CN1220678C - Prepn of N-alkoxyl carbonyl isothiocyanate and its derivative - Google Patents
Prepn of N-alkoxyl carbonyl isothiocyanate and its derivative Download PDFInfo
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- CN1220678C CN1220678C CN 03118386 CN03118386A CN1220678C CN 1220678 C CN1220678 C CN 1220678C CN 03118386 CN03118386 CN 03118386 CN 03118386 A CN03118386 A CN 03118386A CN 1220678 C CN1220678 C CN 1220678C
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Abstract
The present invention relates to a method for preparing N-alkoxyl carbonyl isothiocyante, which comprises: chloroformate and thiocyanate carry out a reaction under the existence of water or an organic solvent and di (4-N, N-dialkyl aminophenyl) methane in catalytic quantity to generate the intermediate product of the N-alkoxyl carbonyl isothiocyante; the intermediate products then react with alcohol, amine, thiol or thiophenol compounds to generate the derivatives of the N-alkoxyl carbonyl isothiocyante. A catalyst used by the present invention has the characteristic of high reaction efficiency. Because the catalyst is solid and has the advantages of low volatility, low toxicity and easy subsequent treatment, the obtained product has high purity.
Description
[technical field] the present invention relates to the preparation of lsothiocyanates and derivative thereof, relate generally to improving one's methods of preparation N--oxyl carbony isorhodanate and derivative thereof, its principal character is to use two (4-N, N-dialkyl amido phenyl) methane as catalyzer in reaction process.
[background technology] from R.E.Doran with Vinyl chloroformate and plumbous rhodanate was the synthetic N-ethoxy carbonyl lsothiocyanates of raw material first in 1896 in ebullient toluene since, synthesizing N--oxyl carbony isorhodanate with haloformate and rhodanide reaction had become the main method for preparing N--oxyl carbony isorhodanate and derivative thereof.
U.S. Pat 4,659,853 disclose a kind ofly in the presence of solvent or water and catalyzer, make haloformate and thiocyanate-(comprising basic metal, alkaline-earth metal and lead or ammonium salt) reaction generate the lsothiocyanates intermediate, and then with general formula be R
1Compound (the R of-Y-H
1Be alkyl, aryl or alkoxyl group, Y is sulphur, oxygen or NR
2, R
2Be hydrogen or R
1) reaction generates the preparation method of N-alkoxy carbonyl isothiocyanic acid ester derivative.The catalyzer that is suitable for comprises pyridine, quinoline, pyrimidine, piperazine, quinoxaline etc.
U.S. Pat 4,778,921 disclose a kind of method that makes haloformate and thiocyanate-prepared in reaction alkoxyl group and aryloxy lsothiocyanates in the presence of water and catalyzer, and used catalyzer comprises the single six-membered rings that contains 1 or 2 nitrogen-atoms or the heteroaromatic compound of ten yuan of fused polycycle.
U.S. Pat 6,066,754, U.S. Pat 6,184,412 public affairs and Chinese patent (publication number) CN1277190 disclose a kind of at N, the existence of N-dialkyl arylamine and solvent prepares the method for N-alkoxyl group (or aryloxy) carbony isorhodanate derivative down, comprising: a) at N, make haloformate and rhodanide reaction prepare N-alkoxyl group (or aryloxy) carbony isorhodanate under the existence of N-dialkyl arylamine and aqueous solvent or organic solvent; B) be R with lsothiocyanates intermediate and general formula
4Compound (the R of-Y-H
4Be C
1-C
10Alkyl, C
6-C
10Aryl or C
1-C
8Alkoxyl group, Y are sulphur, oxygen or NR
5, R
5Be hydrogen or R
4) reaction generation N-alkoxyl group (or aryloxy) carbony isorhodanate derivative.
Catalyst system therefor exists in varying degrees that reaction efficiency is lower, catalyzer is removed difficulty in treating process, contains problems such as the wastewater toxicity of catalyzer is bigger in the preparation method of above-mentioned various N--oxyl carbony isorhodanates and derivative thereof.
[summary of the invention] the purpose of this invention is to provide a kind of method of using effective catalyst to prepare N--oxyl carbony isorhodanate and derivative thereof with high-level efficiency.
The present invention uses two (4-N, N-dialkyl amido phenyl) methane is catalyzer, chloro-formic ester, thiocyanate-are reacted in the presence of water or organic solvent, temperature of reaction is-15 ℃～60 ℃, preferred-5 ℃～15 ℃, generates N--oxyl carbony isorhodanate intermediate product, with this intermediate product and alcohols, amine, mercaptan or phenyl-sulfhydrate compounds reaction, generate N--oxyl carbony isorhodanate derivative, temperature of reaction is 0 ℃～120 ℃, preferred 30 ℃～55 ℃.
Described catalyst molecule general formula is:
4 R wherein
1Independently of one another, represent methylidene or ethyl separately.
Described intermediate product--N--oxyl carbony isorhodanate general molecular formula is:
R wherein
2Represent C
1-C
8Alkyl, C
2-C
4Alkenyl or C
6-C
10Aryl.
Described alcohols, amine, mercaptan or phenyl-sulfhydrate compounds general formula are:
R
3-Y-H
R wherein
3Represent C
1-C
12Alkyl or alkoxyl group, C
6-C
12Aryl or aralkyl, Y represents oxygen, sulphur or NR
4, R wherein
4Represent hydrogen or R
3
Described N--oxyl carbony isorhodanate derivative general formula is:
R in the formula
2Represent C
1-C
8Alkyl, C
2-C
4Alkenyl or C
6-C
10Aryl, R
3Represent C
1-C
12Alkyl or alkoxyl group, C
6-C
12Aryl or aralkyl.
Described chloro-formic ester is selected from one group of chloro-formic ester compound of methyl esters, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, pentyl ester, own ester, 2-ethylhexyl, phenyl ester, benzyl ester and the allyl ester composition of chloroformic acid.
Described thiocyanate-is selected from one group of sulfocyanate compound of Sodium Thiocyanate 99, potassium sulfocyanate and ammonium thiocyanate and plumbous rhodanate composition.
The amount of described two (4-N, N-dialkyl amido phenyl) methane is 0.1～25% of a chloro-formic ester mole number, preferred 1%～5%.
Catalyzer of the present invention has the high characteristics of reaction efficiency, and because catalyzer is a solid, and volatility is little, toxicity is low, is easy to subsequent disposal, the product purity height that utilizes the present invention to obtain.
[embodiment] the present invention further specified by the following example, but be not subjected to the restriction of these embodiment.All umbers and percentage ratio all refer to quality except as otherwise herein provided among the embodiment.
The preparation (catalyst neutralisation) of embodiment 1 N-ethoxy carbonyl lsothiocyanates
With 3.8 parts of purity is that two (4-N, N-dimethylaminophenyl) methane of 98% join in the solution of NaSCN in 50 parts of water of 43.2 parts of purity 98.5%, under agitation this mixture is cooled to-1 ℃～5 ℃ temperature approximately then.55.1 part 98.5% Vinyl chloroformate is added in the reaction mixture in this temperature range and under stirring.After this adds step,, be cooled to about 0 ℃ temperature then with reaction mixture stirring reaction 3 hours under about 2 ℃～5 ℃ temperature.Add in the reaction mixture (with catalyst neutralisation) in about 15 minutes being cooled to the about 0 ℃ solution of 3.1 parts of sulfuric acid dissolutions in 50 parts of water.Subsequently under about 0 ℃ temperature with mixture stir about 15 minutes, stopped to stir this mixture of relief standing demix under about 0 ℃ temperature about 30 minutes.This mixture separation becomes water and organic phase.After water was removed in separation, the organic phase of gained was needed N-ethoxy carbonyl isothiocyanic acid ester products.Liquid-phase chromatographic analysis shows that the yield based on Vinyl chloroformate is 96.8%.
The preparation (catalyst neutralisation) of embodiment 2 N-ethoxy carbonyl-O-second thiocarbonyl group carbamate
To join in 115 parts of ethanol by the N-ethoxy carbonyl isothiocyanic acid ester products of embodiment 1 preparation, the temperature maintenance that makes reaction mixture simultaneously is between about 25 ℃～45 ℃.Then under about 40 ℃～45 ℃ temperature with reaction mixture stir about 2 hours.
The liquid-phase chromatographic analysis of the ethanolic soln of the N-ethoxy carbonyl of gained-O-second thiocarbonyl group carbamate shows that the yield based on Vinyl chloroformate is 94.6%.
The preparation (not catalyst neutralisation) of embodiment 3 N-ethoxy carbonyl-O-iprotiazem carbonylamino manthanoate
With 28 parts of purity is that two (4-N, N-dimethylaminophenyl) methane of 98% join in the solution of NaSCN in 1000 parts of water of 475 parts of purity 98%, under agitation this mixture is cooled to-1 ℃～5 ℃ temperature approximately then.600 part 98.5% Vinyl chloroformate is added in the reaction mixture in this temperature range and under stirring.After adding step, with reaction mixture about 3 ℃～8 ℃ stirring reactions 4 hours.Leaving standstill under about 3 ℃～about 12 ℃ temperature then makes it be separated into water and organic phase.After separating lower floor's water, under agitation with in about 1 hour add 491 parts of Virahols in organic phase, the temperature maintenance that makes reaction mixture simultaneously is between about 8 ℃～about 15 ℃.Organic mixture continued stirring reaction about 3 hours under about 45 ℃～55 ℃ temperature then.
The liquid-phase chromatographic analysis of the aqueous isopropanol of the N-ethoxy carbonyl of gained-O-iprotiazem carbonylamino manthanoate shows that the yield based on Vinyl chloroformate is 94.1%.
The preparation of embodiment 4 N-ethoxy carbonyl-O-iprotiazem carbonylamino manthanoate
With 3.8 parts of purity is that 98% two (4-N, the N-dimethylaminophenyl) methane and the powdery NaSCN of 43.2 parts of purity 98.5% add in 150.3 parts of Virahols, under agitation this mixture is cooled to about 8 ℃～12 ℃ temperature then.55.1 part 98.5% Vinyl chloroformate is added in the reaction mixture in this temperature range and under stirring.After adding step, with reaction mixture about 10 ℃～15 ℃ stirring reactions 4 hours.Make reaction mixture under about 45 ℃～55 ℃ temperature, continue stirring reaction about 2 hours afterwards.Filtering separation is fallen the solid sodium chloride that reaction generates then, and needed N-ethoxy carbonyl-O-iprotiazem carbonylamino manthanoate is in filtrate, and liquid-phase chromatographic analysis shows that the yield based on Vinyl chloroformate is 91.5%.
The preparation of embodiment 5 N-ethoxy carbonyl-N '-ethyl thioureas
With 35 parts of purity is that two (4-N, N-dimethylaminophenyl) methane of 98% join in the solution of NaSCN in 600 parts of water of 475 parts of purity 98%, under agitation this mixture is cooled to-1 ℃～3 ℃ temperature approximately then.600 part 98.5% Vinyl chloroformate is added in the reaction mixture in this temperature range and under stirring.After adding step, with reaction mixture about 2 ℃～5 ℃ stirring reactions 5 hours.Then temperature of reaction is reduced to-1 ℃～about 3 ℃ approximately, under this temperature range and stirring, add the solution of ethamine in 400 parts of water of 361 parts of purity 70%.After adding step, continued stirring reaction 1 hour.Centrifugation then promptly gets N-ethoxy carbonyl-N '-ethyl thiourea solid product.Liquid-phase chromatographic analysis shows that the yield based on Vinyl chloroformate is 94.8%.
Claims (8)
1. the preparation method of N--oxyl carbony isorhodanate and derivative thereof, it is characterized in that: using two (4-N, N-dialkyl amido phenyl) methane is catalyzer,
A) chloro-formic ester, thiocyanate-are reacted in the presence of water or organic solvent, temperature of reaction is-15 ℃～60 ℃, generates N--oxyl carbony isorhodanate;
B) with this intermediate product and alcohols, amine, mercaptan or phenyl-sulfhydrate compounds reaction, temperature of reaction is 0 ℃～120 ℃, generates N--oxyl carbony isorhodanate derivative.
2. method according to claim 1 is characterized in that: described catalyst molecule general formula is:
4 R wherein
1Independently of one another, represent methylidene or ethyl separately.
3. method according to claim 1 is characterized in that: described intermediate product--N--oxyl carbony isorhodanate general molecular formula is:
R wherein
2Represent C
1-C
8Alkyl, C
2-C
4Alkenyl or C
6-C
10Aryl.
4. method according to claim 1 is characterized in that: described alcohols, amine, mercaptan or phenyl-sulfhydrate compounds general formula are:
R
3-Y-H
R wherein
3Represent C
1-C
12Alkyl or alkoxyl group, C
6-C
12Aryl or aralkyl; Y represents oxygen, sulphur or NR
4, R wherein
4Represent hydrogen or R
3
5. method according to claim 1 is characterized in that: described N--oxyl carbony isorhodanate derivative general formula is:
R in the formula
2Represent C
1-C
8Alkyl, C
2-C
4Alkenyl or C
6-C
10Aryl; R
3Represent C
1-C
12Alkyl or alkoxyl group, C
6-C
12Aryl or aralkyl; Y represents oxygen, sulphur or NR
4, R wherein
4Represent hydrogen or R
3
6. method according to claim 1 is characterized in that: described chloro-formic ester is selected from one group of chloro-formic ester compound of methyl esters, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, pentyl ester, own ester, 2-ethylhexyl, phenyl ester, benzyl ester and the allyl ester composition of chloroformic acid.
7. method according to claim 1 is characterized in that: described thiocyanate-is selected from one group of sulfocyanate compound of Sodium Thiocyanate 99, potassium sulfocyanate and ammonium thiocyanate and plumbous rhodanate composition.
8. method according to claim 1 is characterized in that: the amount of described two (4-N, N-dialkyl amido phenyl) methane is 0.1～25% of a chloro-formic ester mole number.
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|---|---|---|---|
| CN 03118386 CN1220678C (en) | 2003-05-16 | 2003-05-16 | Prepn of N-alkoxyl carbonyl isothiocyanate and its derivative |
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|---|---|---|---|
| CN 03118386 CN1220678C (en) | 2003-05-16 | 2003-05-16 | Prepn of N-alkoxyl carbonyl isothiocyanate and its derivative |
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|---|---|
| CN1548418A CN1548418A (en) | 2004-11-24 |
| CN1220678C true CN1220678C (en) | 2005-09-28 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334131C (en) * | 2005-03-23 | 2007-08-29 | 中南大学 | Process for preparing polyester-base thiourea resin |
| AU2008214151B2 (en) | 2007-02-07 | 2012-08-02 | Cytec Technology Corp. | Novel dithiocarbamate collectors and their use in the benefication of mineral ore bodies |
| CN101367755B (en) * | 2007-08-16 | 2011-02-16 | 北京天任瑞创科技发展有限公司 | Process for preparing thiocarbamate |
| CN102167675B (en) * | 2011-03-21 | 2013-06-26 | 中南大学 | Methods for preparing N-alkoxycarbonyl isothiocyanate and derivative thereof |
| CN104761479B (en) * | 2015-03-04 | 2017-01-18 | 沈阳有研矿物化工有限公司 | Synthesis process for ethoxy carbonyl isothiocyanate |
| CN105481740B (en) * | 2015-12-24 | 2017-11-07 | 海利贵溪化工农药有限公司 | The preparation method of isothiocyano methyl formate |
| CN105665148B (en) * | 2016-01-15 | 2018-05-04 | 中南大学 | A kind of isocyanate derivative and its preparation method and application |
| CN112209862A (en) * | 2020-10-28 | 2021-01-12 | 沈阳有色金属研究院有限公司 | Preparation process of alkoxycarbonyl thiourea |
| CN114835617A (en) * | 2022-05-25 | 2022-08-02 | 重庆康普化学工业股份有限公司 | Method for synthesizing fruit essence by using phosgene as raw material |
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