CN105693545A - Carboxamide and amine compounds as well as preparation method and applications thereof - Google Patents

Carboxamide and amine compounds as well as preparation method and applications thereof Download PDF

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CN105693545A
CN105693545A CN201610049761.5A CN201610049761A CN105693545A CN 105693545 A CN105693545 A CN 105693545A CN 201610049761 A CN201610049761 A CN 201610049761A CN 105693545 A CN105693545 A CN 105693545A
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reaction
product
carboxylic acid
under
flask
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CN105693545B (en
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毛丽娟
刘树柏
王松平
张再先
万定飞
彭传扬
丁轶凡
孙兴
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SHAOXING RUIKANG BIOTECHNOLOGY Co Ltd
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SHAOXING RUIKANG BIOTECHNOLOGY Co Ltd
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Priority to CN201710723048.9A priority Critical patent/CN107857723A/en
Priority to CN201610049761.5A priority patent/CN105693545B/en
Priority to CN201710723214.5A priority patent/CN108164446A/en
Priority to CN201710211311.6A priority patent/CN107827833A/en
Publication of CN105693545A publication Critical patent/CN105693545A/en
Priority to PCT/CN2016/108500 priority patent/WO2017128860A1/en
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    • 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
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    • 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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    • C07D211/36—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 invention discloses carboxamide and amine compounds as well as a preparation method and applications thereof as stable and efficient antioxidation sterilizers, belonging to the technical field of invention and preparation of novel antioxidation sterilizer compounds. All the compounds disclosed by the invention are stable antioxidation sterilizers which have different stable structures formed by connecting carboxamide and amine bonds, and meanwhile, products having different lengths of aliphatic chains are produced by adjusting an n value, such that the products can be completely matched with a specific high polymer material in performance, the problems that a micromolecular stabilizer is volatilized fast, easily drawn from high polymer materials and the like are solved, the service life of the material is greatly prolonged, and the carboxamide and amine compounds have relatively strong and durable high polymer material protection performance. Compared with the prior art, the stable high polymer antioxidants disclosed by the invention have relatively high capabilities of resisting hydrolysis, acidolysis, alkaline hydrolysis, degradation in a chemical pollution environment, and these performances provides a new better antioxidant selection range for the development of modern new materials. Furthermore, this kind of carboxamide and amine compounds also have the characteristics of difficulty in volatilization, good matching performance with high polymer materials, good high polymer protection capability, good environmental performance, attractive appearance and durability, low cost and the like.

Description

A kind of carboxylic acid amides or aminated compounds and its preparation method and application
Technical field
The invention belongs to the invention of novel oxidation-resistant stabilizer compounds and preparing technical field, particularly relate to a kind of carboxylic acid amides or aminated compounds and preparation method thereof and they application as novel high polymer material antioxidative stabilizer。
Background technology
Antioxidation stabilization additives selling market, the whole world is very huge, and unitary plastic antioxidant just consumes about 420,000 tons in the whole world in 2011。Current Asian-Pacific area consumption is maximum, is secondly Europe and North America, it is contemplated that within 2016, Asian-Pacific area material against oxidative stabilizer product sales will reach 4,800,000,000 dollars。The emerging market in Asia is transferred in the demand of material against oxidative stabilization additives and production successively from the U.S., West Europe and Japan；Particularly the nations of China and India。The consumption of current domestic antioxidant increases very fast。But, the international suppliers that minority is big still controls material against oxidative stabilizer world market price。Particularly heat stabilizer market, antioxidation stabilization additives market is in India, and Asia-Pacific rate of increase is quickly。Growth and technical development that special antioxidative stabilizer is applied along with polymeric material and increase。
At present, car industry, organic electronic, agricultural, film, plastics, rubber, fiber, the industry such as computer material needs special special antioxidant and stabilizer to expand useful life and the application of these respective material。The demand of antioxidation stabilization additives is also widely used in plastics industry, special vinyl polymer, the development in chlorinated high polymers (PVC) field。PVC product is mainly used in building field, especially for pipeline and hawser manufacture。Antioxidant more than 85% is for this industry。The demand of the expection Asian-Pacific area will increase further。It will be more rapid that light-duty antioxidant increases。Increment especially for polypropylene and polyethylene product will be more considerable。But most polymers material needs to be processed at the temperature more than 200 DEG C or process, and owing to it is in being continuously subjected to high temperature and strong light environment, usual material there will be and shortens service life, and color is easily subject to destroy, the problem such as strength reduction or material surface embrittlement be full of cracks。
Range of application especially as macromolecular material is widened, modified plastics, the use of engineering plastics is in electron trade, automobile industry and aviation field play more and more important effect, along with the unprecedented bigger challenge of natural environmental condition residing for material, along with the appearance of more hitech materials, the performance of the antioxidative stabilizer on market is far from the demand meeting development market new material。Present Domestic market antioxidant kind is few, and molecular weight is little, good not with respective material matching。Especially China in this field but without autonomous patented product commercially, it is impossible to form market fair competition ability with international major company。Existing market product mostly generally is simple function antioxidant; and it is general with ester bond increase molecular weight chain length adjustment and macromolecule matching way; therefore show antioxidative stabilizer and there is migration in material; easily extract; easily hydrolysis, more weak opposing acidolysis alkali resistant solution resistant to hydrolysis antipollution environment degradable ability, it is poor so to cause material quality performance protective capability; materials'use lifetime, all can limit materials application scope etc.。
Summary of the invention
It is an object of the invention to provide a kind of low volatility; good with macromolecular material matching; polymer protection ability is strong; the materials'use life-span is long; the feature of environmental protection is good; oxidation resistance strong and at strong acid, highly basic, carboxylic acid amides stable under extensive chemical contaminated environment or aminated compounds as antioxidative stabilizer and preparation method thereof with as the application of novel high polymer material antioxidative stabilizer。
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 have a structure that
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,
N is the positive integer be 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 are preferably:
The preparation method that the present invention also provides for a kind of carboxylic acid amides or aminated compounds, comprises the following steps:
Preparation formula 1, formula 2 method
The 3 of 1.0mmol, the amine reactant of 5-tertiary butyl-4-hydroxy methyl phenylpropionate and excessive 5%-35%mmol is dissolved in the petroleum ether (1:20w/v) of 60-90 DEG C of boiling point, add catalyst (1-10%w/w), wherein, catalyst is toluenesulfonic acid, hydrochloric acid, carboxylic acid, dilute sulfuric acid, it is also possible to be Lewis acid, it is also possible to be the highly basic such as Feldalat NM。Backflow 24-96 hour under nitrogen protection。TLC follows the tracks of reaction process straight way methyl ester 100% and converts。Under agitation being cooled to 0-5 DEG C, filter the white solid produced, concentrated filtrate recrystallization obtains more solid product；
Preparation formula 3, formula 4 method
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, dinethylformamide solvent adds the p-methyl benzenesulfonic acid of 10-3% or hydrochloric acid or carboxylic acid or dilute sulfuric acid or Lewis acid as catalyst, add 4-amino-2,2,6,6-tetramethyl piperidines。Mixture heating, to backflow, follows the tracks of reaction until carboxylate converts completely。
The method of preparation formula 5
Cyanuric Chloride is dissolved in anhydrous propanone or petroleum ether or second cyanogen or ethanol or dichloromethane, is warming up to 35-75 degree under nitrogen protection, adds equivalent inorganic base or organic base, then dropping and the equimolar R-(CH of Cyanuric Chloride2)-YH, reaction keeps this temperature 3-15 hour, and TLC follows the tracks of reaction process to R-(CH2) disappearance of-YH raw material；Adding 2,6-di-t-butyl-4-OH-benzyl amine or mercaptan or alcohol in reaction system, reaction mixture continues to stir overnight at its temperature。TLC follows the tracks of reaction process, until being fully converted to three substitution reaction products。
The method of preparation formula 6
Acrylic acid methyl ester. is dissolved in petroleum ether or dichloromethane or oxolane or methyl butyl ether or acetone or ethyl acetate, adds lauryl mercaptan and N, N dimethylamine base-4-pyridine or triethylamine, and mixture is stirred at room temperature 5 hours, 40 C overnight。TLC follows the tracks of reaction process, until reacting completely。Adding aqueous hydrochloric acid solution, add ethyl acetate, wash away organic base, organic facies is washed。Dry organic facies, filters, and vacuum removes organic solvent, dry raw product, is further purified。Crude product and the N-METHYLFORMAMIDE that appropriate acrylic acid methyl ester. and lauryl mercaptan react is weighed, at N with reaction under high pressure bottle2Protective condition under, weigh appropriate metallic sodium and join in flask, add dry methanol and react, nitrogen protection, treat that metallic sodium total overall reaction is complete, reactant liquor be transferred completely in reaction under high pressure bottle。At N2Under protective condition, diethyl triamine being joined in reaction under high pressure bottle, reaction temperature oil bath outside is 80 DEG C of response time is 15-30 hour。React complete, add ethyl acetate or dichloromethane or methyl tertiary butyl ether(MTBE) recrystallization provides white solid product。
The method of preparation formula 7
Weigh appropriate Na2S joins in reaction flask, then adds ethanol or methanol or acetone or oxolane in flask, and solution becomes milky, and when dripping dilute sulfuric acid aqueous solution or diluted hydrochloric acid aqueous solution in flask, solution starts to turn yellow, and pH is transferred to 9-12 solution yellowing。Adding acrylic acid methyl ester. under ice-water bath stirring in flask, solution is become colourless by partly yellow milky, and drag has solid precipitation, and under nitrogen protection, ice-water bath is stirred reaction, and the response time is 6-18 hour, and TLC follows the tracks of reaction until completely。After reaction terminates, sucking filtration removes the solid of the inside, then add in filtrate more appropriate dichloromethane product is extracted into dichloromethane mutually in carry out separatory, removing solvent under the final vacuum that separate dichloromethane is dried mutually, to obtain colourless or lurid liquid standby。
Appropriate 18-amine. is joined in reaction flask, is subsequently adding high point petroleum ether (90-120 degree Celsius) or toluene or ethanol, p-methyl benzenesulfonic acid or hydrochloric acid or glacial acetic acid or hydrochloric acid and above-mentioned gained solution。Being placed in thermostatical oil bath and be stirred reaction, temperature is set to 125 DEG C, and logical nitrogen protection is plus condensation water knockout drum。(deadline in response time is 36-48 hour, when the reaction is finished, is cooled to the liquid in room temperature flask and all becomes solid。Stirring downhill reaction flask in add appropriate methanol, then carry out sucking filtration again, with methanol carry out washing 2-4 time, drain final vacuum heat 40 degrees Celsius dry obtain white solid。
The method of preparation formula 8
Lauryl mercaptan is joined in reaction flask; then it is dissolved in ethanol or methanol or oxolane; under ice-water bath and nitrogen protection, it is dividedly in some parts a gram NaOMe, drips 2-chloroethyl amine hydrochlorate after stirring, react after dropwising and stir 3-6 hour under ice-water bath。TLC follows the tracks of reaction until reacting completely。Remove solvent under vacuum, expect that product makes it not allow magazins' layout with other with petroleum ether dissolution。Remove solvent under the final vacuum of dry filter and obtain pale yellowish oil fluid product。
3-sulfo-cetylamine and above-mentioned product join in 50 milliliters of reaction flasks; it is subsequently adding high point petroleum ether (90-120 degree Celsius) or toluene or ethanol and p-methyl benzenesulfonic acid or hydrochloric acid or glacial acetic acid or hydrochloric acid; logical nitrogen protection is plus condensation water knockout drum; reaction is stirred reaction 36-48 hour in 120 degree of thermostatical oil baths; TLC detects reaction process; being cooled to room temperature when the reaction is finished, the liquid in flask all becomes solid。Stirring downhill reaction flask in add appropriate methanol, then carry out sucking filtration again, with methanol carry out washing 2-4 time, drain final vacuum heat 40 degrees Celsius dry obtain white solid。
The reaction equation of described preparation method is:
Described carboxylic acid amides or aminated compounds are as the application, the particularly application of novel high polymer material antioxidant of novel antioxidant。
Described carboxylic acid amides or aminated compounds application in construction material, organic electronic, plastics, rubber, paint, petroleum series product, coating or fiber。
Formula 1 is more stable with the antioxidant being connected so that increasing molecular weight by stable carboxylic acid amides or amine key in formula 2 structural formula; it is thus able to macromolecular material protective value higher; more permanent; opposing hydrolysis compared with this kind of hindered phenolic antioxidative stabilizer esters key most with on international market corresponding product even; opposing acidolysis, the ability of opposing alkaline hydrolysis and opposing chemical contamination environment degradable is higher。The n value regulating CH2 in formula 1 just can produce the fat short different antioxidant of company commander, so as to produce the sterically hindered phenol antioxidative stabilizer mated with specific high molecular chemical characters；N value in change formula two can produce the antioxidative stabilizer of high steric-hindrance amino phenol density, and its sterically hindered phenol density can be equivalent to or higher than Irganox1010 sterically hindered phenol antioxidative stabilizer,
The increase being made light stabilizer molecular weight by carboxylic acid amides or the connection of amine key of formula 3 and formula 4, have adjusted the aliphatic side chains introduced with macromolecular material matching to be connected by carboxylic acid amides or amine key, this junction fragment makes stability of molecule be greatly improved, thus the novel light stabilizer of this new class can help material to keep original performance opposing ectocine more lasting, possesses stronger chemical stability, resistant to hydrolysis, antiacid solution, the ability of anti-chemical degradation。Overcome the deficiencies in the prior art, i.e. product light stabilizer 770 on market, light stabilizer 3853 be all on market in macromolecular material widely used stable polymer material by the light-initiated free radical oxidizing process caused, the junction fragment increasing molecular weight adjustment and macromolecule matching in the structure of 770 and 3853 is carboxylate, the chemical stability of carboxylate and resistant to hydrolysis, antiacid solution, the ability of the anti-chemical degradation of alkali resistant solution is more weak。
Formula 5 connects UV absorption function base triazine parent nucleus and sterically hindered phenol thermally-stabilised function base widely by amine key and is connected in same a part。By natural with auxiliary anti-oxidant hydridization for primary antioxidant muddy become novel major-minor collaborative antioxidative stabilizer, they collect sterically hindered phenol, thioether is in one。Known triazine mother nucleus structure is that an extensive UV light absorbs mother nucleus structure, its UV Absorption scope very wide (referring to http://webbook.nist.gov/chemistry), ratio benzophenone, benzotriazole good absorbing effect。Uv absorption parent nucleus triazine appears in the antioxidative stabilizer molecule of same high molecular。This kind of multi-functional collaborative antioxidative stabilizer can adjust side chain in structure and reach the matching performance with macromolecular material, it is possible to effectively prevents from extracting phenomenon out, can give full play of the protective effect to macromolecular material。In addition the stability of these hydridization synergistic function molecules, resistant to hydrolysis, antiacid solution, alkali resistant solution, the degraded of opposing chemical contamination environment even can be effectively improved by amide and amine key stable keys。
Stablizing carboxylic acid amides key thioether high-temp antioxidizing stabilizer even in formula 6, formula 7 and formula 8 and overcome the shortcoming that corresponding carboxylic acid ester bond product (DSTDP, DSTLP etc.) even is degradable, environmental conservation and operating with, without olfaction, is brought convenience by product。Additionally, the upper two class thioether antioxidant molecules that stable keys is even are more stable, having better resistant to hydrolysis, antiacid solution, alkali resistant solution, environment resistant pollutes degradation property。Therefore they can meet more extensive material aging resistance protection demand。
The compound of the present invention all possesses stable carboxylic acid amides or amine key connects the antioxidative stabilizer agent forming different rock-steady structures; produce the length different product of aliphatic chain by regulating n value simultaneously; mate so as to intact with specific macromolecular material performance; solve little stabilizer molecule and volatilize soon in macromolecular material; the problems such as easy extraction; it is greatly prolonged the materials'use life-span, embodies the higher more lasting macromolecular material protective value of the present invention。Hydrolysis compared with prior art resisted by the stable polymer antioxidant of the present invention, resists acidolysis, and the ability of opposing alkaline hydrolysis and opposing chemical contamination environment degradable is higher, and the development that these characteristics are modern new material provides the new better antioxidant range of choice。The features such as this type of carboxylic acid amides or aminated compounds also have not volatile in addition, good with macromolecular material matching performance, and polymer protection ability is strong, and good environmental protection is attractive and durable, with low cost。
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-butyl-4-hydroxy phenylpropionic acid methyl ester and 5.0 grams to 7.76 grams (excessive) 18-amine. are dissolved in 100-280mL60-90 DEG C of petroleum ether or toluene or methanol or oxolane or glycol dimethyl ether or dimethylformamide, add 0.3-1.7 gram of p-methyl benzenesulfonic acid or hydrochloric acid or glacial acetic acid or dilute sulfuric acid。Reaction backflow 18-38 hour under nitrogen protection, TLC follows the tracks of reaction process and converts completely to methyl ester。Under stirring, cooling reaction is to 0-10 degree Celsius, filters the white solid powder produced, and dries and provides 8.07 grams of products (I), productivity 89.07%。
1HNMR (Bruker, 400MHz) is at 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, CHCl3At CDCl3In)。
Embodiment 2
1, chemical structural formula:
2, synthetic route:
3, product (II) prepare:
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-tetramethylpiperidine (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 is added under stirring nitrogen protection。Mixture is heated to reflux until reacting completely。Removing solvent under vacuum, crude product recrystallization in ethyl acetate and petroleum ether (1:3) obtains product (II) 6.58 gram, productivity 92.9%.
1HNMR (Bruker, 400MHz) is at 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 (CHCl3At CDCl3In)。
Embodiment 3
1, chemical structural formula:
2, synthetic route:
3, the preparation of intermediate (III):
Cyanuric Chloride (5 grams; 27.11 mM) it is dissolved in anhydrous propanone or second cyanogen or oxolane or ethanol or methanol (30 milliliters); 28.47 mMs of sodium carbonate or potassium carbonate or triethylamine or diisopropyl ethyl amine is added under nitrogen protection; then at 50 c; dropping 2 in 20 milliliters of anhydrous propanones or second cyanogen or oxolane or ethanol or methanol; 6-di-t-butyl-4-hydroxyl Bian mercaptan (6.84 grams, 27.11 mMs)。Reactant mixture stirs 5 hours at 50 degrees Celsius, is warming up to 65 degree and stirs 3 hours；
4, the preparation of product (III)
Temperature is down to 50 degrees Celsius, dropping lauryl amine (5.03 grams, 27.11 mMs) in 10 milliliters of above-mentioned intermediate (III), dropwises reaction 65 C overnight。Being down to room temperature, cross elimination solid, wash with solvent and be bonded on solid product, filtrate concentrates under vacuum, and crude product obtains expection product (III), productivity 87.2% at dichloromethane petroleum ether mixed solvent (1:2) inner recrystallization。
1HNMR (Bruker, 400MHz) is at 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 (CHCl3At CDCl3In)。
Embodiment 4
1, chemical structural formula:
2, synthetic route:
3, intermediate (IV) prepare:
Acrylic acid methyl ester. (3 grams, 34.85 mM) it is dissolved in 10-25 milliliter petroleum ether or dichloromethane or oxolane or methyl butyl ether or acetone or ethyl acetate, addition lauryl mercaptan (gram, 34.85 mM) and 2-10%N, N dimethylamine base-4-pyridine or triethylamine, mixture is stirred at room temperature 5 hours, 40 C overnight。TLC follows the tracks of reaction process, until reacting completely。Adding 0.1N aqueous hydrochloric acid solution 20 milliliters, add ethyl acetate 20 milliliters, wash away organic base, organic facies is washed。Dry organic facies, filters, and vacuum removes organic solvent, dry raw product, is further purified and treats that lower step uses。
4, the preparation of product (IV)
First the N-METHYLFORMAMIDE of crude product that the acrylic acid methyl ester. of 50.0g (173.37 mMs) and lauryl mercaptan react and 21.64g is weighed with the reaction under high pressure bottle of 350ml. at N2Protective condition under, weigh in the flask that the metallic sodium of 4.78 grams (207.82 mMs) joins 500ML, add the dry methanol reaction of 60ML, nitrogen protection, treat that metallic sodium total overall reaction is complete, reactant liquor is transferred completely in reaction under high pressure bottle。At N2Under protective condition, joining in reaction under high pressure bottle by 5.9g (56.89 mMs) diethyl triamine, reaction temperature oil bath outside is 80 DEG C of response time is 15-30 hour。React complete, add ethyl acetate or dichloromethane or methyl tertiary butyl ether(MTBE) recrystallization provides white solid product (IV) 42.85 gram, productivity 86.3%。
1HNMR (Bruker, 400MHz) is at 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 at CD3In OD), 4.87 (H2O is at CD3In OD)。
Embodiment 5
1, chemical structural formula:
2, synthetic route:
3. the synthesis of intermediate V
Weigh 71.82gNa2S.9H2O (0.2990 mole) joins in the reaction flask of 500ml, then in flask, add the ethanol of 40ml-100 milliliter or methanol or acetone or oxolane, solution becomes milky, when the dilute sulfuric acid aqueous solution or the diluted hydrochloric acid aqueous solution that drip 1mol/L in flask, solution starts to turn yellow, and pH is transferred to 9-12 solution yellowing。In flask, the acrylic acid methyl ester. (0.5808 mole) of 50g is added under ice-water bath stirring; solution is become colourless by half yellow milky, and drag has solid precipitation, and under nitrogen protection, ice-water bath is stirred reaction; in about 6-18 hour response time, TLC follows the tracks of reaction until completely。After reaction terminates, sucking filtration removes the solid of the inside, then add in filtrate more appropriate dichloromethane product is extracted into dichloromethane mutually in carry out separatory, remove solvent under the final vacuum that separate dichloromethane is dried mutually and obtain colourless or lurid liquid and be product, productivity 79-95%。
4. the preparation method of target product V
26.16g the 18-amine. of (0.1411 mole) joins in 250 milliliters of reaction flasks, it is subsequently adding the high point petroleum ether (90-120 degree Celsius) of 100ml or the intermediate product V of toluene or ethanol, the p-methyl benzenesulfonic acid of 1-10% (mol ratio) or hydrochloric acid or glacial acetic acid or hydrochloric acid and 10g (0.04848 mole)。Being placed in thermostatical oil bath and be stirred reaction, temperature is set to 125 DEG C, and logical nitrogen protection is plus condensation water knockout drum。(about 36-48 hour deadline in response time, along with the solid raised in reaction bulb of temperature is dissolved into liquid, when the reaction is finished, was cooled to the liquid in room temperature flask and all becomes solid。Stirring downhill reaction flask in add appropriate methanol, then carry out sucking filtration again, with methanol carry out washing 2-4 time, drain final vacuum heat 40 degrees Celsius dry obtain white solid, productivity 86-97%。1HNMR (Bruker, 400MHz) is at CDCl3In, chemical shift δ (ppm): 0.0 (s, interior mark 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 (CHCl3inCDCl3In)。
Embodiment 6
1, chemical structural formula:
2, synthetic route:
3, prepared by intermediate (VI):
10 grams of lauryl mercaptans (0.0531 mole) are joined in the reaction flask of 100ml; then the ethanol of 40ml-100 milliliter or methanol or oxolane it are dissolved in; 6.1 grams of NaOMe (0.1122 mole) it are dividedly in some parts under ice-water bath and nitrogen protection; drip 2-chloroethyl amine hydrochlorate after stirring 10 minutes, react after dropwising and stir 3-6 hour under ice-water bath。TLC follows the tracks of reaction until reacting completely。Remove solvent under vacuum, expect that product makes it not allow magazins' layout with other with petroleum ether dissolution。Remove solvent under the final vacuum of dry filter and obtain pale yellowish oil fluid product, productivity 85-96%。
4. the preparation method of target product VI
5 grams of 3-sulfo-cetylamines (0.0203 mole) and intermediate V join in 50 milliliters of reaction flasks, are subsequently adding the high point petroleum ether (90-120 degree Celsius) of 20-30ml or the p-methyl benzenesulfonic acid of toluene or ethanol and 1-10% (mol ratio) or hydrochloric acid or glacial acetic acid or hydrochloric acid。, logical nitrogen protection is plus condensation water knockout drum, and reaction is stirred reaction 36-48 hour in 120 degree of thermostatical oil baths, and TLC detects reaction process, is cooled to room temperature when the reaction is finished, and the liquid in flask all becomes solid。Stirring downhill reaction flask in add appropriate methanol, then carry out sucking filtration again, with methanol carry out washing 2-4 time, drain final vacuum heat 40 degrees Celsius dry obtain white solid, productivity 86-97%。
1HNMR (Bruker, 400MHz) is at CDCl3In, chemical shift δ (ppm): 0.0 (s, interior mark 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 (CHCl3inCDCl3In), 8.02 (bm, NH).
Above example is only in order to illustrate technical scheme and unrestricted, other amendments that technical scheme is made by those of ordinary skill in the art or equivalent replace, without departing from the spirit and scope of technical solution of the present invention, all should be encompassed in scope of the presently claimed invention。

Claims (7)

1. a carboxylic acid amides or aminated compounds, it is characterised in that have a structure that
Wherein X is CH2, S, O, 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,
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。
2. carboxylic acid amides as claimed in claim 1 a kind of or aminated compounds, it is characterised in that described carboxylic acid amides or aminated compounds be:
3. the preparation method of a carboxylic acid amides or aminated compounds, it is characterised in that comprise the following steps:
3,5-tertiary butyl-4-hydroxy methyl phenylpropionates and excessive amine reactant are dissolved in the petroleum ether of 60-90 DEG C of boiling point, add catalyst, under nitrogen protection backflow 24-96 hour。TLC follows the tracks of reaction process straight way methyl ester 100% and converts。Under agitation being cooled to 0-5 DEG C, filter the white solid produced, concentrated filtrate recrystallization obtains more solid product；
Or
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, dinethylformamide solvent adds p-methyl benzenesulfonic acid or hydrochloric acid or carboxylic acid or dilute sulfuric acid or Lewis acid as catalyst, add 4-amino-2,2,6,6-tetramethyl piperidine, heating, to backflow, follows the tracks of reaction until carboxylate converts completely；
Or
Cyanuric Chloride is dissolved in anhydrous propanone or petroleum ether or second cyanogen or ethanol or dichloromethane, is warming up to 35-75 degree under nitrogen protection, adds equivalent inorganic base or organic base, then dropping and the equimolar R-(CH of Cyanuric Chloride2)-YH, reaction keeps this temperature 3-15 hour, and TLC follows the tracks of reaction process to R-(CH2) disappearance of-YH raw material, in reaction system, adding 2,6-di-t-butyl-4-OH-benzyl amine or mercaptan or alcohol, reaction mixture continues to stir overnight at its temperature, and TLC follows the tracks of reaction process, until being fully converted to three substitution reaction products；
Or
Acrylic acid methyl ester. is dissolved in petroleum ether or dichloromethane or oxolane or methyl butyl ether or acetone or ethyl acetate, add lauryl mercaptan and N, N dimethylamine base-4-pyridine or triethylamine, mixture is stirred at room temperature 5 hours, 40 C overnight, and TLC tracks to after reacting completely, add aqueous hydrochloric acid solution, adding ethyl acetate, wash away organic base, organic facies is washed。Dry organic facies, filters, and vacuum removes organic solvent, dry raw product, is further purified。Crude product and the N-METHYLFORMAMIDE that appropriate acrylic acid methyl ester. and lauryl mercaptan react is weighed, at N with reaction under high pressure bottle2Protective condition under, weigh appropriate metallic sodium and join in flask, add dry methanol and react, treat that metallic sodium total overall reaction is complete, reactant liquor is transferred completely in reaction under high pressure bottle, then at N2Under protective condition, diethyl triamine being joined in reaction under high pressure bottle, reaction temperature oil bath outside is 80 DEG C of response time is 15-30 hour, adds ethyl acetate or dichloromethane after completion of the reaction or methyl tertiary butyl ether(MTBE) recrystallization provides white solid product；
Or
Weigh appropriate Na2S joins in reaction flask, then adds ethanol or methanol or acetone or oxolane in flask, becomes milky to solution, drips dilute sulfuric acid aqueous solution or diluted hydrochloric acid aqueous solution in flask, and pH is transferred to 9-12 solution yellowing；In flask, acrylic acid methyl ester. is added under ice-water bath stirring; under nitrogen protection, ice-water bath is stirred reaction; response time is 6-18 hour; sucking filtration removes the solid of the inside; add in filtrate appropriate dichloromethane product is extracted into dichloromethane mutually in carry out separatory; removing solvent under the final vacuum that separate dichloromethane is dried mutually, to obtain colourless or lurid liquid standby
Appropriate 18-amine. is joined in reaction flask, is subsequently adding high point petroleum ether (90-120 degree Celsius) or toluene or ethanol, p-methyl benzenesulfonic acid or hydrochloric acid or glacial acetic acid or hydrochloric acid and above-mentioned gained solution。Being placed in thermostatical oil bath and be stirred reaction, temperature is set to 125 DEG C, and logical nitrogen protection is plus condensation water knockout drum。(deadline in response time is 36-48 hour, when the reaction is finished, is cooled to the liquid in room temperature flask and all becomes solid。Stirring downhill reaction flask in add appropriate methanol, then carry out sucking filtration again, with methanol carry out washing 2-4 time, drain final vacuum heat 40 degrees Celsius dry obtain white solid；
Or
Lauryl mercaptan is joined in reaction flask; then it is dissolved in ethanol or methanol or oxolane; under ice-water bath and nitrogen protection, it is dividedly in some parts a gram NaOMe, drips 2-chloroethyl amine hydrochlorate after stirring, react after dropwising and stir 3-6 hour under ice-water bath。TLC follows the tracks of reaction until reacting completely。Remove solvent under vacuum, expect that product makes it not allow magazins' layout with other with petroleum ether dissolution。Remove solvent under the final vacuum of dry filter and obtain pale yellowish oil fluid product,
3-sulfo-cetylamine and above-mentioned product join in 50 milliliters of reaction flasks, it is subsequently adding high point petroleum ether (90-120 degree Celsius) or toluene or ethanol and p-methyl benzenesulfonic acid or hydrochloric acid or glacial acetic acid or hydrochloric acid, logical nitrogen protection is plus condensation water knockout drum, reaction is stirred reaction 36-48 hour in 120 degree of thermostatical oil baths, TLC detects reaction process, reaction is cooled to room temperature when terminating, after liquid all becomes solid, under agitation add appropriate methanol, carry out sucking filtration again, washing 2-4 time is carried out with methanol, drain final vacuum to heat 40 degrees Celsius and dry obtain white solid。
4. the preparation method of a kind of carboxylic acid amides as claimed in claim 3 or aminated compounds, it is characterised in that: the reaction equation of described preparation method is:
X:S, NH, NR1, O
Y:Y=X, Y are not equal to X, S, NH, NR1, O
R:
n:5,6,7,8,9,10,11,12,13,14,15,16,17,18...
Or
5. a carboxylic acid amides as claimed in claim 1 or aminated compounds are as the application of antioxidant。
6. a carboxylic acid amides as claimed in claim 1 or aminated compounds are as the application of macromolecular material novel antioxidant。
7. carboxylic acid amides as claimed in claim 5 or aminated compounds application in construction material, organic electronic, plastics, rubber, paint, petroleum series product, coating or fiber。
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