Synthesis method of 2-benzylbenzaldehyde derivative

A technology of benzylbenzaldehyde and synthesis method, which is applied in the field of synthesis of important organic synthesis intermediate 2-benzylbenzaldehyde derivatives, and can solve problems such as poor economy of atoms and steps, narrow scope of application of substrates, poor tolerance of functional groups, etc. , to achieve the effect of wide application range, good functional group diversity and low cost

Active Publication Date: 2020-12-04
QILU UNIV OF TECH
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  • Abstract
  • Description
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  • Application Information

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Problems solved by technology

However, these methods have certain limitations, such as harsh reaction conditions, poor atom and step economy, poor regioselectivity, narrow substrate scope, and poor functional group tolerance ( Catal. Commun. 2009, 10 ,1835; J. Org. Chem. 2011, 76 , 7005; J. Org. Chem. 2002, 67 , 1247; J. Am. Chem. Soc. 2015, 137 , 14367; Chem. -Eur. J. 2014, 20 , 3162)

Method used

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  • Synthesis method of 2-benzylbenzaldehyde derivative
  • Synthesis method of 2-benzylbenzaldehyde derivative
  • Synthesis method of 2-benzylbenzaldehyde derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026]

[0027] The specific process is: in a 25 mL schlenk sealed tube, add 2-methylbenzaldehyde compound 1a (0.3 mmol), iodoarene compound 2a (0.45 mmol), Pd(OAc) 2 (10 mol%), silver trifluoroacetate (0.6 mmol), N , N - Dimethylethylenediamine (0.3 mmol), 4A molecular sieves (100 mg) and 2.0 mL of hexafluoroisopropanol, stirred at 120 ºC for 24 hours. The target product 3a (35.9 mg, yield 61%) was obtained by silica gel column chromatography (eluent: petroleum ether (60-90 ºC) / ethyl acetate, v / v = 50:1). The target product was confirmed by NMR and high-resolution mass spectrometry.

[0028] Compound Characterization Data

[0029] 2-Benzylbenzaldehyde derivative (3a), yellow liquid. 1 H NMR (400 MHz, CDCl 3 ) δ 10.16 (s, 1 H),7.76 (d, J = 7.6 Hz, 1 H), 7.43 (t, J = 7.3 Hz, 1 H), 7.31 (t, J = 7.5 Hz, 1H), 7.18 (t, J = 7.5 Hz, 3 H), 7.13–7.01 (m, 3 H), 4.36 (s, 2 H). 13 C{ 1 H) NMR (100 M Hz, CDCl 3 )δ 192.5, 143.1, 140.4, 134.1, 134.0, 132.2, 131.8, 128.9, 12...

Embodiment 2

[0031]

[0032] The specific process is: in a 25 mL schlenk sealed tube, add 2-methylbenzaldehyde compound 1a (0.3 mmol), iodoaromatic compound 2b (0.45 mmol), Pd(OAc) 2 (10 mol%), silver trifluoroacetate (0.6 mmol), N , N - Dimethylethylenediamine (0.3 mmol), 4A molecular sieves (100 mg) and 2.0 mL of hexafluoroisopropanol, stirred at 120 ºC for 24 hours. The target product 3b (41.2 mg, yield 60%) was obtained by silica gel column chromatography (eluent: petroleum ether (60-90 ºC) / ethyl acetate, v / v = 50:1). The target product was confirmed by NMR and high-resolution mass spectrometry.

[0033] Compound Characterization Data

[0034] 2-Benzylbenzaldehyde derivative (3b), yellow liquid. 1 H NMR (400 MHz, CDCl 3 ) δ 10.15 (s, 1 H),7.75 (d, J = 7.6 Hz, 1 H), 7.42 (t, J = 7.4 Hz, 1 H), 7.30 (t, J = 7.5 Hz, 1H), 7.15 (d, J = 7.6 Hz, 1 H), 6.96 (d, J = 8.4 Hz, 2 H), 6.72 (d, J = 8.5Hz, 2 H), 4.28 (s, 2 H), 3.66 (s, 3 H). 13 C{ 1 H) NMR (100 MHz, CDCl 3 )δ192.5...

Embodiment 3

[0036]

[0037] The specific process is: in a 25 mL schlenk sealed tube, add 2-methylbenzaldehyde compound 1a (0.3 mmol), iodoaromatic compound 2c (0.45 mmol), Pd(OAc) 2 (10 mol%), silver trifluoroacetate (0.6 mmol), N , N - Dimethylethylenediamine (0.3 mmol), 4A molecular sieves (100 mg) and 2.0 mL of hexafluoroisopropanol, stirred at 120 ºC for 24 hours. The target product 3c (39.1 mg, yield 62%) was obtained by silica gel column chromatography (eluent: petroleum ether (60-90 ºC) / ethyl acetate, v / v = 50:1). The target product was confirmed by NMR and high-resolution mass spectrometry.

[0038] Compound Characterization Data

[0039] 2-Benzylbenzaldehyde derivative (3c), yellow liquid. 1 H NMR (400 MHz, CDCl 3 )δ 10.16 (s, 1H),7.76 (d, J = 7.6 Hz, 1H), 7.42 (t, J = 7.4 Hz, 1H), 7.30 (t, J = 7.5 Hz, 1H),7.16 (d, J = 8.1 Hz, 1H), 6.99 (d, J = 7.9 Hz, 2H), 6.93 (d, J = 7.9 Hz, 2H),4.31 (s, 2H), 2.21 (s, 3H). 13 C{ 1 H) NMR (100 MHz, CDCl 3 ) δ 192.5, 143.5,...

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Abstract

The invention discloses a synthesis method of an important organic synthesis intermediate 2-benzyl benzaldehyde derivative for constructing bioactive molecules. The synthesis of the 2-benzyl benzaldehyde is realized in one step by taking cheap and easily available 2-methyl benzaldehyde and aryl iodide with structural diversity and multiple reaction centers as raw materials and taking N, N-dimethylethylenediamine as a transient guide group, and the obtained 2-benzyl benzaldehyde derivative can be further converted to generate a functional product. The method has the advantages of easily available raw materials, simple operation, mild synthesis reaction conditions, high reaction efficiency, and diversity of functional groups.

Description

technical field [0001] The invention belongs to the field of chemical organic synthesis, and in particular relates to a synthesis method of an important organic synthesis intermediate 2-benzylbenzaldehyde derivative for constructing bioactive molecules. Background technique [0002] 2-Benzylbenzaldehyde is an important intermediate in organic synthesis, widely used in the synthesis of fused rings, spiro rings, natural products and bioactive molecules ( Adv. Synth. Catal. 2011, 353 , 569; J. Org. Chem. 1985, 50 , 4829; Bioorg. Med. Chem. Lett. 2013, 23 , 5523). [0003] At present, the methods for synthesizing 2-benzylbenzaldehyde are mainly as follows: 1) Realize by oxidation of o-benzyl benzyl alcohol; 2) Realize by Suzuki cross-coupling; 3) Realize by Vilsmeier reaction; 4) Realize by Kumada −Tamao−Corriu reaction to achieve. However, these methods have certain limitations, such as harsh reaction conditions, poor atom and step economy, poor regioselectivity, narro...

Claims

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Application Information

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IPC IPC(8): C07C45/68C07C47/546C07C47/575C07C47/55C07C29/14C07C33/46C07D235/18
CPCC07C45/68C07C29/14C07D235/18C07C47/546C07C47/575C07C47/55C07C33/46Y02P20/584
Inventor 娄江韩文佳
Owner QILU UNIV OF TECH
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