CN120904002A - Preparation method of 1, 4-diamine compound - Google Patents
Preparation method of 1, 4-diamine compoundInfo
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- CN120904002A CN120904002A CN202510741392.5A CN202510741392A CN120904002A CN 120904002 A CN120904002 A CN 120904002A CN 202510741392 A CN202510741392 A CN 202510741392A CN 120904002 A CN120904002 A CN 120904002A
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Abstract
本发明公开一种1,4‑二胺类化合物的制备方法，包括以下的步骤：在有机溶剂中，以双功能N‑自由基前体(1)、非活化烯烃(2)、Michael受体(3)为起始原料，加入光敏剂，于室温下、可见光光照下反应6～12h，制得1,4‑二胺产物(A)；本发明采用可见光诱导烯烃1,4‑二胺化反应策略，实现了不同电子特性及结构多样化烯烃的高效转化。该方法具备反应条件温和、无需过渡金属催化、无需额外氧化剂、反应体系无毒且环境友好等特点。同时，该方法展现出广泛的适用性及优异的区域选择性，具有重要的研究价值和广阔的应用前景。
This invention discloses a method for preparing 1,4-diamine compounds, comprising the following steps: In an organic solvent, using a bifunctional N-radical precursor (1), an inactive olefin (2), and a Michael acceptor (3) as starting materials, a photosensitizer is added, and the reaction is carried out at room temperature under visible light irradiation for 6–12 h to obtain the 1,4-diamine product (A). This invention employs a visible light-induced 1,4-diamineization reaction strategy for olefins, achieving efficient conversion of olefins with different electronic properties and diverse structures. This method features mild reaction conditions, no need for transition metal catalysis, no need for additional oxidants, and a non-toxic and environmentally friendly reaction system. Furthermore, this method exhibits broad applicability and excellent regioselectivity, possessing significant research value and broad application prospects.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of a1, 4-diamine compound.
Background
The 1, 4-diamine skeleton is used as an important organic synthesis intermediate, and has wide application value in medicine development, catalyst design and natural product synthesis.
However, the existing synthesis method of the 1, 4-diamine compound mainly has the following technical problems:
(1) The efficiency of the synthetic route is low, the traditional method depends on multi-step reaction, the reaction condition is harsh, and the atom economy is poor;
(2) The environment friendliness is insufficient, and the existing process often uses toxic reagents or produces harmful byproducts, which does not accord with the development trend of green chemistry.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a visible light catalytic olefin 1, 4-diamine reaction method, solves the problems of transition metal dependence, complicated steps, unfriendly environment and the like in the traditional process, and realizes efficient and green synthesis of 1, 4-diamine products. The method promotes the difunctional N-free radical precursor to generate two N-center free radicals by means of the energy transfer process induced by visible light, and further constructs the 1, 4-diamine product accurately through a tandem reaction mechanism with non-activated olefin and Michael acceptors.
In order to achieve the above purpose, the invention adopts the following technical scheme:
In an organic solvent, taking a difunctional N-free radical precursor (1), non-activated olefin (2) and Michael acceptors (3) as raw materials, adding a photosensitizer, reacting for 6 to 12 hours at room temperature under specific wavelength illumination, and separating and purifying to obtain a1, 4-diamine product (A):
Wherein R 1、R2 is independently selected from at least one of hydrogen, aryl and C1-C8 alkyl, and EWG is selected from one of ester group, cyano group, nitro group, amide group and phosphite group.
Preferably, the photocatalyst is thioxanthone (TXT)、[Ir(ppy)2(dtbbpy)](PF6)、[Ir(dtbbpy)[dF(CF3)ppy]2]PF6、Ir[dF(Me)PPy]2(dtbbpy)PF6、4CzIPN、fac-Ir(ppy)3,, and the use equivalent weight is 2-10mol%.
Preferably, the solvent is ethyl acetate, acetonitrile, isopropyl acetate or dichloromethane, and the use amount is 0.1M.
Preferably, the molar ratio of the bifunctional N-radical precursor 1 to the non-activated olefin 2 and Michael acceptor 3 is 1:2:2, 1:4:2, 1:8:2, 1:0.5:0.5.
Preferably, the illumination condition is 390 nm-4815 nm.
Preferably, the reaction system is subjected to separation and purification post-treatment, the reaction system is concentrated in vacuum and then subjected to rapid column chromatography separation and purification through pre-alkalization silica gel, the eluent is a mixed solvent of petroleum ether and ethyl acetate, the volume ratio of petroleum ether to ethyl acetate is 60:1-5:1, and the eluent is collected and the solvent is removed in vacuum, so that the pure 1, 4-diamine product A is obtained.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention realizes the visible light catalytic synthesis of the alkene 1, 4-diamine reaction for the first time, utilizes a brand new difunctional N-free radical precursor 1 as a nitrogen source, has simple and convenient precursor synthesis step, can generate two N-center free radicals with different reactivity under the condition of visible light photochemistry, and can selectively construct a 1, 4-diamine product in a region.
(2) The synthesis strategy developed by the invention uses a photocatalysis system, uses an easily available photosensitizer as a photocatalyst, and has the advantages of mild reaction conditions, simple experimental operation, no chemical toxicity, environmental friendliness and the like;
(3) The synthetic strategy developed by the invention has wide substrate range, is compatible with various olefins with different electronic characteristics and various structures, and has higher practicability and wider research prospect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a chemical reaction formula for preparing 1, 4-diamines;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the compound A1 prepared in example 1;
FIG. 3 is a nuclear magnetic resonance carbon spectrum of the compound A1 prepared in example 1;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the compound A2 prepared in example 2;
FIG. 5 is a nuclear magnetic resonance carbon spectrum of the compound A2 prepared in example 2;
FIG. 6 is a nuclear magnetic resonance hydrogen spectrum of the compound A3 prepared in example 3;
FIG. 7 is a nuclear magnetic resonance carbon spectrum of the compound A3 prepared in example 3;
FIG. 8 is a nuclear magnetic resonance hydrogen spectrum of the compound A4 prepared in example 4;
FIG. 9 is a nuclear magnetic resonance carbon spectrum of compound A4 prepared in example 4;
FIG. 10 is a nuclear magnetic resonance hydrogen spectrum of the compound A5 prepared in example 5;
FIG. 11 is a nuclear magnetic resonance carbon spectrum of the compound A5 prepared in example 5;
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
1, 4-Diamine reaction of olefins to produce 1, 4-diamine products
General experimental procedure bifunctional N-radical precursor 1 (0.6 mmol,1.0 eq.) and photosensitizer (2-10 mol%) were added to a reaction flask containing a magneton. After the reaction flask was refilled with N 2 3 times, solvent (0.1M), unactivated olefin 2 (0.5 to 8 equivalents), and Michael acceptor 3 (0.5 to 2 equivalents) were added sequentially under an atmosphere of N 2 in a glove box. And stirring the reaction mixture for 6-12 hours under the irradiation of a 390-4815 nm LED light source until the reaction is completed. After the reaction, the volatile substances are dried by spinning, and the corresponding 1, 4-diamine product A is obtained by purifying on pre-alkalization silica gel through flash column chromatography. The reaction general formula is as follows:
Example 1
Using bifunctional N-radical precursor 1 (204.96 mg,0.6 mmol), dimethyl methylenesuccinate (189.78 mg,1.2 mmol) and 1-hexene (101.10 mg,1.2 mmol) as starting materials, 5mol% thioxanthone (TXT) as photosensitizer, ethyl acetate as solvent, 390nm as reaction wavelength, reaction duration of 12h, after completion of the reaction with the general experimental procedure, flash column chromatography and PE: etOAc (30:1 to 5:1, v:v) as eluent gave product A1 (104.8 mg, 60% yield) as a colorless viscous oil. The structural formula of the product A1 is as follows:
characterization data ：1H NMR(400MHz,Chloroform-d)δ7.92(t,J＝5.8Hz,1H),7.87(t,J＝5.5Hz,1.5H),7.48-7.37(m,15H),7.33-7.29(m,5H),7.25-7.22(m,3H),7.20-7.17(m,2H),3.64(s,4.5H),3.63(s,3H),3.60-3.45(m,5H),3.40(s,4.5H),3.25(s,3H),3.01-2.79(m,5H),2.49(dd,J＝14.7,7.2Hz,1.5H),2.34(dd,J＝14.8,4.2Hz,1H),2.20(dd,J＝14.8,8.0Hz,1H),2.04-2.01(m,2H),1.95(d,J＝4.4Hz,1H),1.91(d,J＝4.5Hz,1.5H),1.41-1.37(m,7.5H),1.30-1.26(m,7.5H),0.89(t,J＝6.6Hz,7.5H).13C NMR(101MHz,Chloroform-d)δ173.4(2C),170.7,170.6,170.0,168.7,162.3,162.2,140.8,140.6,137.0,136.2,130.6,130.4,129.0,128.9,128.5(2C),128.3(2C),128.2(2C),128.0,92.9,92.8,67.7,67.1,52.0,51.8(3C),45.4,44.9,42.6,42.5,42.2,41.0,35.0,34.7,34.3,34.2,29.1,28.9,22.9,14.0(2C).HRMS(ESI)(m/z)：[M+H]+calculated for C28H33Cl3N2O5：583.1528,found：583.1533Rf：(petroleum ether/EtOAc 6：1)＝0.28.
Example 2
Using bifunctional N-radical precursor 1 (204.96 mg,0.6 mmol), dimethyl methylenesuccinate (189.78 mg,1.2 mmol) and 1-octene (67.32 mg,1.2 mmol) as starting materials, 2mol% [ Ir (ppy) 2(dtbbpy)](PF6), acetonitrile as solvent, 410nm as reaction wavelength, reaction duration 12h, after completion of the reaction using the general experimental procedure, flash column chromatography and PE: etOAc (30:1 to 5:1, v:v) as eluent gave product A2 (64.1 mg, 35% yield) as a pale yellow viscous oil. The structural formula of the product A2 is as follows:
Characterization data ：1H NMR(400MHz,Chloroform-d)δ7.86(t,J＝5.7Hz,1H),7.82(t,J＝5.3Hz,1.5H),7.49-7.45(m,5H),7.44-7.40(m,7.5H),7.40-7.38(m,1.5H),7.37-7.36(m,1H),7.32-7.29(m,5H),7.24-7.22(m,2.5H),7.20-7.07(m,2.5H),3.63(s,4.5H),3.62(s,3H),3.59-3.40(m,5H),3.39(s,4.5H),3.26(s,3H),3.01-2.80(m,5H),2.47(dd,J＝14.7,7.2Hz,1.5H),2.32(dd,J＝14.8,4.3Hz,1H),2.20(dd,J＝14.8,7.8Hz,1H),2.06-2.00(m,1.5H),1.96(d,J＝4.5Hz,1H),1.92(d,J＝4.5Hz,1.5H),1.41-1.35(m,10H),1.30-1.26(m,15H),0.89-0.86(m,7.5H).13C NMR(101MHz,Chloroform-d)δ173.5,173.3,170.7,170.6,169.9,168.6,162.3,162.1,140.8,140.6,136.9,136.2,130.6,130.4,129.0,128.9,128.5(2C),128.3(2C),128.2(2C),128.0,92.9(2C),67.1(2C),51.9,51.8(2C),51.7,45.5,44.9,42.5(2C),42.1(2C),35.1,34.7,34.6,34.5,31.7(2C),29.5,26.9,26.7,22.6,14.1.HRMS(ESI)(m/z)：[M+H]+ calculated for C30H38Cl3N2O5：611.1841,found：611.1831.Rf：(petroleum ether/EtOAc 6：1)＝0.31.
Example 3
Using bifunctional N-radical precursor 1 (204.96 mg,0.6 mmol), dimethyl methylenesuccinate (189.78 mg,1.2 mmol) and 4-methyl-1-pentene (202.20 mg,2.4 mmol) as starting materials, 2mol% of [ Ir (dtbbpy) [ dF (CF 3)ppy]2]PF6 as photosensitizer), methylene chloride as solvent, 450nm as reaction wavelength, reaction duration 12h, after the end of the reaction using the general experimental procedure, flash column chromatography and PE: etOAc (30:1-5:1, v:v) as eluent gave product A3 (52.4 mg, yield 30%). Product A3 as a pale yellow viscous oil of the formula:
Characterization data ：1H NMR(400MHz,Chloroform-d)δ7.87(t,J＝5.8Hz,1H),7.83(t,J＝5.8Hz,1.5H),7.49-7.46(m,5H),7.45-7.40(m,7.5H),7.38(dq,J＝6.8,1.7Hz,2.5H),7.33-7.30(m,5H),7.25-7.23(m,2.5H),7.20-7.18(m,2.5H),3.64(s,4.5H),3.63(s,3H),3.60-3.47(m,5H),3.41(s,4.5H),3.25(s,3H),3.04-2.79(m,5H),2.50(dd,J＝14.8,8.2Hz,1.5H),2.30(dd,J＝14.8,4.0Hz,1H),2.21(dd,J＝14.8,8.5Hz,1H),2.12-2.10(m,1.5H),1.97-1.96(m,1H),1.89(dd,J＝14.8,4.0Hz,1.5H),1.79-1.73(m,2.5H),1.32-1.25(m,2.5H),1.22-1.18(m,1.5H),1.16-1.12(m,1H),0.91-0.87(m,15H).13C NMR(101MHz,Chloroform-d)δ173.4,173.3,170.8,170.6,170.1,168.7,162.3,162.2,140.8,140.6,137.0,136.1,130.6,130.5,129.0,128.9,128.5(2C),128.3(2C),128.2,128.0,93.0,92.9,67.7,67.1,52.0,51.8(3C),45.3,44.6,44.1,44.0,43.0,42.5,41.0,32.9,32.6,25.1(2C),23.2,23.1,22.4,22.3.HRMS(ESI)(m/z)：[M+H]+calculated for C30H38Cl3N2O5：611.1841,found：611.1831.Rf：(petroleum ether/EtOAc 6：1)＝0.28.
Example 4
Using bifunctional N-radical precursor 1 (204.96 mg,0.6 mmol), dimethyl methylenesuccinate (189.78 mg,1.2 mmol) and allyltrimethylsilane (548.48 mg,4.8 mmol) as starting materials, 5mol% fac-Ir (ppy) 3 as photosensitizer, isoamyl acetate as solvent, 485nm as reaction wavelength, reaction duration 6h, after completion of the reaction using the general experimental procedure, flash column chromatography and PE: etOAc (30:1 to 5:1, v:v) as eluent gave product A4 (106.5 mg, 58% yield) as a pale yellow viscous oil. The structural formula of the product A4 is as follows:
Characterization data ：1H NMR(400MHz,Chloroform-d)δ7.96(t,J＝6.0Hz,1H),7.80(t,J＝5.8Hz,1.5H),7.48-7.37(m,15H),7.39-7.37(m,5H),7.24-7.22(m,3H),7.19-7.17(m,2H),3.63(s,7.5H),3.61-3.59(m,1H),3.54-3.50(m,1.5H),3.45(t,J＝6.6Hz,1H),3.41(s,4.5H),3.36-3.32(m,1.5H),3.23(s,3H),3.02-2.77(m,5H),2.56(dd,J＝14.7,8.2HHz,1.5H),2.38-2.35(m,1H),2.25(dd,J＝14.7,8.3HHz,1H),2.18-2.17(m,1.5H),2.14-2.12(m,1H),1.91(dd,J＝14.7,4.6Hz,1.5H),0.76-0.63(m,5H),0.06(s,9H),0.05(s,13.5H).13C NMR(101MHz,Chloroform-d)δ173.3,173.2,170.6,170.5,169.9,168.7,162.3,162.2,140.8,140.6,137.0,136.1,130.6,130.5,129.0,128.9,128.5,128.4(2C),128.3,128.2(2C),128.0,93.0,67.7,67.3,51.9,51.8(2C),47.4,46.9,45.6,42.6,41.0,32.0,31.9,23.1,22.8,-0.7.HRMS(ESI)(m/z)：[M+H]+calculated for C28H35Cl3N2OsSi：613.1454,found：613.1452.Rf：(petroleum ether/EtOAc 6：1)＝0.35.
Example 5
Using bifunctional N-radical precursor 1 (204.96 mg,0.6 mmol), dimethyl methylenesuccinate (47.45 mg,0.3 mmol) and 6-bromo-1-hexene (48.92 mg,0.3 mmol) as starting materials, 10mol%4CzIPN as photosensitizer, acetonitrile as solvent, 450nm as reaction wavelength, reaction duration of 8h, after completion of the reaction with the general experimental procedure, flash column chromatography and PE: etOAc (30:1 to 5:1, v:v) as eluent gave product A5 (99.0 mg, 58% yield) as a pale yellow viscous oil. The structural formula of the product A5 is as follows:
Characterization data ：1H NMR(400MHz,Chloroform-d)δ7.87(t,J＝5.7Hz,1H),7.83-7.81(m,1.5H),7.62-7.37(m,15H),7.33-7.29(m,5H),7.24-7.20(m,3H),7.19--7.17(m,2H),4.22-3.76(m,2.5H),3.71-3.62(m,7.5H),3.59-3.41(m,5H),3.39-3.32(m,7.5H),3.26(s,2.5H),3.01-2.79(m,5H),2.50(dd,J＝14.7,7.6Hz,1.5H),2.32(dd,J＝14.8,4.1Hz,1H),2.20(dd,J＝14.6,8.1Hz,1H),2.08-2.02(m,1.5H),1.95(d,J＝4.4Hz,1H),1.91(d,J＝5.4Hz,1.5H),1.85-1.79(m,5H),1.64-1.46(m,5H),1.44-1.38(m,3H),1.30-1.26(m,2H).13C NMR(101MHz,Chloroform-d)δ173.4,173.3,170.7,170.6,170.0,168.8,162.4,162.3,140.7,140.5,136.8,136.1,130.5,130.1,128.9,128.7,128.5,128.4,128.3(2C),128.2(2C),128.1,128.0,92.9,92.8,67.7,67.1,52.0,51.9,51.8(2C),45.2,44.4,42.5,42.2,41.9,41.1,41.0,35.1,34.8,33.7,33.6,33.5,32.9,25.6,25.5.HRMS(ESI)(m/z)：[M+H]+calculated for C28H32BrCl3N2O5：661.0633,found：661.0628.Rf：(petroleum ether/EtOAc 5：1)＝0.28.
The general reaction formula is shown in general experimental operation, and the reaction products and the results of different substrate selections are shown in Table 1.
TABLE 1 reaction products and results for different substrate selections
Table 2 (subsequent)
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (7)
1. A preparation method of a 1, 4-diamine compound is characterized by comprising the following steps of adding a photosensitizer into an organic solvent by taking a difunctional N-free radical precursor (1), an unactivated olefin (2) and a Michael acceptor (3) as starting materials, and reacting for 6-12 hours at room temperature under visible light to obtain the 1, 4-diamine compound (A), wherein the structural formulas of the difunctional N-free radical precursor (1), the unactivated olefin (2), the Michael acceptor (3) and the 1, 4-diamine compound (A) are shown as follows:
Wherein R 1、R2 is independently selected from at least one of hydrogen, aryl and C1-C8 alkyl, and EWG is selected from one of ester group, cyano group, nitro group, amide group and phosphite group.
2. The method for preparing 1, 4-diamine compound as described in claim 1, wherein said photosensitizer is selected from one of thioxanthone (TXT)、4CzIPN、fac-Ir(ppy)3、[Ir(ppy)2(dtbbpy)](PF6)、Ir[dF(Me)ppy]2(dtbbpy)PF6、[Ir(dtbbpy)[dF(CF3)ppy]2]PF6.
3. The method for preparing a 1, 4-diamine compound as claimed in claim 2, wherein the amount of the photosensitizer is 2-10mol% of the bifunctional N-radical precursor.
4. The method for preparing 1, 4-diamine compound as described in claim 1, wherein the organic solvent is one of ethyl acetate, acetonitrile, isopropyl acetate and methylene chloride.
5. The process for producing a1, 4-diamine compound as described in claim 4, wherein said organic solvent has a concentration of 0.1M.
6. The method for preparing a1, 4-diamine compound according to claim 1, wherein the molar ratio of the bifunctional N-radical precursor (1) to the inactive olefin (2) to the Michael acceptor (3) is 1 (0.5 to 8) to 0.5 to 2.
7. The method for preparing a1, 4-diamine compound according to claim 1, wherein the wavelength of visible light is 390nm to 4815 nm.
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