Method for synthesizing enantiomorphous pure symmetric trans-dialkyl cyclohexylamine

A synthesis method and dialkyl technology, applied in the field of chemistry, can solve problems such as manufacturing and cost defects, and achieve the effects of simple operation, cheap and easily available reagents, and mild reaction conditions

Inactive Publication Date: 2012-07-04
ANYANG INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0018] Each of the above methods has manufacturing and cost defects to varying degrees.

Method used

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  • Method for synthesizing enantiomorphous pure symmetric trans-dialkyl cyclohexylamine
  • Method for synthesizing enantiomorphous pure symmetric trans-dialkyl cyclohexylamine
  • Method for synthesizing enantiomorphous pure symmetric trans-dialkyl cyclohexylamine

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] Example 1: Preparation of enantiopure N, N'-dimethyl-1,2-cyclohexanediamine

[0038] The first step: 2-methylaminocyclohexanol (IIIa, R=CH 3 ) preparation

[0039] Add epoxycyclohexane (9.8g, 0.1mol) and 25-30% methylamine aqueous solution (18.6g, 0.15mol) into the sealed tube, seal it and heat it to an oil bath temperature of 80°C, and react for 5h. After the system was cooled, the solvent was evaporated under reduced pressure, and the solvent was spin-dried again after adding toluene. After drying, 13 g of 2-methylaminocyclohexanol was obtained, with a yield of 100%;

[0040] The second step: N-methyl-7-azabicyclo[4,1,0]heptane (IVa, R=CH 3 ) preparation

[0041] Add triphenylphosphine (31.44g, 0.12mol) and 2-methylaminocyclohexanol (13g, 0.1mol) into the reaction flask, add solvent CH 2 Cl 2 , slowly add DEAD (22mL, 0.12mol) in CH 2 Cl 2 The solution was raised to room temperature and reacted for 5 hours. After cooling, 2N HCl was added to the system for ext...

Embodiment 2

[0048] Example 2: Preparation of enantiopure N, N'-dimethyl-1,2-cyclohexanediamine

[0049] The first step: 2-methylaminocyclohexanol (IIIa, R=CH 3 ) preparation

[0050] Add epoxycyclohexane (9.8g, 0.1mol) and 25-30% methylamine aqueous solution (18.6g, 0.15mol) into the sealed tube, seal it and heat it to an oil bath temperature of 120°C, and react for 1.5h. After the system was cooled, the solvent was evaporated under reduced pressure, and the solvent was spin-dried again after adding toluene. After drying, 13 g of 2-methylaminocyclohexanol was obtained, with a yield of 100%;

[0051] The second step: N-methyl-7-azabicyclo[4,1,0]heptane (IVa, R=CH 3 ) preparation

[0052] Add triphenylphosphine (31.44g, 0.12mol) and 2-methylaminocyclohexanol (13g, 0.1mol) into the reaction flask, add the solvent THF, slowly add DEAD (22mL, 0.12mol) dropwise under ice bath CH 2 Cl 2 The solution was raised to room temperature and reacted for 6 hours. After cooling, 2N HCl was added to...

Embodiment

[0059] Example 3: Preparation of enantiopure N, N'-diethyl-1,2-cyclohexanediamine

[0060] The first step: 2-ethylaminocyclohexanol (IIIb, R=CH 2 CH 3 ) preparation

[0061] Add epoxycyclohexane (9.8g, 0.1mol) and 70% ethylamine aqueous solution (12.9g, 0.2mol) into the sealed tube, seal it and heat it to an oil bath temperature of 100°C, and react for 3.5h. After the system was cooled, the solvent was evaporated to dryness under reduced pressure, and toluene was added and the solvent was spin-dried again. After drying, 14.3 g of 2-ethylaminocyclohexanol was obtained, with a yield of 100%;

[0062] The second step: N-ethyl-7-azabicyclo[4,1,0]heptane (IVb, R=CH 2 CH 3 ) preparation

[0063] Dissolve triphenylphosphine (31.44g, 0.12mol) and 2-ethylaminocyclohexanol (14.3g, 0.1mol) in tert-butyl methyl ether, and slowly add DIAD (23.8mL, 0.12mol) dropwise under ice-cooling The tert-butyl methyl ether solution was raised to room temperature and reacted for 12 hours. After c...

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Abstract

The invention discloses a method for synthesizing enantiomorphous pure symmetric trans-dialkyl cyclohexylamine, belonging to the field of chemistry. The method comprises the following steps of: carrying out an airtight or reflux reaction on cyclohexene oxide and an aqueous solution of alkylamine for reacting at 80-120 DEG C for 1.5-5h to obtain 2-alkyl-amino cyclohexanol, dropwise adding DEAD (Diethyl Azodicarboxylate) or DIAD (Diisopropyl Azodicarboxylate) to triphenylphosphine, 2-alkyl-amino cyclohexanol and a solvent under an ice bath for reacting for 5-20h at room temperature to obtain N-alkyl-7-azabicyclo[4, 1, 0]heptane, adding a catalyst to the N-alkyl-7-azabicyclo[4, 1, 0]heptane and the aqueous solution of alkylamine at 100-120 DEG C to carry out the airtight or reflux reaction to obtain trans-N,N'-dialkyl-1,2 cyclohexanamine, dissolving the trans-N,N'-dialkyl-1,2 cyclohexanamine in an alcoholic solvent, and adding a tartaric acid type resolving agent with the equivalent weight of 0.5 to the alcoholic solvent to resolve so as to obtain the enantiomorphous pure symmetric trans-dialkyl cyclohexylamine.

Description

technical field [0001] The invention relates to a synthesis method of dialkylcyclohexylamine, in particular to a synthesis method of enantiopure symmetrical trans dialkylcyclohexylamine, which belongs to the field of chemistry. Background technique [0002] Enantiopure symmetrical trans-dialkylcyclohexylamine is a class of important chemical raw materials, and its structure is shown in the structural formula: [0003] [0004] Among them, the configuration of the 1-position and 2-position of the cyclohexyl group can be (1R, 2R), or (1S, 2S). This type of compound is used for the synthesis of chiral reagents and important intermediates as ligands for asymmetric catalysis, and is also important pharmaceutical intermediates. For example, Geon-Joong Kim et al. synthesized a ligand containing an imidazole ring structure using enantiopure symmetrical trans-dialkylcyclohexylamine as an important intermediate, and Ma Menglin et al. A series of new ruthenium complexes were synth...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C211/36C07C209/00
Inventor 申艳红侯绍刚郁有祝赵亮许浒张允
Owner ANYANG INST OF TECH
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