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Aldehyde deuteration and application of aldehyde deuteration in preparation of deuterated aldehyde

A technology of deuterated and deuterated water, applied in the application field of the preparation of deuterated aldehydes, can solve the problems of low deuteration rate and poor regioselectivity, etc.

Pending Publication Date: 2022-02-22
NANKAI UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In this regard, two cases of Ir- and Ru-catalyzed HIE reactions have been reported, but the deuteration rates of these reactions are not high and the regioselectivity is not good, often resulting in by-products of aromatic ring C-H bond deuteration

Method used

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  • Aldehyde deuteration and application of aldehyde deuteration in preparation of deuterated aldehyde
  • Aldehyde deuteration and application of aldehyde deuteration in preparation of deuterated aldehyde
  • Aldehyde deuteration and application of aldehyde deuteration in preparation of deuterated aldehyde

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Example 1: Synthesis of (2S, 5R)-2-isopropyl-5-methylcyclohexyl 3-formylbenzoate-formyl-d1:

[0024] Weigh 0.2mmol (2S, 5R)-2-isopropyl-5-methylcyclohexyl 3 formyl benzoate, 0.01mmol photocatalyst 4CzIPN, 0.08mmol triisopropylsilyl mercaptan ((i- Pr) 3 SiSH), 0.08mmol sodium carbonate (NaCO 3 ) in an 8mL reaction flask, then add 1mL ethyl acetate solution, 1mL deuterated water, blow argon for 30s in the reaction flask, react under 36W 470nm blue light irradiation for 36 hours, spin off the solvent, column chromatography (petroleum ether : ethyl acetate=20:1) to obtain a yellow liquid with a yield of 88% and a deuterated rate of 91%. 1 H NMR (400MHz, CDCl 3 )δ10.10(s, 0.09H), 8.53(s, 1H), 8.32(d, J=7.6Hz, 1H), 8.09(d, J=7.6Hz, 1H), 7.64(t, J=7.6Hz , 1H), 5.00(td, J=10.8, 4.4Hz, 1H), 2.13(d, J=12.0Hz, 1H), 1.95(dtd, J=13.6, 6.8, 2.4Hz, 1H), 1.80-1.70( m, 2H), 1.65-1.51(m, 2H), 1.14(dd, J=23.2, 11.6Hz, 2H), 1.03-0.88(m, 7H), 0.81(d, J=6.8Hz, 3H). 13 C NMR (100MHz, CD...

Embodiment 2

[0025] Example 2: Synthesis of 3-(formyl-d)phenyl 2-(4-isobutylphenyl)propionate:

[0026] Weigh 0.2mmol 3-formylphenyl 2-(4-isobutylphenyl) propionate, 0.01mmol photocatalyst 4CzIPN, 0.08mmol triisopropylsilyl mercaptan ((i-Pr) 3 SiSH), 0.08mmol sodium carbonate (NaCO 3 ) in an 8mL reaction flask, then add 1mL ethyl acetate solution, 1mL deuterated water, blow argon for 30s in the reaction flask, react for 36 hours under 36W 470nm blue light irradiation, spin off the solvent, column chromatography (petroleum ether : ethyl acetate=20:1) to obtain a yellow liquid with a yield of 80% and a deuterated rate of 93%. 1 H NMR (400MHz, CDCl 3)δ9.95(s, 0.07H), 7.71(d, J=7.6Hz, 1H), 7.51(dt, J=15.6, 4.8Hz, 2H), 7.35-7.23(m, 3H), 7.16(t, J=6.4Hz, 2H), 3.96(q, J=7.2Hz, 1H), 2.47(d, J=7.2Hz, 2H), 1.87(tt, J=13.2, 6.8Hz, 1H), 1.61(d, J=7.2Hz, 3H), 0.91(d, J=6.8Hz, 6H). 13 C NMR (100MHz, CDCl 3 )δ191.0 (t, J=27.5Hz), 173.0, 151.5, 141.1, 137.6 (t, J=3.5Hz), 136.9, 130.1, 129.7, 127.8, ...

Embodiment 3

[0027] Example 3: Synthesis of 6-(3-((3r, 5r, 7r)-adamantan-1-yl)-4-methoxyphenyl)-2 naphthaldehyde-d1:

[0028] Weigh 0.2mmol 6-(3-((3r,5r,7r)-adamantan-1-yl)-4-methoxyphenyl)-2 naphthaldehyde, 0.01mmol photocatalyst 4CzIPN, 0.08mmol triisopropyl Silylthiol ((i-Pr) 3 SiSH), 0.08mmol sodium carbonate (NaCO 3 ) in an 8mL reaction flask, then add 1mL ethyl acetate solution, 1mL deuterated water, blow argon for 30s in the reaction flask, react for 36 hours under 36W 470nm blue light irradiation, spin off the solvent, column chromatography (petroleum ether : ethyl acetate=20:1) to obtain a white solid with a yield of 82%, a deuterated rate of 96%, and a melting point of 236-237°C. 1 H NMR (400MHz, CDCl 3 ( d, J=2.4Hz, 1H), 7.56(dd, J=8.4, 2.4Hz, 1H), 7.01(d, J=8.4Hz, 1H), 3.91(s, 3H), 2.18(s, 6H), 2.11(s, 3H), 1.81(s, 6H). 13 C NMR (100MHz, CDCl 3 )δ 191.9 (t, J=27Hz), 159.1, 142.3, 139.1, 136.9, 134.3, 133.7 (t, J=3.1Hz), 132.3, 131.4, 131.3, 129.9, 129.8, 129.2, 126.9, 12...

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Abstract

The invention belongs to the technical field of fine chemicals, and particularly relates to a method for preparing deuterated aldehyde through a deuteration reaction of aldehyde under synergistic catalysis of visible light and small organic molecules. The method comprises the following steps: mixing aldehyde with a photocatalyst 4CzIPN, an organic micromolecular catalyst triisopropylsilyl mercaptan ((i-Pr)3SiSH), sodium carbonate (NaCO3), deuterated water and an organic solvent, blowing argon into a reaction bottle, conducting reacting under the irradiation of blue light with a power of 36 W and a wavelength of 470 nm, removing the solvent through spinning, and carrying out column chromatography to obtain a pure product.

Description

technical field [0001] The invention belongs to the technical field of fine chemicals, and in particular relates to the application of the deuteration reaction of aldehydes co-catalyzed by visible light and small organic molecules in the preparation of deuterated aldehydes. Background technique [0002] Deuterium as a labeling technique plays an important role in the study of reaction mechanism, drug absorption, distribution, metabolism and excretion (ADME), nuclear magnetic resonance spectroscopy and mass spectrometry research. In recent years, the introduction of deuterium atoms into drug molecules to enhance their metabolic and pharmacokinetic properties while maintaining their basic pharmacological activity has developed rapidly. Aldehydes are ubiquitous in medicine and organic synthesis, and deuterated aldehydes can serve as ideal deuterated synthetic building blocks for the construction of more complex molecular structures. Current synthetic methods for deuterated ald...

Claims

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Application Information

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IPC IPC(8): C07C67/30C07C67/28C07C45/61C07C213/08C07J9/00C07D209/26C07D209/18C07D211/90C07J7/00C07C269/06C07C319/20C07C221/00C07D209/08C07D209/86C07D317/54C07D319/18C07F5/02C07B59/00C07C69/76C07C69/616C07C69/738C07C47/575C07C217/74C07C47/546C07C47/55C07C47/542C07C47/565C07C47/228C07C271/28C07C323/22C07C223/06
CPCC07C67/30C07C67/28C07C45/61C07C213/08C07J9/005C07J9/00C07D209/26C07D209/18C07D211/90C07J7/002C07C269/06C07C319/20C07C221/00C07D209/08C07D209/86C07D317/54C07D319/18C07F5/025C07B59/007C07B59/004C07B59/002C07B59/001C07B2200/05C07C2601/14C07C2603/74C07C69/76C07C69/616C07C69/738C07C47/575C07C217/74C07C47/546C07C47/55C07C47/542C07C47/565C07C47/228C07C271/28C07C323/22C07C223/06
Inventor 汪清民董建洋刘玉秀王兹稳宋红健李永强张静静
Owner NANKAI UNIV
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