CN108558706A - Tetramethylurea and preparation method thereof - Google Patents
Tetramethylurea and preparation method thereof Download PDFInfo
- Publication number
- CN108558706A CN108558706A CN201810260950.6A CN201810260950A CN108558706A CN 108558706 A CN108558706 A CN 108558706A CN 201810260950 A CN201810260950 A CN 201810260950A CN 108558706 A CN108558706 A CN 108558706A
- Authority
- CN
- China
- Prior art keywords
- tetramethylurea
- triphosgene
- dimethylamine
- preparation
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
- C07C275/06—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of tetramethylurea of present invention offer and preparation method thereof, wherein preparation method includes the following steps：Step S1, provides dimethylamine and triphosgene；Step S2 makes dimethylamine be reacted with triphosgene and generates the tetramethylurea.The preparation method of tetramethylurea according to the ... of the embodiment of the present invention, using dimethylamine and triphosgene as raw material, wherein, dimethylamine can be dimethylamine agueous solution or dimethylamine gas, triphosgene can be triphosgene itself or triphosgene organic solution, the preparation method is easy to operate, product yield is high, at low cost, and is suitble to industrialized production.
Description
Technical field
The present invention relates to organic chemical synthesis technical fields, and in particular, to tetramethylurea and preparation method thereof.
Background technology
The dielectric constant of tetramethylurea (TMU) is relatively low, suitable for make the isomerization of base catalysis, alkylation, cyaniding and other
The solvent of condensation reaction also serves as the solvent of acetylene and polyacrylonitrile, is a kind of efficient organic solvent, it is for general organic
Compound especially aromatic compound can be completely dissolved, but also be the fine solvent of many organic synthesis reactions.Four
Methylurea is that a kind of important Fine Organic Chemical product can be widely applied to medicine, pesticide, dye as intermediate and catalyst
The synthesis of material.
Currently, the prior synthesizing method of tetramethylurea is mainly two kinds, one is dimethylamine and phosgene reaction, and reaction equation is such as
Following formula (1).
It since the fuel factor in the reaction is very causus, thus is difficult to control in a large amount of prepare, while in lock out operation
When there is also certain difficulties.So first intermediate product separate out in general operation, then again with dimethylamine
It has an effect.
Another method is to replace phosgene, reaction equation following formula (2) with diphenyl carbonate.
Although diphenyl ester is big without phosgene toxicity, operation needs high temperature and pressure.This is complicated for operation, and yield is low, cost
It is high.
Therefore, above two method is not suitable for industrialized production.
Invention content
In view of this, the purpose of the present invention is to provide a kind of easy to operate, high income, the systems of tetramethylurea at low cost
Preparation Method.
The present invention also provides tetramethylureas made from a kind of preparation method of above-mentioned tetramethylurea.
In order to solve the above technical problems, present invention employs following technical schemes：
The preparation method of the tetramethylurea of embodiment according to a first aspect of the present invention, includes the following steps：
Step S1, provides dimethylamine and triphosgene；
Step S2 makes dimethylamine be reacted with triphosgene and generates the tetramethylurea.
Preferably, in the step S1, dimethylamine agueous solution and triphosgene organic solution are provided；In the step S2, to
The triphosgene organic solution is added dropwise in the dimethylamine agueous solution, so that dimethylamine is reacted with triphosgene generates the tetramethyl
Urea.
Further, in the step S2, the same of the triphosgene organic solution is added dropwise into the dimethylamine agueous solution
When, aqueous alkali is also added dropwise, so that dimethylamine reacts under alkaline condition with triphosgene generates the tetramethylurea.
It will be appreciated by persons skilled in the art that dimethylamine is alkalinity, make the mole of dimethylamine sufficiently high, for example,
At 6 times or more of triphosgene mole, dimethylamine can not only be used as reaction substrate, but also have an effect as alkali, at this time may be used
Not have to that aqueous alkali is added.
Further, the alkali in the aqueous alkali of the step S2 is sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid
One or more of potassium, sodium bicarbonate, saleratus.
Still further, the dosage of the alkali is 6 equivalents of the triphosgene dosage or less.
Preferably, in the step S1, dimethylamine agueous solution and triphosgene are provided；In the step S2, to the diformazan
The triphosgene is added in amine aqueous solution, so that dimethylamine is reacted with triphosgene generates the tetramethylurea.
Preferably, in the step S1, dimethylamine gas and triphosgene organic solution are provided；In the step S2, to institute
It states and the dimethylamine gas is added in triphosgene organic solution, so that dimethylamine is reacted with triphosgene generates the tetramethylurea.
Further, in the step S1, the organic solvent used in the triphosgene organic solution is selected from methanol, second
One or more of alcohol, acetonitrile, tetrahydrofuran, dichloromethane.
Further, the dimethylamine is 5~15 equivalents of the triphosgene.
Preferably, in the step S2, reaction temperature be 0~25 DEG C, the reaction time be 2~for 24 hours.
Preferably, the preparation method of tetramethylurea further includes：
Step S3, the reaction solution after the step S2 is reacted are stood, and liquid separation, dichloromethane aqueous phase extracted remerges two
Chloromethanes phase, the dichloromethane after merging mutually use saturated common salt water washing, are hereafter steamed by dry, filtering, concentration, oil pump decompression
It evaporates, obtains refined tetramethylurea.
The tetramethylurea of embodiment according to a second aspect of the present invention is the system according to the tetramethylurea of any of the above-described embodiment
Made from Preparation Method.
The above-mentioned technical proposal of the present invention one of at least has the following effects that：
(1) transport of raw material triphosgene and dimethylamine and easy to operate, it is cheap, cost can be reduced；
(2) this method step is reduced, and yield is higher, is suitable for industrialized production.
Description of the drawings
Fig. 1 is the flow diagram according to the preparation method of the tetramethylurea of the present invention；
Fig. 2 is the flow diagram according to the preparation method of the tetramethylurea of some embodiments of the invention.
Specific implementation mode
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
Attached drawing the technical solution of the embodiment of the present invention is clearly and completely described.Obviously, described embodiment is the present invention
A part of the embodiment, instead of all the embodiments.Based on described the embodiment of the present invention, ordinary skill people
The every other embodiment that member is obtained, shall fall within the protection scope of the present invention.
In the following, in conjunction with Fig. 1-Fig. 2, the preparation method of tetramethylurea according to the ... of the embodiment of the present invention is specifically described.
As shown in Figure 1, the preparation method of tetramethylurea according to the ... of the embodiment of the present invention includes the following steps：
Step S1, provides dimethylamine and triphosgene.
Dimethylamine is gas at room temperature, relative density 0.680g/mL (0 DEG C), -96 DEG C of fusing point, 7.4 DEG C of boiling point, easily
It is dissolved in water, is dissolved in ethyl alcohol and ether, easy firing has alkalescent, and salt soluble easily in water is generated with inorganic acid.Two in the present invention
Methylamine can be commercially available product, can also be by conventional method, such as in the presence of the catalyst at elevated temperature and pressure by ammonia and methanol
It acts on and is made.
Triphosgene is also known as solid phosgene, and chemical name is carbonic acid trichloromethyl ester, bis- (trichloromethyl) carbonic esters, triphosgene
For white crystal, the smell of similar phosgene.Stability is stronger, only a small amount of in boiling point to decompose, and generates trichloromethyl chloroformate
And phosgene.
Due to the physical characteristic of dimethylamine and triphosgene, dimethylamine may be used dimethylamine agueous solution and can also use
Triphosgene itself or triphosgene organic solution may be used in dimethylamine gas, triphosgene.
Wherein, the organic solvent used in triphosgene organic solution can be selected from methanol, ethyl alcohol, acetonitrile, tetrahydrofuran,
One or more of dichloromethane.
Step S2 makes dimethylamine be reacted with triphosgene and generates the tetramethylurea.
As shown in Fig. 2, specifically, which can be following any processes：1. being added dropwise into the dimethylamine agueous solution
The triphosgene organic solution, so that dimethylamine is reacted with triphosgene generates the tetramethylurea；2. water-soluble to the dimethylamine
The triphosgene is added in liquid, so that dimethylamine is reacted with triphosgene generates the tetramethylurea；3. organic to the triphosgene
The dimethylamine gas is added in solution, so that dimethylamine is reacted with triphosgene generates the tetramethylurea.
It is above-mentioned 1. in, according to the concrete condition of used dimethylamine agueous solution and triphosgene organic solution, such as rub
Your concentration, molar ratio etc. can also aqueous alkali be added dropwise into dimethylamine agueous solution simultaneously, so that dimethylamine and triphosgene are in alkali
Property under the conditions of reaction generate the tetramethylurea.Wherein, the alkali in aqueous alkali is sodium hydroxide, potassium hydroxide, sodium carbonate, carbon
One or more of sour potassium, sodium bicarbonate, saleratus.Preferably, the dosage of alkali be the triphosgene dosage 6 equivalents with
Under.It is highly preferred that the dosage of alkali is 6 equivalents of the triphosgene dosage.
The reaction equation that dimethylamine reacts generation tetramethylurea with triphosgene is as follows：
Preferably, dimethylamine is 5~15 equivalents of the triphosgene.
Preferably, the reaction temperature in step S2 be 0~25 DEG C, the reaction time be 2~for 24 hours, the reaction temperature is more advantageous
In the progress of reaction, and the temperature is easier to realize.
Step 3, the reaction solution after the step S2 being reacted is clarified, and liquid separation, dichloromethane aqueous phase extracted remerges dichloro
Methane phase, the dichloromethane after merging mutually use saturated common salt water washing, are hereafter steamed by dry, filtering, concentration, oil pump decompression
It evaporates, obtains refined tetramethylurea.
The preparation method of tetramethylurea according to the ... of the embodiment of the present invention is easy to operate, product yield is high, at low cost, and is suitble to
Industrialized production.
To enable the technical research personnel of this field to be better understood from technical scheme of the present invention, with reference to embodiment
The present invention is described in further detail.
Embodiment 1：
Dimethylamine agueous solution (40%, 3.81Kg, 33.8mol) is added into three-necked flask, ice salt bath controls temperature 15
DEG C or less be added dropwise triphosgene (773.4g, 2.6mol) dichloromethane solution, drop to and finish, reaction solution is gone back up into room temperature naturally
The reaction was continued 2~3 hours, and after reaction solution clarification, liquid separation, DCM aqueous phase extracteds remerge dichloromethane phase, and two after merging
Chloromethanes mutually uses saturated common salt water washing, and hereafter dry, filtering, concentration, oil pump vacuum distillation drying obtain 836g colourless liquids,
GC purity is more than 99%, yield 92%.
Nmr experiments are carried out to obtained product, 0.05mL samples is taken, 0.5mL deuterochloroforms is added, use
400MHz nuclear-magnetisms are analyzed, and data are as follows：
1H NMR(400MHz,CDCl3):δ=2.80 (s, 12H, NCH3)。
Embodiment 2:
Dimethylamine agueous solution (40%, 117g, 1.04mol) is added into three-necked flask, ice salt bath controls temperature at 15 DEG C
The aqueous solution of the dichloromethane solution and 1N sodium hydroxides (62.4g) of triphosgene (77.34g, 260mmol) is added dropwise below, drops to
Finish, reaction solution return to naturally room temperature and the reaction was continued overnight, reaction solution clarification, liquid separation, DCM aqueous phase extracteds remerge dichloro
Methane phase, the dichloromethane after merging mutually use saturated common salt water washing, hereafter dry, filtering, concentration, oil pump vacuum distillation drying
63g colourless liquids are obtained, GC purity is more than 99%, yield 69.5%.
Nmr experiments are carried out to obtained product, 0.05mL samples is taken, 0.5mL deuterochloroforms is added, use
400MHz nuclear-magnetisms are analyzed, and data are as follows：
1H NMR(400MHz,CDCl3):δ=2.78 (s, 12H, NCH3)。
Embodiment 3:
Dimethylamine agueous solution (40%, 117g, 1.04mol) is added into three-necked flask, ice salt bath controls temperature at 15 DEG C
Be passed through triphosgene (77.34g, 260mmol) below, after reaction solution return to naturally room temperature and the reaction was continued overnight, reaction solution
Clarification, liquid separation, DCM aqueous phase extracteds remerge dichloromethane phase, and the dichloromethane after merging mutually uses saturated common salt water washing, this
Dry afterwards, filtering, concentration, oil pump vacuum distillation drying obtain 63g colourless liquids, and GC purity is more than 99%, yield 69.5%.
Nmr experiments are carried out to obtained product, 0.05mL samples is taken, 0.5mL deuterochloroforms is added, use
400MHz nuclear-magnetisms are analyzed, and data are as follows：
1H NMR(400MHz,CDCl3):δ=2.76 (s, 12H, NCH3)。
Embodiment 4:
Triphosgene (77.34g, 260mmol) and dichloromethane are added into three-necked flask, ice salt bath controls temperature at 0 DEG C
Hereinafter, and be slowly introducing excessive dimethylamine gas, drop to and finish, reaction solution returns to room temperature naturally, and the reaction was continued 12 hours, waits for
The clear liquid of reaction solution, liquid separation, DCM aqueous phase extracteds remerge dichloromethane phase, and the dichloromethane after merging is mutually washed with saturated common salt
It washs, hereafter dry, filtering, concentration, oil pump are evaporated under reduced pressure to obtain 79.5g colourless liquids, and GC purity is more than 99%, and yield is
87.5%.
Nmr experiments are carried out to obtained product, 0.05mL samples is taken, 0.5mL deuterochloroforms is added, use
400MHz nuclear-magnetisms are analyzed, and data are as follows：
1H NMR(400MHz,CDCl3):δ=2.75 (s, 12H, NCH3)。
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, it can also make several improvements and retouch, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (12)
1. a kind of preparation method of tetramethylurea, which is characterized in that include the following steps：
Step S1, provides dimethylamine and triphosgene；
Step S2 makes dimethylamine be reacted with triphosgene and generates the tetramethylurea.
2. the preparation method of tetramethylurea according to claim 1, which is characterized in that
In the step S1, dimethylamine agueous solution and triphosgene organic solution are provided,
In the step S2, the triphosgene organic solution is added dropwise into the dimethylamine agueous solution, so that dimethylamine and three light
Solid/liquid/gas reactions generate the tetramethylurea.
3. the preparation method of tetramethylurea according to claim 2, which is characterized in that in the step S2, to described two
While the triphosgene organic solution is added dropwise in methylamine water solution, aqueous alkali is also added dropwise, so that dimethylamine exists with triphosgene
Reaction generates the tetramethylurea under alkaline condition.
4. the preparation method of tetramethylurea according to claim 3, which is characterized in that in the aqueous alkali of the step S2
Alkali be sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, one or more of saleratus.
5. the preparation method of tetramethylurea according to claim 4, which is characterized in that the dosage of the alkali is three light
Below 6 equivalents of gas dosage.
6. the preparation method of tetramethylurea according to claim 1, which is characterized in that
In the step S1, dimethylamine agueous solution and triphosgene are provided；
In the step S2, the triphosgene is added into the dimethylamine agueous solution, so that dimethylamine reacts life with triphosgene
At the tetramethylurea.
7. the preparation method of tetramethylurea according to claim 1, which is characterized in that
In the step S1, dimethylamine gas and triphosgene organic solution are provided；
In the step S2, the dimethylamine gas is added into the triphosgene organic solution, so that dimethylamine and triphosgene
Reaction generates the tetramethylurea.
8. the preparation method of the tetramethylurea according to claim 2 or 7, which is characterized in that in the step S1, described three
One kind in methanol, ethyl alcohol, acetonitrile, tetrahydrofuran, dichloromethane of organic solvent used in phosgene organic solution or
It is several.
9. the preparation method of tetramethylurea according to claim 1, which is characterized in that the dimethylamine is the triphosgene
5~15 equivalents.
10. the preparation method of tetramethylurea according to claim 1, which is characterized in that in the step S2, reaction temperature
Be 0~25 DEG C, the reaction time be 2~for 24 hours.
11. the preparation method of tetramethylurea according to claim 1, which is characterized in that further include：
Step S3, the reaction solution after the step S2 is reacted are clarified, and liquid separation, dichloromethane aqueous phase extracted remerges dichloromethane
Alkane phase, the dichloromethane after merging mutually use saturated common salt water washing, hereafter pass through dry, filtering, concentration, oil pump vacuum distillation,
Obtain refined tetramethylurea.
12. the tetramethylurea being prepared according to the preparation method of claim 1 to 11 any one of them tetramethylurea.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810260950.6A CN108558706A (en) | 2018-03-28 | 2018-03-28 | Tetramethylurea and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810260950.6A CN108558706A (en) | 2018-03-28 | 2018-03-28 | Tetramethylurea and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108558706A true CN108558706A (en) | 2018-09-21 |
Family
ID=63533108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810260950.6A Pending CN108558706A (en) | 2018-03-28 | 2018-03-28 | Tetramethylurea and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108558706A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113264852A (en) * | 2021-05-17 | 2021-08-17 | 南京工业大学 | Method for preparing tetrabutyl urea by oil-water two-phase reaction system |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3904602A (en) * | 1971-02-16 | 1975-09-09 | Ciba Geigy Corp | Process for the manufacture of tetrasubstituted ureas |
| CN101333176A (en) * | 2008-05-30 | 2008-12-31 | 浙江工业大学 | Method for preparing substituent urea and co-producing hydrochloride of corresponding amines |
| CN103553974A (en) * | 2013-10-31 | 2014-02-05 | 上海华谊（集团）公司 | Preparation method of N-alkyl conjugated ion type quaternary ammonium salt |
-
2018
- 2018-03-28 CN CN201810260950.6A patent/CN108558706A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3904602A (en) * | 1971-02-16 | 1975-09-09 | Ciba Geigy Corp | Process for the manufacture of tetrasubstituted ureas |
| CN101333176A (en) * | 2008-05-30 | 2008-12-31 | 浙江工业大学 | Method for preparing substituent urea and co-producing hydrochloride of corresponding amines |
| CN103553974A (en) * | 2013-10-31 | 2014-02-05 | 上海华谊（集团）公司 | Preparation method of N-alkyl conjugated ion type quaternary ammonium salt |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113264852A (en) * | 2021-05-17 | 2021-08-17 | 南京工业大学 | Method for preparing tetrabutyl urea by oil-water two-phase reaction system |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1705173B1 (en) | Binaphthol deratives and their use in optical resolution or optical transformation | |
| CN104829493A (en) | Synthetic method for romatic carbamic acid ester | |
| CN108558706A (en) | Tetramethylurea and preparation method thereof | |
| CN101735029A (en) | Synthesis method of hellebore aldehyde | |
| JP5681985B2 (en) | Production method of urea compounds by carbon dioxide fixation | |
| JP2007238540A (en) | Method for producing optically active alcohol compound | |
| CN106518758A (en) | Preparation method of Betrixaban intermediate N-(5-chloro-2-pyridyl)-2-(4-cyanobenzeneformamido)-5-metoxybenzamide | |
| CN101302157B (en) | Preparation of 3-oxo-2-pentyl cyclopentenyl methyl acetate | |
| JP5057420B2 (en) | Organic bismuth compound and method for producing the same | |
| JPS62111939A (en) | Optically active beta-fluorohydrin compound | |
| Raghavan et al. | Bromosulfonamidation of alkenes using S, S-dimethyl-N-(p-toluenesulfonyl) sulfilimine | |
| TWI592404B (en) | Novel stilbene compounds and methods of making the same | |
| CN106167459A (en) | A kind of new method synthesizing thiazolinyl sulfocyanic ester derivant | |
| JPH10212281A (en) | Production of 3-carene epoxide | |
| US10450253B2 (en) | Preparation process of perfluoroalkyl compound with monohydroperfluoroalkane as starting material | |
| KR19980081393A (en) | Method for preparing chloroketoamine using carbamate | |
| CN109954449A (en) | Double tail amidino groups surfactants and preparation method thereof | |
| CN1307165C (en) | 4-methyl-5-formylthiazole preparation method | |
| JP4255296B2 (en) | Method for producing cyclic fluorinated alcohol | |
| CN114685415B (en) | Synthesis method of kojic acid dimer | |
| CN114989115B (en) | Improved synthesis of alpha- (nitromethyl) -2-furanmethanol and method for maintaining catalyst activity in the process | |
| JP3823339B2 (en) | Perfluoro (2-methyl-1,2-epoxypropyl) ether compound and process for producing the same | |
| CN106167473B (en) | 1,4,2- dioxy nitrogen azole compounds and its synthetic method | |
| CN101104581A (en) | Fluorine-containing alpha, beta-unsaturated ketone and synthetic method thereof | |
| RU2612956C1 (en) | Method for producing 1-adamantyl acetaldehyde |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180921 |