CN106905357B - A kind of preparation method of Silthiopham key intermediate - Google Patents
A kind of preparation method of Silthiopham key intermediate Download PDFInfo
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- CN106905357B CN106905357B CN201710136642.8A CN201710136642A CN106905357B CN 106905357 B CN106905357 B CN 106905357B CN 201710136642 A CN201710136642 A CN 201710136642A CN 106905357 B CN106905357 B CN 106905357B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
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Abstract
The invention discloses a kind of preparation methods of Silthiopham key intermediate, including, trimethyl silicon substrate propiolic acid, thionyl chloride and allyl amine are taken, molar ratio is 1:1.5:1~1:2:1；Trimethyl silicon substrate propiolic acid is dissolved in solvent, and catalyst is added dropwise；Under ice bath, thionyl chloride is added dropwise；At 0~25 DEG C, stirring；Allyl amine is added dropwise in distillation, gained residue under ice bath, reacts；Extraction, it is dry, obtain trimethyl silicon substrate propioloyl allyl amine；Wherein, catalyst is 1:100~5:100 with trimethyl silicon substrate propiolic acid molar ratio；Wherein, solvent is one of toluene, methylene chloride, diethoxymethane or a variety of；Wherein, catalyst is one of n,N-Dimethylformamide, hexamethylphosphoramide or a variety of.The method of the present invention, raw material and reaction process are simple and environmentally-friendly, safe.Reaction time is short, and target product yield is high, reduces production cost, and Atom economy is good, meets the theory of Green Chemistry, has very big competitive advantage and industrial production utility value.
Description
Technical field
The invention belongs to chemical agent technical fields, and in particular to a kind of preparation method of Silthiopham key intermediate.
Background technique
Take-all is one of serious plant disease of wheat, is distributed in worldwide.Mainly occur in China
In northwest, North China spring wheat area, wherein irrigation region is aggrieved heavier.Shaanxi of northern Winter Wheat Area, Shandong, Shanxi, Liaoning, Gansu,
There is generation on the ground such as Ningxia, Inner Mongol, are occurred with Shaanxi, Shandong, Gansu most heavy.Gaeumannomyces graminis is soil invader, small
Wheat entire breeding time can infect, and germ is invaded in root tissue by the internode under the seminal root, germinal layer and rootstock of seedling, can also
To enter in host tissue by plumule and epiblast, root is caused to be fallen ill, later period wheat dead ears are caused when serious.Due to this
Disease can survive for many years in the soil, in addition at present and without disease-resistant variety and good pesticide control, therefore, take-all
Prevention and treatment become a global problem.Although crop rotation has certain effect, but due to being limited by many conditions, difficult
To implement in production.The new chemical medicament of exploitation and screening prevention and treatment full rot have prominent application and market prospects.
Patent US5486621 is made in 4,5- dimethyl -2- (amino) thiophene -3- Ethyl formate with 2- butanone and reaction of Salmon-Saxl
Mesosome, then obtain 4,5- dimethyl -2- (bromine) thiophene -3- formic acid through bromo, hydrolysis, then with butyl lithium and trimethylsilyl chloride silicon substrate
It reacts and obtains final product Silthiopham through amidation after obtaining 4,5- dimethyl -2- (trimethyl silicon substrate) thiophene -3- formic acid.
Synthetic route is as follows:
Since the technique has isomers generation during the reaction, the purity and separation of product are adversely affected, work
Skill yield also only has 2% or so, and technique application value is lower.
Also there is article to be disclosed directly below technical solution, made using 3- methoxy-methyl acrylate and 3- sulfydryl -2- butanone in alkali
Cyclization is carried out with lower generation Michael-Aldol reaction, then sloughs hydroxyl and methoxyl group obtains thiophene compound, then in LiOH
De-ester reaction is first carried out under effect and obtains carboxylic acid lithium salt, is then continued the generation Silanization reaction under the deprotonation effect of LDA and is obtained
To 2- trimethyl silicone hydride compounds, finally react to obtain final Silthiopham product with allyl amine after acyl chlorides.
Synthetic route is as follows:
Its synthesis technology is still relatively complicated, and there are many byproduct in production process, and there are thionyl chlorides to environment
Pollution is very serious, and the side reactions such as desiliconization alkanisation are difficult to overcome the disadvantages of equal.
There are also disclosed synthetic route is as follows:
Its yield improves, but total recovery is also no more than 10%, is still not suitable for large-scale industrial production.
Patent CN201510305488.3, using trimethyl silicane ethyl-acetylene as raw material, butyl lithium effect under with carbonochloridic acid
Methyl esters reacts obtained trimethyl silicon substrate for Methyl propiolate, and olefinic recycle propyl amine reacts to obtain trimethyl silicon substrate generation
Propioloyl allyl amine finally reacts to obtain final product Silthiopham with 3- sulfydryl -2- butanone.
Synthetic route is as follows:
Although this method shortens reaction route, improve overall yield of reaction, but main problem is key intermediate front three
The synthesis condition of base silicon substrate propioloyl allyl amine is more harsh, while higher cost.
About the synthesis of this intermediate, there are mainly three types of methods at present, respectively with trimethyl silicane ethyl-acetylene, acetylene and two
(trimethyl silicon substrate) acetylene is that raw material is reacted with isocyanic acid propylene alcohol ester, and butyl lithium or aluminium chloride is needed to participate in reaction, at
This is very high, it is difficult to meet the requirement of large-scale production.
Respectively with trimethyl silicane ethyl-acetylene (WO 1999-US12502), two (trimethyl silicon substrate) acetylene (WO 1999-
US12502 it) is reacted for raw material with isocyanic acid propylene alcohol ester, cost of material used in both the above method is all very high, and fourth
Base lithium or methanesulfonic acid all have larger risk when carrying out operate in large scale, it is difficult to meet the requirement of large-scale production.
Summary of the invention
The purpose of this section is to summarize some aspects of the embodiment of the present invention and briefly introduce some preferable implementations
Example.It may do a little simplified or be omitted to avoid our department is made in this section and the description of the application and the title of the invention
Point, the purpose of abstract of description and denomination of invention it is fuzzy, and this simplification or omit and cannot be used for limiting the scope of the invention.
In view of the technological gap of above-mentioned and/or existing Silthiopham key intermediate preparation, the present invention is proposed.
Therefore, the one of purpose of the present invention is to solve deficiency in the prior art, and it is crucial to provide a kind of Silthiopham
The preparation method of intermediate.
In order to solve the above technical problems, the present invention provides the following technical scheme that include take trimethyl silicon substrate propiolic acid,
Thionyl chloride and allyl amine, molar ratio are 1:1.5:1~1:2:1；Trimethyl silicon substrate propiolic acid is dissolved in solvent, and is added dropwise
Catalyst；Under ice bath, thionyl chloride is added dropwise；At 0~25 DEG C, stirring；Alkene is added dropwise under ice bath in distillation, gained residue
Propyl amine, reaction；Extraction, it is dry, obtain trimethyl silicon substrate propioloyl allyl amine；Wherein, catalyst is the same as trimethyl silicon substrate third
Acetylenic acid molar ratio is 1:100~5:100；Wherein, solvent is one of toluene, methylene chloride, diethoxymethane or a variety of；
Wherein, catalyst is one of n,N-Dimethylformamide, hexamethylphosphoramide or a variety of.
A kind of preferred embodiment as Silthiopham key intermediate preparation method of the present invention, in which: the front three
Base silicon substrate propiolic acid, thionyl chloride and allyl amine, molar ratio are specially 1:2:1.
A kind of preferred embodiment as Silthiopham key intermediate preparation method of the present invention, in which: the catalysis
Agent is the same as trimethyl silicon substrate propiolic acid molar ratio, specially 1:100.
A kind of preferred embodiment as Silthiopham key intermediate preparation method of the present invention, in which: the catalysis
Agent is N,N-dimethylformamide.
A kind of preferred embodiment as Silthiopham key intermediate preparation method of the present invention, in which: the solvent
For toluene.
A kind of preferred embodiment as Silthiopham key intermediate preparation method of the present invention, in which: the dropwise addition
Allyl amine, time for adding are 50~70min.
A kind of preferred embodiment as Silthiopham key intermediate preparation method of the present invention, in which: the stirring,
Its time is 90~150min.
A kind of preferred embodiment as Silthiopham key intermediate preparation method of the present invention, in which: the reaction,
It is to be stirred to react 100~130min.
A kind of preferred embodiment as Silthiopham key intermediate preparation method of the present invention, in which: the front three
Base silicon substrate propiolic acid, to aoxidize gained by trimethyl silicon substrate propilolic alcohol.
A kind of preferred embodiment as Silthiopham key intermediate preparation method of the present invention, in which: the front three
Base silicon substrate propilolic alcohol, to be made by propilolic alcohol by grignard reaction.
Beneficial effects of the present invention:
Preparation method provided by the invention, the yield that target product is made are stablized 90% or so, reach as high as 95%, excellent
In other methods most 50%.
Total reaction time required for target product is made in preparation method provided by the invention, is guaranteeing 80% or more yield
Under the premise of, most short, specially 240min, better than with yield magnitude average reaction time 7.5min, maximum improves 110min.
Preparation method provided by the invention, raw material and reaction process are simple and environmentally-friendly, safe.Reaction time is short, target product
Yield is high, reduces production cost, and Atom economy is good, meets the theory of Green Chemistry, has very big competitive advantage and work
Industry Commercial cultivation value.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill of field, without any creative labor, it can also be obtained according to these attached drawings other
Attached drawing.Wherein:
Fig. 1 is the MS spectrogram of Silthiopham key intermediate, shows it with correct molecular mass；
Fig. 2 is the 1H NMR spectra of Silthiopham key intermediate, shows it with correct molecular structure.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, right combined with specific embodiments below
A specific embodiment of the invention is described in detail.
In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention, but the present invention can be with
Implemented using other than the one described here other way, those skilled in the art can be without prejudice to intension of the present invention
In the case of do similar popularization, therefore the present invention is not limited by the specific embodiments disclosed below.
Secondly, " one embodiment " or " embodiment " referred to herein, which refers to, may be included at least one realization side of the invention
A particular feature, structure, or characteristic in formula." in one embodiment " that different places occur in the present specification not refers both to
The same embodiment, nor the individual or selective embodiment mutually exclusive with other embodiments.
Embodiment 1
Take trimethyl silicon substrate propiolic acid, thionyl chloride and allyl amine, molar ratio 1:2:1；
Trimethyl silicon substrate propiolic acid is dissolved in toluene solvant, and n,N-Dimethylformamide catalyst is added dropwise, wherein catalysis
Agent is 1:100 with trimethyl silicon substrate propiolic acid molar ratio；
Under ice bath, thionyl chloride, time for adding 60min is added dropwise；
At 0~25 DEG C, 110min is stirred；Distillation, gained residue are added dropwise allyl amine under ice bath, are stirred to react
110min；
Extraction, it is dry, obtain trimethyl silicon substrate propioloyl allyl amine.
Measuring trimethyl silicon substrate propioloyl allyl amine yield is 95%, and the total production time is 280min.
Embodiment 2
Take trimethyl silicon substrate propiolic acid, thionyl chloride and allyl amine, molar ratio 1:1.5:1；
Trimethyl silicon substrate propiolic acid is dissolved in dichloromethane solvent, and hexamethylphosphoramide catalyst is added dropwise, wherein is urged
Agent is 2:100 with trimethyl silicon substrate propiolic acid molar ratio；
Under ice bath, thionyl chloride, time for adding 50min is added dropwise；
At 0~25 DEG C, 90min is stirred；Distillation, gained residue are added dropwise allyl amine under ice bath, are stirred to react
100min；
Extraction, it is dry, obtain trimethyl silicon substrate propioloyl allyl amine.
Measuring trimethyl silicon substrate propioloyl allyl amine yield is 90%, and the total production time is 240min.
Embodiment 3
Take trimethyl silicon substrate propiolic acid, thionyl chloride and allyl amine, molar ratio 1:2:1；
Trimethyl silicon substrate propiolic acid is dissolved in diethoxymethane solvent, and n,N-Dimethylformamide, hexamethyl is added dropwise
Phosphoric triamide mixed catalyst, wherein catalyst is 5:100 with trimethyl silicon substrate propiolic acid molar ratio；
Under ice bath, thionyl chloride, time for adding 70min is added dropwise；
At 0~25 DEG C, 150min is stirred；Distillation, gained residue are added dropwise allyl amine under ice bath, are stirred to react
130min；
Extraction, it is dry, obtain trimethyl silicon substrate propioloyl allyl amine.
Measuring trimethyl silicon substrate propioloyl allyl amine yield is 86%, and the total production time is 350min.
Embodiment 4
Take trimethyl silicon substrate propiolic acid, thionyl chloride and allyl amine, molar ratio 1:2:1；
Trimethyl silicon substrate propiolic acid is dissolved in toluene solvant, and n,N-Dimethylformamide catalyst is added dropwise, wherein catalysis
Agent is 10:100 with trimethyl silicon substrate propiolic acid molar ratio；
Under ice bath, thionyl chloride, time for adding 60min is added dropwise；
At 0~25 DEG C, 110min is stirred；Distillation, gained residue are added dropwise allyl amine under ice bath, are stirred to react
110min；
Extraction, it is dry, obtain trimethyl silicon substrate propioloyl allyl amine.
Measuring trimethyl silicon substrate propioloyl allyl amine yield is 73%, and the total production time is 280min.
Embodiment 5
Take trimethyl silicon substrate propiolic acid, thionyl chloride and allyl amine, molar ratio 1:2:1；
Trimethyl silicon substrate propiolic acid is dissolved in toluene solvant, and n,N-Dimethylformamide catalyst is added dropwise, wherein catalysis
Agent is 1:100 with trimethyl silicon substrate propiolic acid molar ratio；
Under ice bath, thionyl chloride, time for adding 30min is added dropwise；
At 0~25 DEG C, 80min is stirred；Distillation, gained residue are added dropwise allyl amine under ice bath, are stirred to react
80min；
Extraction, it is dry, obtain trimethyl silicon substrate propioloyl allyl amine.
Measuring trimethyl silicon substrate propioloyl allyl amine yield is 55%, and the total production time is 190min.
Embodiment 6
Take trimethyl silicon substrate propiolic acid, thionyl chloride and allyl amine, molar ratio 1:2:1；
Trimethyl silicon substrate propiolic acid is dissolved in toluene solvant, and n,N-Dimethylformamide catalyst is added dropwise, wherein catalysis
Agent is 1:100 with trimethyl silicon substrate propiolic acid molar ratio；
Thionyl chloride, time for adding 100min is added dropwise；
At 0~25 DEG C, 160min is stirred；Distillation, gained residue are added dropwise allyl amine under ice bath, are stirred to react
140min；
Extraction, it is dry, obtain trimethyl silicon substrate propioloyl allyl amine.
Measuring trimethyl silicon substrate propioloyl allyl amine yield is 45%, and the total production time is 400min.
Embodiment 7
Take trimethyl silicon substrate propiolic acid, thionyl chloride and allyl amine, molar ratio 1:4:2；
Trimethyl silicon substrate propiolic acid is dissolved in toluene solvant, and n,N-Dimethylformamide catalyst is added dropwise, wherein catalysis
Agent is 1:100 with trimethyl silicon substrate propiolic acid molar ratio；
Under ice bath, thionyl chloride, time for adding 60min is added dropwise；
At 0~25 DEG C, 110min is stirred；Distillation, gained residue are added dropwise allyl amine under ice bath, are stirred to react
110min；
Extraction, it is dry, obtain trimethyl silicon substrate propioloyl allyl amine.
Measuring trimethyl silicon substrate propioloyl allyl amine yield is 82%, and the total production time is 280min.
Embodiment 8
Take trimethyl silicon substrate propiolic acid, thionyl chloride and allyl amine, molar ratio 1:0.8:0.8；
Trimethyl silicon substrate propiolic acid is dissolved in toluene solvant, and n,N-Dimethylformamide catalyst is added dropwise, wherein catalysis
Agent is 1:100 with trimethyl silicon substrate propiolic acid molar ratio；
Under ice bath, thionyl chloride, time for adding 60min is added dropwise；
At 0~25 DEG C, 110min is stirred；Distillation, gained residue are added dropwise allyl amine under ice bath, are stirred to react
110min；
Extraction, it is dry, obtain trimethyl silicon substrate propioloyl allyl amine.
Measuring trimethyl silicon substrate propioloyl allyl amine yield is 65%, and the total production time is 280min.
As seen from the above-described embodiment, the preparation method of key intermediate provided by the present invention, in target product yield
In terms of total reaction time, there is splendid effect.
The present invention has carried out preferably, to take into account target product yield the step of raw material, catalyst, each technique
And total reaction time.
Firstly, the ratio that the present invention has carried out preferably limiting three kinds of raw materials to material molar ratio is 1:1.5:1~1:2:1.
Compare to obtain by comparing embodiment 1,7,8, under the conditions of the same reaction time, preferred raw material molar ratio range of the present invention,
Acquired product yield is up to 95%, due to the 82% of other material rates and 65%.
Through inventor the study found that carboxyl obtains not if raw material can excessively make thionyl chloride that can not react completely with carboxyl
To complete activation, eventually leads to carboxyl and be unable to fully react with amino, yield is caused to reduce.Because the mechanism of DMF catalysis is first
It is reacted with thionyl chloride and generates intermediate, then react to obtain acyl chlorides with carboxyl again.If material molar ratio reduces, can make
DMF is unable to fully activation thionyl chloride, so that the reaction time extends, yield is reduced.
Secondly, the preferred n,N-Dimethylformamide of the present invention, hexamethylphosphoramide kind is one or more as catalysis
Agent, and preferably it with trimethyl silicon substrate propine molar ratio is 1:100~5:100, while match selection toluene, methylene chloride, two
One of ethoxy methane is a variety of as solvent.
Compare to obtain by embodiment 1,2,3,4, it is currently preferred to urge under preferred material rate, reaction condition
Agent, catalyst molar ratio and related solvents have superior effect in reaction time, target product yield.
Through inventor the study found that because DMF can not be removed by distillation, if catalytic amount is excessively unfavorable for removing, shadow
Ring subsequent reactions progress and product purity.Because the mechanism of DMF catalysis is first to react to generate intermediate with thionyl chloride, then again
It reacts to obtain acyl chlorides with carboxyl.If catalyst molar ratio reduces, DMF can be made to be unable to fully activation thionyl chloride, so that instead
Extend between seasonable, yield reduces.On this basis, the preferred n,N-Dimethylformamide of the present invention is catalyst, if this is because
If using hexamethylphosphoramide as catalyst, because having more methyl in its molecule, steric hindrance is larger, and it is anti-to be unfavorable for activation
The progress answered.
Finally, the present invention control of time of each processing step has been carried out preferably, be including preferred mixing time
90~150min, preferred reaction time are 100~130min, and the time of preferably dropwise addition thionyl chloride is 50~70min, and preferably
Ice bath.
Compared by embodiment 1,5,6 and obtained, the reaction time is below or above preferred scope of the present invention, cannot obtain this
Inventive method prepares the relatively high yield pulp1 of target product.
This is because acyl chlorides is that the unstable substance of one kind can be with sky if mixing time is too long in terms of mixing time
The substances such as the water in gas slowly react, so that other by-products are generated, so that yield reduces.In terms of the reaction time, catalysis
Agent activates thionyl chloride and acid and requires the time with reacting for reactive intermediate, wherein activation step is rate determining step, if when stirring
Between it is too short, thionyl chloride is not sufficiently activated, then will lead to ultimate yield reduction.When reaction time is too long, product itself can be sent out
Raw side reaction, causes yield to reduce.From the point of view of the necessity of ice bath, the excessively high generation that will lead to other side reactions of temperature, temperature
Reactivity reduces when too low, greatly can extend the reaction time.In terms of the time that thionyl chloride is added dropwise, because the reaction is heat release
Reaction, the too fast meeting of drop rate lead to the generation of other side reactions so that reaction temperature raising.
It should be noted that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to preferable
Embodiment describes the invention in detail, those skilled in the art should understand that, it can be to technology of the invention
Scheme is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered in this hair
In bright scope of the claims.
Claims (3)
1. a kind of preparation method of Silthiopham key intermediate, it is characterised in that: take trimethyl silicon substrate propiolic acid, thionyl chloride
And allyl amine, molar ratio 1:2:1；Trimethyl silicon substrate propiolic acid is dissolved in toluene solvant, and N is added dropwise, N- dimethyl methyl
Amide catalysts, wherein catalyst is 1:100 with trimethyl silicon substrate propiolic acid molar ratio；Under ice bath, thionyl chloride is added dropwise,
Time for adding is 60min；At 0~25 DEG C, 110min is stirred；Distillation, gained residue are added dropwise allyl amine under ice bath, stir
Mix reaction 110min；Extraction, it is dry, obtain trimethyl silicon substrate propioloyl allyl amine；Measure trimethyl silicon substrate propioloyl allyl
Base amine yield is 95%, and the total production time is 280min.
2. the preparation method of Silthiopham key intermediate as described in claim 1, it is characterised in that: the trimethyl silicon substrate
Propiolic acid aoxidizes gained by trimethyl silicon substrate propilolic alcohol.
3. the preparation method of Silthiopham key intermediate as claimed in claim 2, it is characterised in that: the trimethyl silicon substrate
Propilolic alcohol is made by propilolic alcohol by grignard reaction.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6140511A (en) * | 1998-06-05 | 2000-10-31 | Monsanto Company | Fungicidal compositions and methods of making thereof |
| CN105111229A (en) * | 2015-06-08 | 2015-12-02 | 杭州师范大学 | Synthetic method for silthiopham |
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2017
- 2017-03-09 CN CN201710136642.8A patent/CN106905357B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6140511A (en) * | 1998-06-05 | 2000-10-31 | Monsanto Company | Fungicidal compositions and methods of making thereof |
| CN105111229A (en) * | 2015-06-08 | 2015-12-02 | 杭州师范大学 | Synthetic method for silthiopham |
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