CN104557595A - Method for restraining side reaction in imidazoline intermediate preparation process - Google Patents
Method for restraining side reaction in imidazoline intermediate preparation process Download PDFInfo
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- CN104557595A CN104557595A CN201310483259.1A CN201310483259A CN104557595A CN 104557595 A CN104557595 A CN 104557595A CN 201310483259 A CN201310483259 A CN 201310483259A CN 104557595 A CN104557595 A CN 104557595A
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Abstract
The invention discloses a method which can effectively restrain a side reaction in an imidazoline intermediate preparation process and increase the product yield greatly. The method is characterized in that an inhibitor for restraining the side reaction is added to a reaction vessel at the beginning of a reaction in the imidazoline intermediate preparation process, and the inhibitor adopts a by-product bisamide substance generated in the imidazoline intermediate preparation process. The method is simple in process, high in operability and capable of effectively reducing the generation possibility of the side reaction, so that the product yield is increased greatly, and industrial production is facilitated.
Description
Technical field
The present invention relates to the preparation field of imidazolinium compounds, refer more particularly to the method suppressing side reaction in imidazoline intermediate preparation process.
Background technology
Imidazolinium compounds and derivative thereof have a wide range of applications field.May be used for the fields such as tensio-active agent, static inhibitor, inhibiter, and show excellent performance, imidazoline type quaternary ammonium salt can as water soluble rust inhibitor, for restrainer, sanitas, sterilant.Low cost, environmental protection, easy method is adopted to synthesize imidazolinium compounds and have good economic implications.
Existing imidazolinium compounds synthetic method mainly contains following three kinds: (1) for raw material with Ester and substituted ethylene diamine, is carried out amidate action under high temperature, obtained alkylamide and be dehydrated into ring again, obtain imidazolinium compounds; (2) there is amidate action in Zhi Fangsuan ester and amine under catalyst action, forms alkylamide, then be dehydrated into ring through negative pressure, obtain imidazolinium compounds; (3) there is amidate action in alkyl nitrile and amine under catalyst action, forms alkylamide, then be dehydrated into ring through negative pressure, obtain imidazolinium compounds.
Above-mentioned three kinds of methods all need to prepare imidazoline intermediate---and alkylamide, is then dehydrated into ring, obtains imidazolinium compounds.Above-mentioned imidazoline intermediate is the compound of following structural formula I or formula II:
Wherein, R
1, R
2, R
3, R
4, R
5separately be selected from hydrogen or C
1~ C
20saturated straight chain, branched paraffin or naphthenic hydrocarbon.Visible, the synthesis of imidazoline intermediate alkylamide is key prepared by tetrahydroglyoxaline, and synthetic method can be expressed as follows with general formula:
Wherein: R
1, R
2, R
3, R
4, R
5separately be selected from hydrogen or C
1~ C
20saturated straight chain, branched paraffin or naphthenic hydrocarbon; X is selected from carboxyl (-COOH), cyano group (-CN) or ester group (-COOR).And the product 1 that reaction produces and product 2 are monoamide, are effective constituent; The product 3 that reaction produces is bisamides, is by product.
Inevitably side reaction is there is in the preparation process of imidazoline intermediate, containing more by product (being mainly bisamide material), bisamide can not Cheng Huan, can not react with alkylating reagent, not only reduce the yield of product, and will be able to have a negative impact to tetrahydroglyoxaline application performance.Prior art is all reduced the content of bisamide in imidazoline products by method of purification, but this fundamentally can not suppress the generation of side reaction in imidazoline intermediate preparation process.
Summary of the invention
The technical problem of solution required for the present invention is: can effectively suppress the generation of side reaction by providing a kind of thus greatly improve the method for product yield in imidazoline intermediate preparation process.
For solving the problems of the technologies described above, the technical solution used in the present invention is: the method suppressing side reaction in described imidazoline intermediate preparation process, be characterized in: in the preparation process of imidazoline intermediate, in reaction vessel, the inhibitor suppressing side reaction is just added, the by product of described inhibitor for producing in the preparation process of imidazoline intermediate when reacting and starting; Described imidazoline intermediate is the compound of following structural formula I or formula II,
Wherein, R
1, R
2, R
3, R
4, R
5separately be selected from hydrogen or C
1~ C
20saturated straight chain, branched paraffin or naphthenic hydrocarbon.
Further, suppress the method for side reaction in aforesaid imidazoline intermediate preparation process, wherein, the structural formula of described inhibitor is as follows:
Wherein, R
1, R
2, R
3, R
4, R
5separately be selected from hydrogen or C
1~ C
20saturated straight chain, branched paraffin or naphthenic hydrocarbon.
Further, suppress the method for side reaction in aforesaid imidazoline intermediate preparation process, wherein, the add-on of described inhibitor is 5% ~ 30% of reaction solution gross weight.
The invention has the beneficial effects as follows: method technique of the present invention is simple, workable, effectively can reduce the generation of side reaction, substantially increase product yield, be beneficial to suitability for industrialized production.
Embodiment
Below by specific embodiment, the invention will be further described, but technical solutions according to the invention are not limited in following examples.
Embodiment 1: use technical scheme provided by the invention, adopts same process condition, preparation N-acetyl quadrol.
(1) processing condition: acetic acid and quadrol are raw material, and mol ratio 1: 1 feeds intake, 100 DEG C of encloses container reaction 10h.
(2) reaction effect when table one lists different inhibitor addition and the situation of by product production rate, by product is bisamide class material---N, N-oxalyl quadrol, as can be seen from Table I, adding of inhibitor, can obviously reduce by product production rate.Said by product production rate, refers in amidate action process, and the weight of newly-generated by product (mainly bisamide) accounts for the ratio of reaction solution gross weight.
(3) inhibitor: be the by product of acetic acid and reacting ethylenediamine.Steamed by target product by flash distillation, by product (being mainly bisamide, N, N-oxalyl quadrol), because boiling point is high, can not be distilled out of, as inhibitor.
Table one
| Reactant | Reaction conditions | Inhibitor addition/wt% | By product production rate/wt% |
| Acetic acid/quadrol=1/1 | 100℃，10h | Nothing | 24.5 |
| Acetic acid/quadrol=1/1 | 100℃，10h | 5 | 19.6 |
| Acetic acid/quadrol=1/1 | 100℃，10h | 10 | 10.7 |
| Acetic acid/quadrol=1/1 | 100℃，10h | 25 | 5.4 |
Embodiment 2: use technical scheme provided by the invention, adopts same process condition, preparation N-acetyl quadrol.
(1) processing condition: methyl acetate and quadrol are raw material, and mol ratio 1: 1 feeds intake, 130 DEG C of encloses container reaction 8h.
(2) reaction effect when table two lists different inhibitor addition and the situation of by product production rate, by product is bisamide class material---N, N-oxalyl quadrol, as can be seen from Table II, adding of inhibitor, can obviously reduce by product production rate.When inhibitor addition reaches reaction solution total amount 20%, by product production rate only has 4.4%.Said by product production rate, refers in amidate action process, and the weight of newly-generated by product (mainly bisamide) accounts for the ratio of reaction solution gross weight.
(3) inhibitor: be the by product of methyl acetate and reacting ethylenediamine.Steamed by target product by flash distillation, by product (being mainly bisamide, N, N-oxalyl quadrol), because boiling point is high, can not be distilled out of, as inhibitor.
Table two
| Reactant | Reaction conditions | Inhibitor addition/wt% | By product production rate/wt% |
| Methyl acetate/quadrol=1/1 | 130℃，8h | Nothing | 19.6 |
| Methyl acetate/quadrol=1/1 | 130℃，8h | 5 | 15.3 |
| Methyl acetate/quadrol=1/1 | 130℃，8h | 20 | 4.4 |
| Methyl acetate/quadrol=1/1 | 130℃，8h | 30 | 3.6 |
Embodiment 3: use technical scheme provided by the invention, adopts same process condition, preparation N-acetyl quadrol.
(1) processing condition: acetonitrile and quadrol are raw material, and mol ratio 1: 1 feeds intake, and adds catalyzer, 120 DEG C of encloses container reaction 24h.
(2) reaction effect when table three lists different inhibitor addition and the situation of by product production rate, by product is bisamide class material---N, N-oxalyl quadrol, as can be seen from Table III, due to adding of catalyzer, its side reaction is less, adding of inhibitor, can reduce by product production rate further.Said by product production rate, refers in amidate action process, and the weight of newly-generated by product (mainly bisamide) accounts for the ratio of reaction solution gross weight.
(3) inhibitor: be the by product of acetonitrile and reacting ethylenediamine.Steamed by target product by flash distillation, by product (being mainly bisamide, N, N-oxalyl quadrol), because boiling point is high, can not be distilled out of, as inhibitor.
Table three
| Reactant | Reaction conditions | Inhibitor addition/wt% | By product production rate/wt% |
| Acetonitrile/quadrol=1/1 | 120 DEG C, 24h, catalyzer | Nothing | 10.8 |
| Acetonitrile/quadrol=1/1 | 120 DEG C, 24h, catalyzer | 5 | 6.3 |
| Acetonitrile/quadrol=1/1 | 120 DEG C, 24h, catalyzer | 10 | 2.3 |
| Acetonitrile/quadrol=1/1 | 120 DEG C, 24h, catalyzer | 15 | 1.5 |
Embodiment 4: use technical scheme provided by the invention, adopts same process condition, preparation N-acetyl-(2,3-dimethyl) quadrol.
(1) processing condition: acetic acid and 2,3-dimethyl-ethylenediamine are raw material, and mol ratio 1: 1 feeds intake, 100 DEG C of encloses container reaction 10h.
(2) reaction effect when table four lists different inhibitor addition and the situation of by product production rate, by product is bisamide class material---N, N-oxalyl-(2,3-dimethyl) quadrol, as can be seen from Table IV, adding of inhibitor, can obviously reduce by product production rate.Said by product production rate, refers in amidate action process, and the weight of newly-generated by product (mainly bisamide) accounts for the ratio of reaction solution gross weight.
(3) inhibitor: the by product reacted for acetic acid and 2,3-dimethyl-ethylenediamine.Steamed by target product by flash distillation, by product (being mainly bisamide, N, N-oxalyl-(2,3-dimethyl) quadrol), because boiling point is high, can not be distilled out of, as inhibitor.
Table four
| Reactant | Reaction conditions | Inhibitor addition/wt% | By product production rate/wt% |
| Acetic acid/2,3-dimethyl-ethylenediamine=1/1 | 100℃，10h | Nothing | 22.5 |
| Acetic acid/2,3-dimethyl-ethylenediamine=1/1 | 100℃，10h | 5 | 17.6 |
| Acetic acid/2,3-dimethyl-ethylenediamine=1/1 | 100℃，10h | 10 | 9.8 |
| Acetic acid/2,3-dimethyl-ethylenediamine=1/1 | 100℃，10h | 25 | 4.4 |
Embodiment 5: use technical scheme provided by the invention, adopts same process condition, preparation N-acetyl-(2,3-dimethyl) quadrol.
(1) processing condition: methyl acetate and 2,3-dimethyl-ethylenediamine are raw material, and mol ratio 1: 1 feeds intake, 130 DEG C of encloses container reaction 8h.
(2) reaction effect when table five lists different inhibitor addition and the situation of by product production rate, by product is bisamide class material---N, N-oxalyl-(2,3-dimethyl) quadrol, as can be seen from Table V, adding of inhibitor, can obviously reduce by product production rate.When inhibitor addition reaches reaction solution total amount 20%, by product production rate only has 4.7%.Said by product production rate, refers in amidate action process, and the weight of newly-generated by product (mainly bisamide) accounts for the ratio of reaction solution gross weight.
(3) inhibitor: the by product reacted for methyl acetate and 2,3-dimethyl-ethylenediamine.Steamed by target product by flash distillation, by product (being mainly bisamide, N, N-oxalyl-(2,3-dimethyl) quadrol), because boiling point is high, can not be distilled out of, as inhibitor.
Table five
| Reactant | Reaction conditions | Inhibitor addition/wt% | By product production rate/wt% |
| Methyl acetate/2,3-dimethyl-ethylenediamine=1/1 | 130℃，8h | Nothing | 20.4 |
| Methyl acetate/2,3-dimethyl-ethylenediamine=1/1 | 130℃，8h | 5 | 18.3 |
| Methyl acetate/2,3-dimethyl-ethylenediamine=1/1 | 130℃，8h | 20 | 4.7 |
| Methyl acetate/2,3-dimethyl-ethylenediamine=1/1 | 130℃，8h | 30 | 3.4 |
Embodiment 6: use technical scheme provided by the invention, adopts same process condition, preparation N-acetyl-(2,3-dimethyl) quadrol.
(1) processing condition: acetonitrile and 2,3-dimethyl-ethylenediamine are raw material, and mol ratio 1: 1 feeds intake, and adds catalyzer, 120 DEG C of encloses container reaction 24h.
(2) reaction effect when table six lists different inhibitor addition and the situation of by product production rate, by product is bisamide class material---N, N-oxalyl-(2,3-dimethyl) quadrol, as can be seen from Table VI, due to adding of catalyzer, its side reaction is less, adding of inhibitor, by product production rate can be reduced further.Said by product production rate, refers in amidate action process, and the weight of newly-generated by product (mainly bisamide) accounts for the ratio of reaction solution gross weight.
(3) inhibitor: the by product reacted for acetonitrile and 2,3-dimethyl-ethylenediamine.Steamed by target product by flash distillation, by product (being mainly bisamide, N, N-oxalyl-(2,3-dimethyl) quadrol), because boiling point is high, can not be distilled out of, as inhibitor.
Table six
| Reactant | Reaction conditions | Inhibitor | By product production rate |
| Acetonitrile/2,3-dimethyl-ethylenediamine=1/1 | 120 DEG C, 24h, catalyzer | Nothing | 9.6％ |
| Acetonitrile/2,3-dimethyl-ethylenediamine=1/1 | 120 DEG C, 24h, catalyzer | 5％ | 5.3％ |
| Acetonitrile/2,3-dimethyl-ethylenediamine=1/1 | 120 DEG C, 24h, catalyzer | 10％ | 1.5％ |
| Acetonitrile/2,3-dimethyl-ethylenediamine=1/1 | 120 DEG C, 24h, catalyzer | 15％ | 1.2％ |
Claims (3)
1. suppress the method for side reaction in imidazoline intermediate preparation process, described imidazoline intermediate is the compound of following structural formula I or formula II,
Wherein, R
1, R
2, R
3, R
4, R
5separately be selected from hydrogen or C
1~ C
20saturated straight chain, branched paraffin or naphthenic hydrocarbon; It is characterized in that: in the preparation process of imidazoline intermediate, in reaction vessel, just adding the inhibitor suppressing side reaction when reacting and starting, the by product of described inhibitor for producing in the preparation process of imidazoline intermediate.
2. suppress the method for side reaction in imidazoline intermediate preparation process according to claim 1, it is characterized in that: the structural formula of described inhibitor is as follows:
Wherein, R
1, R
2, R
3, R
4, R
5separately be selected from hydrogen or C
1~ C
20saturated straight chain, branched paraffin or naphthenic hydrocarbon.
3. suppress the method for side reaction in imidazoline intermediate preparation process according to claim 1 and 2, it is characterized in that: the add-on of described inhibitor is 5% ~ 30% of reaction solution gross weight.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105949077A (en) * | 2016-05-16 | 2016-09-21 | 中国科学院兰州化学物理研究所 | Method for preparing diamide under catalysis of non-noble metal |
| CN111393369A (en) * | 2020-05-13 | 2020-07-10 | 宁夏大学 | Preparation method of 2-hexyl imidazole |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012272A (en) * | 2012-12-21 | 2013-04-03 | 张家港保税区超威电化技术服务有限公司 | Preparation method of imidazoline compound |
-
2013
- 2013-10-16 CN CN201310483259.1A patent/CN104557595A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012272A (en) * | 2012-12-21 | 2013-04-03 | 张家港保税区超威电化技术服务有限公司 | Preparation method of imidazoline compound |
Non-Patent Citations (1)
| Title |
|---|
| R. SMITH著，王保国等译: "《化工过程设计》", 31 July 2002, article "含有平行副反应的反应系统" * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105949077A (en) * | 2016-05-16 | 2016-09-21 | 中国科学院兰州化学物理研究所 | Method for preparing diamide under catalysis of non-noble metal |
| CN111393369A (en) * | 2020-05-13 | 2020-07-10 | 宁夏大学 | Preparation method of 2-hexyl imidazole |
| CN111393369B (en) * | 2020-05-13 | 2022-12-16 | 宁夏大学 | Preparation method of 2-hexyl imidazole |
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