CN114044796A - Stereoselective synthesis method of tetra-substituted allyl azide - Google Patents
Stereoselective synthesis method of tetra-substituted allyl azide Download PDFInfo
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- CN114044796A CN114044796A CN202111371854.7A CN202111371854A CN114044796A CN 114044796 A CN114044796 A CN 114044796A CN 202111371854 A CN202111371854 A CN 202111371854A CN 114044796 A CN114044796 A CN 114044796A
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- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
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Abstract
The invention discloses a stereoselective synthesis method of tetra-substituted allyl azide, which comprises the following steps; ferrocene allene dimethyl phosphate and nitrine nucleophilic reagent NaN3The iodine simple substance reacts at room temperature, and a series of tetra-substituted allyl azide compounds containing different substituents are obtained by dissolving the iodine simple substance in an organic solvent.
Description
Technical Field
The invention belongs to the technical field of tetra-substituted allyl azide, and particularly relates to a stereoselective synthesis method of tetra-substituted allyl azide.
Background
Tetra-substituted allyl azide is an important organic synthesis intermediate. Because of the high activity of the azide group, the azide group is an attractive structural unit in many natural products, medicines and organic functional materials. In addition, the azide compounds can also be used for synthesizing nitrogen-containing heterocyclic compounds, such as aziridine, triazole, pyrazine, pyrrole and other heterocyclic compounds. And simultaneously reduced into amino and cyano, and nitrogen is lost at high temperature to obtain the azido base. The synthesis method of the compound generally has complicated reaction steps, some of the reaction steps use noble metals as catalysts, the universality of substrates is also greatly limited, and the reaction selectivity is not high. In addition, ferrocene is an organic transition metal compound with aromatic property, a variety of derivatives have been synthesized in the reported method, and the ferrocene has wide application in industries such as industry, agriculture, medicine, aerospace, energy conservation, environmental protection and the like.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a stereoselective synthesis method of a tetra-substituted allyl azide, which has the characteristics of high reaction efficiency, good economy, high synthesis rate and simple and convenient operation.
In order to achieve the purpose, the invention adopts the technical scheme that:
a stereoselective synthesis method of tetra-substituted allyl azide comprises the following steps;
ferrocene allene dimethyl phosphate and nitrine nucleophilic reagent NaN3Reacting iodine simple substance at room temperature, and dissolving by an organic solvent to obtain a series of tetra-substituted allyl azide compounds containing different substituent groups, wherein the reaction formula is as follows:
in the above reaction formula: r is phenyl, naphthyl and alkyl and substituted phenyl, R1Is a substituted ferrocenyl group.
The organic solvent is acetonitrile.
The amount of the organic solvent is 1 ml of the organic solvent per 0.1 mmol of ferrocene allene dimethyl phosphate.
The dosage of the sodium azide is 2 times of that of the ferrocene allene dimethyl phosphate.
The ferrocene allene dimethyl phosphate: iodine simple substance: cesium fluoride ═ 1:1.2: 2.
The reaction condition is that the reaction is carried out at room temperature, and the reaction time is 3-4 hours.
The invention has the beneficial effects.
The dimethoxy (3-ferrocenyl-3-azido-2-iodo-1-phenylpropenyl) phosphate prepared by the invention has potential application value in the fields of organic synthesis, pharmacy and new material research and development, and the used raw materials are cheap and easy to obtain;
the method does not need catalytic addition, alkali and additive participation, is simple and convenient to operate, and has higher yield and selectivity;
the reaction speed related by the method is high, and various substituted allyl azide compounds can be prepared within 3-4 hours;
the invention can realize the synthesis of highly selective multi-functionalized tetra-substituted olefin, and synthesize a series of functional group olefin compounds;
the method disclosed by the invention has the advantages that the halogen-promoted addition reaction of ferrocene allene phosphate and nucleophilic reagent sodium azide or organic azide is adopted, and the mild reaction conditions are developed, so that the allyl azide compound containing ferrocene and phosphate ester groups is synthesized at high selectivity, and a simple, convenient and efficient way is provided for the preparation of the functionalized multi-substituted olefin.
The invention provides a method for effectively synthesizing a tetra-substituted allyl azide with high selectivity by using ferrocene allene dimethyl phosphate as a reactant to react with halogen and azide nucleophilic reagents, and provides an effective way for preparing the tetra-substituted allyl azide.
The method of the invention has good adaptability to functional groups, namely ferrocenyl, phenyl, naphthalene ring substituent and alkyl. And various functional groups such as: methyl, methoxy, tertiary butyl, halogen, phenyl and the like have relatively good yield in ortho, meta and para positions of substituted aromatic rings.
In the method, except for the synthesis of the ferrocene allene dimethyl phosphate, other raw materials are all commercialized reagents and do not need special treatment.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
(E) synthesis of (3-ferrocenyl-3-azido-2-iodo-1- (4-methoxy) phenylpropenyl) phosphate
A25 mL reaction flask was charged with ferrocene allene dimethyl phosphate compound (88 mg, 0.20mmol) and NaN in sequence3(26mg, 0.40mmol), elemental iodine (61mg, 0.24 mmol). 2.0ml of CH are subsequently added3CN, stirring at room temperature, detecting the reaction is complete by TLC, and performing column chromatography separation by using petroleum ether: ethyl acetate (V: V) ═ 3:1 as eluent, purified to give a yellow solid in 84% yield. The nuclear magnetic data are as follows:
nuclear magnetic characterization data of the synthesized new compounds:1H NMR(500MHz,DMSO)δ6.93(d,J＝21.0Hz,4H),6.91(s,1H), 4.40(s,1H),4.35(s,1H),4.26(s,5H),4.22(s,2H),3.77(s,3H),3.74– 3.58(m,6H).31P NMR(202MHz,DMSO)δ10.6.13C{1H}NMR(125 MHz,DMSO)δ159.4,140.5,139.2,135.5,135.4,134.9(d,Jpc＝6.9Hz), 130.3(d,Jpc＝68.0Hz),114.3,87.6,69.5,69.0,67.8(d,Jpc＝13.7Hz), 67.5,65.3(d,Jpc＝4.8Hz),55.6,53.4(d,Jpc＝5.8Hz).
example 2:
(E) synthesis of (3-ferrocenyl-3-azido-2-iodo-1-phenylpropenyl) phosphate
A25 mL reaction flask was charged with ferrocene allene dimethyl phosphate compound (81 mg, 0.20mmol) and NaN in sequence3(26mg, 0.40mmol), elemental iodine (61mg, 0.24 mmol). 2.0ml of CH are subsequently added3CN, stirring at room temperature, TLC to detect that the reaction is complete,separating by column chromatography, and purifying with petroleum ether: ethyl acetate (V: V) ═ 3:1 as eluent, purified to give a yellow solid with a yield of 72%. The nuclear magnetic data are as follows:
1H NMR(500MHz,CDCl3)δ7.36(s,3H),7.14(s,1H),7.02(s,1H), 6.78(d,J＝2.3Hz,1H),4.49(s,1H),4.42(d,J＝0.8Hz,1H),4.30(s, 5H),4.23–4.18(m,2H),3.79(d,J＝11.3Hz,3H),3.70(d,J＝11.2Hz, 3H).31P NMR(202MHz,CDCl3)δ10.0.13C{1H}NMR(125MHz, CDCl3)δ142.6(d,Jpc＝7.0Hz),140.2,138.9,135.5,135.3,128.44, 128.3(d,Jpc＝1.9Hz),87.5,69.3,68.6,67.7(d,Jpc＝13.0Hz),67.4,65.4 (d,Jpc＝5.2Hz),53.1(dd,Jpc＝7.5,6.3Hz).
example 3:
(E) synthesis of (3-ferrocenyl-3-azido-2-iodo-1-methylpropenyl) phosphate
A25 mL reaction flask was charged with an alkyl allene phosphate compound (69.2mg, 0.20mmol) and NaN in that order3(26mg, 0.40mmol), elemental iodine (61mg, 0.24 mmol). 2.0ml of CH are subsequently added3CN, stirring at room temperature, detecting the reaction is complete by TLC, and performing column chromatography separation by using petroleum ether: ethyl acetate (V: V) ═ 3:1 as eluent, purified to give a yellow solid with 62% yield. The nuclear magnetic data are as follows:
1H NMR(500MHz,DMSO)δ6.79(s,1H),4.35(s,1H),4.22(s, 5H),4.20(s,2H),4.17(s,1H),3.77(t,J＝12.4Hz,6H),2.02(d,J＝11.9 Hz,3H).31P NMR(202MHz,DMSO)δ13.9.13C{1H}NMR(125MHz, DMSO)δ132.8(dd,Jpc＝88.9,71.1Hz),87.8,69.8,69.4,68.9,67.7(d, Jpc＝18.4Hz),67.4,65.6(d,Jpc＝5.8Hz),53.2(d,Jpc＝5.0Hz),28.4(d, Jpc＝8.9Hz)。
Claims (6)
1. a stereoselective synthesis method of tetra-substituted allyl azide is characterized by comprising the following steps;
ferrocene allene dimethyl phosphate and nitrine nucleophilic reagent NaN3Reacting iodine simple substance at room temperature, and dissolving by an organic solvent to obtain a series of tetra-substituted allyl azide compounds containing different substituent groups, wherein the reaction formula is as follows:
in the above reaction formula: r is phenyl, naphthyl and alkyl and substituted phenyl, R1Is a substituted ferrocenyl group.
2. The method for stereoselective synthesis of a tetra-substituted allyl azide compound according to claim 1, wherein the organic solvent is acetonitrile.
3. The process of claim 1, wherein the organic solvent is used in an amount of 1 ml per 0.1 mmol of ferrocene allene phosphate dimethyl ester.
4. The stereoselective synthesis method of tetra-substituted allyl azide as claimed in claim 1, wherein the amount of sodium azide is 2 times of that of ferrocene-dialkylphosphorodiamidate.
5. The stereoselective synthesis method of a tetra-substituted allyl azide compound according to claim 1, wherein the ratio of ferrocene dialkylene phosphate dimethyl ester: iodine simple substance: cesium fluoride ═ 1:1.2: 2.
6. The method for stereoselective synthesis of tetra-substituted allyl azide compound according to claim 1, wherein the reaction is carried out at room temperature for 3-4 hours.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6322950B1 (en) * | 1999-03-09 | 2001-11-27 | Fuji Photo Film Co., Ltd. | Photosensitive composition and 1,3-dihydro-1-oxo-2H-indene derivative |
| US20120202690A1 (en) * | 2009-10-13 | 2012-08-09 | Syngenta Limited | Herbicidal compounds |
| CN107098939A (en) * | 2017-05-03 | 2017-08-29 | 内蒙古大学 | A kind of preparation method of the allenic compound containing ferrocene and bound phosphate groups |
| CN107759602A (en) * | 2016-08-17 | 2018-03-06 | 中国科学院上海药物研究所 | Compound, its pharmaceutical composition and purposes containing conjugation connection alkene structure |
| CN109851729A (en) * | 2018-12-29 | 2019-06-07 | 福建师范大学 | Preparation method of the one kind containing ferrocene/DOPO base and crosslinking alkenyl polyether ether ketone resin |
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- 2021-11-18 CN CN202111371854.7A patent/CN114044796A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6322950B1 (en) * | 1999-03-09 | 2001-11-27 | Fuji Photo Film Co., Ltd. | Photosensitive composition and 1,3-dihydro-1-oxo-2H-indene derivative |
| US20120202690A1 (en) * | 2009-10-13 | 2012-08-09 | Syngenta Limited | Herbicidal compounds |
| CN107759602A (en) * | 2016-08-17 | 2018-03-06 | 中国科学院上海药物研究所 | Compound, its pharmaceutical composition and purposes containing conjugation connection alkene structure |
| CN107098939A (en) * | 2017-05-03 | 2017-08-29 | 内蒙古大学 | A kind of preparation method of the allenic compound containing ferrocene and bound phosphate groups |
| CN109851729A (en) * | 2018-12-29 | 2019-06-07 | 福建师范大学 | Preparation method of the one kind containing ferrocene/DOPO base and crosslinking alkenyl polyether ether ketone resin |
Non-Patent Citations (1)
| Title |
|---|
| 扈艳红, 刘世领, 仝钦宇, 黄发荣, 沈永嘉, 齐会民, 杜磊: "1, 3-偶极环加成反应合成1-(取代苄基)-1, 2, 3-三唑类化合物", 有机化学, no. 10, pages 1228 - 1232 * |
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