CN106966934B - A kind of preparation method of dialkyl dithio amino formate - Google Patents
A kind of preparation method of dialkyl dithio amino formate Download PDFInfo
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- CN106966934B CN106966934B CN201710225232.0A CN201710225232A CN106966934B CN 106966934 B CN106966934 B CN 106966934B CN 201710225232 A CN201710225232 A CN 201710225232A CN 106966934 B CN106966934 B CN 106966934B
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- C07—ORGANIC CHEMISTRY
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- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/18—Esters of dithiocarbamic acids
- C07C333/20—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to hydrogen atoms or to acyclic carbon atoms
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Abstract
The present invention provides a kind of preparation methods of dialkyl dithio amino formate, comprising the following steps: mixes sodium hydroxide, water, di-n-butylamine, ethyl alcohol, methylene chloride and carbon disulfide, reaction obtains reaction product；The reaction product is used into solvent oil extraction, separation obtains oily phase；The oil is mutually mixed with carrier, filtering obtains mother liquor；The mother liquor is evaporated under reduced pressure, distillation post mother liquor is obtained；The distillation post mother liquor is used into solvent oil extraction, then is evaporated under reduced pressure, dialkyl dithio amino formate is obtained.This method is that one-step method prepares dialkyl dithio amino formate, by solvent oil extraction twice, is handled before vacuum distillation twice and primary vacuum distillation using carrier, achievees the purpose that not to be washed with water, reduce the generation of waste water；Higher product yield and product purity are also achieved simultaneously.The results showed that 99% or more the yield of dialkyl dithio amino formate, and purity is greater than 98%.
Description
Technical field
The present invention relates to dialkyl dithio amino formate preparation technical field more particularly to a kind of dialkyl dithios
The preparation method of carbamate.
Background technique
Dialkyl dithio amino formate class compound is a kind of important organic compound, be widely used in rubber,
The fields such as petroleum, agricultural, mining industry, medicine, environmental protection, analytical chemistry.Dialkyl dithio amino formate is usually by two
Nitric sulfid is reacted with sodium hydroxide, secondary amine and methylene chloride and is made.
Prior art preparation dialkyl dithio amino formate has two-step method and one-step method: such as the reality of US5,015,368
Example 1 discloses the method for preparing dialkyl dithio amino formate using two-step method, the first step, by two sulphur at about 63 DEG C
Change carbon to be added in the mixture containing di-n-butylamine, sodium hydroxide and water；Second step is warming up to 88 DEG C, methylene chloride is added
In above-mentioned reaction mixture, 4 hours are lasted, reacts then at 85~88 DEG C 3 hours after adding methylene chloride, after reaction, divides
Liquid phase is separated out, then is evaporated under reduced pressure to obtain product, nitrogen content 6.5%, sulfur content 30.0%.For another example patent CN1159294
Disclose a kind of method that one-step method prepares dialkyl dithio amino formate.Water-soluble containing di-n-butylamine, sodium hydroxide
In the mixture of liquid, methylene chloride and etoh solvent, it is small that 0.5~5 is reacted in 10~60 DEG C of instillation carbon disulfide, after being added dropwise
When, then be warming up to 50~100 DEG C the reaction was continued 1~12 hour, gasoline extracting a moment is added after reaction, isolates organic
Phase is washed with water to neutrality, and atmospheric and vacuum distillation goes out gasoline and a small amount of water, and yellow transparent product can be obtained.Prior art at present
The dialkyl dithio amino formate yield of preparation is lower, and purity is lower, and a large amount of waste water are generated in water-washing process.Base
In current environmental protection pressure, urgent need, which finds one kind, can improve the cleaning procedure of product yield and purity and waste water.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of preparation method of dialkyl dithio amino formate, it should
The product yield and purity of method preparation are higher, and reduce the generation of waste water.
The present invention provides a kind of preparation methods of dialkyl dithio amino formate, comprising the following steps:
Sodium hydroxide, water, di-n-butylamine, ethyl alcohol, methylene chloride and carbon disulfide are mixed, reaction obtains reaction product；
The reaction product is used into solvent oil extraction, separation obtains oily phase；
The oil is mutually mixed with carrier, is separated by filtration to obtain mother liquor；
The mother liquor is evaporated under reduced pressure, distillation post mother liquor is obtained；
The distillation post mother liquor is used into solvent oil extraction, then is evaporated under reduced pressure, dialkyl dithio amino first is obtained
Acid esters.
Preferably, the pressure of the reaction is 0.01~0.1MPa；The temperature of the reaction is 90~100 DEG C；It is described anti-
The time answered is 3~5h.
Preferably, the carrier is selected from one of polytetrafluoroethylene (PTFE), diatomite, porous polymer bead and red supporter
Or it is a variety of.
Preferably, the oil is mutually and the temperature of carrier mixing is 40~60 DEG C；The oil is mutually and the time of carrier mixing is
10~40min.
Preferably, the mass ratio of the sodium hydroxide, water, di-n-butylamine, ethyl alcohol, methylene chloride and carbon disulfide is 4.2
~6.1:5.5~7.3:1:1~2:0.4~0.6:1.0~1.4.
Preferably, the reaction product is using before solvent oil extraction further include:
The reaction product is evaporated under reduced pressure, reaction product after being distilled；
Reaction product uses solvent oil extraction after distilling.
Preferably, the temperature that the mother liquor is evaporated under reduced pressure is 80~130 DEG C.
Preferably, the reaction product uses the temperature of solvent oil extraction for 50~70 DEG C；The reaction product is using molten
The time of agent oil extraction is 20~40min.
Preferably, the mass ratio of the di-n-butylamine and carrier is 1:3.7~8.7.
The present invention provides a kind of preparation methods of dialkyl dithio amino formate, comprising the following steps: by hydrogen-oxygen
Change sodium, water, di-n-butylamine, ethyl alcohol, methylene chloride and carbon disulfide mixing, reaction and obtains reaction product；By the reaction product
Using solvent oil extraction, separation obtains oily phase；The oil is mutually mixed with carrier, filtering obtains mother liquor；By the mother liquor into
Row vacuum distillation obtains distillation post mother liquor；The distillation post mother liquor is used into solvent oil extraction, then is evaporated under reduced pressure, is obtained
Dialkyl dithio amino formate.Method provided by the invention is that one-step method prepares dialkyl dithio amino formate, is led to
After solvent oil extraction twice, is handled before vacuum distillation twice and primary vacuum distillation using carrier, achievees the purpose that not to be washed with water,
Reduce the generation of waste water；Higher product yield and product purity are also achieved simultaneously.The results showed that dialkyl disulfides
For 99% or more the yield of carbamate, and purity is greater than 98%.
Specific embodiment
The present invention provides a kind of preparation methods of dialkyl dithio amino formate, comprising the following steps:
Sodium hydroxide, water, di-n-butylamine, ethyl alcohol, methylene chloride and carbon disulfide are mixed, reaction obtains reaction product；
The reaction product is used into solvent oil extraction, separation obtains oily phase；
The oil is mutually mixed with carrier, filtering obtains mother liquor；
The mother liquor is evaporated under reduced pressure, distillation post mother liquor is obtained；
The distillation post mother liquor is used into solvent oil extraction, then is evaporated under reduced pressure, dialkyl dithio amino first is obtained
Acid esters.
Method provided by the invention is that one-step method prepares dialkyl dithio amino formate, is taken out by solvent naphtha twice
It mentions, is handled before vacuum distillation twice and primary vacuum distillation using carrier, achieve the purpose that not to be washed with water, reduce the production of waste water
It is raw；Higher product yield and product purity are also achieved simultaneously.
The present invention mixes sodium hydroxide, water, di-n-butylamine, ethyl alcohol, methylene chloride and carbon disulfide, reaction, obtains anti-
Answer product.The present invention preferably first mixes sodium hydroxide, water, di-n-butylamine, ethyl alcohol and methylene chloride, then mixed with carbon disulfide
It closes；The mode of the carbon disulfide mixing is preferably dropwise addition mode；The rate of the dropwise addition is 1.5~3.5mL/min.The hydrogen
Sodium oxide molybdena, water, di-n-butylamine, ethyl alcohol, methylene chloride and the temperature of carbon disulfide mixing are preferably 15~25 DEG C.The present invention is preferred
It is reacted in fast-open type stirred autoclave well known to those skilled in the art.Carbon disulfide be added dropwise after by reaction kettle
Valve is added dropwise to close, so that entire reaction system is in closed state.In the present invention, the pressure of the reaction be preferably 0.01~
0.1MPa；The present invention uses closed system, and has certain pressure, and such material will not lose, and compared with prior art, be not necessarily to
First material is kept the temperature, reaction temperature is directly warming up to and is reacted, shorten generated time.The temperature of the reaction
Preferably 90~100 DEG C；The time of the reaction is preferably 3~5h.
The present invention is to the source of the sodium hydroxide, water, di-n-butylamine, ethyl alcohol, methylene chloride and carbon disulfide without spy
Different limitation, using sodium hydroxide well known to those skilled in the art, water, di-n-butylamine, ethyl alcohol, methylene chloride and carbon disulfide
?.In the present invention, the mass ratio of the sodium hydroxide, water, di-n-butylamine, ethyl alcohol, methylene chloride and carbon disulfide is preferred
For 4.2~6.1:5.5~7.3:1:1~2:0.4~0.6:1.0~1.4.
After obtaining reaction product, the reaction product is used solvent oil extraction by the present invention, and separation obtains oily phase.At this
In invention, the reaction product use solvent oil extraction before it is also preferable to include:
The reaction product is evaporated under reduced pressure, reaction product after being distilled；
Reaction product after the distillation is used into solvent oil extraction.
The reaction product is evaporated under reduced pressure by the present invention, is gone out ethanol distillation therein, is recycled.
In the present invention, the solvent naphtha is preferably gasoline.The reaction product is preferred using the temperature of solvent oil extraction
It is 50~70 DEG C；The reaction product is preferably 20~40min using the time of solvent oil extraction.
Present invention preferably employs separatory funnels well known to those skilled in the art to separate the reaction product after solvent oil extraction,
The inorganic water phase of isolated upper oil phase and lower layer.The inorganic water phase is the use of next batch synthesis feedstock circulation.Due to this technique
Middle raw material sodium hydroxide is excessive substance, so containing a large amount of sodium hydroxide in inorganic water phase, passes through the side of chemistry titration
Method obtains the amount of remaining sodium hydroxide, then calculates the amount for adding sodium hydroxide, and the inorganic water phase for allowing for synthesis in this way can be with
It is recycled, has finally also achieved the purpose that handle this effluent part.
The present invention mutually mixes the oil with carrier, and filtering obtains mother liquor.In the present invention, the carrier is preferably selected from
One of polytetrafluoroethylene (PTFE), diatomite, porous polymer bead and red supporter are a variety of.The oil that the carrier can be isolated
The substances such as insoluble matter and organic macromolecule impurity in phase, so that product reduces the generation of waste water without being washed with massive laundering.
The mass ratio of the di-n-butylamine and carrier is preferably 1:3.7~8.7.The oil mutually and the temperature of carrier mixing be preferably 40~
60℃；The oil is mutually and the time of carrier mixing is preferably 10~40min.
After obtaining mother liquor, the mother liquor is evaporated under reduced pressure by the present invention, obtains distillation post mother liquor.In the present invention, institute
Stating the temperature that mother liquor is evaporated under reduced pressure is preferably 80~130 DEG C.The purpose that mother liquor is evaporated under reduced pressure is distilled out in mother liquor
Remaining ethyl alcohol and low-boiling organic by-products.
After obtaining distillation post mother liquor, the distillation post mother liquor is used solvent oil extraction by the present invention, then is evaporated under reduced pressure,
Obtain dialkyl dithio amino formate.It is preferably vapour that the distillation post mother liquor, which carries out the solvent naphtha of solvent oil extraction use,
Oil.In the present invention, the distillation post mother liquor is preferably 50~70 DEG C using the temperature of solvent oil extraction；The distillation post mother liquor
Time using solvent oil extraction is preferably 20~40min.
It is preferably 120~140 DEG C using the temperature that the distillation post mother liquor after solvent oil extraction is evaporated under reduced pressure；Using molten
The time that distillation post mother liquor after agent oil extraction is evaporated under reduced pressure is preferably 50~100min.Vacuum distillation purpose described herein
It is to remove solvent naphtha, and by-product remaining in reaction product is distilled off, product is subjected to smart purification.
In order to further illustrate the present invention, below with reference to embodiment to a kind of dialkyl dithio amino provided by the invention
The preparation method of formic acid esters is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
48.82g sodium hydrate solid is added in fast-open type stirred autoclave, adds the dissolution of 67.42g water, is cooled to
After room temperature, di-n-butylamine 129.24g, ethyl alcohol 50.32g, methylene chloride 49.89g are sequentially added, two sulphur are then added dropwise at 20 DEG C
Change carbon 78.42g, after being added dropwise, be directly warming up to 90 DEG C and react 5 hours, guarantees that system internal pressure is during reaction
0.1MPa, is evaporated under reduced pressure out ethyl alcohol after reaction, and ethyl alcohol is firstly added 50g 120# solvent naphtha after steaming extracts at 50 DEG C
Half an hour isolates upper oil phase with separatory funnel, and the inorganic water phase isolated is used as next batch synthesis feedstock circulation, oil
20g porous polymer bead GDX is added in phase carries out thermal agitation at 55 DEG C and handle 20 minutes, by it is oily be mutually separated by filtration after
Gasoline and volatile organic compound are evaporated under reduced pressure out at 100 DEG C, the 120# solvent naphtha for finally adding 100g extracts at 60 DEG C
Half an hour is directly evaporated under reduced pressure out gasoline at 140 DEG C, obtains yellowish transparency liquid dialkyl dithio amino formate
Product, the yield 99.3% of product, effective content, i.e. purity are 98.5%.
Embodiment 2
26.32g sodium hydrate solid is added in fast-open type stirred autoclave, adds the nothing in 70.16g embodiment 1
Machine water phase is dissolved, after being cooled to room temperature, sequentially add di-n-butylamine 96.15g, the ethyl alcohol 37.44g that embodiment one steams,
Then carbon disulfide 58.34g is added dropwise in methylene chloride 37.12g at 25 DEG C, after being added dropwise, be warming up to 98 DEG C and react 4 hours,
Guarantee reaction system internal pressure is 0.1MPa, is then evaporated under reduced pressure out ethyl alcohol, ethyl alcohol is firstly added 37g120# solvent after steaming
Oil extracts half an hour at 70 DEG C, isolates upper oil phase with separatory funnel, and the inorganic water phase isolated is as next batch synthesis
Feedstock circulation uses, and 30g porous polymer bead GDX is added in oily phase and carries out thermal agitation processing 30 minutes at 60 DEG C, will be oily
Gasoline and volatile organic compound are evaporated under reduced pressure out after being mutually separated by filtration at 120 DEG C, 73g120# solvent naphtha is finally added and exists
Half an hour is extracted at 60 DEG C, is directly evaporated under reduced pressure out gasoline at 125 DEG C, obtains yellowish transparency liquid dialkyl dithio
Urethane product, the yield of product are 99.0%, and effective content, i.e. purity are 98.4%.
As seen from the above embodiment, the present invention provides a kind of preparation method of dialkyl dithio amino formate, packets
It includes following steps: sodium hydroxide, water, di-n-butylamine, ethyl alcohol, methylene chloride and carbon disulfide is mixed, reaction obtains reaction and produces
Object；The reaction product is used into solvent oil extraction, separation obtains oily phase；The oil is mutually mixed with carrier, filtering obtains
Mother liquor；The mother liquor is evaporated under reduced pressure, distillation post mother liquor is obtained；The distillation post mother liquor is used into solvent oil extraction, then
It is evaporated under reduced pressure, obtains dialkyl dithio amino formate.Method provided by the invention is that one-step method prepares dialkyl group two
Thiocarbamate is handled using carrier before vacuum distillation twice and primary vacuum distillation, is reached by solvent oil extraction twice
To the purpose not being washed with water, reduce the generation of waste water；Higher product yield and product purity are also achieved simultaneously.Experiment knot
Fruit shows: 99% or more the yield of dialkyl dithio amino formate, and purity is greater than 98%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (6)
1. a kind of preparation method of dialkyl dithio amino formate, comprising the following steps:
Sodium hydroxide, water, di-n-butylamine, ethyl alcohol, methylene chloride and carbon disulfide are mixed, reaction obtains reaction product；It is described
The pressure of reaction is 0.01~0.1MPa；The temperature of the reaction is 90~100 DEG C；The time of the reaction is 3~5h；
The reaction product is used into solvent oil extraction, separation obtains oily phase and inorganic water phase, contains hydrogen in affiliated inorganic water phase
Sodium oxide molybdena uses for next batch synthesis feedstock circulation；
The oil is mutually mixed with carrier, filtering obtains mother liquor；It is more that the carrier is selected from polytetrafluoroethylene (PTFE), diatomite, macromolecule
One of hole microballoon and red supporter are a variety of；The oil is mutually and the temperature of carrier mixing is 40~60 DEG C；It is described oil mutually and
The time of carrier mixing is 10~40min；
The mother liquor is evaporated under reduced pressure, distillation post mother liquor is obtained；
The distillation post mother liquor is used into solvent oil extraction, then is evaporated under reduced pressure, dialkyl dithio amino formate is obtained.
2. preparation method according to claim 1, which is characterized in that the sodium hydroxide, water, di-n-butylamine, ethyl alcohol, two
The mass ratio of chloromethanes and carbon disulfide is 4.2~6.1:5.5~7.3:1:1~2:0.4~0.6:1.0~1.4.
3. preparation method according to claim 1, which is characterized in that the reaction product is also wrapped before using solvent oil extraction
It includes:
The reaction product is evaporated under reduced pressure, reaction product after being distilled；
Reaction product uses solvent oil extraction after distilling.
4. preparation method according to claim 1, which is characterized in that the temperature that the mother liquor is evaporated under reduced pressure be 80~
130℃。
5. preparation method according to claim 1, which is characterized in that the reaction product uses the temperature of solvent oil extraction
It is 50~70 DEG C；The reaction product uses the time of solvent oil extraction for 20~40min.
6. preparation method according to claim 1, which is characterized in that the mass ratio of the di-n-butylamine and carrier is 1:
3.7~8.7.
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| CN1364759A (en) * | 2001-01-18 | 2002-08-21 | 中国石油化工股份有限公司 | preparation of dialkyl dithio amino formate |
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| CN1364759A (en) * | 2001-01-18 | 2002-08-21 | 中国石油化工股份有限公司 | preparation of dialkyl dithio amino formate |
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