Preparation method of 4-aminated alcohol through iron catalysis

A technology for amination of alcohols and iron compounds, which can be applied in chemical instruments and methods, organic chemistry, compounds of elements of Group 4/14 of the periodic table, etc. The problem of high price, to achieve the effect of short reaction time, mild conditions and simple operation

Active Publication Date: 2021-11-16
XI AN JIAOTONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In the prior art, direct use of cheap and easy-to-obtain unprotected alcohol compounds as raw materials to synthesize 4-aminated alcohols is rarely reported, mainly using silver, iridium, ruthenium, cerium, etc. as metal catalysts, which are expensive and difficult to react. The operation is difficult, which limits the synthetic development of alcohols to prepare 4-aminoalcohols

Method used

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  • Preparation method of 4-aminated alcohol through iron catalysis
  • Preparation method of 4-aminated alcohol through iron catalysis

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] Add iron trichloride (0.004 mmol), tetrabutylammonium chloride (0.004 mmol), tert-butoxycarbonyl substituted azo compound (0.4 mmol), phenylbutanol (1.2 mmol) to the dry reaction tube successively. mol), anhydrous acetonitrile (4 milliliters), after the addition, stir to dissolve, mix evenly, place the reaction tube under the light (hv) with a wavelength of 390nm and keep stirring. Next, the reaction mixture was transferred to a flask, and the crude product was obtained by distillation under reduced pressure. Flash column chromatography obtained 127.0 mg of the aminated product of phenylbutanol, with a yield of 82%. The product was a colorless oily substance. 1H NMR (400MHz, CDCl3) δ7.46–7.18(m,5H,Ar-H),6.72–5.73(m,1H,NH),5.59–5.00(m,1H,CH),3.87–3.50(m, 2H,CH2),2.39(brs,1H,OH),2.24–1.59(m,4H,CH2×2),1.59–0.95(m,18H,Boc×2).13CNMR(101MHz,CDCl3)δ156.0,155.1, 139.7, 128.4, 127.9, 127.6, 81.4, 81.1, 62.2, 59.2, 29.6, 28.2, 27.4. HRMS (ESI+) m / z: Calcd for C21H34N2O6Na+[M+Na...

Embodiment 2

[0038]According to the method described in Example 1, the difference is that the amount of reagent used is: iron trichloride (0.008 mmol), tetrabutylammonium chloride (0.004 mmol), tert-butoxycarbonyl substituted azo compound (0.4 mmol) mol), 4-methoxyphenylbutanol (208 microliters, 216.7 mg, 1.20 mmol), anhydrous acetonitrile (4 milliliters); the reaction tube was irradiated under light (hv) with a wavelength of 390nm and heated to 60 ℃ and kept stirring, after the reaction was completed, the reaction tube was removed from the light source, the reaction mixture was transferred to a flask, and the crude product was obtained by distillation under reduced pressure, and the amination product of 4-methoxyphenylbutanol was obtained by flash column chromatography, 117.0 mg, yield 71%. 1HNMR (400MHz, CDCl3) δ7.34–7.14 (m, 2H, Ar-H), 6.83 (d, J=8.4Hz, 2H, Ar-H), 6.59–5.62 (m, 1H, NH), 5.60– 4.94(m,1H,CH),3.77(s,3H,CH3),3.78–3.53(m,2H,CH2),2.33–1.77(m,5H,OH+CH2×2),1.64–0.96(m, Boc×2)...

Embodiment 3

[0040] According to the method described in Example 1, the difference is that the amount of reagent used is: iron tribromide (0.012 mmol), tetrabutylammonium chloride (0.004 mmol), tert-butoxycarbonyl substituted azo compound (0.4 mmol) mol), 4-chlorophenylbutanol (240.8 mg, 1.2 mmol), anhydrous acetonitrile (4 milliliters); the reaction tube is placed in the light (hv) of wavelength 390nm to irradiate and heated to 80 ° C, stirring constantly, to be reacted After the completion, the reaction tube was removed from the light source, the reaction mixture was transferred to a flask, and the crude product was obtained by distillation under reduced pressure. The amination product of 4-chlorophenylbutanol was obtained by flash column chromatography, 127.5 mg, with a yield of 76%. 1H NMR (400MHz, CDCl3) δ7.36–7.21(m,4H,Ar-H),6.91–5.74(m,1H,NH),5.76–4.99(m,1H,CH),3.79–3.55(m, 2H,CH2),2.46(brs,1H,OH),2.22–0.99(m,22H,Boc×2+CH2×2).13C NMR(101MHz,CDCl3)δ156.1,155.0,138.1,133.4,130.1,129.3...

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Abstract

The invention relates to a preparation method of 4-aminated alcohol through iron catalysis. The method comprises the following steps: under the action of an iron compound, under the condition of providing a heating temperature and / or light energy, in the presence of an azo compound and an additive, in a corresponding organic solvent, realizing selective 4-carbon hydrogen bond breakage and amination of fatty alcohol to obtain a corresponding 4-amino alcohol compound. The fatty alcohol is directly utilized, and carbon-hydrogen bond amination is selectively carried out; and the method has the advantages of being simple in reaction, easy to operate, short in reaction time, mild in oxidation condition, high in atom economy, high in reaction yield, easy in product separation and purification and the like, and is suitable for synthesizing amino-alcohol-containing compounds and derivatives thereof; the aliphatic alcohol can be directly used as the raw material, the azo compound is cheap and easy to obtain, use of a large amount of heavy metal salt is avoided, and the method is very attractive in industrial production; and meanwhile, the method has very great application potential in the fields of metal catalysis, chemical synthesis, drug modification and the like by using cheap metal for reaction.

Description

technical field [0001] The invention relates to the technical field of chemical synthesis, in particular to a method for preparing iron-catalyzed 4-aminated alcohols. Background technique [0002] Amino alcohols are an important class of organic synthesis intermediates, widely used in complex organic molecules, pharmaceutical intermediates, life sciences, materials science and other fields. Selective carbon-hydrogen bond-breaking amination of fatty alcohols offers favorable opportunities to study molecular complexity and pharmaceutical intermediates, and enables the construction of nitrogen-containing compounds from cheap, readily available and abundant alcohols. [0003] Remote carbon-hydrogen functionalization of alkanols can be achieved by the generation of oxygen radicals from fatty alcohols, followed by intramolecular 1,5-hydrogen atom transfer. In the prior art, direct use of cheap and easy-to-obtain unprotected alcohol compounds as raw materials to synthesize 4-amina...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C281/02C07F7/18C07D209/86C07D209/08
CPCC07C281/02C07F7/1892C07D209/86C07D209/08C07C2601/14C07C2603/74C07C2601/08
Inventor 曾荣郭秦乐熊泥
Owner XI AN JIAOTONG UNIV
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