CN107021885A - A kind of preparation method of the amphoteric surfactant containing unsaturated bond - Google Patents
A kind of preparation method of the amphoteric surfactant containing unsaturated bond Download PDFInfo
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- CN107021885A CN107021885A CN201710206297.0A CN201710206297A CN107021885A CN 107021885 A CN107021885 A CN 107021885A CN 201710206297 A CN201710206297 A CN 201710206297A CN 107021885 A CN107021885 A CN 107021885A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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Abstract
A kind of synthetic method of amphoteric surfactant 3 (the oxo pi-allyl of N, N dimethyl N (E) 3 ' oxygen ethyl 3 ') ammonium succinate monoester inner salt (hereafter same) containing unsaturated bond of this disclosure of the invention.This invention comprises the following steps：The first step, with maleic anhydride and RxAlcohol (hereafter same) produces the maleic acid list R of Formulas I structurexEster；Second step, solvent, mixing maleic acid list R are made with ethyl acetatexEster and N, N dimethylaminoethylacrylate, produce 3 (the oxo pi-allyl of N, N dimethyl N (E) 3 ' oxygen ethyl 3 ') ammonium succinate monoester inner salts of Formula II structure.This invention realizes and is is prepared by the usury use, low cost of 3 (N, N dimethyl N ethyl acrylates base) ammonium succinate monoester inner salts by improving the conditions such as solvent, temperature.
Description
Technical field：
This invention is related to a kind of a kind of amphoteric surfactant containing unsaturated bond of synthesis：3- (N, N- dimethyl-N -s
(E) -3 '-oxo of -3 '-oxygen ethyl pi-allyl) ammonium succinate monoester inner salt method.
Background technology：
Synthesis has unsaturated double-bond and negative and positive amphion surface active cpd simultaneously, is very meaningful, and tool
Challenging problem.Such compound suffers from extremely weighing in terms of weaving, washing, oil, medicine and organic synthesis intermediate
The effect and application wanted.In the molecular structure of surface active cpd, anion and cationic species are had concurrently, can effectively carry
Dissolubility, salt-resistance, the antibiotic property of high surfactant；Contain unsaturated bond active function groups in molecule, structure can be used as
The intermediate of the higher new Gemini type surface-active of activity.
However, the method for common synthetic surfactant, it is impossible to by simply reacting the unsaturation that gets both in the molecule
Double bond and negative and positive amphion surface active cpd.Or limited by physical condition, by longer step or compared with complex conditions system
It is standby that there is unsaturated double-bond and negative and positive amphion surface active cpd simultaneously, have the disadvantage that atom utilization is low, contain by-product
Thing, purity is not good enough.
The content of the invention：
It is an object of the invention to provide a kind of a kind of amphoteric surfactant 3- (N, N- diformazans containing unsaturated bond of synthesis
Base-N- (E) -3 '-oxygen -3 '-oxo of ethyl pi-allyl) ammonium succinate monoester inner salt method, such as following formula：
Synthesis 3- (N, N- dimethyl-N-(E) -3 '-oxygen -3 '-oxo of ethyl pi-allyl) ammonium fourth provided by the present invention
The method of Monomethyl diester inner salt, comprises the following steps：
The first step：Produce the maleic acid list R of Formulas I structurexEster
With maleic anhydride and RxAlcohol produces the maleic acid list R of Formulas I structurexEster.
Second step：Produce 3- (N, N- dimethyl-N-(E) -3 '-oxygen -3 '-oxo of ethyl pi-allyl) ammonium of Formula II structure
Succinate monoester inner salt
Solvent, mixing maleic acid list R are made with ethyl acetatexEster and N, N- dimethylaminoethylacrylate, produce Formula II
3- (N, N- dimethyl-N-(E) -3 '-oxygen -3 '-oxo of ethyl pi-allyl) ammonium succinate monoester inner salt of structure.
In the present invention, the producing process of the first step is：With mol ratio=maleic anhydride: RxAlcohol=1: 1.05, mix horse
Come acid anhydrides and RxAlcohol reacts 1.5 hours in round-bottomed flask, mechanical agitation, 95 DEG C of water-bath temperature control, is cooled to room temperature, obtains Formulas I knot
The maleic acid list R of structurexEster.
In the present invention, second step producing process is that ethyl acetate is added into the maleic acid equipped with the Formulas I structure after cooling
Single RxIn the reaction bulb of ester, low-grade fever dissolving；It is added dropwise N under mechanical agitation, cold bath, N- dimethylaminoethylacrylates, mole
Than=maleic acid list RxEster: N, N- dimethylaminoethylacrylate=1: 1.2,80 DEG C are warming up to after dripping off, 8h is reacted；Reaction
Afterwards, by reaction solution stand be cooled to room temperature, filter out the solid of gained, that is, obtain the Formula II structure of crude product 3- (N, N- dimethyl-
N- (E) -3 '-oxygen -3 '-oxo of ethyl pi-allyl) ammonium succinate monoester inner salt, 3- (N, the N- diformazans of the Formula II structure of crude product
Base-N- (E) -3 '-oxygen -3 '-oxo of ethyl pi-allyl) ammonium succinate monoester inner salt can use re-crystallizing in ethyl acetate, mass ratio
=solute: solvent=1: 10, obtain 3- (N, N- dimethyl-N-(E) -3 '-oxygen ethyl -3 '-oxo alkene of refined Formula II structure
Propyl group) ammonium succinate monoester inner salt.
In the present invention, the maleic acid list R of Formulas I structure can be produced in the first stepxSolvent ethyl acetate is added during ester, this
Operating process will cause the maleic acid list R that can not analyze and identify Formulas I structurexEster, but can not influence to produce Formula II structure 3- (N,
N- dimethyl-N -s (E) -3 '-oxygen -3 '-oxo of ethyl pi-allyl) ammonium succinate monoester inner salt.
The principle of the present invention has dramatically different with the principle that tradition produces double ion surfactant, tertiary amine that will be traditional
Substitution reaction to halo higher fatty acids, changes and does tertiary amine to α, the addition reaction of beta-unsaturated carboxylic acid.This invention is fundamentally
The atom utilization that overcomes traditional approach is low, containing the not good enough shortcoming of accessory substance, purity.This programme is using addition reaction as base
Plinth, has：Can be achieved atom 100% using atom economy, no accessory substance, product be easily isolated purification and can the company of realization
The advantages of continuous production.Realize to 3- (N, N- dimethyl-N-(E) -3 '-oxygen -3 '-oxo of ethyl pi-allyl) ammonium succinic acid list
The usury of ester inner salt is used, prepared by low cost.
Embodiment：
1. prepare 3- (N, N- dimethyl-N-(E) -3 '-oxygen -3 '-oxo of ethyl pi-allyl) ammonium succinic acid Dan Zhengshi tetra-
Ester inner salt
The first step：In 100mL there-necked flasks, mixing 4.9g (0.05mol) maleic anhydrides and 11.26g (0.0525mol) are just
Tetradecyl alchohol, plus 5mL ethyl acetate, mechanical agitation.1.5h is reacted in 95 DEG C, TLC, which is followed the trail of to maleic anhydride point, to disappear, and is cooled to room
Temperature, yield 100%,1HNMR spectrum such as Fig. 1.
Fig. 1：Maleic acid Dan Shisi esters1HNMR is composed
Parsing is shown in Table 1：
Table 1：The esters of maleic acid Dan Zhengshi tetra-1HNMR spectrum parsings
Second step：50mL ethyl acetate is added into the reaction bulb of the first step, stirring forms solution.It is added dropwise with glue head dropper
8.59g (0.06mol) N, N- dimethylaminoethylacrylate, is warming up to 80 DEG C after dripping off, react 8h；After reaction, it will react
Liquid stands and is cooled to room temperature, filters out the faint yellow solid of gained, crude yield 55%；Re-crystallizing in ethyl acetate three times is chased after to TLC
Track to maleic acid Dan Shisi esters point disappears, and obtains white solid, yield 25~35%,1HNMR spectrum such as Fig. 2.
Fig. 2：3- (N, N- dimethyl-N-(E) -3 '-oxygen -3 '-oxo of ethyl pi-allyl) ammonium succinate monoester inner salt1HNMR is composed
Parsing is shown in Table 2：
Table 2：The esters of 3- (N, N- dimethyl-N-(E) -3 '-oxygen -3 '-oxo of ethyl pi-allyl) ammonium succinic acid Dan Zhengshi tetra-
Inner salt1HNMR spectrum parsings
2. prepare 3- (N, N- dimethyl-N-(E) -3 '-oxygen -3 '-oxo of ethyl pi-allyl) ammonium succinic acid Dan Zhengshi bis-
Ester inner salt
The first step：In 100mL there-necked flasks, mixing 4.9g (0.05mol) maleic anhydrides and 9.78g (0.0525mol) are just
Lauryl alcohol, plus 5mL ethyl acetate, mechanical agitation.1.5h is reacted in 95 DEG C, TLC, which is followed the trail of to maleic anhydride point, to disappear, and is cooled to room
Temperature, yield 100%.
Second step：50mL ethyl acetate is added into the reaction bulb of the first step, stirring forms solution.It is added dropwise with glue head dropper
8.59g (0.06mol) N, N- dimethylaminoethylacrylate, is warming up to 80 DEG C after dripping off, react 8h；After reaction, it will react
Liquid stands and is cooled to room temperature, filters out the faint yellow solid of gained, crude yield 57%；Re-crystallizing in ethyl acetate three times is chased after to TLC
Track to maleic acid Dan Shisi esters point disappears, and obtains white solid, yield 28~36%.
3. prepare 3- (N, N- dimethyl-N-(E) -3 '-oxygen -3 '-oxo of ethyl pi-allyl) positive last of the ten Heavenly stems ester of ammonium succinic acid list
Inner salt
The first step：In 100mL there-necked flasks, mixing 4.9g (0.05mol) maleic anhydrides and 8.31g (0.0525mol) are just
Decyl alcohol, plus 5mL ethyl acetate, mechanical agitation.1.5h is reacted in 95 DEG C, TLC, which is followed the trail of to maleic anhydride point, to disappear, and is cooled to room
Temperature, yield 100%.
Second step：50mL ethyl acetate is added into the reaction bulb of the first step, stirring forms solution.It is added dropwise with glue head dropper
8.59g (0.06mol) N, N- dimethylaminoethylacrylate, is warming up to 80 DEG C after dripping off, react 8h；After reaction, it will react
Liquid stands and is cooled to room temperature, filters out the faint yellow solid of gained, crude yield 60%；Re-crystallizing in ethyl acetate three times is chased after to TLC
Track to maleic acid Dan Shisi esters point disappears, and obtains white solid, yield 28~37%.
4. prepare 3- (N, N- dimethyl-N-(E) -3 '-oxygen -3 '-oxo of ethyl pi-allyl) ammonium succinic acid list n-octyl
Inner salt
The first step：In 100mL there-necked flasks, mixing 4.9g (0.05mol) maleic anhydrides and 6.84g (0.0525mol) are just
Octanol, plus 5mL ethyl acetate, mechanical agitation.1.5h is reacted in 95 DEG C, TLC, which is followed the trail of to maleic anhydride point, to disappear, and is cooled to room
Temperature, yield 100%.
Second step：50mL ethyl acetate is added into the reaction bulb of the first step, stirring forms solution.It is added dropwise with glue head dropper
8.59g (0.06mol) N, N- dimethylaminoethylacrylate, is warming up to 80 DEG C after dripping off, react 8h；After reaction, it will react
Liquid stands and is cooled to room temperature, filters out the faint yellow solid of gained, crude yield 65%；Re-crystallizing in ethyl acetate three times is chased after to TLC
Track to maleic acid Dan Shisi esters point disappears, and obtains white solid, yield 30~38%.
Claims (10)
1. it is a kind of synthesize it is a kind of containing unsaturated bond amphoteric surfactant 3- (N, N- dimethyl-N-(E) -3 '-oxygen ethyl -
3 '-oxo pi-allyl) ammonium succinate monoester inner salt method, comprise the following steps：
The first step：Produce the maleic acid list R of Formulas I structurexEster
With maleic anhydride and RxAlcohol produces the maleic acid list R of Formulas I structurexEster；
Second step：Produce 3- (N, N- dimethyl-N-(E) -3 '-oxygen -3 '-oxo of ethyl pi-allyl) ammonium fourth two of Formula II structure
Acid monoester inner salt
Solvent, mixing maleic acid list R are made with ethyl acetatexEster and N, N- dimethylaminoethylacrylate, produce Formula II structure
3- (N, N- dimethyl-N-(E) -3 '-oxygen -3 '-oxo of ethyl pi-allyl) ammonium succinate monoester inner salt.
2. method according to claim 1, it is characterized in that：First step producing process is, with mol ratio=maleic anhydride: RxAlcohol
=1: 1.05, mix maleic anhydride and RxAlcohol reacts 1.5 hours, is cooled in round-bottomed flask, mechanical agitation, 95 DEG C of water-bath temperature control
Room temperature, obtains the maleic acid list R of Formulas I structurexEster.
3. method according to claim 1, it is characterized in that：RxAlcohol can be aliphatic alkylol, alkoxyl alcohol, monoalkyl
Hold polyethylene glycol, monoalkyl end polypropylene glycol, polyol etc.；Aromatic phenol；And the polyhydroxy based high molecular such as carbohydrate.
4. method according to claim 1, it is characterized in that：N, N- dimethylaminoethylacrylate can be N, N- dimethyl
The organic compound containing tertiary amino such as ammonio methacrylate ethyl ester, dimethylaminoethyl acrylate.
5. method according to claim 1, it is characterized in that：Solvent can be the boiling such as methyl acetate, ethyl acetate, tetrahydrofuran
Esters of the point no more than 100 DEG C, ether compound.
6. method according to claim 1, it is characterized in that：Optional catalyst both can be the strong acid such as p-methyl benzenesulfonic acid,
Can be the inorganic bases such as natrium carbonicum calcinatum.
7. method according to claim 1, it is characterized in that：Second step producing process is to add ethyl acetate equipped with cooling
The maleic acid list R of Formulas I structure afterwardsxIn the reaction bulb of ester, low-grade fever dissolving；N, N- dimethyl are added dropwise under mechanical agitation, cold bath
Aminoacrylic acid ethyl ester, mol ratio=maleic acid list RxEster: N, N- dimethylaminoethylacrylate=1: 1.2, risen after dripping off
Temperature reacts 8h to 80 DEG C；After reaction terminates, reaction solution is stood and is cooled to room temperature.The solid of gained is filtered out, that is, obtains crude product
3- (N, N- dimethyl-N-(E) -3 '-oxygen -3 '-oxo of ethyl pi-allyl) ammonium succinate monoester inner salt, crude product of Formula II structure
3- (N, N- dimethyl-N-(E) -3 '-oxygen -3 '-oxo of ethyl pi-allyl) ammonium succinate monoester inner salt of Formula II structure can
With re-crystallizing in ethyl acetate, mass ratio=solute: solvent=1: 10, obtain 3- (N, the N- dimethyl-N -s of refined Formula II structure
(E) -3 '-oxo of -3 '-oxygen ethyl pi-allyl) ammonium succinate monoester inner salt.
8. method according to claim 1, it is characterized in that：The maleic acid list R of Formulas I structure can be produced in the first stepxAdd during ester
Enter solvent, such as ethyl acetate, this behavior will cause the maleic acid list R that can not analyze and identify Formulas I structurexThe consequence of ester, but can not
Change the maleic acid list R for producing Formulas I structurexEster and the 3- of Formula II structure (N, N- dimethyl-N-(E) -3 '-oxygen -3 '-oxygen of ethyl
For pi-allyl) result of ammonium succinate monoester inner salt.
9. according to claim 1 and method according to claim 4, it is characterized in that：The maleic acid list R of Formulas I structurexEster is in second
Concentration in acetoacetic ester is 1.0mol/L.
10. according to claim 2, according to claim 5 and method according to claim 8, it is characterized in that：Formula I is tied
The maleic acid list R of structurexDuring ester, solvent, such as ethyl acetate are previously added, no matter then quantity of solvent or catalytic amount, all can significantly be carried
The esterification yield of high maleic anhydride.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108467349A (en) * | 2018-01-16 | 2018-08-31 | 天津工业大学 | The preparation of three type surfactant of 3- (N, N- dimethyl-N-X alkyl) three ester of ammonium succinic acid triethanolamine |
-
2017
- 2017-03-29 CN CN201710206297.0A patent/CN107021885A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108467349A (en) * | 2018-01-16 | 2018-08-31 | 天津工业大学 | The preparation of three type surfactant of 3- (N, N- dimethyl-N-X alkyl) three ester of ammonium succinic acid triethanolamine |
| CN108467349B (en) * | 2018-01-16 | 2020-10-02 | 天津工业大学 | Preparation of 3- (N, N-dimethyl-N-X) ammonium succinic acid triethanolamine triester triple salt surfactant |
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Application publication date: 20170808 |