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A kind of preparation method of 1,2-dihydronaphthalene derivative

A derivative, dihydronaphthalene technology, applied in the field of organic synthesis

Inactive Publication Date: 2020-10-02
HUNAN INSTITUTE OF SCIENCE AND TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the inventors found that under the conditions of the aforementioned synthesis method, that is, under the condition of using TBHP as a free radical initiator, the addition of methylcyclopropane derivatives and aldehyde hydrogen C(sp 2 )-H bond, the reaction did not occur, which aroused the inventor's interest
As far as the inventors know, there is no prior art report on the combination of methylcyclopropane derivatives with aldehyde hydrogen C(sp 2 )-H bond reaction

Method used

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  • A kind of preparation method of 1,2-dihydronaphthalene derivative
  • A kind of preparation method of 1,2-dihydronaphthalene derivative
  • A kind of preparation method of 1,2-dihydronaphthalene derivative

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Experimental program
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Effect test

Embodiment 18

[0046]

[0047] Add a magnetic stirring bar to the reactor, add the methylenylcyclopropane derivatives (0.2mmol) of formula II-1, benzaldehyde (0.6mmol) and FeCl shown in formula III-2 in sequence 2 (10mol%), then replace the air in the reactor with argon, after replacing 3 times, add free radical initiator DTBP (0.6mmol) and n BuOAc (2 mL), and then the reactor was placed in a 90° C. oil bath with heating and stirring for 24 hours. After the reaction was complete, the solvent was evaporated to dryness with a rotary evaporator, and the residue was separated and purified with a chromatographic column to obtain the target product I-2. Yield 85% ( 1 H NMR (400 MHz, CDCl 3 ):7.74 (d, J = 7.8 Hz, 3H), 7.54 (d, J = 7.0 Hz, 1H), 7.45 (t, J = 7.6 Hz, 2H),7.32-7.27 (m, 5H), 7.25-7.20 (m, 1H), 6.84 (d, J = 7.6 Hz, 1H), 6.78 (d, J =8.4 Hz, 1H), 5.07 (s, 2H), 2.92 (t, J = 8.0 Hz, 2H), 2.75 (t, J = 8.0 Hz,2H); 13 C NMR (100 MHz, CDCl 3 ) : 197.3, 155.6, 139.2, 138.6, 136.8, 1...

Embodiment 19

[0049]

[0050] Add a magnetic stirring bar to the reactor, add the methylenylcyclopropane derivatives (0.2mmol) of formula II-1, p-tolualdehyde (0.6mmol) and FeCl shown in formula III-3 in sequence 2 (10mol%), then replace the air in the reactor with argon, after replacing 3 times, add free radical initiator DTBP (0.6mmol) and n BuOAc (2 mL), and then the reactor was placed in a 90° C. oil bath with heating and stirring for 24 hours. After the reaction was complete, the solvent was evaporated to dryness with a rotary evaporator, and the residue was separated and purified with a chromatographic column to obtain the target product I-3. Yield 81% ( 1 H NMR (400 MHz, CDCl 3 ): 7.58 (s, 1H), 7.37 (t, J = 8.4 Hz, 1H), 7.32-7.29 (m, 4H), 7.26-7.22(m, 3H), 7.20-7.17 (m, 2H), 6.84 (d, J = 7.2 Hz, 1H), 6.76 (d, J = 8.4 Hz,1H), 5.02 (s, 2H), 2.91 (t, J = 8.0 Hz, 2H), 2.75 (t, J = 8.0 Hz, 2H), 2.32(s, 3H); 13 C NMR (100 MHz, CDCl 3 ) : 199.5, 155.6, 139.4, 137.0, 136.8, 136.7...

Embodiment 20

[0052]

[0053] Add a magnetic stirring bar to the reactor, add the methylenylcyclopropane derivatives (0.2mmol) of the formula II-1, p-chlorobenzaldehyde (0.6mmol) and FeCl shown in the formula III-4 in sequence 2 (10mol%), then replace the air in the reactor with argon, after replacing 3 times, add free radical initiator DTBP (0.6mmol) and n BuOAc (2 mL), and then the reactor was placed in a 90° C. oil bath with heating and stirring for 24 hours. After the reaction was complete, the solvent was evaporated to dryness with a rotary evaporator, and the residue was separated and purified with a chromatographic column to obtain the target product I-4. Yield 73% ( 1 H NMR (400 MHz, CDCl 3 ):7.68 (d, J = 6.4 Hz, 3H), 7.42 (s, 1H), 7.40 (s, 1H), 7.35-7.33 (m, 3H),7.32-7.29 (m, 2H), 7.25 (t, J = 8.0 Hz, 1H), 6.84 (d, J = 7.6 Hz, 1H), 6.79(d, J = 8.0 Hz, 1H), 5.07 (s, 2H), 2.91 (t, J = 8.0 Hz, 2H), 2.73 (t, J = 8.4Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ) : 196.0, 155.7, 139.2...

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Abstract

The invention belongs to the technical field of organic synthesis and particularly relates to a novel method of reaction between methene cyclopropane compounds (MCPs) and an aldehyde compound. A methene cyclopropane derivative shown as formula II reacts with the aldehyde compound shown as formula III in the presence of a Lewis acid catalyst, a radical initiator and an organic solvent to form a 1,2-dihydronaphthalene derivative shown as formula I.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and specifically relates to a new method for preparing 1,2-dihydronaphthalene derivatives by reacting methylene cyclopropane compounds (MCPs) with aldehyde compounds. Background technique [0002] Carbon-carbon bond activation / functionalization reactions have very important applications in the synthesis of complex natural products and bioscaffolds. Many synthetic organic chemists have reported the use of carbon-carbon bond activation / functionalization methods to achieve one-step cleavage of a carbon-carbon bond and the construction of two or more chemical bonds. [0003] Methylenecyclopropanes (MCPs) are a three-membered carbocyclic molecular structure with a large angular tension. Its reactivity is very high, so it is often used to synthesize many important ring skeletons in organic synthesis. In recent years, there have been a lot of researches on methylenecyclopropane. Generally, tr...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C49/84C07C45/68C07D317/62
CPCC07C45/68C07D317/62C07C49/84
Inventor 刘宇王巧林唐课文熊碧权
Owner HUNAN INSTITUTE OF SCIENCE AND TECHNOLOGY