CN106167459A - A kind of new method synthesizing thiazolinyl sulfocyanic ester derivant - Google Patents
A kind of new method synthesizing thiazolinyl sulfocyanic ester derivant Download PDFInfo
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- CN106167459A CN106167459A CN201610579617.2A CN201610579617A CN106167459A CN 106167459 A CN106167459 A CN 106167459A CN 201610579617 A CN201610579617 A CN 201610579617A CN 106167459 A CN106167459 A CN 106167459A
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- thiazolinyl
- silver
- ethyl acetate
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- MLSSYIVNWKFGQQ-LUAWRHEFSA-N B/C=C(/CC#CCCCCC)\N=C=S Chemical compound B/C=C(/CC#CCCCCC)\N=C=S MLSSYIVNWKFGQQ-LUAWRHEFSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
- C07C331/02—Thiocyanates
- C07C331/04—Thiocyanates having sulfur atoms of thiocyanate groups bound to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
- C07C331/02—Thiocyanates
- C07C331/10—Thiocyanates having sulfur atoms of thiocyanate groups bound to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/18—Radicals substituted by singly bound hetero atoms other than halogen by sulfur atoms
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Abstract
The invention belongs to medication chemistry synthesis technical field, disclose a kind of method synthesizing thiazolinyl sulfocyanic ester derivant.The method comprises the following steps: in reaction vessel, add alkynes halogen, rhodanate is raw material, being reacting by heating under conditions of catalyst, organic solvent are solvent at silver salt, gained reactant liquor is cooled to room temperature then purification after terminating, obtains described thiazolinyl sulfocyanic ester derivant by reaction；The present invention is with alkynes halogen, rhodanate as raw material, under the catalysis of silver salt, thiocyanation reaction, one-step synthesis thiazolinyl sulfocyanic ester derivant occurs.Avoid the use of the dangerous materials such as concentrated sulphuric acid, mercury salt.Reaction raw materials is simple and easy to get, and operation is safe and simple, course of reaction environmental friendliness, substrate applicability is wide, and functional group compatibility is strong, separates productivity higher, selecting property of product configuration is good, can be amplified to a gram level scale, and the halogen that retains of product can facilitate and further converts.
Description
Technical field
The invention belongs to medication chemistry synthesis technical field, synthesize the new of thiazolinyl sulfocyanic ester derivant particularly to a kind of
Method.
Background technology
The compound of thiocyanate ester has quite varied biological medicine activity, is a lot of bioactive molecule and natural
The important feature unit of product.And there are some researches show that sulfocyanic ester compounds shows superior answering in terms of electrochemical reduction
Use potential.In addition, sulfocyanic ester compounds is important synthetic intermediate, can be transformed into sulfonic acid, sulfonic acid chloride, sulfur generation
Carbamate, mercaptan, the compound such as sulphonyl nitrile.To this end, researcher has carried out substantial amounts of research to this compounds, send out
Now a lot of sulfocyanic ester compounds have strong inhibitory action to parasite, antibacterial and virus etc..Although this compounds has
There is the most important application, but regrettably the synthetic method of sulfocyanic ester compounds is little, builds thiazolinyl Hydrogen thiocyanate
The method of ester type compound is the most less.
Build the dangerous materials such as the prior synthesizing method concentrated sulphuric acid to be used of thiazolinyl sulfocyanic ester derivant, mercury salt
(Giffard M,Cousseau J,Chemical Communications,1979(22):1026-1027；Giffard M,
Cousseau J,Gouin L,Tetrahedron,1985,41(4):801-810；Giffard M,Cousseau J,Gouin
L,et al.,Journal of organometallic chemistry,1985,287(3):287-303).This type of method is
Big haveing a problem in that in production process easily pollutes environment, and has certain toxic action to experimental implementation person；In addition, produce
The configuration preference of thing is not strong, and functional group compatibility difference is also an in esse difficult problem.Therefore, the structure alkene that development environment is friendly
The synthetic method of base sulfocyanic ester derivant is constantly subjected to the extensive concern of scientific circles and industrial quarters.
In Synthetic Organic Chemistry, alkynes halogen is a kind of organic synthesis building block having very much Research Significance and practical value.Closely
Nian Lai, sense dough based on alkynes halogen reaction receives significant attention.(Trofimov A,Chernyak N,Gevorgyan V.,
Journal of the American Chemical Society,2008,130(41):13538-13539；Yun S Y,Kim
M,Lee D,et al.,Journal of the American Chemical Society,2008,131(1):24-25；
Usanov D L,Yamamoto H,Journal of the American Chemical Society,2011,133(5):
1286-1289；Murali R,Rao N N,Cha J K,Organic letters,2015,17(15):3854-3856；Tan
H,Li H,Ji W,et al.,Angewandte Chemie International Edition,2015,54(29):8374-
8377；Lehnherr D,Alzola J M,Lobkovsky E B,et al.,Chemistry–A European Journal,
2015,21(50):18122-18127).But there is presently no utilize alkynes halogen for raw material be directly synthesized thiazolinyl sulfocyanic ester derive
The report of thing.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, the primary and foremost purpose of the present invention is to provide a kind of synthesis thiazolinyl
The new method of sulfocyanic ester derivant.
The purpose of the present invention is realized by following proposal:
A kind of new method synthesizing thiazolinyl sulfocyanic ester derivant, mainly comprises the steps that
In reaction vessel, adding alkynes halogen, rhodanate is raw material, silver salt be catalyst, organic solvent be solvent
Under the conditions of reacting by heating, reaction terminate after gained reactant liquor is cooled to room temperature then purification, obtain described thiazolinyl Hydrogen thiocyanate
Ester derivant.
Its reaction is shown below:
Wherein, R is aryl or fatty alkyl, and X is chlorine, bromine or iodine.
Described rhodanate can be potassium thiocyanate or ammonium thiocyanate.
Described alkynes halogen can be arylalkyne chlorine, arylalkyne bromine, arylalkyne iodine, alkyl alkynes chlorine, alkyl alkynes bromine or alkyl alkynes iodine.
Preferably, described alkynes chlorine is arylalkyne bromine or alkyl alkynes bromine.
It is furthermore preferred that described arylalkyne bromine includes phenylacetylene bromine, 2-chlorobenzene acetylene bromine, 2-bromobenzene acetylene bromine, 2,4-bis-
Methylbenzene acetylene bromine, 3-chlorobenzene acetylene bromine, 3-fluorobenzene acetylene bromine, 3-methylbenzene acetylene bromine, 3-Methoxy-phenylacetylene bromine, 3-bromobenzene
Acetylene bromine, 3-acetylene bromothiophene, 3,5-difluorobenzene acetylene bromines, 4-chlorobenzene acetylene bromine, 4-Methoxy-phenylacetylene bromine, 4-ethoxybenzene
Acetylene bromine, 4-methylbenzene acetylene bromine, 4-Liquid Crystal Compounds Intermediate p-Ethyl-phenylacetylene bromine, 4-trifluoromethyl phenylacetylene bromine, 4-n-propylbenzene acetylene bromine；Described
Alkyl alkynes halogen include: Isosorbide-5-Nitrae-last of the ten Heavenly stems diine bromine, 1,6-heptadiyne bromine, 1-hexin bromine, 1-heptyne bromine, 1-octyne bromine, 1-n-heptylacetylene bromine,
1-decine bromine, 1-acetylenebromide cyclohexene, 3-cyclohexyl-1-propine bromine, 3-phenyl-1-propine bromine, 3-cyclopenta-1-propine
Bromine, 4-phenyl-ethyl acetylene bromine, 5-chloro-1-pentyne bromine, 5-phenyl-1-pentyne bromine, 5-methyl isophthalic acid-hexin bromine, 5-cyano group-1-penta
Alkynes bromine, cyclopenta acetylene bromine.
Alkynes halogen used and the mol ratio of rhodanate are 1:(1～4).
Described silver salt can be silver chloride, Silver monobromide, silver nitrate, silver oxide, silver trifluoromethanesulfonate, Disilver carbonate, tetrafluoro boron
At least one in acid silver, silver acetate and silver trifluoroacetate.Above-mentioned silver catalyst agent is all solid, and they can be dissolved in reaction institute
In the organic solvent needed.
Preferably, described silver salt is silver acetate.
Silver salt used is 0.1:1 with the mol ratio of alkynes halogen.
Described organic solvent is at least one in glacial acetic acid and ethanol.
Described reacting by heating refers to stirring reaction 1～24h at 80～100 DEG C.
Described purification refers to, by reacting liquid filtering, add sodium bicarbonate solution and be extracted with ethyl acetate three times, collects
Organic facies, is dried with magnesium sulfate, and then decompression is distilled off organic solvent, obtains crude product, then enters the crude product of gained
Row column chromatography.
Wherein, the eluent of described column chromatography is the mixed solvent of petroleum ether and ethyl acetate；Petroleum ether and acetic acid second
The volume ratio of ester is (10～200): 1.
Preferably, described petroleum ether and the volume ratio of ethyl acetate are 100:1.
The mechanism of the present invention is:
With alkynes halogen, rhodanate as raw material, under the catalysis of silver salt, there is thiocyanation reaction, one-step synthesis thiazolinyl sulfur cyanogen
Acid ester derivant.
The present invention, relative to prior art, has such advantages as and beneficial effect:
The present invention builds the synthetic method of thiazolinyl sulfocyanic ester, it is to avoid the use of the dangerous materials such as concentrated sulphuric acid, mercury salt.Reaction
Raw material is simple and easy to get, and operation is safe and simple, course of reaction environmental friendliness, and substrate applicability is wide, and functional group compatibility is strong, point
Higher from productivity, selecting property of product configuration is good, can be amplified to a gram level scale, and the halogen that retains of product can facilitate and further turns
Change.The synthesis of this compounds has extensive use in pesticide, medicine and natural product synthesize.
Accompanying drawing explanation
Fig. 1 is the NOE nuclear magnetic resonance map of the product of embodiment 1-16 gained.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 43 products therefrom.
Fig. 3 is the carbon-13 nmr spectra figure of embodiment 43 products therefrom.
Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 53 products therefrom.
Fig. 5 is the carbon-13 nmr spectra figure of embodiment 53 products therefrom.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention do not limit
In this.
In embodiment, agents useful for same all can be buied from market routine.
Embodiment 1
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol phenylacetylene bromine, the acetic acid of 0.02mmol
Silver, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, after stirring is reacted 3 hours under the conditions of 100 DEG C, stop heating and stir
Mixing, be cooled to room temperature, add sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, magnesium sulfate is dried, decompression rotation
Solvent be evaporated off, then by column chromatographic isolation and purification, obtain target product, column chromatography eluent used be volume ratio be 100:
The petroleum ether of 1: ethyl acetate mixed solvent, productivity is 84%.
The structural characterization data of products therefrom are as follows:
IR(KBr):3065,2924,2854,2357,2120,735,692cm-1.
1H NMR(400MHz,CDCl3):δ7.49-7.43(m,5H),6.79(s,1H).
13C NMR(100MHz,CDCl3):δ135.3,134.4,130.2,128.9,128.1,110.6,108.3ppm.
HRMS(ESI)m/z:C9H6BrNS[M+Na]+Value of calculation: 261.9297；Experiment value: 261.9294.
Infer that products therefrom obtains structure and is according to data above:Illustrate to successfully synthesize target product.
Embodiment 2
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol phenylacetylene bromine, the chlorination of 0.02mmol
Silver, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, after stirring is reacted 3 hours under the conditions of 100 DEG C, stop heating and stir
Mixing, be cooled to room temperature, add sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, magnesium sulfate is dried, decompression rotation
Solvent be evaporated off, then by column chromatographic isolation and purification, obtain target product, column chromatography eluent used be volume ratio be 100:
The petroleum ether of 1: ethyl acetate mixed solvent, productivity is 56%.
Embodiment 3
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol phenylacetylene bromine, the bromination of 0.02mmol
Silver, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, after stirring is reacted 3 hours under the conditions of 100 DEG C, stop heating and stir
Mixing, be cooled to room temperature, add sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, magnesium sulfate is dried, decompression rotation
Solvent be evaporated off, then by column chromatographic isolation and purification, obtain target product, column chromatography eluent used be volume ratio be 100:
The petroleum ether of 1: ethyl acetate mixed solvent, productivity is 53%.
Embodiment 4
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol phenylacetylene bromine, the nitric acid of 0.02mmol
Silver, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, after stirring is reacted 3 hours under the conditions of 100 DEG C, stop heating and stir
Mixing, be cooled to room temperature, add sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, magnesium sulfate is dried, decompression rotation
Solvent be evaporated off, then by column chromatographic isolation and purification, obtain target product, column chromatography eluent used be volume ratio be 100:
The petroleum ether of 1: ethyl acetate mixed solvent, productivity is 73%.
Embodiment 5
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol phenylacetylene bromine, the oxidation of 0.02mmol
Silver, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, after stirring is reacted 3 hours under the conditions of 100 DEG C, stop heating and stir
Mixing, be cooled to room temperature, add sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, magnesium sulfate is dried, decompression rotation
Solvent be evaporated off, then by column chromatographic isolation and purification, obtain target product, column chromatography eluent used be volume ratio be 100:
The petroleum ether of 1: ethyl acetate mixed solvent, productivity is 49%.
Embodiment 6
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol phenylacetylene bromine, the trifluoro of 0.02mmol
Methanesulfonic acid silver, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, after under the conditions of 100 DEG C, stirring is reacted 3 hours, stop adding
Heat and stirring, be cooled to room temperature, adds sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, and magnesium sulfate is dried,
Vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is volume ratio
Petroleum ether for 100:1: ethyl acetate mixed solvent, productivity is 62%.
Embodiment 7
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol phenylacetylene bromine, the carbonic acid of 0.02mmol
Silver, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, after stirring is reacted 3 hours under the conditions of 100 DEG C, stop heating and stir
Mixing, be cooled to room temperature, add sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, magnesium sulfate is dried, decompression rotation
Solvent be evaporated off, then by column chromatographic isolation and purification, obtain target product, column chromatography eluent used be volume ratio be 100:
The petroleum ether of 1: ethyl acetate mixed solvent, productivity is 50%.
Embodiment 8
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol phenylacetylene bromine, the tetrafluoro of 0.02mmol
Boric acid silver, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, after stirring is reacted 3 hours under the conditions of 100 DEG C, stop heating
And stirring, it being cooled to room temperature, add sodium bicarbonate aqueous solution after filtration and be extracted with ethyl acetate three times, magnesium sulfate is dried, and subtracts
Pressure rotation is evaporated off solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is that volume ratio is
The petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 51%.
Embodiment 9
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol phenylacetylene bromine, the trifluoro of 0.02mmol
Silver acetate, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, after stirring is reacted 3 hours under the conditions of 100 DEG C, stop heating
And stirring, it being cooled to room temperature, add sodium bicarbonate aqueous solution after filtration and be extracted with ethyl acetate three times, magnesium sulfate is dried, and subtracts
Pressure rotation is evaporated off solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is that volume ratio is
The petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 63%.
Embodiment 10
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol phenylacetylene bromine, the acetic acid of 0.02mmol
Silver, the ammonium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, after stirring is reacted 3 hours under the conditions of 100 DEG C, stop heating and stir
Mixing, be cooled to room temperature, add sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, magnesium sulfate is dried, decompression rotation
Solvent be evaporated off, then by column chromatographic isolation and purification, obtain target product, column chromatography eluent used be volume ratio be 100:
The petroleum ether of 1: ethyl acetate mixed solvent, productivity is 68%.
Embodiment 11
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol phenylacetylene bromine, the acetic acid of 0.02mmol
Silver, the potassium thiocyanate of 0.2mmol and the glacial acetic acid of 2 milliliters, after stirring is reacted 3 hours under the conditions of 100 DEG C, stop heating and stir
Mixing, be cooled to room temperature, add sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, magnesium sulfate is dried, decompression rotation
Solvent be evaporated off, then by column chromatographic isolation and purification, obtain target product, column chromatography eluent used be volume ratio be 100:
The petroleum ether of 1: ethyl acetate mixed solvent, productivity is 73%.
Embodiment 12
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol phenylacetylene bromine, the acetic acid of 0.02mmol
Silver, the potassium thiocyanate of 0.8mmol and the glacial acetic acid of 2 milliliters, after stirring is reacted 3 hours under the conditions of 100 DEG C, stop heating and stir
Mixing, be cooled to room temperature, add sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, magnesium sulfate is dried, decompression rotation
Solvent be evaporated off, then by column chromatographic isolation and purification, obtain target product, column chromatography eluent used be volume ratio be 100:
The petroleum ether of 1: ethyl acetate mixed solvent, productivity is 81%.
Embodiment 13
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol phenylacetylene bromine, the acetic acid of 0.02mmol
Silver, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, after stirring is reacted 3 hours under the conditions of 80 DEG C, stop heating and stir
Mixing, be cooled to room temperature, add sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, magnesium sulfate is dried, decompression rotation
Solvent be evaporated off, then by column chromatographic isolation and purification, obtain target product, column chromatography eluent used be volume ratio be 100:
The petroleum ether of 1: ethyl acetate mixed solvent, productivity is 74%.
Embodiment 14
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol phenylacetylene bromine, the acetic acid of 0.02mmol
Silver, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, after stirring is reacted 3 hours under the conditions of 90 DEG C, stop heating and stir
Mixing, be cooled to room temperature, add sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, magnesium sulfate is dried, decompression rotation
Solvent be evaporated off, then by column chromatographic isolation and purification, obtain target product, column chromatography eluent used be volume ratio be 100:
The petroleum ether of 1: ethyl acetate mixed solvent, productivity is 77%.
Embodiment 15
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol phenylacetylene bromine, the acetic acid of 0.02mmol
Silver, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, after stirring is reacted 1 hour under the conditions of 100 DEG C, stop heating and stir
Mixing, be cooled to room temperature, add sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, magnesium sulfate is dried, decompression rotation
Solvent be evaporated off, then by column chromatographic isolation and purification, obtain target product, column chromatography eluent used be volume ratio be 100:
The petroleum ether of 1: ethyl acetate mixed solvent, productivity is 56%.
Embodiment 16
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol phenylacetylene bromine, the acetic acid of 0.02mmol
Silver, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, under the conditions of 100 DEG C after stirring reaction 24 hours, stop heating and
Stirring, is cooled to room temperature, adds sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, and magnesium sulfate is dried, decompression
Rotation is evaporated off solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is that volume ratio is
The petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 69%.
The NOE nuclear magnetic resonance map of the product of embodiment 1-16 gained is the most as shown in Figure 1.Sulfur cyanogen in the product of gained is described
Acid group and bromine atoms are in the same side of double bond, for cis-structure.
Embodiment 17
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol phenylacetylene chlorine, the acetic acid of 0.02mmol
Silver, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, after stirring is reacted 3 hours under the conditions of 100 DEG C, stop heating and stir
Mixing, be cooled to room temperature, add sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, magnesium sulfate is dried, decompression rotation
Solvent be evaporated off, then by column chromatographic isolation and purification, obtain target product, column chromatography eluent used be volume ratio be 100:
The petroleum ether of 1: ethyl acetate mixed solvent, productivity is 56%.
Embodiment 18
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol phenylacetylene iodine, the acetic acid of 0.02mmol
Silver, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, after stirring is reacted 3 hours under the conditions of 100 DEG C, stop heating and stir
Mixing, be cooled to room temperature, add sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, magnesium sulfate is dried, decompression rotation
Solvent be evaporated off, then by column chromatographic isolation and purification, obtain target product, column chromatography eluent used be volume ratio be 100:
The petroleum ether of 1: ethyl acetate mixed solvent, productivity is 21%.
Embodiment 19
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol phenylacetylene bromine, the acetic acid of 0.02mmol
Silver, the potassium thiocyanate of 0.4mmol and the ethanol of 2 milliliters, after stirring is reacted 3 hours under the conditions of 100 DEG C, stop heating and stir
Mixing, be cooled to room temperature, add sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, magnesium sulfate is dried, decompression rotation
Solvent be evaporated off, then by column chromatographic isolation and purification, obtain target product, column chromatography eluent used be volume ratio be 100:
The petroleum ether of 1: ethyl acetate mixed solvent, productivity is 64%.
Embodiment 20
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol Isosorbide-5-Nitrae-last of the ten Heavenly stems diine bromine, 0.02mmol
Silver acetate, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, under the conditions of 100 DEG C stirring reaction 3 hours after, stop adding
Heat and stirring, be cooled to room temperature, adds sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, and magnesium sulfate is dried,
Vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is volume ratio
Petroleum ether for 100:1: ethyl acetate mixed solvent, productivity is 88%.
The structural characterization data of products therefrom are as follows:
IR(KBr):3074,2935,2863,2357,2160,1738,1599,1459,819,766cm-1.
1H NMR(400MHz,CDCl3): δ 6.87 (s, 1H), 3.40 (d, J=2.0Hz, 2H), 2.21 (tt, J=7.1,
2.1Hz, 2H), 1.56-1.48 (m, 2H), 1.39-1.29 (m, 4H), 0.91 (t, J=7.0Hz, 3H).
13C NMR(100MHz,CDCl3):δ128.6,109.2,108.0,86.7,77.3,31.0,28.2,27.5,
22.1,18.6,13.9ppm.
HRMS(ESI)m/z:C11H14BrNS[M+Na]+Value of calculation: 293.9923；Experiment value: 293.9928.
Infer that products therefrom obtains structure and is according to data above:Illustrate successfully to synthesize
Target product.
Embodiment 21
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 1,6-heptadiyne bromine, 0.02mmol
Silver acetate, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, under the conditions of 100 DEG C stirring reaction 3 hours after, stop adding
Heat and stirring, be cooled to room temperature, adds sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, and magnesium sulfate is dried,
Vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is volume ratio
Petroleum ether for 100:1: ethyl acetate mixed solvent, productivity is 74%.
Embodiment 22
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 1-heptyne bromine, the vinegar of 0.02mmol
Acid silver, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, under the conditions of 100 DEG C after stirring reaction 3 hours, stop heating and
Stirring, is cooled to room temperature, adds sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, and magnesium sulfate is dried, decompression
Rotation is evaporated off solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is that volume ratio is
The petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 96%.
Embodiment 23
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol cyclopenta acetylene bromine, 0.02mmol
Silver acetate, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, after stirring is reacted 3 hours under the conditions of 100 DEG C, stop heating
And stirring, it being cooled to room temperature, add sodium bicarbonate aqueous solution after filtration and be extracted with ethyl acetate three times, magnesium sulfate is dried, and subtracts
Pressure rotation is evaporated off solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is that volume ratio is
The petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 89%.
Embodiment 24
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 1-hexin bromine, the vinegar of 0.02mmol
Acid silver, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, under the conditions of 100 DEG C after stirring reaction 3 hours, stop heating and
Stirring, is cooled to room temperature, adds sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, and magnesium sulfate is dried, decompression
Rotation is evaporated off solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is that volume ratio is
The petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 95%.
Embodiment 25
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 1-n-heptylacetylene bromine, the vinegar of 0.02mmol
Acid silver, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, under the conditions of 100 DEG C after stirring reaction 3 hours, stop heating and
Stirring, is cooled to room temperature, adds sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, and magnesium sulfate is dried, decompression
Rotation is evaporated off solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is that volume ratio is
The petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 92%.
Embodiment 26
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 1-octyne bromine, the vinegar of 0.02mmol
Acid silver, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, under the conditions of 100 DEG C after stirring reaction 3 hours, stop heating and
Stirring, is cooled to room temperature, adds sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, and magnesium sulfate is dried, decompression
Rotation is evaporated off solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is that volume ratio is
The petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 95%.
Embodiment 27
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 1-acetylene bromine cyclohexene,
The silver acetate of 0.02mmol, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, stirring reaction 3 hours under the conditions of 100 DEG C
After, stop heating and stirring, be cooled to room temperature, add sodium bicarbonate aqueous solution after filtration and be extracted with ethyl acetate three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 79%.
Embodiment 28
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 2,4-dimethyl benzene acetylene bromine,
The silver acetate of 0.02mmol, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, stirring reaction 3 hours under the conditions of 100 DEG C
After, stop heating and stirring, be cooled to room temperature, add sodium bicarbonate aqueous solution after filtration and be extracted with ethyl acetate three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 57%.
The structural characterization data of products therefrom are as follows:
IR(KBr):3069,2988,2924,2860,2357,2160,1763,1242,1053,818,746,698cm-1.
1H NMR(400MHz,CDCl3): δ 7.09 (dd, J=14.8,8.8Hz, 3H), 6.48 (s, 1H), 2.34 (s, 6H).
13C NMR(100MHz,CDCl3):δ140.6,136.6,134.8,132.0,131.5,129.8,127.0,
108.3,107.9,21.3,19.4ppm.
HRMS(ESI)m/z:C11H10BrNS[M+Na]+Value of calculation: 289.9610；Experiment value: 289.9612.
Infer that products therefrom obtains structure and is according to data above:Illustrate that successfully synthesizing target produces
Thing.
Embodiment 29
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 2-chlorobenzene acetylene bromine, 0.02mmol
Silver acetate, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, under the conditions of 100 DEG C stirring reaction 3 hours after, stop adding
Heat and stirring, be cooled to room temperature, adds sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, and magnesium sulfate is dried,
Vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is volume ratio
Petroleum ether for 100:1: ethyl acetate mixed solvent, productivity is 52%.
Embodiment 30
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 2-bromobenzene acetylene bromine, 0.02mmol
Silver acetate, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, under the conditions of 100 DEG C stirring reaction 3 hours after, stop adding
Heat and stirring, be cooled to room temperature, adds sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, and magnesium sulfate is dried,
Vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is volume ratio
Petroleum ether for 100:1: ethyl acetate mixed solvent, productivity is 61%.
Embodiment 31
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 3,5-difluorobenzene acetylene bromine,
The silver acetate of 0.02mmol, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, stirring reaction 3 hours under the conditions of 100 DEG C
After, stop heating and stirring, be cooled to room temperature, add sodium bicarbonate aqueous solution after filtration and be extracted with ethyl acetate three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 62%.
Embodiment 32
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 3-phenyl-1-propine bromine,
The silver acetate of 0.02mmol, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, stirring reaction 3 hours under the conditions of 100 DEG C
After, stop heating and stirring, be cooled to room temperature, add sodium bicarbonate aqueous solution after filtration and be extracted with ethyl acetate three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 82%.
Embodiment 33
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 3-fluorobenzene acetylene bromine, 0.02mmol
Silver acetate, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, under the conditions of 100 DEG C stirring reaction 3 hours after, stop adding
Heat and stirring, be cooled to room temperature, adds sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, and magnesium sulfate is dried,
Vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is volume ratio
Petroleum ether for 100:1: ethyl acetate mixed solvent, productivity is 76%.
Embodiment 34
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 3-cyclohexyl-1-propine bromine,
The silver acetate of 0.02mmol, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, stirring reaction 3 hours under the conditions of 100 DEG C
After, stop heating and stirring, be cooled to room temperature, add sodium bicarbonate aqueous solution after filtration and be extracted with ethyl acetate three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 87%.
Embodiment 35
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 3-cyclopenta-1-propine bromine,
The silver acetate of 0.02mmol, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, stirring reaction 3 hours under the conditions of 100 DEG C
After, stop heating and stirring, be cooled to room temperature, add sodium bicarbonate aqueous solution after filtration and be extracted with ethyl acetate three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 89%.
Embodiment 36
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 3-methylbenzene acetylene bromine,
The silver acetate of 0.02mmol, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, stirring reaction 3 hours under the conditions of 100 DEG C
After, stop heating and stirring, be cooled to room temperature, sodium bicarbonate aqueous solution be extracted with ethyl acetate three times after filtration, magnesium sulfate
Being dried, vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is
Volume ratio is the petroleum ether of 100:1: ethyl acetate mixed solvent, and productivity is 57%.
Embodiment 37
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 3-Methoxy-phenylacetylene bromine,
The silver acetate of 0.02mmol, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, stirring reaction 3 hours under the conditions of 100 DEG C
After, stop heating and stirring, be cooled to room temperature, add sodium bicarbonate aqueous solution after filtration and be extracted with ethyl acetate three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 75%.
Embodiment 38
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 3-chlorobenzene acetylene bromine, 0.02mmol
Silver acetate, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, under the conditions of 100 DEG C stirring reaction 3 hours after, stop adding
Heat and stirring, be cooled to room temperature, adds sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, and magnesium sulfate is dried,
Vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is volume ratio
Petroleum ether for 100:1: ethyl acetate mixed solvent, productivity is 71%.
Embodiment 39
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 3-bromobenzene acetylene bromine, 0.02mmol
Silver acetate, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, under the conditions of 100 DEG C stirring reaction 3 hours after, stop adding
Heat and stirring, be cooled to room temperature, adds sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, and magnesium sulfate is dried,
Vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is volume ratio
Petroleum ether for 100:1: ethyl acetate mixed solvent, productivity is 78%.
Embodiment 40
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 3-acetylene bromothiophene, 0.02mmol
Silver acetate, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, under the conditions of 100 DEG C stirring reaction 3 hours after, stop adding
Heat and stirring, be cooled to room temperature, adds sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, and magnesium sulfate is dried,
Vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is volume ratio
Petroleum ether for 100:1: ethyl acetate mixed solvent, productivity is 75%.
Embodiment 41
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 4-phenyl-ethyl acetylene bromine,
The silver acetate of 0.02mmol, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, stirring reaction 3 hours under the conditions of 100 DEG C
After, stop heating and stirring, be cooled to room temperature, add sodium bicarbonate aqueous solution after filtration and be extracted with ethyl acetate three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 76%.
Embodiment 42
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 4-methylbenzene acetylene bromine,
The silver acetate of 0.02mmol, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, stirring reaction 3 hours under the conditions of 100 DEG C
After, stop heating and stirring, be cooled to room temperature, add ethyl acetate after filtration and with the water-soluble sodium bicarbonate aqueous solution of sodium bicarbonate
And extract three times with acetic acid ethyl fluid, magnesium sulfate is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains
Target product, column chromatography eluent used be volume ratio be the petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is
80%.
Embodiment 43
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 4-Methoxy-phenylacetylene bromine,
The silver acetate of 0.02mmol, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, stirring reaction 3 hours under the conditions of 100 DEG C
After, stop heating and stirring, be cooled to room temperature, add sodium bicarbonate aqueous solution after filtration and be extracted with ethyl acetate three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 67%.
The structural characterization data of products therefrom are as follows:
IR(KBr):3065,2937,2839,2357,2158,1560,1503,1456,1297,1249,1175,1027,
833,789cm-1.
1H NMR(400MHz,CDCl3): δ 7.26 (d, J=8.1Hz, 2H), 7.15 (d, J=8.0Hz, 2H), 6.64 (s,
1H), 2.30 (s, 3H), as shown in Figure 2.
13C NMR(100MHz,CDCl3): δ 140.5,134.5,132.5,129.6,128.0,109.6,108.6,
21.3ppm, as shown in Figure 3.
HRMS(ESI)m/z:C10H8BrNOS[M+Na]+Value of calculation: 291.9402；Experiment value: 291.9400.
Infer that products therefrom obtains structure and is according to data above:Illustrate to successfully synthesize target
Product.
Embodiment 44
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 4-chlorobenzene acetylene bromine, 0.02mmol
Silver acetate, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, under the conditions of 100 DEG C stirring reaction 3 hours after, stop adding
Heat and stirring, be cooled to room temperature, adds sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, and magnesium sulfate is dried,
Vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is volume ratio
Petroleum ether for 100:1: ethyl acetate mixed solvent, productivity is 74%.
Embodiment 45
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 4-trifluoromethyl phenylacetylene bromine,
The silver acetate of 0.02mmol, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, stirring reaction 3 hours under the conditions of 100 DEG C
After, stop heating and stirring, be cooled to room temperature, add sodium bicarbonate aqueous solution after filtration and be extracted with ethyl acetate three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 67%.
Embodiment 46
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 4-Liquid Crystal Compounds Intermediate p-Ethyl-phenylacetylene bromine,
The silver acetate of 0.02mmol, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, stirring reaction 3 hours under the conditions of 100 DEG C
After, stop heating and stirring, be cooled to room temperature, add sodium bicarbonate aqueous solution after filtration and be extracted with ethyl acetate three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 81%.
Embodiment 47
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 4-ethoxybenzene acetylene bromine,
The silver acetate of 0.02mmol, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, stirring reaction 3 hours under the conditions of 100 DEG C
After, stop heating and stirring, be cooled to room temperature, add sodium bicarbonate aqueous solution after filtration and be extracted with ethyl acetate three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 66%.
The structural characterization data of products therefrom are as follows:
IR(KBr):3067,2982,2930,2892,2158,1602,1505,1298,1250,1176,835,793,
744cm-1.
1H NMR(400MHz,CDCl3):δ7.39-7.34(m,2H),6.93-6.89(m,2H),6.67(s,1H),4.05
(q, J=7.0Hz, 2H), 1.42 (t, J=7.0Hz, 3H).
13C NMR(100MHz,CDCl3):δ160.4,134.4,129.5,127.5,114.7,108.8,108.7,63.6,
14.7ppm.
HRMS(ESI)m/z:C11H10BrNOS[M+Na]+Value of calculation: 305.9559；Experiment value: 305.9560.
Infer that products therefrom obtains structure and is according to data above:Illustrate to successfully synthesize target
Product.
Embodiment 48
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 4-n-propylbenzene acetylene bromine,
The silver acetate of 0.02mmol, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, stirring reaction 3 hours under the conditions of 100 DEG C
After, stop heating and stirring, be cooled to room temperature, add sodium bicarbonate aqueous solution after filtration and be extracted with ethyl acetate three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 81%.
Embodiment 49
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 1-decine bromine, the vinegar of 0.02mmol
Acid silver, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, under the conditions of 100 DEG C after stirring reaction 3 hours, stop heating and
Stirring, is cooled to room temperature, adds sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, and magnesium sulfate is dried, decompression
Rotation is evaporated off solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is that volume ratio is
The petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 89%.
Embodiment 50
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 5-phenyl-1-pentyne bromine,
The silver acetate of 0.02mmol, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, stirring reaction 3 hours under the conditions of 100 DEG C
After, stop heating and stirring, be cooled to room temperature, add sodium bicarbonate aqueous solution after filtration and be extracted with ethyl acetate three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 74%.
Embodiment 51
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 5-cyano group-1-pentyne bromine,
The silver acetate of 0.02mmol, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, stirring reaction 3 hours under the conditions of 100 DEG C
After, stop heating and stirring, be cooled to room temperature, add sodium bicarbonate aqueous solution after filtration and be extracted with ethyl acetate three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 93%.
Embodiment 52
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 5-methyl isophthalic acid-hexin bromine,
The silver acetate of 0.02mmol, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, stirring reaction 3 hours under the conditions of 100 DEG C
After, stop heating and stirring, be cooled to room temperature, add sodium bicarbonate aqueous solution after filtration and be extracted with ethyl acetate three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 100:1: ethyl acetate mixed solvent, productivity is 93%.
Embodiment 53
Equipped with in 25 milliliters of reaction vessels of reflux condensing tube, add 0.2mmol 5-chloro-1-pentyne bromine, 0.02mmol
Silver acetate, the potassium thiocyanate of 0.4mmol and the glacial acetic acid of 2 milliliters, under the conditions of 100 DEG C stirring reaction 3 hours after, stop adding
Heat and stirring, be cooled to room temperature, adds sodium bicarbonate aqueous solution and be extracted with ethyl acetate three times after filtration, and magnesium sulfate is dried,
Vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is volume ratio
Petroleum ether for 100:1: ethyl acetate mixed solvent, productivity is 91%.
The structural characterization data of products therefrom are as follows:
IR(KBr):3070,2957,2855,2357,2159,1835,1241,1057cm-1.
1H NMR(400MHz,CDCl3): δ 6.55 (s, 1H), 3.59 (t, J=6.1Hz, 2H), 2.79 (t, J=7.2Hz,
2H), 2.15-2.07 (m, 2H), as shown in Figure 4.
13C NMR(100MHz,CDCl3): δ 132.2,108.6,107.7,43.1,33.9,29.9ppm, as shown in Figure 5.
ESI-HRMS m/z:C6H7BrClNS[M+Na]+Value of calculation: 261.9063, experiment value: 261.9060.
Infer that products therefrom obtains structure and is according to data above:Illustrate that successfully synthesizing target produces
Thing.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. the new method synthesizing thiazolinyl sulfocyanic ester derivant, it is characterised in that comprise the following steps:
In reaction vessel, adding alkynes halogen, rhodanate is raw material, silver salt be catalyst, organic solvent be the condition of solvent
Lower reacting by heating, gained reactant liquor is cooled to room temperature then purification after terminating, obtains described thiazolinyl sulfocyanic ester and spread out by reaction
Biological.
The new method of synthesis thiazolinyl sulfocyanic ester derivant the most according to claim 1, it is characterised in that:
Described rhodanate is potassium thiocyanate or ammonium thiocyanate.
The new method of synthesis thiazolinyl sulfocyanic ester derivant the most according to claim 1, it is characterised in that:
Described alkynes halogen is arylalkyne chlorine, arylalkyne bromine, arylalkyne iodine, alkyl alkynes chlorine, alkyl alkynes bromine or alkyl alkynes iodine.
The new method of synthesis thiazolinyl sulfocyanic ester derivant the most according to claim 3, it is characterised in that:
Described alkynes halogen is arylalkyne bromine or alkyl alkynes bromine.
The new method of synthesis thiazolinyl sulfocyanic ester derivant the most according to claim 4, it is characterised in that:
Described arylalkyne bromine includes phenylacetylene bromine, 2-chlorobenzene acetylene bromine, 2-bromobenzene acetylene bromine, 2,4-dimethyl benzene acetylene bromines,
3-chlorobenzene acetylene bromine, 3-fluorobenzene acetylene bromine, 3-methylbenzene acetylene bromine, 3-Methoxy-phenylacetylene bromine, 3-bromobenzene acetylene bromine, 3-acetylene
Bromothiophene, 3,5-difluorobenzene acetylene bromines, 4-chlorobenzene acetylene bromine, 4-Methoxy-phenylacetylene bromine, 4-ethoxybenzene acetylene bromine, 4-methyl
Phenylacetylene bromine, 4-Liquid Crystal Compounds Intermediate p-Ethyl-phenylacetylene bromine, 4-trifluoromethyl phenylacetylene bromine, 4-n-propylbenzene acetylene bromine；
Described alkyl alkynes bromine includes: Isosorbide-5-Nitrae-last of the ten Heavenly stems diine bromine, 1,6-heptadiyne bromine, 1-hexin bromine, 1-heptyne bromine, 1-octyne bromine,
1-n-heptylacetylene bromine, 1-decine bromine, 1-acetylenebromide cyclohexene, 3-cyclohexyl-1-propine bromine, 3-phenyl-1-propine bromine, 3-ring penta
Base-1-propine bromine, 4-phenyl-ethyl acetylene bromine, 5-chloro-1-pentyne bromine, 5-phenyl-1-pentyne bromine, 5-methyl isophthalic acid-hexin bromine, 5-
Cyano group-1-pentyne bromine, cyclopenta acetylene bromine.
The new method of synthesis thiazolinyl sulfocyanic ester derivant the most according to claim 1, it is characterised in that:
Alkynes halogen used and the mol ratio of rhodanate are 1:(1～4)；
Silver salt used is 0.1:1 with the mol ratio of alkynes halogen.
The new method of synthesis thiazolinyl sulfocyanic ester derivant the most according to claim 1, it is characterised in that:
Described silver salt is silver chloride, Silver monobromide, silver nitrate, silver oxide, silver trifluoromethanesulfonate, Disilver carbonate, silver tetrafluoroborate, vinegar
At least one in acid silver and silver trifluoroacetate.
The new method of synthesis thiazolinyl sulfocyanic ester derivant the most according to claim 1, it is characterised in that:
Described organic solvent is at least one in glacial acetic acid and ethanol.
The new method of synthesis thiazolinyl sulfocyanic ester derivant the most according to claim 1, it is characterised in that:
Described reacting by heating refers to stirring reaction 1～24h at 80～100 DEG C.
The new method of synthesis thiazolinyl sulfocyanic ester derivant the most according to claim 1, it is characterised in that:
Described purification refers to, by reacting liquid filtering, add sodium bicarbonate solution and be extracted with ethyl acetate three times, collecting organic
Phase, is dried with magnesium sulfate, and then decompression is distilled off organic solvent, obtains crude product, then the crude product of gained is carried out post
Chromatography；
Wherein, the eluent of column chromatography is the mixed solvent of petroleum ether and ethyl acetate；Petroleum ether and the volume ratio of ethyl acetate
For (10～200): 1.
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| CN110453241A (en) * | 2019-08-14 | 2019-11-15 | 华南理工大学 | A kind of electrochemical preparation method of alkynyl thiocyanates |
| CN113773238A (en) * | 2021-09-01 | 2021-12-10 | 北京理工大学 | Method for synthesizing alkyl thiocyanate by one-step method |
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| SAKAE UEMURA等: "Chlorination and lnterhalogenation of Alkylphenylacetylenes with Antimony Pentachloride", 《J.C.S.PERKIN I》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110453241A (en) * | 2019-08-14 | 2019-11-15 | 华南理工大学 | A kind of electrochemical preparation method of alkynyl thiocyanates |
| CN110453241B (en) * | 2019-08-14 | 2021-08-10 | 华南理工大学 | Electrochemical preparation method of alkynyl thiocyanate |
| CN113773238A (en) * | 2021-09-01 | 2021-12-10 | 北京理工大学 | Method for synthesizing alkyl thiocyanate by one-step method |
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