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Preparation method of 9-azabicyclo [3.3. 1] nonyl-N-oxygen free radical

An azabicyclo, nonane technology, applied in the field of organic chemical synthesis, can solve problems such as being unsuitable for industrial production, and achieve the effects of overcoming high safety and cost, simplifying post-processing operations, and reducing the amount of three wastes

Pending Publication Date: 2021-06-01
PHARMABLOCK SCIENCES (NANJING) INC
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] In order to solve the problem that the preparation method of 9-azabicyclo[3.3.1]nonyl-N-oxyl radical in the prior art is not suitable for industrial production, the present invention provides a 9-azabicyclo[ 3.3.1] The preparation method of nonane:

Method used

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  • Preparation method of 9-azabicyclo [3.3. 1] nonyl-N-oxygen free radical
  • Preparation method of 9-azabicyclo [3.3. 1] nonyl-N-oxygen free radical
  • Preparation method of 9-azabicyclo [3.3. 1] nonyl-N-oxygen free radical

Examples

Experimental program
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Embodiment 1

[0026] Example 1 Preparation of 9-benzyl-9-azabicyclo[3.3.1]nonane

[0027] Add 9-benzyl-9-azabicyclo-[3.3.l]non-3-one (250.0g), ethanol (2500mL), 85% hydrazine hydrate (192.5g), KOH (122.3g ), stirred to dissolve and cool down to room temperature for later use.

[0028] The temperature of the heat transfer oil in the continuous reactor (a stainless steel tubular reactor with an inner diameter of 6mm and an effective volume of 200mL) was set at 215°C. The configured solution is fed into the continuous reactor at a rate of 35.0mL / min by a high-pressure plunger pump, and discharged after being cooled by water. The system pressure is 1.5Mpa. The reaction solution was collected, the solvent was spin-dried at 50°C, water (1500 mL) was added, extracted once with n-heptane (1500 mL), and the solvent was spin-dried to obtain 223.0 g of a light yellow liquid with a yield of 95.0%. 1 H-NMR (CDCl 3 ): δ7.38-7.28(m, 5H), 3.92(s, 2H), 2.84(brs, 2H), 2.14-2.09(m, 6H), 1.71-1.66(m, 2H), 1...

Embodiment 2

[0029] Example 2 Preparation of 9-azabicyclo[3.3.1]nonane

[0030] Add 9-benzyl-9-azabicyclo[3.3.1]nonane (200.0g), methanol (1200mL), 20% palladium hydroxide on carbon (40.00g) into an autoclave (2000mL), and replace with nitrogen 3 times, Replace with hydrogen 3 times, charge hydrogen to 4.0Mpa, set at 50°C, and heat up for 3 hours. After the reaction is complete, the reaction solution is discharged from the kettle, the catalyst is filtered off, and the reaction solution directly enters the next step reaction, and the yield is 100%.

Embodiment 3

[0031] Example 3 Preparation of 9-azabicyclo[3.3.1]nonyl-N-oxyl radical

[0032] Water (600 mL) was added to the reaction solution in the previous step, cooled to 0-10°C in an ice-water bath, sodium tungstate dihydrate (30.6 g) was added, and carbamide peroxide (170.5 g) was added in batches. After the addition, it was naturally raised to room temperature. After 2 hours of reaction, samples were taken and detected, and the reaction was complete. Spin-dry the solvent at 40°C, add water (500mL), extract twice with methyl tert-butyl ether (1000mL), combine the extracts, wash with water (300mL), dry over anhydrous sodium sulfate, filter with suction, spin-dry the filtrate, and dry 104.0 g of a brownish-red solid was obtained, and the two-step yield was 80.0%. MS (EI) [M]+ / z: 141 [M+H].

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Abstract

The invention relates to a preparation method of 9-azabicyclo [3.3. 1] nonyl-N-oxygen free radical. The preparation method comprises the following steps: reducing 9-benzyl-9-azabicyclo [3.3. 1] nonyl-3-ketone serving as a raw material in a continuous reactor, deprotecting, and further oxidizing to obtain the 9-azabicyclo [3.3. 1] nonyl-N-oxygen free radical, thereby obviously enhancing the yield, and solving the problems of industrial production safety, solvent recovery and the like.

Description

technical field [0001] The invention relates to the field of organic chemical synthesis, in particular to a preparation method of 9-azabicyclo[3.3.1]nonyl-N-oxyl free radical. Background technique [0002] 9-Azabicyclo[3.3.1]nonanyl-N-oxyl radical (ABNO) is a highly efficient oxidant, which can be widely used in the production process of alcohol oxidation, and has higher catalytic activity and catalytic ability than Tempo. [0003] Copper(I) / ketoABNO catalyzed aerobic alcohol oxidation.Catalysis Science&Technology,4(6),1720-1725; 2014 and Efficient Aerobic Oxidation ofSecondary Alcohols at Ambient Temperature with an ABNO / NOx CatalystSystem.ACS Catalysis,3(121),6161 ; The preparation method of similar ABNO is disclosed in 2013: [0004] [0005] And there are following problems in this route: 1, the temperature in the reaction of compound 3 to compound 4 is high (220 ℃), and uses 10 equivalents of potassium hydroxide, strong alkalinity, the whole reaction requires high e...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D471/08C07B60/00
CPCC07D471/08C07B61/02C07B2200/03
Inventor 康俊
Owner PHARMABLOCK SCIENCES (NANJING) INC