A kind of preparation method of cyclohexane triketone compound

A technology of cyclohexanetrione and compound, which is applied in the field of preparation of organic compounds, can solve the problems of increased process cost, difficulty in post-processing, pressure on environmental protection, etc., and achieves the effects of fast reaction, less three wastes, and simple post-processing

Active Publication Date: 2015-07-29
MAX RUDONG CHEM +1
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although cyclohexanetriketone compounds can be prepared through the above-mentioned processes, these processes are carried out in the presence of solvents, and catalysts with high toxicity or poor solubility are used, and special treatment methods are required to treat the three wastes generated during the process. Increased process cost, post-processing difficulty and pressure on environmental protection

Method used

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Examples

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preparation example Construction

[0011] The steps of the preparation method of cyclohexanetriketone compound are as follows:

[0012] In the first step, enol ester is used as raw material, and azide quaternary ammonium salt is added under the condition of 25-60°C, and the mass ratio of azide quaternary ammonium salt to enol ester is 0.01-0.5;

[0013] In the second step, organic amine is added, and the molar ratio of organic amine to enol ester is 1.0 to 5.0;

[0014] The third step is to stir until the reaction is complete to obtain cyclohexanetrione compounds.

[0015] The cyclohexane triketone compounds are: ethyl 4-cyclopropylformyl-3,5-diketone cyclohexanecarboxylate, ethyl 4-propionyl-3,5-diketone cyclohexanecarboxylate ester. The azide quaternary ammonium salt is: one or more of tetrabutyl ammonium azide, tetraethyl ammonium azide, tetrapropyl ammonium azide or benzyl triethyl ammonium azide mixture. The organic amine is: one or more mixtures of triethylamine, tributylamine, benzyldiethylamine or i...

Embodiment 1：106.0g 5--4--3-、53.0g 3 and 5.3g 4 1000mL，25℃ to 。300mL and ，pH＝3， to 104.0g4-()-3,5- 2 ，98.0％。4-()-3,5- 2 ：1HNMR(500MHz，CDCl3)：δ4.17～4.21(q,2H)，3.53～3.58(m,1H)，3.04～3.10(m,1H)，2.87～2.96(m,2H)，2.78～2.85(m,1H)，2.69～2.74(m,1H)，1.26～1.32(m,5H)，1.13～1.16(m,1H)。 Embodiment 2

[0017] Example 1: Add 106.0g ethyl 5-cyclopropylformyloxy-4-cyclohexen-3-onecarboxylate, 53.0g triethylamine and 5.3g tetra-n-butylammonium azide to 1000mL for reaction In the bottle, stir at 25°C until the reaction is complete. Add 300mL of a mixture of chloroform and water, adjust the pH to 3 with hydrochloric acid, and desolventize the organic layer to obtain 104.0g of ethyl 4-cyclopropyl(hydroxy)methylene-3,5-diketonecyclohexanecarboxylate. The rate is 98.0%. The nuclear magnetic resonance spectrum data of described 4-cyclopropyl (hydroxyl) methylene-3,5-diketone cyclohexanecarboxylate ethyl ester compound is as follows: 1 HNMR (500MHz, CDCl 3 ): δ4.17~4.21(q,2H), 3.53~3.58(m,1H), 3.04~3.10(m,1H), 2.87~2.96(m,2H), 2.78~2.85(m,1H), 2.69 ~2.74(m, 1H), 1.26~1.32(m, 5H), 1.13~1.16(m, 1H). Example 2: Add 40.0g ethyl 5-acetoxy-4-cyclohexen-3-onecarboxylate, 26.5g benzyldiethylamine and 1.2g benzyltriethylammonium azide to 500mL reaction In the bottle, stir at 60°C until the...

Embodiment 3

[0018] Example 3: Add 53.0g ethyl 5-cyclopropylformyloxy-4-cyclohexen-3-onecarboxylate, 26.5g tributylamine and 2.7g tetraethylammonium azide into a 500mL reaction flask , Stir at 25°C until the reaction is complete. Add 250 mL of a mixture of toluene and water, adjust the pH to 5 with hydrochloric acid, and obtain 50.4 g of ethyl 4-cyclopropyl(hydroxy)methylene-3,5-diketonecyclohexanecarboxylate through precipitation of the organic layer. Yield 95.1%.

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Abstract

The invention discloses a preparation method of cyclohexane trione compounds. The method comprises the following steps: 1. by using enol ester as a raw material, adding nitrine quaternary ammonium salt at 25-60 DEG C, wherein the mass ratio of the nitrine quaternary ammonium salt to the enol ester is 0.01-0.5; 2. adding organic amine, wherein the mole ratio of the organic amine to the enol ester is 1.0-5.0; 3. stirring until the reaction is complete; and 4. adding an organic solvent and water into the reaction mixture, acidifying, stratifying, and desolventizing to obtain the cyclohexane trione compounds. The method lowers the production cost, is simple and safe to operate, has the advantages of quick reaction and simple after-treatment, and is suitable for industrialized operation. The method solves the technical problems of high catalyst toxicity, difficulty in solvent recovery, great environmental pollution and the like in the prior art.

Description

technical field [0001] The invention relates to a method for preparing organic compounds, in particular to a method for preparing cyclohexanetriketone compounds. Background technique [0002] Cyclohexanetrione (cyclohexanetrione) compounds, with structural formula. As a plant growth regulator, it belongs to the gibberellic acid (GAs, A category) plant growth regulator, which has the activity of delaying plant growth and weeding. It can inhibit plant growth, reduce plant height, control plant type, strengthen basal internodes, etc. It has good effect, can be used before the plants bloom, and will not cause fruit deformity and excessive drug residue, which has aroused great interest of plant growth regulator researchers. At present, such compounds that have been commercialized include: Trinexapac-ethyl (US4693745), the chemical name is ethyl 4-cyclopropyl (hydroxyl) methylene-3,5-diketone cyclohexanecarboxylate , Syngenta], Prohexadione-calcium (JP8371264), the chemical na...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C69/757C07C67/31
CPCC07C67/31C07C67/343C07C2601/02C07C2601/14C07C69/757
Inventor 邵玉田蔡国平陈玲盛秋菊陈邦池
Owner MAX RUDONG CHEM
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