CN106316884A - Mosquito repellent natural active compounds and preparing method and application thereof - Google Patents
Mosquito repellent natural active compounds and preparing method and application thereof Download PDFInfo
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- CN106316884A CN106316884A CN201610710486.7A CN201610710486A CN106316884A CN 106316884 A CN106316884 A CN 106316884A CN 201610710486 A CN201610710486 A CN 201610710486A CN 106316884 A CN106316884 A CN 106316884A
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- anophelifuge
- herba ocimi
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/34—Nitriles
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
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- General Health & Medical Sciences (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to a mosquito repellent natural active compound and a preparing method and application thereof, wherein the mosquito repellent natural active compound is named mosquito repellent nitrile, and has the chemical structure formula as follows: (img file='DDA0001087545070000011.TIF' wi='911' he='262' /), in which n stands for positive integer of no more than 20, R stands for alkyl substituents of no more than six carbon. After the activity detection for mosquito repellent nitriles in the invention, the results show that the compound has good mosquito repellent activity, and can provide new compounds or lead compounds which have medicinal value for pharmaceutical industry; the preparing method is simple with a short cycle, which can realize large-scale industrialized production, and achieve the high yield and high purity of products.
Description
Technical field
The invention belongs to pharmaceutical technology field, be specifically related to one extracting and developing purification from plant and there is anophelifuge activity
Compound, particularly relate to a kind of extracting and developing purification one tool from thin Herba Ocimi (Herba Ocimi Pilosi) (Ocimum basilicum L.) herb
There are the aliphatic nitrile compound of anophelifuge activity and extracting method thereof and application.
Background technology
Herba Ocimi (Herba Ocimi Pilosi) leaf is pointed in ellipse, and flower be purple white, distills its leaf and flower can obtain the quintessence oil of clear, colorless, perfume
Taste is like Flos Caryophylli, the synthesis of Folium Pini.It it is a huge family.Herba Ocimi (Herba Ocimi Pilosi) the most of the same race is named because of characteristic or peculiar fragrance.
A lot of researchs of Herba Ocimi (Herba Ocimi Pilosi) focus on extraction and the component analysis aspect of spice.It is mainly used in Italian type, the cooking of French Greece, in east
The India of side and the Thailand's cooking are the most commonly used.Herba Ocimi (Herba Ocimi Pilosi) is cultivated generally as vegetable at China, and it is novel as one
Special vegetable there is the biggest development space.Herba Ocimi (Herba Ocimi Pilosi) contain volatile oil 0.02～0.04%, oil proportion (15 DEG C) 0.900～
0.930, diopter (20 DEG C) 1.4800～1.4950, optical rotation (20 DEG C)-6 °～20 °, it is mainly composed of ocimene, australene
Alkene, 1, 8-Cineole, linalool, geraniol, limonene, 3-carene, estragole, eugenol, methyleugenol,
Methoxybenzene, methyl cinnamate, blatter alcohol, 3-octanone and furfural etc., pure Basil Essential sterilizing rate very 99.
Being mainly used as perfumery raw material, preparing cosmetics, soap are used and edible essence, are also used in toothpaste processed, collutory making correctives.Herb
It is used as medicine, has treatment headache, migraine, otalgia, sinusitis, bronchitis, expectorant, Common Cold, asthma, have the hiccups, flatulence, stomach
Bitterly, stomach spasm, flatulence, dyspepsia, enteritis, diarrhea, uric acid are too much, muscular soreness, staitinodermia, and chest pain, traumatic injury damage
Wound, congestive edema, rheumatic arthritis, fever of children, nephritis, venom, decoct washing eczema and dermatitis pimples, acne, and sheep is insane crazy,
Menstruation has some setbacks, and galactopoiesis is few, engorgement of breasts inflammation, encourages emotion, eases off the pressure, and alleviates melancholy uneasy, promotes the sexual maturity, mends body, anti-
Bacterium, insect bite is hindered.Relieve summer heat, detoxify, stomach invigorating of unstinging, benefit power add the effect such as essence, concerted effort blood vessels.Stem and leaf is obstetrics' medication, can make point
Before childbirth, blood is good；Seed name FRUCTUS OCIMI, cures mainly corneal nebula, and tries out in contraception.
Summary of the invention
Solve the technical problem that: it is an object of the present invention to provide from thin Herba Ocimi (Herba Ocimi Pilosi) herb, extract isolated
A kind of new aliphatic nitrile compound anophelifuge nitrile.
It is a further object to provide the preparation method of above-mentioned aliphatic nitrile compound anophelifuge nitrile.
It is also another object of the present invention to provide above-mentioned aliphatic nitrile compound anophelifuge nitrile preparing anophelifuge medicament and relevant driving
Application in mosquito product.
Technical scheme: a kind of anophelifuge natural active compound, named anophelifuge nitrile, chemical structural formula is:
Wherein n is the positive integer less than 20, and R is the alkyl substituent less than 6 carbon.
The above-mentioned preferred chemical structural formula of anophelifuge natural active compound is:
Molecular formula is C19H33NO2, molecular weight 307.3, chemical entitled 16-itrile group-14-alkene-ethyl palmitate.
The preparation method of above-mentioned anophelifuge natural active compound, concrete preparation process is as follows: (1) extracts: with thin Herba Ocimi (Herba Ocimi Pilosi)
Herb is raw material, after crushed, adds the methanol of 10-20 times of raw materials quality, ethanol or alcohol water mixed solution and carries out refluxing or surpassing
Sound assisted extraction, extracts 2-5 time altogether, each 30-60min, united extraction liquid, is evaporated to do, and obtains dredging Herba Ocimi (Herba Ocimi Pilosi) herb
Extract；(2) suspendible liquid-liquid extraction: thin Herba Ocimi (Herba Ocimi Pilosi) herb extract is scattered in 30-50 DEG C of warm water of its quality 10-20 times
In, carry out liquid-liquid extraction 3-4 time, united extraction liquid with petroleum ether isopyknic with water, ether or hexamethylene respectively, be concentrated into nothing
Solvent, obtains dredging Herba Ocimi (Herba Ocimi Pilosi) extract；(3) column chromatography for separation: by thin Herba Ocimi (Herba Ocimi Pilosi) extract acetic acid ethyl dissolution, adds and second
The column chromatography silica gel that mesh number is 300-400 mesh of the quality such as acetoacetic ester is mixed thoroughly, 50 DEG C of evaporated under reduced pressure, weighs thin Herba Ocimi (Herba Ocimi Pilosi) extraction in advance
Take the column chromatography silica gel of the 300-400 mesh of 8-25 times of quality of thing, use petroleum ether wet method dress post, the silica gel mixed is loaded chromatography
In post, the petroleum ether-ethyl acetate mixed liquor gradient elution with volume ratio as 10:1-1:1, thin layer chromatography inspection, merging obtains
The fraction of compound anophelifuge nitrile, is concentrated into solvent-free, obtains anophelifuge nitrile crude product；(4) purification: by anophelifuge nitrile crude product ethyl acetate
Dissolve, add the column chromatography silica gel that mesh number is 200-300 mesh with the quality such as ethyl acetate and mix thoroughly, 50 DEG C of evaporated under reduced pressure, in advance
Weigh the chromatographic silica gel of the 200-300 mesh post of anophelifuge nitrile 8-10 times of quality of crude product, use petroleum ether wet method dress post, the silicon that will mix
Mucilage binding enters in chromatographic column, the petroleum ether with volume ratio as 10:1-1:1-chloroform mixed liquor gradient elution, thin layer chromatography inspection, closes
And the fraction of compound anophelifuge nitrile, it is concentrated into solvent-free, obtains anophelifuge nitrile sterling.
Above-claimed cpd application in the commercial mosquito repellent product of preparation.
A kind of anophelifuge medicament, effective ingredient is above-mentioned compound.
Beneficial effect: the 1. anophelifuge nitrile in the present invention carries out anophelifuge activity detection, result shows that this compound has well
Anophelifuge activity, can be the medical industry noval chemical compound or the lead compound that are provided with medical value.2. the method is simple,
Cycle is short, can realize large-scale industrialization and produce.3. product yield is high, purity is high.
Accompanying drawing explanation
Fig. 1 anophelifuge nitrile1H-NMR schemes；
Fig. 2 anophelifuge nitrile13C-MNR schemes；
Fig. 3 anophelifuge nitrile13C-MNR (locally) figure；
The ROESY figure of Fig. 4 anophelifuge nitrile；
The HSQC figure of Fig. 5 anophelifuge nitrile；
The HMBC figure of Fig. 6 anophelifuge nitrile；
The DEPT figure of Fig. 7 anophelifuge nitrile；
DEPT (locally) figure of Fig. 8 anophelifuge nitrile；
The COSY figure of Fig. 9 anophelifuge nitrile.
Detailed description of the invention
The following examples can make those skilled in the art that the present invention is more fully understood, but limits this never in any form
Invention.In the case of without departing substantially from spirit and essence, the amendment that the inventive method, step or condition are made and replacement,
Belong to the scope of the present invention.If not specializing, technological means used in embodiment is well known to those skilled in the art
Conventional means.
Embodiment 1
The extraction of aliphatic nitrile compound anophelifuge nitrile and separation
Weigh thin Herba Ocimi (Herba Ocimi Pilosi) herb 4.0kg, after pulverizing, add 50 liters of 80wt.% ethanol waters and carry out circumfluence distillation,
Extract 2 times altogether, each 50min.United extraction liquid, concentrating under reduced pressure, obtain ethanol extraction 150g.Ethanol extraction is scattered in 3
Rise in 40 DEG C of warm water, with hexamethylene negative pressure-cavitation homogenous solid-liquid phase liquid-liquid extraction 4 times, each 3 liters.Aqueous phase after extraction uses ethyl acetate again
Negative pressure-cavitation homogenous solid-liquid phase liquid-liquid extraction 3 times, each 3 liters.Merge hexamethylene extract, be concentrated under reduced pressure to give hexamethylene extract 4g.
By hexamethylene extract 4g acetic acid ethyl dissolution, add that the chromatographic silica gel that 4g mesh number is 300～400 is mixed thoroughly, 50 DEG C of decompressions are steamed
Dry, weigh 100g 300～400 mesh chromatographic silica gel in advance, use petroleum ether wet method dress post, the silica gel having mixed sample is loaded layer
In analysis post, the petroleum ether-ethyl acetate mixed solvent with volume ratio as 10:1-1:1 carries out gradient elution, and thin layer chromatography detects,
Merge the fraction containing compound anophelifuge nitrile, be concentrated to dryness, obtain anophelifuge nitrile crude product.
By anophelifuge nitrile crude product acetic acid ethyl dissolution, the post layer that mesh number is 200～300 of the quality such as addition and ethyl acetate
Analysis silica gel is mixed thoroughly, and 50 DEG C of evaporated under reduced pressure weigh 200～300 mesh column chromatography silica gels of anophelifuge nitrile 8-10 times of quality of crude product in advance, adopt
Fill post by petroleum ether wet method, the silica gel mixed is loaded in chromatographic column, the petroleum ether with volume ratio as 10:1-1:1-chloroform mixing
Liquid gradient elution, thin layer chromatography inspection, merge the fraction of compound anophelifuge nitrile, be concentrated into solvent-free, obtain anophelifuge nitrile sterling
156.6mg。
Aliphatic nitrile compound anophelifuge nitrile Structural Identification
Embodiment 1 compound anophelifuge nitrile is pale yellow oily liquid body, is soluble in organic examinations such as hexamethylene, petroleum ether, chloroform
Agent；Warp1H NMR and13C MNR data are shown in Table 1, compose in conjunction with DEPT, H H Correlated Spectroscopy (H H COSY), ROESY, HSQC, H C phase
Close spectrum (HMQC) and the long-range Correlated Spectroscopy of H C (HMBC), it is determined that the chemical constitution of this compound.Chemical structural formula is as follows:
Table 1 compound anophelifuge nitrile1H NMR and13C NMR data
Anophelifuge is tested
Test is divided into 4 groups, often organizes 10 people, and men and women half and half, one full year of life at age 18-22, test specimen is distributed to experimenter, is subject to
Examination person all wears robe trousers, and the left lower limb bottom of s trouser leg has been drawn, and takes respectively containing anophelifuge nitrile 1.0wt.% ethanol solution, is uniformly applied to left lower limb knee joint and closes
Saving following ankle joint with upper bit, keep coating position the most exposed, in outdoor grove, stand in the intensive place of mosquito, sees at any time
Examining mosquito bite situation, the time bitten in record, and result of implementation nitrile 1.0wt.% ethanol solution effective protecting time Han anophelifuge is
40min, with containing dimethyl phthalate 1.0wt.% ethanol solution for comparison, dimethyl phthalate mosquito repellent time 35min.
Claims (5)
1. an anophelifuge natural active compound, named anophelifuge nitrile, it is characterised in that chemical structural formula is:
Wherein n is the positive integer less than 20, and R is the alkyl substituent less than 6 carbon.
Anophelifuge natural active compound the most according to claim 1, it is characterised in that chemical structural formula is:
The preparation method of anophelifuge natural active compound the most according to claim 1, it is characterised in that concrete preparation process is such as
Under:
(1) extract: with thin Herba Ocimi (Herba Ocimi Pilosi) herb as raw material, after crushed, add the methanol of 10-20 times of raw materials quality, ethanol or alcohol
Water mixed solution carries out refluxing or ultrasound assisted extraction, extracts 2-5 time altogether, each 30-60min, united extraction liquid, concentrating under reduced pressure
To dry, obtain dredging Herba Ocimi (Herba Ocimi Pilosi) herb extract；
(2) suspendible liquid-liquid extraction: thin Herba Ocimi (Herba Ocimi Pilosi) herb extract is scattered in 30-50 DEG C of warm water of its quality 10-20 times, point
Do not carry out liquid-liquid extraction 3-4 time, united extraction liquid with petroleum ether isopyknic with water, ether or hexamethylene, be concentrated into solvent-free,
Obtain dredging Herba Ocimi (Herba Ocimi Pilosi) extract；
(3) column chromatography for separation: by thin Herba Ocimi (Herba Ocimi Pilosi) extract acetic acid ethyl dissolution, adding the mesh number with the quality such as ethyl acetate is
The column chromatography silica gel of 300-400 mesh is mixed thoroughly, 50 DEG C of evaporated under reduced pressure, weighs the 300-of thin Herba Ocimi (Herba Ocimi Pilosi) 8-25 times of quality of extract in advance
The column chromatography silica gel of 400 mesh, uses petroleum ether wet method dress post, loads in chromatographic column by the silica gel mixed, with volume ratio as 10:1-
The petroleum ether-ethyl acetate mixed liquor gradient elution of 1:1, thin layer chromatography inspection, merge the fraction obtaining compound anophelifuge nitrile, dense
It is reduced to solvent-free, obtains anophelifuge nitrile crude product；
(4) purification: by anophelifuge nitrile crude product acetic acid ethyl dissolution, the mesh number of the quality such as addition and ethyl acetate is 200-300 mesh
Column chromatography silica gel mix thoroughly, 50 DEG C of evaporated under reduced pressure, weigh the chromatography of the 200-300 mesh post of anophelifuge nitrile 8-10 times of quality of crude product in advance
Silica gel, uses petroleum ether wet method dress post, loads in chromatographic column by the silica gel mixed, and the petroleum ether with volume ratio as 10:1-1:1-
Chloroform mixed liquor gradient elution, thin layer chromatography inspection, merge the fraction of compound anophelifuge nitrile, be concentrated into solvent-free, obtain anophelifuge
Nitrile sterling.
4. the application in the commercial mosquito repellent product of preparation of the compound described in claim 1 or 2.
5. an anophelifuge medicament, it is characterised in that effective ingredient is the compound described in claim 1 or 2.
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| CN201610710486.7A CN106316884B (en) | 2016-08-23 | 2016-08-23 | A kind of mosquito repellent natural active compound and preparation method and application |
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| CN201610710486.7A CN106316884B (en) | 2016-08-23 | 2016-08-23 | A kind of mosquito repellent natural active compound and preparation method and application |
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| CN106316884A true CN106316884A (en) | 2017-01-11 |
| CN106316884B CN106316884B (en) | 2018-01-12 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB860320A (en) * | 1958-06-12 | 1961-02-01 | Montedison Spa | Seminitrile esters of beta-hydromuconic acid |
| US3012061A (en) * | 1958-06-10 | 1961-12-05 | Montedison Spa | Preparing beta-hydromuconic seminitrile and esters thereof |
| US3146257A (en) * | 1957-11-14 | 1964-08-25 | Montedison Spa | Process for preparing the seminitrile of beta-hydromuconic acid, its chloride and its lower esters, and products thereof |
| CN103635508A (en) * | 2012-03-13 | 2014-03-12 | 因温斯特技术公司 | Nylon polymer and process |
| WO2015200200A1 (en) * | 2014-06-23 | 2015-12-30 | The University Of Toledo | Cross metathesis approach to c11-c13 fatty-chain amino esters form oleic acid derivatives |
-
2016
- 2016-08-23 CN CN201610710486.7A patent/CN106316884B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3146257A (en) * | 1957-11-14 | 1964-08-25 | Montedison Spa | Process for preparing the seminitrile of beta-hydromuconic acid, its chloride and its lower esters, and products thereof |
| US3012061A (en) * | 1958-06-10 | 1961-12-05 | Montedison Spa | Preparing beta-hydromuconic seminitrile and esters thereof |
| GB860320A (en) * | 1958-06-12 | 1961-02-01 | Montedison Spa | Seminitrile esters of beta-hydromuconic acid |
| CN103635508A (en) * | 2012-03-13 | 2014-03-12 | 因温斯特技术公司 | Nylon polymer and process |
| WO2015200200A1 (en) * | 2014-06-23 | 2015-12-30 | The University Of Toledo | Cross metathesis approach to c11-c13 fatty-chain amino esters form oleic acid derivatives |
Non-Patent Citations (1)
| Title |
|---|
| 刘超祥: "亳州疏毛罗勒挥发油化学成分及抗氧化与抑菌活性研究", 《长江大学学报》 * |
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