CN1153774A - Preparation method of thiocarbamate compound - Google Patents
Preparation method of thiocarbamate compound Download PDFInfo
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- CN1153774A CN1153774A CN 96106463 CN96106463A CN1153774A CN 1153774 A CN1153774 A CN 1153774A CN 96106463 CN96106463 CN 96106463 CN 96106463 A CN96106463 A CN 96106463A CN 1153774 A CN1153774 A CN 1153774A
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Abstract
A preparation method of a thiocarbamate compound, which is used for preparing the thiocarbamate compound of a mineral dressing medicament. The method is characterized in that: in the synthesis process, the multi-carbon alcohol which finally reacts with isothiocyanate to generate thiocarbamate is used as a solvent to dissolve thiocyanate, and the multi-carbon alcohol is used as a homogeneous medium in the whole reaction process. The basic reactions of the method can be carried out in the same device and the same medium, the intermediates with high toxicity are all sealed in the same reaction system, separation and purification are not needed, the operation environment is improved, the phase transfer agents tetrabutyl ammonium bromide and water are not used, the repeated dehydration process of the intermediates is omitted, sewage discharge is avoided, water treatment equipment is saved, the intervention of impurities in the process is reduced, the product quality and the yield are improved, the reaction time is shortened, and the production efficiency is greatly improved.
Description
A kind of preparation method of thioamino-formates compounds relates to a kind of preparation method who is used in particular for the thioamino-formates compounds of beneficiation reagent.
Thioamino-formates compounds is a kind of very important mines beneficiation reagent, Cyanamid Co. in the manufacturer U.S. that produces this medicament has the top standard at the producer mask of this product at present, in the patent documentation of the US4479903 of the said firm, disclosed topmost compound in this compounds
Synthetic method, and become the main method of synthetic this compounds, its synthesis technique is roughly:
1. at first that sodium sulfocynanate (NaSCN) is soluble in water, adopt Tetrabutyl amonium bromide as phase-transfer catalyst, make sodium sulfocynanate can enter in the organic phase, controlled temperature, make the chlorallylene reaction in itself and the organic phase, preparation artificial mustard oil intermediate, reaction process is:
2. heat up, reflux, carry out the isomerization process of thiocyanic ester, add water cooling again to lsothiocyanates.
3. above-mentioned reactant is left standstill, separate, remove water.
4. organic phase is warmed up to again residual water of 100 ℃ of pressure reducing and steaming and excessive chlorallylene.
5. add water content less than 0.15% isopropylcarbinol, add tetrabutyl titanate and make catalyzer, under 110 ℃ of temperature, itself and lsothiocyanates are reacted, reaction formula is:
Get the finished product.
Above-mentioned technology is a kind of effective method for preparing thioamino-formates compounds, obtained the wide industrial application, but since the restriction of the technology that above-mentioned technology adopts itself, the production cost of products height, cause valuable product, limited the industrial application of product.Also there is following obvious deficiency in the aforesaid method, mainly contains:
1. technology more complicated, reactions steps is many, and process is discontinuous.
2. adopt Tetrabutyl amonium bromide as phase-transfer catalyst, sodium sulfocynanate is entered in the organic phase, help
3. phase-transfer catalyst also runs off with water, increases production cost on the one hand, also can produce environment on the other hand and pollute.
4. because thiocyanic ester are balanced reactions to the isomerization reaction of lsothiocyanates, the raising temperature helps the carrying out of isomerization reaction, but there is the lower boiling azeotrope to form at aqueous phase, temperature of reaction can only reach 90 ℃ under the normal pressure, reflux temperature can only be about 90 ℃, because reflux temperature is low, be unfavorable for the carrying out of isomerization reaction, limited the raising of product yield.
5. owing to also have the water that does not eliminate after being separated, must reheat to 100 a ℃ decompression steam, the fraction of reaction intermediate also will be sneaked in the water that steams in this course, poisonous intermediate worsens operating environment in this treating processes, the water that steams must increase the difficulty of technology through handling.
Purpose of the present invention is exactly for above shortcomings among the preparation method who overcomes present thioamino-formates compounds, provide a kind of technology simple, can reduce cost effectively, can eliminate the discharge of the nuisance that intermediate produces in the processed repeatedly, and improve Working environment effectively, reduce the preparation method of a kind of new thioamino-formates compounds that pollutes.
The objective of the invention is to be achieved through the following technical solutions.
A kind of preparation method of thioamino-formates compounds, comprise and adopt thiocyanate-and halohydrocarbons reaction generation thiocyanic ester, temperature rising reflux to make the thiocyanic ester isomery become lsothiocyanates and higher alcohols and lsothiocyanates reaction to generate sulfo-amido formate process, it is characterized in that: the higher alcohols that adopts final and lsothiocyanates reaction generation sulfo-amido formate in building-up process is as the dissolution with solvents thiocyanate-, and in entire reaction course, make equal phase medium with this higher alcohols, its technological process is followed successively by:
A. thiocyanate-is dissolved in the higher alcohols, splashes into halohydrocarbon again and prepare thiocyanic ester, processing condition are:
Thiocyanate-: higher alcohols=1: 2～10 (mol ratio);
Thiocyanate-: halohydrocarbon=1: 1.1～2 (mol ratio)
Temperature of reaction: 30～80 ℃
B. temperature rising reflux makes the thiocyanic ester isomery become lsothiocyanates, and processing condition are:
Reflux temperature: 80～140 ℃
Reaction times: 2～10 hours
C. heat up, reflux, lsothiocyanates and higher alcohols are reacted, generate the sulfo-amido formate,
Temperature of reaction: 110 ℃～170 ℃,
Return time: 2～12 hours,
D. cool off, remove by filter the salt that generates in the reaction process,
E. higher alcohols and excessive halohydrocarbon are reclaimed in distillation, and remaining is sulfo-amido formate product of the present invention.
When lsothiocyanates and higher alcohols react, preferably add catalyzer (RO) mTi (Cl) n, RO is the alkoxyl group of four carbon in the formula, and m+n=4,
In the method for the present invention, the thiocyanate-of use comprises potassium sulfocyanate, Sodium Thiocyanate 99, ammonium thiocyanate.
In the method for the present invention, the higher alcohols of use comprises four carbon alcohols, five carbon alcohol, six carbon alcohol.
In the method for the present invention, the halohydrocarbon of use comprises hydrochloric ether and hydrobromic ether.
In the method for the present invention, the halohydrocarbon of use comprises the haloalkane of four carbon to nine carbon.
In the method for the present invention, the halohydrocarbon of use comprises the haloolefin of three carbon to nine carbon.
Owing in the method for the present invention, adopt the higher alcohols of carbon 4,, and, can make reaction because process is used excessive higher alcohols because the temperature of its boiling point generally all is higher than 90 ℃ to carbon 7
The preparation method of a kind of thioamino-formates compounds of the present invention adopts the equal phase medium of the higher alcohols of one of reaction raw materials as entire reaction, and its chemical reaction process is all being reacted in the phase medium.Because reaction is to carry out in alcohol,, make lsothiocyanates newly-generated in the process can carry out following reaction with the alcohol as medium simultaneously at any time simultaneously as the intervention in advance of the alcohol of reactant
Generate final product,, reduced the isothiocyanic acid ester concentration, make reaction because newly-generated lsothiocyanates constantly is consumed
Its primitive reaction of method of the present invention all can be at same device, carry out in the same medium, utilizing heats up continuously controls the carrying out of differential responses section, the intermediate that toxicity is bigger all is closed in the same reaction system, need not separate, purifying, operating environment is improved, do not use the consisting of phase-transferring agent Tetrabutyl amonium bromide to reduce cost in the reaction, reaction process does not make water, removed the intervention that water medium is arranged in original technology, save intermediate this process of processed repeatedly, without sewage discharge has been saved water treating equipment, solves the pollution of environment and the problem of severe operational environment, can also effectively cut down the consumption of energy, improve product yield, also shortened the reaction times, improved production efficiency widely.
The invention will be further described below in conjunction with specific embodiment.
The preparation method of a kind of thioamino-formates compounds of the present invention, comprise and adopt thiocyanate-and halohydrocarbons reaction generation thiocyanic ester, temperature rising reflux to make the thiocyanic ester isomery become lsothiocyanates and higher alcohols and lsothiocyanates reaction to generate sulfo-amido formate process, it is characterized in that: the higher alcohols that adopts final and lsothiocyanates reaction generation sulfo-amido formate in building-up process is as the dissolution with solvents thiocyanate-, and in entire reaction course, make equal phase medium with this higher alcohols, its technological process is followed successively by:
With thiocyanate-(can be Sodium Thiocyanate 99, potassium sulfocyanate, ammonium thiocyanate) 1 part, add in 2～10 parts the higher alcohols, under 30～80 ℃ of temperature, drip 1.1～2 parts of halohydrocarbon, halohydrocarbon is the haloolefin of four carbon to nine carbon haloalkanes, three carbon to nine carbon, particularly various replacements with unsubstituted chlorallylene for thing or bromo-derivative, the prepared in reaction thiocyanic ester.
Be warming up to 80～140 ℃ then, refluxed 2～10 hours, make the thiocyanic ester isomery become the lsothiocyanates reaction,
Then can add catalyzer (RO) mTi (Cl) n, controlled temperature refluxed 2～12 hours greater than 110 ℃～170 ℃, and lsothiocyanates and higher alcohols are reacted, and generated the sulfo-amido formate,
Cool off, remove by filter the salt that generates in the process,
Filtrate decompression distills out excessive higher alcohols and halohydrocarbon, makes sulfo-amido formate product of the present invention.
The resulting product of said process, productive rate can reach 85.46%, and purity reaches 97.7%, analyzes with GC/MS, and the product molecule is from the peak 173, the assorted peak of no intermediate in the infrared spectrum.
Embodiment 1
Raw material: Sodium Thiocyanate 99, isopropylcarbinol, chlorallylene,
Operating process:
In reactor, add 1 mole of isopropylcarbinol earlier, add 0.1 molar sulphur Zassol again, stir and heat up, under 30～40 ℃ of temperature, drip 0.2 mole of chlorallylene, drip off in 1 hour, temperature rising reflux, about 90～100 ℃, refluxed 2 hours, add 0.01 mol catalyst (RO) mTi (Cl) n (m+n=4) again, then heat up and under 110 ℃ of conditions, refluxed 12 hours, the sodium-chlor that cold filtration falls to generate, filtrate decompression distills out excessive pure and mild halohydrocarbon, and remaining is sulfo-amido formate 15 grams of the present invention.
Embodiment 2
Raw material: Sodium Thiocyanate 99, hexanol, allyl bromide 98,
Operating process:
In reactor, add 0.4 mole of hexanol earlier, add 0.2 molar sulphur Zassol again, stir and heat up, under 70～80 ℃ of temperature, drip 0.22 mole of allyl bromide 98,0.5 drip off in hour, temperature rising reflux, about 130～140 ℃, refluxed 10 hours, add 0.0001 mol catalyst (RO) mTi (Cl) n (m+n=4) again, refluxed 2 hours down at 160 ℃～170 ℃, the Sodium Bromide that cold filtration falls to generate, filtrate decompression distills out excessive pure and mild halohydrocarbon, and remaining is sulfo-amido formate 31 grams of the present invention.
Embodiment 3
Raw material: potassium sulfocyanate, mixed alcohol (butanols, amylalcohol, hexanol), chlorallylene,
Operating process:
In reactor, add earlier and mix alcohol (butanols 20%, amylalcohol 60%, hexanol 20%), add 0.2 molar sulphur potassium cyanate again, stir and heat up, under 50～60 ℃ of temperature, drip 0.3 mole of chlorallylene, drip off in 1 hour, then refluxed 5 hours at 110 ℃, add 0.001 mol catalyst (RO) mTi (Cl) n (m+n=4) again, refluxed 8 hours under 130 ℃ of temperature, other condition gets product 29.8 grams with example 1 again.
Embodiment 4
Raw material: ammonium thiocyanate, mixed alcohol (butanols, amylalcohol), chlorallylene,
Operating process:
In reactor, add 1 mole earlier and mix alcohol (butanols 30%, amylalcohol 70%), add 0.2 molar sulphur ammonium cyanate again, stirring is warmed up to 50 ℃, drip 0.4 mole of chlorallylene, drip in 1 hour, then under 100～110 ℃ of temperature, refluxed 6 hours, add 0.003 mol catalyst (Ro) mTi (cl) n (m+n=4) again, refluxed under 130 ℃ 6 hours, other condition gets product 29 grams with embodiment 1 again.
Embodiment 5
Raw material: Sodium Thiocyanate 99, amylalcohol, allyl bromide 98,
Operating process:
In reactor, add 1 mole of amylalcohol earlier, add 0.1 molar sulphur Zassol again, at 40～50 ℃, drip 0.2 mole of allyl bromide 98, drip in 1 hour, heat up and under 110 ℃ of temperature, refluxed 10 hours, then continuing heats up refluxed under 140 ℃ 12 hours again, do not add catalyzer, other condition gets product 12.1 grams with embodiment 1.
Embodiment 6
Raw material: Sodium Thiocyanate 99, amylalcohol, 1-phenyl-chlorallylene,
Operating process:
In reactor, add 1 mole of amylalcohol earlier, add 0.1 molar sulphur Zassol again, intensification drips 0.2 mole of 1-phenyl-chlorallylene down at 50 ℃, drip in 1 hour, intensification refluxed 10 hours under 110 ℃ of temperature, added 0.01 mol catalyst (RO) mTi (Cl) n (m+n=4) again, refluxed under 140 ℃ 12 hours again, other condition gets product 10.1 grams with embodiment 1.
Embodiment 7
Raw material: Sodium Thiocyanate 99, hexanol, bromotoluene,
Operating process:
In reactor, add 1 mole of hexanol earlier, add 0.1 molar sulphur Zassol again, stir and heat up, under 50～60 ℃, drip 0.2 mole of bromotoluene, drip in 1 hour, then heat up and under 140 ℃ of temperature, refluxed 10 hours, add 0.002 mol catalyst (RO) mTi (Cl) n (m+n=4), refluxed 12 hours at 160～170 ℃, other condition gets product 6.2 grams with embodiment 1.
Claims (25)
1. the preparation method of a thioamino-formates compounds, comprise and adopt thiocyanate-and halohydrocarbons reaction generation thiocyanic ester, temperature rising reflux to make the thiocyanic ester alienation become lsothiocyanates and higher alcohols and lsothiocyanates reaction to generate sulfo-amido formate process, it is characterized in that: the higher alcohols that adopts final and lsothiocyanates reaction generation sulfo-amido formate in building-up process is as the dissolution with solvents thiocyanate-, and in entire reaction course, make equal phase medium with this higher alcohols, its technological process is followed successively by:
A. thiocyanate-is dissolved in the higher alcohols, splashes into halohydrocarbon again and prepare thiocyanic ester, processing condition are:
Thiocyanate-: higher alcohols=1: 2～10 (mol ratio);
Thiocyanate-: halohydrocarbon=1: 1.1～2 (mol ratio)
Temperature of reaction: 30～80 ℃
B. temperature rising reflux makes the thiocyanic ester isomery become the lsothiocyanates processing condition to be:
Reflux temperature: 80～140 ℃
Reaction times: 2～10 hours
C. heat up, reflux, lsothiocyanates and higher alcohols are reacted, generate the sulfo-amido formate,
Temperature of reaction: 110 ℃～170 ℃
Return time: 2～12 hours,
D. cool off, remove by filter the salt that generates in the reaction process,
E. higher alcohols and excessive halohydrocarbon are reclaimed in distillation, and remaining is sulfo-amido formate product of the present invention.
2. the preparation method of a kind of thioamino-formates compounds according to claim 1 when it is characterized in that lsothiocyanates and higher alcohols react, preferably adds catalyzer (RO) mTi (Cl) n, and RO is the alkoxyl group of four carbon in the formula, m+n=4,
3. the preparation method of a kind of thioamino-formates compounds according to claim 1 is characterized in that the thiocyanate-that uses comprises potassium sulfocyanate.
4. the preparation method of a kind of thioamino-formates compounds according to claim 1 is characterized in that the thiocyanate-that uses comprises Sodium Thiocyanate 99.
5. the preparation method of a kind of thioamino-formates compounds according to claim 1 is characterized in that the thiocyanate-that uses comprises ammonium thiocyanate.
6. the preparation method of a kind of thioamino-formates compounds according to claim 1 is characterized in that the higher alcohols that uses comprises four carbon alcohols.
7. the preparation method of a kind of thioamino-formates compounds according to claim 1 is characterized in that the higher alcohols that uses comprises five carbon alcohol.
8. the preparation method of a kind of thioamino-formates compounds according to claim 1 is characterized in that the higher alcohols that uses comprises six carbon alcohol.
9. the preparation method of a kind of thioamino-formates compounds according to claim 1 is characterized in that the halohydrocarbon that uses comprises hydrochloric ether.
10. the preparation method of a kind of thioamino-formates compounds according to claim 1 is characterized in that the halohydrocarbon that uses comprises hydrobromic ether.
11. the preparation method of a kind of thioamino-formates compounds according to claim 1 is characterized in that the halohydrocarbon that uses comprises haloalkane.
12., it is characterized in that the haloalkane that uses comprises the haloalkane of four carbon according to the preparation method of claim 1 and the described a kind of thioamino-formates compounds of claim 11.
13., it is characterized in that the haloalkane that uses comprises the haloalkane of five carbon according to the preparation method of claim 1 and the described a kind of thioamino-formates compounds of claim 11.
14., it is characterized in that the haloalkane that uses comprises the haloalkane of six carbon according to the preparation method of claim 1 and the described a kind of thioamino-formates compounds of claim 11.
15., it is characterized in that the haloalkane that uses comprises the haloalkane of seven carbon according to the preparation method of claim 1 and the described a kind of thioamino-formates compounds of claim 11.
16., it is characterized in that the haloalkane that uses comprises the haloalkane of eight carbon according to the preparation method of claim 1 and the described a kind of thioamino-formates compounds of claim 11.
17., it is characterized in that the haloalkane that uses comprises the haloalkane of nine carbon according to the preparation method of claim 1 and the described a kind of thioamino-formates compounds of claim 11.
18. the preparation method of a kind of thioamino-formates compounds according to claim 1 is characterized in that the halohydrocarbon that uses comprises haloolefin.
19., it is characterized in that the halohydrocarbon that uses comprises the haloolefin of three carbon according to the preparation method of claim 1 and the described a kind of thioamino-formates compounds of claim 18.
20., it is characterized in that the halohydrocarbon that uses comprises the haloolefin of four carbon according to the preparation method of claim 1 and the described a kind of thioamino-formates compounds of claim 18.
21., it is characterized in that the halohydrocarbon that uses comprises the haloolefin of five carbon according to the preparation method of claim 1 and the described a kind of thioamino-formates compounds of claim 18.
22., it is characterized in that the halohydrocarbon that uses comprises the haloolefin of six carbon according to the preparation method of claim 1 and the described a kind of thioamino-formates compounds of claim 18.
23., it is characterized in that the halohydrocarbon that uses comprises the haloolefin of seven carbon according to the preparation method of claim 1 and the described a kind of thioamino-formates compounds of claim 18.
24., it is characterized in that the halohydrocarbon that uses comprises the haloolefin of eight carbon according to the preparation method of claim 1 and the described a kind of thioamino-formates compounds of claim 18.
25., it is characterized in that the halohydrocarbon that uses comprises the haloolefin of nine carbon according to the preparation method of claim 1 and the described a kind of thioamino-formates compounds of claim 18.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106463A CN1045086C (en) | 1995-11-02 | 1996-08-09 | Preparation method of thiocarbamate compound |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95117935.7 | 1995-11-02 | ||
| CN95117935 | 1995-11-02 | ||
| CN96106463A CN1045086C (en) | 1995-11-02 | 1996-08-09 | Preparation method of thiocarbamate compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1153774A true CN1153774A (en) | 1997-07-09 |
| CN1045086C CN1045086C (en) | 1999-09-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN96106463A Expired - Fee Related CN1045086C (en) | 1995-11-02 | 1996-08-09 | Preparation method of thiocarbamate compound |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225369A (en) * | 2011-05-18 | 2011-10-26 | 河南省岩石矿物测试中心 | Beneficiation method for separating copper-lead-zinc multi-metal complex ore embedded with fine particles |
| CN101759616B (en) * | 2009-04-27 | 2013-05-08 | 南通泰禾化工有限公司 | Method for producing and purifying triocarbamate liquid compound |
| CN104693083A (en) * | 2013-12-06 | 2015-06-10 | 沈阳有色金属研究院 | Improved preparation method of allyl thiocarbamate |
| CN106432022A (en) * | 2015-08-06 | 2017-02-22 | 北京天任瑞创科技发展有限公司 | Preparation method for alkyl xanthate allyl ester compound |
| CN108947880A (en) * | 2018-08-06 | 2018-12-07 | 青岛科技大学 | One kind being based on light-catalysed thiocarbamate compound preparation method |
| CN112934472A (en) * | 2021-01-28 | 2021-06-11 | 上海翱鹤矿业有限公司 | Preparation method and application of thiamine ester collecting agent |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061276B (en) * | 2015-08-14 | 2017-05-24 | 沈阳有研矿物化工有限公司 | Synthetic process of N-allyl-O- isobutyl thionocarbamate |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU507566A1 (en) * | 1974-09-06 | 1976-03-25 | Предприятие П/Я А-7253 | The method of obtaining-methyl-o-isopropylthionocarbamate |
| ZA794780B (en) * | 1978-10-05 | 1981-04-29 | British Petroleum Co | Mass transfer equipment |
| US4479903A (en) * | 1982-08-23 | 1984-10-30 | American Cyanamid Company | Process for the preparation of N-allyl-O-alkyl thionocarbamates |
| DE69221698T2 (en) * | 1991-10-15 | 1998-02-19 | Du Pont | Process for the preparation of sulfonylureas |
-
1996
- 1996-08-09 CN CN96106463A patent/CN1045086C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759616B (en) * | 2009-04-27 | 2013-05-08 | 南通泰禾化工有限公司 | Method for producing and purifying triocarbamate liquid compound |
| CN102225369A (en) * | 2011-05-18 | 2011-10-26 | 河南省岩石矿物测试中心 | Beneficiation method for separating copper-lead-zinc multi-metal complex ore embedded with fine particles |
| CN104693083A (en) * | 2013-12-06 | 2015-06-10 | 沈阳有色金属研究院 | Improved preparation method of allyl thiocarbamate |
| CN104693083B (en) * | 2013-12-06 | 2017-03-29 | 沈阳有色金属研究院 | A kind of preparation method of improved pi-allyl thiocarbamate |
| CN106432022A (en) * | 2015-08-06 | 2017-02-22 | 北京天任瑞创科技发展有限公司 | Preparation method for alkyl xanthate allyl ester compound |
| CN106432022B (en) * | 2015-08-06 | 2017-09-01 | 北京天任瑞创科技发展有限公司 | The preparation method of alkyl xanthogenic acid pi-allyl ester type compound |
| CN108947880A (en) * | 2018-08-06 | 2018-12-07 | 青岛科技大学 | One kind being based on light-catalysed thiocarbamate compound preparation method |
| CN112934472A (en) * | 2021-01-28 | 2021-06-11 | 上海翱鹤矿业有限公司 | Preparation method and application of thiamine ester collecting agent |
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| CN1045086C (en) | 1999-09-15 |
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Owner name: BEIJING TIANREN RUICHUANG SCIENCE AND TECHNOLOGY D Free format text: FORMER OWNER: BEIJING GENERAL RESEARCH INSTITUTE OF MINING AND METALLURGY Effective date: 20100108 |
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Effective date of registration: 20100108 Address after: Room B107, science and technology building, 5 South Avenue, Beijing, Haidian District, Zhongguancun Patentee after: Beijing Tian Ren Rui Chuang Technology Development Co., Ltd. Address before: No.1, foreign language Hing Street, Beijing, Xizhimen Patentee before: Beijing General Research Institute of Mining & Metallurgy |
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