Synthesis method of palladium-catalyzed C-1 deuterated aromatic aldehyde

A C-1, aromatic aldehyde technology, applied in the field of palladium-catalyzed synthesis of C-1 deuterated aromatic aldehydes, can solve the problem that reaction conditions affect the scope of application of substrates, it is difficult to apply to practical applications in industrial production, and the deuterium selectivity is poor, etc. problem, to achieve the effect of good industrial application prospects, good adaptability and high reaction efficiency

Pending Publication Date: 2022-06-24
NANJING FORESTRY UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, these methods are often limited by harsh reaction conditions, which affect the scope of application of the substrate, and under some conditions, the product deuterated chlorine is low, and the deuterated selectivity is poor
Difficult to apply to practical applications in industrial production

Method used

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  • Synthesis method of palladium-catalyzed C-1 deuterated aromatic aldehyde
  • Synthesis method of palladium-catalyzed C-1 deuterated aromatic aldehyde
  • Synthesis method of palladium-catalyzed C-1 deuterated aromatic aldehyde

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] In a reaction tube with a stirrer, under the atmosphere of carbon monoxide, the catalyst PdCl was added in sequence 2 (PPh 3 ) 2 (0.02mmol, 10mol%), tris(1-naphthyl)phosphine as ligand (0.04mmol, 20mol%), aryl sulfate compound (0.2mmol, 1equiv), sodium deuterated formate (0.6mmol, 3equiv), tris Ethylamine (0.4mmol, 2equiv), the solvent is N,N-dimethylformamide solvent, and stirred at 120°C for 12h. After the reaction, the reaction mixture was filtered with celite, rinsed with ethyl acetate, the organic phases were combined, and the solvent was removed by a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate. The ester was used as the eluent to finally give the compound of formula 1 (83% isolated yield).

[0035]

[0036] 1 H NMR (400MHz, CDCl 3 )δ7.87-7.82(m, 2H), 7.02-6.99(m, 2H), 3.89(s, 3H); 13 CNMR (151MHz, CDCl 3 )δ190.6(t, J=26.5Hz), 164.6, 132.0, 129.9(t...

Embodiment 2

[0038] In a reaction tube with a stirrer, under the atmosphere of carbon monoxide, the catalyst PdCl was added in sequence 2 (PPh 3 ) 2 (0.02mmol, 10mol%), tris(1-naphthyl)phosphine as ligand (0.04mmol, 20mol%), aryl sulfate compound (0.2mmol, 1equiv), sodium deuterated formate (0.6mmol, 3equiv), tris Ethylamine (0.4mmol, 2equiv), the solvent is N,N-dimethylformamide solvent, and stirred at 120°C for 12h. After the reaction, the reaction mixture was filtered with celite, rinsed with ethyl acetate, the organic phases were combined, and the solvent was removed by a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate. The ester was used as the eluent to finally give the compound of formula 2 (isolated yield 64%).

[0039]

[0040] 1H NMR (600MHz, CDCl 3 )δ7.85-7.82(m, 2H), 7.53-7.51(m, 2H); 13 C NMR (151 MHz, CDCl 3 )δ190.6(t, J=26.9Hz), 141.0, 134.6(t, J=4.0Hz), 130.9, ...

Embodiment 3

[0042] In a reaction tube with a stirrer, under the atmosphere of carbon monoxide, the catalyst PdCl was added in sequence 2 (PPh 3 ) 2 (0.02mmol, 10mol%), tris(1-naphthyl)phosphine as ligand (0.04mmol, 20mol%), aryl sulfate compound (0.2mmol, 1equiv), sodium deuterated formate (0.6mmol, 3equiv), tris Ethylamine (0.4mmol, 2equiv), the solvent is N,N-dimethylformamide solvent, and stirred at 120°C for 12h. After the reaction, the reaction mixture was filtered with celite, rinsed with ethyl acetate, the organic phases were combined, and the solvent was removed by a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate. The ester was used as the eluent to finally give the compound of formula 3 (isolated yield 65%).

[0043]

[0044] 1 H NMR (400MHz, CDCl 3 )δ9.96(s, 0.01H), 7.82-7.79(m, 2H), 7.37-7.35(m, 2H), 2.61-2.55(m, 1H), 1.91-1.74(m, 5H), 1.49-1.35 (m, 4H), 1.30-1.24 ...

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Abstract

The invention discloses a method for synthesizing C-1 deuterated aromatic aldehydes by catalyzing an aryl sulfosalt compound through palladium, and belongs to the field of synthesis of organic deuterated compounds. The method comprises the following steps: by taking an aryl sulfur salt compound, sodium deuterated formate and carbon monoxide as raw materials, palladium salt as a catalyst and tris (1-naphthyl) phosphine as a ligand, adding triethylamine, and reacting in an N, N-dimethylformamide solvent at 120 DEG C for 12 hours to obtain the C-1 deuterated aromatic aldehyde compound after the reaction is finished. According to the synthesis method, the substrate and the deuteration reagent are cheap and easy to obtain, the reaction efficiency is high, the deuteration rate is high, the adaptability of functional groups is very good, the reaction conditions are simple and convenient to operate, and the method has a good industrial application prospect.

Description

technical field [0001] The invention belongs to the field of organic deuterated compound synthesis, in particular to a method for synthesizing C-1 deuterated aromatic aldehyde catalyzed by palladium. Background technique [0002] Deuterium technology has a great impact on the fields of pharmacy, materials science, biochemistry, and experimental testing. In 2017, Austedo, developed by TEVA, became the first deuterated drug approved by the U.S. Food and Drug Administration. Therefore, the synthesis of deuterated compounds has attracted the attention of organic chemists. Aromatic aldehydes are an important class of organic compounds, not only important fragments of many biologically active molecules, but also important intermediates for synthetic materials, pharmaceuticals and agrochemicals. [0003] In recent years, organic chemists from various countries have invested in the synthesis of C-1 deuterated aromatic aldehydes. The classical method to generate C-1 deuterated aro...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C47/575C07C47/55C07C47/546C07C45/56C07C233/33C07C231/12C07D333/22C07C49/86C07C45/68C07D317/54C07D213/64C07C69/738C07C67/343B01J31/24
CPCC07C45/567C07C231/12C07D333/22C07C45/68C07D317/54C07D213/64C07C67/343B01J31/2404C07B2200/05B01J2231/4205B01J2531/824C07C2601/14C07C47/546C07C47/55C07C47/575C07C233/33C07C49/86C07C69/738
Inventor 赵斌林朱天翔王秋竹
Owner NANJING FORESTRY UNIV
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