CN103071423B - Pyridine carbamyl quaternary ammonium surfactant and preparation method thereof - Google Patents
Pyridine carbamyl quaternary ammonium surfactant and preparation method thereof Download PDFInfo
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- CN103071423B CN103071423B CN201310052820.0A CN201310052820A CN103071423B CN 103071423 B CN103071423 B CN 103071423B CN 201310052820 A CN201310052820 A CN 201310052820A CN 103071423 B CN103071423 B CN 103071423B
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Abstract
The invention relates to a pyridine carbamyl quaternary ammonium surfactant and a preparation method thereof. The structural formula of the pyridine carbamyl quaternary ammonium surfactant is shown as follows: , wherein n is 7, 9, 11, 13 and 15, and X is Cl. A specific synthetic method of the pyridine carbamyl quaternary ammonium surfactant provided by the invention comprises the following three steps of: carrying out amidation on aminopyridine and chloroacetyl chloride, carrying out esterification reaction on dimethylethanolamine and fatty acid, and carrying out quaternary ammonium salinization reaction on N-(2-pyridyl)-2-chloroacetamide and fatty acid dimethylethanolamine ester. According to the pyridine carbamyl quaternary ammonium surfactant and the preparation method thereof, raw materials are easily obtained, reaction conditions are mild and liable to control, the operation is simple, the pyridine carbamyl quaternary ammonium surfactant is easily purified, and the yield is high; and a molecular structure of the pyridine carbamyl quaternary ammonium surfactant contains an amido bond and an ester group, so that the pyridine carbamyl quaternary ammonium surfactant has good biological degradability.
Description
Technical field
the present invention relates to field of fine chemical, particularly relate to pyridine carbamyl quaternary ammonium surfactant and preparation method thereof.
Background technology
quaternary ammonium salt surface active agent is a most important class in surfactant, at many industrial circles, has a wide range of applications especially in industry such as washing, printing and dyeing, agricultural chemicals, medicine, tertiary oil recovery, sterilizing, sewage disposals.Pyridine ring surfactant is that a class has good biologically active and surface-active surfactant.For a long time, such surfactant is subject to the extensive concern of researchers always, their surface-active and the existing bibliographical information of antibacterial activity research.But what the fast development of 21 century industry faced is not only the challenge in cost benefit, and the more important thing is the surfactant molecule that acquisition Environmental compatibility is good, object reduces toxicity and reduce to use rear pollution on the environment.The main method of current solution is the functional group introducing cleavable or easily degraded in surfactant molecule structure, as ester bond, amido link etc.Synthesis and property research about this type of surfactant just becomes petrochemical industry, the focus of the area researches such as medicine, agricultural chemicals and industrial wastewater.
Summary of the invention
the object of the invention is to provide a kind of pyridine carbamyl quaternary ammonium surfactant and preparation method thereof, to solve the problems referred to above that prior art exists.
the invention provides a kind of pyridine carbamyl quaternary ammonium surfactant, its structural formula is:
wherein n is 7,9,11,13,15; X is Cl.
when n is 7, this surfactant is ethyl caprilate dimethyl-2-pridylamino formyl methyl ammonium chloride;
when n is 9, this surfactant is ethyl caprate dimethyl-2-pridylamino formyl methyl ammonium chloride;
when n is 11, this surfactant is ethyl laurate dimethyl-2-pridylamino formyl methyl ammonium chloride;
when n is 13, this surfactant is ethyl myristate dimethyl-2-pridylamino formyl methyl ammonium chloride;
when n is 15, this surfactant is ethyl palmitate dimethyl-2-pridylamino formyl methyl ammonium chloride;
the present invention also provides the preparation method preparing above-mentioned pyridine carbamyl quaternary ammonium surfactant, comprises the steps:
1) amidation process
by PA and chloracetyl chloride under acid binding agent and organic solvent exist, under-5 DEG C ~-8 DEG C conditions, carry out amidation process obtain intermediate (I) N-(2-pyridine radicals)-2-chloroacetamide, wherein the mol ratio of PA and chloracetyl chloride is 1:1 ~ 1.5, preferred 1:1.25.
2) esterification
dimethylethanolamine and aliphatic acid are carried out esterification in 130 DEG C ~ 150 DEG C in presence of an acid catalyst and obtains intermediate (II) myristalkonium monoethanolamine ester, wherein the mol ratio of dimethylethanolamine and aliphatic acid is 1:2 ~ 2.5, preferred 1:2.3.
3) quaternization reaction
by intermediate (I) with intermediate (II) carried out quaternization be in organic solvent obtained by reacting target product, wherein intermediate (I) be 1:1.2 ~ 1.6 by the mol ratio of intermediate (II), preferred 1:1.5.
below with aminopyridine, chloracetyl chloride, sad, dimethylethanolamine for raw material, the reaction principle of preparation method of the present invention is described:
the synthesis of the first step: N-(2-pyridine radicals)-2-chloroacetamide
second step: the synthesis of myristalkonium monoethanolamine ester
3rd step: the synthesis of ethyl caprilate dimethyl-2-pridylamino formyl methyl ammonium chloride
pyridine carbamyl quaternary ammonium surfactant of the present invention is introduced pyridine ring in molecular structure, strengthens the electropositive of molecule.Molecule is more easily adsorbed and stretches into bacterium inside, make bacterial death.In pyridine carbamyl quaternary ammonium surfactant molecular structure of the present invention, existing pyridine heterocycle, in turn introduce amido link and ester group, this structure makes surfactant not only have good biologically active in use but also have good biological degradability.
pyridine carbamyl quaternary ammonium surfactant of the present invention and preparation method thereof has following beneficial effect: preparation method's Raw is easy to get, and reaction condition gentleness is easy to control, and easy and simple to handle, product is easily purified, and yield is high.Containing amido link and ester group, there is good biological degradability in molecular structure.
Detailed description of the invention
following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
example 1
the synthesis of the first step: N-(2-pyridine radicals)-2-chloroacetamide
in the reaction bulb that carrene 40 mL is housed, add PA 6.58 g (0.070 mol) and pyridine 8.30 g (0.105 mol) respectively, stir at-5 DEG C ~-8 DEG C, then slowly instill chloracetyl chloride 9.80 g (0.0875 mol) with constant pressure funnel to react with the mixed solution of carrene 20 mL, 1 h dropwises, follow the tracks of reaction process with TLC, about 1.5 ~ 3.0 h stop reaction.Saturated sodium bicarbonate solution 45 mL is added in reactant mixture, collect dichloromethane layer, steaming vibrating dichloromethane obtains product, product is with n-hexane (15 mL × 3), drying obtains yellow solid N-(2-pyridine radicals) 2-chloroacetamide 10.89 g, yield 91.51%.
1
the displacement of H nmr chemical (400 MHz, DMSO-d
6
, ppm)
δ: 4.36 (2H), 7.11 (1H), 7.82 (1H), 8.05 (1H), 8.34 (1H), 10.83 (1H).
second step: the synthesis of sad dimethylethanolamine ester
in the reaction bulb that rectifying column is housed, add sad 3.31 g (0.023 mol), dimethylethanolamine 0.89 g (0.01 mol) and Catalyzed by p-Toluenesulfonic Acid agent 0.08 g respectively, frit reaction is stirred at 130 DEG C ~ 150 DEG C, reaction process is followed the tracks of by the content of the water separated in water knockout drum, after about 8 ~ 10 h, the water yield separated stops reaction when reaching 95% of the theoretical point water yield, and gained reactant is dissolved in CHCl
3
, boil off organic solvent after washing, with anhydrous magnesium sulfate drying, obtain product sad dimethylethanolamine ester weak yellow liquid 1.82 g, yield 84.65%.
3rd step: the synthesis of ethyl caprilate dimethyl-2-pridylamino formyl methyl ammonium chloride
in the reaction bulb that condenser pipe is housed, add N-(2-pyridine radicals) 2-chloroacetamide 0.68 g (0.004 mol), sad dimethylethanolamine ester 1.29 g (0.006 mol) and acetonitrile 20 mL, magnetic agitation heating reflux reaction, TLC follows the tracks of reaction process, after about 10 h, reaction terminates, pressure reducing and steaming solvent, obtain yellow lotion, (V (acetonitrile): V (ethyl acetate)=10:2.0) recrystallization in the mixed solvent of acetonitrile and ethyl acetate, obtain white plates crystal 1.29 g, yield 83.77%.
1
H?NMR?(400?MHz,?CDCl
3
)?
δ:?0.86?(3H),?1.22-1.29?(8H),?1.53-1.57?(2H),?2.31?(2H),?3.65?(6H)?4.29(2H),?4.63?(2H),?5.30?(2H),?7.03?(1H),?7.63?(1H),?7.88?(1H),?8.34?(1H),?11.48?(1H)。
example 2
second step: the synthesis of capric acid dimethylethanolamine ester
in the reaction bulb that rectifying column is housed, add capric acid 3.96 g (0.023 mol), dimethylethanolamine 0.89 g (0.01 mol) and Catalyzed by p-Toluenesulfonic Acid agent 0.09 g respectively, frit reaction is stirred at 130 DEG C ~ 150 DEG C, reaction process is followed the tracks of by the content of the water separated in water knockout drum, after about 8 ~ 10 h, the water yield separated stops reaction when reaching 95% of the theoretical point water yield, and gained reactant is dissolved in CHCl
3
, boil off organic solvent after washing, with anhydrous magnesium sulfate drying, obtain product capric acid dimethylethanolamine ester weak yellow liquid 2.06g, yield 84.77%.
3rd step: the synthesis of ethyl caprate dimethyl-2-pridylamino formyl methyl ammonium chloride
in the reaction bulb that condenser pipe is housed, add N-(2-pyridine radicals) 2-chloroacetamide 0.68 g (0.004 mol), capric acid dimethylethanolamine ester 1.46 g (0.006 mol) and acetonitrile 20 mL, magnetic agitation heating reflux reaction, TLC follows the tracks of reaction process, after about 10 h, reaction terminates, pressure reducing and steaming solvent, obtain yellow lotion, (V (acetonitrile): V (ethyl acetate)=10:2.0) recrystallization in the mixed solvent of acetonitrile and ethyl acetate, obtain white plates crystal 1.38 g, yield 83.64%.
1
H?NMR?(400?MHz,?CDCl
3
)?
δ:?0.87?(3H),?1.22-1.29?(8H),?1.52-1.56?(2H),?2.29?(2H),?3.66?(6H)?4.30?(2H),?4.63?(2H),?5.29?(2H),?7.02?(1H),?7.63?(1H),?7.89?(1H),?8.33?(1H),?11.46?(1H)。
example 3
second step: the synthesis of dodecylic acid dimethylethanolamine ester
in the reaction bulb that rectifying column is housed, add dodecylic acid 4.60 g (0.023 mol), dimethylethanolamine 0.89 g (0.01 mol) and Catalyzed by p-Toluenesulfonic Acid agent 0.10 g respectively, frit reaction is stirred at 130 DEG C ~ 150 DEG C, reaction process is followed the tracks of by the content of the water separated in water knockout drum, after about 8 ~ 10 h, the water yield separated stops reaction when reaching 95% of the theoretical point water yield, and gained reactant is dissolved in CHCl
3
, boil off organic solvent after washing, with anhydrous magnesium sulfate drying, obtain product dodecylic acid dimethylethanolamine ester weak yellow liquid 2.25g, yield 83.03%.
3rd step: the synthesis of ethyl laurate dimethyl-2-pridylamino formyl methyl ammonium chloride
in the reaction bulb that condenser pipe is housed, add N-(2-pyridine radicals) 2-chloroacetamide 0.68 g (0.004 mol), dodecylic acid dimethylethanolamine ester 1.63 g (0.006 mol) and acetonitrile 20 mL, magnetic agitation heating reflux reaction, TLC follows the tracks of reaction process, after about 10 h, reaction terminates, pressure reducing and steaming solvent, obtain yellow lotion, (V (acetonitrile): V (ethyl acetate)=10:2.0) recrystallization in the mixed solvent of acetonitrile and ethyl acetate, obtain white plates crystal 1.48 g, yield 84.09%.
1
H?NMR?(400?MHz,?CDCl
3
)?
δ:?0.87?(3H),?1.22-1.29?(8H),?1.52-1.56?(2H),?2.29?(2H),?3.65?(6H)?4.30?(2H),?4.63?(2H),?5.30?(2H),?7.02?(1H),?7.63?(1H),?7.88?(1H),?8.34?(1H),?11.46?(1H)。
example 4
second step: the synthesis of tetradecanoic acid dimethylethanolamine ester
in the reaction bulb that rectifying column is housed, add tetradecanoic acid 5.25 g (0.023 mol), dimethylethanolamine 0.89 g (0.01 mol) and Catalyzed by p-Toluenesulfonic Acid agent 0.12 g respectively, frit reaction is stirred at 130 DEG C ~ 150 DEG C, reaction process is followed the tracks of by the content of the water separated in water knockout drum, after about 8 ~ 10 h, the water yield separated stops reaction when reaching 95% of the theoretical point water yield, and gained reactant is dissolved in CHCl
3
, boil off organic solvent after washing, with anhydrous magnesium sulfate drying, obtain product tetradecanoic acid dimethylethanolamine ester weak yellow liquid 2.56g, yield 85.62%.
3rd step: the synthesis of ethyl myristate dimethyl-2-pridylamino formyl methyl ammonium chloride
in the reaction bulb that condenser pipe is housed, add N-(2-pyridine radicals) 2-chloroacetamide 0.68 g (0.004 mol), tetradecanoic acid dimethylethanolamine ester 1.80 g (0.006 mol) and acetonitrile 20 mL, magnetic agitation heating reflux reaction, TLC follows the tracks of reaction process, after about 10 h, reaction terminates, pressure reducing and steaming solvent, obtain yellow lotion, (V (acetonitrile): V (ethyl acetate)=10:2.0) recrystallization in the mixed solvent of acetonitrile and ethyl acetate, obtain white plates crystal 1.59 g, yield 84.57%.
1
H?NMR?(400?MHz,?CDCl
3
)?
δ:?0.88?(3H),?1.20-1.32?(8H),?1.51-1.54?(2H),?2.28?(2H),?3.63?(6H)?4.27?(2H),?4.64?(2H),?5.22?(2H),?7.02?(1H),?7.63?(1H),?7.88?(1H),?8.33?(1H),?11.30?(1H)。
example 5
second step: the synthesis of hexadecanoic acid dimethylethanolamine ester
in the reaction bulb that rectifying column is housed, add hexadecanoic acid 5.89 g (0.023 mol), dimethylethanolamine 0.89 g (0.01 mol) and Catalyzed by p-Toluenesulfonic Acid agent 0.13 g respectively, frit reaction is stirred at 130 DEG C ~ 150 DEG C, reaction process is followed the tracks of by the content of the water separated in water knockout drum, after about 8 ~ 10 h, the water yield separated stops reaction when reaching 95% of the theoretical point water yield, and gained reactant is dissolved in CHCl
3
, boil off organic solvent after washing, with anhydrous magnesium sulfate drying, obtain product hexadecanoic acid dimethylethanolamine ester weak yellow liquid 2.79g, yield 85.32%.
3rd step: the synthesis of ethyl palmitate dimethyl-2-pridylamino formyl methyl ammonium chloride
in the reaction bulb that condenser pipe is housed, add N-(2-pyridine radicals) 2-chloroacetamide 0.68 g (4 mmol), hexadecanoic acid dimethylethanolamine ester 1.96 g (6 mmol) and acetonitrile 20 mL, magnetic agitation heating reflux reaction, TLC follows the tracks of reaction process, after about 10 h, reaction terminates, pressure reducing and steaming solvent, obtain yellow lotion, (V (acetonitrile): V (ethyl acetate)=10:2.0) recrystallization in the mixed solvent of acetonitrile and ethyl acetate, obtain white plates crystal 1.70 g, crystallization yield 85.43%.
1
H?NMR?(400?MHz,?CDCl
3
)?
δ:?0.88?(3H),?1.22-1.30?(8H),?1.54-1.57?(2H),?2.32?(2H),?3.64?(6H)?4.26?(2H),?4.63?(2H),?5.31?(2H),?7.04?(1H),?7.65?(1H),?7.88?(1H),?8.36?(1H),?11.55?(1H)。
as can be seen from the above embodiments, the pyridine carbamyl quaternary ammonium surfactant that the embodiment of the present invention provides is without the reaction condition of harshness, and raw material is easy to get, solvent recoverable.Compared with prior art, introduce pyridine ring, ester group and amido link in the pyridine carbamyl quaternary ammonium surfactant molecular structure that example 1-5 obtains, this structure makes surfactant not only have good biological degradability when applying but also have good biologically active.
Claims (5)
1.
pyridine carbamyl quaternary ammonium surfactant, is characterized in that, its general structure is as follows:
wherein n is 7,9,11,13,15; X is Cl.
2.
prepare the method for pyridine carbamyl quaternary ammonium surfactant according to claim 1, it is characterized in that, comprise the steps:
1) amidation process
by PA and chloracetyl chloride under acid binding agent and organic solvent exist, under-5 DEG C ~-8 DEG C conditions, carry out amidation process obtain intermediate (I) N-(2-pyridine radicals)-2-chloroacetamide, wherein the mol ratio of PA and chloracetyl chloride is 1:1 ~ 1.5;
2) esterification
by dimethylethanolamine and aliphatic acid in presence of an acid catalyst, carry out esterification in 130 DEG C ~ 150 DEG C and obtain intermediate (II) myristalkonium monoethanolamine ester, wherein the mol ratio of dimethylethanolamine and aliphatic acid is 1:2 ~ 2.5;
3) quaternization reaction
intermediate (I) and intermediate (II) are carried out quaternization in organic solvent and is obtained by reacting target product, wherein intermediate (I) is 1:1.2 ~ 1.6 with the mol ratio of intermediate (II).
3.
preparation method according to claim 2.It is characterized in that, step 1) described in acid binding agent be pyridine, organic solvent is carrene.
4.
preparation method according to claim 2.It is characterized in that, step 2) described in acidic catalyst be p-methyl benzenesulfonic acid.
5.
preparation method according to claim 2.It is characterized in that, step 3) described in organic solvent be acetonitrile.
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| CN103933893A (en) * | 2014-04-28 | 2014-07-23 | 河南师范大学 | Choline ionic liquid surfactant and preparation method thereof |
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| CN104610092B (en) * | 2015-02-10 | 2016-08-17 | 齐齐哈尔大学 | A kind of quaternary cationics and preparation method thereof |
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| CN105727828B (en) * | 2016-03-03 | 2017-10-31 | 江南大学 | Cationic surfactant and preparation method thereof |
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| CN106512848B (en) * | 2016-09-30 | 2018-07-17 | 武汉工程大学 | A kind of cyclic quaternary ammonium salts Gemini surface active agent and preparation method thereof |
| CN107410318A (en) * | 2017-04-20 | 2017-12-01 | 齐齐哈尔大学 | A kind of pyridine heterocycle quaternary cationics disinfectant use in agriculture |
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| US6515134B1 (en) * | 1999-02-16 | 2003-02-04 | Kaneka Corporation | Substituted acetylpridine derivatives and process for the preparation of intermediates for optically active beta-3 agonist by the use of the same |
| CN1973625A (en) * | 2006-12-20 | 2007-06-06 | 东华大学 | Pyridyl quaternary ammonium salt antiseptic and its prepn process |
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