CN104387304B - One prepares the method for 1-phenyl-2 (2-thiosalicylic acidic group) ethene - Google Patents
One prepares the method for 1-phenyl-2 (2-thiosalicylic acidic group) ethene Download PDFInfo
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Abstract
The invention discloses the method that one prepares 1 phenyl 2 (2 thiosalicylic acidic group) ethene, including step: 1) by 2,2 ' dithio-salicylic acids and phenylacetylene add in reactor, under alkaline environment, add organic solvent, under 110～150 DEG C of oil baths, react 46～50 hours, and TLC tracking and measuring in whole reaction；2) naturally cool to room temperature, post-treated obtain described 1 phenyl 2 (2 thiosalicylic acidic group) the thick product of ethene；Direct, mild condition, simple under conditions of, with 2,2 ' dithio-salicylic acids directly react with phenylacetylene, 1 phenyl 2 (2 thiosalicylic acidic group) ethene is synthesized under there is no metallic catalyst effect, it is high that the thiazolinyl thioether of synthesis has productivity, separate the features such as productivity 97%, high orientation effect and stereoselectivity are good.
Description
Technical field
The present invention relates to technical field of organic chemistry, particularly relate to one and prepare 1-phenyl-2 (2-thiosalicylic acidic group) second
The method of alkene.
Background technology
There is the compound of sulfur-containing group as the important chemical raw material of a class, be found to have important in many fields
Using value.Especially thiazolinyl sulfide, they are the key intermediates synthesizing a lot of important compound, are also many kinds simultaneously
The presoma of functional molecular.Additionally, they also have biologically active widely, many has the natural products of notable biological activity
Thiazolinyl sulfur functional group is all contained with compound.Meanwhile, this compounds is also used widely in new material scientific domain,
Therefore thiazolinyl sulfide is constantly subjected to pay close attention to widely, becomes the focus of research in the present age.
The easiest, be the most also the method for the synthesis thiazolinyl thioether that most there is Atom economy be that hydrogen vulcanizes alkyne reaction,
Up to now, scientists has had been developed that the method for multiple hydrogen reaction of Salmon-Saxl, urges including alkali promotion law, free radical method and metal
Agent methods etc., have also synthesized a lot of sulfide containing thiazolinyl.But, these methods there is also a lot of weak point, such as synthesis
In be used mostly and there is the mercaptan of unpleasant taste as raw material, some uses noble metal or transition metal-catalyzed, some
The catalyst using complexity makes the post processing of reaction loaded down with trivial details, or uses and have virose free radical accelerant A IBN, and some is anti-
Answering condition harsher, problems above causes these reactions to be difficult to be applied in actual production, limits thiazolinyl sulphur
The large-scale production of compound.
Method with mercaptan synthesis thiazolinyl thioether:
((1-Phenyl-2-(2-Thiosalicyl) ethene), has another name called 1-phenyl-2 (2-thiosalicylic acidic group) ethene
1-phenyl-2 (2-carboxy phenyl) sulphur is for ethene ((1-Phenyl-2-(2-Carboxy phenyl) thio) ethane), or benzene second
Thiazolinyl (2-carboxy phenyl) thioether Styryl (2-Carboxy phenyl) thioether, or styryl (2-carboxy phenyl) sulfane
Styrul (2-Carboxy phenyl) sulfane, is a kind of thiazolinyl sulfide getting a good eye meaning and using value, because
It not only has the character of thiazolinyl sulfide, and it is also with a carboxyl that can continue to react, and can be into one
Step synthesis or group conversion provide convenient.But, due to a carboxylic group, and it is at ortho position, this directly affects
Arrive the synthesis to it so that it has had the biggest difference with other thiazolinyl sulfide, and up to the present, various methods all do not have
See the report to 1-phenyl-2 (2-thiosalicylic acidic group) ethylene synthase.
The structural formula of 1-phenyl-2 (2-thiosalicylic acidic group) ethene:
Summary of the invention
The technical problem to be solved be to provide a kind of in direct, mild condition, simple under conditions of, system
The method of standby 1-phenyl-2 (2-thiosalicylic acidic group) ethene.
For solving above-mentioned technical problem, the technical scheme is that
One prepares the method for 1-phenyl-2 (2-thiosalicylic acidic group) ethene, including step:
1) DSTA and phenylacetylene are added in reactor, under alkaline environment, add organic solvent,
Under 110～150 DEG C of oil baths, react 46～50 hours, and TLC tracking and measuring in whole reaction；
2) naturally cool to room temperature, post-treated obtain described 1-phenyl-2 (2-thiosalicylic acidic group) the thick product of ethene.
The synthetic method reaction equation of 1-phenyl-2 (2-thiosalicylic acidic group) ethene is:
As preferred technical scheme, described DSTA is 1.5 with the amount ratio of the material of described phenylacetylene
: 1.5～4.
As further preferred technical scheme, the amount of the material of described DSTA and described phenylacetylene
Ratio is 1.5: 2.
As preferred technical scheme, the alkaline solution that described alkaline environment uses be tetramethylammonium hydroxide aqueous solution,
The 4-n-butyl ammonium hydroxide aqueous solution, potassium tert-butoxide, sodium hydroxide solution, potassium hydroxide solution, TMAH methyl alcohol
One in solution or the TPAOH aqueous solution.
As preferred technical scheme, described organic solvent is DMF or DMSO.
As preferred technical scheme, described post processing includes step:
1), after reaction terminates, reactant liquor has solid to separate out after being cooled to room temperature, filters to get filtrate and filter cake；
2) filtrate is extracted with ethyl acetate, and be extracted in liquid organic layer saturated aqueous common salt washing extract is organic
Phase；
3) it is dried, solvent is evaporated off obtains solid；
4) solid obtained in step 3 is merged with described filter cake, obtain thick product
5) by step 4) in the thick product that obtains carry out purification through silicagel column and obtain eluent；
6) rotation of above-mentioned eluent is evaporated, obtains described 1-phenyl-2 (2-thiosalicylic acidic group) ethene.
As preferred technical scheme, described purification is first to wash a silicagel column with the petroleum ether of boiling range 60～90 DEG C, so
After by thick product loading, then be wash-out with boiling range 60～the petroleum ether of 90 DEG C with the mixed liquor that volume ratio is 10: 1 of ethyl acetate
Agent carries out column chromatography, collects RfValue is the eluent of 0.3.
The invention have the advantage that
1, high yield and condition are simple: productivity is up to 97% in optimal conditions.Course of reaction is urged without adding metal
Change, without gas shield, obtain target product under relatively mild conditions.
2. greatly reduce production cost: the present invention, without using the organic metal of all kinds of complex and expensive, stops simultaneously
Metallic pollution, organic alkali number used is catalytic amount.
Instant invention overcomes the deficiency of prior art synthesis of diaryl thiazolinyl sulphide process, have found a kind of ideal
The method of synthesis 1-phenyl-2 (2-thiosalicylic acidic group) ethene.DSTA (Formulas I) and phenylacetylene (Formula II)
For raw material, reaction is carried out under the conditions of comparatively gentle, obtains 1-phenyl-2 (2-thiosalicylic acidic group) ethene (formula III).This
Reaction system is different from other reaction systems outstanding feature and is to be added without under any metal catalytic, air conditions entering
Row and productivity are high.Therefore reduce the difficulty of post-reaction treatment, reduce reaction cost, the product list obtained by this method
One, there is no other curing product or markovnikov's rule (Markovnikov) side reaction product, and with the product of current existing report
Thing is different, and in two kinds of anti-Markonikov's rule cis-trans-isomers that we obtain, cis-isomer accounts for the overwhelming majority about 86%, and leads to
The cis-isomer obtained in Chang Fangfa is little.In addition, we have selected DSTA cheap and easy to get and are
Raw material, prepares 1-phenyl-2 (2-thiosalicylic acid by adding a small amount of alkaline solution with phenylacetylene generation hydrogen vulcanization reaction
Base) ethene, reduce cost, it is simple to realize industrialized production.
Owing to have employed technique scheme, one prepares the method for 1-phenyl-2 (2-thiosalicylic acidic group) ethene, bag
Include step: 1) DSTA and phenylacetylene are added in reactor, under alkaline environment, add organic solvent,
Under 110～150 DEG C of oil baths, react 46～50 hours, and TLC tracking and measuring in whole reaction；2) room temperature is naturally cooled to, warp
Post processing obtains described 1-phenyl-2 (2-thiosalicylic acidic group) the thick product of ethene；At direct, mild condition, simple bar
Under part, directly react with phenylacetylene with DSTA, under there is no metallic catalyst effect, synthesize 1-phenyl-2
(2-thiosalicylic acidic group) ethene, it is high that the thiazolinyl thioether of synthesis has productivity, separates productivity 97%, high orientation effect and three-dimensional choosing
The features such as selecting property is good.
Accompanying drawing explanation
The nuclear magnetic resonance H spectrogram of Fig. 1 synthetic product of the present invention；
Fig. 2 is the partial enlarged drawing of the nuclear magnetic resonance H spectrogram of Fig. 1；
The nuclear magnetic resonance C spectrogram of Fig. 3 synthetic product of the present invention；
The high resolution mass spectrum spectrogram of Fig. 4 synthetic product of the present invention；
The infrared spectrum spectrogram of Fig. 5 synthetic product of the present invention.
Detailed description of the invention
Below in conjunction with the accompanying drawings and embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate this
Bright rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, art technology
The present invention can be made various changes or modifications by personnel, and these equivalent form of values fall within the application appended claims equally and limited
Fixed scope.
One prepares the method for 1-phenyl-2 (2-thiosalicylic acidic group) ethene, including step:
1) DSTA and phenylacetylene are added in reactor, under alkaline environment, add organic solvent,.
Under 110～150 DEG C of oil baths, react 46～50 hours, and TLC tracking and measuring in whole reaction；
2) naturally cool to room temperature, post-treated obtain described 1-phenyl-2 (2-thiosalicylic acidic group) the thick product of ethene.
As preferred technical scheme, described DSTA is 1.5 with the amount ratio of the material of described phenylacetylene
: 1.5～4.
Described DSTA is 1.5: 2 with the amount ratio of the material of described phenylacetylene.
The alkaline solution that described alkaline environment uses is that tetramethylammonium hydroxide aqueous solution, 4-n-butyl ammonium hydroxide are water-soluble
Liquid, potassium tert-butoxide, sodium hydroxide solution, potassium hydroxide solution, TMAH methanol solution or TPAOH
One in the aqueous solution.
Described organic solvent is DMF or DMSO.
Described post processing includes step:
1), after reaction terminates, reactant liquor has solid to separate out after being cooled to room temperature, filters to get filtrate and filter cake；
2) filtrate is extracted with ethyl acetate, and be extracted in liquid organic layer saturated aqueous common salt washing extract is organic
Phase；
3) it is dried, solvent is evaporated off obtains solid；
4) solid obtained in step 3 is merged with described filter cake, obtain thick product
5) by step 4) in the thick product that obtains carry out purification through silicagel column and obtain eluent；
6) rotation of above-mentioned eluent is evaporated, obtains described 1-phenyl-2 (2-thiosalicylic acidic group) ethene.
As preferred technical scheme, described purification is first to wash a silicagel column with the petroleum ether of boiling range 60～90 DEG C, so
After by thick product loading, then be wash-out with boiling range 60～the petroleum ether of 90 DEG C with the mixed liquor that volume ratio is 10: 1 of ethyl acetate
Agent carries out column chromatography, collects RfValue is the eluent of 0.3.
The testing conditions of product is:
Wherein13C NMR and1H NMR Bruker Aance-500 nmr determination；Product column chromatography (silica gel
200-300 mesh) purifies and separates；High resolution mass spectrum Bruker company ESI-Q-q-TOF mass spectrograph measures.
Embodiment 1
1.5mmol (0.4595g) DSTA and 2mmol (0.22mL) phenylacetylene are added in reaction tube,
Add the 0.2mL40% 4-n-butyl ammonium hydroxide aqueous solution, add 2mLDMF.Heating for dissolving, under 130 DEG C of oil baths, reaction.
TLC tracking and measuring reacts reaction in 48 hours completely.Naturally cool to room temperature, in mother liquor, add 20mL ethyl acetate 2mL saturated
Saline solution extracts, and takes organic layer.Washing extract with saturated aqueous common salt after extracting three times, then anhydrous magnesium sulfate is dried, and rotates
Solvent evaporated obtains thick product.First wash a pillar with the petroleum ether of boiling range 60～90 DEG C, by thick product loading, then by volume ratio be
The boiling range 60 of 10: 1～the mixed liquor of the petroleum ether of 90 DEG C and ethyl acetate are that eluant, eluent carries out column chromatography, collect RfValue is 0.3
Eluent, rotate be evaporated eluant, eluent, i.e. obtain 1-phenyl-2 benzoic acid neighbour's sulfydryl ethylene yield 97% (E: Z, 14: 86).In vain
Look solid.
Elementary analysis C:70.48%H:4.79%O:12.89%N:＜ 0.30%；mp 121.7-122.8℃.1H NMR
(500MHz, CDCl3): δ 6.51 (d, J=10.5Hz, 1H, Z form), 6.87 (d, J=10.5Hz, 1H, Z form), 6.92
(d, J=15.5Hz, 1H, E form), 7.07 (d, J=15.5Hz, 1H, E form), 7.24-7.29 (m, 6H, E and Z
Forms), 7.34-7.55 (m, 8H, E and Z forms), 7.63-7.65 (m, 4H, E and Z forms), 8.11-8.12
(m, 2H, E and Z forms)；13C NMR (126MHz, CDCl3, for major isomer): δ 123.35,125.45,
127.38,127.72,128.39,128.85,129.17,132.10,132.52,133.41,135.98,141.43,171.61；
HRMS caled for C15H12O2S[M+H]+257.0631Found 257.0631。
Embodiment 2
4.5mmol (1.3786g) DSTA and 4mmol (0.44mL) phenylacetylene are added in reaction tube,
Adding 5mmol (0.2g) NaOH, add 7mLDMF, heating for dissolving, 130 DEG C of oil baths, lower reaction, TLC tracking and measuring is anti-
Answer reaction in 48 hours completely.Naturally cool to room temperature, in mother liquor, add the extraction of 20mL ethyl acetate 2mL saturated aqueous common salt, take
Organic layer.Washing extract with saturated aqueous common salt after extracting three times, then anhydrous magnesium sulfate is dried, and rotation solvent evaporated obtains slightly produces
Product.First wash a pillar with the petroleum ether of boiling range 60～90 DEG C, by thick product loading, then by the boiling range 60 that volume ratio is 10: 1～
The petroleum ether of 90 DEG C and the mixed liquor of ethyl acetate are that eluant, eluent carries out column chromatography, collect RfValue is the eluent of 0.3, rotates and steams
Dry eluant, eluent, i.e. obtains 1-phenyl-2 (2-thiosalicylic acidic group) ethylene yield 22%.White solid.
Embodiment 3
1.5mmol (0.4595g) DSTA and 2mmol (0.22mL) phenylacetylene are added in reaction tube,
Adding 2mmol (0.8g) NaOH, add 2mLDMF, heating for dissolving, react under 130 DEG C of oil baths, TLC tracking and measuring reacts
Reaction in 48 hours is completely.Naturally cool to room temperature, in mother liquor, add the extraction of 20mL ethyl acetate 2mL saturated aqueous common salt, taken
Machine layer.Washing extract with saturated aqueous common salt after extracting three times, then anhydrous magnesium sulfate is dried, and rotation solvent evaporated obtains slightly produces
Product.First wash a pillar with the petroleum ether of boiling range 60～90 DEG C, by thick product loading, then by the boiling range 60 that volume ratio is 10: 1～
The petroleum ether of 90 DEG C and the mixed liquor of ethyl acetate are that eluant, eluent carries out column chromatography, collect RfValue is the eluent of 0.3, rotates and steams
Dry eluant, eluent, i.e. obtains 1-phenyl-2 (2-thiosalicylic acidic group) ethylene yield 43%.White solid.
Embodiment 4
1.5mmol (0.4595g) DSTA and 1mmol (0.11mL) phenylacetylene are added in reaction tube,
Adding 2mmol (0.8g) NaOH, add 2mLDMF, heating for dissolving, react under 130 DEG C of oil baths, TLC tracking and measuring reacts
Reaction in 48 hours is completely.Naturally cool to room temperature, in mother liquor, add the extraction of 20mL ethyl acetate 2mL saturated aqueous common salt, taken
Machine layer.Washing extract with saturated aqueous common salt after extracting three times, then anhydrous magnesium sulfate is dried, and rotation solvent evaporated obtains slightly produces
Product.First wash a pillar with the petroleum ether of boiling range 60～90 DEG C, by thick product loading, then by the boiling range 60 that volume ratio is 10: 1～
The petroleum ether of 90 DEG C and the mixed liquor of ethyl acetate are that eluant, eluent carries out column chromatography, collect RfValue is the eluent of 0.3, rotates and steams
Dry eluant, eluent, i.e. obtains 1-phenyl-2 (2-thiosalicylic acidic group) ethylene yield 29%.White solid.
Embodiment 5
1.5mmol (0.4595g) DSTA and 1.5mmol (0.16mL) phenylacetylene are added reaction tube
In, add 2mmol (0.8g) NaOH, add 2mLDMF, heating for dissolving, react under 130 DEG C of oil baths.TLC tracking and measuring
React reaction in 48 hours completely.Naturally cool to room temperature, in mother liquor, add the extraction of 20mL ethyl acetate 2mL saturated aqueous common salt,
Take organic layer.Washing extract with saturated aqueous common salt after extracting three times, then anhydrous magnesium sulfate is dried, and rotates solvent evaporated and obtains slightly
Product.First wash a pillar with the petroleum ether of boiling range 60～90 DEG C, by thick product loading, then by the boiling range 60 that volume ratio is 10: 1
～the mixed liquor of the petroleum ether of 90 DEG C and ethyl acetate is that eluant, eluent carries out column chromatography, collect RfValue is the eluent of 0.3, rotates
It is evaporated eluant, eluent, i.e. obtains 1-phenyl-2 (2-thiosalicylic acidic group) ethylene yield 22%.White solid.
Embodiment 6
1.5mmol (0.4595g) DSTA and 1.5mmol (0.16mL) phenylacetylene are added reaction tube
In, add 2mmol (0.1122g) potassium hydroxide, add 2mLDMF, heating for dissolving, react under 130 DEG C of oil baths.TLC follows the tracks of survey
Surely reaction reaction in 48 hours is completely.Naturally cool to room temperature, in mother liquor, add 20mL ethyl acetate 2mL saturated aqueous common salt extraction
Take, take organic layer.Washing extract with saturated aqueous common salt after extracting three times, then anhydrous magnesium sulfate is dried, and rotates solvent evaporated
Obtain thick product.First wash a pillar with the petroleum ether of boiling range 60～90 DEG C, by thick product loading, then be the boiling of 10: 1 by volume ratio
The mixed liquor of journey 60～the petroleum ether of 90 DEG C and ethyl acetate is that eluant, eluent carries out column chromatography, collects RfValue is the eluent of 0.3,
Rotation is evaporated eluant, eluent, i.e. obtains 1-phenyl-2 (2-thiosalicylic acidic group) Ethylene vinyl productivity 25%.White solid.
Embodiment 7
1.5mmol (0.4595g) DSTA and 2mmol (0.22mL) phenylacetylene are added in reaction tube,
Add 0.1mL potassium tert-butoxide, add 2mLDMF, heating for dissolving, react under 130 DEG C of oil baths.TLC tracking and measuring reacts 48 hours
Reaction is completely.Naturally cool to room temperature, in mother liquor, add the extraction of 20mL ethyl acetate 2mL saturated aqueous common salt, take organic layer.Extraction
Washing extract with saturated aqueous common salt after taking three times, then anhydrous magnesium sulfate is dried, and rotates solvent evaporated and obtains thick product.First with boiling
The petroleum ether of journey 60～90 DEG C washes a pillar, by thick product loading, then with the boiling range 60 that volume ratio is 10: 1～the stone of 90 DEG C
The mixed liquor of oil ether and ethyl acetate is that eluant, eluent carries out column chromatography, collects RfValue is the eluent of 0.3, rotates and is evaporated wash-out
Agent, i.e. obtains 1-phenyl-2 (2-thiosalicylic acidic group) ethylene yield 46%.White solid.
Embodiment 8
1.5mmol (0.4595g) DSTA and 2mmol (0.22mL) phenylacetylene are added in reaction tube,
Add the 0.1mL40% 4-n-butyl ammonium hydroxide aqueous solution, add 2mLDMF, heating for dissolving, react under 130 DEG C of oil baths.TLC
Tracking and measuring reacts reaction in 48 hours completely.Naturally cool to room temperature, in mother liquor, add 20mL ethyl acetate 2mL saturated common salt
Water extracts, and takes organic layer.Washing extract with saturated aqueous common salt after extracting three times, then anhydrous magnesium sulfate is dried, and rotation is evaporated
Solvent obtains thick product.First wash a pillar with the petroleum ether of boiling range 60～90 DEG C, by thick product loading, then be 10: 1 by volume ratio
Boiling range 60～the mixed liquor of the petroleum ether of 90 DEG C and ethyl acetate be that eluant, eluent carries out column chromatography, collect RfValue is 0.3 washes
De-liquid, rotates and is evaporated eluant, eluent, i.e. obtain 1-phenyl-2 (2-thiosalicylic acidic group) ethylene yield 55%.White solid.
Embodiment 9
1.5mmol (0.4595g) DSTA and 2mmol (0.22mL) phenylacetylene are added in reaction tube,
Add 0.2mL10% sodium hydrate aqueous solution, add 2mLDMF, heating for dissolving, react under 130 DEG C of oil baths.TLC tracking and measuring
React reaction in 48 hours completely.Naturally cool to room temperature, in mother liquor, add the extraction of 20mL ethyl acetate 2mL saturated aqueous common salt,
Take organic layer.Washing extract with saturated aqueous common salt after extracting three times, then anhydrous magnesium sulfate is dried, and rotates solvent evaporated and obtains slightly
Product.First wash a pillar with the petroleum ether of boiling range 60～90 DEG C, by thick product loading, then by the boiling range 60 that volume ratio is 10: 1
～the mixed liquor of the petroleum ether of 90 DEG C and ethyl acetate is that eluant, eluent carries out column chromatography, collect RfValue is the eluent of 0.3, rotates
It is evaporated eluant, eluent, i.e. obtains 1-phenyl-2 (2-thiosalicylic acidic group) ethylene yield 42%.White solid.
Embodiment 10
1.5mmol (0.4595g) DSTA and 2mmol (0.22mL) phenylacetylene are added in reaction tube,
Add 0.1mL10% sodium hydrate aqueous solution, add 2mLDMF, heating for dissolving, react under 130 DEG C of oil baths.TLC tracking and measuring
React reaction in 48 hours completely.Naturally cool to room temperature, in mother liquor, add the extraction of 20mL ethyl acetate 2mL saturated aqueous common salt,
Take organic layer.Washing extract with saturated aqueous common salt after extracting three times, then anhydrous magnesium sulfate is dried, and rotates solvent evaporated and obtains slightly
Product.First wash a pillar with the petroleum ether of boiling range 60～90 DEG C, by thick product loading, then by the boiling range 60 that volume ratio is 10: 1
～the mixed liquor of the petroleum ether of 90 DEG C and ethyl acetate is that eluant, eluent carries out column chromatography, collect RfValue is the eluent of 0.3, rotates
It is evaporated eluant, eluent, i.e. obtains 1-phenyl-2 (2-thiosalicylic acidic group) ethylene yield 59%.White solid.
Embodiment 11
1.5mmol (0.4595g) DSTA and 2mmol (0.22mL) phenylacetylene are added in reaction tube,
Add 0.1mL10% potassium hydroxide aqueous solution, add 2mLDMF, heating for dissolving, react under 130 DEG C of oil baths.TLC tracking and measuring
React reaction in 48 hours completely.Naturally cool to room temperature, in mother liquor, add the extraction of 20mL ethyl acetate 2mL saturated aqueous common salt,
Take organic layer.Washing extract with saturated aqueous common salt after extracting three times, then anhydrous magnesium sulfate is dried, and rotates solvent evaporated and obtains slightly
Product.First wash a pillar with the petroleum ether of boiling range 60～90 DEG C, by thick product loading, then by the boiling range 60 that volume ratio is 10: 1
～the mixed liquor of the petroleum ether of 90 DEG C and ethyl acetate is that eluant, eluent carries out column chromatography, collect RfValue is the eluent of 0.3, rotates
It is evaporated eluant, eluent, i.e. obtains 1-phenyl-2 (2-thiosalicylic acidic group) ethylene yield 88%.White solid.
Embodiment 12
1.5mmol (0.4595g) DSTA and 2mmol (0.22mL) phenylacetylene are added in reaction tube,
Add 2mL10% sodium hydrate aqueous solution, heating for dissolving, react under 130 DEG C of oil baths.TLC tracking and measuring reacts reaction in 48 hours
Completely.Naturally cool to room temperature, in mother liquor, add the extraction of 20mL ethyl acetate 2mL saturated aqueous common salt, take organic layer.Extraction three
Washing extract with saturated aqueous common salt after secondary, then anhydrous magnesium sulfate is dried, and rotates solvent evaporated and obtains thick product.First with boiling range 60
～the petroleum ether of 90 DEG C washes a pillar, by thick product loading, then with the boiling range 60 that volume ratio is 10: 1～the petroleum ether of 90 DEG C
It is that eluant, eluent carries out column chromatography with the mixed liquor of ethyl acetate, collects RfValue is the eluent of 0.3, rotates and is evaporated eluant, eluent, i.e.
Obtain 1-phenyl-2 (2-thiosalicylic acidic group) ethylene yield 32%.White solid.
Embodiment 13
1.5mmol (0.4595g) DSTA and 2mmol (0.22mL) phenylacetylene are added in reaction tube,
Add 0.1mL10% potassium hydroxide aqueous solution, add 2mLDMF, heating for dissolving, react under 130 DEG C of oil baths.TLC tracking and measuring is anti-
Answer reaction in 48 hours completely.Naturally cool to room temperature, in mother liquor, add the extraction of 20mL ethyl acetate 2mL saturated aqueous common salt, take
Organic layer.Washing extract with saturated aqueous common salt after extracting three times, then anhydrous magnesium sulfate is dried, and rotation solvent evaporated obtains slightly produces
Product.First wash a pillar with the petroleum ether of boiling range 60～90 DEG C, by thick product loading, then by the boiling range 60 that volume ratio is 10: 1～
The petroleum ether of 90 DEG C and the mixed liquor of ethyl acetate are that eluant, eluent carries out column chromatography, collect RfValue is the eluent of 0.3, rotates and steams
Dry eluant, eluent, i.e. obtains 1-phenyl-2 (2-thiosalicylic acidic group) ethylene yield 74%.White solid.
Embodiment 14
1.5mmol (0.4595g) DSTA and 2mmol (0.22mL) phenylacetylene are added in reaction tube,
0.2mL25% TMAH methanol solution, adds 2mLDMF, heating for dissolving, reacts under 130 DEG C of oil baths.TLC follows the tracks of
Measure reaction reaction in 48 hours completely.Naturally cool to room temperature, in mother liquor, add 20mL ethyl acetate 2mL saturated aqueous common salt extraction
Take, take organic layer.Washing extract with saturated aqueous common salt after extracting three times, then anhydrous magnesium sulfate is dried, and rotates solvent evaporated
Obtain thick product.First wash a pillar with the petroleum ether of boiling range 60～90 DEG C, by thick product loading, then be the boiling of 10: 1 by volume ratio
The mixed liquor of journey 60～the petroleum ether of 90 DEG C and ethyl acetate is that eluant, eluent carries out column chromatography, collects RfValue is the eluent of 0.3,
Rotation is evaporated eluant, eluent, i.e. obtains 1-phenyl-2 (2-thiosalicylic acidic group) ethylene yield 82%.White solid.
Embodiment 15
1.5mmol (0.4595g) DSTA and 2mmol (0.22mL) phenylacetylene are added in reaction tube,
Add the 0.2mL25% tetraethyl ammonium hydroxide aqueous solution, add 2mLDMF, heating for dissolving, react under 130 DEG C of oil baths.TLC with
Track measures reaction reaction in 48 hours completely.Naturally cool to room temperature, in mother liquor, add 20mL ethyl acetate 2mL saturated aqueous common salt
Extraction, takes organic layer.Washing extract with saturated aqueous common salt after extracting three times, then anhydrous magnesium sulfate is dried, and rotation is evaporated molten
Agent obtains thick product.First wash a pillar with the petroleum ether of boiling range 60～90 DEG C, by thick product loading, then be 10: 1 by volume ratio
The mixed liquor of boiling range 60～the petroleum ether of 90 DEG C and ethyl acetate is that eluant, eluent carries out column chromatography, collects RfValue is the wash-out of 0.3
Liquid, rotates and is evaporated eluant, eluent, i.e. obtain 1-phenyl-2 (2-thiosalicylic acidic group) ethylene yield 70%.White solid.
Embodiment 16
1.5mmol (0.4595g) DSTA and 2mmol (0.22mL) phenylacetylene are added in reaction tube,
Add the 0.2mL2m/L TPAOH aqueous solution, add 2mLDMF, heating for dissolving, react under 130 DEG C of oil baths.TLC with
Track measures reaction reaction in 46 hours completely.Naturally cool to room temperature, in mother liquor, add 20mL ethyl acetate 2mL saturated aqueous common salt
Extraction, takes organic layer.Washing extract with saturated aqueous common salt after extracting three times, then anhydrous magnesium sulfate is dried, and rotation is evaporated molten
Agent obtains thick product.First wash a pillar with the petroleum ether of boiling range 60～90 DEG C, by thick product loading, then be 10: 1 by volume ratio
The mixed liquor of boiling range 60～the petroleum ether of 90 DEG C and ethyl acetate is that eluant, eluent carries out column chromatography, collects RfValue is the wash-out of 0.3
Liquid, rotates and is evaporated eluant, eluent, i.e. obtain 1-phenyl-2 (2-thiosalicylic acidic group) ethylene yield 63%.White solid.
Embodiment 17
1.5mmol (0.4595g) DSTA and 2mmol (0.22mL) phenylacetylene are added in reaction tube,
Add the 0.2mL40% 4-n-butyl ammonium hydroxide aqueous solution, add 2mLDMSO, heating for dissolving, react under 130 DEG C of oil baths.
TLC tracking and measuring reacts reaction in 50 hours completely.Naturally cool to room temperature, in mother liquor, add 20mL ethyl acetate 2mL saturated
Saline solution extracts, and takes organic layer.Washing extract with saturated aqueous common salt after extracting three times, then anhydrous magnesium sulfate is dried, and rotates
Solvent evaporated obtains thick product.First wash a pillar with the petroleum ether of boiling range 60～90 DEG C, by thick product loading, then by volume ratio be
The boiling range 60 of 10: 1～the mixed liquor of the petroleum ether of 90 DEG C and ethyl acetate are that eluant, eluent carries out column chromatography, collect RfValue is 0.3
Eluent, rotate be evaporated eluant, eluent, i.e. obtain 1-phenyl-2 (2-thiosalicylic acidic group) ethylene yield 71%.White solid.
The general principle of the present invention, principal character and advantages of the present invention have more than been shown and described.The technology of the industry
Personnel, it should be appreciated that the present invention is not restricted to the described embodiments, simply illustrating this described in above-described embodiment and specification
The principle of invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, and these become
Change and improvement both falls within scope of the claimed invention.Claimed scope by appending claims and
Equivalent defines.
All all fall within the present invention's without the Structural Transformation done by creative work from the present invention is to devise
Within protection domain.
Claims (5)
1. the method preparing 1-phenyl-2 (2-thiosalicylic acidic group) ethene, it is characterised in that include step:
1) DSTA and phenylacetylene are added in reactor, under alkaline environment, add organic solvent, 110～
Under 150 DEG C of oil baths, react 46～50 hours, and TLC tracking and measuring in whole reaction；
2) naturally cool to room temperature, post-treated obtain described 1-phenyl-2 (2-thiosalicylic acidic group) the thick product of ethene；
Described alkaline environment use alkaline solution be tetramethylammonium hydroxide aqueous solution, the 4-n-butyl ammonium hydroxide aqueous solution,
Potassium tert-butoxide, sodium hydroxide solution, potassium hydroxide solution, TMAH methanol solution or TPAOH are water-soluble
One in liquid；
Described organic solvent is DMF or DMSO.
2. the method preparing 1-phenyl-2 (2-thiosalicylic acidic group) ethene as claimed in claim 1, it is characterised in that: described
DSTA is 1.5: 1.5～4 with the amount ratio of the material of described phenylacetylene.
3. the method preparing 1-phenyl-2 (2-thiosalicylic acidic group) ethene as claimed in claim 2, it is characterised in that: described
DSTA is 1.5: 2 with the amount ratio of the material of described phenylacetylene.
4. the method preparing 1-phenyl-2 (2-thiosalicylic acidic group) ethene as claimed in claim 1, it is characterised in that described
Post-process and include step:
1), after reaction terminates, reactant liquor has solid to separate out after being cooled to room temperature, filters to get filtrate and filter cake；
2) filtrate is extracted with ethyl acetate, and is extracted the organic phase in liquid organic layer saturated aqueous common salt washing extract；
3) it is dried, solvent is evaporated off obtains solid；
4) by step 3) in the solid that obtains merge with described filter cake, obtain thick product；
5) by step 4) in the thick product that obtains carry out purification through silicagel column and obtain eluent；
6) rotation of above-mentioned eluent is evaporated, obtains described 1-phenyl-2 (2-thiosalicylic acidic group) ethene.
5. the method preparing 1-phenyl-2 (2-thiosalicylic acidic group) ethene as claimed in claim 4, it is characterised in that: described
Purification is first to wash a silicagel column with the petroleum ether of boiling range 60～90 DEG C, then by thick product loading, then with boiling range 60～90 DEG C
The mixed liquor that volume ratio is 10: 1 of petroleum ether and ethyl acetate be that eluant, eluent carries out column chromatography, collect RfValue is 0.3 washes
De-liquid.
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