CN107311882B - A kind of Dehydroabietic acid dipeptides surfactant and its performance - Google Patents
A kind of Dehydroabietic acid dipeptides surfactant and its performance Download PDFInfo
- Publication number
- CN107311882B CN107311882B CN201710455818.6A CN201710455818A CN107311882B CN 107311882 B CN107311882 B CN 107311882B CN 201710455818 A CN201710455818 A CN 201710455818A CN 107311882 B CN107311882 B CN 107311882B
- Authority
- CN
- China
- Prior art keywords
- surfactant
- phe
- dehydroabietic acid
- synthesis
- acid dipeptides
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Peptides Or Proteins (AREA)
Abstract
The present invention relates to the synthesis and its performance of a kind of Dehydroabietic acid dipeptides surfactant R -6-Phe.Wherein the molecular structure of R-6-Phe is as follows:The present invention gives the molecular structures and synthetic method of this novel Dehydroabietic acid dipeptides surfactant.The surfactant has good ability of aggregation, and the critical micelle concentration at 25 DEG C is 1.01mmolL‑1, while also showing that good emulsifiability.The main synthesis material dehydroabietic acid and amino acid of the surfactant are natural products, have many advantages, such as that renewable, biodegradable, abundance, structure are easy to modify, the environmental protection concept for meeting Green Chemistry can be used for the multiple fields such as detergent, daily chemical products, emulsifier.
Description
Technical field
The present invention relates to a kind of using dehydroabietic acid as the dipeptides surfactant of Material synthesis, and it is living to belong to natural products surface
The synthesis and application field of property agent.
Background technique
As the theory of environmental protection and sustainable development is more and more rooted in the hearts of the people, mild safety is researched and developed, it is degradable
Green surfactant becomes one of the important topic of academia's concern.And seek natural products as the green surface-active of synthesis
The raw material of agent is the direction of Development of Industrial Surfactant.Rosin is a kind of renewable forest resources abundant, be resin acid and
The solid mixture of a small amount of fatty acid and neutral substance composition, is the important raw material sources of green surfactant.Resin acid
Tricyclic diterpene structure has very strong hydrophobicity, and hydrophilic group, feasibility study are introduced in rosin using the method for chemical modification
With their own characteristics with rosin structure, and novel surfactant degradable, that pollution is small, performance is good is produced, original is met
The characteristics of expecting " greenization ".However due to containing double bond in rosin, so that rosin resin acid molecule is easily oxidized, to obtain
The surfactant of rock-steady structure, it usually needs rosin is carried out structurally-modified.The disproportionated rosin that rosin is generated through disproportionated reaction
In containing 50% or so dehydroabietic acid, chemical property is relatively stable, is very common raw material in synthesis of surfactant.
Amino acid is also a kind of natural products, is found that before about 40 years using amino acid as Material synthesis surfactant
Value.20 kinds of standard amino acids and its derivative are used equally for synthetic surfactant.Amino acid type surfactant safety
Property it is high, irritation is small, and has excellent blistering, emulsification, antibacterial and bactericidal property, and biological degradability is good, also has good
Biocompatibility.
The present invention selects amino acid molecular appropriate to react with it using dehydroabietic acid as raw material, obtains a kind of with novel
The surfactant of the easily biological-degradable of structure meets the environmental protection concept of Green Chemistry.For further expanding natural products pine
Fragrant application range, the added value for improving rosin also have active influence.
Summary of the invention
The purpose of the present invention is to have many advantages, such as the master in renewable, biodegradable, abundance disproportionated rosin
Wanting ingredient dehydroabietic acid is raw material, passes through serial reaction with amino acid, synthesizes a kind of Dehydroabietic acid dipeptides surfactant, and
Its basic performance is provided.
To achieve the above object, the present invention adopts the following technical scheme:
Using the main component dehydroabietic acid in disproportionated rosin as raw material, a kind of Dehydroabietic acid dipeptides surfactant is synthesized
R-6-Phe, structural formula are as follows:
The synthetic route of the surfactant is as follows:
Its specific synthesis step is as follows:
The synthesis of compound 1: at 35 DEG C, sequentially added in methylene chloride 6-aminocaprolc acid methyl ester hydrochloride, triethylamine,
4-dimethylaminopyridine (DMAP), dehydroabietic acid and 2- (7- aoxidizes benzotriazole)-N, N, N', N'- tetramethylurea hexafluoro phosphorus
Acid esters (HATU) reacts 5h.After reaction, it is extracted with dichloromethane, anhydrous Na2SO4It is dry.After suction filtration, rotary evaporation is removed
Methylene chloride.With column chromatography purified product.
The synthesis of R-6: being first dissolved in ethyl alcohol for NaOH, rear that compound 1 is added, and is warming up to 70 DEG C, reacts 1.5h.End of reaction
Afterwards, it is cooled to room temperature, has solid precipitation, obtains R-6.
The synthesis of compound 2: dilute HCl being added in the aqueous solution of R-6, is made solution in acidity, is extracted with ethyl acetate, nothing
Water MgSO4Dry, after suction filtration, revolving removes ethyl acetate, obtains compound 2.
The synthesis of compound 3: at 35 DEG C, sequentially added in methylene chloride L-phenylalanine methyl ester hydrochloride, triethylamine,
4-dimethylaminopyridine (DMAP), compound 2 and HATU react 3h.After reaction, it is extracted with dichloromethane, anhydrous Na2SO4
It is dry.After suction filtration, rotary evaporation removes methylene chloride.With column chromatography purified product.
The synthesis of R-6-Phe: being first dissolved in ethyl alcohol for NaOH, rear that compound 3 is added, and is warming up to 70 DEG C, reacts 1h.Reaction knot
Shu Hou has solid precipitation after ethyl acetate is added, filters to obtain target product R-6-Phe.
The surface-active of surfactant: preparing the aqueous solution (pH=12) of the surfactant R -6-Phe of various concentration,
Its surface-active is measured with hanging ring method.
The emulsifiability of surfactant: preparing the aqueous surfactant solution of various concentration, and is added in equal volume just
Decane is as oily phase, emulsifying 2min, is observed after emulsion is placed 1 day at 25 DEG C and the macrostate after 7 days, and with surpassing
Depth of field three-dimensional microscopic system VHX-1000 observes the granular size of emulsion, is analyzed by Nano Measurer software
Emulsion particle diameter distribution.
Beneficial effect
Using the important derivatives dehydroabietic acid of rosin as raw material, Dehydroabietic acid dipeptides table is obtained by serial synthesis step
Face activating agent R-6-Phe.The surfactant has good ability of aggregation, its critical micelle concentration is at 25 DEG C
1.01mmol·L-1；Surfactant R -6-Phe is higher than 1mmolL in concentration-1System in can make emulsion stabilization 7 days with
On, show that the surfactant has good emulsifiability to n-decane.
Detailed description of the invention
Fig. 1 surfactant R -6-Phe's1H NMR。
Fig. 2 surfactant R -6-Phe surface tension γ with concentration C change curve (25 DEG C).
Fig. 3 surfactant R -6-Phe stable n-decane/aqueous emulsion is placed 1 day (a) at 25 DEG C and is placed 7 days
(b) (surfactant concentration is from left to right respectively 0.1,1,4,6mmolL to appearance photo-1)。
Fig. 4 surfactant R -6-Phe is in 6mmolL-1Microphoto of the emulsion standing of Shi Wending after 7 days.
Fig. 5 surfactant R -6-Phe is in 6mmolL-1The grain size distribution of the emulsion of Shi Wending.
Specific embodiment
Embodiment 1: 6-aminocaprolc acid methyl ester hydrochloride (32.7g, 0.18mol) synthesis of compound 1: is dissolved in dichloromethane
In alkane, triethylamine (72.8g, 0.72mol), 4-dimethylaminopyridine (DMAP) (0.8g, 0.006mol) and dehydrogenation are sequentially added
2- (7- aoxidizes benzotriazole)-N, N, N', N'- tetramethylurea hexafluorophosphoric acid ester is then added in abietic acid (48g, 0.16mol)
(HATU) (76.0g, 0.20mol), temperature rise to 35 DEG C, react 5h.After reaction, it is extracted with dichloromethane, organic layer is used
After deionization is washed 5-6 times, anhydrous Na is used2SO4It is dry.After suction filtration, rotary evaporation removes methylene chloride.Purified with column chromatography
Product (eluant, eluent is petroleum ether: ethyl acetate=2:1), obtains colorless viscous shape liquid.
The synthesis of embodiment 2:R-6: the second of NaOH (5.2g, 0.13mol) and 200mL are added into the single port bottle of 500mL
Alcohol, stirring are completely dissolved to NaOH, add compound 1 (47.0g, 0.11mol), are warming up to 70 DEG C, react 1.5h.It has reacted
Bi Hou is cooled to room temperature, there is solid precipitation, filters to obtain R-6.
Embodiment 3: the synthesis of compound 2: R-6 (38.3g, 0.088mol) is soluble in water, and dilute HCl, which is added, makes the solution be in
Acidity is extracted with ethyl acetate, and 5-6 rear anhydrous MgSO is washed with deionized water in organic layer4It is dry, after suction filtration, rotary evaporation
Ethyl acetate is removed, compound 2 is obtained.
Embodiment 4: L-phenylalanine methyl ester hydrochloride (5.6g, 0.028mol) synthesis of compound 3: is dissolved in dichloromethane
In alkane, sequentially adds triethylamine (11.0g, 0.108mol), 4-dimethylaminopyridine (DMAP) (0.2g, 0.0016mol) and change
It closes object 2 (9g, 0.0216mol), 2- (7- aoxidizes benzotriazole)-N, N, N', N'- tetramethylurea hexafluorophosphoric acid ester is then added
(HATU) (11.4g, 0.03mol) reacts 3h at 35 DEG C.After reaction, it is extracted with dichloromethane, organic layer deionized water
After washing 5-6 times, anhydrous Na is used2SO4It is dry.After suction filtration, rotary evaporation removes methylene chloride, with (the elution of column chromatography purified product
Agent is ethyl acetate: petroleum ether=2:1), obtain colorless viscous shape liquid.
The synthesis of embodiment 5:R-6-Phe: NaOH (0.9g, 0.019mol) and 80mL are added into the single port bottle of 250mL
Ethyl alcohol, stirring is completely dissolved to NaOH, adds compound 3 (8.8g, 0.0176mol), be warming up to 70 DEG C, reacts 1h.Instead
After answering, there is solid precipitation after ethyl acetate is added, filter, obtains target product R-6-Phe after vacuum dried, it is solid for white
Body.
Embodiment 6: the R-6-Phe for weighing certain mass is dissolved in the water, and (experimental water is resistivity 18.2M Ω cm's
The pH=12 that NaOH adjusts solution is added in ultrapure water), compound concentration 25mmolL-1Mother liquor, then quantitative mother liquor is taken to dilute
A series of equivalent aqueous surfactant solution for being configured to various concentrations is placed in weighing disk, is used after constant temperature balance 1h at 25 DEG C
Du No ü y hanging ring method measures the equilibrium surface tension of the surfactant.
Embodiment 7: a series of surfactant that various concentration volumes are 7mL is prepared respectively in the column bottle of 25mL
Aqueous solution adds isometric n-decane as oily phase, and it is 11000rpm that condition, which is arranged, in homogenizer, emulsifies 2min, observation cream
Macrostate after shape liquid is placed 1 day and after 7 days, judges emulsion intercalation method.
Claims (4)
1. a kind of Dehydroabietic acid dipeptides surfactant R -6-Phe, molecular structure are as follows:
2. a kind of Dehydroabietic acid dipeptides surfactant R -6-Phe according to claim 1, which is characterized in that be by
It reacts to obtain according to following formula:
3. a kind of Dehydroabietic acid dipeptides surfactant R -6-Phe according to claim 1, which is characterized in that 25 DEG C
Under, the critical micelle concentration of surfactant R -6-Phe is 1.01mmolL-1。
4. a kind of Dehydroabietic acid dipeptides surfactant R -6-Phe according to claim 1, which is characterized in that dense
Degree is higher than 1mmolL-1System in n-decane/aqueous emulsion can be made to stablize 7 days or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710455818.6A CN107311882B (en) | 2017-06-16 | 2017-06-16 | A kind of Dehydroabietic acid dipeptides surfactant and its performance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710455818.6A CN107311882B (en) | 2017-06-16 | 2017-06-16 | A kind of Dehydroabietic acid dipeptides surfactant and its performance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107311882A CN107311882A (en) | 2017-11-03 |
| CN107311882B true CN107311882B (en) | 2019-04-09 |
Family
ID=60181888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710455818.6A Active CN107311882B (en) | 2017-06-16 | 2017-06-16 | A kind of Dehydroabietic acid dipeptides surfactant and its performance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107311882B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108821991A (en) * | 2018-06-27 | 2018-11-16 | 江南大学 | A kind of Dehydroabietic acid serine surfactant and its viscoelastic solution |
| CN108889151B (en) * | 2018-07-06 | 2020-11-03 | 宁德师范学院 | Stable emulsion and preparation method thereof |
| WO2020140326A1 (en) | 2019-01-04 | 2020-07-09 | 江南大学 | Rosin-based small molecule hydrogel agent and application thereof |
| CN113185448B (en) * | 2021-04-27 | 2023-05-26 | 华侨大学 | Rosin-based amphoteric ion surfactant, and preparation method and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475498B (en) * | 2009-01-13 | 2011-07-20 | 中国林业科学研究院林产化学工业研究所 | Preparation method of 3-dehydroabietylamine-2-hydroxypropyl trimethyl ammonium chloride |
| CN101972614A (en) * | 2010-10-11 | 2011-02-16 | 东北石油大学 | Dehydroabietylamide ethyl sulfonate surfactant, synthesis method and application of surfactant in tertiary oil recovery |
| WO2016051013A1 (en) * | 2014-10-02 | 2016-04-07 | University Of Helsinki | Abietane-type diterpenoids |
| 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 |
| CN105413577B (en) * | 2015-11-16 | 2017-06-30 | 江南大学 | The viscoelastic solution that a kind of abietyl amino acid surfactant is constructed |
| CN106140006A (en) * | 2016-06-28 | 2016-11-23 | 江南大学 | A kind of Dehydroabietic acid anion surfactant and the stable foam of formation thereof |
-
2017
- 2017-06-16 CN CN201710455818.6A patent/CN107311882B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107311882A (en) | 2017-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107311882B (en) | A kind of Dehydroabietic acid dipeptides surfactant and its performance | |
| NL2004835C2 (en) | Process for extracting materials from biological material. | |
| CN104645874B (en) | A kind of abietyl choline quaternary surfactant and preparation method thereof | |
| WO2013188508A1 (en) | Green glycine betaine derivative compounds and compositions containing same | |
| CN107308883B (en) | A kind of stable foam formed by abietyl amino acid surfactant | |
| Pernak et al. | Ammonium ionic liquids with anions of natural origin | |
| CN102781232A (en) | Pest controlling composition | |
| CN103965373A (en) | (2-hydroxy-3-dehydroabieticoxy) propyl chitosan-oligosaccharide and preparation method thereof | |
| CN108837773A (en) | A kind of viscoelastic solution formed by abietyl dipeptides surfactant | |
| CN105707071A (en) | Wetting agent for pesticide preparations, method for preparing wetting agent and application of wetting agent to pesticide preparations | |
| Hashizaki et al. | Possibility of vitamin C to induce the formation of lecithin organogel | |
| Manko et al. | Sugar-based surfactants as alternative to synthetic ones | |
| CN109400871B (en) | Quaternary ammonium salt of monodisperse octadecyl three-arm polyglycol ether and preparation method thereof | |
| ITMI991086A1 (en) | SURFACE MIXTURES SUITABLE FOR USE AS BATHERS AND EMULSIFIED IN AGROCHEMICAL COMPOSITIONS | |
| KR102129965B1 (en) | Manufacturing method of fatty acid ester | |
| CN106866533B (en) | Pyraclostrobin crystal form and preparation method thereof | |
| CN109486213A (en) | A kind of antibacterial film and preparation method thereof | |
| CN105432606B (en) | Composition containing benziothiazolinone and preparing method thereof | |
| CN108821991A (en) | A kind of Dehydroabietic acid serine surfactant and its viscoelastic solution | |
| CN106922655A (en) | A kind of bactericidal composition containing stabilizer | |
| CN106632162B (en) | The synthetic method of 4 methyl 4 (cis 3 hexenyl) 4 butyrolactone | |
| CN111233948A (en) | Rhamnolipid calcium, preparation method and application | |
| CN102351562B (en) | Preparation method of stearamide concrete foaming agent compounded component and application thereof | |
| KR102166783B1 (en) | Novel trehalose-cored amphiphiles and uses thereof | |
| RU2011150078A (en) | LATERATED DRUG AND METHOD FOR ITS PRODUCTION |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |