CN1266130C - Ester derivative of indole, its preparation method and application - Google Patents

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

Info

Publication number
CN1266130C
CN1266130C CN 200410036388 CN200410036388A CN1266130C CN 1266130 C CN1266130 C CN 1266130C CN 200410036388 CN200410036388 CN 200410036388 CN 200410036388 A CN200410036388 A CN 200410036388A CN 1266130 C CN1266130 C CN 1266130C
Authority
CN
China
Prior art keywords
base
propionate
giantreed
reaction
indole
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN 200410036388
Other languages
Chinese (zh)
Other versions
CN1651411A (en
Inventor
于良民
姜晓辉
徐焕志
张志明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ocean University of China
Original Assignee
Ocean University of China
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ocean University of China filed Critical Ocean University of China
Priority to CN 200410036388 priority Critical patent/CN1266130C/en
Publication of CN1651411A publication Critical patent/CN1651411A/en
Application granted granted Critical
Publication of CN1266130C publication Critical patent/CN1266130C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Paints Or Removers (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention relates to an indole ester derivate which is characterized in that the molecular formula of the derivate is C11H7X1X2 NO2R1R2, wherein in the molecular formula, X1 is H, Cl or Br, X2 is H, Cl or Br, R1 is CH3, CH2CH3, CH2(CH3)2, CH2CH2 CH2CH3 or CH2CH2CH2CH3CH2CH2-CH3)2, and R2 is H or CH2N(CH3)2. Sodium polysulfide and alkyl acrylates react to prepare dialkyl dithiobipropionate in preparation; the alkyl acrylates reacts with indole, halogeno-indole and gramine or halogeno-gramine. The dosage molar ratio of the reactant of the sodium polysulfide by the disulfide reaction and the alkyl acrylates is 0.1 to 5: 1, and the reaction temperature is from-15 DEG C to 70 DEG C. The reaction molar ratio of the dialkyl dithiobipropionate and the indole, the halogeno-indole and the gramine or the halogeno-gramine is 1: 0.1 to 10, the reaction temperature is from-10 DEG C to 60 DEG C, and the reaction time is from 0.5 hr to 3 hr. The indole ester derivate of the present invention can serve as an antifoulant for preparing antifouling marine coating. The indole ester derivate is a high-efficiency compound with antifouling activity, has significant bactericidal activity and basically has no toxicity on non-target organisms.

Description

Ester derivative 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 preparation method and the application in the preparation marine antifouling coating of ester derivative of indoles.
Background technology
As everyone knows, fouling organisms such as barnacle, mussel, marine alga usually can cooling system and other underwater facility attached to shell, netting gear, power plant on, this corrosion speed of also having quickened when causing these facilities surfaces stained.And the most popular method that solves this marine biofouling 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, promptly the multipolymer of methacrylic acid tributyl tin ester and methyl methacrylate and Red copper oxide (Cu 2O) composition is coated on surfaces such as hull bottom as a kind of antifouling paint, can prevent the harm of marine fouling organism effectively.Its mechanism of action is sustained release poison material tributyl tin (TBT) and Red copper oxide, the fouling organism that commute is attached to hull, maritime facilities surface has lethal effect, but TB.T can cause gender variation and the housing distortion of oyster, blood clam and mussel, seriously endangers the marine eco-environment and sea farming industry.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 self polishing copolymer antifouling paint has been ruled antifouling paint market and has been reached 20 years.Yet to the eighties, people recognize that gradually this organo-tin compound has very strong toxicity, can be dirty. dye environment, even have influence on human beings'health by food chain.For this reason, need the not stanniferous marine antifouling coating of exploitation to replace the organotin marine antifouling coating.
Summary of the invention
The purpose of this invention is to provide ester derivative 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 ester derivative of indoles, the molecular formula that it is characterized in that it is C 11H 7X 1X 2NO 2R 1R 2, structural formula is:
Figure C20041003638800041
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) 2, CH 2CH 2CH 2CH 3Or CH 2CH 2CH 2CH 2CH 2CH (CH 3) 2R 2Be H or CH 2N (CH 3) 2
The preparation method of the ester derivative of above-mentioned indoles, it is characterized in that generating the dithio dipropyl acid dialkyl ester with sodium polysulphide and alkyl acrylate reaction, the latter and indoles, halogeno indole, gramine or the reaction of halo gramine, the reactant sodium polysulphide and the alkyl acrylate consumption mol ratio of described dithio reaction are 0.1～5: 1, temperature of reaction is-15～70 ℃, reaction times is 3～12 hours, described dithio dipropyl acid dialkyl ester and indoles, halogeno indole, the mol ratio of gramine or the reaction of halo gramine is 1: 0.1～10, temperature of reaction is-10～60 ℃, and the reaction times is 0.5～3 hour.
The ester derivative of above-mentioned indoles is as the application of stain control agent in the preparation marine antifouling coating.
The ester derivative of indoles of the present invention is a kind of compound with efficient antifouling activity, has important 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.
Methyl acrylate in the present embodiment is replaced with ethyl propenoate, isopropyl acrylate, butyl acrylate or Isooctyl acrylate monomer can obtain β-dithio dipropyl diethyl phthalate, β-dithio dipropyl acid diisopropyl ester, β-dithio dipropyl dibutyl phthalate or β-dithio dipropyl acid di-isooctyl respectively.
2, the preparation of 3-(1-(5,6-dichloro giantreed base)) methyl propionate
Take by weighing 5,6-dichloro gramine 2.4g (0.01mol) adds anhydrous N in small beaker, and dinethylformamide (DMF) 10g stirs, and gets colourless transparent solution, is transferred in the 60mL dropping funnel.In the 500mL there-necked flask, take by weighing NaH (NaH content is 60%) 0.6g, add dry DMF 10g, with above-mentioned 5,6-dichloro gramine solution splashes under agitation condition.Along with 5, the dropping of 6-dichloro gramine DMF solution produces a large amount of bubbles.Obtain 5 of certain transparency, the DMF solution of 6-dichloro gramine sodium salt.
To above-mentioned 5, drip the mixed solution of 2.4g (0.01mol) β-dithio dipropyl dimethyl phthalate and 10g dry DMF in the DMF solution of 6-dichloro gramine sodium salt.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 410g dry ether solution 12～24 hours, rotary evaporation.With toluene is solvent, and toluene is that eluent carries out the column chromatography separation, gets yellow thick liquid, its productive rate about 60%.
β in the present embodiment-dithio dipropyl dimethyl phthalate is replaced with β-dithio dipropyl diethyl phthalate, β-dithio dipropyl acid diisopropyl ester, β-dithio dipropyl dibutyl phthalate or β-dithio dipropyl acid di-isooctyl; 5,6-dichloro gramine replaces with the halo gramine can obtain 3-(1-halo giantreed base) methyl propionate, 3-(1-halo giantreed base) ethyl propionate, 3-(1-halo giantreed base) isopropyl propionate, 3-(1-halo giantreed base) butyl propionate or 3-(1-halo giantreed base) the different monooctyl ester of propionic acid respectively.
With 5 in the present embodiment, 6-dichloro gramine replaces with indoles can obtain 3-(1-indyl) methyl propionate.Can obtain 3-(1-indyl) ethyl propionate, 3-(1-indyl) isopropyl propionate, 3-(1-indyl) butyl propionate or the different monooctyl ester of 3-(1-indyl) propionic acid respectively if again β-dithio dipropyl dimethyl phthalate is replaced with β-dithio dipropyl diethyl phthalate, β-dithio dipropyl acid diisopropyl ester, β-dithio dipropyl dibutyl phthalate or β-dithio dipropyl acid di-isooctyl.
With 5 in the present embodiment, 6-dichloro gramine replaces with halogeno indole can obtain 3-(1-halogeno indole base) methyl propionate.Can obtain 3-(1-halogeno indole base) ethyl propionate, 3-(1-halogeno indole base) isopropyl propionate, 3-(1-halogeno indole base) butyl propionate or 3-(1-halogeno indole base) the different monooctyl ester of propionic acid respectively if again β-dithio dipropyl dimethyl phthalate is replaced with β-dithio dipropyl diethyl phthalate, β-dithio dipropyl acid diisopropyl ester, β-dithio dipropyl dibutyl phthalate or β-dithio dipropyl acid di-isooctyl.
With 5 in the present embodiment, 6-dichloro gramine replaces with gramine can obtain 3-(1-giantreed base) methyl propionate.Can obtain 3-(1-giantreed base) ethyl propionate, 3-(1-giantreed base) isopropyl propionate, 3-(1-giantreed base) butyl propionate or 3-(1-giantreed base) the different monooctyl ester of propionic acid respectively if again β-dithio dipropyl dimethyl phthalate is replaced with β dithio dipropyl diethyl phthalate, β-dithio dipropyl acid diisopropyl ester, β-dithio dipropyl dibutyl phthalate or β-dithio dipropyl acid di-isooctyl.
With products therefrom with nucleus magnetic resonance ( 1H NMR) method characterizes, and has proved that the compound of gained is compound of the present invention.The molecular formula of this compound is C 11H 7X 1X 2NO 2R 1R 2, structural formula is:
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) 2, CH 2CH 2CH 2CH 3Or CH 2CH 2CH 2CH 3CH 2CH (CH 3) 2R 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 40% 50g acrylic resin butylacetate solution, 2.5g clorafin, 12g red iron oxide, the aerosil of 2.5g, (1-(5 for 33g 3-, 6-dichloro-indole base)) mixture of methyl propionate 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 " (GB 5370-85), 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 ?4
Annotate: 0,3,20,40,100 is the bond area percentage ratios of marine organisms on model.

Claims (5)

1, a kind of ester derivative of indoles, the molecular formula that it is characterized in that it is C 11H 7X 1X 2NO 2R 1R 2, structural formula is:
Figure C2004100363880002C1
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) 2, CH 2CH 2CH 2CH 3Or CH 2CH 2CH 2CH 2CH 2CH (CH 3) 2R 2Be H or CH 2N (CH 3) 2
2, the preparation method of the ester derivative of the described indoles of claim 1, it is characterized in that generating the dithio dipropyl acid dialkyl ester with sodium polysulphide and alkyl acrylate reaction, the latter and indoles, halogeno indole, gramine or the reaction of halo gramine, the reactant sodium polysulphide and the alkyl acrylate consumption mol ratio of described dithio reaction are 0.1～5: 1, temperature of reaction is-15～70 ℃, reaction times is 3～12 hours, described dithio dipropyl acid dialkyl ester and indoles, halogeno indole, the mol ratio of gramine or the reaction of halo gramine is 1: 0.1～10, temperature of reaction is-10～60 ℃, and the reaction times is 0.5～3 hour.
3, preparation method as claimed in claim 2, the ester derivative that it is characterized in that described indoles is 3-(1-halo giantreed base) methyl propionate, 3-(1-halo giantreed base) ethyl propionate, 3-(1-halo giantreed base) isopropyl propionate, 3-(1-halo giantreed base) butyl propionate, 3-(1-halo giantreed base) the different monooctyl ester of propionic acid, 3-(1-indyl) methyl propionate, 3-(1-indyl) ethyl propionate, 3-(1-indyl) isopropyl propionate, 3-(1-indyl) butyl propionate, the different monooctyl ester of 3-(1-indyl) propionic acid, 3-(1-halogeno indole base) methyl propionate, 3-(1-halogeno indole base) ethyl propionate, 3-(1-halogeno indole base) isopropyl propionate, 3-(1-halogeno indole base) butyl propionate, 3-(1-halogeno indole base) the different monooctyl ester of propionic acid, 3-(1-giantreed base) methyl propionate, 3-(1-giantreed base) ethyl propionate, 3-(1-giantreed base) isopropyl propionate, 3-(1-giantreed base) butyl propionate or 3-(1-giantreed base) the different monooctyl ester of propionic acid.
4, the application of the amide derivatives of the described indoles of claim 1 in the preparation marine antifouling coating.
5, application as claimed in claim 4, it is characterized in that described marine antifouling coating is by resin solution, softening agent, the ester derivative of the described indoles of stopping composition and claim 1 is formed, their weight percentage scope is 20～60,1～20,1～30 and 1～50, resin in the described resin solution is an acrylic resin, chlorinated rubber, zinc acrylate resin or acrylate resin, solvent is an ethyl acetate, butylacetate, dimethylbenzene, toluene or butanols, the concentration expressed in percentage by weight of resin solution is 20%～60%, described softening agent is a Vaseline, clorafin, dibutyl phthalate or dioctyl phthalate (DOP), described stopping composition are red iron oxide, talcum powder, titanium dioxide, aerosil or zinc oxide.
CN 200410036388 2004-11-23 2004-11-23 Ester derivative of indole, its preparation method and application Expired - Fee Related CN1266130C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 200410036388 CN1266130C (en) 2004-11-23 2004-11-23 Ester derivative of indole, its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 200410036388 CN1266130C (en) 2004-11-23 2004-11-23 Ester derivative of indole, its preparation method and application

Publications (2)

Publication Number Publication Date
CN1651411A CN1651411A (en) 2005-08-10
CN1266130C true CN1266130C (en) 2006-07-26

Family

ID=34868514

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 200410036388 Expired - Fee Related CN1266130C (en) 2004-11-23 2004-11-23 Ester derivative of indole, its preparation method and application

Country Status (1)

Country Link
CN (1) CN1266130C (en)

Families Citing this family (6)

* 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
CN102161533A (en) * 2010-05-25 2011-08-24 兰州理工大学 Preparation method of environmentally-friendly antifoulant containing dyhydroxy donaxine
JP6037277B2 (en) * 2012-12-19 2016-12-07 国立研究開発法人農業・食品産業技術総合研究機構 Auxin biosynthesis inhibitor
CN104073045B (en) * 2013-03-26 2016-12-28 中国科学院烟台海岸带研究所 Halogeno indole and derivant thereof are as the application of marine antifoulant
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
CN108467354A (en) * 2018-04-09 2018-08-31 西尼尔（江西）化工科技有限公司 3,3 '-dithiodipropionic acids are double（Isooctanol ester）Preparation method and applications

Also Published As

Publication number Publication date
CN1651411A (en) 2005-08-10

Similar Documents

Publication Publication Date Title
CN1709925B (en) Resin of zinc acrylate or copper acrylate containing capsaicin function group, its preparation and use
CN102300944B (en) Marine organism anti-fouling paint and preparing method and use thereof
EP0069559B1 (en) Marine paint
CN1709921B (en) Resin of zinc acrylate or copper acrylate containing indole function group, its preparation and use
CN1266130C (en) Ester derivative of indole, its preparation method and application
US4654380A (en) Marine anti-fouling paint
CN106700787A (en) Environmentally-friendly ocean antifouling paint based on self-polishing polymer/butenolide and derivatives thereof
RU2190000C2 (en) Enhancement of self-polishing properties of nonfouling paints
CN1266132C (en) Amide derivative of indole, its preparation method and application
JPH05331008A (en) Attachment inhibitor for marine attaching organism
JPH0790201A (en) Underwater antifouling coating compound
CN1317270C (en) Alkoxy ethoxy propyl isothiazolinone and its preparation process and use
CN1273457C (en) Alkoxy propyl isothiazolinone and its preparation process and use
JP2001233716A (en) Method for controlling microorganism
US8785679B2 (en) Hydrophilic biocidal coatings
CN1709868B (en) Dithio dipropyl acidamide, and its preparing method and use
CN1181182A (en) Phenylamides as marine antifouling agents
AU2009247593B2 (en) Novel environmental friendly anti-microbial adhesion agents for anti-fouling paints and anti-fouling paints containing them
JPH01146969A (en) Antifouling paint
JPS5940124B2 (en) Aquatic biofouling prevention agent
JP3128631B2 (en) Underwater pest adhesion inhibitor
US20090054470A1 (en) Use of mitochondrial electron transport inhibitors to control fouling organisms
WO1999011601A1 (en) Iodopropagylamine compounds, and industrial antimicrobial and antifungal agents, algicides, and antifouling agents containing the same
WO1996008967A1 (en) Aquatic surface antifouling compositions
JPH02268108A (en) Elimination of algae

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20060726

Termination date: 20141123

EXPY Termination of patent right or utility model