CN105461514B - A sponge diterpene compound, a preparing method thereof and applications of the diterpene compound - Google Patents
A sponge diterpene compound, a preparing method thereof and applications of the diterpene compound Download PDFInfo
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- CN105461514B CN105461514B CN201510800208.6A CN201510800208A CN105461514B CN 105461514 B CN105461514 B CN 105461514B CN 201510800208 A CN201510800208 A CN 201510800208A CN 105461514 B CN105461514 B CN 105461514B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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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
- A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
- A01N31/06—Oxygen or sulfur directly attached to a cycloaliphatic ring system
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
- C07C35/37—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with a hydroxy group on a condensed system having three rings
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Abstract
The invention relates to the field of marine natural antifouling agents, and particularly relates to a sponge diterpene compound, a preparing method thereof and applications of the diterpene compound in marine antifouling agents. The structure of the diterpene compound is shown as a formula I. The preparing method includes washing hymerhabdia intertidal sponge with seawater, removing sand attached to the surface and attached materials, cutting into small blocks, freeze-drying, smashing, digesting with an organic solvent, extracting with solvents, and performing repeated column chromatography separation to obtain the compound shown as the formula I. The diterpene compound is a small-molecule natural organic compound with a novel structure, and can be prepared easily. The diterpene compound has obvious activity for resisting marine organism fouling, and can be used for preparing efficient marine antifouling agents.
Description
Technical field
The present invention relates to marine natural anti-fouling agent field, specifically a kind of sponge diterpene-kind compound and preparation method
And its application in marine antifoulant.
Background technology
Marine biofouling is all the time that the mankind are engaged in the significant problem that Activities of Ocean is faced.Marine environment
In, some fouling organisms are attached on ship and artificial ocean facility, not only speed up corrosion of metal, are increased marine fuel oil and are disappeared
Consumption, affects the yield and quality of aquaculture, but also can bring alien species, many to the balance and biology of marine ecosystems
Sample threatens.The marine antifouling coating that application contains anti-fouling agent on ship and artificial ocean facility is to solve marime fouling
The effective ways of problem.The organic tin anti-fouling agent being widely used all the time, due to stronger toxicity and non-specificity, and
And can not degrade quickly in marine environment, serious threat is caused to the marine eco-environment, in 2008 by International Maritime
Tissue disabling.At present, the novel antifouling agent of the organic insecticide that organic tin anti-fouling agent has been combined by copper-containing compound replaces.
But in recent years, the harm as organic insecticides such as Irgarol 1051 and Diuron to marine environment also increasingly causes section of various countries
The attention of scholar.Therefore, develop and the friendly nontoxic anti-fouling agent of development environment has become domestic and international marine biofouling study on prevention
Focus.
All the time, find from marine organisms and there is anti-fouling activity natural products, and it is logical as lead compound
Cross chemistry and bionics means develop environmental protection anti-fouling agent, be the main direction of studying of marine biofouling preventing and treating.Sea-
The exploitation of Nine 211 is exactly a good example.Sea-Nine 211 belongs to environmentally friendly anti-fouling agent, is last century 90
Age U.S. Rohm＆Haas company's nontoxic anti-fouling agent for successfully developing and putting on market, its thiazolinone structure is exactly by imitative
Life learns to do section and a kind of structure of modification of marine natural anti-fouling agent is formed.Therefore, fouling resistance guideization is found from marine organisms
Compound is a kind of effective way for developing marine antifoulant.
Sponge is many cells marine organisms of most original in ocean, and widely distributed, species is various.Its biological species is various
Property, the diversity of metabolic pathway, the complexity of living environment and the uncertainty of homobium, determine its secondary metabolite
With the diversity of physiologically active.Sponge can produce during evolution each as the common set marine organisms of a class in ocean
The secondary metabolite of kind of various kinds as chemical defensive substance to resist living environment in suffered threat, such as predator catches
Food, the invasion and attack of pathogen and the attachment of marine fouling organism.As can be seen here, sponge is the main of ocean anti-fouling activity material
Source, research shows have more than half to be obtained from sponge in the anti-fouling activity compound obtained from marine organisms.
The content of the invention
It is an object of the invention to provide a kind of sponge diterpene-kind compound and preparation method and its in marine antifoulant
Using.
For achieving the above object, the technical solution used in the present invention is：
A kind of sponge diterpene-kind compound, sponge diterpene-kind compound structure be formula I shown in,
A kind of preparation method of sponge diterpene-kind compound：
1) repeatedly cold soaking is extracted will to clean and crush rear sponge (Hymerhabdia sp.) organic solvent, merges extract,
Be evaporated to it is solvent-free steam, obtain crude extract medicinal extract；
2) take step 1) in gained the crude extract medicinal extract distilled water dissolved dilution of its 8-10 times of volumes, be subsequently adding molten
The ethyl acetate of 1-1.5 times of solution crude extract medicinal extract distilled water volume is extracted repeatedly, and combining extraction liquid is concentrated to give extract medicinal extract,
It is standby；
3) take step 2) in the extract medicinal extract that obtains carry out silica gel column chromatography separation, with petroleum ether-acetone or petroleum ether-
Ethyl acetate carries out gradient elution for eluant, eluent, collects each component eluent, the detection of Jing thin-layer chromatographies；
4) above-mentioned volume ratio 20 is collected:1–10:Eluant component under 1 eluent carries out successively gel column, anti-phase
Silicagel column and normal-phase silica gel column chromatography are isolated and purified, and are compound shown in formula I for 0.4-0.5 with thin-layer chromatography detection Rf.
The step 1) by after sponge (Hymerhabdia sp.) seawater flushing, removing debris, chopping, freeze-drying
40-100 mesh is crushed to, is then taken 3-4 times with the extraction of organic solvent normal temperature, 24 hours every time, merge each extract, treated
With.
The organic solvent can be 1 for acetone, ethanol, methyl alcohol or volume ratio:1 dichloromethane-methyl alcohol.
The step 4) in gel filtration chromatography eluent can be volume ratio 1:1 chlorine imitation-carbinol or dichloromethane-methyl alcohol；
Reversed-phase silica gel column chromatography eluent can be volume ratio 80:20-95:5 methyl alcohol-water or ethanol-water；Normal-phase silica gel column chromatography is eluted
Liquid can be 8 for volume ratio:1-3:1 petroleum ether-acetone or volume ratio are 15:1-5:1 petroleum ether-ethyl acetate.
Step 4) described in thin-layer chromatography detection solvent be volume ratio 10:1-2:1 petroleum ether-acetone.
A kind of application of sponge diterpene-kind compound, sponge diterpene-kind compound is used as marine antifoulant shown in the formula I
Application.
Application of the sponge diterpene-kind compound shown in the formula I as the marine antifoulant for suppressing kentrogon.
The present invention has advantages below：
1. the Diterpenes natural products that the present invention is obtained by extracting and developing to sponge sample purifying, belongs to new little
Molecule natural organic-compound, structure is novel, easily prepares.
2. sponge according to the present invention is a kind of common temperate zone intertidal belt submarine of Bohai Rim for Hymerhabdia category
Silk floss, is distributed widely in the coastal areas such as Shandong Province of China, Liaoning, and biological sample is easily gathered.
3. the sponge diterpene-kind compound Jing marine biofouling active testings of the present invention show that the compound has significantly
The activity lethal to kentrogon, its LC50It is worth for 3.63 ± 0.30 mcg/mls.
Description of the drawings
Fig. 1 is sponge diterpene-kind compound structure chart provided in an embodiment of the present invention.
Specific embodiment
Following embodiment is that the present invention is further illustrated, but present disclosure is not limited thereto.
Embodiment 1：
Sponge diterpene-kind compound structural formula is formula I, shown：
The preparation of compound shown in formula I：
Material source：Sample collection belongs to Demospongiae from Shandong Yantai Coast temperate zone intertidal zone
(Demospongiae) sea of little axle Spongiidae (Axinellidae) the Hymerhabdia category of Halichondrida (Halichondrida)
It is continuous.
Extract and separate：
By the sponge sample seawater flushing for collecting, remove debris, chopping, freeze-dried back.After taking 1kg dryings
Sample, extracted 4 times with methyl alcohol normal temperature, 24 hours every time, merge extract, in 40 DEG C or so reduced pressure concentrations of temperature, reclaim first
Alcohol, obtains crude extract medicinal extract 100g.Add 2L distilled water it is suspended in water the crude extract medicinal extract of gained, then with etc. body
Long-pending ethyl acetate is extracted 3 times, and combining extraction liquid is concentrated to give extract medicinal extract.Acetic acid ethyl ester extract medicinal extract (20g) is entered
Row normal phase silicagel column (200-300 mesh) chromatography, with petroleum ether-acetone be eluant, eluent by volume be 100:1,50:1,
20:1,10:1,5:1,2:1,1:1,1:2,1:5,0:1 ratio carries out gradient elution, each component eluent is collected, according to thin layer
Analysis (TLC) detection, the color feature and Rf values of 10% sulfuric acid-ethanol developer merge same or like part, obtain 6 groups
Divide (A-F).By component C (500mg, petroleum ether-acetone 5:1 elution fraction) successively Jing Sephadex LH-20 gel columns,
Reverse phase silica gel post and normal-phase silica gel column chromatography are isolated and purified, eluent volume ratio 1 during Sephadex LH-20 gel filtration chromatographies:
1 methylene chloride-methanol, reversed phase column chromatography volume ratio is 90:10 methanol-water is eluted, silica gel column chromatography volume
Than for 8:1 petroleum ether-acetone system is eluted.And detected with TLC, solvent is volume ratio 5:1 petroleum ether-acetone
System, purified pool Rf values are 0.4-0.6 part, that is, obtain compound (30mg) shown in formula I.Jing TLC are detected, in single, equal
Even yellow green spot, is defined as pure compound.Jing nmr analysis, its Structural Identification is a kind of novel diterpene of structure
Class compound, shown in structural formula I, is named as Hymerhabdrin A (table 1).
The physicochemical property and Spectral Characteristic of type I compound (Hymerhabdrin A)：Clear crystal (methyl alcohol), is soluble in two
Chloromethanes, acetone, ethyl acetate, dissolve in methyl alcohol, are insoluble in water.High resolution mass spectrum (HRESIMS) m/z：329.2449[M+
Na]+, calculated value is C20H34O2Na, 329.2457.Proton nmr spectra (1H-NMR,CDCl3, 500MHz) and δ 2.01 (1H, dd, J
=14.5,2.5Hz, H-1a), 1.21 (1H, m, H-1b), 4.13 (1H, m, H-2), 3.23 (1H, d, J=4.0Hz, H-3),
0.91 (1H, dd, J=11.7,3.0Hz, H-5), 1.62 (2H, m, H-6), 1.89 (1H, dt, J=12.5,3.3Hz, H-7a),
1.24 (1H, m, H-7b), 1.18 (1H, m, H-9), 1.50 (2H, m, H-11), 1.79 (1H, m, H-12a) 1.68 (1H, m, H-
12b), 1.97 (1H, brd, J=9.6Hz, H-13), 4.90 (1H, s, H-15a), 4.69 (1H, s, H-15b), 1.74 (3H, s,
H-16), 0.70 (3H, s, H-17), 1.04 (3H, s, H-18), 1.03 (3H, s, H-19), 1.20 (3H, s, H-20).Nuclear-magnetism is total to
The carbon that shakes spectrum (13C-NMR, CDCl3, 125MHz) and δ 43.9 (t, C-1), 71.1 (d, C-2), 78.8 (d, C-3), 38.1 (s, C-4),
56.3 (d, C-5), 19.0 (t, C-6), 41.0 (t, C-7), 43.5 (s, C-8), 63.5 (d, C-9), 36.5 (s, C-10), 19.6
(t, C-11), 24.9 (t, C-12), 58.4 (d, C-13), 145.6 (s, C-14), 111.2 (t, C-15), 24.8 (q, C-16),
14.9 (q, C-17), 16.9 (q, C-18), 29.7 (q, C-19), 16.2 (q, C-20).
The type I compound of table 11H-1H COSY, HMBC and NOESY compose main related data
The structure of type I compound (Hymerhabdrin A) is derived：The high resolution mass spectrum of compound shows that its molecular formula is
C20H34O2, degree of unsaturation is 4.Compound13C-NMR spectrums have 20 carbon signals (4 C, 5 CH, 6 CH2And 5 CH3), with
And the degree of unsaturation of the molecule understands the diterpene-kind compound that the compound is a tricyclic structure.1H-NMR composes δH4.90 (1H,
S) and 4.69 (1H, s) and13C-NMR composes δC145.6 (C) and 111.2 (CH2) show there is the knot of a terminal double bond in molecule
Tile section.δC78.8 (CH) and 71.1 (CH) are two methine carbon signals for being connected with hydroxyl.With reference to its two dimensional NMR
(1H-1H COSY, HSQC, HMBC and NOESY) spectrum (table 1) analysis, it is right1H- and13C-NMR spectrum in hydrogen signal and carbon signal with
It is that the 6/6/5 of a structure novelty is thick so as to obtain the concrete structure of type I compound and the position of substituent is determined
The diterpene-kind compound of ring structure, as shown in Figure 1.
The simultaneously structural formula according to formula I, those skilled in the art also can be obtained by synthesis mode.
Embodiment 2：
Difference from Example 1 is
By the sponge sample seawater flushing for collecting, remove debris, chopping, freeze-dried back.After taking 1kg dryings
Sample, use dichloromethane：Methyl alcohol 1:1 normal temperature is extracted 4 times, 24 hours every time, merges extract, and in temperature, 40 DEG C or so subtract
Pressure concentration, recycling design obtains crude extract medicinal extract.2L distilled water is added it is suspended in water the crude extract medicinal extract of gained,
Then extracted 3 times with isopyknic ethyl acetate, combining extraction liquid is concentrated to give extract medicinal extract.Acetic acid ethyl ester extract is soaked
Cream carries out normal phase silicagel column (200-300 mesh) chromatography, with petroleum ether-ethyl acetate be eluant, eluent by volume be 100:
1,50:1,20:1,10:1,5:1,2:1,1:1,1:2,1:5,0:1 ratio carries out gradient elution, collects each component eluent, root
Detect according to thin-layer chromatography (TLC), the color feature and Rf values of 10% sulfuric acid-ethanol developer, merge same or like part,
Obtain 6 components (A-F).By component C (petroleum ether-ethyl acetate 5:1 elution fraction) successively Jing Sephadex LH-20 coagulate
Glue post, reverse phase silica gel post and normal-phase silica gel column chromatography are isolated and purified, eluent body during Sephadex LH-20 gel filtration chromatographies
Product compares 1:1 chloroform-methanol, reversed phase column chromatography volume ratio is 85:15 alcohol-water is eluted, silica gel column chromatography body
Product is than being 5:1 petroleum ether-ethyl acetate system is eluted, and is detected with TLC, and solvent is volume ratio 4:1 oil
Ether-ethyl acetate, purified pool Rf values are 0.3-0.5 part, that is, obtain compound shown in formula I.Jing TLC detect, in it is single,
Uniform yellow green spot, is defined as pure compound.Jing nmr analysis, its Structural Identification is a kind of novel two of structure
Terpenoid, shown in structural formula I, is named as Hymerhabdrin A (table 1).
Embodiment 3：The anti-fouling activity experiment of type I compound
Screening active ingredients model：The anti-fouling activity experimental model that the present invention is adopted is most widely used for barnacle at present
The killing activity of II phase larva.
The culture of the barnacle young：Take barnacle adult to be placed in 2000 milliliters of beakers, add 1500 milliliters of fresh seawater, use one
Little inflator pump is slowly inflated, strong illumination, more than 25 DEG C of room temperature, 1-2 hours releasable II phase larvas.
The lethal method of kentrogon：24 porocyte culture plates are taken, add 950 microlitres to contain 20 per hole --- 25 phases of barnacle II
The fresh filtering sea of larva, makes test cultures plate.The sample sets of blank control group and each concentration respectively set four parallel holes,
Blank control group adds 50 microlitres of dimethyl sulfoxide (DMSO) (DMSO) solvents, sample sets that 50 microlitres of formulas dissolved with DMSO are added per hole per hole
(I) compound sample shown in, makes each group sample final concentration be respectively 5,10,20,40,80,100 mcg/mls.20 DEG C of cultures
In case after no light culture 24 hours, the detection under binocular anatomical lens counts kentrogon dead individuals number.
Kentrogon killing activity represents that computing formula is as follows with corrected mortality：
Corrected mortality=(control group survival rate-treatment group survival rate)/control group survival rate × 100%.
Experimental result：Diterpene-kind compound had significant killing activity to kentrogon at 24 hours shown in formula (I),
Its LC50It is worth for 3.63 ± 0.30 mcg/mls.
Claims (8)
1. a kind of sponge diterpene-kind compound, it is characterised in that：Sponge diterpene-kind compound structure be formula I shown in,
2. a kind of preparation method of the sponge diterpene-kind compound as described in claim 1, it is characterised in that：
1) repeatedly cold soaking is extracted will to clean and crush rear sponge Hymerhabdia sp. organic solvents, merges extract, is reduced pressure dense
Be reduced to it is solvent-free steam, obtain crude extract medicinal extract；
2) take step 1) in gained the crude extract medicinal extract distilled water dissolved dilution of its 8-10 times of volumes, be subsequently adding dissolving slightly
The ethyl acetate that 1-1.5 times of extract medicinal extract distilled water volume is extracted repeatedly, and combining extraction liquid is concentrated to give extract medicinal extract, standby
With；
3) take step 2) in the extract medicinal extract that obtains carry out silica gel column chromatography separation, with petroleum ether-acetone or petroleum ether-acetic acid
Ethyl ester carries out gradient elution for eluant, eluent, collects each component eluent, the detection of Jing thin-layer chromatographies；
4) above-mentioned volume ratio 20 is collected:1–10:Eluant component under 1 eluent carries out successively gel column, reverse phase silica gel
Post and normal-phase silica gel column chromatography are isolated and purified, and are compound shown in formula I for 0.4-0.5 with thin-layer chromatography detection Rf.
3. the preparation method of the sponge diterpene-kind compound as described in claim 2, it is characterised in that：Step 1) by sponge
Crush after Hymerhabdia sp. seawater flushings, removing debris, chopping, freeze-drying, then extracted with organic solvent normal temperature
Take 3-4 times, 24 hours every time, merge each extract, it is stand-by.
4. the preparation method of the sponge diterpene-kind compound as described in Claims 2 or 3, it is characterised in that：The organic solvent
Can be 1 for acetone, ethanol, methyl alcohol or volume ratio:1 dichloromethane-methyl alcohol.
5. the preparation method of the sponge diterpene-kind compound as described in claim 2, it is characterised in that：Step 4) in gel column layer
Analysis eluent is chlorine imitation-carbinol or dichloromethane-methyl alcohol；Reversed-phase silica gel column chromatography eluent is methyl alcohol-water or ethanol-water；Just
Phase silica gel column chromatography eluent is petroleum ether-acetone or petroleum ether-ethyl acetate.
6. the preparation method of the sponge diterpene-kind compound as described in claim 2, it is characterised in that：Step 4) described in thin layer
Chromatography detection solvent is volume ratio 10:1-2:1 petroleum ether-acetone.
7. the application of the sponge diterpene-kind compound described in a kind of claim 1, it is characterised in that：Sponge two shown in the formula I
Application of the terpenoid as marine antifoulant.
8. the application of the sponge diterpene-kind compound as described in claim 7, it is characterised in that：Sponge diterpene shown in the formula I
Application of the class compound as the marine antifoulant for suppressing kentrogon.
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