CN108329201A - The synthesis technology of 1,3- indandione rodenticides - Google Patents
The synthesis technology of 1,3- indandione rodenticides Download PDFInfo
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- CN108329201A CN108329201A CN201810294263.6A CN201810294263A CN108329201A CN 108329201 A CN108329201 A CN 108329201A CN 201810294263 A CN201810294263 A CN 201810294263A CN 108329201 A CN108329201 A CN 108329201A
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- ethyl acetate
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- synthesis technology
- indandione
- filter cake
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/48—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation involving decarboxylation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
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- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to medicine intermediate synthesis technical field, more particularly to a kind of synthesis technology of 1,3 indandione rodenticides includes the following steps：Step 1, repefral and ethyl acetate are added in reaction vessel, open stirring, sodium methoxide is added, be heated to stopping heating at 40 50 DEG C；Step 2, continue to be stirred to react, wait for that reaction system solidifies shape in yellow, add ethyl acetate, after keeping reaction system to be reacted 34 hours under conditions of temperature is 70 80 DEG C, be cooled to 20 DEG C hereinafter, filtering, filter cake is eluted with ethyl acetate, is dried, is obtained intermediate；Step 3, it takes intermediate made from step 1 to be added in reaction vessel, concentrated hydrochloric acid and water is added in reaction vessel after mixing, open stirring, be heated to 45 55 DEG C, insulation reaction is not until have bubble formation；20 DEG C are cooled to hereinafter, filtering, filter cake is collected in the elution of filter cake ethyl acetate, and 1,3 indandione rodenticide of product is made in vacuum drying；The synthesis technology is simple, mild condition, product yield high.
Description
Technical field
The invention belongs to medicine intermediate synthesis technical fields, the more particularly to synthesis technology of one kind 1,3- indandione rodenticides.
Background technology
Special existence form of the fullerene as the carbon simple substance found earliest, because of property such as its special structure and light, electricity, magnetic
Matter is paid attention in fields such as physics, chemistry, material science by height.How to be prepared with the fully synthetic method of chemistry rich electric
The fullerene of son, has become a hot research topic in recent years.1,3- indandione rodenticides are to prepare importantization of fullerene precursor
Object is closed, while being also important chemical intermediate, is played an important role in terms of the synthesis such as medicine, biology, pesticide.
Chinese patent CN103121887A discloses a kind of former based on diethyl phthalate and dimethyl malenate
Material, sodium methoxide are alkali, and two steps synthesize the preparation method of 1,3- indandione rodenticide class compounds；In the technique, diethyl phthalate
Not only it is used as reactant, but also as raw material, recycling is subsequently evaporated off again, wastes raw material and energy consumption, and raw material malonic acid dimethyl
Ester is more expensive, and totle drilling cost is higher.
There is document (Journal of the Chemical Society, Perkin Transactions 1：Organic
And Bio-Organic Chemistry, 21,2985-2988,1992) it discloses former based on chlorobenzoyl chloride and malonyl chloride
Material, passes through Friedel-Crafts reaction cyclization, one-step synthesis method 1,3- indandione rodenticide class compounds；But the raw materials technology higher price synthesizes item
Part is more harsh, higher to factors dictates such as temperature, times, and product crude product is more miscellaneous, and post-processing is difficult, and yield is low.
Another document (Bulletin of the Korean Chemical Society, 30,2918-2920,2009)
It discloses using dibutyl phthalate and ethyl acetate as main material, through condensation, hydrolysis, decarboxylation, three-step approach synthesizes 1,3- indenes
The method of diketone；But technique post-processing is difficult, and yield is low.
Invention content
The present invention solves the above-mentioned technical problems in the prior art, provides the synthesis technology of one kind 1,3- indandione rodenticides.
To solve the above problems, technical scheme is as follows：
The synthesis route of 1,3- indandione rodenticides is as follows：
The synthesis technology of 1,3- indandione rodenticide, includes the following steps：
Step 1, repefral and ethyl acetate are added in reaction vessel, open stirring, sodium methoxide is added,
It is heated to stopping heating at 40-50 DEG C；
Step 2, continue to be stirred to react, wait for that reaction system solidifies shape in yellow, add ethyl acetate, reaction system is kept to exist
After temperature is reacted 3-4 hours under conditions of being 70-80 DEG C, 20 DEG C are cooled to hereinafter, filtering, filter cake is eluted with ethyl acetate, is dried
It is dry, obtain intermediate；
Step 3, it takes intermediate made from step 1 to be added in reaction vessel, concentrated hydrochloric acid and water is added instead after mixing
It answers in container, opens stirring, be heated to 45-55 DEG C, insulation reaction is not until have bubble formation；Be cooled to 20 DEG C hereinafter, filter,
Filter cake ethyl acetate elutes, and collects filter cake, and product 1,3- indandione rodenticides is made in vacuum drying.
Preferably, repefral in the step 1, ethyl acetate, sodium methoxide mass ratio be 1:1-1.5:
0.6。
Preferably, the quality that ethyl acetate is added in the step 2 is the 2.5- of raw material repefral quality
3.5 again.
Preferably, yellow solid in the step 3, concentrated hydrochloric acid, water mass ratio be 1:0.9-1.2:2-3.
Preferably, the yellow solid that the step 2 obtains is dried using infrared lamp.
Compared with the existing technology, advantages of the present invention is as follows,
The synthesis technology of the present invention 1,3- indandione rodenticides can be dropped using repefral, ethyl acetate as primary raw material
Low cost, by the optimization to processing step and reaction condition, product yield high, purity is high, and synthesis technology is simple, condition temperature
With without complicated post-processing step, it is environmentally protective, economize on resources and energy consumption.
Specific implementation mode
Embodiment 1：
The synthesis technology of 1,3- indandione rodenticide, includes the following steps：
(1) first step, condensation
1.5kg repefrals and 1.5L ethyl acetate are taken, is added in 10L reaction bulbs, stirring, interior temperature 12 are opened
℃.Then 918g sodium methoxides are added, white turbid solution is slightly exothermic.Heating is opened, stops heating when being warming up to 40-50 DEG C.Instead
Heat release, interior temperature is answered to rise automatically.When interior temperature automatically ramps up to 76 DEG C, system is in red tan solution, more sticky, there is bubble generation.
When interior temperature automatically ramps up to 86 DEG C, there are a large amount of solids to be precipitated, system solidifies shape in yellow, needs to add ethyl acetate, can just stir
It is dynamic, 4L ethyl acetate is added altogether, and system is in yellow turbid solution, more sticky, keeps the temperature 70-80 DEG C and reacts 3-4 hours.Reaction solution drops
For temperature to 20 DEG C hereinafter, filtering, the elution of filter cake 500ml ethyl acetate is primary, and infrared lamp drying obtains intermediate 1860g, yellow is solid
Body.
(2) second step, hydrolysis decarboxylation
It takes 1860g first step products to be added in 10L reaction bulbs, then first mixes 1754ml concentrated hydrochloric acids and 3700ml water equal
It is even, it is then added in reaction bulb, stirs, yellow turbid solution is heated to 45-55 DEG C, has bubble generation, then insulation reaction.
After reacting 4h, off-white color turbid solution is obtained, continues insulation reaction 1h, until not having bubble formation.Be cooled to 20 DEG C hereinafter, filter,
Filter cake is primary with the elution of 1.0L ethyl acetate.Filter cake is collected, vacuum drying obtains faint yellow to off-white powder 936g, yield
83.2%.It is detected by GC, product purity 99%；It is detected by NMR, product purity 98%.
Embodiment 2：
With embodiment 1, repefral, the acetic acid that reaction bulb is added in first step condensation reaction for the first time are only changed
The mass ratio of ethyl ester, sodium methoxide prepares 1,3- indandione rodenticides, and calculates its yield；
| Group | The mass ratio of repefral, ethyl acetate, sodium methoxide | Yield % |
| A groups | 1:1:0.6 | 82.7 |
| B groups | 1:1.5:0.6 | 84.5 |
| C groups | 1:0.5:0.6 | 40.7 |
| D groups | 1:2:0.6 | 69.8 |
Embodiment 3：
With embodiment 1, only changes and add ethyl acetate and raw material repefral in first step condensation reaction
Mass ratio prepares 1,3- indandione rodenticides, and calculates its yield；
| Group | Repefral, the mass ratio for adding ethyl acetate | Yield % |
| A groups | 1:3.0 | 83.1 |
| B groups | 1:3.5 | 82.8 |
| C groups | 1:1.5 | 67.6 |
| D groups | 1:4.5 | 72.5 |
Embodiment 4：
With embodiment 1, the mass ratio of intermediate, concentrated hydrochloric acid, water in the reaction of second step hydrolysis decarboxylation is only changed, prepares 1,3-
Indandione rodenticide, and calculate its yield；
| Group | The mass ratio of intermediate, concentrated hydrochloric acid, water | Yield % |
| A groups | 1:0.9:2 | 82.2 |
| B groups | 1:1.2:3 | 84.0 |
| C groups | 1:0.6:1 | 36.8 |
| D groups | 1:1.5:4 | 58.9 |
It should be noted that above-described embodiment is only presently preferred embodiments of the present invention, there is no for the purpose of limiting the invention
Protection domain, the equivalent replacement or replacement made on the basis of the above all belong to the scope of protection of the present invention.
Claims (5)
- The synthesis technology of 1.1,3- indandione rodenticides, which is characterized in that include the following steps：Step 1, repefral and ethyl acetate are added in reaction vessel, open stirring, sodium methoxide, heating is added To stopping heating at 40-50 DEG C；Step 2, continue to be stirred to react, wait for that reaction system solidifies shape in yellow, add ethyl acetate, keep reaction system in temperature After being reacted 3-4 hours under conditions of being 70-80 DEG C, 20 DEG C are cooled to hereinafter, filtering, filter cake is eluted with ethyl acetate, is dried, is obtained To intermediate；Step 3, it takes intermediate made from step 1 to be added in reaction vessel, concentrated hydrochloric acid is added after mixing with water and reacts appearance In device, stirring is opened, is heated to 45-55 DEG C, insulation reaction is not until have bubble formation；20 DEG C are cooled to hereinafter, filtering, filter cake Ethyl acetate elutes, and collects filter cake, and product 1,3- indandione rodenticides is made in vacuum drying.
- 2. the synthesis technology of 1,3- indandione rodenticides as described in claim 1, which is characterized in that phthalic acid in the step 1 Dimethyl ester, ethyl acetate, sodium methoxide mass ratio be 1:1-1.5:0.6.
- 3. the synthesis technology of 1,3- indandione rodenticides as described in claim 1, which is characterized in that add acetic acid second in the step 2 The quality of ester is 2.5-3.5 times of raw material repefral quality.
- 4. the synthesis technology of 1,3- indandione rodenticides as described in claim 1, which is characterized in that yellow solid in the step 3, dense Hydrochloric acid, water mass ratio be 1:0.9-1.2:2-3.
- 5. the synthesis technology of 1,3- indandione rodenticides as described in claim 1, which is characterized in that the yellow that the step 2 obtains is solid Body is dried using infrared lamp.
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| CN201810294263.6A CN108329201A (en) | 2018-03-30 | 2018-03-30 | The synthesis technology of 1,3- indandione rodenticides |
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| CN201810294263.6A CN108329201A (en) | 2018-03-30 | 2018-03-30 | The synthesis technology of 1,3- indandione rodenticides |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111470961A (en) * | 2020-04-14 | 2020-07-31 | 南京欧纳壹有机光电有限公司 | Efficient synthesis method of halogenated 1, 3-indene diketone compounds |
-
2018
- 2018-03-30 CN CN201810294263.6A patent/CN108329201A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111470961A (en) * | 2020-04-14 | 2020-07-31 | 南京欧纳壹有机光电有限公司 | Efficient synthesis method of halogenated 1, 3-indene diketone compounds |
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