CN108164446A - A kind of carboxamides and its preparation method and application - Google Patents

A kind of carboxamides and its preparation method and application Download PDF

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CN108164446A
CN108164446A CN201710723214.5A CN201710723214A CN108164446A CN 108164446 A CN108164446 A CN 108164446A CN 201710723214 A CN201710723214 A CN 201710723214A CN 108164446 A CN108164446 A CN 108164446A
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carboxamides
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毛丽娟
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SHAOXING RUIKANG BIOTECHNOLOGY Co Ltd
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SHAOXING RUIKANG BIOTECHNOLOGY Co Ltd
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    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/32—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C07C235/34—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
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    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
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Abstract

The present invention disclose a kind of carboxamides and preparation method thereof and their applications as stability and high efficiency antioxidative stabilizer, belongs to novel oxidation-resistant stabilizer compounds and invents and preparing technical field.The compound of the present invention all has stable carboxylic acid amides and is keyed the antioxidative stabilizer agent to form different rock-steady structures; the length different product of aliphatic chain is generated by adjusting n values simultaneously; it is allowed to and the specific intact matching of high molecular material performance; it solves small molecule stabilizer to volatilize in high molecular material soon; the problems such as easily extracting out; the materials'use service life is greatly prolonged, embodies the stronger more longlasting high molecular material protective value of the present invention.The stable polymer antioxidant of the present invention resists hydrolysis compared with prior art, resists acidolysis, and the ability for resisting alkaline hydrolysis and resistance chemical contamination environment degradable is stronger, these characteristics provide new better antioxidant range of choice for the development of modern new material.In addition such carboxamides also have not volatile, and good with high molecular material matching performance, polymer protection ability is strong, good environmental protection, attractive and durable, it is of low cost the features such as.

Description

A kind of carboxamides and its preparation method and application
Technical field
The invention belongs to the inventions of novel oxidation-resistant stabilizer compounds and preparing technical field more particularly to a kind of carboxylic acyl Amine or aminated compounds and preparation method thereof and their applications as novel high polymer material antioxidative stabilizer.
Background technology
The anti-oxidant stabilization additives selling market in the whole world is very huge, unitary plastic antioxidant 2011 the whole world just Consume 420,000 tons or so.Asian-Pacific area dosage is maximum at present, is secondly Europe and North America, it is contemplated that Asian-Pacific area material in 2016 Antioxidative stabilizer product sales will be up to 4,800,000,000 dollars.The demands of material against oxidative stabilization additives and production successively from The U.S., West Europe and Japan are transferred to the emerging market in Asia；Particularly the nations of China and India.The consumption of country's antioxidant at present Increase very fast.But a small number of big international suppliers still control material against oxidative stabilizer world market price.Antioxygen Change stabilization additives market particularly heat stabilizer market in India, Asia-Pacific growth rate is quickly.Special antioxidative stabilizer with The growth of polymer material application and technology develop and increase.
At present, the industries such as car industry, organic electronic, agricultural, film, plastics, rubber, fiber, computer material need spy Different special antioxidant and stabilizer expand the service life of these respective materials and application.Anti-oxidant stable addition The demand of agent is also widely used in plastics industry, special vinyl polymer, the development in chlorinated high polymers (PVC) field.PVC is produced Product are mainly used for building field, are particularly manufactured for pipeline and hawser.Antioxidant more than 85% is used for this Industry.It is expected that the demand of the Asian-Pacific area will further increase.Light-duty antioxidant growth will be more rapid.Particularly use It will be more considerable in the increment of polypropylene and polyethylene product.However most polymers material needs the temperature at 200 DEG C or more It is processed or handles under degree, and since it is in high temperature and strong light environment is continuously subjected to, usual material will appear using the longevity The problems such as life shortens, and color is easily destroyed, and strength reduction or material surface embrittlement are cracked.
It is widened especially as the application range of high molecular material, modified plastics, the use of engineering plastics is in electronics row Increasingly important role is played in industry, automobile industry and aviation field, natural environmental condition is unprecedented with residing for material Bigger challenge, with the appearance of more hitech materials, the performance of antioxidative stabilizer in the market is continuous far from meeting The demand of developing market new material.Current domestic market antioxidant type is few, and molecular weight is small, inadequate with respective material matching It is good.Especially China in this field there are no autonomous patented product on the market, it is public that market can not be formed with international major company Flat competitiveness.Existing market product is generally mostly simple function antioxidant, and generally increases the adjustment of molecular weight chain length with ester bond With macromolecule matching way, therefore existing antioxidative stabilizer has migration in material, easily extracts, and easily hydrolyzes, weaker Resistance acidolysis alkali resistant solution resistant to hydrolysis antipollution environment degradable ability, it is poor to material quality performance protective capability to cause in this way, material Material service life shortens, and material application range etc. can all be limited.
Invention content
The purpose of the present invention is to provide a kind of low volatilities, good with high molecular material matching, polymer protection ability By force, materials'use long lifespan, the feature of environmental protection is good, and oxidation resistance is strong and in strong acid, highly basic, stablizes under extensive chemical pollution environment Carboxylic acid amides or aminated compounds as antioxidative stabilizer and preparation method thereof and are used as the anti-oxidant stabilization of novel high polymer material The application of agent.Based on above-mentioned purpose, the present invention adopts the following technical scheme that：A kind of carboxylic acid amides or aminated compounds, feature It is to have following structure：
Wherein X is CH2, SO, NH or NR,
N is positive integer；
Or
Wherein n is positive integer；
Or
Wherein n is positive integer；
Or
Wherein n is positive integer；
Or
Wherein X is S, O, NH or NR1,
Y is X, S, O, NH, NR1,
R for Me,
N is the positive integer more than or equal to 5；
Or
Wherein X is S, O, NH or NR1,
N is positive integer
Or
Wherein n is positive integer；
Or
Wherein n is positive integer.
The carboxylic acid amides or aminated compounds be preferably：
The present invention also provides the preparation methods of a kind of carboxylic acid amides or aminated compounds, include the following steps：
The method of formula 1, formula 2
3, the 5- tertiary butyl-4-hydroxies methyl phenylpropionate of 1.0mmol and the amine reactant of excess 5%-35% mmol are dissolved in The petroleum ether (1 of 60-90 DEG C of boiling point：20w/v), catalyst (1-10%w/w) is added in, wherein, catalyst is toluenesulfonic acid, salt Acid, carboxylic acid, dilute sulfuric acid or Lewis acid or the highly basic such as sodium methoxide.Reflux 24-96 is small under nitrogen protection When.TLC tracking reaction process straight ways methyl esters 100% converts.It is cooled to 0-5 DEG C under stiring, filters the white solid of generation, Concentration filtrate is recrystallized to give more solid products；
The method of formula 3, formula 4
Carboxylate methyl ester or carboxylic acid dimethyl ester are dissolved in 90-120 DEG C of petroleum ether or methanol or ethyl alcohol or second cyanogen or N, N- dimethyl The p-methyl benzenesulfonic acid of addition 10-3% or hydrochloric acid or carboxylic acid or dilute sulfuric acid or Lewis acid add as catalyst in formamide solvent Enter 4- amino-2,2,6,6-tetramethylpiperidines.Mixture is heated to flowing back, and tracking reaction is until carboxylate conversion is complete.
The method of formula 5
Cyanuric Chloride is dissolved in anhydrous propanone or petroleum ether or second cyanogen or ethyl alcohol or dichloromethane, is warming up under nitrogen protection 35-75 degree adds in equivalent inorganic base or organic base, is then added dropwise and the equimolar R- (CH of Cyanuric Chloride2)-YH, reaction guarantor Hold this temperature 3-15 hours, TLC tracks reaction process to R- (CH2) disappearance of-YH raw materials；2,6- are added in into reaction system Di-t-butyl -4-OH- benzyls amine or mercaptan or alcohol, reaction mixture continuation are stirred overnight at a temperature of it.TLC tracking is anti- Process is answered, until being fully converted to three substitution reaction products.
The method of formula 6
Methyl acrylate is dissolved in petroleum ether or dichloromethane or tetrahydrofuran or methyl butyl ether or acetone or acetic acid second Ester, adds in lauryl mercaptan and N, TMSDMA N dimethylamine base -4- pyridines or triethylamine, and mixture is stirred at room temperature 5 hours, and 40 Celsius spend Night.TLC tracks reaction process, until the reaction was complete.Aqueous hydrochloric acid solution is added in, ethyl acetate is added, washes away organic base, have Machine is mutually washed.Organic solvent is removed in vacuum in dry organic phase, filtering, and dry crude product is further purified.Use reaction under high pressure Bottle weighs crude product and N-METHYLFORMAMIDE that appropriate methyl acrylate is reacted with lauryl mercaptan, in N2Protective condition under, claim Appropriate metallic sodium is taken to be added in flask, dry methanol is added and is reacted, metallic sodium total overall reaction is treated in nitrogen protection It is complete, reaction solution is transferred completely into reaction under high pressure bottle.In N2Under protective condition, diethyl triamine is added to reaction under high pressure In bottle, it is 15-30 hours that reaction temperature oil bath outside, which is 80 DEG C of reaction time,.Reaction finishes, and adds in ethyl acetate or dichloromethane Or methyl tertiary butyl ether(MTBE) recrystallization provides white solid product.
The method of formula 7
Weigh appropriate Na2S is added in reaction flask, and ethyl alcohol or methanol or acetone or tetrahydrochysene are then added in into flask Furans, solution become milky, start to turn yellow when dilute sulfuric acid aqueous solution or diluted hydrochloric acid aqueous solution, solution are added dropwise into flask, pH 9-12 solution is transferred to turn yellow.Methyl acrylate is added under ice-water bath stirring into flask, solution is become by half yellow milky Colourless, drag has solid precipitation, and the lower ice-water bath of nitrogen protection is stirred reaction, and the reaction time is 6-18 hours, TLC Tracking reaction is until complete.After reaction, the solid for removing the inside is filtered, then adds in suitable dichloro into filtrate again Product is extracted into dichloromethane phase and carries out liquid separation by methane, and separation dichloromethane removes under vacuum molten after being mutually dried It is spare that agent obtains colourless or lurid liquid.
Suitable octadecylamine is added in reaction flask, then add in high point petroleum ether (90-120 degrees Celsius) or Toluene or ethyl alcohol, p-methyl benzenesulfonic acid or hydrochloric acid or glacial acetic acid or hydrochloric acid and above-mentioned acquired solution.It is placed in thermostatical oil bath and carries out It is stirred to react, temperature setting is 125 DEG C, leads to nitrogen protection plus condensation water knockout drum.(deadline in reaction time is 36-48 Hour, when the reaction is finished, the liquid being cooled to room temperature in flask all becomes solid.It is added under stirring into reaction flask Suitable methanol, is then filtered again, is carried out washing 2-4 times with methanol, is drained rear 40 degrees Celsius of heating in vacuum and be dried to obtain White solid.
The method of formula 8
Lauryl mercaptan is added in reaction flask, is then dissolved in ethyl alcohol or methanol or tetrahydrofuran, in ice A gram NaOMe is added portionwise under water-bath and nitrogen protection, 2- chloroethylamine hydrochlorides are added dropwise after stirring, reaction is in ice after being added dropwise It is stirred 3-6 hours under water-bath.TLC tracking reaction is until the reaction is complete.Solvent is removed under vacuum, is expected to produce with petroleum ether dissolution Object makes it impurity not allowed to detach with other.Solvent is removed after dry filter under vacuum and obtains pale yellowish oil fluid product.
The thio cetylamines of 3- and above-mentioned product are added in 50 milliliters of reaction flasks, then add in high point petroleum ether (90-120 degrees Celsius) or toluene or ethyl alcohol and p-methyl benzenesulfonic acid or hydrochloric acid or glacial acetic acid or hydrochloric acid lead to nitrogen protection plus cold Solidifying water knockout drum reacts and reaction 36-48 hours is stirred in 120 degree of thermostatical oil baths, and TLC detection reaction process works as reaction At the end of be cooled to room temperature, the liquid in flask all becomes solid.Suitable methanol is added under stirring into reaction flask, Then it is filtered again, carries out washing 2-4 times with methanol, drain rear 40 degrees Celsius of heating in vacuum and be dried to obtain white solid.
The reaction equation of the preparation method is：
The reaction equation of the preparation method is：
Application of the carboxylic acid amides or aminated compounds as novel antioxidant, particularly novel high polymer material The application of antioxidant.
The carboxylic acid amides or aminated compounds are in construction material, organic electronic, plastics, rubber, paint, petroleum series Application in product, coating or fiber.
It is connected in formula 1 and 2 structural formula of formula by stable carboxylic acid amides or amine key and increases the antioxidant of molecular weight More stablize, it is thus possible to it is stronger to high molecular material protective value, more for a long time, this kind of hindered phenolic antioxidative stabilizer with The corresponding product of most esters key even resists acidolysis compared to hydrolysis is resisted on international market, resists alkaline hydrolysis and resists chemistry The ability for polluting environment degradable is stronger.The n values of CH2 are adjusted in formula 1 can generate the short different antioxidant of fatty company commander, make Generation and the matched sterically hindered phenol antioxidative stabilizer of specific high molecular chemical characters；N values in change formula two can generate high steric-hindrance amino phenol The antioxidative stabilizer of density, sterically hindered phenol density can be equivalent to or higher than the anti-oxidant stabilization of 1010 sterically hindered phenols of Irganox Agent,
The increase that light stabilizer molecular weight is connected by carboxylic acid amides or amine key of formula 3 and formula 4, has adjusted and high score The aliphatic side chains that sub- match materials are introduced are connected by carboxylic acid amides or amine key, and this junction fragment makes stability of molecule significantly It improves, thus the novel light stabilizer of this new class can help material to keep original performance resistance ectocine more lasting, Have stronger chemical stability, resistant to hydrolysis, antiacid solution, the ability of anti-chemical degradation.The deficiencies in the prior art are overcome, i.e., Product light stabilizer 770 in the market, light stabilizer 3853 are all widely used stable polymers in high molecular material in the market Material is by light-initiated caused free radical oxidation process, the adjustment of increase molecular weight and macromolecule in 770 and 3853 structure Junction fragment with property is carboxylate, the chemical stability and resistant to hydrolysis of carboxylate, antiacid solution, the anti-chemical degradation of alkali resistant solution Ability it is weaker.
Formula 5 connects extensive UV absorption functions base triazine parent nucleus by amine key and sterically hindered phenol thermostabilization function base is connected to In same molecule.By primary antioxidant and auxiliary anti-oxidant hydridization it is natural it is muddy into it is novel it is major-minor cooperate with antioxidative stabilizer, in them Collect sterically hindered phenol, thioether is in one.Known triazine mother nucleus structure is an extensive UV light absorption mother nucleus structure, its ultraviolet light is inhaled It is very wide (referring to http to receive range：//webbook.nist.gov/chemistry), than Benzophenone, benzotriazole absorbs effect Fruit is good.UV absorption parent nucleus triazine is appeared in the antioxidative stabilizer molecule of same high molecular weight.This kind of multi-functional collaboration Antioxidative stabilizer can adjust side chain in structure and reach matching performance with high molecular material, can effectively prevent extraction Phenomenon can give full play of the protective effect to high molecular material.It in addition even can be effective by amide and amine key stable keys Improve the stability of these hydridization synergistic function molecules, resistant to hydrolysis, antiacid solution, alkali resistant solution, the drop of resistance chemical contamination environment Solution.
Stablize the thioether high-temp antioxidizing stabilizer of carboxylic acid amides key even in formula 6, formula 7 and formula 8 and overcome corresponding carboxylic acid ester bond The shortcomings that product (DSTDP, DSTLP etc.) even is degradable, product to environmental protection and operates with the side of bringing without smelling Just.In addition, the upper two classes thioether antioxygen agent molecule of stable keys even is more stablized, there are better resistant to hydrolysis, antiacid solution, alkali resistant Solution, environment resistant pollution degradation property.Therefore they can meet the anti-aging protection demand of more extensive material.
The compound of the present invention all has stable carboxylic acid amides or amine key connects to form the anti-oxidant steady of different rock-steady structures Determine agent agent, while the length different product of aliphatic chain is generated by adjusting n values, be allowed to intact with specific high molecular material performance Matching, solves small molecule stabilizer and volatilizees in high molecular material soon, the problems such as easily extraction out, greatly prolongs the materials'use longevity Life embodies the stronger more longlasting high molecular material protective value of the present invention.The present invention stable polymer antioxidant with it is existing Technology is compared to resist and be hydrolyzed, and resists acidolysis, and the ability for resisting alkaline hydrolysis and resistance chemical contamination environment degradable is stronger, these are special Property for the development of modern new material provide new better antioxidant range of choice.In addition such carboxylic acid amides or amine chemical combination Object also has not volatile, and good with high molecular material matching performance, polymer protection ability is strong, good environmental protection, beautiful resistance to With, it is of low cost the features such as.
Below by way of specific embodiment, the present invention is further elaborated.
Embodiment
Embodiment 1
1, chemical structural formula：
2, synthetic route：
3, product (I) preparation method：
5.00 grams of (17.0992mmol) 3,5- di-t-butyls -4- hydroxy phenylpropionic acids methyl esters and 5.0 grams to 7.76 grams (mistakes Amount) octadecylamine be dissolved in 100-280mL 60-90 DEG C petroleum ethers or toluene or methanol or tetrahydrofuran or glycol dimethyl ether or In dimethylformamide, 0.3-1.7 grams of p-methyl benzenesulfonic acid or hydrochloric acid or glacial acetic acid or dilute sulfuric acid are added in.It is anti-under nitrogen protection It should flow back 18-38 hours, TLC tracking reaction process is complete to being converted to methyl esters.The lower cooling of stirring is reacted to 0-10 degrees Celsius, The white solid powder generated is filtered, drying provides 8.07 grams of products (I), yield 89.07%.
1H NMR (Bruker, 400MHz) are in CDCl3In, chemical shift δ (ppm)： 0.88(m,3H),1.21-1.35 (m,30H),1.41-1.50(m,18H),1.98 (m,2H),2.48(t,2H),2.87(t,2H),3.23(m,2H),6.99(s, 2H), 7.26(s,CHCl3In CDCl3In).
Embodiment 2
1, chemical structural formula：
2, synthetic route：
3, prepared by product (II)：
Methyl stearate (5 grams, 16.75 mMs) is dissolved in (50 milliliters) solvent, and solvent can be petroleum ether or toluene Or ethyl alcohol or methanol or second cyanogen or dimethylformamide.4- amino -2,2,6,6- tetramethyl piperazines are added under stirring nitrogen protection Pyridine (3.14 grams, 20.10 mMs) and 5% (W/W) catalyst acid p-methyl benzenesulfonic acid or carboxylic acid or hydrochloric acid or dilute sulfuric acid or Lewis acid.Mixture is heated to reflux until the reaction is complete.Solvent is removed under vacuum, crude product is in ethyl acetate and petroleum ether (1：3) (II) 6.58 gram of product, yield 92.9%. are recrystallized to give in
1H NMR (Bruker, 400MHz) are in CDCl3In, chemical shift δ (ppm)： 0.89(t,3H),1.16-1.35 (m,40H),1.57-1.77(m,4H),1.89(dd, 2H),2.13(t,2H),4.26(m,1H),7.26(CHCl3In CDCl3 In).
Embodiment 3
1, chemical structural formula：
2, synthetic route：
3, the preparation of intermediate (III)：
Cyanuric Chloride (5 grams, 27.11 mMs) is dissolved in anhydrous propanone or second cyanogen or tetrahydrofuran or ethyl alcohol or methanol (30 Milliliter), nitrogen protection is lower to add in 28.47 mMs of sodium carbonate or potassium carbonate or triethylamine or diisopropyl ethyl amine, Ran Hou Under 50 degrees Celsius, be added dropwise in 20 milliliters of anhydrous propanones or second cyanogen or tetrahydrofuran or ethyl alcohol or methanol 2,6- di-t-butyls- 4- hydroxyl Bians mercaptan (6.84 grams, 27.11 mMs).Reaction mixture stirs 5 hours at 50 degrees Celsius, is warming up to 65 degree and stirs It mixes 3 hours；
4, the preparation of product (III)
Temperature is down to 50 degrees Celsius, be added dropwise in 10 milliliters of above-mentioned intermediates (III) lauryl amine (5.03 grams, 27.11 mmoles You), 65 C overnights of reaction are added dropwise.Room temperature is down to, filters off solid, is washed with solvent and is sticked to product on solid, filtrate It concentrates under vacuum, crude product is in dichloromethane petroleum ether mixed solvent (1：2) expected product is recrystallized to give in (III), yield 87.2%.
1H NMR (Bruker, 400MHz) are in CDCl3In, chemical shift δ (ppm)： 0.96(t,3H),1.28-1.36 (m,54H),1.53(m,2H),3.07(t,2H), 4.16-4.19(dd,4H),7.02(s,4H),7.26(CHCl3In CDCl3 In).
Embodiment 4
1, chemical structural formula：
2, synthetic route：
3, prepared by intermediate (IV)：
Methyl acrylate (3 grams, 34.85 mMs) be dissolved in 10-25 milliliters of petroleum ethers or dichloromethane or tetrahydrofuran or Methyl butyl ether or acetone or ethyl acetate, addition lauryl mercaptan (gram, 34.85 mMs) and 2-10%N, TMSDMA N dimethylamine base- 4- pyridines or triethylamine, mixture are stirred at room temperature 5 hours, 40 C overnights.TLC tracks reaction process, until having reacted Entirely.20 milliliters of 0.1N aqueous hydrochloric acid solutions are added in, add in 20 milliliters of ethyl acetate, wash away organic base, organic phase washing.Drying has Organic solvent is removed in vacuum in machine phase, filtering, and dry crude product is further purified and treats that lower step uses.
4, the preparation of product (IV)
The methyl acrylate and lauryl mercaptan of 50.0g (173.37 mMs) are weighed with the reaction under high pressure bottle of 350ml first The crude product of reaction and the N-METHYLFORMAMIDE of 21.64g are in N2Protective condition under, weigh 4.78 grams (207.82 mMs) Metallic sodium be added in the flask of 500ML, add 60ML drying methanol reaction, nitrogen protection, treat that metallic sodium is complete Portion has been reacted, and reaction solution is transferred completely into reaction under high pressure bottle.In N2Under protective condition, by 5.9g (56.89 mMs) two Ethyl triamine is added in reaction under high pressure bottle, and it is 15-30 hours that reaction temperature oil bath outside, which is 80 DEG C of reaction time,.Reaction finishes, It adds in ethyl acetate or dichloromethane or methyl tertiary butyl ether(MTBE) recrystallization provides (IV) 42.85 gram of white solid product, yield 86.3%.
1H NMR (Bruker, 400MHz) are in CD3In OD, chemical shift δ (ppm)： 0.82-0.93(m,3CH3,9H), 1.23-1.42(m,30CH2,60H),1.56(m,3CH2, 6H),2.42(t,3SCH2,4H),2.53(t,3COCH2,4H), 2.69-2.2,78(m, 3SCH2,4NCH2,14H),3.30(CH3OH is in CD3In OD), 4.87 (H2O is in CD3In OD).
Embodiment 5
1, chemical structural formula：
2, synthetic route：
3. the synthesis of intermediate V
Weigh 71.82g Na2S.9H2O (0.2990 mole) is added in the reaction flask of 500ml, then into flask The ethyl alcohol or methanol or acetone or tetrahydrofuran, solution for adding in 40ml-100 milliliters become milky, when being added dropwise into flask The dilute sulfuric acid aqueous solution or diluted hydrochloric acid aqueous solution of 1mol/L, solution start to turn yellow, and pH is transferred to 9-12 solution and turns yellow.Ice water The methyl acrylate (0.5808 mole) of 50g is added under bath stirring into flask, solution becomes colourless by half yellow milky, burns There is solid precipitation in bottom of bottle portion, and the lower ice-water bath of nitrogen protection is stirred reaction, and the reaction time is about 6-18 hours, TLC tracking Reaction is until complete.After reaction, the solid for removing the inside is filtered, then adds in suitable dichloromethane into filtrate again Product is extracted into dichloromethane phase and carries out liquid separation, removing solvent under vacuum after separation dichloromethane is mutually dried obtains It is product to colourless or lurid liquid, yield 79-95%.
4. the preparation method of target product V
The octadecylamine of 26.16g (0.1411 mole) is added in 250 milliliters of reaction flasks, then adds in the height of 100ml Boiling petroleum ether (90-120 degrees Celsius) or toluene or ethyl alcohol, the p-methyl benzenesulfonic acid or hydrochloric acid or ice vinegar of 1-10% (molar ratio) Acid or the intermediate product V of hydrochloric acid and 10g (0.04848 mole).It is placed in thermostatical oil bath and is stirred reaction, temperature is set 125 DEG C are set to, leads to nitrogen protection plus condensation water knockout drum.(deadline in reaction time is about 36-48 hours, with temperature Solid in the raising reaction bulb of degree is dissolved into liquid, and when the reaction is finished, the liquid being cooled to room temperature in flask all becomes Solid.Suitable methanol is added under stirring into reaction flask, is then filtered again, washing 2-4 times is carried out with methanol, takes out 40 degrees Celsius of heating in vacuum is dried to obtain white solid, yield 86-97% after dry.1H NMR (Bruker, 400MHz) exist CDCl3In, chemical shift δ (ppm)：0.0 (s, internal standard SiMe4), 0.83-0.91(m,2CH3,CH2,8H),1.23-1.39(m, 29CH2,58H), 1.467-1.59(m,2CH2,4H),2.43-2.51(m,SCH2,2H),2.79-2.86(t,SCH2, 2H), 2.89-2.95(t,SCH2,2H),3.26(m,2NCH2, 4H), 7.261 (CHCl3in CDCl3In).
Embodiment 6
1, chemical structural formula：
2, synthetic route：
3, prepared by intermediate (VI)：
10 grams of lauryl mercaptans (0.0531 mole) are added in the reaction flask of 100ml, are then dissolved in 6.1 grams of NaOMe are added portionwise under ice-water bath and nitrogen protection in 40ml-100 milliliters of ethyl alcohol or methanol or tetrahydrofuran 2- chloroethylamine hydrochlorides are added dropwise in (0.1122 mole), stirring after ten minutes, are reacted after being added dropwise and stir 3-6 under ice-water bath Hour.TLC tracking reaction is until the reaction is complete.Remove solvent under vacuum, with petroleum ether dissolution be expected product make its with it is other Impurity is not allowed to detach.Solvent is removed after dry filter under vacuum and obtains pale yellowish oil fluid product, yield 85-96%.
4. the preparation method of target product VI
5 grams of thio cetylamines of 3- (0.0203 mole) and intermediate V are added in 50 milliliters of reaction flasks, are then added in The high point petroleum ether (90-120 degrees Celsius) or toluene or ethyl alcohol of 20-30ml and the p-methyl benzenesulfonic acid of 1-10% (molar ratio) Or hydrochloric acid or glacial acetic acid or hydrochloric acid., lead to nitrogen protection plus condensation water knockout drum, react and stirred in 120 degree of thermostatical oil baths Reaction 36-48 hours is mixed, TLC detection reaction process is cooled to room temperature, the liquid in flask all becomes when the reaction is finished Solid.Suitable methanol is added under stirring into reaction flask, is then filtered again, washing 2-4 times is carried out with methanol, takes out 40 degrees Celsius of heating in vacuum is dried to obtain white solid, yield 86-97% after dry.
1H NMR (Bruker, 400MHz) are in CDCl3In, chemical shift δ (ppm)：0.0 (s, internal standard SiMe4),0.91- 0.99(t,2CH3,6H),1.33-1.42(m,18CH2,36H), 1.62-1.67(m,2CH2,4H),2.39-2.48(m, 2SCH2,4H), 2.53-2.60(m,2CH2,4H),2.69-2.75(m,4SCH2,8H), 3.56-3.62(m,2NCH2, 4H), 7.26(CHCl3in CDCl3In), 8.02 (bm, NH)
The above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, those of ordinary skill in the art to this Other modifications or equivalent replacement that the technical solution of invention is made, without departing from the spirit and model of technical solution of the present invention It encloses, should all cover in scope of the presently claimed invention.

Claims (7)

1. a kind of carboxamides, it is characterised in that have following structure：
Wherein X is S, O, NH or NR1,
N is positive integer；
Or
Wherein n is positive integer.
2. a kind of carboxamides as described in claim 1, it is characterised in that the carboxamides are：
3. a kind of preparation method of carboxamides, it is characterised in that include the following steps：
Methyl acrylate is dissolved in petroleum ether or dichloromethane or tetrahydrofuran or methyl butyl ether or acetone or ethyl acetate, adds in Lauryl mercaptan and N, TMSDMA N dimethylamine base -4- pyridines or triethylamine, mixture are stirred at room temperature 5 hours, 40 C overnights, TLC with Track adds in aqueous hydrochloric acid solution, adds ethyl acetate to after the reaction was complete, washes away organic base, organic phase washing.Drying is organic Organic solvent is removed in vacuum in phase, filtering, and dry crude product is further purified.Appropriate methyl acrylate is weighed with reaction under high pressure bottle The crude product and N-METHYLFORMAMIDE reacted with lauryl mercaptan, in N2Protective condition under, weigh appropriate metallic sodium and be added to burning In bottle, add dry methanol and reacted, treat that metallic sodium total overall reaction is complete, reaction solution is transferred completely into reaction under high pressure bottle In, then in N2Under protective condition, diethyl triamine is added in reaction under high pressure bottle, reaction warm oil bath outside is 80 DEG C of reactions Time is 15-30 hours, adds in ethyl acetate or dichloromethane after completion of the reaction or methyl tertiary butyl ether(MTBE) recrystallization provides white Solid product；
Or
Lauryl mercaptan is added in reaction flask, is then dissolved in ethyl alcohol or methanol or tetrahydrofuran, in ice-water bath A gram NaOMe is added portionwise under being protected with nitrogen, 2-chloroethyl amine hydrochloride is added dropwise after stirring, reaction is under ice-water bath after being added dropwise Stirring 3-6 hours.TLC tracking reaction is until the reaction is complete.Remove solvent under vacuum, with petroleum ether dissolution be expected product make its with It is other that impurity is not allowed to detach.Solvent is removed after dry filter under vacuum and obtains pale yellowish oil fluid product,
The thio cetylamines of 3- and above-mentioned product are added in 50 milliliters of reaction flasks, then add in high point petroleum ether (90-120 Degree Celsius) or toluene or ethyl alcohol and p-methyl benzenesulfonic acid or hydrochloric acid or glacial acetic acid or hydrochloric acid, lead to nitrogen protection plus condensation water knockout drum, Reaction is stirred reaction 36-48 hours in 120 degree of thermostatical oil baths, and TLC detection reaction process is cooled at the end of reaction Room temperature after liquid all becomes solid, adds in suitable methanol, then filtered, washing 2-4 is carried out with methanol under stiring It is secondary, it drains rear 40 degrees Celsius of heating in vacuum and is dried to obtain white solid.
4. a kind of preparation method of carboxamides as claimed in claim 3, it is characterised in that：The preparation method Reaction equation is：
5. a kind of application of carboxamides as described in claim 1 as antioxidant.
6. a kind of application of carboxamides as described in claim 1 as high molecular material novel antioxidant.
7. carboxamides as claimed in claim 5 are in construction material, organic electronic, plastics, rubber, paint, oil Application in series of products, coating or fiber.
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Application publication date: 20180615