CN107857723A - A kind of carboxamides and its preparation method and application - Google Patents
A kind of carboxamides and its preparation method and application Download PDFInfo
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- CN107857723A CN107857723A CN201710723048.9A CN201710723048A CN107857723A CN 107857723 A CN107857723 A CN 107857723A CN 201710723048 A CN201710723048 A CN 201710723048A CN 107857723 A CN107857723 A CN 107857723A
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- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- 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
- C07C323/60—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 with the carbon atom of at least one of the carboxyl groups bound to nitrogen atoms
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- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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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 possesses the antioxidative stabilizer agent that stable carboxylic acid amides key connection forms different rock-steady structures; the length different product of aliphatic chain is produced by adjusting n values simultaneously; it is allowed to and the specific intact matching of high polymer material performance; solve small molecule stabilizer to volatilize in high polymer material soon; the problems such as easily extracting out; the materials'use life-span is greatly prolonged, embodies the stronger more longlasting high polymer material protective value of the present invention.The stable polymer antioxidant of the present invention resists hydrolysis compared with prior art, resists acidolysis, resists that the ability of alkaline hydrolysis and resistance chemical contamination environment degradable is stronger, and these characteristics provide new more preferable antioxidant range of choice for the development of modern new material.In addition such carboxamides also have the features such as not volatile, good with high polymer material matching performance, polymer protection ability is strong, good environmental protection, attractive and durable, and cost is cheap.
Description
Technical field
The invention belongs to the invention of novel oxidation-resistant stabilizer compounds and preparing technical field, more particularly to a kind of carboxylic acid amides
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 resists within 2016
Oxidation stabilizers product sales will be up to 4,800,000,000 dollars.The demand of material against oxidative stabilization additives and production are successively from U.S.
State, West Europe and Japan are transferred to the emerging market in Asia；Particularly the nations of China and India.The consumption of current domestic antioxidant increases
Comparatively fast.But a small number of big international suppliers still control material against oxidative stabilizer world market price.Anti-oxidant stabilization
Additive market particularly heat stabilizer market is in India, and Asia-Pacific growth rate is quickly.Special antioxidative stabilizer is with polymer
The growth of materials application and technology develop and increased.
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 useful life of these respective materials and application.Anti-oxidant stabilization additives
Demand be also widely used in plastics industry, special vinyl polymer, the development in chlorinated high polymers (PVC) field.PVC product masters
It is used for building field, is particularly manufactured for pipeline and hawser.Antioxidant more than 85% is used for this industry.In advance
The phase demand of the Asian-Pacific area will further increase.Light-duty antioxidant increases will be more rapid.Particularly it is used for polypropylene
Increment with polyethylene product will be more considerable.But most polymers material needs to carry out at a temperature of more than 200 DEG C
Processing or processing, and because it is in high temperature and strong light environment is continuously subjected to, usual material occurs that service life shortens, color
Easily destroyed, the problems such as the brittle cracking of strength reduction or material surface.
Widened especially as the application of high polymer material, modified plastics, the use of engineering plastics is in electronics row
More and more important effect 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 the antioxidative stabilizer of in the market is continuous far from meeting
The demand of developing market new material.Current domestic market antioxidant species is few, and molecular weight is small, inadequate with respective material matching
It is good.Especially China's also no autonomous patented product in this field commercially, it is public can not to form market with international major company
Flat competitiveness.Existing market product is typically mostly simple function antioxidant, and typically with ester bond increase molecular weight chain length adjustment
With macromolecule matching way, therefore existing antioxidative stabilizer has migration in material, and easily extraction, easily hydrolysis, weaker
Acidolysis alkali resistant solution resistant to hydrolysis antipollution environment degradable ability is resisted, it is poor to material quality performance protective capability so to cause, material
Service life is shortened, and materials application scope etc. can all be limited.
The content of the invention
It is good with high polymer material matching it is an object of the invention to provide a kind of low volatility, polymer protection ability
By force, materials'use long lifespan, the feature of environmental protection is good, and oxidation resistance is strong and pollutes carboxylic stable under environment in strong acid, highly basic, extensive chemical
Acid amides or aminated compounds as antioxidative stabilizer and preparation method thereof and are used as novel high polymer material antioxidative stabilizer
Application.Based on above-mentioned purpose, the present invention adopts the following technical scheme that：A kind of carboxylic acid amides or aminated compounds, it is characterised in that
With 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 be Me,Or
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.
Described carboxylic acid amides or aminated compounds be preferably：
Or
Or
Or
Or
The present invention also provides a kind of preparation method of carboxylic acid amides or aminated compounds, comprises the following steps：
The method of formula 1, formula 2
1.0mmol 3,5- tertiary butyl-4-hydroxies methyl phenylpropionate and excessive 5%-35% mmol amine reactant are dissolved in
The petroleum ether (1 of 60-90 DEG C of boiling point：20w/v), catalyst (1-10%w/w) is added, wherein, catalyst is toluenesulfonic acid, salt
Acid, carboxylic acid, the highly basic such as dilute sulfuric acid or Lewis acid or sodium methoxide.The 24-96 that flows back under nitrogen protection is small
When.TLC tracking reaction process straight ways methyl esters 100% converts.0-5 DEG C is cooled under agitation, and white solid caused by filtering is dense
Contracting 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 ethanol or second cyanogen or N, N- dimethyl
Addition 10-3% p-methyl benzenesulfonic acid or hydrochloric acid or carboxylic acid or dilute sulfuric acid or Lewis acid are used as catalyst in formamide solvent, add
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 ethanol or dichloromethane, is warming up under nitrogen protection
35-75 degree, equivalent inorganic base or organic base are added, be 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 into reaction system
Di-t-butyl -4-OH- benzyls amine or mercaptan or alcohol, reaction mixture continue to be stirred overnight at a temperature of it.TLC tracking reactions
Process, 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 ethyl acetate,
Add lauryl mercaptan and N, TMSDMA N dimethylamine base -4- pyridines or triethylamine, mixture are stirred at room temperature 5 hours, 40 C overnights.
TLC tracks reaction process, complete until reacting.Aqueous hydrochloric acid solution is added, ethyl acetate is added, washes away organic base, organic phase
Washing.Organic phase is dried, filtering, organic solvent is removed in vacuum, crude product is dried, is further purified.Weighed with reaction under high pressure bottle
Appropriate methyl acrylate and the crude product and N-METHYLFORMAMIDE of lauryl mercaptan reaction, in N2Protective condition under, weigh appropriate
Metallic sodium is added in flask, is added dry methanol and is reacted, and nitrogen protection, treats that metallic sodium total overall reaction is complete, will be anti-
Liquid is answered to be transferred completely into reaction under high pressure bottle.In N2Under protective condition, diethyl triamine is added in reaction under high pressure bottle, reacted
Warm oil bath outside be 80 DEG C of reaction time be 15-30 hours.Reaction finishes, and adds ethyl acetate or dichloromethane or methyl- tert fourth
Base ether recrystallization provides white solid product.
The method of formula 7
Weigh appropriate Na2S is added in reaction flask, and ethanol or methanol or acetone or tetrahydrochysene furan are then added into flask
Mutter, solution becomes milky, and when into flask, dropwise addition dilute sulfuric acid aqueous solution or diluted hydrochloric acid aqueous solution, solution start to turn yellow, pH is adjusted
To 9-12 solution yellowings.Methyl acrylate is added into flask under ice-water bath stirring, solution becomes nothing by half yellow milky
Color, drag have a solid precipitation, and the lower ice-water bath of nitrogen protection is stirred reaction, and the reaction time is 6-18 hours, TLC with
Track is reacted until complete.After reaction terminates, the solid for removing the inside is filtered, then adds appropriate 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
Colourless or lurid liquid is standby.
Appropriate octadecylamine is added in reaction flask, then add high point petroleum ether (90-120 degrees Celsius) or
Toluene or ethanol, p-methyl benzenesulfonic acid or hydrochloric acid or glacial acetic acid or hydrochloric acid and above-mentioned resulting solution.It is placed in thermostatical oil bath and carries out
Stirring reaction, temperature setting are 125 DEG C, lead to nitrogen protection plus condensation water knockout drum.(deadline in reaction time is that 36-48 is small
When, when the reaction is finished, the liquid being cooled in room temperature flask all becomes solid.Added in right amount into reaction flask under stirring
Methanol, then filtered again, with methanol carry out washing 2-4 times, drain 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 ethanol 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
3-6 hours are stirred under water-bath.TLC tracking reaction is until reaction is complete.Solvent is removed under vacuum, product is expected with petroleum ether dissolution
It is set not allow impurity to separate 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 high point petroleum ether (90-
120 degrees Celsius) or toluene or ethanol and p-methyl benzenesulfonic acid or hydrochloric acid or glacial acetic acid or hydrochloric acid, logical nitrogen is protected divides water plus condensation
Device, react and reaction 36-48 hours are stirred in 120 degree of thermostatical oil baths, TLC detection reaction process, when the reaction is finished
It is cooled to room temperature, the liquid in flask all becomes solid.Appropriate methanol is added under stirring into reaction flask, is then entered again
Row filters, and carries out washing 2-4 times with methanol, drains rear 40 degrees Celsius of heating in vacuum and be dried to obtain white solid.
The reaction equation of the preparation method is：
Application of the described carboxylic acid amides or aminated compounds as novel antioxidant, particularly novel high polymer material resist
The application of oxidant.
Described carboxylic acid amides or aminated compounds are in construction material, organic electronic, plastics, rubber, paint, petroleum series production
Application in product, coating or fiber.
Formula 1 is connected with the carboxylic acid amides or amine key in the structural formula of formula 2 by stabilization increases the antioxidant of molecular weight
It is more stable, it is thus possible to it is stronger to high polymer material protective value, more for a long time, this kind of hindered phenolic antioxidative stabilizer and state
The corresponding product of the most esters key of border in the market even hydrolyzes compared to resistance, resists acidolysis, resists alkaline hydrolysis and resistance chemical contamination
The ability of environment degradable is stronger.CH2 n values are adjusted in formula 1 can produce the short different antioxidant of fatty company commander, be allowed to produce
The sterically hindered phenol antioxidative stabilizer matched with specific high molecular chemical characters；N values in change formula two can produce high steric-hindrance amino phenol density
Antioxidative stabilizer, its sterically hindered phenol density can equivalent to or higher than the sterically hindered phenol antioxidative stabilizers of Irganox 1010,
The increase that light stabilizer molecular weight is connected by carboxylic acid amides or amine key of formula 3 and formula 4, have adjusted and macromolecule
The aliphatic side chainses that match materials are introduced are connected by carboxylic acid amides or amine key, and this junction fragment makes stability of molecule carry significantly
Height, thus the new light stabilizer of this new class can help material to keep original performance resistance ectocine more lasting, possess
Stronger chemical stability, resistant to hydrolysis, antiacid solution, the ability of anti-chemical degradation.Overcome the deficiencies in the prior art, i.e. in the market
Product light stabilizer 770, light stabilizer 3853 be all in the market high polymer material widely used stable polymer material by
Free radical oxidizing process caused by light-initiated, increase molecular weight adjustment and the company of macromolecule matching in 770 and 3853 structure
Tab segments are carboxylate, the chemical stability and resistant to hydrolysis of carboxylate, antiacid solution, the ability of the anti-chemical degradation of alkali resistant solution compared with
It is weak.
Formula 5 connects extensive UV absorption functions base triazine parent nucleus and sterically hindered phenol thermostabilization function base by amine key and is connected to together
In one molecule.By primary antioxidant and auxiliary anti-oxidant hydridization it is natural it is muddy into it is new it is major-minor cooperate with antioxidative stabilizer, collect in them
Sterically hindered phenol, thioether is in one.Known triazine mother nucleus structure is an extensive UV light absorbs mother nucleus structure, its UV Absorption model
Enclose very wide (referring to http：//webbook.nist.gov/chemistry), than Benzophenone, benzotriazole good absorbing effect.
UV absorption parent nucleus triazine is appeared in the antioxidative stabilizer molecule of same HMW.This kind of multi-functional collaboration is anti-oxidant
Stabilizer can adjust side chain in structure and reach matching performance with high polymer material, can effectively prevent from extracting phenomenon, energy out
Give full play of the protective effect to high polymer material.In addition these can effectively even be improved by acid amides and amine key stable keys
The stability of hydridization synergistic function molecule, resistant to hydrolysis, antiacid solution, alkali resistant solution, the degraded of resistance chemical contamination environment.
The thioether high-temp antioxidizing stabilizer of stable carboxylic acid amides key even overcomes corresponding carboxylic acid ester bond in formula 6, formula 7 and formula 8
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 stable, there is a more preferable resistant to hydrolysis, antiacid solution, alkali resistant solution,
Environment resistant pollutes degradation property.Therefore they can meet the anti-aging protection demand of more extensive material.
The compound of the present invention all possesses 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 produced by adjusting n values, be allowed to and specific intact of high polymer material performance
Match somebody with somebody, solve small molecule stabilizer and volatilized in high polymer material soon, the problems such as easily extraction out, greatly prolong the materials'use life-span,
Embody the stronger more longlasting high polymer material protective value of the present invention.The stable polymer antioxidant and prior art of the present invention
Hydrolyzed compared to resistance, resistance acidolysis, the ability of resistance alkaline hydrolysis and resistance chemical contamination environment degradable is stronger, and these characteristics are existing
Development for new material provides new more preferable antioxidant range of choice.In addition such carboxylic acid amides or aminated compounds also have
Not volatile, good with high polymer material matching performance, polymer protection ability is strong, and good environmental protection is attractive and durable, and cost is cheap
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 (excess)
Octadecylamine is dissolved in 100-280mL 60-90 DEG C petroleum ethers or toluene or methanol or tetrahydrofuran or glycol dimethyl ether or diformazan
In base formamide, 0.3-1.7 grams of p-methyl benzenesulfonic acid or hydrochloric acid or glacial acetic acid or dilute sulfuric acid are added.The lower reaction backflow of nitrogen protection
18-38 hours, TLC tracking reaction process are complete to being converted to methyl esters.To 0-10 degrees Celsius, filtering produces the lower cooling reaction of stirring
White solid powder, drying provide 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 ethanol 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 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 ethanol or methanol (30
Milliliter), nitrogen protection is lower to add 28.47 mMs of sodium carbonate or potassium carbonate or triethylamine or diisopropyl ethyl amine, Ran Hou
Under 50 degrees Celsius, 2,6- di-t-butyls -4- is added dropwise in 20 milliliters of anhydrous propanones or second cyanogen or tetrahydrofuran or ethanol or methanol
Hydroxyl Bian mercaptan (6.84 grams, 27.11 mMs).Reactant mixture stirs 5 hours at 50 degrees Celsius, is warming up to 65 degree of stirrings 3
Hour；
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 bonded at product on solid, filtrate
Concentrate under vacuum, crude product is in dichloromethane petroleum ether mixed solvent (1：2) expected product (III) is recrystallized to give in,
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 CDCl3In).
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 petroleum ether 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, complete until reacting.
20 milliliters of 0.1N aqueous hydrochloric acid solutions are added, add 20 milliliters of ethyl acetate, wash away organic base, organic phase washing.Dry organic phase,
Filtering, organic solvent is removed in vacuum, dries crude product, be further purified and treat 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 350ml reaction under high pressure bottle first
The crude product of reaction and 21.64g N-METHYLFORMAMIDE are in N2Protective condition under, weigh 4.78 grams (207.82 mMs)
Metallic sodium be added in 500ML flask, add 60ML drying methanol reaction, nitrogen protection, treat metallic sodium whole
It has been reacted that, reaction solution has been transferred completely into reaction under high pressure bottle.In N2Under protective condition, by 5.9g (56.89 mMs) diethyl
Base triamine is added in reaction under high pressure bottle, reaction warm oil bath outside be 80 DEG C of reaction time be 15-30 hours.Reaction finishes, and adds
Enter 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,3OCH2,60H),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. intermediate V synthesis
Weigh 71.82g Na2S.9H2O (0.2990 mole) is added in 500ml reaction flask, then into flask
The ethanol or methanol or acetone or tetrahydrofuran, solution for adding 40ml-100 milliliters become milky, when being added dropwise into flask
1mol/L dilute sulfuric acid aqueous solution or diluted hydrochloric acid aqueous solution, solution start to turn yellow, and pH is transferred to 9-12 solution yellowings.Ice-water bath
50g methyl acrylate (0.5808 mole) is added under stirring into flask, solution becomes colourless by half yellow milky, flask bottom
There is solid precipitation in portion, and the lower ice-water bath of nitrogen protection is stirred reaction, and the reaction time is about 6-18 hours, TLC tracking reactions
Until complete.After reaction terminates, the solid for removing the inside is filtered, then adds appropriate dichloromethane by product into filtrate again
Be extracted into dichloromethane phase and carry out liquid separation, separation dichloromethane removed after being mutually dried under vacuum solvent obtain it is colourless or
Lurid liquid is product, yield 79-95%.
4. target product V preparation method
26.16g (0.1411 mole) octadecylamine is added in 250 milliliters of reaction flasks, then adds 100ml height boiling
Point petroleum ether (90-120 degrees Celsius) or toluene or ethanol, 1-10% (mol ratio) p-methyl benzenesulfonic acid or hydrochloric acid or glacial acetic acid
Or hydrochloric acid and 10g (0.04848 mole) intermediate product V.It is placed in thermostatical oil bath and is stirred reaction, temperature setting
For 125 DEG C, lead to nitrogen protection plus condensation water knockout drum.(deadline in reaction time is about 36-48 hours, with temperature
The solid dissolving in reaction bulb is raised into liquid, when the reaction is finished, the liquid being cooled in room temperature flask all becomes solid.
Appropriate methanol is added under stirring into reaction flask, is then filtered again, washing 2-4 times is carried out with methanol, it is true after draining
40 degrees Celsius of sky heating is dried to obtain white solid, yield 86-97%.1H NMR (Bruker, 400MHz) are in CDCl3In, change
Displacement study 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 100ml reaction flask, are then dissolved in 40ml-
100 milliliters of ethanol or methanol or tetrahydrofuran, under ice-water bath and nitrogen protection 6.1 grams of NaOMe are added portionwise (0.1122 rubs
You), 2- chloroethylamine hydrochlorides are added dropwise after 10 minutes in stirring, reaction stirring 3-6 hours under ice-water bath after being added dropwise.TLC with
Track reaction is until reaction is complete.Solvent is removed under vacuum, being expected product with petroleum ether dissolution makes it not allow impurity to separate with other.
Solvent is removed after dry filter under vacuum and obtains pale yellowish oil fluid product, yield 85-96%.
4. target product VI preparation method
5 grams of thio cetylamines of 3- (0.0203 mole) and intermediate V are added in 50 milliliters of reaction flasks, are then added
20-30ml high point petroleum ether (90-120 degrees Celsius) or toluene or ethanol and 1-10% (mol ratio) p-methyl benzenesulfonic acid or
Hydrochloric acid or glacial acetic acid or hydrochloric acid., lead to nitrogen protection plus condensation water knockout drum, react and be stirred in 120 degree of thermostatical oil baths
React 36-48 hours, TLC detection reaction process, be cooled to room temperature when the reaction is finished, the liquid in flask all becomes solid
Body.Appropriate methanol is added under stirring into reaction flask, is then filtered again, washing 2-4 times is carried out with methanol, after draining
40 degrees Celsius of heating in vacuum is dried to obtain white solid, yield 86-97%.
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 are to this hair
Other modifications or equivalent substitution that bright technical scheme is made, without departing from the spirit and scope of technical solution of the present invention,
It all should cover in scope of the presently claimed invention.
Claims (6)
1. a kind of carboxamides, it is characterised in that there is following structure：
Wherein n is positive integer；
Or
Wherein n is positive integer.
2. a kind of preparation method of carboxamides, it is characterised in that comprise the following steps：
Carboxylate methyl ester or carboxylic acid dimethyl ester are dissolved in 90-120 DEG C of petroleum ether or methanol or ethanol or second cyanogen or N, N- dimethyl formyl
P-methyl benzenesulfonic acid or hydrochloric acid or carboxylic acid or dilute sulfuric acid are added in amine solvent or Lewis acid is used as catalyst, adds 4- amino -2,2,
6,6- tetramethyl piperidines, it is heated to flowing back, tracking reaction is until carboxylate conversion is complete.
A kind of 3. preparation method of carboxamides as claimed in claim 3, it is characterised in that：The preparation method
Reaction equation is：
Or
A kind of 4. application of the carboxamides as antioxidant as claimed in claim 1.
A kind of 5. application of the carboxamides as high polymer material novel antioxidant as claimed in claim 1.
6. 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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