CN110078720B - Halogenated benzofuran-coumarin derivative and application thereof in preparation of anti-fouling agent - Google Patents
Halogenated benzofuran-coumarin derivative and application thereof in preparation of anti-fouling agent Download PDFInfo
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- CN110078720B CN110078720B CN201910454057.1A CN201910454057A CN110078720B CN 110078720 B CN110078720 B CN 110078720B CN 201910454057 A CN201910454057 A CN 201910454057A CN 110078720 B CN110078720 B CN 110078720B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
Abstract
The invention relates to a halogenated benzofuran-coumarin derivative and application thereof in preparing an anti-fouling agent, wherein the preparation method of the halogenated benzofuran-coumarin derivative comprises the following steps:
Description
Technical Field
The invention belongs to the field of pollution resistance, and particularly relates to a halogenated benzofuran-coumarin derivative and application thereof in preparation of an anti-pollution agent.
Background
Marine biofouling is the damage caused by marine organisms (barnacles, mussels, oysters, etc.) attached to underwater equipment (hulls, pipelines, oil platforms). Barnacles are a major marine fouling organism, and their larvae can attach to the hull of a ship, increase the weight and navigation resistance of the ship, corrode the hull of the ship, and greatly increase shipping costs. The present inventors have recently found that benzofuran-substituted coumarin amine derivatives, which have high inhibitory activity (EC) against the attachment of Balanus Amphitrite in barnacle larvae501.24 μ g/m L), and the positive drug Sea-none 211TMThe activity is equivalent, but the toxicity to balanus amphitite of barnacle larvae is far lower than that of the positive drug; is a marine organism antifouling agent with high efficiency and low toxicity. In order to further research the anti-fouling mechanism of the compounds and the using effect of the compounds in preparing anti-fouling agents, the invention provides a halogenated benzofuran-coumarin derivative and an anti-fouling agent thereof.
Disclosure of Invention
The invention provides a halogenated benzofuran-coumarin derivative or pharmaceutically acceptable salt thereof, which is characterized in that the halogenated benzofuran-coumarin derivative has a structure shown in a formula I:
another embodiment of the present invention provides a method for preparing the above-mentioned halogenated benzofuran-coumarin derivative, which is characterized by comprising the steps of:
and (2) carrying out reflux reaction on 6-aminocoumarin and 5-chlorobenzofuran-2-formaldehyde in an organic solvent for 5-6 hours, naturally cooling to room temperature, adding sodium borohydride in an ice bath, and reacting for 4-5 hours to obtain the halogenated benzofuran-coumarin derivative with the structure shown in the formula I.
Wherein the mol ratio of the 6-aminocoumarin, the 5-chlorobenzofuran-2-formaldehyde and the sodium borohydride is preferably 1:1.2-1.4: 2.0-2.5; the organic solvent is preferably toluene or ethanol.
Another embodiment of the present invention provides a process for preparing the above-mentioned halogenated benzofuran-coumarin derivative, which is characterized by optionally further comprising the step of preparing 5-chlorobenzofuran-2-carbaldehyde as follows:
(1) dissolving 5-chloro salicylaldehyde and ethyl bromoacetate in an organic solvent, adding cesium carbonate, carrying out reflux reaction for 36-48 hours, filtering to remove solids, concentrating the filtrate, diluting with ethyl acetate, washing with water and saturated sodium chloride in sequence, combining organic layers, drying with anhydrous sodium sulfate, concentrating, and recrystallizing with ethanol to obtain a colorless crystal, namely 5-chlorobenzofuran-2-ethyl formate;
(2) dissolving 5-chlorobenzofuran-2-ethyl formate in an organic solvent, adding lithium aluminum hydride, stirring and reacting for 3-4 hours at room temperature, adding a saturated sodium carbonate solution to stop the reaction under ice bath, extracting with ethyl acetate, drying an organic layer with anhydrous sodium sulfate, concentrating, drying, directly dissolving in dichloromethane, adding a Dess-Martin reagent, reacting for 2-3 hours at room temperature, filtering, diluting a filtrate with dichloromethane, washing with water and saturated sodium chloride in sequence, combining the organic layers, drying with anhydrous sodium sulfate, concentrating, and performing silica gel column chromatography to obtain 5-chlorobenzofuran-2-formaldehyde.
In the step (1), the mol ratio of the 5-chlorosalicylaldehyde to the ethyl bromoacetate to the cesium carbonate is preferably 1:1.3:2.0, and the organic solvent is preferably MeCN, DMF, THF or CH2Cl2、CHCl3One or more of the components are mixed; the mol ratio of the 5-chlorobenzofuran-2-ethyl formate, the lithium aluminum hydride and the Dess-Martin reagent in the step (2) is preferably 1:0.8: 1.2; the organic solvent is preferably MeCN, DMF, THF, CH2Cl2、CHCl3One or more of them are mixed.
Another embodiment of the present invention provides the use of the above-mentioned halobenzofuran-coumarin derivative or a pharmaceutically acceptable salt thereof for the control of marine biofouling.
Another embodiment of the present invention provides the use of the above-described halobenzofuran-coumarin derivative or a pharmaceutically acceptable salt thereof in the preparation of an anti-fouling agent.
Another embodiment of the present invention provides an anti-fouling agent, characterized in that the anti-fouling agent has the above-mentioned halogenated benzofuran-coumarin derivative or a pharmaceutically acceptable salt thereof as an active ingredient.
Another embodiment of the present invention provides an anti-fouling agent, characterized in that the anti-fouling agent comprises the following components in parts by weight:
1 part of rosin, 2-3 parts of acrylic resin, 2 parts of titanium dioxide, 1 part of bentonite and 0.1-1.0 part of a compound with a structure shown in a formula I.
Drawings
FIG. 1 is a diagram showing the plate hanging experiment result of a negative control plate;
FIG. 2 is a graph showing the experimental results of the hanging plate of sample 2;
FIG. 3 is a graph showing the results of the panel experiment of sample 1.
Detailed Description
In order to facilitate a further understanding of the invention, the following examples are provided to illustrate it in more detail. However, these examples are only for better understanding of the present invention and are not intended to limit the scope or the principle of the present invention, and the embodiments of the present invention are not limited to the following.
Example 1
(1) Dissolving 5-chloro salicylaldehyde (10mmol) and ethyl bromoacetate (13mmol) in a MeCN-DMF mixed solvent (40m L, volume ratio of 1:1), adding cesium carbonate (20mmol), carrying out reflux reaction for 48 hours, filtering to remove solids, concentrating the filtrate, diluting with ethyl acetate, sequentially washing with water and saturated sodium chloride, combining organic layers, drying with anhydrous sodium sulfate, concentrating, and recrystallizing with ethanol to obtain a colorless crystal (1.90g, yield is about 84.8%) which is ethyl 5-chlorobenzofuran-2-carboxylate;1H NMR(CDCl3,400MHz)7.65(dd,J＝0.48,2.16Hz,1H),7.51(dt,J＝0.59,8.82Hz,1H),7.46(d,J＝0.90Hz,1H),7.42(dd,J＝2.16,8.82Hz,1H),4.46(q,J＝7.16Hz,2H),1.45(t,J＝7.16Hz,3H)；ESI-MS(m/z)：225.03[M+H]+、227.03[M+2+H]+。
(2) dissolving 5-chlorobenzofuran-2-ethyl formate (5.0mmol) in THF (15m L), adding lithium aluminum hydride (4.0mmol), stirring at room temperature for 3 hours, adding saturated sodium carbonate solution under ice bath to terminate the reaction, extracting with ethyl acetate, directly dissolving the organic layer in dichloromethane (15m L) after drying, concentrating and drying, adding Dess-Martin reagent (6.0mmol), reacting at room temperature for 2 hours, filtering, diluting the filtrate with dichloromethane, washing with water and saturated sodium chloride in sequence, combining the organic layers, drying with anhydrous sodium sulfate, concentrating, and carrying out silica gel column chromatography to obtain 5-chlorobenzofuran-2-formaldehyde (yellow solid, 689mg, yield about 76.3%);1H NMR(CDCl3,400MHz)9.89(s,1H),7.72(dd,J＝0.46,2.12Hz,1H),7.54(dt,J＝0.67,8.84Hz,1H),7.50(d,J＝0.90Hz,1H),7.47(dd,J＝2.12,8.84Hz,1H)；13C NMR(CDCl3,100MHz)180.0,154.8,153.9,130.0,129.6,128.0,123.2,116.7,114.0；ESI-MS(m/z)：180.00[M+H]+、182.00[M+2+H]+。
example 2
Taking 6-aminocoumarin (1.0mmol) and 5-chlorobenzofuran-2-formaldehyde (1.4mmol) to perform reflux reaction in absolute ethyl alcohol (15m L) for 6 hours, naturally cooling to room temperature, adding sodium borohydride (2.5mmol) in ice bath, performing reduced pressure concentration to remove ethanol after reacting for 4 hours, adding dichloromethane for extraction, washing with water, combining organic phases for concentration, and performing silica gel column chromatography (petroleum ether/ethyl acetate ═ 6/1-5/1) to obtain a light yellow solid (278mg, the yield is about 85.3 percent), namely the halogenated benzofuran-coumarin derivative with the structure shown in the formula I:1H NMR(400MHz,CDCl3):7.62(d,J＝9.6Hz,1H,H-4),7.54-7.30(m,4H),6.96-6.85(m,3H),6.41(d,J＝9.6Hz,1H,H-3),4.54(d,J＝5.0Hz,2H,C 2H)，4.50(s,1H,NH)；ESI-MS(m/z)：326.06[M+H]+、328.06[M+2+H]+。
example 3
Taking 6-aminocoumarin (1.0mmol) and 5-chlorobenzofuran-2-formaldehyde (1.2mmol) to perform reflux reaction in toluene (15m L) for 5 hours, naturally cooling to room temperature, adding sodium borohydride (2.0mmol) in ice bath, performing reaction for 5 hours, performing reduced pressure concentration to remove toluene, adding dichloromethane for extraction, washing with water, combining organic phases for concentration, and performing silica gel column chromatography (petroleum ether/ethyl acetate ═ 6/1-5/1) to obtain a light yellow solid (252mg, the yield is about 77.3%) which is the halogenated benzofuran-coumarin derivative with the structure shown in the formula I.
Example 4 anti-barnacle attachment Activity test
The compounds of formula I according to the invention were tested for their inhibitory activity against the attachment of Balanus Amphitite by the method described in the literature (Thiyagarajan V, et al. Mar. biol. (Berlin)2003,143: 543-554) as Sea-Nine 211TMIs a positive control. The results are shown in the following table.
| Test compounds | EC50(μg/mL) | LC50(μg/mL) | LC50/EC50 |
| A compound of formula I | 0.62 | 124.60 | >200 |
| Sea-Nine 211TM | 0.92 | 23.89 | 25.97 |
Example 5 preparation of anti-fouling agent and hanging plate experiment
The formula is as follows: 1 part of rosin, 2 parts of acrylic resin, 2 parts of titanium dioxide, 1 part of bentonite and 0.1 part of a compound with a structure shown in a formula I.
According to the formula, 10g of rosin, 20g of acrylic resin, 20g of titanium dioxide, 10g of bentonite and 1.0g of a structural compound shown in the formula I are taken, xylene is taken as a solvent (100m L), the mixture is ground by a conical mill and dispersed to obtain a paint film feed liquid, and the paint film feed liquid is coated on the surface of a PVC plate by a film coating machine (counted as sample 1).
According to the formula, 10g of rosin, 20g of acrylic resin, 20g of titanium dioxide, 10g of bentonite and 1.0g of compound with the structure of formula II (the structure of the compound with the structure of formula II is shown in the specification)
Prepared from 6-aminocoumarin and benzofuran-2-formaldehyde according to the method of the invention), xylene is used as a solvent (100m L), the xylene is ground by a conical mill and dispersed to obtain a paint film feed liquid, and the paint film feed liquid is coated on the surface of a PVC plate by a film coating machine (counted as sample 2).
The negative control is a PVC plate which does not contain the compound with the structure shown in the formula I and is coated with rosin, acrylic resin, titanium dioxide and bentonite with the same concentration.
Samples 1 and 2 and negative control are subjected to plate hanging experiments (half year time) in barnacle fouling sea areas, and the results are shown in figures 1-3, and the results show that the marine organism adhesion resistance of the compound with the structure shown in the formula I is obviously higher than that of the compound with the structure shown in the formula II.
Claims (8)
1. A halogenated benzofuran-coumarin derivative or a pharmaceutically acceptable salt thereof, wherein said halogenated benzofuran-coumarin derivative has the structure shown in formula I:
2. a process for the preparation of halobenzofuran-coumarin derivatives as claimed in claim 1, characterized in that it comprises the following steps:
and (2) carrying out reflux reaction on 6-aminocoumarin and 5-chlorobenzofuran-2-formaldehyde in an organic solvent for 5-6 hours, naturally cooling to room temperature, adding sodium borohydride in an ice bath, and reacting for 4-5 hours to obtain the halogenated benzofuran-coumarin derivative with the structure shown in the formula I.
3. The process according to claim 2, wherein the molar ratio of 6-aminocoumarin, 5-chlorobenzofuran-2-carbaldehyde and sodium borohydride is preferably 1:1.2-1.4: 2.0-2.5; the organic solvent is preferably toluene or ethanol.
4. The production method as described in any one of claims 2 to 3, characterized by further comprising a step of producing 5-chlorobenzofuran-2-carbaldehyde by:
(1) dissolving 5-chloro salicylaldehyde and ethyl bromoacetate in an organic solvent, adding cesium carbonate, carrying out reflux reaction for 36-48 hours, filtering to remove solids, concentrating the filtrate, diluting with ethyl acetate, washing with water and saturated sodium chloride in sequence, combining organic layers, drying with anhydrous sodium sulfate, concentrating, and recrystallizing with ethanol to obtain a colorless crystal, namely 5-chlorobenzofuran-2-ethyl formate;
(2) dissolving 5-chlorobenzofuran-2-ethyl formate in an organic solvent, adding lithium aluminum hydride, stirring and reacting for 3-4 hours at room temperature, adding a saturated sodium carbonate solution to stop the reaction under ice bath, extracting with ethyl acetate, drying an organic layer with anhydrous sodium sulfate, concentrating, drying, directly dissolving in dichloromethane, adding a Dess-Martin reagent, reacting for 2-3 hours at room temperature, filtering, diluting a filtrate with dichloromethane, washing with water and saturated sodium chloride in sequence, combining the organic layers, drying with anhydrous sodium sulfate, concentrating, and performing silica gel column chromatography to obtain 5-chlorobenzofuran-2-formaldehyde.
5. The process according to claim 4, wherein the molar ratio of 5-chlorosalicylaldehyde to ethyl bromoacetate to cesium carbonate in step (1) is 1:1.3:2.0, and the organic solvent is selected from the group consisting of MeCN, DMF, THF, CH2Cl2、CHCl3One or more of them are mixed.
6. The process according to claim 4, wherein the molar ratio of ethyl 5-chlorobenzofuran-2-carboxylate, lithium aluminum hydride and Dess-Martin reagent in step (2) is 1:0.8: 1.2; the organic solvent is selected from MeCN, DMF, THF, CH2Cl2、CHCl3One or more ofAnd (4) mixing.
7. An anti-fouling agent, characterized in that the anti-fouling agent comprises the halogenated benzofuran-coumarin derivative or the pharmaceutically acceptable salt thereof according to claim 1 as an active ingredient.
8. An anti-fouling agent, characterized in that the anti-fouling agent comprises the following components in parts by weight:
1 part of rosin, 2 to 3 parts of acrylic resin, 2 parts of titanium dioxide, 1 part of bentonite, and 0.1 to 1.0 part of the halogenated benzofuran-coumarin derivative or the pharmaceutically acceptable salt thereof according to claim 1.
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