CN85106474A - The method for making of nitrogen-thiophene chlor(o)acetamide - Google Patents
The method for making of nitrogen-thiophene chlor(o)acetamide Download PDFInfo
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- CN85106474A CN85106474A CN85106474.4A CN85106474A CN85106474A CN 85106474 A CN85106474 A CN 85106474A CN 85106474 A CN85106474 A CN 85106474A CN 85106474 A CN85106474 A CN 85106474A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention introduces formula I compound
R is C in the formula
1-4Alkoxyl group, C
2-4Alkyl, C wherein
1-4Alkyl and the N atom that is connected R 2 the C atoms of being separated by at least, R
2And R
4Be respectively CH
3Or C
2H
5, R
5Be H or CH
3Also introduce the preparation of formula I compound and the application in producing N-(thiene-3-yl-)-chlor(o)acetamide.
Description
The invention provides the method for making and the application in producing nitrogen (the following N of using)-thiophene chlor(o)acetamide thereof of new tetramethylene sulfide-3-subunit imine compound.
Particularly, the present invention proposes the new tetramethylene sulfide amine shown in the formula I.
R is C in the formula
1-4Alkoxy-C
2-4Alkyl, C wherein
1-4At least 2 the C atoms of being separated by between alkoxyl group and the N atom that is connected R, R
2And R
4Be respectively CH
3Or C
2H
5, R
5Be H or CH
3
Discoverable type I compound is easy to dehydrogenation, production II compound.
R, R in the formula
2, R
4And R
5Definition as above.
Formula II compound is known as the intermediate of producing formula III compound
R, R in the formula
2, R
4And R
5Definition is also as above-mentioned.
Formula III compound is known as weedicide.
Compound ii and III are referred in English Patent 2114566A specification sheets.This specification sheets is referred to several method for makings of formula III compound, but the method that this specification sheets or other document are referred to, and does not have a kind ofly can produce formula III compound from the starting material that are easy to obtain.
The present invention discloses a kind of approach of producing formula III compound very easily.
The one side that the present invention relates to is to produce formula II compound by the dehydrogenation of formula I compound.
Above-mentioned certain embodiments can be carried out effectively by katalysis or by means of the oxygenizement of oxygen or oxygenant (as sulphur, sulfuryl chloride and thionyl chloride).Wherein again with the oxygenizement effect of katalysis or thionyl chloride for well.Especially find that thionyl chloride is particularly suitable for the certain embodiments of formula I compound.
The catalytic dehydrogenation of formula I compound can be used any dehydrogenation catalyst.Knownly be applicable to that the representative of the dehydrogenation catalyst of dehydrogenation reaction of the present invention is precious metal (as platinum or a palladium), other metal is (as Cr
2O
3) or the mixture of they and other metal (as CuO).Catalytic dehydrogenation can be finished under such reacts known conditions.For example when catalyzer was platinum, platinode was easy to be uniformly distributed in carrier (as coke) and goes up (is 5% as platinum/charcoal ratio).Dehydrogenation reaction is suitable for carrying out under heating state, and preferably temperature is higher than 180 ℃, as 220 ℃ or higher, and is in the noble gas atmosphere (as N
2Gas-bearing formation) in.
Formula I compound and oxygen reaction (even below room temperature) generate intermediate product, and this intermediate product is met thermolysis (typical temperature is about 100 ℃ or higher), production II compound.This transformation can be in appropriate solvent (as aromatic solvents such as toluene), and more than the decomposition point, and under refluxad, oxidation step is finished very easily.
When adding oxygenant, oxidising process is easy to carry out in inactive solvent under being in reaction conditions.The representative of suitable solvent is that hydrochloric ether is (as CH
2Cl
2) and hydrocarbon (as toluene or hexanaphthene).If oxygenant is a sulphur, oxidizing reaction is suitable under heating condition carries out, if oxygenant is sulfuryl chloride or thionyl chloride, temperature of reaction with-30 ℃～+ 80 ℃ for well, such as at room temperature (about 20 ℃～30 ℃).
Thionyl chloride is made catalyzer in this reaction suitable especially: reaction can be finished under appropriate condition, there is no unwanted side reaction (as chlorination, further oxidation etc.).
The formula II compound that makes like this changes formula III compound into through the N-chloroacetylation.Described N-chloroacetylation can be finished by the known method for preparing chlor(o)acetamide (under the reaction conditions of referring at English Patent 2114566A specification sheets) by corresponding amine.
If formula I compound, just can make the formula II compound of the acid adduct form of hydrochloride with sulfuryl chloride or thionyl chloride oxidation.Described hydrochloride does not need to separate from reaction mixture earlier, just can react with chloroacetyl chloride, when alkali does not exist, draws the formula III compound product of some amount.
Formula I compound is easy to from the tetrahydro thiophene-3-ketone of corresponding formula IV
(R in the formula
2, R
4And R
5Definition as above-mentioned) with the amine of formula V
(wherein the definition of R is the same) reaction makes.
This condensation reaction under being in reaction conditions in the inactive solvent of character (as hexanaphthene or toluene) be easy to carry out.Reaction preferably heating (such as under reflux temperature) is finished.Reaction product is with water trap or suitable molecular sieve (5 dust) drying.This can be by adopting water cooler (as water cooler) and condensation product being carried out continuously by the adsorption column that molecular sieve is housed, and the most handy nitrogen protection in the post is to get rid of the oxygen in the atmosphere.
The above-mentioned entire reaction course of producing formula III compound through formula I and formula II compound by formula IV compound can be carried out in same reactor, can obtain considerable formula I and formula II compound but needn't they be separated from reactor for next step reaction.
Formula IV compound is new.Be easy to make by the cyclisation of formula VI compound.
R in the formula
2, R
4And R
5Define the same.
This cyclisation can be finished under Lu's coffee cyclisation now or its improvement condition.
This cyclisation is easily carried out under heating: Ba(OH)
2, MnCO
3, Fe powder, Fe, Co(II) or the Ni(II) acetate, acetic anhydride/LiCl or tertiary amine such as the existence of this class condensing agent of trialkylamine, can quicken cyclisation.With Fe powder or Fe, Co(II) or the Ni(II) acetate to make condensing agent especially superior.
Be meant at acetate one speech of this used Fe and comprise the Fe(II) and the Fe(II) acetate compound such as Fe(acetate)
2And Fe(OH)
2-(acetate).
Formula VI compound also is new, the available raw material through type VII compound that is easy to get
(R in the formula
2Define the same) and formula VIII compound
(R in the formula
4And R
5Define the same) addition reaction make.
The addition of formula VII and formula VIII compound can be carried out under Michael reaction or its improvement condition.This addition is carried out under heating.Formula VII compound uses the form (carboxylate salt) of its salt, such as resembling the such alkali metal salt of carboxylic acid sodium form.But formula VII compound is also used its free acid form, and in this case, addition reaction is promptly to resemble the such trialkylamine of three (normal-butyl) amine or Fe, Co(II at tertiary amine) or the Ni(II) acetate carry out when existing.The another kind of form of back one method can be without solvent, and the reaction development is rapid, output height, recyclable nonreactive starting material.
But formula VI compound cyclisation accepted way of doing sth IV compound and needn't separate type VI compound.
R
2, R
4And R
5Be respectively CH
3, CH
3With H for well.R is preferably CH(CH
3) CH
2OCH
3, CH
2CH
2-O-nC
3H
7Or CH
2CH
2-O-iC
3H
7, CH(CH preferably)
3-CH
2-OCH
3
Following example specifies content of the present invention, uses centigradetemperature.
Example 1:N-(1-methoxy third-2-yl)-2, the 4-dimethyl
Tetramethylene sulfide-3-subunit imines
Reaction vessel is furnished with thermometer, watercooler and fills the post of 31 mol sieves (5 dust).
Fill 0.2 mole 2 in the reaction vessel, 4-dimethyl tetrahydro thiophene-3-ketone, the mixture of 0.225 mole of 1-methoxyl group-2-aminopropane and 50 milliliters of hexanaphthenes.Reaction vessel is equipped with thermometer, and watercooler and the method that fills 31 mol sieves (5 dust) are to make ebullient reaction mixture condensation product pass through molecular sieve continuously.This device N
2Protection is to get rid of atmosphericoxygen.
Reaction mixture boiling 9 hours.With the vacuum distilling under 0.5 backing pressure power condition of the compound shown in the title, boiling range is 65-80 ° then.
Example 2:N-(1-methoxy third-2-yl)-2,4-dimethyl-3-aminothiophene
0.1 the mole thionyl chloride is dissolved in 20 milliliters of toluene, in the time of 10-20 °, the limit is stirred, is cooled off the limit and splashes into 80 milliliters 0.1 mole N-(1-methoxy third-2-yl)-2, in 4-dimethyl-tetramethylene sulfide-3-subunit imines.
Reaction mixture was stirred one hour, make it be alkalescence with the caustic soda strong solution then.Isolate and contain water, wash organic phase with water, drying is fallen toluene distillation in a vacuum.Distillation leftover under 0.2 backing pressure power condition promptly gets compound shown in the title, boiling point 70-72 °.
Example 3:N-(1-methoxy third-2-yl)-2,4-dimethylamino thiophene
0.01 mole of N-(1-methoxy third-2-yl)-2,4-dimethyl tetrahydro thiophene-3-subunit imines splashes into 0.013 mole of SULPHUR POWDER and 2 milliliters boil (under refluxad) in the solution that toluene forms in 5 minutes.Mixture is restir 5 minutes under refluxad, and under 0.5 holder and 150-170 ° of condition, the rough residue of distillation in bulb must transparent overhead product be a compound shown in the title.
Example 4:N-(1-methyl-prop-2-yl)-2,4-dimethylamino thiophene
0.1 mole of N-(1-methoxy third-2-yl)-2,4-dimethyl tetrahydro thiophene-3-subunit imines under nitrogen atmosphere with 2 gram 5% platinum/coke 200 ℃ of time heating 11 hours.The elimination catalyzer, distillation filtrate gets compound shown in the title in the time of boiling range 68-71 ° when 0.1 holder.
Example 5:N-(2,4-thioxene-3-yl)-N-(1-methoxy third-2-yl)-chlor(o)acetamide
1) the formula II compound of use salt form
0.02 mole of thionyl chloride is dissolved in 5 milliliters of toluene, in 40 minutes, splash into 0.02 mole of N-(1-methoxy third-2-base being dissolved in 10 milliliters of toluene-)-2, in 4-dimethyl tetrahydro thiophene-3-subunit imines (20 ° time).Stirred reaction mixture 2 hours, N-(-1-methoxy third-2-base-)-2, the hydrochloride of 4-dimethyl-3-aminothiophene.Add the 0.02 mole of chloroacetyl chloride that is dissolved in 5 milliliters of toluene then.This mixture was under refluxad heated 1 hour, and HCl overflows.Obtain compound shown in the title with the column chromatography that hexanaphthene/acetate acetoacetic ester (8: 2) carries out on silica gel, boiling point 148-150 °/0.03 holder.
2) the formula II compound of usefulness alkali form
At 1500 milliliters of CH
2Among the Cl 315 gram (1.58 moles) N-(1-methyl-2-methoxyl group-ethyl)-2, the gram of 240 in 4-dimethyl-3-aminothiophene and 250 ml waters (1.75 moles) K
2CO
3Mixture in, at room temperature the limit firmly stir the limit splash into 200 the gram (1.77 moles) chloro-acetyl chlorides.After at room temperature reacting half an hour, isolate organic phase, Na is used in water (2 * 200 milliliters) washing
2SO
4Drying, evaporation concentration.
Separate in the enterprising circumstances in which people get things ready for a trip spectrum of silica gel with hexane/diethyl ether (85: 15), get compound shown in the title.Rf value=0.3(silica gel; Diethyl ether/hexane 2: 1) boiling point 148-150 °/0.03 holder.
Example 6:2,4-dimethyl tetrahydro thiophene-3-ketone
2, the cyclisation of 5-dimethyl-3-thiophene hexanodioic acid
1) uses the Fe powder
With 100 part 2,5-dimethyl-3-thiophene hexanodioic acid and 7.5 parts of iron powders are 180-220 ° of heating.The gained overhead product is dissolved in CH
2Cl
2, use saturated NaHCO
3Solution washing is used Na
2SO
4Dry.Distillation title compound when 2 holders, temperature is 39-40 °.
2) use Ba(OH)
2
With 0.94 mole 2,5-dimethyl-3-thiophene hexanodioic acid and 10 gram Ba(OH)
2Mixture placed the matrass stirring heating 24 hours, temperature is 230-250 °.Overhead product extracts with diethyl ether, and under reduced pressure, drying (is used MgSO
4) and the distillation ethereal solution, boiling point is 39-40 ° during 2 holders.
3) use acetic anhydride
With 0.5 mole 2,5-dimethyl-3-thiophene hexanodioic acid, 300 milliliters of acetic anhydride and 4 gram LiCl stirred 6 hours at 120 °.Crude mixture is poured on ice, adds 10 cubic centimetres of vitriol oils.Then mixture is stirred and spend the night, make it be alkalescence, with the ice cube cooling, several times with the diethyl ether extraction with concentrated NaOH solution.Ether washes with water mutually, uses MgSO
4Drying is used evaporation concentration.Residue distills with Vigreux column, gets title compound, and boiling point is 81-88 ° during 20 holders.
Example 7:2,5-dimethyl-3-thiophene hexanodioic acid
In the solution of 320 gram (8 moles) NaOH and 1300 ml waters, in 15 minutes, add 424 gram (4 moles) thiolactic acids.Slow down back (35 °) in thermopositive reaction, add 344 gram (4 moles) methacrylic acids, then stirred reaction mixture 18 hours in the time of 80 °.
Mixture is chilled to 50 °, is poured on the mixture of 3 kilograms of ice and 750 milliliters of dense HCl, use 1000 milliliters of CH at every turn
2Cl
2Extraction, coextraction 4 times.CH
2Cl
2Extract Na
2SO
4Drying, organic phase concentrates with rotating the rapid evaporation method, generates compound shown in the title, and fusing point 78-80 °, clear crystal.
Example 8:2,5-dimethyl tetrahydro thiophene-3-ketone
1) uses tertiary amine
In the mixture of 0.2 mole of thiolactic acid and 0.2 mole of methacrylic acid, splash into 0.2 mole of tributylamine, make temperature of reaction rise to 60 °.Make reaction mixture 150-160 ° of heating 1 hour, heat is to 210-220 ° then.Under these conditions, the distillation title compound, the mixture of water and tributylamine, temperature is 150-170 °, and mixture is dissolved in ethyl acetate, and dilute with water neutralizes with 10%HCl.Organic phase 2N NaOH extraction, washing are to neutral, and drying is also used evaporation concentration.Residue distillation when 15 holders generates compound shown in the title, and boiling range is 70-73 ℃.
2) with iron acetate (II)
The mixtures of 85.9 gram thiolactic acids, 70.0 gram methacrylic acids and 0.8 gram iron acetate are stirred and heat 1 hour to 150 °-160 °.Add 0.8 gram iron acetate again, reheat two hours, temperature rises to 200 °-210 ℃, generates 103.9 gram overhead products.Make it be dissolved in 200 milliliters of hexanaphthenes, make it be alkalescence with sodium hydroxide, and in separating funnel, separate.Containing water extracts with 100 milliliters of hexanaphthenes.The bonded organic layer washes with water, uses MgSO
4Drying, evaporation when 15 holders generates title compound.
Dichloromethane extraction is used in waterbearing stratum spirit of salt acidifying.Extract washes with water, uses MgSO
4Drying, evaporation when 15 holders, the mixture of generation 10.6 gram methacrylic acids and thiolactic acid, its ratio is 2: 1.
Example 9:N-(1-methoxy third-2-yl)-2,4-dimethyl-3-aminothiophene
With 2 gram (0.01 mole) N-(1-methoxies, third-2-base-2, the solution of 4-dimethyl tetrahydro thiophene-3-subunit imines in 3 gram tetracol phenixin stirred one hour under room temperature and oxygen atmosphere.Consume O
2200 milliliters, the nuclear magnetic resonance spectrum of solution is in aromatics part no signal.Under 0.2 holder and 150 ° of-180 ° of free air temperatures, this product of distillation in bulb, compound shown in the generation title.
Errata
Claims (19)
1, the method for making of formula II compound
R is C in the formula
1-4Alkoxy-C
2-4Alkyl, wherein, C
1-4At least 2 the C atoms of being separated by between alkoxyl group and the N atom that is connected R, R
2And R
4Be respectively CH
3Or C
2H
5, R
5Be H or CH
3Even this method for making formula I compound dehydrogenation
R, R in the formula
2, R
4And R
5Definition is described with this claim.
2,, produce formula III compound according to the method for making of the 1st claim
R, R in the formula
2, R
4And R
5Definition is described with the 1st claim.This method for making is the dehydrogenation of wushu I compound, and production II compound carries out the N-chloroacetylation with gained formula II compound again.
3, according to the method for making of the 1st or 2 claim, its Chinese style I compound is by the tetrahydro thiophene-3-ketone of formula IV
(R in the formula
2, R
4And R
5Definition is described with first claim) with the amine of formula V
(the R definition is described with first claim in the formula) reaction makes.
4, according to the method for making of the 1st to 3 claim, its Chinese style IV compound is made by the cyclisation of formula VI compound.
R in the formula
2, R
4And R
5Definition is described with first claim.
5, according to the method for making of the 4th claim, its Chinese style VI compound is by formula VII compound
(R in the formula
2Definition is described with first claim) and formula VIII compound
(R in the formula
4And R
5Definition is described with first claim) addition makes.
6, according to the method for making of the 4th or the 5th claim, the addition of its Chinese style VII compound and formula VIII compound and the cyclisation of formula VI compound are all in tertiary amine or Fe, Ni(II) or the Co(II) acetate carry out when existing.
7, according to the method for making of the 6th claim, wherein addition and cyclization are in Fe, Ni(II) or the Co(II) acetate carry out when existing.
8, according to each method for making in the 1st to 7 claim, the dehydrogenation O of its Chinese style I compound
2Or oxidizer catalytic is carried out.
9, according to the method for making of the 8th claim, dehydrogenation is carried out under catalytic condition.
10, according to the method for making of the 8th claim, dehydrogenation is carried out with oxygenant.
11, according to the method for making of the 10th claim, oxygenant is selected for use from sulphur, thionyl chloride and sulfuryl chloride.
12, according to the method for making of the 11st claim, oxygenant is a thionyl chloride.
13, according to the method for making of the 1st to 12 claim, or the II compound carries out chloroacetylation with the hydrochloride form.
14, the method for making of each that requires according to aforesaid right is produced N-(2,4-thioxene-3-yl)-N-(1-methoxy the third-2 base)-chlor(o)acetamide.
15, formula I compound is as described in the 1st claim.
16, formula IV compound is as described in the 3rd claim.
17, formula VI compound is as described in the 4th claim.
18, according to each the compound in the 15th to 17 claim, produce formula III compound.
19, according to the compound of the 15th to 18 claim, wherein R is 1-methoxy propyl-2-base, R
2Be CH
3, R
4Be CH
3, R
5Be hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85106474A CN1013113B (en) | 1983-12-20 | 1985-08-29 | Process for the preparation of n-thienyl chloroacetamides |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH6760/83A CH657129A5 (en) | 1983-12-20 | 1983-12-20 | Process for preparing N-thienylchloroacetamides |
| CN85106474A CN1013113B (en) | 1983-12-20 | 1985-08-29 | Process for the preparation of n-thienyl chloroacetamides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85106474A true CN85106474A (en) | 1987-04-29 |
| CN1013113B CN1013113B (en) | 1991-07-10 |
Family
ID=25700129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85106474A Expired CN1013113B (en) | 1983-12-20 | 1985-08-29 | Process for the preparation of n-thienyl chloroacetamides |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1013113B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397395A (en) * | 2016-08-31 | 2017-02-15 | 帕潘纳(北京)科技有限公司 | Method for preparing 2,4-dimethyl thiophane-3-ketone |
| CN106749168A (en) * | 2016-12-31 | 2017-05-31 | 帕潘纳(北京)科技有限公司 | A kind of method for preparing the ketone of 2,4 dimethyl tetrahydro thiophene 3 |
| CN108084148A (en) * | 2017-11-15 | 2018-05-29 | 凯莱英医药集团（天津）股份有限公司 | The preparation method of substituted thiophene -3- ketone compounds |
| CN108148041A (en) * | 2017-11-15 | 2018-06-12 | 凯莱英医药集团（天津）股份有限公司 | The continuity synthetic method of substituted thiophene -3- ketone compounds |
| CN110066268A (en) * | 2018-01-22 | 2019-07-30 | 北京颖泰嘉和生物科技股份有限公司 | The preparation method of 3- amino -2,4- thioxene |
| CN113024505A (en) * | 2019-12-25 | 2021-06-25 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of dimethenamid |
-
1985
- 1985-08-29 CN CN85106474A patent/CN1013113B/en not_active Expired
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397395A (en) * | 2016-08-31 | 2017-02-15 | 帕潘纳(北京)科技有限公司 | Method for preparing 2,4-dimethyl thiophane-3-ketone |
| CN106397395B (en) * | 2016-08-31 | 2018-09-04 | 帕潘纳(北京)科技有限公司 | A method of preparing 2,4- dimethyl tetrahydro thiophene -3- ketone |
| CN106749168A (en) * | 2016-12-31 | 2017-05-31 | 帕潘纳(北京)科技有限公司 | A kind of method for preparing the ketone of 2,4 dimethyl tetrahydro thiophene 3 |
| CN106749168B (en) * | 2016-12-31 | 2019-02-01 | 帕潘纳(北京)科技有限公司 | A method of preparing 2,4- dimethyl tetrahydro thiophene -3- ketone |
| CN108084148A (en) * | 2017-11-15 | 2018-05-29 | 凯莱英医药集团（天津）股份有限公司 | The preparation method of substituted thiophene -3- ketone compounds |
| CN108148041A (en) * | 2017-11-15 | 2018-06-12 | 凯莱英医药集团（天津）股份有限公司 | The continuity synthetic method of substituted thiophene -3- ketone compounds |
| CN110066268A (en) * | 2018-01-22 | 2019-07-30 | 北京颖泰嘉和生物科技股份有限公司 | The preparation method of 3- amino -2,4- thioxene |
| CN110066268B (en) * | 2018-01-22 | 2020-11-06 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of 3-amino-2, 4-dimethylthiophene |
| CN113024505A (en) * | 2019-12-25 | 2021-06-25 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of dimethenamid |
| CN113024505B (en) * | 2019-12-25 | 2022-03-01 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of dimethenamid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1013113B (en) | 1991-07-10 |
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