CN101230039B - Compound having anti-fouling activity as well as extraction method and use thereof - Google Patents
Compound having anti-fouling activity as well as extraction method and use thereof Download PDFInfo
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- CN101230039B CN101230039B CN2008100706391A CN200810070639A CN101230039B CN 101230039 B CN101230039 B CN 101230039B CN 2008100706391 A CN2008100706391 A CN 2008100706391A CN 200810070639 A CN200810070639 A CN 200810070639A CN 101230039 B CN101230039 B CN 101230039B
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Abstract
The invention relates to a compound with antifouling activity and the distilling method as well as the application, in particular to an isoquinoline compound, and provides a compound with antifouling activity and the distilling method as well as the application. The compound is 3-methoxy-5 hydroxy-7-aldehyde group isoquinoline, and the molecular formula is C11H9NO3. Dry root of excoecaria agallocha is crushed to obtain root shivers; the shivers are dipped into solvents to obtain extracting solutions; the extracting solution goes through filtration and decompression, and the dry solvent is made into extracts; the extracts are scattered in water and distilled with ethyl acetate, which is removed to obtain crude products; the crude products are processed with petroleum aether; the acetone isused as eluent to purify the silica gel column, which is re-crystallized in the acetone. And then, methanol is used as solvents to refine the silica gel column to obtain the pure compound with the antifouling activity (3-methoxy-5 hydroxy-7-aldehyde group isoquinoline). The compound can be used for producing high-efficiency antifouling agents.
Description
Technical field
The present invention relates to a kind of isoquinoline compound, especially relate to and a kind ofly have the effect of fouling resistance biological attachment, and can suppress new compound and extraction separation purification process and application that the barnacle young adheres to.
Background technology
Marine fouling organism (fouling organisms) is to perch in the ocean environment or attached on boats and ships and the various artificial under water facility, the general name of animal, plant and the microorganism that economical activities of mankind is had a negative impact, it is not only the important factor that influences maritime facilities safety and work-ing life, also is the problem that the mankind are paid close attention to when beginning to contact the ocean.Worldwide, the fouling organism on artificial facility surface has caused serious technology and environmental problem in the seawater, and they cause the loss of annual multi-million dollar in the world wide to the serious harm of naval vessel, submarine mine, harbour, offshore platform, undersea cable, buoy, border on the sea power station cooling duct and net cage for sea farming etc.To fouling organism adhere to the research of control technology also because of it is subjected to the world's national generally attention of respectively bordering on the sea in economical and military important meaning always, the funds of research and development that is used for this field every year is already above 2,000,000,000 dollars.
Since having developed antifouling paint from 20 beginnings of the century, solved the marine organisms attachment issue basically.After the seventies in 20th century, along with the forbidding of stain control agents such as mercury, arsenic, organo-tin compound becomes representational stain control agent.Since the eighties in 20th century, found that organotin has toxicity to most of marine organisms, thereby various countries make laws one after another, forbid or limit the use of the organotin antifouling paint, by 2008, organotin will be forbidden comprehensively.Red copper oxide class antifouling paint is occupied an leading position at present, but because copper can particularly gather in the harbour in the ocean in a large number, causes the mass mortality of marine alga, thereby destroys the eubiosis, therefore finally also with disabled.
Traditional stain control agent has toxic action to settled organism, causes expendable damage, and pollutes the environment, and destroy the eubiosis, and the ideal marine antifoulant should satisfy simultaneously: have activity under (1) lower concentration; (2) economy; (3) harmless to human body and other organism; (4) be applicable to various attaching substratums; (5) pollution-free; (6) has biodegradability.Natural antifouling activity material derives from nature, and is basic near above-mentioned 6 conditions, is expected to substitute environmentally harmful stain control agent.
The sea lacquer is the poisonous plants of Euphorbiaceae, a kind of for China's mangrove is born near the mud bank the high water mark, also can be grown in the silt beach, mixed lifes such as many and Hai Lian, Bruguiera conjugata mainly are distributed in Guangdong, Guangxi, Taiwan, Fujian and Hainan and India, Philippines and Oceania of China.This plant up to 7～10m, reaches as high as 20m for fallen leaves or half aiphyllium.Bark and timber this plant of Thailand are the flatulent traditional medications of treatment, at TaiWan, China and resin of this plant of Okinawa of Japan and milk is used as agalloch eaglewood as spices surrogate.It treats epilepsy, conjunctivitis, dermatitis, blood urine, leprosy, toothache among the people also being used as in addition.
Publication number provides a kind of application that relates to some 5-acylphenylamine-halogenated alkyl thiazole as biocide and marine antifoulant for the application for a patent for invention of CN1299589.Publication number provides a kind of application that can be used as the natural product tubatoxin of marine antifoulant for the application for a patent for invention of CN1802913.
Summary of the invention
The object of the present invention is to provide a kind of compound and extracting method thereof with anti-fouling activity.
Another object of the present invention is to provide application of compound with anti-fouling activity.
Compound with anti-fouling activity of the present invention is 4-methoxyl group-5 hydroxyls-7-aldehyde radical isoquinoline 99.9, and the molecular formula of this compound is C
11H
9NO
3, molecular weight is 203, for yellow needle-like crystal (methyl alcohol), is soluble in chloroform, ethyl acetate, acetone, dissolves in methyl alcohol, is insoluble in water, has to suppress the activity that the large-scale fouling organism barnacle young adheres to.
The chemical structural formula of compound 4-methoxyl group-5 hydroxyls-7-aldehyde radical isoquinoline 99.9 is:
The compound 4-methoxyl group-5 hydroxyls-single accumulation site of 7-aldehyde radical isoquinoline 99.9 in natural phant: compound 4-methoxyl group-5 hydroxyls-7-aldehyde radical isoquinoline 99.9 is present in the root of natural phant sea lacquer at least, does not then accumulate at positions such as stem, leaves.
Extracting method with compound (4-methoxyl group-5 hydroxyls-7-aldehyde radical isoquinoline 99.9) of anti-fouling activity of the present invention may further comprise the steps:
The root of the sea lacquer that 1) will do is pulverized, and gets extra large lacquer root fragment;
2) sea is coated with lacquer root fragment soaked in solvent, get extracting solution;
3) with extracting liquid filtering, decompression is drained solvent and is made medicinal extract;
4) medicinal extract is dispersed in the water and uses ethyl acetate extraction, remove ethyl acetate and obtain crude product;
5) with the crude product sherwood oil: acetone is the eluent purification by silica gel column chromatography, and recrystallization in acetone is refining for the solvent column chromatography with methyl alcohol again, obtains the pure compound with anti-fouling activity (4-methoxyl group-5 hydroxyls-7-aldehyde radical isoquinoline 99.9).
The size of sea lacquer root fragment is preferably 0.1～0.5cm.Described solvent can be with 70%～95% ethanol/water, or 70%～90% methanol, or 40%～70% acetone, and the time of immersion is preferably 48～72h, soaks and preferably repeats 3 times.
In step 3), can adopt the Rotary Evaporators decompression, drain solvent.
In step 4), medicinal extract is dispersed in water can adopts every 100g medicinal extract 200ml water, the used ethyl acetate and the volume ratio of water are preferably 1: 1; Remove ethyl acetate and can adopt Rotary Evaporators.
Sherwood oil: the two-phase solvent ratio of acetone is (3.5～4.5): 1, be preferably 4: 1.Column chromatography can adopt Sephedex-LH20 column chromatography (column length 150cm, diameter 5cm).
Of the present invention have the compound (4-methoxyl group-5 hydroxyls-7-aldehyde radical isoquinoline 99.9) of anti-fouling activity owing to can prevent and kill off adhering to of fouling organism barnacle by the mode that the inhibition barnacle young adheres to, thereby play antifouling effect, therefore described compound (4-methoxyl group-5 hydroxyls-7-aldehyde radical isoquinoline 99.9) with anti-fouling activity can be used to prepare stain control agent efficiently.
The present invention's separation from the lacquer of mangrove sea has obtained a kind of new stable compound (4-methoxyl group-5 hydroxyls-7-aldehyde radical isoquinoline 99.9), and it has the activity that the inhibition barnacle young adheres to.Therefore this compound is eco-friendly stain control agent because be naturally occurring composition.Compound 4-methoxyl group-5 hydroxyls-7-aldehyde radical isoquinoline 99.9 is a kind of stain control agent efficiently in addition, suppresses the barnacle young and adheres to EC
50(503nhibiting concentration) is 0.24 μ g/cm
2, minimal effective concentration is 03 μ g/cm
2The lipophilicity of compound 4-methoxyl group-5 hydroxyls-7-aldehyde radical isoquinoline 99.9 is good, water insoluble, is soluble in organic solvents such as chloroform, acetone, ethyl acetate, its release rate easy to control, when guaranteeing effectively to ooze out concentration, avoiding too fast must dissolve and run off, and helps long-acting utilization.Compound 4-methoxyl group-5 hydroxyls-7-aldehyde radical isoquinoline 99.9 is relatively simple for structure with respect to the natural product with antifouling activity of other reports in addition, helps synthetic in the future the utilization.
Description of drawings
Fig. 1 has the compound (4-methoxyl group-5 hydroxyls-7-aldehyde radical isoquinoline 99.9) of anti-fouling activity for the embodiment of the invention is described HMBC is correlated with.
Fig. 2 is the described biological activity assay result with compound (4-methoxyl group-5 hydroxyls-7-aldehyde radical isoquinoline 99.9) of anti-fouling activity of the embodiment of the invention.In Fig. 2, X-coordinate is concentration (μ g/cm
2), ordinate zou is the active percentage of this compound.The data representation adhesive rate of stain, the data representation mortality ratio of white point.
Embodiment
Below by description, describe in detail but do not limit the present invention the embodiment of the invention.
The preparation of embodiment 1 compound
Material source: the sample of sea lacquer picks up from Hainan Dong Zhaigang, and kind is awarded evaluation by life science institute of Xiamen University woods benefit penetrating judgment, and sample is deposited in ecological institute of life science institute of Xiamen University.
Extract and separates: the root of the sea lacquer that will do is ground into the particle of particle diameter 0.1～0.5cm size, and the usefulness 95% alcohol immersion 48h with after the pulverizing repeats 3 times; With extracting liquid filtering and boil off solvent with Rotary Evaporators and make medicinal extract; Medicinal extract is dispersed in the water (every 100g medicinal extract 200ml water) and, boils off ethyl acetate with Rotary Evaporators again and obtain crude product with ethyl acetate (with water volume ratio 1: 1) extraction; With the crude product sherwood oil: acetone is eluent (4: 1) purification by silica gel column chromatography, recrystallization in acetone, be solvent Sephedex-LH20 column chromatography refining (column length 150cm, diameter 5cm) with methyl alcohol again, obtain pure compound (4-methoxyl group-5 hydroxyls-7-aldehyde radical isoquinoline 99.9).
The structure of embodiment 2 compounds (4-methoxyl group-5 hydroxyls-7-aldehyde radical isoquinoline 99.9) is identified
The physico-chemical property of compound: compound (4-methoxyl group-5 hydroxyls-7-aldehyde radical isoquinoline 99.9) is yellow needle-like crystal (methyl alcohol), is soluble in chloroform, ethyl acetate, acetone, dissolves in methyl alcohol, is insoluble in water.ESI-MS：226(M+Na)
+。
1H?NMR(CDCl
3，600Hz)δ：9.96(1H，s)，9.17(1H，s)，8.52(1H，s)，7.95(1H，d，J＝3.0Hz)，7.13(1H，dd，J＝3.0，0.6Hz)，4.00(3H，s)。
13C?NMR(CDCl
3，600Hz)δ：185.1，164.7，149.7，148.2，148.1，130.3，125.1，124.4，115.0，113.5，52.5。
Table 1 has provided two dimensional NMR spectrum data and (has detected
1The heteronuclear Multiple-Quantum Coherences (HMQC) of H detects
1The heteronuclear multikey of H (HMBC) (referring to the Fig. 1) that be correlated with.
Table 1 two dimensional NMR spectrum data
The structure of compound is derived:
Compound (4-methoxyl group-5 hydroxyls-7-aldehyde radical isoquinoline 99.9) has 11 carbon, wherein 52.5 is the carbon of methylol, and 185.1 is the carbon of aldehyde carbon back, and remaining carbon is all between 110～170, chemical shift in conjunction with coupled hydrogen, can infer that these all are the carbon of aromatic ring, and these carbon have 9, so infer that fragrant heterocyclic structure is arranged, and 9.17,8.52 the chemical shift of hydrogen lower than general aromatic ring hydrogen, and meet the chemical shift of the assorted ring hydrogen of nitrogenous virtue, further confirmed deduction.And, be nitrogenous compound according to mass-spectrometric data, and then its parent nucleus is quinoline or isoquinoline 99.9, and 4 hydrogen are arranged, other 3 hydrogen are being replaced by hydroxyl, methylol and aldehyde radical.According to 7.13 and 7.95 coupling constant know they be in phenyl ring between the position, and other 2 hydrogen are unimodal, so these 4 hydrogen all can not be at the ortho position, and 2 hydrogen are respectively arranged at aromatic ring and fragrant heterocycle, all know that 9.17 and 8.52 hydrogen is on nitrogen heterocyclic, and know them on the α position of nitrogen according to their chemical shift, be isoquinoline 99.9 so know its parent nucleus.Can infer these hydrogen and substituent definite position in conjunction with their HMBC again.Thereby obtain the compound concrete structure.
The distribution of embodiment 3 these compounds (4-methoxyl group-5 hydroxyls-7-aldehyde radical isoquinoline 99.9) in the Different Organs of sea lacquer
Gather root, stem and the leaf of sea lacquer, they are dried in the shade, respectively get 100g, sample is ground into the particle of particle diameter 0.1～0.5cm size with pulverizer.With 95% ethanol lixiviate 48h, repeat 3 times, extracting solution is merged, become medicinal extract with the Rotary Evaporators concentrating under reduced pressure.Obtain the heavy respectively 7.35g of medicinal extract of root, stem, leaf, 5.04g, 3.84g.The medicinal extract of gained is detected with TLC, and contrast with the pure product of this compound that obtains, compound itself is yellow, sees that from TLC the extract of leafing and stem does not have the spot corresponding with sample, and the extract of root then has very significantly spot.Determined that this active substance mainly is distributed in root.
The biological test and the mensuration (referring to Fig. 2) of embodiment 4 compounds (4-methoxyl group-5 hydroxyls-7-aldehyde radical isoquinoline 99.9) fouling resistance effect
The biological detection model adopts at present and uses at most, the most extensive, topmost a kind of biological detection model---the barnacle cypris larva adhere to inhibition test.Detection material is dissolved in is mixed with a series of concentration gradients in the seawater, is control group with the seawater that does not add detection material, all establishes 3 parallel group.Water-fast material to be detected is mixed with certain density solution (ethyl acetate, methylene dichloride, methyl alcohol) earlier, and getting 1ml is the culture dish of 6cm in diameter, and evaporating solvent makes determinand form the finite concentration coating on the culture dish surface.25-30 cypris larva put into the experiment water body of 5ml.Bright at 28 ℃ and 15h: after the periodicity of illumination that 9h is dark is cultivated 48h down, observe and the calculating cypris larva adhere to number.Can obtain the EC of 48h according to experimental result
50(half suppresses to adhere to concentration, promptly suppresses young adhesive rate and is the maximum 50% o'clock pairing concentration that suppresses young adhesive rate) is by EC
50The height of detection material antifouling activity as can be known.And behind 24h, calculate the mortality of the young, can obtain the LC of 24h according to experimental result
50(toxic limit medium dose) is by LC
50Detection material is to the toxicity size of the barnacle young as can be known.
The EC of compound
50(503nhibiting concentration) is 0.24 μ g/cm
2(95%lower is 0.23 μ g/cm
2, 95%uper is 0.24 μ g/cm
2).Minimal effective concentration is 0.3 μ g/cm in test
2, the highest invalid concentration is 0.2 μ g/cm
2The LC of compound
50(toxic limit medium dose) is 1.13 μ g/cm
2(95%lower is 1.12 μ g/cm
2, 95%uper is 1.15 μ g/cm
2), minimal effective concentration is 1 μ g/cm
2, the highest invalid concentration is 0.5 μ g/cm
2And the LC of compound
50Much larger than compd E C
50So compound is not to work by toxicity, belongs to the low toxicity stain control agent.
Claims (8)
1. the compound with anti-fouling activity is characterized in that being 4-methoxyl group-5 hydroxyls-7-aldehyde radical isoquinoline 99.9, and molecular formula is C
11H
9NO
3, chemical structural formula is:
Be soluble in chloroform, ethyl acetate, acetone, dissolve in methyl alcohol, be insoluble in water, have and suppress the activity that the large-scale fouling organism barnacle young adheres to.
2. the extracting method with compound of anti-fouling activity as claimed in claim 1 is characterized in that may further comprise the steps:
The root of the sea lacquer that 1) will do is pulverized, and gets extra large lacquer root fragment;
2) sea is coated with lacquer root fragment soaked in solvent, get extracting solution, described solvent is 70%～95% ethanol/water, or 70%～90% methanol, or 40%～70% acetone;
3) with extracting liquid filtering, decompression is drained solvent and is made medicinal extract;
4) medicinal extract is dispersed in the water and uses ethyl acetate extraction, remove ethyl acetate and obtain crude product;
5) with the crude product sherwood oil: acetone is the eluent purification by silica gel column chromatography, and recrystallization in acetone is refining for the solvent column chromatography with methyl alcohol again, obtains having the compound of anti-fouling activity.
3. the extracting method with compound of anti-fouling activity as claimed in claim 2 is characterized in that the size of sea lacquer root fragment is 0.1～0.5cm.
4. the extracting method with compound of anti-fouling activity as claimed in claim 2 is characterized in that the time of soaking is 48～72h, soaks and repeats 3 times.
5. the extracting method with compound of anti-fouling activity as claimed in claim 2 is characterized in that in step 4), and medicinal extract is dispersed in hydromining with every 100g medicinal extract 200ml water, and the used ethyl acetate and the volume ratio of water are 1: 1.
6. the extracting method with compound of anti-fouling activity as claimed in claim 2 is characterized in that sherwood oil: the two-phase solvent ratio of acetone is 3.5～4.5: 1.
7. the extracting method with compound of anti-fouling activity as claimed in claim 6 is characterized in that sherwood oil: the two-phase solvent ratio of acetone is 4: 1.
8. a kind of purposes of compound in the preparation stain control agent as claimed in claim 1 with anti-fouling activity.
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| CN2008100706391A CN101230039B (en) | 2008-02-15 | 2008-02-15 | Compound having anti-fouling activity as well as extraction method and use thereof |
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| CN101230039A CN101230039A (en) | 2008-07-30 |
| CN101230039B true CN101230039B (en) | 2010-12-08 |
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