CN103694174B - Alpha- (N-benzyl) amino-caprolactam compound and preparation method and application thereof - Google Patents

Alpha- (N-benzyl) amino-caprolactam compound and preparation method and application thereof Download PDF

Info

Publication number
CN103694174B
CN103694174B CN201410004971.3A CN201410004971A CN103694174B CN 103694174 B CN103694174 B CN 103694174B CN 201410004971 A CN201410004971 A CN 201410004971A CN 103694174 B CN103694174 B CN 103694174B
Authority
CN
China
Prior art keywords
amino
benzyl
caprolactam
preparation
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201410004971.3A
Other languages
Chinese (zh)
Other versions
CN103694174A (en
Inventor
郭凯
方正
李小林
曾文波
欧阳平凯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Tech University
Original Assignee
Nanjing Tech University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Tech University filed Critical Nanjing Tech University
Priority to CN201410004971.3A priority Critical patent/CN103694174B/en
Publication of CN103694174A publication Critical patent/CN103694174A/en
Application granted granted Critical
Publication of CN103694174B publication Critical patent/CN103694174B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
    • C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings 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
    • C07D223/12—Nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyamides (AREA)

Abstract

An alpha- (N-benzyl) amino-caprolactam compound represented by the following general formula I, wherein R1～R5Are respectively and independently any one of H, alkane, phenyl, halogen, hydroxyl, N-substituted amino, nitro and alkoxy, and R1～R5Not both can be H. The invention also discloses a preparation method and application of the compound. The compounds of the invention can be used for the preparation of polyamides.

Description

α-(N-benzyl) amino-e-caprolactam compounds and preparation method thereof and application
Technical field
The invention belongs to technical field of organic synthesis, be specifically related to α-(N-benzyl) amino-e-caprolactam compounds and its preparation method and application.
Background technology
Polymeric amide is commonly called as nylon (Nylon), English name Polyamide (be called for short PA) be on molecular backbone chain containing recurring amide radical group-NHCO-thermoplastic resin general name.Mainly comprise: fatty polyamide, fat-aromatic polyamide and aromatic polyamide, in five large-engineering plastics, its consumption is maximum, kind is maximum, qualification is the oldest.The specific tenacity of nylon is higher than metal, satisfactory mechanical property, there is good thermotolerance, wearability, flame retardant resistance, endurance and self lubricity, frictional coefficient is low, high comprehensive performance, handling ease, suitable with glass fibre etc. material fill, enhancing modified, be widely used in the aspects such as automobile, electronic apparatus, packaging, machinery, Sport & Casual and daily necessities.
The Carothers of du pont company in 1931 has invented nylon, and before 20 century 70s, the development of nylon is mainly to develop new product, as nylon66 fiber, NYLON610, nylon 6, nylon 11, nylon 12, nylon 46s etc., also have nylon 1010 in addition, nylon 4, nylon 8, nylon 9, MC nylon, polyaramide and various modification by copolymerization nylon etc.After 20 century 70s, mainly nylon material study on the modification and synthesize some long carbon chain nylons and aromatic nylon, modification is carried out by carrying out the methods such as blended, copolymerization, grafting, filling to simple nylon material, improve the over-all properties of nylon, its a certain property outstanding, the constantly Application Areas of expansion nylon material.In nylon material, the consumption of nylon 6 and nylon66 fiber is maximum, accounts for 90% of polymeric amide aggregate consumption.The maximum consumption market of nylon 6 is automotive fields, exceedes 1/3 of aggregate consumption.The parts that automobile can use nylon 6 and modified product thereof make to have in air filter, fan, wheelhouse portions, flow deflector, upholstery part, water storage equipment lid, car various electric connectors etc.; Packaging film is also a large Application Areas of nylon 6, and nylon 6 film barrier is good, OTR oxygen transmission rate is low, transparency is high, and oil resistant, high temperature resistant, resistance to boiling, anti-puncture performance are strong.Nylon66 fiber is also mainly used in automotive industry, is widely used in the production of the parts such as scatterer, engine; Nylon 12 and nylon 11, because water-absorbent is low, adhesive property is good, are used for the production of automotive hose and hot melt adhesive.
Current, the mankind more and more pay close attention to environment, wish to reduce the dependency to oil simultaneously, and the exploitation of green, environmental protection, economic nylon monomer, has become an important directions of nylon exploitation.Based on this, the natural resources of chemical research directional steering reproducible utilization has been carried out the development research of related products by people.At present the domestic and international Study and appliance exploitation preparing nylon at bio-based nylon monomer also obtains some successful precedents, in succession occur PA610, the bio-based engineering resins such as PA1010 and PA1012.According to patent US7977450B2 and WO2005/123669A1, alpha-amino group-ε-caprolactam is directly prepared by biofermentation products Methionin, and aminocaproic lactam can be sloughed alpha-amino group and obtain nylon 6 monomer hexanolactam.Utilize the aminocaproic lactam derivative of band rigid annular side chain to prepare nylon as monomer, not yet find that there is research and development successfully report.
As the monomer preparing nylon 6, the average annual consumption of caprolactam monomer is increasing.Caprolactam derivatives with branched group has certain potentiality on modified function polymeric amide.In addition, side chain is introduced intensity and thermotolerance that annular rigid structure can improve synthetic materials.
Summary of the invention
Technical problem to be solved by this invention is to provide a series of α-(N-benzyl) amino-e-caprolactam compounds, by alpha-amino group-ε-caprolactam and compound of benzaldehyde category, by the benzyl structure that amination reduction reaction introducing phenyl ring is substituted, prepare a series of caprolactam derivatives.
The technical problem that the present invention also will solve is to provide the preparation technology of above-mentioned α-(N-benzyl) amino-e-caprolactam compounds.
The technical problem that the present invention finally will solve is to provide the application of above-mentioned α-(N-benzyl) amino-e-caprolactam compounds.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of α-(N-benzyl) amino-e-caprolactam compounds represented by following formula I:
Wherein, R 1~ R 5be independently any one in H, alkane, phenyl, halogen, hydroxyl, N-substituted-amino, nitro and alkoxyl group, and R 1~ R 5can not be H simultaneously.
Preferably, α of the present invention-(N-benzyl) amino-e-caprolactam compounds (I) structural formula is as following table:
The preparation method of above-mentioned α-(N-benzyl) amino-e-caprolactam compounds, the method comprises the steps:
(1) alpha-amino group-ε-caprolactam hydrochloride II first reacts with compound of benzaldehyde category III in the basic conditions;
(2) reaction solution of step (1) is under cold condition, adds reductive agent, is obtained by reacting α-(N-benzyl) amino-e-caprolactam compounds I.
Wherein, R 1~ R 5be independently any one in H, alkane, phenyl, halogen, hydroxyl, N-substituted-amino, nitro and alkoxyl group, and R 1~ R 5can not be H simultaneously.
In step (1), described alkaline condition is for using and compound ii equimolar KOH, NaOH, K 2cO 3or Na 2cO 3.
In step (1), compound ii and compound (III) molar ratio are 1:1 ~ 2.5.
In step (1), reaction solvent is methyl alcohol or ethanol.
In step (1), temperature of reaction controls at 10 ~ 30 DEG C, and the reaction times is 0.5 ~ 4 hour.
In step (2), described reductive agent is NaBH 4or NaBH 3cN; The mol ratio of reductive agent charging capacity and compound ii is 1 ~ 2:1.
In step (2), described cold condition is-10 ~ 5 DEG C.
In step (2), the reaction times is 0.5 ~ 8 hour.
Above-mentioned α-(N-benzyl) amino-e-caprolactam compounds is preparing the application in polymeric amide.
Beneficial effect: the α that the present invention obtains for Material synthesis with lysine derivative alpha-amino group-ε-caprolactam-(N-benzyl) amino-e-caprolactam compounds, has the agent structure of hexanolactam ring, ring-opening polymerization can prepare polymeric amide.In addition, introduce at this compounds side chain intensity and the thermotolerance that annular rigid structure can improve synthetic materials.
Embodiment
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, the content described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
Embodiment 1: α-(N-(2-hydroxyphenylmethyl)) preparation of amino-e-caprolactam.
Alpha-amino group-ε-caprolactam hydrochloride 16.5g (0.1mol), sodium carbonate 10.6g(0.1mol will be added in the there-necked flask of 1L) and methyl alcohol 500ml, stirring and dissolving.Under room temperature condition, add Benzaldehyde,2-hydroxy 18.3g (0.15mol), continue stirring reaction 1 hour.Under reaction solution transfers to 0 DEG C of condition, add borane reducing agent sodium hydride 4.54g(0.12mol), react 1 hour.Reacted with the method for underpressure distillation removing methyl alcohol, added 500ml methylene dichloride and dissolve, with 100ml distilled water wash 3 times, once, anhydrous sodium sulfate drying, filters, and collects filtrate in saturated common salt water washing, and underpressure distillation removing methylene dichloride obtains crude product.Crude product Diethyl ether recrystallization, obtains α-(N-(2-hydroxyphenylmethyl)) amino-e-caprolactam 18.5g, productive rate 79%.ESI-MS m/z:(M+H)=235.1434。 1H NMR(CDCl 3):δ(ppm)=1.34-1.99(m,6H),3.14-3.34(m,3H),3.94(dd,J 1=111.9Hz,J 2=8.1Hz,2H),6.46(s,1H),6.75-7.26(m,4H)； 13CNMR(CDCl 3):δ(ppm)=28.05,28.75,31.97,41.80,51.46,59.07,116.41,118.95,122.57,128.60,128.70,158.12,177.01。
Embodiment 2: α-(N-(2-chlorophenylmethyl)) preparation of amino-e-caprolactam.
Alpha-amino group-ε-caprolactam hydrochloride 16.5g (0.1mol), sodium carbonate 10.6g(0.1mol will be added in the there-necked flask of 1L) and methyl alcohol 500ml, stirring and dissolving.Under 30 DEG C of conditions, add 2-chlorobenzaldehyde 16.9g (0.12mol), continue stirring reaction 0.5 hour.Under reaction solution transfers to 5 DEG C of conditions, add borane reducing agent sodium hydride 3.78g(0.10mol), react 4 hours.Reacted with the method for underpressure distillation removing methyl alcohol, added 500ml methylene dichloride and dissolve, with 100ml distilled water wash 3 times, once, anhydrous sodium sulfate drying, filters, and collects filtrate in saturated common salt water washing, and underpressure distillation removing methylene dichloride obtains crude product.Crude product Diethyl ether recrystallization, obtains α-(N-(2-chlorophenylmethyl)) amino-e-caprolactam 16.18g, productive rate 64.2%.ESI-MS m/z:(M+H)=253.1109。 1H NMR(CDCl 3):δ(ppm)=1.53-2.16(m,6H),2.48(br,1H),3.14-3.33(m,3H),3.90(dd,J 1=44.7Hz,J 2=8.4Hz,2H),6.40(s,1H),7.16-7.47(m,4H)； 13CNMR(CDCl 3):δ(ppm)=28.07,29.09,31.86,41.96,49.28,59.93,126.75,128.02,129.30,129.73,133.70,137.87,178.15。
Embodiment 3: α-(N-(3-methylbenzyl)) preparation of amino-e-caprolactam.
Alpha-amino group-ε-caprolactam hydrochloride 16.5g (0.1mol), sodium hydroxide 4.0g(0.1mol will be added in the there-necked flask of 1L) and methyl alcohol 500ml, stirring and dissolving.Under 30 DEG C of conditions, add 3-tolyl aldehyde 21.6g (0.18mol), continue stirring reaction 4 hours.Under reaction solution transfers to-5 DEG C of conditions, add reductive agent sodium cyanoborohydride 7.54g(0.12mol), react 8 hours.Reacted with the method for underpressure distillation removing methyl alcohol, added 500ml methylene dichloride and dissolve, with 100ml distilled water wash 3 times, once, anhydrous sodium sulfate drying, filters, and collects filtrate in saturated common salt water washing, and underpressure distillation removing methylene dichloride obtains crude product.Crude product Diethyl ether recrystallization, obtains α-(N-(3-methylbenzyl)) amino-e-caprolactam 15.47g, productive rate 66.7%.ESI-MS m/z:(M+H)=233.1659。 1H NMR(CDCl 3):δ(ppm)=1.25-1.99(m,6H),2.17(s,3H),2.34(s,1H),3.20-3.33(m,3H),3.75(dd,J 1=45.6Hz,J 2=7.8Hz,2H),5.79(s,1H),7.04-7.26(m,4H)； 13CNMR(CDCl 3):δ(ppm)=21.62,27.79,28.88,31.63,41.68,51.67,59.44,124.91,127.36,128.40,129.82,136.31,138.22,178.15。
Embodiment 4: α-(N-(4-Brombenzyl)) preparation of amino-e-caprolactam.
Alpha-amino group-ε-caprolactam hydrochloride 16.5g (0.1mol), sodium carbonate 10.6g(0.1mol will be added in the there-necked flask of 1L) and methyl alcohol 500ml, stirring and dissolving.Under 10 DEG C of conditions, add 4-bromobenzaldehyde 27.8g (0.15mol), continue stirring reaction 2.5 hours.Under reaction solution transfers to-4 DEG C of conditions, add reductive agent sodium cyanoborohydride 11.31g(0.18mol), react 4 hours.Reacted with the method for underpressure distillation removing methyl alcohol, added 500ml methylene dichloride and dissolve, with 100ml distilled water wash 3 times, once, anhydrous sodium sulfate drying, filters, and collects filtrate in saturated common salt water washing, and underpressure distillation removing methylene dichloride obtains crude product.Crude product Diethyl ether recrystallization, obtains α-(N-(4-Brombenzyl)) amino-e-caprolactam 22.35g, productive rate 75.5%.ESI-MS m/z:(M+H)=297.0591。 1H NMR(CDCl 3):δ(ppm)=1.43-1.99(m,6H),2.35(br,1H),3.13-3.48(m,3H),3.73(dd,J 1=52.5Hz,J 2=8.1Hz,2H),6.34(s,1H),7.22-7.47(m,4H)； 13CNMR(CDCl 3):δ(ppm)=28.03,29.01,31.95,41.91,51.56,59.74,120.56,129.85,131.34,139.39,178.15。
Embodiment 5: α-(N-(4-methylbenzyl)) preparation of amino-e-caprolactam.
Alpha-amino group-ε-caprolactam hydrochloride 16.5g (0.1mol), salt of wormwood 13.8g(0.1mol will be added in the there-necked flask of 1L) and ethanol 500ml, stirring and dissolving.Under 20 DEG C of conditions, add 4-tolyl aldehyde 12.0g (0.10mol), continue stirring reaction 4 hours.Under reaction solution transfers to 0 DEG C of condition, add borane reducing agent sodium hydride 7.57g(0.20mol), react 3 hours.Reacted with the method for underpressure distillation removing ethanol, added 500ml methylene dichloride and dissolve, with 100ml distilled water wash 3 times, once, anhydrous sodium sulfate drying, filters, and collects filtrate in saturated common salt water washing, and underpressure distillation removing methylene dichloride obtains crude product.Crude product Diethyl ether recrystallization, obtains α-(N-(4-methylbenzyl)) amino-e-caprolactam 13.02g, productive rate 56.1%.ESI-MS m/z:(M+H)=233.1659。 1H NMR(CDCl 3):δ(ppm)=1.39-1.98(m,6H),2.32(s,3H),2.37(s,1H),3.15-3.31(m,3H),3.74(dd,J 1=39.9Hz,J 2=7.8Hz,2H),6.42(s,1H),7.17(dd,J 1=34.5Hz,J 2=4.8Hz,4H)； 13CNMR(CDCl 3):δ(ppm)=20.81,27.79,28.88,31.63,41.68,51.67,59.44,127.91,128.76,136.10,137.02,178.15。
Embodiment 6: α-(N-(4-benzyl)) preparation of amino-e-caprolactam.
Alpha-amino group-ε-caprolactam hydrochloride 16.5g (0.1mol), sodium carbonate 10.6g(0.1mol will be added in the there-necked flask of 1L) and methyl alcohol 500ml, stirring and dissolving.Under 18 DEG C of conditions, add 4-fluorobenzaldehyde 24.8g (0.20mol), continue stirring reaction 2.5 hours.Under reaction solution transfers to-10 DEG C of conditions, add borane reducing agent sodium hydride 5.67g(0.15mol), react 8 hours.Reacted with the method for underpressure distillation removing methyl alcohol, added 500ml methylene dichloride and dissolve, with 100ml distilled water wash 3 times, once, anhydrous sodium sulfate drying, filters, and collects filtrate in saturated common salt water washing, and underpressure distillation removing methylene dichloride obtains crude product.Crude product Diethyl ether recrystallization, obtains α-(N-(4-benzyl)) amino-e-caprolactam 16.80g, productive rate 71.2%.ESI-MS m/z:(M+H)=237.1388。 1H NMR(CDCl 3):δ(ppm)=1.52-2.00(m,6H),2.35(br,1H),3.14-3.29(m,3H),3.74(dd,J 1=49.2Hz,J 2=7.8Hz,2H),6.27(s,1H),6.97-7.33(m,4H)； 13CNMR(CDCl 3):δ(ppm)=27.83,28.84,31.74,41.72,51.33,59.54,114.82,129.46,135.83,162.63,177.97。
Embodiment 7: α-(N-(4-dimethylamino phenmethyl)) preparation of amino-e-caprolactam.
Alpha-amino group-ε-caprolactam hydrochloride 16.5g (0.1mol), sodium hydroxide 4.0g(0.1mol will be added in the there-necked flask of 1L) and methyl alcohol 500ml, stirring and dissolving.Under room temperature condition, add 4-dimethylaminobenzaldehyde 20.9g (0.14mol), continue stirring reaction 4 hours.Under reaction solution transfers to 0 DEG C of condition, add borane reducing agent sodium hydride 4.54g(0.12mol), react 6 hours.Reacted with the method for underpressure distillation removing methyl alcohol, added 500ml methylene dichloride and dissolve, with 100ml distilled water wash 3 times, once, anhydrous sodium sulfate drying, filters, and collects filtrate in saturated common salt water washing, and underpressure distillation removing methylene dichloride obtains crude product.Crude product Diethyl ether recrystallization, obtains α-(N-(4-dimethylamino phenmethyl)) amino-e-caprolactam 15.35g, productive rate 58.8%.ESI-MS m/z:(M+H)=262.1919。 1H NMR(CDCl 3):δ(ppm)=1.37-1.97(m,6H),2.25(br,1H),2.92(s,6H),3.16-3.32(m,3H),3.69(dd,J 1=33.3Hz,J 2=7.5Hz,2H),6.13(s,1H),7.70-7.26(m,4H)； 13CNMR(CDCl 3):δ(ppm)=27.98,29.17,31.80,40.77,41.95,51.61,59.47,112.77,128.36,129.15,149.81,178.42。
Embodiment 8: α-(N-(2,5-dihydroxy-benzene methyl)) preparation of amino-e-caprolactam.
Alpha-amino group-ε-caprolactam hydrochloride 16.5g (0.1mol), potassium hydroxide 5.6g(0.1mol will be added in the there-necked flask of 1L) and ethanol 500ml, stirring and dissolving.Under 10 DEG C of conditions, add 2,5-Dihydroxy benzaldehyde 34.5g (0.25mol), continue stirring reaction 0.5 hour.Under reaction solution transfers to-5 DEG C of conditions, add borane reducing agent sodium hydride 4.54g(0.12mol), react 4 hours.Reacted with the method for underpressure distillation removing ethanol, added 500ml methylene dichloride and dissolve, with 100ml distilled water wash 3 times, once, anhydrous sodium sulfate drying, filters, and collects filtrate in saturated common salt water washing, and underpressure distillation removing methylene dichloride obtains crude product.Crude product Diethyl ether recrystallization, obtains α-(N-(2,5-dihydroxy-benzene methyl)) amino-e-caprolactam 17.02g, productive rate 68.0%.ESI-MS m/z:(M+H)=251.1387。 1H NMR(CDCl 3):δ(ppm)=1.34-1.99(m,6H),3.14-3.34(m,3H),3.94(dd,J 1=111.9Hz,J 2=8.1Hz,2H),6.46(s,1H),6.75-7.26(m,3H)； 13CNMR(CDCl 3):δ(ppm)=28.05,28.75,31.97,41.80,51.46,59.07,116.41,118.95,122.57,128.60,128.70,158.12,177.01。
The synthesis of embodiment 9 ~ 18:I-9 ~ 18
I-9 ~ 18 obtain with reference to embodiment 1 method.Mass spectrum, nmr analysis result conform to structural formula of compound.
Embodiment 19: α-(N-benzyl) amino-e-caprolactam compounds of above-described embodiment 1 ~ 18 gained prepares the performance test of polymeric amide.
The present invention adopts industrial the most frequently used normal pressure continuous polymerization to prepare polymeric amide, and method is as follows:
The production technique that normal pressure is turbid continuously mainly contains the operations such as melting, polymerization, Cast Strip section, water hot extraction, drying.First make α-(N-benzyl) amino-e-caprolactam compounds melting in fusion boiler of crystallization, and mix with water and auxiliary agent etc., deliver to after preheating and be heated in the polymerization under atmospheric pressure tower of 260 DEG C.In polymerization tower, α-(N-benzyl) amino-e-caprolactam compounds is polymerized about 10h and reaches equilibrium state, then, with toothed gear pump, the polymkeric substance of melting is got at the bottom of pipe, after Cast Strip, section, with water hot extraction to remove low-molecular weight polymer, finally under vacuum or rare gas element, dry at about 100 DEG C, obtain polyamide product.
Table 1
Concrete data are in table 1.

Claims (10)

1. α-(N-benzyl) amino-e-caprolactam compounds:
Described α-(N-benzyl) amino-e-caprolactam compounds (I) structural formula is as following table:
2. the preparation method of α according to claim 1-(N-benzyl) amino-e-caprolactam compounds, it is characterized in that, the method comprises the steps:
(1) alpha-amino group-ε-caprolactam hydrochloride II first reacts with compound of benzaldehyde category III in the basic conditions;
(2) reaction solution of step (1) is under cold condition, adds reductive agent, is obtained by reacting α-(N-benzyl) amino-e-caprolactam compounds I.
3. the preparation method of α according to claim 2-(N-benzyl) amino-e-caprolactam compounds, is characterized in that, in step (1), described alkaline condition is for using and compound ii equimolar KOH, NaOH, K 2cO 3or Na 2cO 3.
4. the preparation method of α according to claim 2-(N-benzyl) amino-e-caprolactam compounds, is characterized in that, in step (1), compound ii and compound (III) molar ratio are 1:1 ~ 2.5.
5. the preparation method of α according to claim 2-(N-benzyl) amino-e-caprolactam compounds, is characterized in that, in step (1), reaction solvent is methyl alcohol or ethanol.
6. the preparation method of α according to claim 2-(N-benzyl) amino-e-caprolactam compounds, is characterized in that, in step (1), temperature of reaction controls at 10 ~ 30 DEG C, and the reaction times is 0.5 ~ 4 hour.
7. the preparation method of α according to claim 2-(N-benzyl) amino-e-caprolactam compounds, is characterized in that, in step (2), described reductive agent is NaBH 4or NaBH 3cN; The mol ratio of reductive agent charging capacity and compound ii is 1 ~ 2:1.
8. the preparation method of α according to claim 2-(N-benzyl) amino-e-caprolactam compounds, is characterized in that, in step (2), described cold condition is-10 ~ 5 DEG C.
9. the preparation method of α according to claim 2-(N-benzyl) amino-e-caprolactam compounds, is characterized in that, in step (2), the reaction times is 0.5 ~ 8 hour.
10. α according to claim 1-(N-benzyl) amino-e-caprolactam compounds is preparing the application in polymeric amide.
CN201410004971.3A 2014-01-06 2014-01-06 Alpha- (N-benzyl) amino-caprolactam compound and preparation method and application thereof Active CN103694174B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410004971.3A CN103694174B (en) 2014-01-06 2014-01-06 Alpha- (N-benzyl) amino-caprolactam compound and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410004971.3A CN103694174B (en) 2014-01-06 2014-01-06 Alpha- (N-benzyl) amino-caprolactam compound and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN103694174A CN103694174A (en) 2014-04-02
CN103694174B true CN103694174B (en) 2015-09-02

Family

ID=50355865

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410004971.3A Active CN103694174B (en) 2014-01-06 2014-01-06 Alpha- (N-benzyl) amino-caprolactam compound and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN103694174B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104387323B (en) * 2014-10-31 2016-09-14 南京工业大学 Alpha- (N-disubstituted) amino-caprolactam compound and preparation method and application thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH497428A (en) * 1968-01-22 1970-10-15 Agripat Sa Process for the preparation of 1-formyl-3-nitro-azacyclo-heptanone- (2)
US3651023A (en) * 1968-07-02 1972-03-21 Stamicarbon Preparation of polyamides with special properties
US4374177A (en) * 1981-12-24 1983-02-15 Ppg Industries, Inc. Aqueous sizing composition for glass fibers and sized glass fibers for thermoplastic reinforcement
MX2007016064A (en) * 2005-06-16 2008-03-10 Novartis Ag Compositions and methods for viral inhibition.
CN102093292B (en) * 2010-12-24 2012-03-21 南京工业大学 Method for synthesizing DL-alpha-aminocaprolactam
CN102850273A (en) * 2012-09-12 2013-01-02 北京万全德众医药生物技术有限公司 Novel synthesizing method of (R)-alpha-amino-epsilon-caprolactam

Also Published As

Publication number Publication date
CN103694174A (en) 2014-04-02

Similar Documents

Publication Publication Date Title
CN104387581B (en) The preparation method of semiaromatic copolyamide resin and resin
CN103154087B (en) Molded polyamide resin article
EP2697285B1 (en) Stabilised polyamide
CN101260232A (en) Mixing type nonisocyanate polyurethane and preparation method thereof
JP6243706B2 (en) Polyamide resin
EP2448997B1 (en) Modified polyamide composition
WO2014051120A1 (en) Polyamide resin composition
KR20220055474A (en) Polyamides and Corresponding Polymer Compositions, Articles and Methods of Making and Using
CN105330850B (en) A kind of method for preparing polyamide
JP4595883B2 (en) Manufacturing method of hinged molded article
EP2130853B1 (en) Process for producing polyamide
WO2012140099A1 (en) Stabilised polyamide composition
CN104448794A (en) Moulding compound based on a partially aromatic copolyamide
CN110156985A (en) A kind of high fluidity random copolymerization semi-aromatic nylon and preparation method thereof
CN103694174B (en) Alpha- (N-benzyl) amino-caprolactam compound and preparation method and application thereof
WO2004003044A2 (en) Dynamers: polymeric materials exhibiting reversible formation and component exchange
JP6777294B2 (en) Polyamide resin composition and its molded product
CN105295033B (en) Long carbon chain semiaromatic polyamide composition and its synthetic method
JP6247906B2 (en) Long fiber reinforced polyamide resin composition
JP3395390B2 (en) Method for producing polyamide
CN110016228A (en) Amilan polyamide resin composition and formed body
WO2018229126A1 (en) Polyamides obtainable from 3-(aminoalkyl)benzoic acid
CN111566143B (en) Process for producing polyamide comprising amide molecular weight regulator and polyamide produced thereby
CN106893096A (en) A kind of biological poly acid amides and preparation method thereof
CN104710613A (en) Solvothermal preparation method of semi-aromatic polyamide

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant