CN107011221B - A kind of preparation method of diethylamino ethanethiol - Google Patents
A kind of preparation method of diethylamino ethanethiol Download PDFInfo
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- CN107011221B CN107011221B CN201710125033.2A CN201710125033A CN107011221B CN 107011221 B CN107011221 B CN 107011221B CN 201710125033 A CN201710125033 A CN 201710125033A CN 107011221 B CN107011221 B CN 107011221B
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- disulfide
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- diethylamino ethanethiol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/06—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols from sulfides, hydropolysulfides or polysulfides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
Abstract
The present invention relates to a kind of preparation methods of diethylamino ethanethiol, it includes the following steps that organic solvent and water are put into mixing vessel by (1), then sodium disulfide is added, after stirring 1-2h, lignocaine halogenated hydrocarbons is slowly added dropwise, controlling reaction temperature is 15 DEG C -20 DEG C, until reaction terminates, generates disulfide；(2) disulfide that step (1) obtains is put into another container and is slowly added to reducing agent, maintain temperature at 20 DEG C, stir 8-12h, until reaction terminates, generate diethylamino ethanethiol；Operation of the present invention is simple, at low cost, high income.
Description
Technical field
The present invention relates to a kind of preparation methods of diethylamino ethanethiol, and especially one kind is with lignocaine halogenated hydrocarbons and two
Vulcanized sodium is raw material, restores the preparation method for obtaining diethylamino ethanethiol.
Background technique
Tiamulin is a kind of for preventing and treating poultry respiratory disease and promoting the diterpene alkenes livestock and poultry of growth of animal special
Use antibiotic.Diethylamino ethanethiol is the important intermediate for producing Tiamulin.
According to domestic and international bibliography, it is found that the report about diethylamino ethanethiol is less.Wang Yanlin etc. is in the patent
It mentions and prepares diethylamino ethanethiol at present and have following several method: sulfuric acid list vinegar and sodium hydrosulfide；(2) lignocaine chloroethene
Alkane and sodium hydrosulfide；(3) sulfuric acid list vinegar and sulphur pulpating method: (4) thioether method.
There are some defects in the above several method, need to research and develop a kind of high income, and production cost is low, be suitable for high-volume
Industrial preparation method.
Summary of the invention
The object of the present invention is to provide a kind of easy to operate, at low cost, the preparation sides of diethylamino ethanethiol of high income
Method.
To achieve the above object, include the following steps,
(1) organic solvent and water are put into mixing vessel, sodium disulfide is then added, after stirring 1-2h, be slowly added dropwise two
Ethylamino halogenated hydrocarbons, control reaction temperature are 15 DEG C -20 DEG C, stir 8-12h, generate disulfide；
(2) disulfide that step (1) obtains is put into another container and is slowly added to reducing agent, temperature is maintained to exist
20 DEG C, 8-12h is stirred, generates diethylamino ethanethiol.
Preferably: its described organic solvent is one of methanol, ethyl alcohol, isopropanol, acetone, ether or a variety of.
Preferably: when organic solvent and water are put into mixing vessel, the volume ratio of organic solvent and water is 2:1 ~ 4:1.
Preferably: the reducing agent is Fe/HCl or Zn/HCl.
Preferably: the molar ratio of sodium disulfide and lignocaine halogenated hydrocarbons is 1-1.3 ~ 1:2, and disulfide and reducing agent rub
You than be 1:1 ~: 1:2.
Preferably: organic solvent and water are put into mixing vessel, the gross mass and sodium disulfide of organic solvent and water
Mass ratio is 5:1.
Preferably: the lignocaine amino halogen hydrocarbon is lignocaine chloroethanes.
Preferably: in the Fe/HCl, the molar ratio of Fe and HCl are 1:2 ~ 1:5.
Preferably: in the Zn/HCl, the molar ratio of Zn and HCl are 1:2 ~ 1:5.
Good effect of the present invention is as follows:
The present invention is using lignocaine halogenated hydrocarbons as raw material, by reacting with sodium disulfide, obtains lignocaine disulfide, and two
Ethylamino disulfide obtains diethylamino ethanethiol through reduction again.This method is easy to operate, and cost is relatively low, high income, can be obtained
Pure diethylamino ethanethiol is that the good process for preparing diethylamino ethanethiol illustrates by mass spectrogram analysis
Disulfide purity is high is also very high by the yield that diethylamino ethanethiol is calculated.
Detailed description of the invention
Fig. 1 is the diethylamino ethanethiol makings figure of the embodiment of the present invention 1；
The disulfide makings figure of Fig. 2 embodiment of the present invention 1；
Fig. 3 is the diethylamino ethanethiol standard specimen makings figure of the embodiment of the present invention 1；
The disulfide standard specimen makings figure of Fig. 4 embodiment of the present invention 1.
Specific embodiment
It will make further narration in detail to the embodiment of the present invention below.
Embodiment 1
(1) ethyl alcohol 120mL, water 30mL is added in 500mL there-necked flask, sodium disulfide 24.49g is then added, stir 1.5h,
Lignocaine chloroethanes 40.97g is slowly added dropwise, after charging, reacts at a reflux temperature, control reaction temperature is 15 DEG C,
8h is stirred, TLC, which tracks to reaction, to be terminated.Toluene extraction, split-phase, organic phase concentration obtain disulfide 37.87g.GC-MS detection, figure
Spectrum such as Fig. 2, compares, spectrogram is consistent with standard specimen.
(2) disulfide 36.67g is added in 500mL there-necked flask, reducing agent Fe/HCl is added, wherein iron 11.67g is added,
20%HCl76.06g is slowly added dropwise, maintains temperature at 20 DEG C, stirs 10h, reaction terminates.It is quantitative to sample HPLC, obtains lignocaine
Ethyl mercaptan 48.78g, conversion ratio: 96.3%.GC-MS detection, map such as Fig. 1 and standard specimen control, map are consistent.
HPLC method: detector: evaporation Laser Light Scattering detector；Mobile phase: 5mmol L-1 sodium dihydrogen phosphate-methanol
(90:10)；Sample volume: 20uL.
Embodiment 2
(1) ethyl alcohol 120mL, water 40mL is added in 500mL there-necked flask, sodium disulfide 26.94g is then added, stir 1.5h,
Lignocaine chloroethanes 44.25g is slowly added dropwise, after charging, reacts at a reflux temperature, control reaction temperature is 15 DEG C,
10h is stirred, TLC, which tracks to reaction, to be terminated.Toluene extraction, split-phase, organic phase concentration obtain disulfide 40.90g.
(2) disulfide 40.12g is added in 500mL there-necked flask, reducing agent Fe/HCl is added, wherein iron 8.51g is added,
20%HCl 83.16g is slowly added dropwise, maintains temperature at 20 DEG C, stirs 10h, reaction terminates.It is quantitative to sample HPLC, obtains lignocaine
Ethyl mercaptan 38.98g, conversion ratio: 96.3%.
HPLC method: detector: evaporation Laser Light Scattering detector；Mobile phase: 5mmol L-1 sodium dihydrogen phosphate-methanol
(90:10)；Sample volume: 20uL.
Embodiment 3
(1) ethyl alcohol 120mL, water 60mL is added in 500mL there-necked flask, sodium disulfide 30.94g is then added, stir 1.5h,
Lignocaine chloroethanes 50.88g is slowly added dropwise, after charging, reacts at a reflux temperature, control reaction temperature is 15 DEG C,
12h is stirred, TLC, which tracks to reaction, to be terminated.Toluene extraction, split-phase, organic phase concentration obtain disulfide 47.03g.
(2) disulfide 46.89g is added in 500mL there-necked flask, reducing agent Fe/HCl is added, wherein iron 19.89g is added,
20%HCl 324.14g is slowly added dropwise, maintains temperature at 20 DEG C, stirs 10h, reaction terminates.It is quantitative to sample HPLC, obtains diethylamino
Base ethyl mercaptan 45.55g, conversion ratio: 96.3%.Mass spectrogram and standard specimen control, unanimously.
HPLC method: detector: evaporation Laser Light Scattering detector；Mobile phase: 5mmol L-1 sodium dihydrogen phosphate-methanol
(90:10)；Sample volume: 20uL.
Embodiment 4
(1) ethyl alcohol 120mL, water 60mL is added in 500mL there-necked flask, sodium disulfide 30.94g is then added, stir 1.5h,
Lignocaine chloroethanes 50.82g is slowly added dropwise, after charging, reacts at a reflux temperature, control reaction temperature is 15 DEG C,
8h is stirred, TLC, which tracks to reaction, to be terminated.Toluene extraction, split-phase, organic phase concentration obtain disulfide 46.98g.
(2) disulfide 45.79g is added in 500mL there-necked flask, reducing agent Zn/HCl is added, wherein iron 10.60g is added,
20%HCl63.31g is slowly added dropwise, maintains temperature at 20 DEG C, stirs 10h, reaction terminates.It is quantitative to sample HPLC, obtains lignocaine
Ethyl mercaptan 44.48g, conversion ratio: 96.3%.Mass spectrogram and standard specimen control, unanimously.
HPLC method: detector: evaporation Laser Light Scattering detector；Mobile phase: methanol: 5mmol L-1 sodium dihydrogen phosphate-first
Alcohol (90:10)；Sample volume: 20ul.
Embodiment 5
(1) methanol 120mL, 30 mL of water is added in 500mL there-necked flask, sodium disulfide 24.94g is then added, stir 1h,
Lignocaine chloroethanes 61.44g is slowly added dropwise, after charging, reacts at a reflux temperature, control reaction temperature is 18 DEG C,
TLC, which tracks to reaction, to be terminated, and 12h is stirred.Toluene extraction, split-phase, organic phase concentration obtain disulfide 56.81g.
(2) disulfide 55..12g is added in 500mL there-necked flask, reducing agent Zn/HCl is added, wherein Zn zinc is added
20%HCl 304.80g is slowly added dropwise in 27.14g, maintains temperature at 20 DEG C, stirs 8h, and reaction terminates.It is quantitative to sample HPLC, obtains
Diethylamino ethanethiol 53.88g, conversion ratio: 96.9%.Mass spectrogram and standard specimen control, unanimously.
HPLC method: detector: evaporation Laser Light Scattering detector；Mobile phase: methanol: 5mmol L-1 sodium dihydrogen phosphate-first
Alcohol (90:10)；Sample volume: 20ul.
Embodiment 6
(1) isopropanol 120mL, 40 mL of water is added in 500mL there-necked flask, sodium disulfide 26.94g, stirring is then added
Lignocaine chloroethanes 59.74 is slowly added dropwise in 2h, after charging, reacts at a reflux temperature, and control reaction temperature is 20
DEG C, 12h is stirred, LC, which tracks to reaction, to be terminated.Toluene extraction, split-phase, organic phase concentration obtain disulfide 55.22g.
(2) disulfide 51.10g is added in 500mL there-necked flask, reducing agent Zn/HCl is addedx, wherein being added
20%HCl 264.94g is slowly added dropwise in Zn18.87g, maintains temperature at 20 DEG C, stirs 8h, and reaction terminates.It is quantitative to sample HPLC,
Obtain diethylamino ethanethiol 49.80g, conversion ratio: 96.6%.Mass spectrogram and standard specimen control, unanimously.
HPLC method: detector: evaporation Laser Light Scattering detector；Mobile phase: methanol: 5mmol L-1 sodium dihydrogen phosphate-first
Alcohol (90:10)；Sample volume: 20ul.
Comparative example 1
It takes 645g potassium rhodanide and 450g ethylene carbonate to be added in 1.5L round-bottomed flask, is warming up to 80 DEG C, heat preservation 5 is small
When, it collects the thiirane distilled out around here and is placed in the cooling storage of sealing in recipient.
300g thiirane and 365g diethylamine that upper step obtains are added to simultaneously in 1000mL four-hole boiling flask, in temperature
For back flow reaction 4 hours between 75 DEG C, air-distillation operation was then carried out between 60 DEG C, steams excessive diethylamine, flask
In remaining material be diethylamino ethanethiol finished product about 600g.Conversion ratio is 91%.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments in the case where not departing from the spirit or scope of the invention patent.Therefore, originally
Invention is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein
Consistent widest scope.
Claims (9)
1. a kind of preparation method of diethylamino ethanethiol, it is characterised in that: include the following steps,
(1) organic solvent and water are put into mixing vessel, sodium disulfide is then added, after stirring 1-2h, diethylamino is slowly added dropwise
Base halogenated hydrocarbons, control reaction temperature are 15 DEG C -20 DEG C, stir 8-12h, generate disulfide；
(2) disulfide that step (1) obtains is put into another container and is slowly added to reducing agent, maintain temperature 20
DEG C, 8-12h is stirred, diethylamino ethanethiol is generated.
2. a kind of preparation method of diethylamino ethanethiol according to claim 1, it is characterised in that: described its is organic molten
Agent is one of methanol, ethyl alcohol, isopropanol, acetone, ether or a variety of.
3. a kind of preparation method of diethylamino ethanethiol according to claim 1, it is characterised in that: by organic solvent and
When water is put into mixing vessel, the volume ratio of organic solvent and water is 2:1 ~ 4:1.
4. a kind of preparation method of diethylamino ethanethiol according to claim 1, it is characterised in that: the reducing agent is
Fe/HCl or Zn/HCl.
5. a kind of preparation method of diethylamino ethanethiol according to claim 1, it is characterised in that: sodium disulfide and two
The molar ratio of ethylamino halogenated hydrocarbons is 1-1.3 ~ 1:2, the molar ratio of disulfide and reducing agent be 1:1 ~: 1:2.
6. a kind of preparation method of diethylamino ethanethiol according to claim 1, it is characterised in that: by organic solvent and
Water is put into mixing vessel, and the mass ratio of the gross mass and sodium disulfide of organic solvent and water is 5:1.
7. according to a kind of preparation method of diethylamino ethanethiol according to claim 1, it is characterised in that: the diethyl
Amino halogenated hydrocarbons is lignocaine chloroethanes.
8. according to a kind of preparation method of diethylamino ethanethiol according to claim 4, it is characterised in that: the Fe/
In HCl, the molar ratio of Fe and HCl are 1:2 ~ 1:5.
9. according to a kind of preparation method of diethylamino ethanethiol according to claim 4, it is characterised in that: the Zn/
In HCl, the molar ratio of Zn and HCl are 1:2 ~ 1:5.
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| DE3631073A1 (en) * | 1986-09-12 | 1988-03-24 | Basf Ag | METHOD FOR REDUCING ORGANIC SULFUR COMPOUNDS |
| US4734527A (en) * | 1986-10-17 | 1988-03-29 | Merrell Dow Pharmaceuticals Inc. | Process for preparing 2,6-di-tertiarybutyl-4-mercaptophenol |
| CN101250145B (en) * | 2008-04-02 | 2010-08-18 | 苏州科技学院 | Method for preparing diethylamino ethanethiol |
| CN101607930A (en) * | 2008-06-19 | 2009-12-23 | 天津市化学试剂研究所 | The preparation method of benzyldithio toluene |
| CN101434567B (en) * | 2008-12-19 | 2012-10-24 | 李扬 | Preparation method of lignocaine ethanethiol |
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Effective date of registration: 20190618 Address after: 071000 Pang Village, Yujiazhuang Township, Mancheng District, Baoding City, Hebei Province Patentee after: Baoding Jiahe Fine Chemical Co., Ltd. Address before: 050000 No. 70 Yuhua East Road, Shijiazhuang City, Hebei Province Patentee before: Hebei University of Science and Technology |
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