CN109320439A - A kind of N '-(4- alkane phenyl)-N, the synthesis separation method of N- dimethylamidine - Google Patents
A kind of N '-(4- alkane phenyl)-N, the synthesis separation method of N- dimethylamidine Download PDFInfo
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- CN109320439A CN109320439A CN201811266854.9A CN201811266854A CN109320439A CN 109320439 A CN109320439 A CN 109320439A CN 201811266854 A CN201811266854 A CN 201811266854A CN 109320439 A CN109320439 A CN 109320439A
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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
- C07C257/10—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 with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
- C07C257/14—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 with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to acyclic carbon atoms
Abstract
The present invention provides a kind of N '-(4- alkane phenyl)-N, the synthesis separation methods of N- dimethylamidine.The step of this method includes: that 4- alkyl benzene amine is dissolved in acetonitrile, after being heated to preset temperature, N is added, N- dimethylformamide dimethylacetal is reacted；It is after reaction that reaction system is cooling, after reaction system layering, the distillation of lower layer's liquid pressure-reducing is taken to get product is arrived.This method is used as reaction dissolvent and extractant simultaneously using acetonitrile, using the difference of reaction raw materials and the product solubility in acetonitrile, realizes that reaction is coupled with extraction and separation, obtains N '-(4- alkane phenyl)-N of high-purity, N- dimethylamidine.The yield of this method can reach 90% or more, and product N '-(4- alkane phenyl)-N, the purity of N- dimethylamidine can further improve to 95% or more after extraction and separation.The reaction of this method is carried out simultaneously with separating, and is shortened generated time, is improved combined coefficient.N '-alkane benzene carbon amidine of the invention can use pesticide, medical and a kind of novel C O2/N2Switch surfactant.
Description
Technical field
The invention belongs to technical field of organic synthesis, more particularly to a kind of N '-(4- alkane phenyl)-N, N- dimethyl
The synthesis separation method of amidine.
Background technique
N '-alkane phenyl amidine compound can be used as anti-inflammatory, antimicrobial, also some type N '-alkane phenyl amidine compound tool
There is preferable anticancer property.It is agriculturally being widely used as insecticide, is having the advantages that low toxicity, high living, environmental protection.N '-alkane benzene carbon amidine
Class compound is also used as the intermediate of organic synthesis, for the synthesis containing heterocyclic nitrogen compound.N '-long-chain alkyl-phenyl
Amidine is as CO2/N2Surfactant is switched, there is greater advantage in terms of demulsification performance.Under normal conditions, in CO2Switching mode surface
During the protonation and deprotonation of surfactant system, deprotonation is more difficult to carry out, the deprotonation, that is, surfactant
Surface-active is lost to the process of emulsion breaking.The degree of alkalinity of end group will affect the balance of system deprotonation reaction.It grinds
Study carefully and show that end group alkalinity is lower, deprotonation process is easier to carry out.Compared with acid amidine class surfactant, alkane benzene carbon amidine class
End group has lower alkalinity, thus its deprotonation process can be more rapidly and thorough.With N '-dodecyl-N, N- diformazan
Base ethanamidine/aqueous systems deprotonation ability is compared, and is passed through Ar, alkane benzene carbon amidine carbonic acid into surfactant system at room temperature
Hydrogen salt/aqueous systems conductivity declines rapidly, is basically completed deprotonation process in a short time.And dodecyl ethanamidine bicarbonate
Salt/aqueous systems are interior at the same time, and conductivity only has dropped less than 20%, and most of ethanamidine is still protonation state
(Fowler C I,Jessop P G,Cunningham M F.Aryl amidine and tertiary amine
switchable surfactants and their application in the emulsion polymerization
of methyl methacrylate[J].Macromolecules,2012,45:2955-2962.)。
Currently, the synthesis of the N '-alkane benzene carbon amidine class of open report is mostly used with primary amine and n,N-dimethylacetamide diformazan
Base acetal is amide acetals method (Jitendra R.Harjani, Chen L, the Jessop P G.A synthesis of of raw material
acetamidines[J].The Journal of Organic Chemistry,2011,76:1683-1691)。
Following three kinds of modes can be used in this method:
(1) primary amine (3.18mmol) is mixed with n,N-dimethylacetamide dimethylacetal (3.82mmol), at 60 DEG C
Under, heat 2h.Reaction mixture rotates at room temperature on the rotary evaporator, and under high vacuum condition, 55 DEG C are continued to heat 8h, obtains
Product, solid amine are solvent with THF (5mL)；
(2) it is added dropwise primary amine (3.18mmol), drips in n,N-dimethylacetamide dimethylacetal (3.82mmol)
At 5 minutes or more between added-time, stir 10 minutes at room temperature at the same time.After reacting 18h at room temperature, removed using Rotary Evaporators
Volatile component.Continue to heat 8h under 55 DEG C of high vacuum later, to obtain product.It is molten with THF (5mL) for solid amine
N,N-dimethylacetamide dimethylacetal is added dropwise in agent dropwise in the THF solution of amine；
(3) DMAC N,N' dimethyl acetamide dimethylacetal (3.82mmol) and Me2NH (3.8mL, 2M are dissolved in THF,
It 7.64mmol) mixes in circular base bottle, stirs at room temperature.At room temperature, it is added dropwise decyl amine (3.18mmol), is added dropwise
Time 5 minutes or more.Stirring 10 minutes, is protected from light 18 hours.Revolving removes THF and Me later2NH.Then under a high vacuum
55 DEG C of stirring 8h.
Fowler etc., in round-bottomed flask, 4- decyl aniline (4.2mol) and n,N-dimethylacetamide dimethylacetal
(4.2mmol) reacts 30min at 60 DEG C and obtains N '-(4- last of the ten Heavenly stems phenyl)-N after reaction solution removes methanol by rotary evaporation,
N- dimethyl ethanamidine (Fowler C I, Jessop P G, Cunningham M F.Aryl amidine and tertiary
amine switchable surfactants and their application in the emulsion
polymerization of methyl methacrylate[J].Macromolecules,2012,45:2955-2962.)。
The above method carries out in two stages.It is different because of reaction temperature difference the time required to first stage.It is anti-at room temperature
It should about need 18 hours；Reaction needs 30min~120min at 60 DEG C.Second stage then in high vacuum conditions, give birth to by abstraction reaction
At pure and mild addition solvent, which needs ongoing operation about 8 hours, with the product of obtained higher degree.This method synthesized
It is longer the time required to journey, and alkanamine or alkyl benzene amine are dissolved sometimes for a certain amount of solvent (e.g., tetrahydrofuran) is added, it is molten
Agent will be removed in second stage.
In conclusion need to provide a kind of N '-(4- alkane phenyl)-N at present, the high-efficiency synthesis method of N- dimethylamidine,
Under the premise of obtaining the final products of high-purity, shorten generated time.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of N '-(4- alkane phenyl)-N, the synthesis separation side of N- dimethylamidine
Method, this method collection, which is reacted, to carry out simultaneously with separating, and shortens generated time, improves combined coefficient.
In order to achieve the goal above, the invention adopts the following technical scheme:
A kind of N '-(4- alkane phenyl)-N, the synthesis separation method of N- dimethylamidine, the reaction equation of this method are as follows:
Wherein, R1For C12-C18Alkyl, R2For H or-CH3。
Specifically, method includes the following steps:
4- alkyl benzene amine is dissolved in acetonitrile, after being heated to preset temperature, N, N- dimethylformamide dimethylacetal is added
It is reacted；
It is after reaction that reaction system is cooling, after reaction system layering, take the distillation of lower layer's liquid pressure-reducing to get
To product N '-(4- alkane phenyl)-N, N- dimethylamidine.
Reaction system layering can directly stratification be also layered by means such as centrifugations.Supernatant liquid is acetonitrile, not anti-
The 4- alkyl benzene amine and acetal answered；By supernatant liquor in pressure 1kPa-100kPa, second is recycled in 30 DEG C of -100 DEG C of vacuum distillations of temperature
The acetonitrile of nitrile, recycling can be recycled 1-10 times；Preferably, access times are 5-7 times.
Method of the invention introduces acetonitrile as solvent on the basis of amide acetals method.Acetonitrile is as dissolution raw material 4-
While the solvent of alkyl benzene amine, as the extractant of reactive separation process, reaction raw materials and product N '-(4- alkane benzene are utilized
Base)-N, dissolubility difference of the N- dimethylamidine in acetonitrile, the separation of realization product and reactant during the reaction.Reaction
After, after reaction solution cooling and standings layering, it can be obtained N '-(4- alkane phenyl)-N containing a small amount of solvent, N- dimethyl
Amidine product, is handled by vacuum distillation, can obtain N '-(4- alkane phenyl)-N of high-purity, N- dimethylamidine rapidly.And containing not
The acetonitrile of the raw material of fully reacting can be recycled by rectification under vacuum.This method is that one kind is strengthened by solution extraction process
Chemical reaction, realize N '-(4- alkane phenyl)-N, the high-efficiency synthesis method of N- dimethylamidine.
In above method, it is preferable that the volume ratio of the acetonitrile and 4- alkyl benzene amine is 5:1-20:1.
In above method, 4- alkyl benzene amine is dissolved in acetonitrile, is heated to preset temperature so that acetonitrile flows back, to accelerate
Reaction process shortens the reaction time.Preferably, the preset temperature is 50-90 DEG C.
In above method, N need to be taken, the reaction raw materials of N- dimethylformamide dimethylacetal and 4- alkyl benzene amine are than high
In the scheme of reactive chemistry metering ratio, so that alkyl benzene amine fully reacting as far as possible.Preferably, the N, N- dimethylformamide two
The molar ratio of methyl acetal and 4- alkyl benzene amine is 1:1-2:1.
Preferably, the reaction is synthesis under normal pressure 10min-20min.Preferably, the pressure of the vacuum distillation is 1kPa-
100kPa, temperature are 30 DEG C -100 DEG C.
N '-(4- alkane phenyl)-N of the invention, in the synthetic method of N- dimethylamidine, the acetal of use is preferably N, N- bis-
The combination of one or both of methylformamide dimethylacetal and DMAC N,N' dimethyl acetamide dimethylacetal.
Preferably, it is C that the alkyl benzene amine, which is the alkyl of 4- alkyl benzene amine,12-C18Alkyl.
Another aspect of the present invention provides N '-(4- alkane phenyl)-N that the above method is prepared, N- dimethylamidine, structural formula
It is as follows:
Wherein R1For C12-C18Alkyl, R2For H or-CH3。
Method of the invention, as reaction dissolvent and extractant, utilizes reactive component 4- alkyl benzene amine, N, N- using acetonitrile
Dimethylformamide acetal and N '-(4- alkane phenyl)-N, N- dimethylamidine dissolubility difference in acetonitrile realize reaction and extraction point
From coupling, obtain N '-(4- alkane phenyl)-N of high-purity, N- dimethylamidine.This method N '-obtained (4- alkane phenyl)-
The yield of N, N- dimethylamidine can reach 90% or more, product N '-(4- alkane phenyl)-N after extraction and separation, N- dimethylamidine it is pure
Degree can further improve to 95% or more.And effectively shorten the operating time, improve combined coefficient, the operation of this method Reaction Separation
Simply, extractant can be recycled.N '-(4- alkane phenyl)-N of the invention, N- dimethylamidine can use pesticide, medical drugs
Object and a kind of novel C O2/N2Switch surfactant.
Detailed description of the invention
Fig. 1 is N '-(4- tetradecane phenyl)-N prepared in embodiment 1, N- dimethyl ethanamidine1H NMR(CDCl3,
500M) spectrogram.
Fig. 2 is N '-(4- tetradecane phenyl)-N prepared in embodiment 1, the infrared spectrum of N- dimethyl ethanamidine.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Involved chemical reagent commercially available acquisition unless otherwise specified in the embodiment of the present invention.
Embodiment 1
A kind of N '-(4- tetradecane phenyl)-N is present embodiments provided, N- dimethyl ethanamidine is synthesized by following steps
It arrives:
The 4- myristyl aniline of 5mmol is added in the brown flask with reflux unit, the acetonitrile of 10mL is added,
In constant temperature oil bath, magnetic agitation, revolving speed 200r/min are opened；The N of 7mmol, N- bis- are slowly added dropwise when temperature rises to 78 DEG C
Methylacetamide dimethylacetal reacts 15min into solution under normal pressure；Reaction solution is sucked out and is moved into separatory funnel, it is cold
But to room temperature, layer depth brown liquid is removed after stratification；It is residual that 10min removing is rotated under the conditions of pressure 5kPa, temperature 50 C
Solvent is stayed to get dark brown liquid, as product N '-(4- tetradecane phenyl)-N, N- dimethyl ethanamidine is arrived.
Fig. 1 is product N '-(4- tetradecane phenyl)-N, N- dimethyl ethanamidine1H NMR(CDCl3, 500M) and spectrogram, Fig. 2
For product N '-(4- tetradecane phenyl)-N, the infrared spectrum of N- dimethyl ethanamidine, 3000-3200cm in spectrogram-1There is weak absorbing at place
Peak is the absorption peak of C-H bond on phenyl ring；1400-1600cm-1Locating four bands of a spectrum is the conjugated bonds absorption peak on phenyl ring；
1600cm-1The absorption peak at place is carbon-to-nitrogen double bon absorption peak.
It is 97% that nucleus magnetic hydrogen spectrum, which analyzes product purity,.The total yield of target product is 90%.
Embodiment 2
A kind of N '-(4- tetradecane phenyl)-N is present embodiments provided, N- dimethyl carbonamidine is synthesized by following steps
It arrives:
The 4- myristyl aniline of 9mmol is added in the brown flask with reflux unit, the acetonitrile of 15mL is added,
In constant temperature oil bath, magnetic agitation, revolving speed 200r/min are opened；Heating, when temperature rises to 80 DEG C, is slowly added dropwise the N of 18mmol,
Dinethylformamide dimethylacetal reacts 15min under the conditions of normal pressure a into solution；Reaction solution is sucked out and moves into liquid separation
In funnel, be cooled to room temperature, after solution left standstill layering after under, remove layer depth brown liquid；In pressure 5kPa, temperature 50 C condition
Lower revolving 10min removes residual solvent, and obtaining dark brown liquid is product N '-(4- tetradecane phenyl)-N, N- dimethyl methyl
Amidine.
With1H NMR(CDCl3, 500M) and analysis product, purity 98%.The total yield of target product is 92%.
Embodiment 3
A kind of N '-(4- dodecylphenyl)-N, N- dimethyl ethanamidine is present embodiments provided, is synthesized by following steps
It obtains:
The 4- dodecyl polyaniline of 5mmol is added in the flask with reflux unit, the acetonitrile of 11mL is added, in constant temperature
In oil bath, magnetic agitation, revolving speed 200r/min are opened；Heating, when temperature rises to 80 DEG C, is slowly added dropwise the N of 6mmol, N- bis-
Methylacetamide dimethylacetal reacts 15min into solution in atmospheric conditions；Reaction solution is sucked out and moves into separatory funnel
In, it is cooled to room temperature, after solution left standstill layering, removes layer depth brown liquid；In pressure 10kPa, temperature 50 C condition backspin
It steams 10min and removes residual solvent, obtaining dark brown liquid is product N '-(4- dodecylphenyl)-N, N- dimethyl ethanamidine.
With1H NMR(CDCl3, 500M) and analysis product, purity 96%.The total yield of target product is 90%.
Embodiment 4
A kind of N '-(4- hexadecane phenyl)-N is present embodiments provided, N- dimethyl ethanamidine is synthesized by following steps
It arrives:
By the 4- hexadecylaniline of 5mmol into the flask for having reflux unit, the acetonitrile of 15mL is added, in thermostatical oil
In bath, magnetic agitation, revolving speed 200rad/min are opened；Heating, when temperature rises to 82 DEG C, is slowly added dropwise the N of 6mmol, N- bis-
Methylacetamide dimethylacetal reacts 20min into solution in atmospheric conditions；Reaction solution is sucked out and moves into separatory funnel
In, it is cooled to room temperature, after solution left standstill layering, removes layer depth brown liquid；In pressure 10kPa, temperature 50 C condition backspin
It steams 10min and removes residual solvent, obtaining dark brown liquid is product N '-(4- hexadecane phenyl)-N, N- dimethyl ethanamidine.
With1H NMR(CDCl3, 500M) and analysis product, purity 96%.The total yield of target product is 91%.
Embodiment 5
A kind of N '-(4- octadecane phenyl)-N is present embodiments provided, N- dimethyl ethanamidine is synthesized by following steps
It arrives:
By the 4- octadecyl aniline of 5mmol into the flask for having reflux unit, the acetonitrile of 20mL is added, in thermostatical oil
In bath, magnetic agitation, revolving speed 200r/min are opened；Heating, when temperature rises to 82 DEG C, is slowly added dropwise the N of 7mmol, N- diformazan
Yl acetamide dimethylacetal reacts 20min into solution in atmospheric conditions；Reaction solution is sucked out and is moved into separatory funnel,
It is cooled to room temperature, after solution left standstill layering, removes layer depth brown liquid；It is rotated under the conditions of pressure 10kPa, temperature 50 C
15min removes residual solvent, and obtaining dark brown liquid is product N '-(4- octadecane phenyl)-N, N- dimethyl ethanamidine.
With1H NMR(CDCl3, 500M) and analysis product, purity 95%.The total yield of target product is 90%.
Above embodiments explanation, N '-of the invention (4- alkane phenyl)-N, the synthetic method of N- dimethylamidine, N '-(4- alkane
Phenyl)-N, the yield of N- dimethylamidine is up to 90%, and Chun Du≤95% of product, operation is simple, and the reaction time shortens,
Extractant acetonitrile is easily recycled.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate examples made by the present invention, and is not to this
The restriction of the embodiment of invention for those of ordinary skill in the art on the basis of the above description can be with
It makes other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to the present invention
The obvious changes or variations extended out of technical solution still in the scope of protection of the present invention.
Claims (10)
1. a kind of N '-(4- alkane phenyl)-N, the synthesis separation method of N- dimethylamidine, which is characterized in that this method includes following
Step:
4- alkyl benzene amine is dissolved in acetonitrile, after being heated to preset temperature, N is added, N- dimethylformamide dimethylacetal carries out
Reaction；
It is after reaction that reaction system is cooling, after reaction system layering, the distillation of lower layer's liquid pressure-reducing is taken to get production is arrived
Product N '-(4- alkane phenyl)-N, N- dimethylamidine.
2. synthesis separation method according to claim 1, which is characterized in that the volume ratio of the acetonitrile and 4- alkyl benzene amine
For 5:1-20:1.
3. synthesis separation method according to claim 1, which is characterized in that the preset temperature is 50-90 DEG C.
4. synthesis separation method according to claim 1, which is characterized in that the N, N- dimethylformamide dimethylacetal
Molar ratio with 4- alkyl benzene amine is 1:1-2:1.
5. synthesis separation method according to claim 1, which is characterized in that the reaction is synthesis under normal pressure 10min-
20min。
6. synthesis separation method according to claim 1, which is characterized in that the pressure of the vacuum distillation is 1kPa-
100kPa, temperature are 30 DEG C -100 DEG C.
7. synthesis separation method according to claim 1, which is characterized in that the N, N- dimethylformamide dimethylacetal
For one of N,N-dimethylformamide dimethylacetal and DMAC N,N' dimethyl acetamide dimethylacetal or two kinds of group
It closes.
8. synthesis separation method according to claim 1, which is characterized in that the alkyl in the 4- alkyl benzene amine is C12-
C18Alkyl.
9. synthesis separation method according to claim 1, which is characterized in that this method is further comprising the steps of: by upper layer
Liquid pressure-reducing is distilled to recover acetonitrile.
10. N '-(4- alkane phenyl)-N that any one of the claim 1-9 synthesis separation method is prepared, N- dimethylamidine,
Structural formula is as follows:
Wherein R1For C12-C18Alkyl, R2For H or-CH3。
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2018
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| CN102690213A (en) * | 2011-03-23 | 2012-09-26 | 中国石油天然气集团公司 | Synthetic method of N'-long-chain alkyl-N,N-dimethyl amidine |
| US20130200291A1 (en) * | 2012-01-27 | 2013-08-08 | Queen's University At Kingston | Tertiary Amine-Based Switchable Cationic Surfactants and Methods and Systems of Use Thereof |
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