CN1651412A - Amide derivative of indole, its preparation method and application - Google Patents

Amide derivative of indole, its preparation method and application Download PDF

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CN1651412A
CN1651412A CN 200410036387 CN200410036387A CN1651412A CN 1651412 A CN1651412 A CN 1651412A CN 200410036387 CN200410036387 CN 200410036387 CN 200410036387 A CN200410036387 A CN 200410036387A CN 1651412 A CN1651412 A CN 1651412A
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propionic acid
acid amide
propyl group
base
giantreed
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CN1266132C (en
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于良民
姜晓辉
徐焕志
张志明
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Ocean University of China
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Ocean University of China
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Abstract

An indoleamide derivative C14H14X1X2N2O2R1R2 used as antifoulant for preparing marine anti-fouling point is prepared through reaction between sodium polysulfide and methyl acrylate to obtain dimethyl dithiobipropionate, reaction on alkoxypropylamine to obtain N,N'-dialkylpropyl dithiopropanamide, and reaction on indole, haloindole, gramine, or halogramine to obtain target product.

Description

Amide derivatives of a kind of indoles and its production and application
Technical field
The present invention relates to a kind of indole derivatives, particularly relate to a kind of amide derivatives and preparation method thereof and the application in the preparation marine antifouling coating of indoles.
Background technology
When fishing net, hull bottom, underwater facility etc. are exposed in the seawater for a long time, outward appearance and function very easily stick to its surface growth because of various marine fouling organisms and breeding suffers damage, these marine fouling organisms comprise animals such as barnacle, hydra, Ascidian, algae and mushrooms such as bacterium, fungi such as diatom, green alga.The special mesh that results in blockage when above-mentioned marine fouling organism sticks on the fishing net surface growth and breeding makes resistance increase, catch decline; Make the inside and outside water body of aquaculture net cage exchange minimizing, the dissolved oxygen content in the case reduces, and cultures the speed of growth decline even the death of sea-food; Make the weight of fishing net and the resistance of current increase, shorten the work-ing life of netting gear.And the most popular method that solves this sea marine organism pollution is the coating that brushing contains stain control agent.At present, the stain control agent of widely applying is organotin and Red copper oxide both at home and abroad, for example, and a kind of multipolymer and Red copper oxide (Cu that has comprised methacrylic acid tributyl tin ester and methyl methacrylate 2O) composition as a kind of antifouling paint, is coated on surfaces such as hull bottom, can prevent the harm of marine fouling organism effectively.Multipolymer in this antifouling paint is the meeting hydrolysis in seawater, can discharge tributyl tin (TBT), brings into play antifouling effect.Yet TBT has endangered the marine eco-environment and sea farming industry, causes gender variation and the housing distortion of oyster, blood clam and mussel as TBT.European patent EP-A-51930 discloses the self polishing copolymer antifouling paint of a kind of TBT of containing, and this patent is the work of the milestone of announcement TBT multipolymer.Since then the TBT antifouling paint has been ruled antifouling paint market and has been reached 20 years.Yet to the end of the eighties, people recognize that gradually this organo-tin compound has very strong toxicity, pollutes the environment, even has influence on human beings'health by food chain.Therefore, need development not contain the antifouling paint of organotin.
Summary of the invention
The purpose of this invention is to provide amide derivatives of a kind of indoles and preparation method thereof, and it is applied to prepare marine antifouling coating, to satisfy the demand of prior art.
A kind of amide derivatives of indoles, the molecular formula that it is characterized in that it is C 14H 14X 1X 2N 2O 2R 1R 2, structural formula is:
Figure A20041003638700041
In the formula, X 1Be H, Cl or Br, X 2Be H, Cl or Br; R 1Be CH 3, CH 2CH 3, CH (CH 3) 2Or CH 2CH 2CH 2CH 3R 2Be H or CH 2N (CH 3) 2
The preparation method of the amide derivatives of above-mentioned indoles, it is characterized in that generating the dithio dipropyl dimethyl phthalate with sodium polysulphide and methyl acrylate reaction, it generates N with alkoxypropan ammonia aminolysis reaction again, N '-dialkoxy propyl disulfide is for dipropyl acidamide, latter's indoles, halogeno indole, gramine or the reaction of halo gramine, the reactant sodium polysulphide of described dithio reaction and the mol ratio of methyl acrylate consumption are 0.1～5: 1, temperature of reaction is-15～60 ℃, reaction times is 3～12 hours, the reactant dithio dipropyl dimethyl phthalate of described aminolysis reaction and alkoxypropan ammonia consumption mol ratio are 1: 0.1～10, temperature of reaction is-10～55 ℃, reaction times is 12～48 hours, described acid amides and indoles, halogeno indole, the mol ratio of gramine or the reaction of halo gramine is 1: 0.1～10, temperature of reaction is 0～60 ℃, and the reaction times is 0.5～3 hour.
The amide derivatives of above-mentioned indoles is used to prepare marine antifouling coating as stain control agent.
The amide derivatives of indoles of the present invention is a kind of indole derivatives with efficient antifouling activity, and it has significant fungicidal activity, and nontarget organism is not almost had toxicity.
Embodiment
1, the preparation of β-dithio dipropyl dimethyl phthalate
In the beaker of 250ml, add 45.0g (0.19mol) Na 2S.9H 2O and 8.8g (0.28mol) sulphur powder is heated to boiling, and until whole dissolvings, cooling back suction filtration obtains red clarifying sodium polysulfide solution, be chilled to-5～10 ℃ standby.
In the there-necked flask of the 500ml that whipping appts, condenser, thermometer are housed, add 200g 10% (concentration expressed in percentage by weight, down together) NaHCO successively 3The aqueous solution, 21.7g (0.25mol) methyl acrylate are cooled to-5～10 ℃ and remain under this temperature, drip above-mentioned aqueous sodium polysulfide in 2 hours.Drip and finish, continue reaction 6h under the room temperature, reaction finishes.Standing demix adds the Na of 120g 1mol/L in oil reservoir behind the branch vibration layer 2SO 3The aqueous solution continues reaction 3h down at 50 ℃ then, and reaction finishes.Standing demix again, oil reservoir washes with water behind the branch vibration layer.The gained crude product gets flaxen oily matter 26.8g through underpressure distillation, and productive rate is 89.3%, and boiling point is 182-185 ℃/7mmHg.
2, N, N '-dimethoxy propyl disulfide is for the preparation of dipropyl acidamide
In being housed, the 500mL there-necked flask of whipping appts, condenser, thermometer adds 26.7g (0.3mol) γ-methoxy propyl ammonia, 2.5g triethylamine successively, the control temperature of reaction system is 0 ℃ and remains under this temperature, drips above-mentioned β-dithio dipropyl dimethyl phthalate 23.8g in 1.5 hours.Dropwise, at room temperature continue reaction 24 hours, finish reaction, obtain golden yellow solid.Suction filtration obtains the faint yellow solid product.Dry back dehydrated alcohol recrystallization.Obtain white plates crystal 2 4.1g, productive rate is 68.4%.Fusing point: 103.3～105.1 ℃.
γ in the present embodiment-methoxy propyl ammonia is replaced with γ-ethoxy-c ammonia, γ-isopropoxy third ammonia, γ-butoxy third ammonia can obtain N respectively, N '-diethoxy propyl disulfide is for dipropyl acidamide, N, N '-diisopropoxy propyl disulfide is for dipropyl acidamide, N, and N '-dibutoxy propyl disulfide is for dipropyl acidamide.
3, N-(3-methoxyl group) propyl group-3-(preparation of 1-(5,6-dichloro giantreed base) propionic acid amide
Take by weighing 5,6-dichloro gramine 2.4g (0.01mol) adds anhydrous N in small beaker, and dinethylformamide (DMF) 10g stirs, and is transferred in the 60mL dropping funnel.In the 500mL there-necked flask, take by weighing NaH (NaH content is 60%) 0.6g, add no DMF10g, with 5,6-dichloro gramine solution splashes under agitation condition.Along with 5, the dropping of 6-dichloro gramine solution produces a large amount of bubbles.Get 5 of certain transparency, the DMF solution of 6-dichloro gramine sodium salt.
To 5, drip the N of 3.6g (0.01mol) in the DMF solution of 6-dichloro gramine sodium salt, N '-dimethoxy propyl disulfide is for the mixed solution of dipropyl acidamide and 10g dry DMF.Room temperature reaction 1.5 hours gets yellow-green soln at last.Add the saturated NH of 10g 4The Cl aqueous solution, system become yellow turbid liquid.With extracted with diethyl ether three times, use 20mL approximately at every turn.The gained ether extraction liquid is merged, wash ether extraction liquid twice then with water, get the yellow transparent diethyl ether solution.Use anhydrous MgSO 4Dry ether solution 12～24 hours, rotary evaporation gets a small amount of yellow oil.With toluene is solvent, and toluene is that eluent carries out the column chromatography separation, gets yellow thick liquid, and its productive rate is 55%.
With the N in the present embodiment, N '-dimethoxy propyl disulfide replaces with N for dipropyl acidamide, N '-diethoxy propyl disulfide is for dipropyl acidamide, N, N '-diisopropoxy propyl disulfide is for dipropyl acidamide or N, N '-dibutoxy propyl disulfide is for dipropyl acidamide, 5,6-dichloro gramine replaces with the halo gramine can obtain N-(3-methoxyl group) propyl group-3-(1-halo giantreed base) propionic acid amide respectively, N-(3-oxyethyl group) propyl group-3-(1-halo giantreed base) propionic acid amide, N-(3-isopropoxy) propyl group-3-(1-halo giantreed base) propionic acid amide or N-(3-butoxy) propyl group-3-(1-halo giantreed base) propionic acid amide.
With 5 in the present embodiment, 6-dichloro gramine replaces with indoles, can obtain N-(3-methoxyl group) propyl group-3-(1-indyl) propionic acid amide.If again with N, N '-dimethoxy propyl disulfide replaces with N for dipropyl acidamide, N '-diethoxy propyl disulfide is for dipropyl acidamide, N, N '-diisopropoxy propyl disulfide is for dipropyl acidamide or N, and N '-dibutoxy propyl disulfide can obtain N-(3-oxyethyl group) propyl group-3-(1-indyl) propionic acid amide, N-(3-isopropoxy) propyl group-3-(1-indyl) propionic acid amide or N-(3-butoxy) propyl group-3-(1-indyl) propionic acid amide respectively for dipropyl acidamide.
With 5 in the present embodiment, 6-dichloro gramine replaces with halogeno indole, can obtain N-(3-methoxyl group) propyl group-3-(1-halogeno indole base) propionic acid amide.If again with N, N '-dimethoxy propyl disulfide replaces with N for dipropyl acidamide, N '-diethoxy propyl disulfide is for dipropyl acidamide, N, N '-diisopropoxy propyl disulfide is for dipropyl acidamide or N, and N '-dibutoxy propyl disulfide can obtain N-(3-oxyethyl group) propyl group-3-(1-halogeno indole base) propionic acid amide, N-(3-isopropoxy) propyl group-3-(1-halogeno indole base) propionic acid amide or N-(3-butoxy) propyl group-3-(1-halogeno indole base) propionic acid amide respectively for dipropyl acidamide.
With 5 in the present embodiment, 6-dichloro gramine replaces with gramine, can obtain N-(3-methoxyl group) propyl group-3-(1-giantreed base) propionic acid amide.If again with N, N '-dimethoxy propyl disulfide replaces with N for dipropyl acidamide, N '-diethoxy propyl disulfide is for dipropyl acidamide, N, N '-diisopropoxy propyl disulfide is for dipropyl acidamide or N, and N '-dibutoxy propyl disulfide can obtain N-(3-oxyethyl group) propyl group-3-(1-giantreed base) propionic acid amide, N-(3-isopropoxy) propyl group-3-(1-giantreed base) propionic acid amide or N-(3-butoxy) propyl group-3-(1-giantreed base) propionic acid amide respectively for dipropyl acidamide.
With products therefrom with nucleus magnetic resonance ( 1H NMR) method characterizes, and has proved that the compound of gained is The compounds of this invention.The molecular formula of this compound is C 14H 14X 1X 2N 2O 2R 1R 2, structural formula is:
Figure A20041003638700061
In the formula, X 1Be H, Cl or Br, X 2Be H, Cl or Br, X 1, X 2Can be identical also can be different; R 1Be CH 3, CH 2CH 3, CH (CH 3) 2Or CH 2CH 2CH 2CH 3R 2Be H or CH 2N (CH 3) 2
Compound of the present invention can be used for preparing marine antifouling coating, this marine antifouling coating is made up of resin solution, softening agent, one or more stopping composition and one or more compounds of the present invention, and their weight percentage scope is 20～60,1～20,1～30 and 1～50.Described resin solution concentration range is 20%～60% (concentration expressed in percentage by weight, down together), can adopt acrylic resin soln, chlorinated rubber solution, zinc acrylate resin solution or acrylate resin solution, filming function is arranged, and organic solvent can be ethyl acetate, butylacetate, dimethylbenzene, toluene or butanols; Described softening agent is Vaseline, clorafin, dibutyl phthalate or dioctyl phthalate (DOP); Described stopping composition is red iron oxide, talcum powder, titanium dioxide, aerosil or zinc oxide.During preparation, with concentration be butylacetate solution, 2.5g clorafin, 12g red iron oxide, the 2.5g of 40% 50g acrylic resin aerosil, (1-(5 for 33g N-(3-alkoxyl group) propyl group-3-, 6-dichloro-indole base) mixture of propionic acid amide vibration 2 hours in a paint shaker that contains granulated glass sphere is filtered with 100 purpose strainers then.The antifouling property of the antifouling paint that obtains for test, with reference to national standard " antifouling varnish model shallow sea soak test method " (GB5370-85), with the antifouling paint brushing plate long for 250mm, wide be that the experiment model adopts use iron bolt in the rectangular batten of trough of belt two to fix on 150mm, the thick soft steel experiment model for 2mm.Should test model and hang over Deep sea net cage culture zone, Xun Shan town, Rongcheng City (2 years) and obtained goodish experimental result, as shown in the table.
6 months 12 months 24 months
Blank model 20 40 100
Soaked the model of antifouling paint 0 0 7
Annotate: 0,3,20,40,100 is the bond area percentage ratios of marine organisms on model.

Claims (5)

1. a kind of amide derivatives of indoles, the molecular formula that it is characterized in that it is C 14H 14X 1X 2N 2O 2R 1R 2, structural formula is:
In the formula, X 1Be H, Cl or Br, X 2Be H, Cl or Br; R 1Be CH 3, CH 2CH 3, CH (CH 3) 2Or CH 2CH 2CH 2CH 3R 2Be H or CH 2N (CH 3) 2
2, the preparation method of the amide derivatives of the described indoles of claim 1, it is characterized in that generating the dithio dipropyl dimethyl phthalate with sodium polysulphide and methyl acrylate reaction, it generates N with alkoxypropan ammonia aminolysis reaction again, N '-dialkoxy propyl disulfide is for dipropyl acidamide, the latter and indoles, halogeno indole, gramine or the reaction of halo gramine, the reactant sodium polysulphide and the methyl acrylate consumption mol ratio of described dithio reaction are 0.1～5: 1, the reactant dithio dipropyl dimethyl phthalate of described aminolysis reaction and alkoxypropan ammonia consumption mol ratio are 1: 0.1～10, described acid amides and indoles, halogeno indole, the mol ratio of gramine or the reaction of halo gramine is 1: 0.1～10.
3, preparation method as claimed in claim 2, the amide derivatives that it is characterized in that described indoles is N-(3-methoxyl group) propyl group-3-(1-halo giantreed base) propionic acid amide, N-(3-oxyethyl group) propyl group-3-(1-halo giantreed base) propionic acid amide, N-(3-isopropoxy) propyl group-3-(1-halo giantreed base) propionic acid amide, N-(3-butoxy) propyl group-3-(1-halo giantreed base) propionic acid amide, N-(3-methoxyl group) propyl group-3-(1-indyl) propionic acid amide, N-(3-oxyethyl group) propyl group-3-(1-indyl) propionic acid amide, N-(3-isopropoxy) propyl group-3-(1-indyl) propionic acid amide, N-(3-butoxy) propyl group-3-(1-indyl) propionic acid amide, N-(3-methoxyl group) propyl group-3-(1-halogeno indole base) propionic acid amide, .N-(3-oxyethyl group) propyl group-3-(1-halogeno indole base) propionic acid amide, N-(3-isopropoxy) propyl group-3-(1-halogeno indole base) propionic acid amide, N-(3-butoxy) propyl group-3-(1-halogeno indole base) propionic acid amide, N-(3-methoxyl group) propyl group-3-(1-giantreed base) propionic acid amide, N-(3-oxyethyl group) propyl group-3-(1-giantreed base) propionic acid amide, N-(3-isopropoxy) propyl group-3-(1-giantreed base) propionic acid amide, N-(3-butoxy) propyl group-3-(1-giantreed base) propionic acid amide.
4, the amide derivatives of the described indoles of claim 1 is used to prepare marine antifouling coating.
5, marine antifouling coating as claimed in claim 4, it is characterized in that it is made up of the amide derivatives of resin solution, softening agent, one or more stopping composition and described one or more indoles of claim 1, their weight percentage scope is 20～60,1～20,1～30 and 1～50, resin in the described resin solution is acrylic resin, chlorinated rubber, zinc acrylate resin or acrylate resin, solvent is ethyl acetate, butylacetate, dimethylbenzene, toluene or butanols, and the concentration of resin solution is 20%～60%.
CN 200410036387 2004-11-23 2004-11-23 Amide derivative of indole, its preparation method and application Expired - Fee Related CN1266132C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1709921B (en) * 2005-04-18 2011-09-28 中国海洋大学 Resin of zinc acrylate or copper acrylate containing indole function group, its preparation and use
CN103664736A (en) * 2013-12-13 2014-03-26 中国海洋大学 Ester derivative containing acrylamide indole, preparation method and application thereof
CN103694160A (en) * 2013-12-13 2014-04-02 中国海洋大学 Amide derivative containing double-bond gramine and preparation method and application thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1709921B (en) * 2005-04-18 2011-09-28 中国海洋大学 Resin of zinc acrylate or copper acrylate containing indole function group, its preparation and use
CN103664736A (en) * 2013-12-13 2014-03-26 中国海洋大学 Ester derivative containing acrylamide indole, preparation method and application thereof
CN103694160A (en) * 2013-12-13 2014-04-02 中国海洋大学 Amide derivative containing double-bond gramine and preparation method and application thereof
CN103694160B (en) * 2013-12-13 2015-04-15 中国海洋大学 Amide derivative containing double-bond gramine and preparation method and application thereof
CN103664736B (en) * 2013-12-13 2015-09-30 中国海洋大学 A kind of ester derivative containing acrylamido indoles and its preparation method and application

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