CN104098601A - Allyl phosphite ester compound and synthesizing method thereof - Google Patents
Allyl phosphite ester compound and synthesizing method thereof Download PDFInfo
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Abstract
The invention relates to an allyl phosphite ester compound and a synthesizing method thereof. According to the synthesizing method, in an organic solvent, the reaction temperature is controlled at 25-85 DEG C, diisopropyl phosphite and allyl carbonic acid methyl ester compound are taken as raw materials; Pd2(dba)3 and ligands react to generate a palladium complex so as to serve as a catalyst; the raw materials react at the presence of the catalyst for 1-12 h to obtain an allyl diisopropyl phosphite compound. Compared with the prior art, the allyl phosphite ester compound has the advantages that the catalyst is easy to get, the catalytic activity is high, the condition is mild and the application range of substrates is broad and the like.
Description
Technical field
The present invention relates to, by the allyl carbonate methyl esters of palladium metal complex catalysis, the allylation reaction of diisopropyl phosphite, especially relate to a kind of allyl group diisopropyl phosphite compounds and synthetic method thereof.
Background technology
Organic phosphites compound is the very useful compound of a class, because they can be widely used in all respects such as organic synthesis, pharmaceutical chemistry, materials chemistry, catalyzer.(1) (a) Dang, Q.; Liu, Y.; Cashion, D.K.; Kasibhatla, S.R.; Jiang, T.; Taplin, F.; Jacintho, J.D.; Li, H.; Sun, Z.; Fan, Y.; DaRe, J.; Tian, F.; Li, W.; Gibson, T.; Lemus, R.; Van Poelje, P.D.; Potter, S.C.; Erion, M.D.J.Med.Chem.2011,54,153. (b) Chen, X.; Kopecky, D.J.; Mihalic, J.; Jeffries, S.; Min, X.; Heath, J.; Deignan, J.; Lai, S.; Fu, Z.; Guimaraes, C.; Shen, S.; Li, S.; Ohnstone, S.; Thibault, S.; Xu, H.; Cardozo, M.; Shen, W.; Walker, N.; Kayser, F.; Wang, Z.J.Med.Chem.2012,55,3837. (c) Onouchi, H.; Miyagawa, T.; Furuko, A.; Maeda, K.; Yashima, E.J.Am.Chem.Soc.2005,127,2960. (d) Queffelec, C.; Petit, M.; Janvier, P.; Knight, D.A.; Bujoli, B.Chem.Rev.2012,112,3777. (e) Netherton, M.R.; Fu, G.C.Org.Lett.2001,3,4295. (f) Tang, W.; Zhang, X.Chem.Rev.2003,103,3029. (g) Surry, D.S.; Buchwald, S.L.Angew.Chem., Int.Ed.2008,47,6338. but up to the present the report by allylation reaction synthesis of organo-phosphines compound is also fewer.By research, we have invented a kind of method of the efficient synthetic allyl group diisopropyl phosphite compounds with height regioselectivity.
Summary of the invention
Object of the present invention is exactly to provide a kind of allyl group phosphite ester compound and synthetic method thereof in order to overcome the defect that above-mentioned prior art exists.
Object of the present invention can be achieved through the following technical solutions: a kind of allyl family estate phosphate compounds, it is characterized in that, and the structural formula of this compound is as follows:
Wherein, R is selected from arbitrarily phenyl ring or contains substituent aryl or alkyl, and iPr is sec.-propyl.
A synthetic method for allyl group phosphite ester compound, is characterized in that, the method is in organic solvent, and controlling temperature of reaction is 25 DEG C～85 DEG C, taking diisopropyl phosphite and allyl carbonate methyl compound as raw material, with Pd
2(dba)
3as catalyzer, reaction 1-12h makes allyl group diisopropyl phosphite compounds with the palladium complex of part effect generation.
Reaction formula is as follows:
Described allyl carbonate methyl compound, diisopropyl phosphite, Pd
2(dba)
3, part mol ratio be 1: 1-2: 0.01: 0.02.Allyl carbonate methyl compound, diisopropyl phosphite, Pd
2(dba)
3, part is commercially available prod.
The structural formula of described diisopropyl phosphite is
Described allyl carbonate methyl compound structural formula is:
r is selected from arbitrarily phenyl ring or containing substituent aryl or alkyl, described aryl is phenyl or naphthyl; Me represents methyl;
Described part is optical purity part, and structural formula is as follows:
wherein PPh
2represent diphenylphosphine.
Described organic solvent is toluene, methylene dichloride, tetrahydrofuran (THF) or nitrogen dimethylformamide.
The synthetic allyl group diisopropyl phosphite compounds product obtaining is through the separation of thin-layer chromatography, column chromatography or underpressure distillation.As the method with thin-layer chromatography, column chromatography, developping agent used is the mixed solvent of non-polar solvent and polar solvent.Recommend solvent to can be sherwood oil-methylene dichloride, petroleum ether-ethyl acetate, the mixed solvents such as sherwood oil-ether, its volume ratio can be respectively: non-polar solvent: polar solvent=1: 1.For example: petrol ether/ethyl acetate=1/1.
Compared with prior art, the invention provides one effectively using palladium complex as catalyzer, by the method for allyl carbonate methyl esters, the efficient synthetic allyl group diisopropyl phosphite compounds of diisopropyl phosphite; The method of preparing multiple allyl group diisopropyl phosphite compounds is provided.The method is applicable to dissimilar allyl carbonate methyl esters compounds, and reaction conditions gentleness is easy and simple to handle.Also better (being generally 65%-95%) of the productive rate of reaction in addition.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
The research of allyl carbonate methyl esters, diisopropyl phosphite ratio, temperature and the solvent of palladium complex catalysis, and the impact on reaction of different palladiums source, part.Wherein X refers to the figure that leaves away, L assignment body, and solvent refers to solvent, T refers to temperature.
Wherein DCM is methylene dichloride, and Toluene is toluene, and THF is that tetrahydrofuran (THF) DMF is nitrogen dimethylformamide.The different part using in reaction: Pd
2(dba)
3be three (dibenzalacetone) two palladiums, Pd (PPh
3)
4for tetrakis triphenylphosphine palladium.
Embodiment 2
The allyl carbonate methyl esters of palladium complex catalysis, diphenyl phosphate oxygen allylation reaction
In the reaction tubes of a dry argon shield, add successively Pd
2(dba)
3(0.002mmol), part (0.004mmol) toluene (2.0mL) reacts 30 minutes at 25 DEG C.In reaction tubes, add allyl carbonate methyl esters (0.2mmol), 85 DEG C of stirring reactions of diisopropyl phosphite (0.24mmol).After reaction finishes, after removal of solvent under reduced pressure, residue thin-layer chromatography obtains target product 3 (petrol ether/ethyl acetate=1: 1, v/v).
Pl:(E)-3-phenyl-allyl group phosphorous acid isopropyl ester
Colourless liquid, 92% yield.
1H?NMR(400MHz，CDCl3)δ＝7.35(d，J＝7.4Hz，1H)，7.31(d，J＝7.3Hz，1H)，7.22(t，J＝7.0Hz，1H)，6.51(dd，J＝15.8，5.0Hz，1H)，6.16(dq，J＝14.8，7.4Hz，1H)，4.85-4.56(m，1H)，2.72(dd，J＝22.2，7.4Hz，1H)，1.31(t，J＝6.8Hz，6H).
13C?NMR(100MHz，CDCl3)δ＝137.0(d，J＝3.3Hz)，134.5(d，J＝14.9Hz)，128.5，127.5，126.2(d，J＝2.0Hz)，119.4(d，J＝11.9Hz)，70.5(d，J＝6.8Hz)，32.2(d，J＝140.1Hz)，24.0(dd，J＝7.5Hz).
31P?NMR(162MHz，CDCl3)δ＝24.97(s).IR(KBr)：v
max(cm
-1)＝3015，2953，2881，1429，1191，1158，1126，1063，915，843，656，525，459.HRMS(EI)calcd?for?C
15H
23NaO
3P[M+Na]
+：305.1277，found：305.1277.
P2:(E)-3-((4-methyl)-phenyl)-allyl group phosphorous acid isopropyl ester
Colourless liquid, 95% yield.
1H?NMR(400MHz，CDC13)δ＝7.43-7.19(m，1H)，7.13(d，J＝7.9Hz，1H)，6.49(dd，J＝15.8，5.1Hz，1H)，6.12(dq，J＝14.9，7.4Hz，1H)，4.88-4.57(m，1H)，2.72(dd，J＝22.2，7.5Hz，1H)，2.34(s，1H)，1.32(dd，J＝7.9，6.4Hz，5H).
13C?NMR(100MHz，CDCl3)δ＝137.3(d，J＝1.2Hz)，134.3(d，J＝15.0Hz)，134.2，129.2，126.1(d，J＝2.0Hz)，118.2(d，J＝11.9Hz)，70.4(d，J＝6.8Hz)，32.2(d，J＝140.0Hz)，24.1(dd，J＝6.8Hz)，21.2.
31P?NMR(162MHz，CDCl3)δ＝25.19(s).IR(KBr)：v
max(cm
-1)＝3270，2979，2928，1384，1247，976，545，444.HRMS(EI)calcd?for?C
16H
25NaO
3P[M+Na]
+：319.1434，found：319.1426.
P3:(E)-3-((4-fluorine)-phenyl)-allyl group phosphorous acid isopropyl ester
Colourless liquid, 71% yield.
1H?NMR(400MHz，CDCl3)δ＝7.41-7.23(m，1H)，6.99(t，J＝8.6Hz，1H)，6.47(dd，J＝15.8，5.0Hz，1H)，6.08(dq，J＝14.9，7.4Hz，1H)，4.71(dh，J＝12.3，6.1Hz，1H)，2.71(dd，J＝22.2，7.5Hz，1H)，1.31(dd，J＝8.8，6.3Hz，6H).
13C?NMR(100MHz，CDCl3)δ＝162.2(d，J＝145.1Hz)，133.2(d，J＝15Hz)，133.1(d，J＝3.4Hz)，127.6(dd，J＝10.0Hz)，119.1(dd，J＝14.0Hz)，115.4(d，J＝21.5Hz)，70.5(d，J＝6.8Hz)，32.6(d，J＝140.0Hz)，24.0(dd，J＝7.1Hz).
19F?NMR(377MHz，CDCl3)δ＝-114.61(d，J＝1.6Hz).
31P?NMR(162MHz，CDCl3)δ＝24.91(s).IR(KBr)：v
max(cm
-1)＝3038，2979，2934，1506，1390，1226，1113，982，750，500.HRMS(EI)calcd?for?C
15H
22FNaO
3P[M+Na]
+：323.1183，found：323.1180.
P4:(E)-3-((4-chlorine)-phenyl)-allyl group phosphorous acid isopropyl ester
Colourless liquid, 65% yield.
1H?NMR(400MHz，CDCl3)δ＝7.27(s，1H)，6.46(dd，J＝15.8，5.1Hz，1H)，6.29-6.05(m，1H)，4.71(dq，J＝12.5，6.2Hz，1H)，2.71(dd，J＝22.3，7.5Hz，1H)，1.31(dd，J＝9.5，6.2Hz，3H).
13C?NMR(100MHz，CDCl3)δ＝135.4(d，J＝3.5Hz)，133.2(d，J＝15.0Hz)，133.1，128.7，127.3(d，J＝2.0Hz)，120.2(d，J＝11.9Hz)，70.5(d，J＝6.8Hz)，55.2，32.2(d，J＝140.0Hz)，24.0(dd，J＝6.8Hz).
31P?NMR(162MHz，CDCl3)δ＝24.65(s).IR(KBr)：v
max(cm
-1)＝3030，2973，2926，2366，1485，1390，1244，1107，991，884，774，557.HRMS(EI)calcd?for?C
15H
22ClNaO
3P[M+Na]
+：339.0887，found：339.0892.
P5:(E)-3-((3-methoxyl group)-phenyl)-allyl group phosphorous acid isopropyl ester
Colourless liquid, 93% yield.
1H?NMR(400MHz，CDCl3)δ＝7.23(t，J＝7.9Hz，1H)，6.95(d，J＝7.6Hz，1H)，?6.89(s，1H)，6.79(d，J＝8.2Hz，1H)，6.48(dd，J＝15.8，5.1Hz，1H)，6.16(dq，J＝14.9，7.4Hz，1H)，4.83-4.56(m，2H)，3.81(s，3H)，2.72(dd，J＝22.3，7.5Hz，2H)，1.37-1.27(m，12H).
13C?NMR(100MHz，CDCl3)δ＝159.8，138.4(d，J＝3.4Hz)，134.3(d，J＝14.9Hz)，129.5，119.7(d，J＝11.8Hz)，118.9(d，J＝2.0Hz)，113.1，111.6(d，J＝1.9Hz)，70.5(d，J＝6.8Hz)，55.2，32.2(d，J＝140.1Hz)，24.0(dd，J＝7.2Hz).
31P?NMR(162MHz，CDCl3)δ＝24.93(s).IR(KBr)：v
max(cm
-1)＝3241，2976，2923，1578，1394，1245，983，775，552.HRMS(EI)calcd?for?C
16H
25FNaO
4P[M+Na]+：335.1383，found：335.1376.
P6:(E)-3-((3-fluorine)-phenyl)-allyl group phosphorous acid isopropyl ester
Colourless liquid, 87% yield.
1H?NMR(400MHz，CDCl3)δ＝7.28(dt，J＝14.0，7.1Hz，1H)，7.13(d，J＝7.7Hz，1H)，7.06(d，J＝10.1Hz，1H)，6.93(t，J＝8.2Hz，1H)，6.49(dd，J＝15.8，4.8Hz，1H)，6.19(dq，J＝14.8，7.4Hz，1H)，4.84-4.61(m，2H)，2.74(dd，J＝22.3，7.5Hz，2H)，1.33(t，J＝7.1Hz，11H).
13C?NMR(100MHz，CDCl3)δ＝162.2(d，J＝243.7Hz)，139.2(dd，J＝11.1Hz)，133.3(d，J＝17.4Hz)，129.9(d，J＝8.0Hz)，122.0(dd，J＝4.6Hz)，121.0(d，J＝11.8Hz)，114.2(d，J＝21.1Hz)，112.5(dd，J＝23.5Hz)，70.5(d，J＝6.9Hz)，32.1(d，J＝141.1Hz)，24.0(dd，J＝6.2Hz).
19F?NMR(377MHz，CDCl3)δ＝-113.57(s).
31P?NMR(162MHz，CDCl3)δ＝24.54(s).IR(KBr)：v
max(cm
-1)＝3036，2977，2926，1584，1450，1388，1248，1141，1105，986，888，772，543，525.HRMS(EI)calcd?for?C
15H
22FNaO
3P[M+Na]
+：323.1183，found：323.1179.
P7:(E)-3-((3-trifluoromethyl)-phenyl)-allyl group phosphorous acid isopropyl ester
Colourless liquid, 65% yield.
1H?NMR(400MHz，CDCl3)δ＝7.58(s，1H)，7.53(d，J＝7.6Hz，1H)，7.48(d，J＝?7.6Hz，1H)，7.42(t，J＝7.7Hz，1H)，6.54(dd，J＝15.8，5.0Hz，1H)，6.25(dq，J＝15.0，7.4Hz，1H)，4.82-4.61(m，2H)，2.75(dd，J＝22.4，7.5Hz，2H)，1.38-1.27(m，12H).?
13C?NMR(100MHz，CDCl3)δ＝137.7(d，J＝3.4Hz)，133.0(d，J＝14.8Hz)，131.0(d，J＝31.9Hz)，129.2，129.0，125.4，124.0(d，J＝2.6Hz)，122.8(dd，J＝5.8Hz)，121.7(d，J＝11.8Hz)，70.5(d，J＝6.8Hz)，32.2(d，J＝140.2Hz)，24.0(dd，J＝5.1Hz).
19F?NMR(377MHz，CDCl3)δ＝-62.83(s).
31P?NMR(162MHz，CDCl3)δ＝24.36(s).IR(KBr)：v
max(cm
-1)＝3042，2982，2935，1388，1337，1251，1167，1132，989，772，700，555，507.HRMS(E1)calcd?for?C
16H
22F
3NaO
3P[M+Na]
+：373.1151，found：373.1150.
P8:(E)-3-(2-naphthyl)-allyl group phosphorous acid isopropyl ester
White solid, fusing point 68.9-70.5 DEG C, 75% yield.
1H?NMR(400MHz，CDCl3)δ＝7.78(t，J＝7.2Hz，3H)，7.69(s，1H)，7.58(d，J＝8.5Hz，1H)，7.53-7.33(m，2H)，6.66(dd，J＝15.8，4.9Hz，1H)，6.29(dq，J＝14.9，7.4Hz，1H)，4.73(dh，J＝12.4，6.2Hz，2H)，2.78(dd，J＝22.2，7.4Hz，2H)，1.32(t，J＝6.8Hz，12H).
13C?NMR(100MHz，CDCl3)δ＝134.6(d，J＝14.9Hz)，134.4(d，J＝3.6Hz)，133.6，132.9，128.2，127.9，127.7，126.3，125.9(d，J＝2.7Hz)，125.8，123.4(d，J＝1.2Hz)，119.8(d，J＝11.9Hz)，70.5(d，J＝6.9Hz)，32.4(d，J＝140.0Hz)，24.0(dd，J＝7.3Hz).
31P?NMR(162MHz，CDCl3)δ＝24.95(s).IR(KBr)：v
max(cm
-1)＝3054，2974，2929，1465，1373，1251，983，882，784，555，477.HRMS(EI)calcd?for?C
19H
25NaO
3P[M+Na]
+：355.1434，found：355.1431.
P9:(E)-3-(2-thienyl)-allyl group phosphorous acid isopropyl ester
Colourless liquid, 65% yield.
1H?NMR(400MHz，CDCl3)δ＝7.13(d，J＝4.9Hz，1H)，6.94(dd，J＝9.1，4.1Hz，2H)，6.63(dd，J＝15.6，5.1Hz，1H)，5.99(dq，J＝15.2，7.5Hz，1H)，4.88-4.51(m，2H)，?2.68(ddd，J＝22.3，7.6，0.9Hz，2H)，1.31(t，J＝6.2Hz，12H).
13C?NMR(100MHz，CDCl3)δ：142.0(d，J＝4.1Hz)，127.5(d，J＝15.3Hz)，127.3，125.2(d，J＝2.8Hz)，124.0(d，J＝1.7Hz)，119.1(d，J＝12.3Hz)，70.6(d，J＝6.9Hz)，32.2(d，J＝140.0Hz)，24.0(dd，J＝7.4Hz).
31P?NMR(162MHz，CDCl3)δ＝24.58(s).IR(KBr)：v
max(cm
-1)＝2979，2925，1375，1256，991，750，545，488.HRMS(EI)calcd?for?C
13H
21NaO
3PS[M+Na]
+：311.0841，found：311.0841。
Claims (6)
1. an allyl group phosphite ester compound, is characterized in that, the structural formula of this compound is as follows:
Wherein, R is selected from arbitrarily phenyl ring or contains substituent aryl or alkyl, and iPr is sec.-propyl.
2. the synthetic method of an allyl group phosphite ester compound as claimed in claim 1, it is characterized in that, the method is in organic solvent, and controlling temperature of reaction is 25 DEG C～85 DEG C, taking diisopropyl phosphite and allyl carbonate methyl compound as raw material, with Pd
2(dba)
3as catalyzer, reaction 1-12h makes allyl group diisopropyl phosphite compounds with the palladium complex of part effect generation.
3. the synthetic method of a kind of allyl group phosphite ester compound according to claim 2, is characterized in that, described allyl carbonate methyl compound, diisopropyl phosphite, Pd
2(dba)
3, part mol ratio be 1: 1-2: 0.01: 0.02.
4. according to the synthetic method of a kind of allyl group phosphite ester compound described in claim 2 or 3, it is characterized in that, the structural formula of described diisopropyl phosphite is
Described allyl carbonate methyl compound structural formula is:
r is selected from arbitrarily phenyl ring or contains substituent aryl or alkyl; Me represents methyl;
Described part is optical purity part, and structural formula is as follows:
wherein PPh
2represent diphenylphosphine.
5. the synthetic method of a kind of allyl group phosphite ester compound according to claim 2, is characterized in that, described organic solvent is toluene, methylene dichloride, tetrahydrofuran (THF) or nitrogen dimethylformamide.
6. the synthetic method of a kind of allyl group phosphite ester compound according to claim 2, is characterized in that, the synthetic allyl group diisopropyl phosphite compounds product obtaining is through the separation of thin-layer chromatography, column chromatography or underpressure distillation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410301477.3A CN104098601B (en) | 2014-06-27 | A kind of pi-allyl phosphite ester compound and synthetic method thereof |
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|---|---|---|---|
| CN201410301477.3A CN104098601B (en) | 2014-06-27 | A kind of pi-allyl phosphite ester compound and synthetic method thereof |
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| Publication Number | Publication Date |
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| CN104098601A true CN104098601A (en) | 2014-10-15 |
| CN104098601B CN104098601B (en) | 2016-11-30 |
Family
ID=
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685762A (en) * | 2022-04-26 | 2022-07-01 | 陕西延长石油（集团）有限责任公司 | Preparation method of hydrophobic bisphosphite organic polymer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5693826A (en) * | 1995-09-14 | 1997-12-02 | Director-General Of Agency Of Industrial Science And Technology | Process for the production of unsaturated phosphonic ester |
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5693826A (en) * | 1995-09-14 | 1997-12-02 | Director-General Of Agency Of Industrial Science And Technology | Process for the production of unsaturated phosphonic ester |
Non-Patent Citations (4)
| Title |
|---|
| G. EVANO等: "Copper-mediated cross-coupling of 1,1-dibromo-1-alkenes with dialkyl phosphites: a convenient synthesis of 1-alkenylphosphonates", 《CHEM. COMMUN.》 * |
| R. MALET等: "PALLADIUM-CATALYZED PREPARATION OF DIALRYL ALLYLPHOSPHONATES. A NEW PREPARATION OF DIETHYL 2-OXOETHYLPHOSPHONATE", 《SYNTHETIC COMMUNICATIONS》 * |
| S. DEPRELE等: "Palladium-Catalyzed Hydrophosphinylation of Alkenes and Alkynes", 《J. AM. CHEM. SOC.》 * |
| Y. C. SHEN等: "Stereoselective Synthesis of Substituted Allylphosphonates via the CuBr-catalysed Reaction of Vinylic Phosphonium Salts", 《J. CHEM. RESEARCH (S)》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685762A (en) * | 2022-04-26 | 2022-07-01 | 陕西延长石油（集团）有限责任公司 | Preparation method of hydrophobic bisphosphite organic polymer |
| CN114685762B (en) * | 2022-04-26 | 2023-09-05 | 陕西延长石油（集团）有限责任公司 | Preparation method of hydrophobic bisphosphite organic polymer |
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