CN107686455B - A kind of N- octadecyl ethanimidic acid methyl esters and its synthetic method - Google Patents
A kind of N- octadecyl ethanimidic acid methyl esters and its synthetic method Download PDFInfo
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- CN107686455B CN107686455B CN201710691654.7A CN201710691654A CN107686455B CN 107686455 B CN107686455 B CN 107686455B CN 201710691654 A CN201710691654 A CN 201710691654A CN 107686455 B CN107686455 B CN 107686455B
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- 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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Abstract
The present invention provides a kind of N- octadecyl ethanimidic acid methyl esters and its synthetic methods.The synthetic method includes: that acetal and octadecylamine are dissolved in methanol, and the molar ratio of acetal and octadecylamine is 1:1-1.5:1, and the weight of methanol is the 50%-99% of total weight；It is heated to assigned temperature, synthesis under normal pressure 0.1h-12h；It is decompressed to 0.01MPa-0.08MPa, 0.25h-12h is reacted at 20 DEG C -120 DEG C, stops reaction, obtains N- octadecyl ethanimidic acid methyl esters.The present invention also provides the N- octadecyl ethanimidic acid methyl esters obtained by above-mentioned synthetic method.The yield of the N- substituted imine acid esters of the synthetic method synthesis of N- octadecyl ethanimidic acid methyl esters of the invention can reach 71% or more, and easy to operate, volatile products are easily recycled, environmental-friendly.
Description
Technical field
The present invention relates to a kind of synthetic method more particularly to a kind of synthetic method of N- octadecyl ethanimidic acid methyl esters,
Belong to technical field of organic synthesis.
Background technique
N- substituted imine acid esters is a kind of important organic synthesis intermediate, and the important source material of medicine research and development, is to close
At amidine class, imidazoline, benzimidazole, oxazole, oxazoline, benzoxazoles, the main intermediate (Patai of the compounds such as thiazoline
S,Rappoport Z.The Chemistry of amidines and imidates[M].Wiley,1975)。
Currently, the synthesis of N- substituted imine ester compound has:
Pinner reaction: i.e. nitrile and alcohol generate the hydrochloric acid of polyurethane, generation are being reacted with amine under sour (such as hydrochloric acid) catalysis
(Jiang Hu, Liu Yin, Liu Xiaole wait new synthetic method [J] of .N- cyan ethyl ethylimidoote to answer to N- substituted imine ester compound
With chemical industry, 2013,42 (2): 274-278).
Silver salt alkylation: Lander is alkylated under silver oxide effect by amide derivatives, obtains N- substituted imine acid
Ester (Roger R, Neilson D G.The Chemistry of Imidates. [J] .Chemical Reviews, 1961,61
(2):179-211)。
Unsaturated system synthesis: primary amine and ethoxyacetylene produce a small amount of imidoether under alcohol reflux effect
(Patai S,Rappoport Z.The Chemistry of amidines and imidates[M].Wiley,1975)。
By simple imidoether, conversion forms (Schmidt in the presence of equivalent amino-acid ester (common hydrochloric acid amino acid)
It is proposed) (Roger R, Neilson D G.The Chemistry of Imidates. [J] .Chemical Reviews,
1961,61(2):179-211)。
Triethyl orthoformate method, i.e. aminolysis reaction (Xu Zhenyuan, Zhang Guanglu, the Yan Wei .N- (substituted-phenyl) of acid catalysis original ester
Synthesis [J] application chemical industry of imido grpup Ethyl formate, 1985 (1): 17-20).
But there are some disadvantages in above several synthetic methods in the application.Pinner reaction method consumes a large amount of salt
Acid can cause environmental pollution.In silver salt alkylated reaction method, silver salt is unstable, and illumination and heat promote its decomposition.Unsaturated body
It is imidoether low yield in synthetic method and triethyl orthoformate method；And Schmidt reaction process is complicated, it is cumbersome.
Moreover, the synthetic method of the above N- substituted imine acid esters is mainly limited to the target product of the functional group of short carbon chain,
And there is no open source literature report so far for the production method of the imidic acid methyl esters of Long carbon chain such as N- octadecyl ethanimidic acid methyl esters
Road.
In conclusion providing a kind of yield height, the N- octadecyl ethanimidic acid methyl esters that synthetic method is simple, environmental-friendly
Production method help to fill up the blank of this field.
Summary of the invention
In order to solve the above-mentioned technical problem, the purpose of the present invention is to provide a kind of synthetic methods it is simple, environmental-friendly and
The synthetic method of the high N- substituted imine acid esters of the yield of alkyl imino acid rouge.
In order to achieve the above technical purposes, the present invention provides a kind of synthesis sides of N- octadecyl ethanimidic acid methyl esters
Method, the synthetic method the following steps are included:
Acetal and octadecylamine are dissolved in methanol, wherein the molar ratio of acetal and octadecylamine is 1:1-1.5:1, methanol
Weight is the 50%-99% of octadecylamine, acetal and methanol total weight；
20 DEG C -100 DEG C are heated to, synthesis under normal pressure 0.1h-12h；
It is decompressed to 0.01MPa-0.08MPa, 0.25h-12h is reacted at 20 DEG C DEG C -120 DEG C, stops reaction, obtains N- ten
Eight alkyl ethanimidic acid methyl esters.
In the synthetic method of N- octadecyl ethanimidic acid methyl esters of the invention, it is preferable that the acetal used is N, N-
Dimethylacetamide dimethylacetal and/or N, N- diethyl acetamide dimethylacetal；It is highly preferred that the acetal used is N,
N- dimethylacetamide dimethylacetal.
In the synthetic method of N- octadecyl ethanimidic acid methyl esters of the invention, it is preferable that acetal and octadecylamine rub
You are than being 1.2:1.
In the synthetic method of N- octadecyl ethanimidic acid methyl esters of the invention, it is preferable that the absolute pressure of synthesis under normal pressure
Power is 0.05MPa-0.15MPa；It is highly preferred that the absolute pressure of synthesis under normal pressure is 0.1MPa.
The present invention also provides a kind of N- octadecyl ethanimidic acid methyl esters, the N- octadecyl ethanimidic acid methyl esters be by
What the synthetic method of above-mentioned N- octadecyl ethanimidic acid methyl esters synthesized.
N- octadecyl ethanimidic acid methyl esters provided by the invention, it is preferable that have the following structure formula:
The synthetic method of N- octadecyl ethanimidic acid methyl esters of the invention, using octadecylamine and acetal as raw material, in solvent
It reacts in methanol, and is directly synthesized under conditions of constantly removing dimethylamine, first subtracted again through synthesis under normal pressure in reaction process
Pressure reaction, removing volatile materials and solvent while reaction, until obtaining N- octadecyl ethyleneimine after solvent removes completely
Sour methyl esters.
The synthetic method of N- octadecyl ethanimidic acid methyl esters of the invention, using acetal and octadecylamine as raw material, Ke Yishi
The complete conversion of existing raw material, the yield of N- octadecyl ethanimidic acid methyl esters can reach 71% or more.
The manufacturing technique method of the synthetic method of N- octadecyl ethanimidic acid methyl esters of the invention is simple, target product produces
Rate is high, environmental-friendly, has filled up N- octadecyl ethanimidic acid methyl esters production technology blank.
Detailed description of the invention
Fig. 1 is the mass spectrogram (dilution in acetonitrile) of reaction product in embodiment 1.
Fig. 2 is reaction product in embodiment 11H NMR(CDCl3, 500M) and spectrogram.
Fig. 3 is reaction product in embodiment 113C NMR(CDCl3, 125M) and spectrogram.
Fig. 4 is the infrared spectrum of reaction product in embodiment 1.
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.
Embodiment 1
A kind of N- octadecyl ethanimidic acid methyl esters is present embodiments provided, through the following steps that synthesis obtained:
The octadecylamine of 2.78g is weighed into the four-hole boiling flask for having condenser pipe, vacuum plant and thermometer, is added 55mL's
Methanol is heated to octadecylamine and is completely dissolved in constant temperature oil bath；
When temperature rises to 70 DEG C, the n,N-dimethylacetamide dimethylacetal of 1.72g is slowly added dropwise into solution,
2.8h is reacted under 0.1MPa；
With thin-layer chromatography (VCHCl3:CH3OH=3:1) point sample climbs plate, and no raw material point occurs, and illustrates that octadecylamine converts completely；
It is decompressed to 0.07MPa, in 50 DEG C of the reaction was continued 30min, obtains flaxen product liquid, as N- octadecyl
Ethanimidic acid methyl esters, the yield of N- octadecyl ethanimidic acid methyl esters are 71.3%.
The mass spectrogram (dilution in acetonitrile) for the product that the present embodiment synthesizes is as shown in Figure 1, wherein m/z=326.3419
For the molecular weight of target product N- octadecyl ethanimidic acid methyl esters [M+H], calculated value 326.3417.
The product that the present embodiment synthesizes1H NMR(CDCl3, 500M) and spectrogram is as shown in Figure 2, wherein contain N- ten
The chemical shift of the hydrogen of eight alkyl ethanimidic acid methyl esters: 0.88 (t；3H；CH3C17H34)；1.26(m；30H；
CH3C15H30CH2CH2N)；1.52(m；2H；CH3C15H30CH2CH2N)；1.86(s；3H；(CH3)-C-O)；3.18(t；2H；
C17H35CH2N)；3.61(s,3H；OCH3) (chemical displacement value corresponding to the position of products obtained therefrom hydrogen as in Fig. 2 chemical formula marked
Note).
The product that the present embodiment synthesizes13C NMR(CDCl3, 125M) and spectrogram is as shown in Figure 3, wherein contain target
The chemical shift peak of product N- octadecyl ethanimidic acid methyl esters: 14.10 (C-CH3)；14.38(C17H34CH3)；22.68-
29.70 (multiplet, C15H30CH3)；31.92(NCH2CH2)；49.35(NCH2)；52.01(OCH3)；(161.16 C=N).
The infrared spectrum for the product that the present embodiment synthesizes is as shown in Figure 4, wherein wavelength 1255.432cm-1For=C-
The absorption peak of O-C key, wavelength 1687.408cm-1It is N- octadecyl second for the absorption peak of C=N (imines ester compounds) key
The characteristic peak of imidic acid methyl esters.
Embodiment 2
A kind of N- octadecyl ethanimidic acid methyl esters is present embodiments provided, through the following steps that synthesis obtained:
The octadecylamine of 2.83g is weighed into the four-hole boiling flask for having condenser pipe, vacuum plant and thermometer, is added 60mL's
Methanol is heated to octadecylamine and is completely dissolved in constant temperature oil bath；
When temperature rises to 50 DEG C, the n,N-dimethylacetamide dimethylacetal of 2.02g is slowly added dropwise into solution,
8h is reacted under 0.1MPa；
With thin-layer chromatography (VCHCl3:CH3OH=3:1) point sample climbs plate, and no raw material point occurs, and illustrates that octadecylamine converts completely；
It is decompressed to 0.08MPa, in 45 DEG C of the reaction was continued 15min, obtains flaxen product liquid, as N- octadecyl
Ethanimidic acid methyl esters, the yield of the N- octadecyl ethanimidic acid methyl esters of the present embodiment are 70.8%.
Above embodiments explanation, the synthetic method of N- octadecyl ethanimidic acid methyl esters of the invention, N- substituted imine acid
The yield of ester can reach 71% or so, and operation is simple, and volatile products are easily recycled, environmental-friendly.
Claims (5)
1. a kind of synthetic method of N- octadecyl ethanimidic acid methyl esters, which is characterized in that the synthetic method the following steps are included:
Acetal and octadecylamine are dissolved in methanol, wherein the molar ratio of acetal and octadecylamine is 1:1-1.5:1, the weight of methanol
For octadecylamine, the 50%-99% of acetal and methanol total weight；
20 DEG C -100 DEG C are heated to, synthesis under normal pressure 0.1h-12h；
It is decompressed to 0.01MPa-0.08MPa, 0.25h-12h is reacted at 20 DEG C -120 DEG C, stops reaction, obtains the N- 18
Alkyl ethanimidic acid methyl esters；
The acetal is DMAC N,N' dimethyl acetamide dimethylacetal and/or N, N- diethyl acetamide dimethylacetal.
2. the synthetic method of N- octadecyl ethanimidic acid methyl esters according to claim 1, which is characterized in that the acetal
For DMAC N,N' dimethyl acetamide dimethylacetal.
3. the synthetic method of N- octadecyl ethanimidic acid methyl esters according to claim 1, which is characterized in that the acetal
Molar ratio with octadecylamine is 1.2:1.
4. the synthetic method of N- octadecyl ethanimidic acid methyl esters according to claim 1, which is characterized in that the normal pressure
The absolute pressure of reaction is 0.05MPa-0.15MPa.
5. the synthetic method of N- octadecyl ethanimidic acid methyl esters according to claim 1 or 4, which is characterized in that described
The absolute pressure of synthesis under normal pressure is 0.1MPa.
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Non-Patent Citations (1)
| Title |
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| A Synthesis of Acetamidines;Jitendra R. Harjani et al.;《J. Org. Chem.》;20110211;第76卷;1683–1691 * |
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