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Method for preparing gamma and delta unsaturated ketone

An unsaturated, C1-C4 technology, applied in chemical instruments and methods, preparation of carbon-based compounds, preparation of organic compounds, etc., can solve the problems of limited transportation, dangerous production operations, and high production costs, and is easy to recycle and apply. , The raw materials are easy to obtain, the raw materials are cheap and the effect

Active Publication Date: 2014-05-07
SHANGHAI HEGNO PHARMA HLDG +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The disadvantages of this method are: the raw material diketene is a highly toxic drug, the transportation is limited, the production operation is dangerous, and it is not suitable for industrialized large-scale production
The disadvantage of this method is that either a pressure vessel or mineral spirits is required as a solvent, and the production cost is high

Method used

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  • Method for preparing gamma and delta unsaturated ketone
  • Method for preparing gamma and delta unsaturated ketone
  • Method for preparing gamma and delta unsaturated ketone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Preparation of geranylacetone (6,10-dimethyl-5,9-undecadien-2-one):

[0030] In a reaction vessel with a distillation device, under nitrogen protection, add linalool (100.0 g, 0.65 mol) and 5.0 g of triethanolamine solution containing 10% (mass ratio) sodium ethoxide, and stir to raise the temperature. When the temperature of the system was raised to 100° C., ethyl acetoacetate (84.5 g, 0.65 mol) was added dropwise, and the dropwise was completed within 2 hours by controlling the speed. After the dropwise addition, the temperature of the system was raised to 160° C., and the reaction was kept for 5 hours. Remove the low-boiling components generated in the reaction process, and then carry out vacuum distillation to obtain 10.0 g of the front fraction at 25-55 ° C / 50 Pa; 115.1 g of the main fraction (geranyl acetone) at 55-65 ° C / 50 Pa. The yield was 91.3%, and the purity detected by GC was 97.5%.

Embodiment 2

[0032] Preparation of Geranylacetone

[0033] In a reaction vessel with a distillation device, under nitrogen protection, add linalool (100.0 g, 0.65 mol) and 10.0 g of triethanolamine solution containing 5% (mass ratio) sodium methoxide, and stir to raise the temperature. When the temperature of the system was raised to 150° C., methyl acetoacetate (86 g, 0.74 mol) was added dropwise, and the dropwise was completed within 3 hours at a controlled rate. After the dropwise addition, the temperature of the system was raised to 190° C. and kept for 8 hours. The low-boiling components generated during the reaction were removed, and distillation under reduced pressure was started. Obtain 13.5g of the front fraction at 25-55°C / 50Pa; 113.2g of the main fraction (geranylacetone) at 55-65°C / 50Pa, with a yield of 89.7% and a purity of 98.5%.

Embodiment 3

[0035] The preparation of geranyl acetone (combined alkali recovery applies mechanically):

[0036] Under the protection of nitrogen, in the reaction vessel left with the distillation raffinate in Example 1, add (100.0 g, 0.65 mol) linalool and 10.0 g of the fraction before distillation, and stir to raise the temperature. When the temperature of the system was raised to 100° C., ethyl acetoacetate (89 g, 0.68 mol) was added dropwise at a controlled rate within 2 hours. After the dropwise addition, the temperature of the system was raised to 180° C. and kept for 6 hours. The low-boiling components generated during the reaction were removed, and distillation under reduced pressure was started. Obtain 10.2g of the front fraction at 25-50°C / 50Pa; 118.1g of the main fraction at 50-80°C / 50Pa, with a yield of 93.7% and a purity of 97.6%.

[0037] The same method was applied mechanically 7 times again, and the yield and purity of the main fraction are shown in Table 1.

[0038] Tab...

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Abstract

The invention discloses a method for preparing gamma and delta unsaturated ketone, which comprises the steps of: leading unsaturated alcohol to have alkyl ester reaction with acetoacetic acid under the action of combined alkali catalyst, collecting products and obtaining the target product gamma and delta unsaturated ketone with high purity and high yield. The combined alkali catalyst adopted in the method is easily recovered and applied mechanically, the reaction selectivity is high, and the cost of raw materials is greatly reduced, so that the method is suitable for industrialized production.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a synthesis method of a vitamin E intermediate-γ,δ-unsaturated ketone. Background technique [0002] γ, δ-unsaturated ketones are important intermediates for the synthesis of vitamins, spices and medicines, such as geranyl acetone (formula I) and farnesyl acetone (formula II) are important intermediates for the synthesis of vitamin E. [0003] [0004] Formula (I) Formula (II) [0005] There are many literatures and patents on the synthesis of such unsaturated ketones. The first is the acetoacetate method invented by Roche (see US2795617), using alkyl acetoacetate (generally ethyl acetoacetate and methyl acetoacetate) as C 3 Source, Carroll reaction occurs with unsaturated enol under the catalysis of aluminum isopropoxide to obtain unsaturated ketone. The disadvantage of this method is that the catalyst aluminum isopropoxide is easily deactivated under the actio...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C49/203C07C45/65
CPCY02P20/584
Inventor 刘德铭鲁向阳闫静
Owner SHANGHAI HEGNO PHARMA HLDG