent to can be sherwood oil-methylene dichloride, mixed solvents such as petroleum ether-ethyl acetate, its volume ratio can be respectively: non-polar solvent: polar solvent=100-20: 1.For example: petrol ether/ethyl acetate=100-20/1, sherwood oil/methylene dichloride=100-20/1.
A kind of described phenyl-(3-aryl-2-propenyl) selenide compounds is used for the synthetic intermediate that contains selenium heterocyclic compound, or the purposes in anticancer, the oxidation resistant chemicals.
A kind ofly be used to prepare described phenyl-(3-aryl-2-propenyl) selenide compounds enols used and close the purposes of the ring selenium compound that ring forms.
The present invention compares with prior art, has following advantage and beneficial effect:
The present invention is by selenophenol sodium salt and the high regioselectivity synthetic of allyl carbonate ester compound phenyl-(3-aryl-2-propenyl) selenide compounds; The method of preparation multiple phenyl-(3-aryl-2-propenyl) selenide compounds is provided, and this method is applicable to dissimilar allyl carbonate ester compounds, and the reaction conditions gentleness is easy and simple to handle; The productive rate of reaction is better (being generally 40%-74%) also, and regioselectivity height (being generally 89: 11～99: 1), synthetic phenyl of the present invention-(3-aryl-2-propenyl) selenide compounds can also close ring and obtain encircling selenium compound; The most important thing is that the present invention is the technology of first example by transition metal-iridium catalytic synthesis of allyl selenium compound.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1～16
In the reaction tubes of an exsiccant argon shield, add [Ir (COD) Cl] 2, chiral ligand L, Tri N-Propyl Amine (0.2mL) and THF (0.5mL) successively, 50 ℃ were reacted 30 minutes down, naturally cool under the room temperature rear pump or output pump and drain.In reaction tubes, add selenophenol sodium salt 1 and allyl carbonate 2 and organic solvent more successively, after reaction is carried out 12 hours, make phenyl-(3-aryl-2-propenyl) selenide compounds 3; After reaction finishes, after the removal of solvent under reduced pressure residue thin-layer chromatography obtain target product (sherwood oil/methylene dichloride=20/1, or petrol ether/ethyl acetate=20: 1, v/v).Reaction equation is as follows:
Chiral ligand L is:
Temperature of reaction among the embodiment 1-16, R
2, catalytic amount, substrate proportioning be different with solvent, specifically as shown in table 1:
Table 1
Wherein: DCE is 1, and 2-ethylene dichloride, DCM are methylene dichloride, and Toluene is a toluene, and THF is a tetrahydrofuran (THF), and NR is not for reacting, and rt is a room temperature.Catalyst for reaction: metal [Ir (COD) Cl] 2 is 1: 2 with the mol ratio of ligand L; The amount of reaction substrate 1 is 0.1mmol; 1/2, the 3/4th, molar ratio, the 3/4th, to measure by the 1H NMR of crude product, productive rate is an isolated yield.
Embodiment 17-25
The reaction of the catalytic selenophenol sodium allyl of iridium complex selenide:
In the reaction tubes of an exsiccant argon shield, add successively [Ir (COD) Cl]
2(0.003mmol), chiral ligand L (0.006mmol), Tri N-Propyl Amine (0.2mL) and THF (0.5mL), 50 ℃ of reactions 30 minutes down naturally cool under the room temperature rear pump or output pump and drain.In reaction tubes, add selenophenol sodium salt 1 (0.2mmol), allyl carbonate 2 (0.24mmol), DCE (2mL), stirring at room reaction more successively.After reaction finishes, after the removal of solvent under reduced pressure residue thin-layer chromatography obtain target product (sherwood oil/methylene dichloride=20/1, or petrol ether/ethyl acetate=20: 1, v/v).
Chiral ligand L is:
Wherein, the R of the catalytic selenophenol sodium allyl of iridium complex selenideization among each embodiment
1, R
2Difference, its reaction result is as shown in table 2:
Table 2
| Embodiment | R 1 | R 2 | 3(％) | 3/4 |
| 17 | Ph | Et | 3-1，74 | ＞99/1 |
| 18 | 4-MeOC 6H 4 | Et | 3-2，56 | ＞99/1 |
| 19 | 4-ClC 6H 4 | Me | 3-3，51 | ＞99/1 e |
| 20 | 4-MeC 6H 4 | Et | 3-4，68 | ＞99/1 |
| 21 | 3-MeOC 6H 4 | Et | 3-5，63 | ＞99/1 |
| 22 | 3-CF 3C 6H 4 | Et | 3-6，72 | ＞99/1 |
| 23 | 2-Thienyl | Me | 3-7，40 | ＞99/1 e |
| 24 | C 6H 4CH 2CH 2 | Et | 3-8，68 | ＞99/1 |
| 25 | CH 3CH 2CH 2 | Me | 3-9，54 | ＞89/11 |
In the table 2: the 1/2, the 3/4th, molar ratio, the 3/4th, to measure by the 1H NMR of crude product, productive rate is an isolated yield.
The characterization data of products therefrom is as follows:
The product 3-1:(E of embodiment 17)-phenyl-(3-phenyl-2-allyl group) selenide
White powder, 74% yield, 3-1/4＞99: 1.
1H?NMR(400MHz，CDCl
3)δ＝7.53-7.51(m，2H)，7.18-7.28(m，8H)，6.33(dt，J＝15.6Hz，7.6Hz，1H)，6.23(d，J＝15.6Hz，1H)，3.69(d，J＝7.6Hz，2H).
The product 3-2:(E of embodiment 18)-phenyl-(3-(4-p-methoxy-phenyl)-2-allyl group) selenide
White powder, 56% yield, 3-2/4＞99: 1.
1H?NMR(400MHz，CDCl
3)δ＝7.53-7.51(m，2H)，7.26-7.20(m，5H)，6.82(d，J＝8.8Hz，2H)，6.23-6.13(m，2H)，3.79(s，3H)，3.67(d，J＝6.4Hz，2H).
The product 3-3:(E of embodiment 19)-phenyl-(3-(4-chloro-phenyl-)-2-allyl group) selenide
Pale yellow powder, 51% yield, 3-3/4＞99: 1.
1H?NMR(400MHz，CDCl
3)δ＝7.52-7.50(m，2H)，7.26-7.23(m，5H)，7.18(d，J＝8.8Hz，2H)，6.28(dt，J＝15.6，7.6Hz，1H)，6.15(d，J＝15.6Hz，1H)，3.66(d，J＝7.6Hz，2H).
The product 3-4:(E of embodiment 20)-phenyl-(3-(4-aminomethyl phenyl)-2-allyl group) selenide
White powder, 68% yield, 3-4/4＞99: 1, fusing point: 67.0-68.2 ℃.
1H?NMR(400MHz，CDCl
3)δ＝7.52-7.50(m，2H)，7.24-7.22(m，3H)，7.16(d，J＝8Hz，2H)，7.07(d，J＝8Hz，2H)，6.27(dt，J＝15.6，7.2Hz，1H)，6.20(d，J＝15.6Hz，1H)，3.66(d，J＝6.8Hz，2H)，2.31(s，3H).
13C?NMR(100MHz，CDCl
3)δ＝137.2，134.0，133.9，132.0，130.0，129.1，128.9，127.2，126.1，124.8，30.8，21.1.
MS(EI，m/z，rel.intensity)131(100)，288(M
+)；
HRMS(EI)calcd?for?C
16H
16Se(M
+)：288.0417，Found：288.0414.
IR(KBr)：vmax(cm
-1)＝3428，2917，2362，1645，1629，1565，1503，1469，1263，1021，757，699，662.
The product 3-5:(E of embodiment 21)-phenyl-(3-(3-p-methoxy-phenyl)-2-allyl group) selenide.
Weak yellow liquid, 63% yield, 3-5/4＞99: 1.
1H?NMR(400MHz，CDCl
3)δ＝7.53-7.51(m，2H)，7.26-7.25(m，3H)，7.19(t，J＝8Hz，1H)，6.87(d，J＝7.6Hz，1H)，6.81(s，1H)，6.76(d，J＝8Hz，1H)，6.32(dt，J＝15.6Hz，7.6Hz，1H).6.20(d，J＝15.6Hz，1H)，3.80(s，3H)，3.68(d，J＝7.6Hz，2H).
13C?NMR(100MHz，CDCl
3)δ＝159.7，138.3，134.0，132.0，129.4，129.0，127.4，126.2，119.0，113.1，111.6，91.7，55.2，30.6.
HRMS(EI)calcd?for?C
16H
16OSe(M
+)：304.0366，Found：304.0367.
IR(KBr)：v
max(cm
-1)＝3054，2934，2841，1645，1566，1430，1263，1147，971，702，659.
The product 3-6:(E of embodiment 22)-phenyl-(3-(3-trifluoromethyl)-2-allyl group) selenide.
White powder, 68% yield, 3-6/4＞99: 1, fusing point: 54.8-55.8 ℃.
1H?NMR(400MHz，CDCl
3)δ＝7.53-7.51(m，2H)，7.48(s，1H)7.46-7.38(m，3H)，7.27-7.26(m，3H)，6.39(dt，J＝15.6，7.6Hz，1H)，6.20(d，J＝15.6Hz，1H)，3.68(d，J＝7.6Hz，2H).
13C?NMR(75MHz，CDCl
3)δ＝137.6，134.2，130.9(q，J＝31.9Hz)，130.5，129.5，129.3，129.0，128.9，128.0，127.6，124.1(q，J＝270.7Hz)，123.9(q，J＝3.8Hz)，122.9(q，J＝3.8Hz)，30.4.
19F?NMR(376MHz，CDCl3)δ＝-62.63(s).
MS(EI，m/z，rel.intensity)185(100)，342(M
+)；
HRMS(EI)calcd?for?C
16H
13F
3Se(M+)：342.0135，Found：342.0138.
IR(KBr)：vmax(cm
-1)＝3050，2941，1579，1476，1449，1333，1300，1180，1127，1064，991，951，891，791，745，729，705，685，662.
The product 3-7:(E of embodiment 23)-phenyl-(3-(1-thienyl)-2-allyl group) selenide.
White powder, 40% yield, 3-7/4＞99: 1, fusing point: 56.7-57.4 ℃.
1H?NMR(300MHz，CDCl
3)δ＝7.53-7.51(m，2H)，7.27-7.25(m，3H)，7.11(d，J＝5.6Hz，1H)，6.92(dd，J＝7.6，7.6Hz，1H)，6.84(d，J＝3.6Hz，1H)，6.36(d，J＝15.6Hz，1H)，6.16(dt，J＝15.6，7.6Hz，1H)，3.47(d，J＝7.6Hz，2H).
13C?NMR(100MHz，CDCl
3)δ＝141.8，134.0，129.7，129.0，127.4，127.3，125.6，125.3，125.2，124.0，30.5.
HRMS(EI)calcd?for?C
13H
12SSe(M+)：279.9825，Found：279.9853.
IR(KBr)：v
max(cm
-1)＝3468，2353，1696，1679，1636，1632，1257，950，725，696.
The product 3-8:(E of embodiment 24)-phenyl-(5-phenyl-pentenyl) selenide
White powder, 68% yield, 3-8/4＞99: 1.
1H?NMR(400MHz，CDCl
3)δ＝7.49-7.47(m，2H)，7.28-7.24(m，5H)，7.17(t，J＝7.2Hz，1H)，7.10(d，J＝7.2Hz，，2H)，5.60(dt，J＝15.2，7.2Hz，1H)，5.42(dt，J＝15.2，6.4Hz，1H)，3.48(d，J＝7.6Hz，2H)，2.56(t，J＝7.6Hz，2H)，2.27(dt，J＝8，7.2Hz，2H).
The product 3-9:(E of embodiment 25)-phenyl-(2-hexenyl) selenide
White powder, 54% yield, 3-9/4＞89: 11.
1H?NMR(400MHz，CDCl
3)δ＝7.53-7.47(m，2H)，7.25-7.24(m，3H)，6.56(dt，J＝15.2Hz，7.6Hz，1H)，5.39(dt，J＝15.2，6.8Hz，1H)，3.50(d，J＝7.2Hz，2H)，1.93(dt，J＝7.2，7.2Hz，2H)，1.33-1.24(m，2H)，0.82(t，J＝7.2Hz，3H).
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. phenyl-(3-aryl-2-propenyl) selenide compounds, it is characterized in that: such compound structure is shown below:
Wherein:
R
1Be selected from C
1-C
16Alkyl, aryl, the heteroaryl of sulfur-bearing.
2. phenyl according to claim 1-(3-aryl-2-propenyl) selenide compounds, it is characterized in that: described alkyl is selected from methyl, propyl group or styroyl; Described aryl is selected from Ph, 4-MeOC
6H
4, 4-ClC
6H
4, 3-CF
3C
6H
4, 3-MeOC
6H
4Or 4-MeC
6H
4The heteroaryl of described sulfur-bearing is a thienyl group.
3. the preparation method of claim 1 or 2 described phenyl-(3-aryl-2-propenyl) selenide compounds, it is characterized in that: this method is shown below:
In organic solvent, temperature of reaction is-10 ℃～50 ℃, with [Ir (COD) Cl]
2The iridium complex that generates with chiral ligand L effect is a catalyzer, and allyl carbonate ester compound 2 and 1 reaction of selenophenol sodium salt after reaction is carried out 6-48 hour, make phenyl-(3-aryl-2-propenyl) selenide compounds 3.
4. the preparation method of phenyl according to claim 3-(3-aryl-2-propenyl) selenide compounds is characterized in that: in the described allyl carbonate ester compound 2, and R
1Be selected from C
1-C
16Alkyl, aryl, the heteroaryl of sulfur-bearing, wherein: alkyl is selected from methyl, propyl group or styroyl, aryl is selected from Ph, 4-MeOC
6H
4, 4-ClC
6H
4, 3-CF
3C
6H
4, 3-MeOC
6H
4Or 4-MeC
6H
4, the heteroaryl of sulfur-bearing is a thienyl group; R
2Be selected from methyl, ethyl or the tertiary butyl.
5. the preparation method of phenyl according to claim 3-(3-aryl-2-propenyl) selenide compounds is characterized in that: described selenophenol sodium salt 1, allyl carbonate ester compound 2, [Ir (COD) Cl]
2, chiral ligand L mol ratio be 1-2: 1.2-3: 0.01-0.04: 0.02-0.08; Preferred mol ratio is 1: 1.2: 0.03: 0.06.
6. the preparation method of phenyl according to claim 3-(3-aryl-2-propenyl) selenide compounds, it is characterized in that: described chiral ligand is the optically pure part with following structural formula:
7. the preparation method of phenyl according to claim 3-(3-aryl-2-propenyl) selenide compounds, it is characterized in that: described organic solvent is selected from toluene, methylene dichloride, 1, a kind of in 2-ethylene dichloride or the tetrahydrofuran (THF).
8. the preparation method of phenyl according to claim 3-(3-aryl-2-propenyl) selenide compounds is characterized in that: further, need to add amine substance in this method prepares the step of catalyzer, wherein: amine substance is a Tri N-Propyl Amine; Gained phenyl-(3-aryl-2-propenyl) selenide compounds separates through the method for thin-layer chromatography, column chromatography or underpressure distillation.
9. one kind is used for the synthetic intermediate that contains selenium heterocyclic compound with claim 1 or 2 described phenyl-(3-aryl-2-propenyl) selenide compounds, or the purposes in anticancer, the oxidation resistant chemicals.
10. one kind is used to prepare claim 1 or 2 described phenyl-(3-aryl-2-propenyl) selenide compounds enols used and closes the purposes of the ring selenium compound that ring forms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102204940A CN102249969A (en) | 2011-08-03 | 2011-08-03 | Phenyl-(3-aryl-2-allyl)selenide compounds, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102204940A CN102249969A (en) | 2011-08-03 | 2011-08-03 | Phenyl-(3-aryl-2-allyl)selenide compounds, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102249969A true CN102249969A (en) | 2011-11-23 |
Family
ID=44977582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102204940A Pending CN102249969A (en) | 2011-08-03 | 2011-08-03 | Phenyl-(3-aryl-2-allyl)selenide compounds, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102249969A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103204820A (en) * | 2012-01-11 | 2013-07-17 | 同济大学 | 3-triazolyl-substituted-1-propylene compound and synthetic method thereof |
| CN104529849A (en) * | 2014-12-11 | 2015-04-22 | 湖南大学 | Synthesis of (Z) type seleno-thio olefin compound under catalysis of inorganic alkali metal or alkali metal salt |
| CN106866480A (en) * | 2017-04-06 | 2017-06-20 | 盐城工学院 | Many cyclophane selenide analog derivatives and preparation method thereof |
| CN113200899A (en) * | 2021-05-19 | 2021-08-03 | 成都理工大学 | Aryl selenide compound and synthetic method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274908A (en) * | 2008-05-16 | 2008-10-01 | 华东理工大学 | Organic selenide synthetic method using environment-friendly catalyst |
-
2011
- 2011-08-03 CN CN2011102204940A patent/CN102249969A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274908A (en) * | 2008-05-16 | 2008-10-01 | 华东理工大学 | Organic selenide synthetic method using environment-friendly catalyst |
Non-Patent Citations (8)
| Title |
|---|
| 《CHEMISTRY LETTERS》 19900927 Schin-ichi FUKUZAWA等 《Samarium(Ⅱ)Di-iodide Induced Synthesis of Allylic Phenyl Selenides from Allylic Acetates and Diphenyl Diselenides in the Presence of Palladium Catalyst》 第926-928页 2-10 第19卷, 第6期 * |
| HÉLIO A.STEFANI等: "《Study Toward the Synthesis of Selenofurans via Seleno-Claisen Rearrangement of Allyl Arylselenides》", 《SYNTHETIC COMMUNICATION》, vol. 33, no. 12, 17 August 2006 (2006-08-17), pages 2161 - 2166 * |
| HISAO NISHIYAMA等: "《(PHENYLSELENODESILYLATION OF ALLYLSILANES AND REGIOSPECIFIC TRANSFORMATION OF ALLYLSILANES TO ALLYLIC ALCOHOLS VIA ALLYLSELENIDES》", 《TETRAHEDRON LETTERS》, vol. 22, no. 52, 31 December 1981 (1981-12-31), pages 5285 - 5288 * |
| SCHIN-ICHI FUKUZAWA等: "《Samarium(Ⅱ)Di-iodide Induced Synthesis of Allylic Phenyl Selenides from Allylic Acetates and Diphenyl Diselenides in the Presence of Palladium Catalyst》", 《CHEMISTRY LETTERS》, vol. 19, no. 6, 27 September 1990 (1990-09-27), pages 927 - 930 * |
| SHENGCAI ZHENG等: "《Regio- and Enantioselective Iridium-Catalyzed Allylation of Thiophenol: Synthesis of Enantiopure Allyl Phenyl Sulfides》", 《ORG. LETT.》, vol. 12, no. 20, 23 September 2010 (2010-09-23), pages 4454 - 4457 * |
| 周鹏: "《有机硒药物研究进展》", 《医药导报》, vol. 27, no. 9, 30 September 2008 (2008-09-30), pages 1086 - 1089 * |
| 赵华绒等: "《醋酸烯丙酯选择性合成烯丙基硒醚》", 《有机化学》, vol. 22, no. 11, 30 November 2002 (2002-11-30), pages 926 - 928 * |
| 郑云法等: "《铟促进的烯丙基硒醚、炔丙基硒醚的合成》", 《丽水师专学报》, vol. 19, no. 2, 30 April 1997 (1997-04-30), pages 11 - 13 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103204820A (en) * | 2012-01-11 | 2013-07-17 | 同济大学 | 3-triazolyl-substituted-1-propylene compound and synthetic method thereof |
| CN103204820B (en) * | 2012-01-11 | 2016-02-24 | 同济大学 | A kind of 3-triazol radical replaces-1-propene compound and synthetic method thereof |
| CN104529849A (en) * | 2014-12-11 | 2015-04-22 | 湖南大学 | Synthesis of (Z) type seleno-thio olefin compound under catalysis of inorganic alkali metal or alkali metal salt |
| CN106866480A (en) * | 2017-04-06 | 2017-06-20 | 盐城工学院 | Many cyclophane selenide analog derivatives and preparation method thereof |
| CN113200899A (en) * | 2021-05-19 | 2021-08-03 | 成都理工大学 | Aryl selenide compound and synthetic method thereof |
| CN113200899B (en) * | 2021-05-19 | 2022-11-04 | 成都理工大学 | Aryl selenide compound and synthetic method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102249969A (en) | Phenyl-(3-aryl-2-allyl)selenide compounds, and preparation method and application thereof | |
| CN107857743B (en) | Method for preparing roxatidine acetate hydrochloride and intermediate | |
| US10906860B2 (en) | Method for synthesizing chiral beta-hydroxy acid ester compound | |
| CN107141246B (en) | A kind of preparation method of Isatine derivatives | |
| CN104448898B (en) | A kind of synthetic method of pyronin derivative dye | |
| CN101575298B (en) | Method for preparing chiral medicinal intermediate 2-amido-1-phenylethylalcohol | |
| CN111925356B (en) | Synthesis method and application of chiral quinoline-imidazoline ligand | |
| CN112877721A (en) | Method for synthesizing isocoumarin compounds by electrochemical oxidative dehydrogenation coupling | |
| Bandgar et al. | Regioselective ring opening of epoxides with thiols under solvent free and mild conditions using heterogeneous catalyst | |
| CN112962111A (en) | Method for electrochemically synthesizing isocoumarin compounds | |
| CN108558715B (en) | Method for preparing enantiopure tert-butyl sulfenamide | |
| CN106966889A (en) | One kind (E) β, γ alkene-carboxylic acid's derivatives and preparation method thereof | |
| CN107513056B (en) | A kind of synthetic method of the quinolines of the group containing tetrahydrofuran | |
| US20080194825A1 (en) | Process for obtaining montelukast | |
| US20140275578A1 (en) | 2-(alkoxy or aryloxy carbonyl)-4-methyl-6-(2,6,6-trimethylcyclohex-1- enyl)hex-2-enoic acid compounds, its preparation and use | |
| CN109456221A (en) | A kind of synthetic method of acetanilide derivative | |
| WO2015122502A1 (en) | Method for producing optically active compound, and novel metal-diamine complex | |
| CN109265409B (en) | Synthesis method of 2-substituted benzoxazole, 2-substituted benzothiazole and derivatives thereof | |
| CN109574890B (en) | N-sulfenyl-N-allyl substituted amide compound and preparation method thereof | |
| CN108727323B (en) | Method for catalytically synthesizing trifluoromethyl substituted homoisoflavone compound by using N-heterocyclic carbene | |
| US20210130376A1 (en) | Beta-amino phosphonic acid derivative and preparation method therefor | |
| JP5448572B2 (en) | Acetyl compound, method for producing the acetyl compound, and method for producing a naphthol compound using the acetyl compound | |
| CN109748892B (en) | Preparation method of 3-halogenated tetrahydrofuran | |
| CN106854125B (en) | Method for preparing α -fluoro- β -ethynyl ketone compound containing two chiral centers | |
| CN105130982A (en) | Imidazo heterocyclic amino dithiocarbamate and preparation method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20111123 |