CN1045086C - Preparation method of thiocarbamate compound - Google Patents

Preparation method of thiocarbamate compound Download PDF

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Publication number
CN1045086C
CN1045086C CN96106463A CN96106463A CN1045086C CN 1045086 C CN1045086 C CN 1045086C CN 96106463 A CN96106463 A CN 96106463A CN 96106463 A CN96106463 A CN 96106463A CN 1045086 C CN1045086 C CN 1045086C
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thiocarbamate
carbon
preparation
roh
thiocyanate
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CN1153774A (en
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栾和林
姚文
武荣成
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Beijing Tian Ren Rui Chuang Technology Development Co Ltd
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Beijing General Research Institute of Mining and Metallurgy
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Abstract

A method for preparing thiocarbamate compounds, which is used for preparing thiocarbamate compounds of beneficiation reagents. The method is characterized in that: in the synthesis process, alcohol ROH (R ═ C) which finally reacts with isothiocyanate to generate thiocarbamate is adopted4-6Alkyl) as a solvent to dissolve the thiocyanate and to act as a homogeneous medium throughout the reaction. The reaction of the method can be carried out in the same device and the same medium, and the intermediates with high toxicity are all sealed in the same reaction system without separation and purification, thereby improvingThe method has the advantages of saving the operation environment, using no phase transfer agent tetrabutylammonium bromide and water, omitting the repeated dehydration process of the intermediate, having no sewage discharge, saving water treatment equipment, reducing the intervention of impurities in the process, improving the product quality and yield and greatly improving the production efficiency.

Description

Preparation method of thiocarbamate compound
A preparation method of thiocarbamate compounds, relating to a preparation method of thiocarbamate compounds especially used for mineral dressing medicaments.
Thiocarbamate compounds are important mine beneficiation reagents, and currently the Cyanamid Co, in the United states of the manufacturers producing such reagents, has a leading level in the production of the product, and in the company's US4479903 patent document, the most prominent compounds of this class are disclosedThe synthesis method of (2) and becomes a main method for synthesizing the compounds, and the synthesis process is approximately as follows:
① firstly dissolving sodium thiocyanide (NaSCN) in water, adopting tetrabutylammonium bromide as phase transfer catalyst to make sodium thiocyanide enter into organic phase, controlling temperature to make it react with allyl chloride in organic phase to prepare artificial mustard oil intermediate, the reaction process is:
and (3) nucleophilic reaction.
② heating, refluxing, isomerizing thiocyanate to isothiocyanate, and cooling with water.
③ the reaction mixture was allowed to stand, separated and the aqueous phase was removed.
④ the organic phase is warmed to 100 ℃ again and the residual water and excess allyl chloride are distilled off under reduced pressure.
⑤ adding isobutanol with water content less than 0.15%, adding titaniumTetrabutyl acid is used as a catalyst, and reacts with isothiocyanate at the temperature of 110 ℃, and the reaction formula is as follows:and obtaining a final product.
The technology is an effective method for preparing the thiocarbamate compound, and has been widely applied industrially, but the technology has the limitation of the adopted process, so the production cost of the product is high, the product price is high, and the industrial application of the product is limited. The above method also has the following obvious disadvantages, mainly:
① the process is complicated, the reaction steps are many, and the process is discontinuous.
② Tetrabutylammoniabromide is used as phase transfer catalyst to make sodium thiocyanide enter organic phase for reaction
The use of the phase transfer catalyst also increases the dissolution of the intermediate in the water phase, on one hand, the standing phase separation time is prolonged, on the other hand, the discharged water phase carries a large amount of toxic organic intermediate besides sodium chloride, which poses a threat to the environmental protection and increases the byproduct treatment process.
③ the phase transfer catalyst is lost with the water phase, which increases the production cost and pollutes the environment.
④ since the isomerization reaction of thiocyanate to isothiocyanate is a balanced reaction, the temperature is raised to favor the proceeding of isomerization reaction, but there is low boiling point azeotrope formed in water phase, the reaction temperature can only reach 90 ℃ under normal pressure, the reflux temperature can only be about 90 ℃, the reflux temperature is low to favor the proceeding of isomerization reaction, and the product yield is limited to be raised.
⑤ since there is water left unremoved after phase separation, it must be heated again to 100 deg.C and decompressed to distill, during this process, the distillate of reaction intermediate will be mixed into the distilled water, the toxic intermediate will deteriorate the operation environment during this process, the distilled water must be treated, increasing the difficulty of the process.
The invention aims to overcome the defects in the existing preparation method of the thiocarbamate compound, and provides a novel preparation method of the thiocarbamate compound, which has the advantages of simple process, effective cost reduction, capability of eliminating the discharge of harmful substances generated in the repeated dehydration treatment of an intermediate, effective improvement of the working environment and pollution reduction.
The purpose of the invention is realized by the following technical scheme.
A preparation method of thiocarbamate compounds comprises the steps of adopting thiocyanate MSCN to react with halogenated hydrocarbon R-X to generate thiocyanate, heating and refluxing to ensure that the thiocyanate is isomerized into isothiocyanate and alcohol ROH reacts with the isothiocyanate to generate thiocarbamate, and is characterized in that: m of thiocyanate MSCN being K, Na, NH4 +(ii) a R of halogenated hydrocarbon R-X is C3-9Hydrocarbyl, X is Cl, Br; r of the alcohol ROH is C4-6An alkyl group; in the synthesis process, ROH which finally reacts with isothiocyanate to generate thiocarbamate is used as a solvent to dissolve thiocyanate, and the ROH is used as a homogeneous medium in the whole reaction process, and the technological process sequentially comprises the following steps:
a. dissolving thiocyanate in ROH, and then dripping R-X to prepare the thiocyanate, wherein the process conditions are as follows:
the mol ratio of MSCN to ROH is 1: 2-10,
the mol ratio of MSCN to R-X is 1: 1.1-2,
reaction temperature: 30-80 ℃;
b. the process conditions for isomerizing the thiocyanate into the isothiocyanate by heating and refluxing are as follows:
reflux temperature: 80-140 deg.C
Reaction time: 2-10 hours
c. Heating and refluxing to react the isothiocyanate with ROH to generate thiocarbamate,
reaction temperature: 110-170 DEG C
Refluxing time: the reaction time is 2-12 hours,
d. cooling and filtering to remove salt generated in the reaction process;
e. ROH and excess R-X are recovered by distillation, the remainder being the thiocarbamate product of the invention.
When the isothiocyanate is reacted with ROH, it is preferable to add a catalyst (RO) mTi (Cl) n, wherein RO is a four-carbon alkoxy group and m + n is 4.
In the process of the present invention, the thiocyanate used comprises potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate.
In the method of the present invention, ROH used is a four-carbon alcohol, a five-carbon alcohol or a six-carbon alcohol.
In the process of the invention, R-X used are chlorohydrocarbons and bromohydrocarbons.
In the process of the present invention, R-X used is a four-to nine-carbon alkyl halide.
In the process of the present invention, R-X used is a three-to nine-carbon halogenated olefin.
Because the ROH used in the method of the invention is four-carbon alcohol, five-carbon alcohol and six-carbon alcohol, the boiling point temperature of the ROH is generally higher than 90 ℃, and because the excess ROH is used in the process, the reaction can be carried out
The reflux temperature of RSCN ⇔ RNCS is greatly raised to 90-140 deg.c, which is favorable to the conversion of thiocyanate into isothiocyanate.
The preparation method of the thiocarbamate compound adopts ROH which is one of reaction raw materials as a homogeneous medium of the whole reaction, and the chemical reaction process is carried out in the homogeneous medium. Because the reaction is carried out in alcohol and the alcohol as reactant is introduced in advance, the isothiocyanate newly formed in the process can be reacted with the alcohol as medium at any time
Figure C9610646300071
The final product is produced, and the isothiocyanate concentration is reduced due to the continuous consumption of the newly produced isothiocyanate, allowing the reaction
The RSCN ⇔ RNCS moves towards the direction which is beneficial to generating the RNCS, so that the reaction is carried out quickly and thoroughly, the total yield is improved, the dosage of the catalyst is greatly reduced, and the reaction time is saved.
To favor CH generation2＝CHCH2The direction of SCN. The reaction for generating thiocarbamate and the isomerization reaction of isothiocyanate are almost simultaneously carried out, so that the production efficiency can be greatly improved.
The basic reactions of the method can be carried out in the same device and the same medium, the continuous heating is utilized to control the progress of different reaction sections, the intermediates with higher toxicity are all sealed in the same reaction system, the separation and the purification are not needed, the operation environment is improved, the cost can be reduced by not using a phase transfer agent tetrabutyl ammonium bromide in the reaction, water is not used in the reaction process, the intervention of the aqueous medium in the prior art is eliminated, the process of the repeated dehydration treatment of the intermediates is omitted, no sewage is discharged, water treatment equipment is saved, the problems of environmental pollution and severe operation environment are solved, the energy consumption is effectively reduced, the product yield is improved, the reaction time is shortened, and the production efficiency is greatly improved.
The invention will be further described with reference to specific embodiments.
The invention relates to a preparation method of a thiocarbamate compound, which comprises the steps of adopting thiocyanate MSCN to react with halogenated hydrocarbon R-X to generate thiocyanate, heating and refluxing to ensure that the thiocyanate is isomerized into isothiocyanate and alcohol ROH reacts with the isothiocyanate to generate the thiocarbamate, and is characterized in that: m of thiocyanate MSCN being K, Na, NH4 +(ii) a R of halogenated hydrocarbon R-X is C3-9Alkyl, X is Cl, Br; r of the alcohol ROH is C4-6An alkyl group; in the synthesis process, ROH which finally reacts with isothiocyanate to generate thiocarbamate is used as a solvent to dissolve thiocyanate, and the ROH is used as a homogeneous medium in the whole reaction process, and the technological process sequentially comprises the following steps:
adding 1 part of thiocyanate (sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate) into 2-10 parts of ROH, and dropwise adding 1.1-2 parts of R-X at the temperature of 30-80 ℃, wherein R-X is four-carbon to nine-carbon alkyl halide and three-carbon to nine-carbon halogenated olefin, in particular various substituted and unsubstituted allyl chloride or bromide, to react to prepare the thiocyanate.
Then heating to 80-140 deg.C, refluxing for 2-10 hr to make thiocyanate isomerize into isothiocyanate.
Then adding catalyst (RO) mTi (Cl) n, controlling the temperature to be more than 110-170 ℃, refluxing for 2-12 hours, and reacting isothiocyanate with ROH to generate thiocarbamate. Cooling and filtering to remove salt generated in the process, and distilling excess ROH) and R-X from the filtrate under reduced pressure to obtain the thiocarbamate product.
The product obtained by the above process has a yield of 85.46% and a purity of 97.7%, and has a product molecular peak separation 173 by GC/MS analysis, and no intermediate impurity peak in an infrared spectrogram.
Example 1
Raw materials: sodium thiocyanate, isobutanol, allyl chloride,
the operation process is as follows:
adding 1 mol of isobutanol and 0.1 mol of sodium thiocyanate into a reactor, stirring and heating, dropwise adding 0.2 mol of allyl chloride at the temperature of 30-40 ℃, completing the dropwise addition within 1 hour, heating and refluxing, refluxing for 2 hours at the temperature of 90-100 ℃, adding 0.01 mol of catalyst (RO) mTi (Cl) n, (m + n) ═ 4, heating and refluxing for 12 hours at the temperature of 110 ℃, cooling and filtering out generated sodium chloride, and distilling the filtrate under reduced pressure to remove excessive alcohol and R-X, wherein the rest is 15 g of thiocarbamate.
Example 2
Raw materials: sodium thiocyanate, hexanol, allyl bromide,
the operation process is as follows:
0.4 mol of hexanol and 0.2 mol of sodium thiocyanate are added into a reactor, the mixture is stirred and heated, 0.22 mol of allyl bromide is dripped at the temperature of 70-80 ℃, the dripping is finished within 0.5 hour, the mixture is heated and refluxed at the temperature of 130 ℃ and 140 ℃ for 10 hours, 0.0001 mol of catalyst (RO) mTi (Cl) n, (m + n) ═ 4 is added, the mixture is refluxed at the temperature of 160 ℃ and 170 ℃ for 2 hours, the generated sodium bromide is cooled and filtered, the filtrate is decompressed and distilled to remove excessive alcohol and R-X, and the rest is 31 g of thiocarbamate.
Example 3
Raw materials: potassium thiocyanate, mixed alcohols (butanol, pentanol, hexanol), allyl chloride,
the operation process is as follows:
the mixed alcohol (20% butanol, 60% pentanol, 20% hexanol) was added to the reactor, 0.2 mol potassium thiocyanate was added, the temperature was raised with stirring, 0.3 mol allyl chloride was added dropwise at 50-60 ℃ over 1 hour, and then the mixture was refluxed at 110 ℃ for 5 hours, 0.001 mol catalyst (RO) mti (cl) n, m + n was 4, and the mixture was refluxed at 130 ℃ for 8 hours, and 29.8 g of the product was obtained under the same conditions as in example 1.
Example 4
Raw materials: ammonium thiocyanate, mixed alcohols (butanol, pentanol), allyl chloride,
the operation process is as follows:
1 mol of mixed alcohol (30 percent of butanol and 70 percent of amyl alcohol) is added into a reactor, then 0.2 mol of ammonium thiocyanate is added, the temperature is raised to 50 ℃ by stirring, 0.4 mol of allyl chloride is added dropwise within 1 hour, then the mixture is refluxed for 6 hours at the temperature of 100 ℃ and 110 ℃, then 0.003 mol of catalyst (RO) mTi (Cl) n, m + n is 4 is added, the mixture is refluxed for 6 hours at the temperature of 130 ℃, and the other conditions are the same as the conditions in the example 1, thus obtaining 29 g of the product.
Example 5
Raw materials: sodium thiocyanate, amyl alcohol, allyl bromide,
the operation process is as follows:
1 mol of pentanol is added into a reactor, 0.1 mol of sodium thiocyanate is added, 0.2 mol of allyl bromide is dripped at 40-50 ℃ within 1 hour, the temperature is raised and the mixture is refluxed at 110 ℃ for 10 hours, then the mixture is continuously heated and the mixture is refluxed at 140 ℃ for 12 hours, no catalyst is added, and the other conditions are the same as the conditions in the example 1, so that 12.1 g of a product is obtained.
Example 6
Raw materials: sodium thiocyanate, amyl alcohol, 1-phenyl-3-chloropropene,
the operation process is as follows:
1 mol of pentanol is added into a reactor, 0.1 mol of sodium thiocyanate is added, 0.2 mol of 1-phenyl-3-chloropropene is added dropwise at the temperature of 50 ℃ within 1 hour, the temperature is increased and the reflux is carried out for 10 hours at the temperature of 110 ℃, 0.01 mol of catalyst (RO) mTi (Cl) n, m + n is 4 is added, the reflux is carried out for 12 hours at the temperature of 140 ℃, and the other conditions are the same as in example 1, so that 10.1 g of the product is obtained.
Example 7
Raw materials: sodium thiocyanate, hexanol, benzyl bromide,
the operation process is as follows:
adding 1 mol of hexanol and 0.1 mol of sodium thiocyanate into a reactor, stirring and heating, dropwise adding 0.2 mol of benzyl bromide at 50-60 ℃ within 1 hour, heating and refluxing at 140 ℃ for 10 hours, then adding 0.002 mol of catalyst (RO) mTi (Cl) n, m + n is 4, refluxing at 160-170 ℃ for 12 hours, and obtaining 6.2 g of a product under the same conditions as in example 1.

Claims (25)

1. A preparation method of thiocarbamate compounds comprises the steps of adopting thiocyanate MSCN to react with halogenated hydrocarbon R-X to generate thiocyanate, heating and refluxing to ensure that the thiocyanate is isomerized into isothiocyanate and alcohol ROH reacts with the isothiocyanate to generate thiocarbamate, and is characterized in that: m of thiocyanate MSCN being K, Na, NH4 +(ii) a R of halogenated hydrocarbon R-X is C3-9Hydrocarbyl, X is Cl, Br; r of the alcohol ROH is C4-6An alkyl group; in the synthesis process, ROH which finally reacts with isothiocyanate to generate thiocarbamate is used as a solvent to dissolve thiocyanate, and the ROH is used as a homogeneous medium in the whole reaction process, and the technological process sequentially comprises the following steps:
a. dissolving thiocyanate in ROH, and then dripping R-X to prepare the thiocyanate, wherein the process conditions are as follows:
the mol ratio of MSCN to ROH is 1: 2-10,
the mol ratio of MSCN to R-X is 1: 1.1-2,
reaction temperature: 30-80 ℃;
b. the process conditions for isomerizing the thiocyanate into the isothiocyanate by heating and refluxing are as follows:
reflux temperature: 80-140 deg.C
Reaction time: 2-10 hours
c. Heating and refluxing to react the isothiocyanate with ROH to generate thiocarbamate,
reaction temperature: 110-170 DEG C
Refluxing time: the reaction time is 2-12 hours,
d. cooling and filtering to remove salt generated in the reaction process;
e. ROH and excess R-X are recovered by distillation, the remainder being the thiocarbamate product of the invention.
2. The process for preparing a thioamino methyl ester compound as claimed in claim 1, wherein the reaction of isothiocyanate with ROH is carried out by adding catalyst (RO) mti (cl) n, where RO is a four-carbon alkoxy group and m + n is 4.
3. The process for preparing thiocarbamates according to claim 1, wherein M of MSCN used is K.
4. The process for preparing thiocarbamates according to claim 1, wherein M of MSCN used is Na.
5. The process for preparing thiocarbamates according to claim 1, wherein M of MSCN used is NH4 +。
6. The method for producing thiocarbamates according to claim 1, wherein ROH used is a four carbon alcohol.
7. The method for producing thiocarbamates according to claim 1, wherein ROH used is a five-carbon alcohol.
8. The method for producing thiocarbamates according to claim 1, wherein ROH used is a six carbon alcohol.
9. The method for preparing thiocarbamates according to claim 1, wherein R-X used is a chlorinated alkane of four to nine carbons or a chlorinated alkene of three to nine carbons.
10. The method according to claim 1, wherein R-X is a four-to nine-carbon alkyl bromide or a three-to nine-carbon olefin bromide.
11. The method for preparing thiocarbamates according to claim 1, wherein R-X used is a halogenated alkane of four to nine carbons.
12. The process for the preparation of a thiocarbamate compound according to claim 1 or claim 11, wherein R-X is a four-carbon alkyl halide.
13. The process for the preparation of a thiocarbamate compound according to claim 1 or claim 11 characterised in that R-X used is a five carbon alkyl halide.
14. The process for the preparation of a thiocarbamate compound according to claim 1 or claim 11 characterised in that R-X used is a six carbon alkyl halide.
15. The process for the preparation of a thiocarbamate compound according to claim 1 or claim 11 characterised in that R-X used is a heptacarbon alkyl halide.
16. The process for the preparation of a thiocarbamate compound according to claim 1 or claim 11 characterised in that R-X used is an eight carbon alkyl halide.
17. The process for the preparation of a thiocarbamate compound according to claim 1 or claim 11, wherein R-X is a nonacarbon alkyl halide.
18. The method for preparing thiocarbamates according to claim 1, wherein R-X used is a halogenated olefin of three to nine carbons.
19. The process for the preparation of a thiocarbamate compound according to claim 1 or claim 18 characterised in that R-X used is a three-carbon haloolefin.
20. The process for the preparation of a thiocarbamate compound according to claim 1 or claim 18 characterised in that R-X used is a four carbon haloolefin.
21. The process for the preparation of a thiocarbamate compound according to claim 1 or claim 18 characterised in that R-X used is a five carbon haloolefin.
22. The process for the preparation of a thiocarbamate compound according to claim 1 or claim 18 characterised in that R-X used is a six carbon haloolefin.
23. The process for the preparation of a thiocarbamate compound according to claim 1 or claim 18 characterised in that R-X used is a seven-carbon haloolefin.
24. The process for the preparation of a thiocarbamate compound according to claim 1 or claim 18 characterised in that R-X used is an eight carbon haloolefin.
25. The process for the preparation of a thiocarbamate compound according to claim 1 or claim 18 characterised in that R-X used is a nine-carbon haloolefin.
CN96106463A 1995-11-02 1996-08-09 Preparation method of thiocarbamate compound Expired - Fee Related CN1045086C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105061276A (en) * 2015-08-14 2015-11-18 沈阳有研矿物化工有限公司 Synthetic process of N-allyl-O- isobutyl thionocarbamate

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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
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
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
CN108947880B (en) * 2018-08-06 2020-06-02 青岛科技大学 Preparation method of thiocarbamate compound based on photocatalysis
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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SU507566A1 (en) * 1974-09-06 1976-03-25 Предприятие П/Я А-7253 The method of obtaining-methyl-o-isopropylthionocarbamate
EP0010877A1 (en) * 1978-10-05 1980-05-14 The British Petroleum Company p.l.c. Valve tray
US4479903A (en) * 1982-08-23 1984-10-30 American Cyanamid Company Process for the preparation of N-allyl-O-alkyl thionocarbamates
EP0537585A2 (en) * 1991-10-15 1993-04-21 E.I. Du Pont De Nemours And Company Process for preparing sulfonylureas

Patent Citations (4)

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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
EP0010877A1 (en) * 1978-10-05 1980-05-14 The British Petroleum Company p.l.c. Valve tray
US4479903A (en) * 1982-08-23 1984-10-30 American Cyanamid Company Process for the preparation of N-allyl-O-alkyl thionocarbamates
EP0537585A2 (en) * 1991-10-15 1993-04-21 E.I. Du Pont De Nemours And Company Process for preparing sulfonylureas

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105061276A (en) * 2015-08-14 2015-11-18 沈阳有研矿物化工有限公司 Synthetic process of N-allyl-O- isobutyl thionocarbamate
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

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