CN105001132B - One class (Z)-3-dimethylamino-α 4 '-substituted benzene sulfydryl-α, β-discord aromatic amides and preparation method thereof - Google Patents
One class (Z)-3-dimethylamino-α 4 '-substituted benzene sulfydryl-α, β-discord aromatic amides and preparation method thereof Download PDFInfo
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Abstract
One class (Z) 3 dimethylamino α 4 ' substituted benzene sulfydryl α, β unsaturation aromatic amides, in the presence of proper temperature, coordinative solvent and alkali, amidine 1 reacts virtue with α 4 ' substituted benzene mercaptoacetyl chlorine compound 2, (Z) 3 dimethylamino α 4 ' substituted benzene sulfydryl α, β unsaturation aromatic amides is obtained after purified.Course of reaction of the present invention is simple, safe and environment-friendly；The selecting property of solid of the carbon-carbon double bond being newly formed is high (generation of only Z formula alkene), and reactions steps is few, mild condition, low in raw material price, it is simple to operation；And products obtained therefrom purity is high, comply fully with the prescription as pharmaceutical intermediate, provides advantage for its industrialized production.
Description
Technical field
The invention belongs to the synthesis technical field of amide-type organic compound, be specifically related to one and prepare ((Z)-3-two
Methylamino-α 4 '-substituted benzene sulfydryl-α, β-unsaturation aromatic amides and preparation method thereof.
Background technology
Containing α, beta-unsaturated acyl amine in many medicines and pesticide.Such as convulsion, antidepressant, anti-estrogen, pain relieving
And antibiotic property etc., α, beta-unsaturated acyl amine is also widely used in the key areas such as agricultural, materials industry.α, β-insatiable hunger
With amides compound with its multi-functional construction features, it has also become the intermediate that in organic synthesis, a class is important, Ke Yiyong
In preparing the multiple heterocycles compounds such as quinoline, quinolinone, furan, piperidones, pyridine, pyridone, pyrroles.In general, α, β-
The reaction of unsaturated acyl aminated compounds mainly has: with the reaction of electrophilic reagent, and the reaction of nucleopilic reagent, electrocyclic reaction,
Reduction and oxidation reaction.From structure, this α, the existing nucleophilicity of beta-unsaturated acyl amine also has electrophilicity, both can try with nucleophilic
Agent reaction can react with electrophilic reagent again.α, the preparation method of beta-unsaturated acyl aminated compounds, (U.S. is special for patent 1
Profit the 2nd, 451, No. 436), patent 2(Japanese Unexamined Patent Publication 4-208258 publication) and Japanese Unexamined Patent Publication 6-199752 publication)
The method disclosing the N,N-DMAA using acrylate.But, this method not only needs carried out by acrylic acid
Esterification, but also need to be converted into the ester group of gained ester compounds the step of amide groups.Generally, by ester group to amide groups
In conversion, need the polyol compounds such as glycerol as solvent, need product the most after the completion of reaction from solvent
The step separated.Therefore, in terms of yield, expense, there is too high problem.
In prior art, other prepares α, and the method for beta-unsaturated acyl amine is: first unsaturated acids is made acyl chlorides, the most again
Carry out amidation process with secondary amine and obtain product.Produced acyl chlorides by unsaturated acids it is generally required to use oxalyl chloride, Phosphorous chloride.,
The chemical drugs that phosphorus oxychloride or thionyl chloride etc. are volatile, zest and corrosivity strong, toxicity is bigger, not only produces environment
Raw pollution, and too increase the difficulty of the separation in production process and purification.Saturated amide compound can be at α, and β position is dehydrated
Prepare α, beta-unsaturated acyl amines, such as, and patent CN1826314 A(2006) disclose a kind of α, β-unsaturation
The preparation method of amide compound, first introduces saturated amide compound by blocking group, in dehydrogenation and applicable oxidation
It is dehydrated in the presence of agent, reacts formation double bond, finally remove blocking group and obtain end product, but whole course of reaction institute
Needing chemical reagent many, the response time is long, complicated condition.European Journal of Organic Chemistry in 2013 [(Eur.J.Org.Chem., 2013
(7) use cupric perchlorate catalysis benzoic acid and Carbox amide synthesis acid amide compounds: 1218)] are reported.But
This catalyst system and catalyzing is high to substrate requirements and reacts needs and carries out under the high temperature of 100 ° of C.Chinese patent in 2014
CN103232357B has reported one and has prepared α, and the method for beta-unsaturated acyl amine, in an inert atmosphere, with cinnamic acid compound
It is reactant with Carbox amide, with iron salt and oxidant as catalyst system and catalyzing, prepares product by amidation process
α, beta-unsaturated acyl amine.The method not only uses various iron salt as catalyst, but also wants tert-butyl hydroperoxide etc. for oxygen
Agent.
Huang Zhizhen, Wu Luling at Chin. J. Org. Chem., 1996,16 (4): 340-343 report (E)-
α, the Stereo-selective synthesis of beta-unsaturated acyl amine.The method is under Metal Palladium and dibutyl tellurid effect, bromo acetamide and aldehyde
Target compound is generated by azaWittig reaction.(Z)-3-dimethylamino-α 4 '-substituted benzene sulfydryl-α, β-unsaturation
Aromatic amides there is no report in the literature. (Z)-N-benzyl-2-(benzylthio)-3-(dimethylamino)
The compound of acrylamide class has been reported.
The initiation material [(Z)-N-benzyl-2-(benzylthio)-3-chloroacrylamide] of the method must synthesize through multistep
Can obtain.Further, only benzyl-mercapto compound [Organic & Biomolecular Chemistry, 2452-2472,
2011】.It addition, (Z)-3-morpholino-2-(phenylthio)-N-(p-tolyl) acrylamide is through high temperature, tube sealing
Obtain [Tetrahedron, 5494-5499,2011] with multistep reaction.
Summary of the invention
It is an object of the invention to provide the preparation one class (Z)-3 that a kind of high selectivity, course of reaction are simple, safe and environment-friendly
-dimethylamino-α 4 '-substituted benzene sulfydryl-α, the method for β-unsaturation aromatic amides.
For achieving the above object, the technical solution used in the present invention is:
One class (Z)-3-dimethylamino-α 4 '-substituted benzene sulfydryl-α, β-unsaturation aromatic amides, under
State the compound 3 represented in formula；
In formula: in virtue amidine 1: R1For independent-H ,-F ,-Cl, Br ,-I ,-CN ,-NO2,-OH ,-CO2Me ,-CO2Et ,-
CONHMe ,-CONHEt, C1-C6Alkyl；R2For independent H ,-F ,-OH ,-CN；R3For independent-H ,-CN ,-NO2；
In α-4 '-substituted benzene mercaptoacetyl chlorine compound 2: R4For independent-F ,-Cl, Br ,-I ,-CN ,-NO2,
-CO2Me, -CO2Et。
One class (Z)-3-dimethylamino-α 4 '-substituted benzene sulfydryl-α, the preparation of β-unsaturation aromatic amides
Method, comprises the steps: in the presence of proper temperature, coordinative solvent and alkali, virtue amidine 1 and α 4 '-substituted benzene mercaptoacetyl
Chlorine compound 2 reacts, purified after the fragrant acyl of (Z)-3-dimethylamino-α 4 '-substituted benzene sulfydryl-α, β-unsaturation
Amine.
Described proper temperature is-78oC -5 oC。
Described coordinative solvent is dichloromethane, 1,2-dichloroethanes, carbon tetrachloride, chloroform, oxolane, ethyl acetate,
Toluene, benzene, any one of acetonitrile.
Described virtue amidine 1 is 1:1 4 with the mol ratio of α 4 '-substituted benzene mercaptoacetyl chlorine compound 2.
The described alkali stated be triethylamine, diisopropylethylamine, pyridine, 3,5-lutidines, 4-N, N-lutidines,
Sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, sodium phosphate any one.
The method of described purification is for steaming solvent, recrystallization, silica gel column chromatography, decompression distillation.
The invention has the beneficial effects as follows: course of reaction of the present invention is simple, safe and environment-friendly；Standing of the carbon-to-carbon double bond being newly formed
Selecting property of body is high (generation of only Z-formula alkene), and reactions steps is few, mild condition, low in raw material price, it is simple to operation；And institute
Obtain product purity height, comply fully with the prescription as pharmaceutical intermediate, provide advantage for its industrialized production.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment one
By (E)-N '-(4-ethoxyphenyl)-N, N-dimethylamino carbonamidine (7.69 grams, 0.04 mole), carbon tetrachloride (30 milliliters), carbon
Acid potassium (6.91 grams, 0.05 mole) and magneton join in the single necked round bottom flask of 100 milliliters, start magnetic agitation
Device, is placed in 5 by reaction bulboIn the cryostat of C.It is slowly added dropwise 2-(4 '-chlorobenzene sulfydryl with syringe) and chloroacetic chloride (13.3 grams, 0.06
Mole), whole dropping process the most about 50 minutes.After dripping, reactant mixture is at room temperature stirred overnight.Rotation is evaporated off
Solvent.Then in reaction bulb, add ethyl acetate (20 milliliters) and water (20 milliliters) and stir 10 minutes, being transferred into one
In individual separatory funnel, separate lower floor's inorganic phase.Inorganic phase ethyl acetate (10 milliliters) extracts.Merge organic facies and use saturated food
Saline (20 milliliters) and water (20 milliliters) wash respectively.Organic facies anhydrous sodium sulfate is dried.After recycling design is steamed in rotation, remaining
Thing silica gel column chromatography (ethyl acetate/normal hexane: 1:7) obtains product (Z)-3-(dimethylamino)-N-(4-ethoxyphenyl)-α-
(4 ' chlorobenzene sulfydryl) acrylamide [(Z)-2-((4-chlorophenyl) thio)-3-(dimethylamino)-N-(4-
Ethoxyphenyl) acrylamide] 6.93 grams, productivity 46%.1H NMR (CDCl3),300 MHz (ppm ): 10.04
(1H, s ,-NH), 7.68 (2H, m), 7.40-7.51 (4H, m), 7.01 (1H, s), 6.83 (2H, d), 3.73
(2H, q),2.99 (3H, s), 3.02 (3H, s), 1.35 3H, t);MS:m/z(M+1) 377.12.
Embodiment two
By (E)-N '-(4-ethoxyphenyl)-N, N-dimethylamino carbonamidine (3.84 grams, 0.02 mole), toluene (20 millis
Rise), sodium hydroxide (0.8 gram, 0.02 mole) and magneton join in the single necked round bottom flask of 100 milliliters, start
Magnetic stirring apparatus, is placed in-45 by reaction bulboIn the cryostat of C.It is slowly added dropwise 2-(4 '-chlorobenzene sulfydryl with syringe) chloroacetic chloride
(6.6 grams, 0.03 mole), whole dropping process the most about 35 minutes.After dripping, reactant mixture is at room temperature stirred
Overnight.Rotation is evaporated off solvent.Then in reaction bulb, add ethyl acetate (20 milliliters) and water (20 milliliters) and stir 10 points
Clock, is transferred in a separatory funnel, separates lower floor's inorganic phase.Inorganic phase ethyl acetate (10 milliliters) extracts.Merge
Organic facies is also washed respectively with saturated aqueous common salt (20 milliliters) and water (20 milliliters).Organic facies anhydrous sodium sulfate is dried.Rotation
After steaming recycling design, residue over silica gel column chromatography (ethyl acetate/normal hexane: 1:7) obtains product (Z)-3-(dimethylamino)-N-
(4-ethoxyphenyl)-α-(4 ' chlorobenzene sulfydryl) acrylamide [(Z)-2-((4-chlorophenyl) thio)-3-
(dimethylamino)-N-(4-ethoxyphenyl) acrylamide] 3.01 grams, productivity 40%.
Embodiment three
By (E)-N '-(4-ethoxyphenyl)-N, N-dimethylamino carbonamidine (3.84 grams, 0.02 mole), ethyl acetate
(20 milliliters), sodium phosphate (4.92 grams, 0.03 mole) and magneton join in the single necked round bottom flask of 100 milliliters,
Start magnetic stirring apparatus, reaction bulb is placed in 0oIn the frozen water cryostat of C.Then it is slowly added dropwise 2-(4 '-chlorobenzene mercapto with syringe
Base) chloroacetic chloride (8.84 grams, 0.04 mole), whole dropping process the most about 40 minutes.Drip 2-(4 '-chlorobenzene sulfydryl) second
After acyl chlorides, reactant mixture is at room temperature stirred overnight.Rotation is evaporated off solvent.Then in reaction bulb, add ethyl acetate
(20 milliliters) and water (20 milliliters) also stir 10 minutes, are transferred in a separatory funnel, separate lower floor's inorganic phase.Nothing
Machine extracts by ethyl acetate (10 milliliters) mutually.Merge organic facies and distinguish with saturated aqueous common salt (20 milliliters) and water (20 milliliters)
Washing.Organic facies anhydrous sodium sulfate is dried.After recycling design is steamed in rotation, residue over silica gel column chromatography (ethyl acetate/just own
Alkane: 1:7) obtain product (Z)-3-(dimethylamino)-N-(4-ethoxyphenyl)-2-(4 ' chlorobenzene sulfydryl) acrylamide [(Z)-α-
((4-chlorophenyl) thio)-3-(dimethylamino)-N-(4-ethoxyphenyl) acrylamide] 4.59 grams,
Productivity 61%.
Embodiment four
By (E)-N '-(4-ethoxyphenyl)-N, N-dimethylamino carbonamidine (1.92 grams, 0.01 mole), dichloromethane (10
Milliliter), potassium carbonate (4.14 grams, 0.03 mole) and magneton join in the single necked round bottom flask of 50 milliliters, start
Magnetic stirring apparatus, is placed in-78 by reaction bulboIn the cryostat of C.Then it is slowly added dropwise 2-(4 '-chlorobenzene sulfydryl with syringe) acetyl
Chlorine (6.63 grams, 0.03 mole), whole dropping process the most about 20 minutes.After dripping, reactant mixture is at room temperature stirred
Mix overnight.Rotation is evaporated off solvent.Then in reaction bulb, add ethyl acetate (20 milliliters) and water (20 milliliters) and stir 10 points
Clock, is transferred in a separatory funnel, separates lower floor's inorganic phase.Inorganic phase ethyl acetate (10 milliliters) extracts.Merge
Organic facies is also washed respectively with saturated aqueous common salt (20 milliliters) and water (20 milliliters).Organic facies anhydrous sodium sulfate is dried.Rotation
After steaming recycling design, (Z)-3-(dimethylamino)-N-(4-ethoxyphenyl)-2-(4 ' chlorobenzene sulfydryl) acrylamide [(Z)-α-
((4-chlorophenyl) thio)-3-(dimethylamino)-N-(4-ethoxyphenyl) acrylamide] 2.34 grams,
Productivity 62%.
Embodiment five
By (E)-N '-(4-ethoxyphenyl)-N, N-dimethylamino carbonamidine (3.84 grams, 0.02 mole), chloroform (40 millis
Rise), sodium hydroxide (0.8 gram, 0.02 mole) and magneton join in the single necked round bottom flask of 100 milliliters, start
Magnetic stirring apparatus, is placed in-20 by reaction bulboIn the cryostat of C.Then it is slowly added dropwise 2-(4 '-chlorobenzene sulfydryl with syringe) acetyl
Chlorine (15.5 grams, 0.07 mole), whole dropping process the most about 60 minutes.After dripping, reactant mixture is at room temperature stirred
Mix overnight.Rotation is evaporated off solvent.Then in reaction bulb, add ethyl acetate (20 milliliters) and water (20 milliliters) and stir 10 points
Clock, is transferred in a separatory funnel, separates lower floor's inorganic phase.Inorganic phase ethyl acetate (10 milliliters) extracts.Merge
Organic facies is also washed respectively with saturated aqueous common salt (20 milliliters) and water (20 milliliters).Organic facies anhydrous sodium sulfate is dried.Rotation
After steaming recycling design, residue obtains product (Z)-3-(dimethylamino)-N-(4-ethoxyphenyl through recrystallization)-2-(4 ' chlorobenzene mercapto
Base) acrylamide [(Z)-α-((4-chlorophenyl) thio)-3-(dimethylamino)-N-(4-ethoxyphenyl)
Acrylamide] 4.75 grams, productivity 63%.
Embodiment six
By (E)-N '-(4-ethoxyphenyl)-N, N-dimethylamino carbonamidine (7.69 grams, 0.04 mole), acetonitrile (20 millis
Rise), potassium hydroxide (2.8 grams, 0.05 mole) and magneton join in the single necked round bottom flask of 100 milliliters, start
Magnetic stirring apparatus, is placed in 0 by reaction bulboIn the frozen water cryostat of C.Then it is slowly added dropwise 2-(4 '-chlorobenzene sulfydryl with syringe) second
Acyl chlorides (17.7 grams, 0.08 mole), whole dropping process the most about 80 minutes.After dripping, reactant mixture at room temperature by
It is stirred overnight.Rotation is evaporated off solvent.Then in reaction bulb, add ethyl acetate (20 milliliters) and water (20 milliliters) and stir 10
Minute, it is transferred in a separatory funnel, separates lower floor's inorganic phase.Inorganic phase ethyl acetate (10 milliliters) extracts.Close
And organic facies washing respectively with saturated aqueous common salt (20 milliliters) and water (20 milliliters).Organic facies anhydrous sodium sulfate is dried.
Rotation is steamed after recycling design, residue over silica gel column chromatography (ethyl acetate/normal hexane: 1:6) product (Z)-3-(dimethylamino)-
N-(4-ethoxyphenyl)-2-(4 ' chlorobenzene sulfydryl) acrylamide [(Z)-α-((4-chlorophenyl) thio)-3-
(dimethylamino)-N-(4-ethoxyphenyl) acrylamide] 8.44 grams, productivity 56%.
Obviously, embodiments described above is only a part of embodiment of the present invention rather than whole embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art obtained under not making creative work premise all its
His embodiment, broadly falls into the scope of protection of the invention.
Claims (6)
1. a class (Z)-3-dimethylamino-α 4 '-substituted benzene sulfydryl-α, the preparation side of β-unsaturation aromatic amides
Method, it is characterised in that this compound is the compound 3 represented in following formula；
In formula: in virtue amidine 1: R1For independent-H ,-F ,-Cl, Br ,-I ,-CN ,-NO2,-OH ,-CO2Me ,-CO2Et ,-
CONHMe ,-CONHEt, C1-C6Alkyl；R2For independent H ,-F ,-OH ,-CN；R3For independent-H ,-CN ,-NO2；α -4’-
In substituted benzene mercaptoacetyl chlorine compound 2: R4For independent-F ,-Cl, Br ,-I ,-CN ,-NO2, -CO2Me, -
CO2Et；Preparation method comprises the steps: in the presence of proper temperature, coordinative solvent and alkali, virtue amidine 1 and α 4 '-substituted benzene
Mercaptoacetyl chlorine compound 2 reacts, purified after (Z)-3-dimethylamino-α 4 '-substituted benzene sulfydryl-α, β-unsaturation
Aromatic amides.
A class (Z) the most as claimed in claim 1-3-dimethylamino-α 4 '-substituted benzene sulfydryl-α, β-unsaturation fragrance
The preparation method of amide compound, it is characterised in that described proper temperature is-78oC -5 oC。
A class (Z) the most as claimed in claim 1-3-dimethylamino-α 4 '-substituted benzene sulfydryl-α, β-unsaturation fragrance
The preparation method of amide compound, it is characterised in that described coordinative solvent is dichloromethane, 1,2-dichloroethanes, four chlorinations
Carbon, chloroform, oxolane, ethyl acetate, toluene, benzene, any one of acetonitrile.
A class (Z) the most as claimed in claim 1-3-dimethylamino-α 4 '-substituted benzene sulfydryl-α, β-unsaturation fragrance
The preparation method of amide compound, it is characterised in that described virtue amidine 1 and α 4 '-substituted benzene mercaptoacetyl chlorine compound 2 mole
Ratio is 1:1 4.
A class (Z) the most as claimed in claim 1-3-dimethylamino-α 4 '-substituted benzene sulfydryl-α, β-unsaturation fragrance
The preparation method of amide compound, it is characterised in that described alkali be triethylamine, diisopropylethylamine, pyridine, 3,5-dimethyl
Pyridine, 4-N, N-lutidines, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, phosphoric acid
Any one of sodium.
A class (Z) the most as claimed in claim 1-3-dimethylamino-α 4 '-substituted benzene sulfydryl-α, β-unsaturation fragrance
The preparation method of amide compound, it is characterised in that the method for described purification for steam solvent, recrystallization, silica gel column chromatography,
Decompression distillation.
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