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Preparation method of (1R, 2S)-2, 6-dimethyl-1-aminoindan

A technology of aminoindene and dimethyl, applied in the field of herbicide triazine indenazone synthesis, can solve the problems of low yield, inconvenient compound, low dr value and the like, and achieves the effects of low cost and easy operation

Active Publication Date: 2018-11-13
SHANGHAI PUYI CHEM CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

First raw material is not easy to get, and synthetic structure is that the compound of formula (VII) is inconvenient; Secondary use expensive palladium catalyst, and yield is not high, and the yield of CN106414420A report cyclization only has 55%; The dr value of product is not very in addition high, according to literature Chemistry A European Journal. 2014, 20 (35), 11084-90 reported that the dr value of the analogue without methyl on its benzene ring could only be 98:2, and only achieved gram-level preparation; finally did not provide from the racemic intermediate (II ) to the preparation method of single isomer (1R, 2S)-2,6-dimethyl-1-aminoindane RS-(I)

Method used

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  • Preparation method of (1R, 2S)-2, 6-dimethyl-1-aminoindan

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0057] Example 1: Preparation of 2,6-dimethyl-1-aminoindan and its salts

[0058] 1. 2,6-Dimethyl-1-aminoindane acetate (1-3)

[0059]

[0060] Dissolve 200g of 2,6-dimethyl-1-indanone (1-1) in 1000mL of ethanol solution, and quickly drop 2000mL of aqueous solution containing 307g of sodium acetate into the reaction system. Heat to reflux, TLC detects that the reaction is complete in 2-3 hours. The ethanol was concentrated to remove, the reaction liquid was extracted with ethyl acetate, and the combined organic matter was dried and concentrated to obtain a light yellow oily crude product.

[0061] In a 1000mL hydrogenation kettle, dissolve 240g of the above crude product in 600mL of methanol, add 24g of 10% Pd / C, 24mL of acetic acid, pressurize the hydrogen to 2.0MPa, heat to about 55°C, and react overnight. Remove the Pd / C catalyst by filtration, concentrate and recover methanol, and recrystallize the crude product with methanol to obtain 2,6-dimethyl-1-aminoindane aceta...

Embodiment 2

[0068] Example 2: Preparation of trans-2,6-dimethyl-1-aminoindan (2-1) by palladium-catalyzed hydrogenation

[0069]

[0070] Add 160 g of 6-dimethyl-1-aminoindane acetate (1-3) (the ratio of trans and cis isomers is 60:40) into 1.6 L of anhydrous methanol, add 5% Pd / C (Hangzhou Lianzhi) 16g, the reaction solution was pressurized to 35atm under the atmosphere of hydrogen, and reacted at 80-90°C for 48 hours, after the reaction was completed, it was cooled to room temperature, the palladium carbon catalyst was removed by filtration, and the filtrate was spin-dried to obtain 160g Trans-2,6-dimethyl-1-aminoindane (2-1) oil, detected by HPLC, 2,6-dimethyl-1-aminoindane acetate (2-1 ) in the ratio of trans to cis isomers is 85:15.

[0071] Table 1: The reaction results of trans-2,6-dimethyl-1-aminoindan prepared by palladium-catalyzed hydrogenation under different substrate and catalyst conditions

[0072]

Embodiment 3

[0073] Example 3: Preparation of trans-2,6-dimethyl-1-aminoindan (2-2) using the recovered isomer

[0074]

[0075] Free the waste isomers recovered in each step to obtain 50 g of 6-dimethyl-1-aminoindan (1-5) (RS-(I), SR-(I), RR-(I ) to the four isomers of SS-(I) in the ratio of 20:70:5:5) was added to 500mL of anhydrous methanol, and 5% Pd / C (Hangzhou Lianzhi) was added, and the reaction solution was pressurized to 30atm, and reacted at 110°C for 24 hours. After the reaction was completed, the temperature was lowered to room temperature, the palladium carbon catalyst was removed by filtration, and the filtrate was spin-dried to obtain 50g trans-2,6-dimethyl-1-aminoindan ( 2-2) Oil, detected by chiral HPLC, RS-(I), SR-(I), RR-(I) in the product 2,6-dimethyl-1-aminoindan (2-2) The ratio with the four isomers of SS-(I) is 42:43:7:8.

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Abstract

The invention relates to a preparation method of (1R, 2S)-2, 6-dimethyl-1-aminoindan (I). The method includes: with a mixture (III) of four isomers as a raw material, preparing a compound shown as a formula (II) and enriched with trans-isomer through a method of hydrogenation at the presence of a palladium catalyst, or a method of salifying crystallization with achiral organic acid or the two methods; using R-mandelic acid to split an enantiomer mixture shown as a formula (II) to obtain enantiomer RS-(I) enriched (1R, 2S)-2, 6-dimethyl-1-aminoindan. Waste isomer generated in the preparation method can be converted into the compound shown as the formula (II) and enriched with the trans-isomer through a palladium catalytic hydrogenation method for recycling. The preparation method has the advantages that raw materials are cheap and the preparation process is simple, is free of emission of the waste isomer and suitable for industrial production.

Description

technical field [0001] The invention relates to the technical field of synthesis of herbicide indaziflam, in particular to a preparation method of (1R,2S)-2,6-dimethyl-1-aminoindan. Background technique [0002] Indaziflam is a new type of herbicide developed by Bayer Crop Science Company, which is mainly used to control annual weeds (such as crabgrass, goosegrass, bluegrass, etc.) and 65 kinds of weeds in lawns, flowers and vegetation. Other grasses and broadleaf weeds. Among them, (1R,2S)-2,6-dimethyl-1-aminoindan (formula RS-I)) is one of the key intermediates for the synthesis of indachlor. [0003] [0004] As for the synthesis of (1R,2S)-2,6-dimethyl-1-aminoindan RS-(I), there are not many preparation methods reported so far. such as literature Tetrahedron 2007, 63 (29), 6755-6763 reported to use 2,6-dimethyl-1-indanone (V) as raw material, in the presence of rhodium or ruthenium-based chiral catalysts, asymmetric hydrogenation to obtain ( 1S,2S)-2,6-Dimethyl-1-...

Claims

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Application Information

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IPC IPC(8): C07C209/88C07C211/42
CPCC07C209/40C07C209/88C07C249/08C07B2200/07C07C211/42C07C251/44
Inventor 祁彥涛李涛王博
Owner SHANGHAI PUYI CHEM CO LTD
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