CN104370773A - Rosinyl carbamate and preparation method thereof - Google Patents
Rosinyl carbamate and preparation method thereof Download PDFInfo
- Publication number
- CN104370773A CN104370773A CN201410546589.5A CN201410546589A CN104370773A CN 104370773 A CN104370773 A CN 104370773A CN 201410546589 A CN201410546589 A CN 201410546589A CN 104370773 A CN104370773 A CN 104370773A
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- rosinyl
- carbamate
- preparation
- cyclic carbonate
- reaction
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- 0 CC(C1(C2CC3C(C)(CCC4)C(CC5)C4(C)C(OCC(CO4)OC4=O)=O)C(OCC(C*4)OC4=O)=O)C2=CC35C1C(OCC(CO1)OC1=O)=O Chemical compound CC(C1(C2CC3C(C)(CCC4)C(CC5)C4(C)C(OCC(CO4)OC4=O)=O)C(OCC(C*4)OC4=O)=O)C2=CC35C1C(OCC(CO1)OC1=O)=O 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
The invention discloses a rosinyl carbamate and a preparation method thereof. The method utilizes rosinyl cyclic carbonate to be subjected to a reaction with an amine compound to prepare the rosinyl carbamate. The rosinyl carbamate prepared by the method is low in raw material cost, wide in source, and safe and non-toxic in preparation process; and because a molecular structure has a carbamate polar group having an antibacterial activity, the rosinyl carbamate has good water solubility, good biocompatibility and excellent antibacterial and bactericidal properties, and can be used in the fields of antibacterial agents, bactericidal agents and the like.
Description
The divisional application that the present invention is application number 201310222679.4, name is called the application of " preparation method of a kind of rosinyl cyclic carbonate ester and quaternary ammonium salt antibiotic derivative thereof ".
Technical field
The invention discloses a kind of rosinyl carbamate and preparation method thereof, particularly relate to and a kind ofly react with rosinyl cyclic carbonate ester and amino-complex the method preparing rosinyl carbamate.
Background technology
Rosin is a kind of important natural resource, and have biodegradable, renewable and wide material sources, lower-price characteristic, its main component is resinous acid, containing groups such as triatomic ring luxuriant and rich with fragrance skeleton, double bond and carboxylic acids in molecular structure.By to rosin chemical structure modification, dissimilar derivative can be prepared.Wherein, rosinyl carbamate, rosinyl cationic quaternary compound are subject to extensive concern because of the advantage such as low toxicity, nonirritant and good emulsifying power, inhibition power, antibacterial and fungicidal activity.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 can improve the water-soluble of compound and biological degradability effectively, makes that it is more green, environmental protection.
Summary of the invention
The object of the present invention is to provide a kind of rosinyl carbamate and preparation method thereof.
The present invention is by the following technical solutions: a kind of rosinyl carbamate, and its structural formula is:
Described rosinyl carbamate reacts preparation in organic solvent with rosinyl cyclic carbonate ester and amino-complex, and reaction formula is:
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, and the reaction times is 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) etc.
Beneficial effect of the present invention:
1. the present invention with renewable resources rosin for raw material prepares biomass-based cyclic carbonate ester, carbamate, raw materials cost is low, wide material sources, safe preparation process, nontoxic, and the rosinyl cyclic carbonate ester of preparation, carbamate have biodegradability, environmental friendliness.
2. the rosinyl carbamate prepared of the present invention, has antibacterial, the bactericidal property of well water-soluble, biocompatibility and excellence, can be used for the fields such as antibacterial, sterilant.
Accompanying drawing explanation
The infrared spectrogram of Fig. 1 rosinyl cyclic carbonate ester (R-C).
The infrared spectrogram of Fig. 2 rosinyl carbamate (R-Ca).
Embodiment
Maleopimaric acid epoxy resin of the present invention presses 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 is realized 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
2be 0.5 ~ 5MPa to pressure, prepare rosinyl cyclic carbonate ester at 80 ~ 150 DEG C of reaction 2 ~ 24h, reaction as shown in Equation 1.
Described catalyzer is the compound system of metal halide/vicinal diamines compounds, and the mass ratio of metal halide and vicinal diamines compounds 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; Vicinal diamines compounds 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 with the ratio 1:1 of amino-complex by amount of substance, and at 25 ~ 100 DEG C, react 2 ~ 8h prepare rosinyl carbamate, reaction as shown in Equation 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.
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, poured out while hot by product, with hot wash removing catalyzer and NMP, underpressure distillation removing moisture obtains rosinyl cyclic carbonate ester (R-C).The oxirane value of assay products, obtaining its epoxy group(ing) transformation efficiency is 98.6%.
Product rosinyl cyclic carbonate ester (R-C) in embodiment 1
1h NMR (500 MHz, CDCl
3, δ ppm): δ 5.37 (– C=CH –); δ 4.87 ~ 5.08 (methine hydrogens of cyclic carbonategroup); 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 (R-C) in embodiment 1
13c NMR (500 MHz, 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 – CH
2–); 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 spectra of product rosinyl cyclic carbonate ester (R-C) 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
With in four mouthfuls of round-bottomed flasks of 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, i.e. rosinyl carbamate (R-Ca).
Product rosinyl carbamate (R-Ca) in embodiment 2
1h NMR (500 MHz, 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 (R-Ca) in embodiment 2
13cNMR (500 MHz, 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 spectra 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).
Embodiment 3
The anti-microbial property test of rosinyl carbamate: 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 distinguish each bacterial classification of picking in right amount in sterilized water with transfering loop, make the bacterial classification concentration of bacteria suspension be 10
5~ 10
6cFU/mL.2. the preparation of filter paper and process: the filter paper dick preparing some amount diameter 5.0mm with punch tool, 121 DEG C of rearmounted oven for drying of sterilizing 20min are for subsequent use.Getting the filter paper of sterilizing post-drying with aseptic nipper, be immersed in 12h in the testing compound solution of various different concns respectively, is simultaneously blank with coordinative solvent.Use ultraviolet sterilization 30min.Front 30min is used to drain.3. filter paper enzyme is adopted to carry out bacteriostatic activity test to compound: under aseptic technique, draw bacteria suspension 0.1mL with aseptic straw to drip at corresponding slat chain conveyor primary surface, smear evenly with spreading rod and after placement 30min, the filter paper be immersed in different solutions is attached to every ware containing on bacterium flat board, every ware 5 filter paper, be uniformly distributed, after staphylococcus aureus, intestinal bacteria, subtilis and bacillus thuringiensis 37 DEG C of constant temperature culture 24h, streptomyces microflavus 28 DEG C of constant temperature culture 3d, measure its antibacterial circle diameter with right-angled intersection method, compare fungistatic effect.More than test repetition twice, data average (see table 1).
The antibacterial circle diameter (mm) of table 1 rosinyl carbamate
Wherein, R-Ca is rosinyl carbamate.
Rosinyl carbamate prepared by the present invention all has good anti-microbial activity to staphylococcus aureus, intestinal bacteria, subtilis, bacillus thuringiensis and streptomyces microflavus.
Claims (4)
1. a rosinyl carbamate, is characterized in that: the structural formula of rosinyl carbamate is:
n＝2～5。
2. prepare the method for rosinyl carbamate according to claim 1, it is characterized in that: described rosinyl carbamate reacts preparation in organic solvent with rosinyl cyclic carbonate ester and amino-complex, and reaction formula is:
n＝2～5。
3. prepare the method for rosinyl carbamate as claimed in claim 2, it is characterized in that: 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 organic solvent is any one in sherwood oil, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF).
4. prepare the method for rosinyl carbamate as claimed in claim 2, it is characterized in that: described amino-complex is any one in N, N-dimethylamino quadrol, dimethylaminopropylamine or 4-dimethylamino butylamine.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310222679.4A CN103304534B (en) | 2013-06-05 | 2013-06-05 | Preparation method of rosinyl cyclic carbonate and quaternary ammonium salt antibacterial derivative thereof |
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|---|---|---|---|
| CN201310222679.4A Division CN103304534B (en) | 2013-06-05 | 2013-06-05 | Preparation method of rosinyl cyclic carbonate and quaternary ammonium salt antibacterial derivative thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104370773A true CN104370773A (en) | 2015-02-25 |
| CN104370773B CN104370773B (en) | 2016-01-20 |
Family
ID=49130293
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310222679.4A Expired - Fee Related CN103304534B (en) | 2013-06-05 | 2013-06-05 | Preparation method of rosinyl cyclic carbonate and quaternary ammonium salt antibacterial derivative thereof |
| CN201410547344.4A Expired - Fee Related CN104370774B (en) | 2013-06-05 | 2013-06-05 | A kind of rosinyl carbamate quaternary ammonium salt derivative and preparation method thereof |
| CN201410546589.5A Expired - Fee Related CN104370773B (en) | 2013-06-05 | 2013-06-05 | A kind of rosinyl carbamate and preparation method thereof |
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| CN201310222679.4A Expired - Fee Related CN103304534B (en) | 2013-06-05 | 2013-06-05 | Preparation method of rosinyl cyclic carbonate and quaternary ammonium salt antibacterial derivative thereof |
| CN201410547344.4A Expired - Fee Related CN104370774B (en) | 2013-06-05 | 2013-06-05 | A kind of rosinyl carbamate quaternary ammonium salt derivative and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105504272A (en) * | 2016-01-22 | 2016-04-20 | 中国林业科学研究院林产化学工业研究所 | POSS modified rosin nonisocyanate polyurethane and preparation method of nonisocyanate polyurethane |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104645874B (en) * | 2015-02-05 | 2017-03-15 | 中国林业科学研究院林产化学工业研究所 | A kind of abietyl choline quaternary surfactant and preparation method thereof |
| CN105061388B (en) * | 2015-08-04 | 2017-06-23 | 中国林业科学研究院林产化学工业研究所 | A kind of gallic acid basic ring carbonic ester, non-isocyanate polyurethane and preparation method thereof |
| CN115260046B (en) * | 2022-08-22 | 2023-06-27 | 贵州大学 | Rosin acid ester compound and preparation method and application thereof |
| CN115417970B (en) * | 2022-09-21 | 2024-05-24 | 中国林业科学研究院林产化学工业研究所 | Transparent rosin-based self-repairing polyurethane elastomer and synthetic method and application thereof |
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| EP0599265A1 (en) * | 1992-11-24 | 1994-06-01 | Takeda Chemical Industries, Ltd. | Antibacterial, antifungal compound and its production method |
| US20040236119A1 (en) * | 2003-04-24 | 2004-11-25 | Jurgen Van Holen | Process using a cyclic carbonate reactant and beta-hydroxyurethanes thereby obtained |
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| CN101249400B (en) * | 2008-04-09 | 2011-07-20 | 广西大学 | Maleated rosin based quaternaries cation surface active agent and method of preparing the same |
| CN101914029B (en) * | 2010-06-03 | 2013-07-03 | 东北林业大学 | Preparation method of rosin-based Gemini surface active agent |
| CN102206324B (en) * | 2011-03-29 | 2012-12-12 | 中国科学院宁波材料技术与工程研究所 | Full-biobased epoxy resin composition and condensate |
-
2013
- 2013-06-05 CN CN201310222679.4A patent/CN103304534B/en not_active Expired - Fee Related
- 2013-06-05 CN CN201410547344.4A patent/CN104370774B/en not_active Expired - Fee Related
- 2013-06-05 CN CN201410546589.5A patent/CN104370773B/en not_active Expired - Fee Related
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| EP0599265A1 (en) * | 1992-11-24 | 1994-06-01 | Takeda Chemical Industries, Ltd. | Antibacterial, antifungal compound and its production method |
| US20040236119A1 (en) * | 2003-04-24 | 2004-11-25 | Jurgen Van Holen | Process using a cyclic carbonate reactant and beta-hydroxyurethanes thereby obtained |
| CN1796435A (en) * | 2004-12-22 | 2006-07-05 | 中国科学院化学研究所 | Modified butanediol ester poly succinic acid and synthetic method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105504272A (en) * | 2016-01-22 | 2016-04-20 | 中国林业科学研究院林产化学工业研究所 | POSS modified rosin nonisocyanate polyurethane and preparation method of nonisocyanate polyurethane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103304534B (en) | 2014-12-10 |
| CN104370774B (en) | 2016-01-20 |
| CN104370773B (en) | 2016-01-20 |
| CN103304534A (en) | 2013-09-18 |
| CN104370774A (en) | 2015-02-25 |
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