CN103304534B - Preparation method of rosinyl cyclic carbonate and quaternary ammonium salt antibacterial derivative thereof - Google Patents

Preparation method of rosinyl cyclic carbonate and quaternary ammonium salt antibacterial derivative thereof Download PDF

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CN103304534B
CN103304534B CN201310222679.4A CN201310222679A CN103304534B CN 103304534 B CN103304534 B CN 103304534B CN 201310222679 A CN201310222679 A CN 201310222679A CN 103304534 B CN103304534 B CN 103304534B
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rosinyl
cyclic carbonate
ammonium salt
quaternary ammonium
carbonate ester
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CN103304534A (en
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孔振武
刘贵锋
陈彩凤
吴国民
陈健
霍淑平
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Institute of Chemical Industry of Forest Products of CAF
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Institute of Chemical Industry of Forest Products of CAF
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Abstract

The invention discloses a preparation method of rosinyl cyclic carbonate and a quaternary ammonium salt antibacterial derivative thereof. The preparation method comprises the following steps of: reacting maleopimaric acid epoxy resin with CO2 under the action of a catalyst, so as to synthesize rosinyl cyclic carbonate; reacting the rosinyl cyclic carbonate with an amino compound to prepare rosinyl carbamic acid ester; and further carrying out a quaterisation reaction so as to obtain a novel rosinyl quaternary ammonium salt antibacterial derivative containing carbamic acid ester groups. The rosinyl quaternary ammonium salt antibacterial derivative is low in raw material cost, wide in resource and safe and non-toxic in preparation process; as carbamic acid ester polar groups with antibacterial activity are introduced into the molecular structure, the quaternary ammonium salt antibacterial derivative has good water solubility, biocompatibility and excellent antibacterial and bactericidal performances, and can be applied to fields of antibacterial, bactericides and the like.

Description

The preparation method of a kind of rosinyl cyclic carbonate ester and quaternary ammonium salt antibiotic derivative thereof
Technical field
The invention discloses the preparation method of a kind of rosinyl cyclic carbonate ester and quaternary ammonium salt antibiotic derivative thereof, relate in particular to a kind of with maleopimaric acid epoxy resin and CO 2the preparation method of rosinyl cyclic carbonate ester and acid esters containing urethane groups quaternary ammonium salt derivative thereof is prepared in reaction.
Background technology
Rosin is a kind of important natural resource, has biodegradable, renewable and wide material sources, lower-price characteristic, and its main component is resinous acid, contains the groups such as the luxuriant and rich with fragrance skeleton of triatomic ring, two key and carboxylic acid in molecular structure.By to rosin chemical structure modification, can prepare dissimilar derivative.Wherein, cationic quarternary ammonium salt compound is subject to extensive concern because of advantages such as low toxicity, nonirritant and good emulsifying power, inhibition power, antibacterial and fungicidal activities.But traditional quarternary ammonium salt compound difficult degradation, easily cause environmental pollution.Now there are some researches show, in quaternary ammonium salt molecular structure, introduce ether, ester, acid amides, carbamate and hydroxyl isopolarity functional group and can effectively improve the water-soluble and biological degradability of compound, make its more green, environmental protection.
Summary of the invention
The object of the present invention is to provide a kind of rosinyl cyclic carbonate ester and amido-containing acid ester based quaternary ammonium salt antibiotic derivative and preparation method.
The present invention is by the following technical solutions: a kind of rosinyl cyclic carbonate ester and amido-containing acid ester based quaternary ammonium salt derivative thereof, the structural formula of described rosinyl cyclic carbonate ester is the structural formula of described rosinyl carbamate is n=2～5; The structural formula of described Abietyl quaternary ammonium salt derivative is n=2～5, m=2～22.
A method of preparing rosinyl cyclic carbonate ester and amido-containing acid ester based quaternary ammonium salt derivative thereof, described rosinyl cyclic carbonate ester is with maleopimaric acid epoxy resin and CO 2reaction preparation under the effect of catalyzer, reaction formula is:
Formula one
Described catalyzer is the compound system of metal halide/vicinal diol compound, and the mass ratio of metal halide and adjacent glycol is 1:0.1～1:2.Wherein, metal halide is lithiumbromide (LiBr), lithium chloride (LiCl), potassiumiodide (KI), Potassium Bromide (KBr), zinc bromide (ZnBr 2) in one, consumption is 0.1～5% of maleopimaric acid epoxy resin quality; Adjacent glycols compound is ethylene glycol, 1,2-PD, the one in 1,2-butyleneglycol.
The reaction of preparing rosinyl cyclic carbonate ester is taking N-Methyl pyrrolidone or DMF as solvent, and maleopimaric acid epoxy resin is placed in to closed reactor, passes into CO 2to pressure be 0.5～5MPa, 80～150 DEG C reaction 2～24h.
Described rosinyl carbamate is in organic solvent, to react preparation with amino-complex with rosinyl cyclic carbonate ester, and reaction formula is:
Formula two
Described amino-complex is (CH 3) 2nR 1nH 2, wherein, R 1for C 2～C 5alkyl, described temperature of reaction is 25～100 DEG C, reaction times 2～8h.
Described amino-complex is N, N-dimethylamino quadrol, N, N-dimethylaminopropylamine, 4-dimethylamino butylamine etc.
Described organic solvent is any one in sherwood oil, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF).
Described Abietyl quaternary ammonium salt derivative is in organic solvent, to react preparation with brominated alkanes with rosinyl carbamate, and reaction formula is:
Formula three
Described brominated alkanes is for containing C 2～C 22the brominated alkanes of alkyl.
Described temperature of reaction is 60～100 DEG C, and the reaction times is 5～24h.
Beneficial effect of the present invention:
1. the present invention prepares biomass-based cyclic carbonate ester, carbamate and quaternary ammonium salt derivative thereof taking renewable resources rosin as raw material, raw materials cost is low, wide material sources, safe preparation process, nontoxic, and cyclic carbonate ester, carbamate and the quaternary ammonium salt derivative thereof of preparation have biodegradability, environmental friendliness.
2. the Abietyl quaternary ammonium salt antibiotic derivative that prepared by the present invention, because introducing and have the carbamate polar group of anti-microbial activity in molecular structure, thereby has well water-soluble, biocompatibility and excellent antibacterial, bactericidal property.
Brief description of the drawings
The infrared spectrogram of Fig. 1 rosinyl cyclic carbonate ester (R-C).
The infrared spectrogram of Fig. 2 rosinyl carbamate (R-Ca).
The infrared spectrogram of Fig. 3 n-propyl-Abietyl quaternary ammonium salt (QAS-a).
The infrared spectrogram of Fig. 4 n-hexyl-Abietyl quaternary ammonium salt (QAS-b).
The infrared spectrogram of Fig. 5 dodecyl-Abietyl quaternary ammonium salt (QAS-c).
Embodiment
Maleopimaric acid epoxy resin of the present invention is pressed the method preparation in reference (thermosetting resin, 1996,11 (2), 19-22.).
The preparation method of a kind of rosinyl cyclic carbonate ester and amido-containing acid ester based quaternary ammonium salt derivative thereof.
The method realizes by following steps:
The first step, in autoclave, is dissolved in a certain amount of N-Methyl pyrrolidone or DMF by the maleopimaric acid epoxy resin of certain mass and catalyzer, passes into CO after sealing 2to pressure be 0.5～5MPa, 80～150 DEG C reaction 2～24h prepare rosinyl cyclic carbonate ester, reaction as shown in Equation 1.
Formula 1
Described catalyzer is the compound system of metal halide/adjacent glycols compound, and the mass ratio of metal halide and adjacent glycols compound is 1:0.1～1:2.Wherein, metal halide is lithiumbromide (LiBr), lithium chloride (LiCl), potassiumiodide (KI), Potassium Bromide (KBr), zinc bromide (ZnBr 2) in one, consumption is 0.1～5% of maleopimaric acid epoxy resin quality; Adjacent glycols compound is ethylene glycol, 1,2-PD, 1,2-butyleneglycol etc.; Described reaction pressure the best is 2MPa, and temperature of reaction the best is 120 DEG C, and reaction times the best is 7h.
Second step, is dissolved in a small amount of organic solvent by rosinyl cyclic carbonate ester, and mixes by the ratio 1:1 of amount of substance with amino-complex, reacts 2～8h and prepare rosinyl carbamate at 25～100 DEG C, and reaction as shown in Equation 2.
Formula 2
Described organic solvent is any one in sherwood oil, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF); Described amino-complex is (CH 3) 2nR 1nH 2, wherein, R 1for C 2～C 5alkyl; As N, N-dimethylamino quadrol, dimethylaminopropylamine, 4-dimethylamino butylamine etc.; Described temperature of reaction is 25～100 DEG C, reaction times 2～8h; Described temperature of reaction the best is 70 DEG C, and reaction times the best is 2h.
The 3rd step, is dissolved in a small amount of organic solvent by rosinyl carbamate, and mixes than 1:1 by amount of substance with brominated alkanes, reacts 5～24h and prepare Abietyl quaternary ammonium salt derivative at 60～100 DEG C, and reaction as shown in Equation 3.
Formula 3
Described organic solvent is any one in methyl alcohol, ethanol, sherwood oil, acetone, cyclobutanone, ethyl acetate, tetrahydrofuran (THF); Described brominated alkanes is for containing C 2～C 22the bromo alkyl of alkyl, more preferably containing C 2～C 16the bromo alkyl of alkyl, as n-propyl bromide, bromo normal hexane, bromododecane, bromohexadecane, isobutane bromide, bromo-iso-octane etc.; Described temperature of reaction the best is 70 DEG C, and reaction times the best is 12h.
Embodiment 1
In 1L autoclave, add 200g maleopimaric acid epoxy resin, 2g lithiumbromide, 1g ethylene glycol and 70mL N-Methyl pyrrolidone (NMP), be warming up to 120 DEG C, pass into CO 2to certain pressure, emptying after leak detection.Repetitive operation three times, thoroughly gets rid of air in still, passes into CO 2keep pressure at 2MPa, stirring reaction 7h.After having reacted, remaining CO in emptying still 2, product is poured out while hot, remove catalyzer and NMP with hot wash, underpressure distillation is removed moisture and is obtained rosinyl cyclic carbonate ester.The oxirane value of assay products, obtaining its epoxy group(ing) transformation efficiency is 98.6%.
Product rosinyl cyclic carbonate ester in embodiment 1 1h NMR (500MHz, CDCl 3, δ ppm): δ 5.37 (– C=CH –); δ 4.87～5.08 (methine hydrogens of cyclic carbonate group); δ 4.02～4.23 (methylene hydrogens of cyclic carbonate group); δ 4.26～4.65 (O – CH 2–); δ 2.95～3.00 (CH – C=); δ 2.87～2.91 (CH – C=O); δ 2.52～2.65 (CH – CH 3); δ 1.05～1.86 (CH 2, CH 3).
Product rosinyl cyclic carbonate ester in embodiment 1 13c NMR (500MHz, CDCl 3, δ ppm): δ 177.9,172.1,171.9 (carbonyl carbon); 154.7 (cyclicarbonate carbon); δ 147.3,123.3 (– C=C –); δ 73.9 (methine carbons of cyclic carbonate); δ 66.0 (O – CH2 –); δ 63.3 (methylene carbons of cyclic carbonate); δ 55.7,53.8,49.3,47.3,40.9,37.5,36.5,34.5,32.3,30.5,28.2,21.6,21.1,20.2,19.5,17.4,16.7,16.5,15.5.
In embodiment 1, the infrared spectrogram of product rosinyl cyclic carbonate ester is shown in accompanying drawing 1, IR:2932,2868cm -1(CH 2, CH 3); 1791cm -1(C=O); 1724cm -1(C=O); 1457,1388cm -1(CH 3, CH 2); 1161,1095,1049cm -1(C – O – C).
Embodiment 2
In the four-hole round-bottomed flask with agitator, thermometer and reflux condensing tube, add 40g rosinyl cyclic carbonate ester, 40mL ethanol, under stirring, be warming up to 70 DEG C, treat that rosinyl cyclic carbonate ester dissolves, drip 11.5g dimethylaminopropylamine, TLC follows the tracks of reaction, reacts completely to cyclic carbonate ester.Underpressure distillation is except desolventizing, and thick product, through ethanol/re-crystallizing in ethyl acetate purifying, obtains brown solid product, i.e. rosinyl carbamate.
Product rosinyl carbamate in embodiment 2 1h NMR (500MHz, CDCl 3, δ ppm): δ 5.37 (– C=CH –); δ 3.64～4.39 (O – CH 2–, CH – OH, CH 2– OH, O – CH); δ 3.14～3.36(N – CH 2–); δ 2.85～2.95 (CH – C=O); δ 2.54～2.65 (CH – CH 3); δ 2.21 (N – CH 3); δ 1.04～1.80 (CH 2, CH 3).
Product rosinyl carbamate in embodiment 2 13c NMR (500MHz, CDCl 3, δ ppm): δ 178.5,173.3,172.1 (carbonyl carbon); 156.8 (NH – CO); δ 148.3,123.6 (– C=C –); δ 62.5～72.5 (O – CH 2–, CH – OH, CH 2– OH); δ 56.7 (N – CH 2–); δ 45.1 (N – CH 3); δ 53.8,52.1,49.2,47.1,39.4,37.5,36.3,34.9,32.4,30.5,29.4,26.9,21.6,21.1,20.2,19.5,17.4,16.7,16.5,15.5.
In embodiment 2, the infrared spectrogram of product rosinyl carbamate (R-Ca) is shown in accompanying drawing 2, IR:3338cm -1(– OH); 2943,2866cm -1(CH 2, CH 3); 1716cm -1(C=O); 1530cm -1(N – H); 1461,1385cm -1(CH 3, CH 2); 1140cm -1(N – C); 1101,1038cm -1(C – O – C).
The a small amount of organic solvent dissolution of rosinyl carbamate prepared by aforesaid method, mixes by the ratio 1:1 of amount of substance with brominated alkanes, at 60～100 DEG C, reacts 5～24h.Concrete grammar is shown in embodiment 3～5.
Embodiment 3
Being equipped with in the four-hole boiling flask of thermometer, agitator, prolong, add 20.0g rosinyl carbamate, 40mL ethanol, be stirred to completely and dissolve, be warming up to 70 DEG C, drip 1.87g n-propyl bromide, back flow reaction 15h.Underpressure distillation is except desolventizing, and thick product, through ethanol/re-crystallizing in ethyl acetate, obtains dark brown solid product, i.e. n-propyl-Abietyl quaternary ammonium salt derivative.
Product n-propyl-Abietyl quaternary ammonium salt derivative in embodiment 3 1h NMR (500MHz, CDCl 3, δ ppm): δ 5.34 (– C=CH –); δ 3.45～4.30 (O – CH 2–, CH – OH, CH 2– OH, O – CH); δ 3.18～3.32 (NH – CH 2–); δ 3.05 (N +– CH 3); δ 2.87～2.91 (N +– CH 2); δ 2.79～2.85 (CH – C=O); δ 2.60～2.69 (N +– CH 2); δ 2.48～2.58 (CH – CH 3); δ 0.90～1.98 (CH 2, CH 3).
Product n-propyl-Abietyl quaternary ammonium salt derivative in embodiment 3 13c NMR (500MHz, CDCl 3, δ ppm): δ 178.2,173.6,172.7 (carbonyl carbon); 156.9 (NH – CO); δ 147.7,123.9 (– C=C –); δ 61.6～72.5 (O – CH 2–, CH – OH, CH 2– OH, N +– CH 2); δ 49.8 (N +– CH 3); δ 55.3,49.4,48.2,42.8,37.4,36.6,35.4,34.5,32.3,30.2,28.4,25.7,22.9,21.5,20.2,19.4,17.1,16.5,16.0,15.6,9.6.
The infrared spectrogram of product in embodiment 3 (QAS-a) n-propyl-Abietyl quaternary ammonium salt derivative is shown in accompanying drawing 3, IR:3324cm -1(– OH); 2944,2869cm -1(CH 2, CH 3); 1712cm -1(C=O); 1528cm -1(N – H); 1461,1386cm -1(CH 3, CH 2); 1177cm -1(N +– C); 1150cm -1(N – C); 1103,1042cm -1(C – O – C).
Embodiment 4
Being equipped with in the four-hole boiling flask of thermometer, agitator, prolong, add 40.0g rosinyl carbamate, 40mL ethanol, be stirred to completely and dissolve, be warming up to 70 DEG C, drip 5.02g bromo normal hexane, back flow reaction 12h.Underpressure distillation is except desolventizing, and thick product, through ethanol/re-crystallizing in ethyl acetate, obtains dark brown solid product, i.e. n-hexyl-Abietyl quaternary ammonium salt derivative.
Product n-hexyl-Abietyl quaternary ammonium salt derivative in embodiment 4 1h NMR (500MHz, CDCl 3, δ ppm): δ 5.37 (– C=CH –); δ 3.48～4.27 (O – CH 2–, CH – OH, CH 2– OH, O – CH); δ 3.17～3.35 (NH – CH 2–); δ 3.08 (N +– CH 3); δ 2.87～2.93 (N +– CH 2); δ 2.75～2.83 (CH – C=O); δ 2.54～2.65 (N +– CH 2); δ 2.36～2.43 (CH – CH 3); δ 0.91～1.99 (CH 2, CH 3).
Product n-hexyl-Abietyl quaternary ammonium salt derivative in embodiment 4 13c NMR (500MHz, CDCl 3, δ ppm): δ 178.2,173.4,173.2 (carbonyl carbon); 156.8 (NH – CO); δ 147.7,123.7 (– C=C –); δ 61.5～72.2 (O – CH 2–, CH – OH, CH 2– OH, N +– CH 2); δ 49.6 (N +– CH 3); δ 52.0,48.8,48.2,41.9,40.5,37.1,36.9,36.0,35.3,32.0,31.7,30.5,25.2,22.9,22.5,21.7,21.1,19.2,16.2,15.0,12.5.
The Infrared Characterization of product in embodiment 4 (QAS-b) n-hexyl-rosinyl quaternary ammonium-salt derivative is shown in accompanying drawing (4), IR:3338cm -1(– OH); 2930,2868cm -1(CH 2, CH 3); 1713cm -1(C=O); 1531cm -1(N – H); 1464,1386cm -1(CH 3, CH 2); 1177cm -1(N +– C); 1149cm -1(N – C); 1104,1039cm -1(C – O – C).
Embodiment 5
Being equipped with in the four-hole boiling flask of thermometer, agitator, prolong, add 30.0g rosinyl carbamate, 40mL ethanol, be stirred to completely and dissolve, be warming up to 75 DEG C, drip 5.69g N-dodeeyl bromide, back flow reaction 17h.Underpressure distillation is except desolventizing, and ethanol/re-crystallizing in ethyl acetate, obtains dark brown solid product, i.e. dodecyl-Abietyl quaternary ammonium salt derivative.
Product dodecyl-Abietyl quaternary ammonium salt derivative (QAS-c) in embodiment 5 1hNMR (500MHz, CDCl 3, δ ppm): δ 5.39 (– C=CH –); δ 3.58～4.33 (O – CH 2–, CH – OH, CH 2– OH, O – CH); δ 3.24～3.37 (NH – CH 2–); δ 3.13 (N +– CH 3); δ 2.85～2.94 (N +– CH 2); δ 2.73～2.83 (CH – C=O); δ 2.51～2.62 (N +– CH 2); δ 2.36～2.42 (CH – CH 3); δ 0.89～2.00 (CH 2, CH 3).
Product dodecyl-Abietyl quaternary ammonium salt derivative in embodiment 5 13c NMR (500MHz, CDCl 3, δ ppm): δ 178.2,173.4,172.8 (carbonyl carbon); 156.8 (NH – CO); δ 147.6,124.0 (– C=C –); δ 61.5～72.5 (O – CH 2–, CH – OH, CH 2– OH, N +– CH 2); δ 49.8 (N +– CH 3); δ 52.1,48.8,48.2,42.0,37.1,36.2,35.3,34.2,32.1,31.3,29.0,28.9,28.7,28.5,25.7,22.6,22.0,21.8,21.2,20.1,19.3,16.4,15.7,15.0,12.8.
In embodiment 5, the infrared spectrogram of product dodecyl-Abietyl quaternary ammonium salt derivative is shown in accompanying drawing 5, IR:3329cm -1(– OH); 2923,2853cm -1(CH 2, CH 3); 1715cm -1(C=O); 1530cm -1(N – H); 1465,1386cm -1(CH 3, CH 2); 1177cm -1(N +– C); 1150cm -1(N – C); 1103,1038cm -1(C – O – C).
Embodiment 6
The anti-microbial property test of rosinyl carbamate and quaternary ammonium salt antibiotic derivative thereof: the 1. preparation of bacteria suspension: four kinds of experiments such as staphylococcus aureus, intestinal bacteria, subtilis and bacillus thuringiensis are inoculated on beef-protein medium inclined-plane with bacterium, 37 DEG C of activation 24h, streptomyces microflavus is inoculated in Gao Shi I medium slant, 28 DEG C of activation 3d, then with transfering loop, the each bacterial classification of picking is in right amount in sterilized water respectively, and the bacterial classification concentration that makes bacteria suspension is 10 5～10 6cFU/mL.2. the preparation of filter paper and processing: prepare the filter paper dick of some amount diameter 5.0mm with punch tool, 121 DEG C of rearmounted oven for drying of sterilizing 20min are for subsequent use.Get the filter paper of sterilizing post-drying with aseptic nipper, be immersed in respectively 12h in the testing compound solution of various different concns, simultaneously taking coordinative solvent as blank.Use ultraviolet sterilization 30min.Before using, 30min drains.3. adopt filter paper method to carry out bacteriostatic activity test to compound: under aseptic technique, drawing bacteria suspension 0.1mL with aseptic straw drips on corresponding plate culture medium surface, after placing 30min after smearing evenly with spreading rod, the filter paper being immersed in different solutions is attached to every ware containing on bacterium flat board, 5 filter paper of every ware, be uniformly distributed, after staphylococcus aureus, intestinal bacteria, subtilis and 37 DEG C of constant temperature culture 24h of bacillus thuringiensis, 28 DEG C of constant temperature culture 3d of streptomyces microflavus, measure its antibacterial circle diameter with right-angled intersection method, relatively fungistatic effect.More than experiment repeats twice, data average (in table 1).
The antibacterial circle diameter (mm) of table 1 rosinyl carbamate and quaternary ammonium salt derivative thereof
Wherein, QAS-a is n-propyl-Abietyl quaternary ammonium salt; QAS-b is n-hexyl-Abietyl quaternary ammonium salt; QAS-c is dodecyl-Abietyl quaternary ammonium salt; R-Ca is rosinyl carbamate.
Rosinyl carbamate and quaternary ammonium salt derivative thereof that the present invention is prepared all have good anti-microbial activity to staphylococcus aureus, intestinal bacteria, subtilis, bacillus thuringiensis and streptomyces microflavus.

Claims (4)

1. a rosinyl cyclic carbonate ester, is characterized in that: the structural formula of rosinyl cyclic carbonate ester is:
2. the method for preparation rosinyl cyclic carbonate ester claimed in claim 1, is characterized in that: described rosinyl cyclic carbonate ester is with maleopimaric acid epoxy resin and CO 2reaction preparation under the effect of catalyzer, reaction formula is:
3. the method for preparing rosinyl cyclic carbonate ester as claimed in claim 2, is characterized in that: reaction, taking N-Methyl pyrrolidone or DMF as solvent, passes into CO in closed reactor 2to pressure be 0.5～5MPa, 80～150 DEG C reaction 2～24h.
4. the method for preparing rosinyl cyclic carbonate ester as claimed in claim 2, it is characterized in that: described catalyzer be taking metal halide as Primary Catalysts, adjacent glycols compound is the compound system of promotor, the mass ratio of metal halide and adjacent glycols compound is 1:0.1～1:2; Wherein, described metal halide is the one in lithiumbromide, lithium chloride, potassiumiodide, Potassium Bromide, zinc bromide, and consumption is 0.1～5% of maleopimaric acid epoxy resin quality; Described adjacent glycols compound is ethylene glycol, 1,2-PD, the one in 1,2-butyleneglycol.
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