CN109928868A - The synthetic method and its application of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- - Google Patents
The synthetic method and its application of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- Download PDFInfo
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Abstract
The invention discloses one kind 1; 3- bis- (2; 5- 3,5-dimethylphenyl) propyl- 2- ketone synthetic method, be with 2,5- dimethyl phenyl acetic acid be raw material; intermediate 2 is obtained through acylation, ethyl esterified reaction; 5- dimethyl phenyl acetic acid ethyl ester, then under basic catalyst, target product 1 is synthesized by condensation, hydrolysis, decarboxylic reaction; bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 3-；The invention also discloses a kind of applications of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3-, it can be used as standard items, for detecting and monitoring the synthesis of pesticide spiral shell worm ethyl ester intermediate.Synthetic method provided by the present invention is easy to operate, and process is easily controllable, gained 1, and the yield of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 3- is 56.5%.
Description
Technical field
The invention belongs to fine chemistry and pharmaceutical fields, are related to a kind of synthetic method of organic intermediate, specifically, being
A kind of synthetic method and its application of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3-.
Background technique
In the synthesis process of drug, the generation of impurity can not only generate tremendous influence to synthetic reaction, but also generate
Impurity can be direct or indirect the quality for affecting drug, therefore also influence the application of drug.To miscellaneous during synthesis
Matter carries out effective monitoring and plays a key role for guaranteeing product yield and reducing influence of the impurity to drug effectiveness.
Spiral shell worm ethyl ester (spirotetramat) is a kind of novel second generation tetronic acid insecticides of Beyer Co., Ltd's exploitation,
Chemical name is cis-3- (2,5- 3,5-dimethylphenyl) -8- methoxyl group -2- oxo -1- azaspiro [4.5]-last of the ten Heavenly stems 3- alkene 4- base second
Acetoacetic ester；Chemical formula is C21H27NO5.Structural formula is as follows:
2,5- dimethyl phenyl acetic acids are the key intermediates of spiral shell worm ethyl ester, can be using through cyano in its synthetic route of document report
Change, hydrolysis acquisition (J.Amer.Chem.Soc.58 (1936) 629-35), can also directly be catalyzed carbonyl from 2,5- dimethyl benzyl chloride
Glycosylation reaction obtains (WO2012122747, CN102140062).Wherein, carbonyl compound at 2,5- dimethyl phenyl acetic acid method
It is more in line with environmental requirement.Its synthetic route is as follows:
But in carbonylation processes, 2,5- dimethyl phenyl acetic acid can be not only generated, can also generate impurity, even if adjustment reaction
Condition, the impurity still remain, and through column chromatography for separation and identify, determine that the impurity is bis- (2, the 5- 3,5-dimethylphenyl) propyl-s of 1,3-
2- ketone, is retrieved through domestic and foreign literature, this substance is to separate for the first time and obtain structure determination.The presence of the impurity will affect product 2,
The quality of 5- dimethyl phenyl acetic acid, therefore it is conducive to the screening of reaction condition in reaction process to the monitoring of the impurity.
Therefore seek a kind of bis- (2,5- 3,5-dimethylphenyl) propyl- 2- ketone of 1,3- easy to operate, easily controllable, mild condition
Synthetic method, and using it as standard items detect 2,5- dimethyl phenyl acetic acid product quality and monitoring 2,5- dimethyl benzene
The synthesis process of acetic acid is of great significance.
Summary of the invention
The technical problem to be solved in the present invention is to provide for the conjunction of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- of one kind
At method, it is intended to 2,5- dimethyl phenyl acetic acid for raw material, through acylation, ethyl esterified obtained intermediate 2,5- dimethyl phenyl acetic acid second
Ester, this intermediate synthesize bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- by condensation, hydrolysis, decarboxylation under alkaline condition, should
Synthetic method is easy to operate, and process is easily controllable, gained 1, and the yield of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 3- is 56.5%.
Another object of the present invention is to provide a kind of application of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3-, it
As standard items, it can be used for detecting and monitoring spiral shell worm ethyl ester intermediate 2, the synthesis process of 5- dimethyl phenyl acetic acid.
In order to solve the above technical problems, the technical scheme adopted by the invention is that:
The synthetic method of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- of one kind, the synthetic method is with 2,5- dimethyl phenyl acetic acid
For raw material, intermediate 2,5- dimethyl phenyl acetic acid ethyl ester, 2, the 5- dimethyl phenyl acetic acid second are obtained through acylation, ethyl esterified reaction
Ester again existing for the basic catalyst under the conditions of, condensation, hydrolysis, decarboxylic reaction synthesis bis- (2, the 5- diformazans of 1,3- occur
Base phenyl) propyl- 2- ketone；
Its synthetic route is as follows:
As the restriction to the above method: the synthetic method sequentially carries out in accordance with the following steps:
(1) preparation of 2,5- dimethyl phenyl acetic acid ethyl ester
By raw material 2 at 25 DEG C, 5- dimethyl phenyl acetic acid is added in solvent dry toluene, after being warming up to 70 DEG C, is slowly added dropwise
SOCl2, enable temperature be warming up to 90 DEG C, 1.5 ~ 2 h of reaction at 110 DEG C after being added dropwise, generation 2,5- dimethyl benzene chloroacetic chloride, 80
Excessive SOCl is evaporated off at DEG C2；Dehydrated alcohol is slowly added dropwise after being down to 25 DEG C, the reaction was continued 0.5h, then in three times respectively plus
Enter 50mL water, separate two-phase, remove origin impurity, organic phase revolving obtains intermediate 2,5- dimethyl phenyl acetic acid ethyl ester, content
Greater than 95.0%；
(2) preparation of intermediate A
N2Under environment, lye is added in solvent dry toluene, is made reaction system B, then by 2,5- dimethyl obtained by step (1)
Ethyl phenylacetate is added dropwise in reaction system B, maintain temperature 45 DEG C hereinafter, being added dropwise after, be heated to 90 DEG C of reaction 4h；Instead
Reaction solution should be cooled down after the completion, temperature control is saturated metabisulfite solution hereinafter, being added dropwise at 10 DEG C, and it is molten that dilute hydrochloric acid is added dropwise again later
Liquid steams solvent toluene at 110 DEG C, obtains intermediate A；
(3) preparation of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3-
20% dilute hydrochloric acid is added into intermediate A obtained by step (2), 8h is reacted at 108 DEG C, after reaction, uses alkane solvents
In 65 DEG C of progress extraction heats, after gained organic phase is down to 25 DEG C, 1h is stirred under the conditions of ice-water bath, solid is precipitated, is filtered, is done
Dry, obtained solid is recrystallized through alcohols solvent up to bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1, the 3-.
Limit as to lye in the above method: the lye is sodium hydride solution, sodium methoxide solution, methanol potassium solution
Or potassium tert-butoxide solution.
Limited as to alkane solvents in the above method: the alkane solvents as normal heptane, hexamethylene or just oneself
Alkane, or wherein 2 kinds of mixtures.
Limit as to alcohols solvent in the above method: the alcohols solvent is methanol or ethyl alcohol.
As the restriction to step in the above method (2): in the preparation of step (2) intermediate A, lye amount used with
The equivalent proportion of 2,5- dimethyl phenyl acetic acid ethyl ester is 3~20:1.
As in the preparation for further defining that the step (2) intermediate A to step in the above method (2), nothing used
The dosage of water-toluene and the equivalent proportion of 2,5- dimethyl phenyl acetic acid ethyl ester dosage are 5 ~ 10:1.
As the further restriction to step in the above method (2): used in the preparation of step (2) intermediate A
The mass fraction of dilute hydrochloric acid is 15% ~ 25%.
As the restriction to step in the above method (3): bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- of step (3) 1,3-
In the preparation of ketone, the equivalent proportion of 20% dilute hydrochloric acid amount used and 2,5- dimethyl phenyl acetic acid ethyl ester dosage is 1.1 ~ 1.5:1
Invention additionally provides a kind of a kind of application of bis- (2,5- 3,5-dimethylphenyl) propyl- 2- ketone of made 1, the 3- of above-mentioned synthetic method,
Bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- are used as standard items, are applied to detect and monitor among pesticide spiral shell worm ethyl ester
The synthesis of body.
Due to the adoption of the above technical solution, compared with prior art, acquired technological progress is the present invention:
The synthetic method provided through the invention, using industrialization small-molecule starting material 2,5- dimethyl phenyl acetic acid, by acylation, second
Esterification obtains intermediate 2,5- dimethyl phenyl acetic acid ethyl ester, and condensation reaction occurs under basic catalyst for this intermediate, then
Bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- are synthesized through hydrolysis, decarboxylic reaction, easy to operate, process is easy to control, especially
Product isolation and purification method is simple, and product yield is up to 56.5%.
The present invention is described in further detail below in conjunction with specific embodiment.
Detailed description of the invention
Fig. 1 is 2,5- dimethyl phenyl acetic acid ethyl ester1HNMR figure；
Fig. 2 is bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3-1HNMR figure；
Fig. 3 is the liquid matter figure of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3-；
Fig. 4 is that the IR of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- schemes；
Fig. 5 is the efficient liquid phase figure of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3-；
Fig. 6 is the high-efficient liquid phase chromatogram of 2,5- dimethyl phenyl acetic acid；
Fig. 7 is the high-efficient liquid phase chromatogram of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone synthesis reaction solutions of 1,3-.
Specific embodiment
Reagent as used in the following examples is existing commercial reagent unless otherwise specified, and test method is such as without special theory
It is bright to be all made of existing test method.
A kind of synthetic method of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of the 1,3- of embodiment 1
(1) preparation of 2,5- dimethyl phenyl acetic acid ethyl ester
By raw material 2 at 25 DEG C, 5- dimethyl phenyl acetic acid 30g is added in 150mL solvent dry toluene, after being warming up to 70 DEG C, slowly
The SOCl of 26.08g is added dropwise2, enable temperature be warming up to 90 DEG C, react 1.5h after being added dropwise at 110 DEG C, generate 2,5- dimethyl
Phenyllacetyl chloride, 80 DEG C are evaporated off excessive SOCl2, dehydrated alcohol 16.83g is slowly added dropwise after being down to 25 DEG C, after the reaction was continued 0.5h
Add water 50mL to be extracted respectively in three times, remove origin impurity, organic phase rotates up to 36.39g yellow liquid, and content is greater than
95.0%。
2,5- dimethyl phenyl acetic acid ethyl ester obtained in the present embodiment1HNMR figure is as shown in Figure 1.
(2) preparation of intermediate A
N2Under environment, 20.55g sodium hydride is added in 33mL dry toluene solvent, reaction system B is made, then by step (1) institute
2,5- dimethyl phenyl acetic acid ethyl ester 10g be added dropwise in reaction system B, maintain temperature 45 DEG C hereinafter, being added dropwise after, heating
To 90 DEG C of reaction 4h.Reaction solution is cooled down after the reaction was completed, temperature control is saturated metabisulfite solution hereinafter, being added dropwise at 10 DEG C, it
20% dilute hydrochloric acid solution is added dropwise again afterwards, steams solvent toluene at 110 DEG C, obtains intermediate A.
The equivalent proportion of sodium hydride solution and 2,5- dimethyl phenyl acetic acid ethyl ester is 5:1 in this step；Dry toluene used is molten
The equivalent proportion of agent and 2,5- dimethyl phenyl acetic acid ethyl ester is 6:1；The mass fraction of dilute hydrochloric acid used is 20%.
(3) preparation of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3-
20% dilute hydrochloric acid 10mL is added into intermediate A reaction solution obtained by step (2), reacts 8h at 108 DEG C, after reaction, uses
Normal heptane is in 65 DEG C of progress extraction heats, and after gained organic phase is down to 25 DEG C, 1h is stirred under the conditions of ice-water bath, solid, mistake is precipitated
Filter, dry, the solid obtained from is through recrystallizing methanol up to bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1, the 3-.
The equivalent proportion 1.43:1 of 20% dilute hydrochloric acid and 2,5- dimethyl phenyl acetic acid ethyl ester dosage in this step；Alkane used
Class reagent is normal heptane；Alcohols solvent used is methanol.
Bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- made from the present embodiment1HNMR figure is as shown in Figure 2；And 1,3-
The liquid matter figure of bis- (2,5- 3,5-dimethylphenyl) propyl- 2- ketone is then as shown in Figure 3；Bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3-
IR figure is as shown in Figure 4.
A kind of synthetic method of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of the 1,3- of embodiment 2~6
Embodiment 2~6 is respectively the synthetic method of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- of one kind, the synthetic method
It is identical as the synthetic method of embodiment 1, the difference is that reaction condition and substance used involved in each step has
Difference, is specifically shown in Table 1
Table 1
The application of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 7 1,3- of embodiment
It present embodiments provides and a kind of utilizes bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of any one 1,3- in Examples 1 to 6
The application of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- obtained by synthetic method.Due in synthesis spiral shell worm ethyl ester intermediate
During 2,5- dimethyl phenyl acetic acids, there is impurity 1, bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 3-, and the presence of impurity
It not only will affect intermediate and end product quality, the yield of reaction but will be substantially reduced.
The present invention (2,5- 3,5-dimethylphenyl) propyl- 2- ketone bis- to 1,3- synthesized by Examples 1 to 6 provide one kind and answer
With, i.e., it can be used as standard reference material detection spiral shell worm ethyl ester intermediate 2,5- dimethyl phenyl acetic acid with the presence or absence of 1,3- it is bis- (2,
5- 3,5-dimethylphenyl) propyl- 2- ketone and its content how much, this is significant to the improvement of reaction condition.
Detection method: high performance liquid chromatography
Testing conditions are that the volume ratio of mobile phase acetonitrile/water is 80/20；Formic acid adjusts pH4.0-4.5；Flow velocity: 1.0mL/min；
Detection wavelength: 220nm；Column temperature: 25 DEG C.Testing result is as follows:
The efficient liquid phase figure of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- is shown in Fig. 5；
The high-efficient liquid phase chromatogram of 2,5- dimethyl phenyl acetic acid is shown in Fig. 6；
The high-efficient liquid phase chromatogram of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone synthesis reaction solutions of 1,3- is shown in Fig. 7.
Spiral shell worm ethyl ester intermediate 2,5- dimethyl phenyl acetic acid sample can be obtained through detection containing certain in conjunction with Fig. 5 and Fig. 7 analysis
Bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of the 1,3- of amount.
Claims (10)
1. one kind 1, the synthetic method of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 3-, it is characterised in that: the synthetic method is with 2,5-
Dimethyl phenyl acetic acid is raw material, obtains intermediate 2,5- dimethyl phenyl acetic acid ethyl ester, 2, the 5- bis- through acylation, ethyl esterified reaction
Methylphenyl acetic acid ethyl ester again existing for the basic catalyst under the conditions of, occur condensation, hydrolysis, decarboxylic reaction synthesis it is described 1,3-
Bis- (2,5- 3,5-dimethylphenyl) propyl- 2- ketone；
Its synthetic route is as follows:
。
2. the synthetic method of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- according to claim 1, it is characterised in that:
The synthetic method sequentially carries out in accordance with the following steps:
(1) preparation of 2,5- dimethyl phenyl acetic acid ethyl ester
By raw material 2 at 25 DEG C, 5- dimethyl phenyl acetic acid is added in solvent dry toluene, and after being warming up to 70 DEG C, SOCl is slowly added dropwise2,
It enables temperature be warming up to 90 DEG C, reacts 1.5 ~ 2 h after being added dropwise at 110 DEG C, generate 2,5- dimethyl benzene chloroacetic chloride, steamed at 80 DEG C
Except excessive SOCl2；Dehydrated alcohol is slowly added dropwise after being down to 25 DEG C, then the reaction was continued 0.5h is separately added into 50mL in three times
Water separates two-phase, removes origin impurity, and organic phase revolving obtains intermediate 2,5- dimethyl phenyl acetic acid ethyl ester, content is greater than
95.0%；
(2) preparation of intermediate A
N2Under environment, lye is added in solvent dry toluene, is made reaction system B, then by 2,5- dimethyl obtained by step (1)
Ethyl phenylacetate is added dropwise in reaction system B, maintain temperature 45 DEG C hereinafter, being added dropwise after, be heated to 90 DEG C of reaction 4h；Instead
Reaction solution should be cooled down after the completion, temperature control is saturated metabisulfite solution hereinafter, being added dropwise at 10 DEG C, and it is molten that dilute hydrochloric acid is added dropwise again later
Liquid steams solvent toluene at 110 DEG C, obtains intermediate A；
(3) preparation of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3-
20% dilute hydrochloric acid is added into intermediate A obtained by step (2), 8h is reacted at 108 DEG C, after reaction, uses alkane solvents
In 65 DEG C of progress extraction heats, after gained organic phase is down to 25 DEG C, 1h is stirred under the conditions of ice-water bath, solid is precipitated, is filtered, is done
Dry, obtained solid is recrystallized through alcohols solvent up to bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1, the 3-.
3. the synthetic method of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- according to claim 2, it is characterised in that:
The lye is sodium hydride solution, sodium methoxide solution, methanol potassium solution or potassium tert-butoxide solution.
4. the synthetic method of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- according to claim 2, it is characterised in that:
The alkane solvents are normal heptane, hexamethylene or n-hexane, or wherein 2 kinds of mixtures.
5. the synthetic method of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- according to claim 2, it is characterised in that:
The alcohols solvent is methanol or ethyl alcohol.
6. the synthetic method of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- according to claim 2, it is characterised in that:
In the preparation of step (2) contracting intermediate A, the equivalent proportion of lye amount used and 2,5- dimethyl phenyl acetic acid ethyl ester is 3~20:1.
7. the synthetic method of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- according to claim 2, it is characterised in that:
In the preparation of step (2) intermediate A, the dosage of dry toluene used and the equivalent proportion of 2,5- dimethyl phenyl acetic acid ethyl ester dosage are
5~10:1。
8. the synthetic method of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- according to claim 2, it is characterised in that:
In the preparation of step (2) intermediate A, the mass fraction of dilute hydrochloric acid used is 15% ~ 25%.
9. the synthetic method of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- according to claim 2, it is characterised in that:
The step (3) 1, in the preparation of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 3-, 20% dilute hydrochloric acid amount used and intermediate A dosage
Equivalent proportion be 1.1 ~ 1.5:1.
10. the synthetic method of bis- (2,5- 3,5-dimethylphenyl) the propyl- 2- ketone of 1,3- described in any one of claim 1-9 is made
A kind of application of 1,3- bis- (2,5- 3,5-dimethylphenyl) propyl- 2- ketone, it is characterised in that: 1, the 3- is bis- (2,5- 3,5-dimethylphenyl)
Propyl- 2- ketone is used as standard items, applied to the synthesis for detecting and monitoring pesticide spiral shell worm ethyl ester intermediate.
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| CN1732145A (en) * | 2002-12-10 | 2006-02-08 | 冬姆佩股份公司 | Chiral arylketones in the treatment of neutrophil-dependent inflammatory diseases |
| DE102008020361A1 (en) * | 2007-04-24 | 2008-12-04 | Daicel Chemical Industries, Ltd. | Preparing 2,5-dimethylphenylthioacetomorpholide comprises reacting 2,5-dimethylacetophenone with sulfur and morpholine in a liquid reaction system |
| CN102070629A (en) * | 2010-12-28 | 2011-05-25 | 上海师范大学 | Novel nicotine and clothianidin analogue pesticide and preparation method thereof |
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