CN109912479A - A kind of environment-friendly preparation method of Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds - Google Patents
A kind of environment-friendly preparation method of Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds Download PDFInfo
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- CN109912479A CN109912479A CN201910228784.6A CN201910228784A CN109912479A CN 109912479 A CN109912479 A CN 109912479A CN 201910228784 A CN201910228784 A CN 201910228784A CN 109912479 A CN109912479 A CN 109912479A
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Abstract
The invention discloses a kind of environment-friendly preparation methods of Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds.Under ultrasonic wave effect, lactic acid is catalyzed thio propiolate compound, selenium cyanate and water and carries out three component addition reactions, generates Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds；After reaction, water dilution is added into system, high-purity Z-3- selenium cyanic acid ester group thioacrylic acid ester products can be precipitated；This method good product selectivity, high income, separation process is simple, catalyst low cost, environmentally friendly, is conducive to industrialized production and application.
Description
Technical field
The present invention relates to a kind of environment-friendly preparation methods of Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds, in particular to
It is a kind of to be catalyzed thio propiolate compound, selenium cyanate and one step addition reaction of water synthesis Z-3- using ultrasonic wave auxiliary lactic acid
The method of selenium cyanic acid ester group thioacrylic acid ester compounds, belongs to Manufacturing Technologies of Organic Intermediates field.
Background technique
Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds not only have very important physiological activity, the selenium contained
Cyanic acid functional group, thio ester group, alkenyl group is all important can modify functional group, is a kind of very important drug and organic conjunction
At midbody compound.There is eutectic solvent to be catalyzed the three of thio propiolate compound, Potassium Selenocyanate and water in the prior art
Component reacts to obtain Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds, such as (ACS Sustainable
Chem.Eng.2019,7,2169-2175), but the reaction limits its practical application there is also following deficiency:
1) eutectic solvent needs to prepare, commercial-free product.
2) yield of Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds is 77~94%, and there are E formula isomeries in reaction
The decomposition product propiolic acid and unreacted thio propiolate raw materials of compound of body and thio propiolate compound, purity
It is not high.
3) separation of product needs to extract using volatile organic solvent, and the purification of product is needed through silica gel column chromatography point
From separation process is not only complicated, at high cost, can also generation environment pollution.
The three components reaction synthesis of existing presence of acidic ionic liquid catalyst thio propiolate compound, Potassium Selenocyanate and water
The method concrete condition of Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds is as follows:
Summary of the invention
The existing technology of synthesis and separation for Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds in the prior art
Problem is catalyzed thio propiolate compound, selenium cyanate using cheap lactic acid the purpose of the invention is to provide a kind of
With the method for water one pot reaction synthesis Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds, this method good product selectivity is received
Rate is high, and separation process is simple, low cost, environmental-friendly, is conducive to industrialized production and application.
In order to achieve the above technical purposes, the present invention provides a kind of Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds
Environment-friendly preparation method, this method is under ultrasonic wave effect, and lactic acid is catalyzed thio propiolate compound, selenium cyanate and water
Addition reaction is carried out, Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds are obtained.
Preferred scheme, thio propiolate compound have 1 structure of formula；
The Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds have 2 structure of formula:
Wherein,
R is selected from alkyl, aryl or aryl alkyl.
Preferred scheme, R can be alkyl, such as C1~C10Alkyl, such as straight chained alkyl, or branched alkane
Base, or be C3~C7Naphthenic base, specific such as methyl, ethyl, isobutyl group, cyclohexyl.R can be aryl, specifically aryl
For the substituted-phenyl containing common substituent group on phenyl or phenyl ring, substituted-phenyl is on phenyl ring comprising common substituent group, such as C1
~C5Short-chain alkyl, C1~C5Alkoxy, halogenic substituent (fluorine, chlorine, bromine etc.), trifluoromethyl, nitro, cyano, amino,
C2~C5Ester group or hydroxyl.The position of substituent group is unlimited, and substituent group quantity can be one or more, generally takes containing one
Dai Ji.R can be aryl alkyl, and the group of aryl substituent, such as benzyl, phenylethyl are contained such as on alkyl.
Preferred scheme, the selenium cyanate are Potassium Selenocyanate.Theoretically easily ionizable goes out the selenium cyanate of selenium cyanate radical all
It adapts to, preferably common Potassium Selenocyanate on the market.
Preferred scheme, thio propiolate, selenium cyanate, water and lactic acid molar ratio be 1:1~2:1~2:2~5.
Most preferred molar ratio is 1:1.2:1:3.
Preferred scheme, the condition of the addition reaction are as follows: at room temperature, ultrasonic power is 25~45 W, supersonic frequency
For the KHz of 28 KHz~60, the reaction time is 15~40min.Ultrasonic power still more preferably is 30W.Still more preferably
Supersonic frequency be 44KHz.Lactic acid, which is carried out, under preferred ultrasound condition auxiliary is catalyzed thio propiolate compound, selenium cyanic acid
The addition reaction of salt and water can not only shorten the reaction time, moreover it is possible to promote conversion ratio.
Preferred scheme after the completion of addition reaction, water dilution is added into reaction system, Z-3- selenium cyanic acid ester group sulphur is precipitated
For acrylate product, the separation of product and lactic acid aqueous solution is realized by filtering or liquid separation, obtains Z-3- selenium cyanic acid ester group sulphur
For acrylate compounds product.The present invention uses water diluting reaction mix products, and high-purity Z-3- selenium cyanate can be precipitated
Base thioacrylic acid ester compounds do not need to extract using traditional organic solvent, and silica gel column chromatography separation method avoids completely
The use of volatile organic solvent.
Preferred scheme, water additional amount are 5 times or more of lactic acid quality.It is preferred that water more than 5 times of quality, can guarantee Z-3-
Selenium cyanic acid ester group thioacrylic acid ester compounds are smoothly precipitated.
The lactic acid that the present invention uses is in addition reaction while being used as catalyst and reaction medium.
The present invention carries out addition reaction by thio propiolate compound, Potassium Selenocyanate and water and synthesizes Z-3- selenium cyanic acid ester group
The route of thioacrylic acid ester compounds is as follows:
Shown in specific reaction principle following reaction formula: lactic acid activates thio propiolate compound first and obtains in connection alkene
Mesosome IM2, selenium cyanate radical nucleophilic attack, which joins, forms intermolecular hydrogen bonding with lactic acid after the beta carbon of alkene intermediate compound I M2, obtains
Mesosome IM3；The proton that intermediate compound I M3 is generated from the capture hydrone ionization of the opposite direction of hydrogen bond, obtains trans-addition product Z-3-
Selenium cyanic acid ester group thioacrylic acid ester compounds.
Compared with the prior art, technical solution of the present invention bring advantageous effects:
1) present invention is easily recycled using lactic acid as reaction medium and catalyst, safe and non-toxic, environmentally friendly,
Source is easy to get, cheap.
2) present invention reacts at room temperature, mild condition.
3) present invention is wide to the selectivity of thio propiolate compound, and functional group compatibility is good, is easy to various groups and repairs
Decorations.
4) present invention promotes reaction using ultrasonic wave, and while shortening the reaction time, feed stock conversion is quantitative, product choosing
Selecting property 100% does not have the generation of E formula isomers in reaction.
5) present invention only needs the water that 5 times of lactic acid amounts are added in the reactive mixture, and product layering can be made to be precipitated, produced
It is complicated to avoid the Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds separating-purifying process synthesized in the prior art for object sterling
Problem.
6) lactic acid of the invention can be recycled and is recycled for multiple times, and be recycled 5 times, and efficiency reduces by 2%, kept higher and urged
Change activity, has a clear superiority compared to eutectic solvent.
7) Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds of the invention have the selenium cyanic acid official of important physiological activity
Can roll into a ball and alkenyl group, thio ester group can be modified etc., important organic intermediate is provided for drug and organic synthesis.
Specific embodiment
Following specific embodiments are intended to further illustrate the content of present invention, rather than limit the protection of the claims in the present invention
Range.
Comparative examples:
Following control experiment group 1~14 is reacted by following reaction equation:
Concrete operation step are as follows: in 20mL reaction tube, sequentially add thio Methyl propiolate (1 equivalent, 10mmol), selenium
Potassium cyanate, water and biomass acid, gained mixed liquor supersonic reaction device in react 30min.After reaction, it is added
The water of 13.5mL, can be obtained target product, and gas phase calculates yield.
Experimental group 1~6 has investigated various reaction mediums to thio Methyl propiolate, Potassium Selenocyanate, three component of water in upper table
The influence of addition reaction can be mentioned obviously from experimental data as can be seen that reacting other opposite reaction mediums in lactic acid medium
The efficiency of high three components addition reaction, and reacting has single reaction addition selective.
Experimental group 1 and 7~8 has been investigated lactic acid dosage and has been added to thio Methyl propiolate, Potassium Selenocyanate, three component of water in upper table
At the influence of reaction, it is shown experimentally that the optimum molar dosage of lactic acid is 3 equivalents；When lactic acid dosage is higher than 3 equivalent, reaction
Efficiency does not improve；When lactic acid dosage is lower than 3 equivalent, the yield of target product is reduced.
Experimental group 1 and 9~12 has investigated ultrasonic wave added and has been total to addition to thio Methyl propiolate, Potassium Selenocyanate, water in upper table
The influence of reaction, is shown experimentally that and is reacted by ultrasonic wave added, can greatly shorten the reaction time, improves reaction efficiency, special
It is not ultrasonic power when to be 30W/ frequency be 44KHz, addition reaction effect is best altogether, can obtain within a short period of time optimal
Target product yield.
Experimental group 1 and 13~14 has investigated reaction raw materials KSeCN dosage to thio Methyl propiolate, selenium cyanic acid in upper table
Potassium, three component addition reaction of water influence, be shown experimentally that KSeCN optimum molar dosage be 1.2 equivalents；KSeCN dosage
When too low, the yield of target product is reduced, and when KSeCN dosage is excessively high, the yield of target product does not significantly improve.
Circulation experiment result
In 20mL reaction tube, sequentially add thio Methyl propiolate (10mmol), Potassium Selenocyanate (12mmol, 1.16g),
Water (10mmol, 0.18g), lactic acid (30mmol, 2.7g), gained mixed liquor react in the supersonic reaction device of 30W/44KHz
30 minutes.After reaction, 13.5ml water is added and lactic acid forms lactic acid aqueous solution, Z-3- selenium cyanic acid ester group thioacrylic acid ester
It insoluble in lactic acid aqueous solution, is precipitated, liquid separation, is dried in vacuo calculated weight.The water in lactic acid aqueous solution is removed under reduced pressure, is directly used in
Next circulation experiment, gained yield data are as follows.
| 1 | 2 | 3 | 4 | 5 |
| 94% | 94% | 93% | 92% | 92% |
Examples 1 to 3
It is reacted by following reaction equation following example 1~3:
Concrete operation step are as follows: in 20mL reaction tube, sequentially add propine thio-methyl ester (10mmol), Potassium Selenocyanate
(12mmol, 1.16g), water (10mmol, 0.18g), lactic acid (30mmol, 2.70g), gained mixed liquor is in the super of 30W/44KHz
It is reacted 30 minutes in phonoresponse device.After reaction, 13.5ml water is added and lactic acid forms lactic acid aqueous solution, Z-3- selenium cyanic acid
Ester group propylene thio-methyl ester does not dissolve in lactic acid aqueous solution, is precipitated, liquid separation, is dried in vacuo calculated weight.
Embodiment 1
Raw material:Target product:
S-(p-tolyl)(Z)-3-selenocyanatoprop-2-enethioate:
Yield: 95%
1H NMR(400MHz,CDCl3) δ 7.79 (d, J=8.0Hz, 1H), 7.36 (d, J=8.0Hz, 2H), 7.29 (d, J
=8.0Hz, 2H), 7.04 (d, J=8.0Hz, 1H), 2.41 (s, 3H)
13C NMR(100MHz,CDCl3)δ191.3,140.9,138.7,134.3,130.5,124.7,121.9,105.7,
21.4.
HRMS Calcd(EI)m/z for C11H9NOSSe:[M]+282.9570,found:282.9574.
Embodiment 2
Raw material:Target product:
S-phenyl(Z)-3-selenocyanatoprop-2-enethioate:
Yield: 94%
1H NMR(400MHz,CDCl3)δ7.53–7.52(m,2H),7.45–7.42(m,2H),7.38–7.37(m,1H),
7.20 (d, J=9.6Hz, 1H), 6.37 (d, J=9.6Hz, 1H)
13C NMR(100MHz,CDCl3)δ186.1,148.2,134.6,131.0,129.4,129.1,128.4,118.4.
Embodiment 3
Raw material:Target product:
S-benzyl(Z)-3-selenocyanatoprop-2-enethioate:
Yield: 94%
1H NMR(400MHz,CDCl3) δ 7.73 (d, J=8.4Hz, 1H), 7.35-7.29 (m, 5H), 6.95 (d, J=8.0
Hz,1H),4.28(s,3H).
13C NMR(100MHz,CDCl3)δ191.1,137.4,135.9,128.8,128.7,127.8,125.2,105.7,
33.6.
Claims (8)
1. a kind of environment-friendly preparation method of Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds, it is characterised in that: in ultrasonic wave
Under effect, lactic acid is catalyzed thio propiolate compound, selenium cyanate and water and carries out addition reaction, obtains Z-3- selenium cyanic acid ester group
Thioacrylic acid ester compounds.
2. a kind of environment-friendly preparation method of Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds according to claim 1,
It is characterized by:
The thio propiolate compound has 1 structure of formula；
The Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds have 2 structure of formula:
Wherein, R is selected from alkyl, aryl or aryl alkyl.
3. a kind of environment-friendly preparation method of Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds according to claim 2,
It is characterized by:
The alkyl is C1~C10Alkyl；
The aryl includes phenyl, or includes C1~C5Alkyl, halogen, nitro, cyano, amino, C2~C5Ester group, hydroxyl
Base, trifluoromethyl, C1~C5At least one of alkoxy substituent group phenyl；
The aryl alkyl is benzyl or phenylethyl.
4. a kind of environment-friendly preparation method of Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds according to claim 1,
It is characterized by: the selenium cyanate is Potassium Selenocyanate.
5. a kind of environment-friendly preparation method of Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds according to claim 1,
It is characterized by: thio propiolate compound, selenium cyanate, water and lactic acid molar ratio be 1:1~2:1~2:2~4.
6. the environmental protection of described in any item a kind of Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds according to claim 1~5
Preparation method, it is characterised in that: the condition of the addition reaction are as follows: at room temperature, ultrasonic power is 25~45W, supersonic frequency
For 28KHz~60KHz, the reaction time is 15~40min.
7. the environmental protection of described in any item a kind of Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds according to claim 1~5
Preparation method, it is characterised in that: after the completion of addition reaction, water dilution is added into reaction system, Z-3- selenium cyanic acid ester group is precipitated
Thioacrylic acid ester compounds obtain Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds by filtering or liquid separation.
8. a kind of environment-friendly preparation method of Z-3- selenium cyanic acid ester group thioacrylic acid ester compounds according to claim 7,
It is characterized by: water additional amount is 5 times or more of lactic acid quality.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438308A (en) * | 2018-12-14 | 2019-03-08 | 湖南科技学院 | One kind (Z)-β-selenium cyanic acid ester group propylene thioester compound and its synthetic method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109438308A (en) * | 2018-12-14 | 2019-03-08 | 湖南科技学院 | One kind (Z)-β-selenium cyanic acid ester group propylene thioester compound and its synthetic method |
Non-Patent Citations (3)
| Title |
|---|
| CHAO WU等: "Natural Deep Eutectic Solvent-Catalyzed Selenocyanation of Activated Alkynes via an Intermolecular H‑Bonding Activation Process", 《ACS SUSTAINABLE CHEM. ENG.》 * |
| CHAO WU等: "Ultrasound-promoted Brønsted acid ionic liquid-catalyzed hydrothiocyanation of activated alkynes under minimal solvent conditions", 《GREEN CHEMISTRY》 * |
| LING-HUI LU等: "Sustainable routes for quantitative green selenocyanation of activated alkynes", 《CHINESE CHEMICAL LETTERS》 * |
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