CN106083611B - A kind of synthetic method of N,N-dimethylformamide dimethylacetal - Google Patents
A kind of synthetic method of N,N-dimethylformamide dimethylacetal Download PDFInfo
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- CN106083611B CN106083611B CN201610594398.5A CN201610594398A CN106083611B CN 106083611 B CN106083611 B CN 106083611B CN 201610594398 A CN201610594398 A CN 201610594398A CN 106083611 B CN106083611 B CN 106083611B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
- C07C257/04—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines without replacement of the other oxygen atom of the carboxyl group, e.g. imino-ethers
- C07C257/06—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines without replacement of the other oxygen atom of the carboxyl group, e.g. imino-ethers having carbon atoms of imino-carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms, or to carbon atoms of rings other than six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
Abstract
The invention discloses a kind of N, the synthetic method of dinethylformamide dimethylacetal, the synthetic method is first with N, dinethylformamide and dimethyl suflfate reaction generate imino-complex, again imino-complex is reacted to obtain n,N-Dimethylformamide dimethylacetal with the solid sodium methylate of dispersion in organic solvent；The organic solvent is at least one of isoparaffin, solvent naphtha, white oil.The present invention uses new organic solvent, can reduce the reaction condition (20-30 DEG C of temperature) of imino-complex and sodium methoxide, reaction condition is milder.In addition, reacting the solution rate of the product of generation faster for the reaction temperature of reaction temperature of the invention compared to original -5-0 DEG C, it can be dissolved into organic solvent in time, the product for generating organic solvent to reaction carries out dissolution package, avoids generation by-product, improves yield.Experiment shows the yield of n,N-Dimethylformamide dimethylacetal of the present invention up to 85% or more.
Description
Technical field
The present invention relates to a kind of synthetic method of fine medicine intermediate, in particular to a kind of n,N-Dimethylformamide two
The synthetic method of dimethoxym ethane, belongs to technical field of fine.
Background technique
N,N-Dimethylformamide dimethylacetal, English entitled N, N-dimethylformamide dimethyl
Acetal is abbreviated as DMF-DMA, and CAS registration number is 4637-24-5, and molecular formula is C5H13NO2, molecular weight 119.16, structure
Formula are as follows:
N,N-Dimethylformamide dimethylacetal has extensive purposes, is the important intermediate of synthesizing heterocyclic compound,
Also be a kind of good methylating reagent and esterification dehydrating agent, especially it is as medical synthetic intermediate, can be used for carbonamidine,
The synthesis of the drugs such as 1,2,3- three ketones, indoles, quinolone drugs, Ofloxacin, milrinone and Allopurinol.
The synthesis early stage of N,N-dimethylformamide dimethylacetal uses SOCl2And POCl3Equal chlorination reagents make formamide chlorine
Metaplasia produces dichloride amine, and dichloride amine is reacted with sodium methoxide again generates n,N-Dimethylformamide dimethylacetal, but such is anti-
Answer complexity, yield lower (10%-40%), generation waste material is more, and economic benefit and environmental benefit are bad.In recent years, N, N- bis-
The synthesis of methylformamide dimethylacetal mainly utilizes N,N-dimethylformamide (DMF) and dimethyl suflfate to react and generates Asia
Amine complex (first step reaction), imino-complex react to obtain n,N-Dimethylformamide dimethylacetal (again with sodium methoxide
The reaction of two steps), this method raw material is cheap, easy to operate, and yield height is mainly determined by second step reaction.Domestic scholars are to this
Method production N,N-dimethylformamide dimethylacetal has carried out some researchs.Chen Mei skin of bamboo et al. is suspended in using solid sodium methylate
In petroleum ether, reaction generates product n,N-Dimethylformamide dimethylacetal, and product n,N-Dimethylformamide dimethylacetal is molten
In petroleum ether, yield is in 65% or so (preparation of n,N-Dimethylformamide dimethylacetal, Shandong chemical industry, 2002).Pan Yi
Et al. use liquid methanol sodium, methanol is evaporated off, petroleum ether is then added, yield increases, but second step reaction in still
Using petroleum ether as solvent, when reaction, needs to control 0 DEG C of temperature hereinafter, severe reaction conditions (n,N-Dimethylformamide two
Dimethoxym ethane optimum preparation condition, fine-chemical intermediate, 2008).Therefore, develop that a kind of reaction condition is mild, yield is higher
N,N-dimethylformamide dimethylacetal synthetic method is of great significance.
Summary of the invention
To solve the above-mentioned problems, the object of the present invention is to provide a kind of synthesis of n,N-Dimethylformamide dimethylacetal
Method, this method participate in reaction using new organic solvent, and reaction condition is mild, and yield greatly improves.
To achieve the goals above, the technical scheme adopted by the invention is that:
A kind of synthetic method of n,N-Dimethylformamide dimethylacetal, the synthetic method are first with N, N- dimethyl
Formamide and dimethyl suflfate reaction generate imino-complex, then the solid first by imino-complex and dispersion in organic solvent
Sodium alkoxide reacts to obtain N,N-dimethylformamide dimethylacetal；
The organic solvent is at least one of isoparaffin, solvent naphtha, white oil.
The temperature that imino-complex is reacted with the solid sodium methylate of dispersion in organic solvent is 20-30 DEG C.
The synthetic method of the n,N-Dimethylformamide dimethylacetal, comprising the following steps:
(1) n,N-Dimethylformamide is heated to 60-80 DEG C, heat preservation is added dropwise dimethyl suflfate, reacts after completion of dropwise addition
2-5h obtains imino-complex, is cooled to room temperature, spare；Wherein, the molar ratio of n,N-Dimethylformamide and dimethyl suflfate
For 1:1；
(2) in organic solvent by solid sodium methylate dispersion, 20-30 DEG C is adjusted the temperature to, imines complexing is added dropwise in heat preservation
Object reacts 1-3h after completion of dropwise addition, filtering, filtrate is fractionated under normal pressure, collects 105-108 DEG C of fraction, obtains N, N- dimethyl
Formamide dimethylacetal；Wherein, the molar ratio of sodium methoxide and imino-complex is 1:1；
The organic solvent is at least one of isoparaffin, solvent naphtha, white oil.
The ratio of solid sodium methylate and organic solvent is that every 1mol sodium methoxide is dispersed at least 200ml organic solvent.
The isoparaffin is at least one of isomery dodecane, isomery hexadecane.
The solvent naphtha be 200# solvent naphtha, 260# solvent naphtha, D40 solvent naphtha, D60 solvent naphtha, in D80 solvent naphtha extremely
Few one kind.
Coal tar that the white oil is 140-200 DEG C of boiling range, at least one of 180-230 DEG C of boiling range of coal tar.
The mode of the dispersion is mechanical stirring dispersion or ultrasonic disperse.
The reaction equation of the synthesis of N,N-dimethylformamide dimethylacetal of the present invention:
Beneficial effects of the present invention:
1, the present invention screens to obtain new organic solvent by repetition test, this is organic molten on the basis of forefathers' research
Agent can reduce the reaction condition of imino-complex and sodium methoxide, makes reaction temperature from original -5-0 DEG C, is increased to 20-30
DEG C, reaction condition is milder.
2, the present invention uses new organic solvent, and reaction temperature requires low (20-30 DEG C), the i.e. controllable temperature of simple water cooling
Degree does not need to provide the refrigeration equipment and technique of control temperature condition, can reduce cost, and waste material generation is greatly reduced, mentions
High economy and environmental benefit.
3, new organic solvent itself boiling point that the present invention uses is higher (140-260 DEG C), and product itself low boiling point 105-
108 DEG C, thus product can from organic solvent simple, quick separating.Meanwhile organic solvent of the invention can recycle circulation
It utilizes, reaction condition is mild, practicability is wide, is suitble to industrialized production n,N-Dimethylformamide dimethylacetal.
4, the present invention uses new organic solvent, reaction of the reaction temperature between 20-30 DEG C, compared to original -5-0 DEG C
For temperature, the solution rate for reacting the product of generation faster, can be dissolved into organic solvent in time, make organic solvent to anti-
The product that should be generated carries out dissolution package, avoids generation by-product, improves yield.Experiment shows N of the present invention, N- dimethyl
The yield of formamide dimethylacetal is up to 85% or more.
Detailed description of the invention
Fig. 1 is the infrared spectrogram for the N,N-dimethylformamide dimethylacetal that the present invention synthesizes.
Specific embodiment
Specific embodiments of the present invention will be described in further detail with reference to embodiments.
Embodiment 1
A kind of synthetic method of n,N-Dimethylformamide dimethylacetal, comprising the following steps:
(1) n,N-Dimethylformamide being heated to 60 DEG C, heat preservation is added dropwise dimethyl suflfate, reacts 5h after completion of dropwise addition,
Imino-complex is obtained, is cooled to room temperature, it is spare；Wherein, n,N-Dimethylformamide and the molar ratio of dimethyl suflfate are 1:
1；
(2) solid sodium methylate is added in isomery dodecane, mechanical stirring dispersion adjusts the temperature to 20 DEG C, keeps the temperature, is added dropwise
Imino-complex reacts 3h after completion of dropwise addition, filtering, filtrate is fractionated under normal pressure, collects 105-108 DEG C of fraction, obtains N, N-
Dimethylformamide dimethyl acetal, yield 72.6%, purity 97%；Wherein, the molar ratio of sodium methoxide and imino-complex
For 1:1；
The ratio of solid sodium methylate and isomery dodecane is that every 1mol sodium methoxide is dispersed in 200ml isomery ten in step (2)
In dioxane.
Embodiment 2
A kind of synthetic method of n,N-Dimethylformamide dimethylacetal, comprising the following steps:
(1) n,N-Dimethylformamide being heated to 70 DEG C, heat preservation is added dropwise dimethyl suflfate, reacts 4h after completion of dropwise addition,
Imino-complex is obtained, is cooled to room temperature, it is spare；Wherein, n,N-Dimethylformamide and the molar ratio of dimethyl suflfate are 1:
1；
(2) solid sodium methylate is added in 200# solvent naphtha, ultrasonic disperse, adjusts the temperature to 25 DEG C, imines is added dropwise in heat preservation
Complex compound reacts 2h after completion of dropwise addition, filtering, filtrate is fractionated under normal pressure, collects 105-108 DEG C of fraction, obtains N, N- diformazan
Base formamide dimethylacetal, yield 75.3%, purity 97%；Wherein, the molar ratio of sodium methoxide and imino-complex is 1:
1；
The ratio of solid sodium methylate and 200# solvent naphtha is that be dispersed in 250ml 200# molten for every 1mol sodium methoxide in step (2)
In agent oil.
Embodiment 3
A kind of synthetic method of n,N-Dimethylformamide dimethylacetal, comprising the following steps:
(1) n,N-Dimethylformamide being heated to 80 DEG C, heat preservation is added dropwise dimethyl suflfate, reacts 2h after completion of dropwise addition,
Imino-complex is obtained, is cooled to room temperature, it is spare；Wherein, n,N-Dimethylformamide and the molar ratio of dimethyl suflfate are 1:
1；
(2) solid sodium methylate is added in D80 solvent naphtha, ultrasonic disperse, adjusts the temperature to 30 DEG C, imines is added dropwise in heat preservation
Complex compound reacts 1h after completion of dropwise addition, filtering, filtrate is fractionated under normal pressure, collects 105-108 DEG C of fraction, obtains N, N- diformazan
Base formamide dimethylacetal, yield 74.6%, purity 97%；Wherein, the molar ratio of sodium methoxide and imino-complex is 1:
1；
The ratio of solid sodium methylate and D80 solvent naphtha is that every 1mol sodium methoxide is dispersed in 300ml D80 solvent in step (2)
In oil.
Embodiment 4
The synthetic method of the n,N-Dimethylformamide dimethylacetal of embodiment 4 with embodiment 2, the difference is that: this
Embodiment organic solvent is isoparaffin and solvent naphtha mixture: isomery dodecane, isomery hexadecane, D80 solvent naphtha (volume ratio
1:1:1), the yield for obtaining n,N-Dimethylformamide dimethylacetal is 83.6%, purity 97%.
Embodiment 5
The synthetic method of the n,N-Dimethylformamide dimethylacetal of embodiment 5 with embodiment 2, the difference is that: this
Embodiment organic solvent be mixing white oil: 140-200 DEG C of boiling range of coal tar, 180-230 DEG C of boiling range of coal tar (volume ratio 2:
1) yield for, obtaining n,N-Dimethylformamide dimethylacetal is 85.2%, purity 97%.
Embodiment 6
The synthetic method of the n,N-Dimethylformamide dimethylacetal of embodiment 6 with embodiment 2, the difference is that: this
Embodiment organic solvent be mixed solvent oil: D40 solvent naphtha, D60 solvent naphtha, 260# solvent naphtha mixture (volume ratio 2:1:
1) yield for, obtaining n,N-Dimethylformamide dimethylacetal is 85.4%, purity 97%.
Infrared spectrum analysis, the result is shown in Figure 1 are carried out to the n,N-Dimethylformamide dimethylacetal that the present invention synthesizes.
From figure 1 it appears that 2990~2783cm-1It is the stretching vibration peak of C-H, 1682cm-1It is the flexible vibration of tertiary amine
Dynamic peak, 1445~1381cm-1It is-CH3Flexural vibrations peak, 1346cm-1It is the flexural vibrations peak of-CH-, 1298~999cm-1
It is the stretching vibration peak of C-O, since the absorption of C-O-C is stronger, shows 1057cm on map-1Display is comprehensive compared with strong absworption peak
Corresponding group feature given by infared spectrum is consistent with the molecular formula of N,N-dimethylformamide dimethylacetal.
Claims (5)
1. a kind of synthetic method of n,N-Dimethylformamide dimethylacetal, which is characterized in that the synthetic method be first with
N,N-Dimethylformamide and dimethyl suflfate reaction generate imino-complex, then by imino-complex and are dispersed in organic solvent
In solid sodium methylate react to obtain N,N-dimethylformamide dimethylacetal；
The organic solvent is at least one of isoparaffin, solvent naphtha, white oil；The isoparaffin is isomery 12
At least one of alkane, isomery hexadecane；The solvent naphtha is 200# solvent naphtha, 260# solvent naphtha, D40 solvent naphtha, D60 solvent
At least one of oil, D80 solvent naphtha；The white oil is 140-200 DEG C of boiling range of coal tar, 180-230 DEG C of boiling range of coal tar
At least one of oil.
2. the synthetic method of n,N-Dimethylformamide dimethylacetal according to claim 1, which is characterized in that imines network
Closing the temperature that object is reacted with the solid sodium methylate of dispersion in organic solvent is 20-30 DEG C.
3. the synthetic method of n,N-Dimethylformamide dimethylacetal according to claim 2, which is characterized in that including with
Lower step:
(1) n,N-Dimethylformamide is heated to 60-80 DEG C, heat preservation is added dropwise dimethyl suflfate, reacts 2- after completion of dropwise addition
5h obtains imino-complex, is cooled to room temperature, spare；Wherein, n,N-Dimethylformamide and the molar ratio of dimethyl suflfate are
1:1；
(2) in organic solvent by solid sodium methylate dispersion, 20-30 DEG C is adjusted the temperature to, imino-complex, drop is added dropwise in heat preservation
1-3h is reacted after adding, is filtered, and filtrate is fractionated under normal pressure, collects 105-108 DEG C of fraction, obtains n,N-Dimethylformamide
Dimethylacetal；Wherein, the molar ratio of sodium methoxide and imino-complex is 1:1；
The organic solvent is at least one of isoparaffin, solvent naphtha, white oil.
4. the synthetic method of n,N-Dimethylformamide dimethylacetal according to claim 1-3, feature exist
In the ratio of solid sodium methylate and organic solvent is that every 1mol sodium methoxide is dispersed at least 200ml organic solvent.
5. the synthetic method of n,N-Dimethylformamide dimethylacetal according to claim 1-3, feature exist
In the mode of the dispersion is mechanical stirring dispersion or ultrasonic disperse.
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| CN109651198A (en) * | 2018-12-29 | 2019-04-19 | 常州沃腾化工科技有限公司 | A kind of synthetic method of dimethylamino diethyl methylenemalonate |
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