CN101891630A - Synthesis method of N,N-dimethyl-p-phenylenediamine - Google Patents
Synthesis method of N,N-dimethyl-p-phenylenediamine Download PDFInfo
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- CN101891630A CN101891630A CN2010102214098A CN201010221409A CN101891630A CN 101891630 A CN101891630 A CN 101891630A CN 2010102214098 A CN2010102214098 A CN 2010102214098A CN 201010221409 A CN201010221409 A CN 201010221409A CN 101891630 A CN101891630 A CN 101891630A
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- nitro
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- phenylenediamine
- hydrazine hydrate
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- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 title abstract description 8
- 238000001308 synthesis method Methods 0.000 title abstract 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 25
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000002798 polar solvent Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 26
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 239000012046 mixed solvent Substances 0.000 claims description 13
- 238000001953 recrystallisation Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000010949 copper Substances 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- QJAIOCKFIORVFU-UHFFFAOYSA-N n,n-dimethyl-4-nitroaniline Chemical compound CN(C)C1=CC=C([N+]([O-])=O)C=C1 QJAIOCKFIORVFU-UHFFFAOYSA-N 0.000 abstract 1
- 238000001514 detection method Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 230000009466 transformation Effects 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 150000002828 nitro derivatives Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- -1 aromatic nitro compound Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of N,N-dimethyl-p-phenylenediamine, which comprises the following steps: in a proton polar solvent, in the presence of a catalyst CuO/C, p-nitro-N,N-dimethylaniline shown in formula (II) is stirred to react with hydrazine hydrate at the temperature of 20-100 DEG C, TLC tracks until the completeness of the reaction, after the reaction is finished, and then aftertreatment is carried out on the reaction liquid to prepare the N,N-dimethyl-p-phenylenediamine shown in formula (II); the ratio of amount of substance of the N,N-dimethyl-p-phenylenediamine shown in formula (II) to the hydrazine hydrate is 1:1-5; and the charge capacity of CuO in the catalyst CuO/C is 8-10%. The synthesis method utilizes hydrazine hydrate reduction to react to generate nitrogen and water, thus solving the problem of pollution on the environment; moreover, a compound containing copper is taken as a catalyst, which is not only cheap but also has good catalytic effect; and the synthesis method has mild reaction condition, high yield and low requirements to equipment, thus being a green synthesis technology with application prospect.
Description
Technical field
The present invention relates to a kind of N, N-dimethyl-p-phenylenediamine's synthetic method, particularly relating to a kind of is raw material with the hydrazine hydrate, CuO/C is that catalyst reaction prepares N, N-dimethyl-p-phenylenediamine's method.
Background technology
N, the N-dimethyl-p-phenylenediamine is mainly used in the production of dyestuff, agricultural chemicals and photographic developer, also can be used for synthesized solidified dose, also is the reagent of measuring vanadium.Traditional production route is with N, and the N-xylidene(s) is a raw material, carries out nitrosification earlier, uses the zinc powder reduction gained again.Traditional nitroreduction has: (1) metallic reducing, in theory, the every electromotive force of all metals be in hydrogen above can with proton donor.As acid, alcohol, water, ammonia etc., under certain condition as reductive agent, the iron of the aluminium of metal commonly used such as basic metal, alkaline-earth metal, three races, the tin of the 4th family, the 8th family etc., the industrial iron filings of using in the reduction of aromatic nitro compound more.But because the iron powder reducing method discharges a large amount of Halogen aniline waste waters, and the processing of waste residue is very difficult, from environment protection and reduce labor intensity, is replaced by hydrogenating reduction or other reduction method substantially.(2) sodium sulfide reducing is used Na more generally in sodium sulfide reducing
2S, NaHS and Na
2S
2, its reaction product is Na
2S
2O
3This reaction need under high pressure be carried out, and the catalyst system therefor costliness, and wastewater treatment is cumbersome.(3) shortening method nitro compound reducing, this method is carried out under neutrallty condition, therefore those are had the compound of the group of facile hydrolysis under acidity or alkaline condition, available this method reduction, but it is high that this method requires plant and instrument, should pressure exerting device, require instrument airtight again, the operational requirement strictness.In addition, the reduction selectivity of catalytic hydrogenation method is relatively poor, contains the group that other easily are hydrogenated in the nitro-compound molecule, can not adopt this method.(4) metal hydride also can nitro compound reducing.This method in reduction process, the existence of cyano group, halogen, ester group, carbon-to-carbon double bond etc., all unaffected, but it is more expensive to go back the original reagent price, is difficult to obtain.(5) CO/H
2The O reduction method be with ruthenium or rhodium as catalyzer, in basic solution, react, but the method for CO amines preparation by reducing aromatic needs a large amount of catalyzer, and the easy inactivation of catalyzer.
Summary of the invention
The purpose of this invention is to provide a kind of N, N-dimethyl-p-phenylenediamine's synthetic method, it uses hydrazine hydrate to provide the hydrogen electronics to reduce, and has avoided the danger of reaction under high pressure, and mild condition is convenient to operation, environmentally safe.
For achieving the goal the present invention by the following technical solutions:
A kind of N shown in formula I, N-dimethyl-p-phenylenediamine's synthetic method, described method is: in proton polar solvent, in the presence of Catalysts Cu O/C, shown in formula II to nitro-N, accelerine and hydrazine hydrate are at 20～100 ℃ of following stirring reactions, TLC tracks to and reacts completely, usually the reaction times is 1 ~ 20 hour, and the aftertreatment of reaction end afterreaction liquid makes the N shown in formula I, N-dimethyl-p-phenylenediamine; Described shown in formula II to nitro-N, the amount of substance of accelerine, hydrazine hydrate is than for 1:1 ~ 5; Described Catalysts Cu O/C is to be carrier with C, and Supported CuO is the catalyzer of active ingredient, and wherein the charge capacity of CuO is 8 ~ 10%.
Described Catalysts Cu O/C with to nitro-N, the mass ratio of accelerine is 1:5 ~ 15.
The charge capacity of CuO is preferably 8% among the described Catalysts Cu O/C.
Described proton polar solvent is the mixing of following one or more arbitrary proportions: water, methyl alcohol or ethanol, preferred alcohol.
The volumetric usage of described proton polar solvent is with to nitro-N, and the amount of substance of accelerine is counted 1～10 mL/mmol.
Described reaction solution post-treating method is: after reaction finished, reacting liquid filtering was got filtrate and is concentrated except that desolvating, and gets enriched material and gets product N, the N-dimethyl-p-phenylenediamine with ethyl acetate and sherwood oil with volume ratio 1:2 blended mixed solvent recrystallization.
Described to nitro-N, the amount of substance ratio of accelerine, hydrazine hydrate is preferably 1:2.
Comparatively concrete, N of the present invention, the synthetic method of N-dimethyl-p-phenylenediamine compound recommends to carry out according to the following steps: in proton polar solvent, in the presence of Catalysts Cu O/C, shown in formula II to nitro-N, accelerine and hydrazine hydrate are at 20～100 ℃ of following stirring reactions, TLC tracks to and reacts completely, usually the reaction times is 1 ~ 20 hour, reaction finishes afterreaction liquid and filters, get filtrate and concentrate, get enriched material and get product N, the N-dimethyl-p-phenylenediamine with volume ratio 1:2 blended mixed solvent recrystallization with ethyl acetate and sherwood oil except that desolvating; Described shown in formula II to nitro-N, the amount of substance of accelerine, hydrazine hydrate is than for 1:1 ~ 5; The charge capacity of CuO is 8% among the described Catalysts Cu O/C, described Catalysts Cu O/C with to nitro-N, the mass ratio of accelerine is 1:5 ~ 15.
Catalysts Cu O/C of the present invention can make by oneself by the following method and obtain:
CuCl
2Water-soluble wiring solution-forming, charge capacity according to CuO is 8 ~ 10% adding gacs again, stirred 4 ~ 5 hours, underpressure distillation dewaters, oven dry, the NaOH aqueous solution that drips while stirring then adjusting pH is 6～7,4 ~ 5 hours postcooling of heated and boiled, suction filtration, filter cake obtained the CuO/C catalyzer in 4 ~ 5 hours 120 ℃ of dryings.This is the known preparation methods of those skilled in the art.
Preparation method of the present invention, preparation technology is simple, and is easy to operate, basic non-environmental-pollution.And the present invention utilizes hydrazine hydrate reduction, what reaction generated is the nitrogen G﹠W, solved the pollution problem that environment is brought, and with the copper-containing compound is catalyzer, not only cheapness but also good catalytic effect is arranged, reaction conditions gentleness, productive rate height, simple to equipment requirements make this technology be convenient to operation and handle, having solved the pollution and the emission problem of last handling process, is a kind of green synthesis techniques that application prospect is arranged.
Embodiment
Below in conjunction with specific embodiment preparation method of the present invention is described further, but protection scope of the present invention is not limited thereto.
Embodiment 1 Catalysts Cu O/C's is synthetic
In the flask of 50 mL, add CuCl
20.3g, be dissolved in 10 mL distilled water; Add gac 2.0 g again, stir 4.0 h, underpressure distillation dewaters, oven dry, and it is 7 that the NaOH aqueous solution that drips 100 mg/g then while stirring is adjusted to pH, heated and boiled 4.0 h, cooling, suction filtration; Filter cake is at 120 ℃ of drying 4.0 h, and the Catalysts Cu O/C that makes 2.04g charge capacity 8% is standby.
Embodiment 2 N, the N-dimethyl-p-phenylenediamine's is synthetic
In the flask of 100mL, add nitro-N, accelerine 2.49g(0.015mol), aqueous ethanolic solution 30 mL of massfraction 20%, CuO/C 0.23g, be heated to 50 ℃, drip hydrazine hydrate 3.0mL(0.06mol), stirring reaction, TLC follows the tracks of detection, reacted completely in 13 hours, filter, get filtrate concentrating, get enriched material and use ethyl acetate and sherwood oil with volume ratio 1:2 blended mixed solvent recrystallization, get solid 1.74g, yield is 86%, and transformation efficiency 100%, the fusing point that records are 35 ~ 36 ℃.
Embodiment 3 N, the N-dimethyl-p-phenylenediamine's is synthetic
In the flask of 100mL, add to nitro-N accelerine 2.49g(0.015mol), ethanol 30mL, CuO/C 0.23g is heated to 75 ℃, drips hydrazine hydrate 1.5mL(0.03mol), stirring reaction, TLC follows the tracks of detection, reacts completely in 5 hours, filter, get filtrate concentrating, get enriched material and use ethyl acetate and sherwood oil with 1:2 blended mixed solvent recrystallization, get solid 1.92g, productive rate is 95%, and transformation efficiency 100%, the fusing point that records are 35 ~ 36 ℃.
Embodiment 4 N, the N-dimethyl-p-phenylenediamine's is synthetic
In the flask of 100mL, add to nitro-N accelerine 2.49g(0.015mol), ethanol 30mL, CuO/C 0.23g is heated to 70 ℃, drips hydrazine hydrate 1.5mL(0.03mol), stirring reaction, TLC follows the tracks of detection, reacts completely in 8 hours, filter, get filtrate concentrating, get enriched material and use ethyl acetate and sherwood oil with volume ratio 1:2 blended mixed solvent recrystallization, get solid 1.86g, productive rate is 92%, and transformation efficiency 100%, the fusing point that records are 35 ~ 36 ℃.
Embodiment 5 N, the N-dimethyl-p-phenylenediamine's is synthetic
In the flask of 100mL, add to nitro-N accelerine 4.50g(0.027mol), ethanol 60mL, CuO/C 0.45g is heated to 60 ℃, drips hydrazine hydrate 1.5mL(0.03mol), stirring reaction, TLC follows the tracks of detection, reacts completely in 10 hours, filter, get filtrate concentrating, get enriched material and use ethyl acetate and sherwood oil with volume ratio 1:2 blended mixed solvent recrystallization, get solid 3.34g, productive rate is 91%, and transformation efficiency 100%, the fusing point that records are 35 ~ 36 ℃.
Embodiment 6 N, the N-dimethyl-p-phenylenediamine's is synthetic
In the flask of 100mL, add to nitro-N accelerine 2.49g(0.015mol), ethanol 15mL, CuO/C 0.23g is heated to 65 ℃, drips hydrazine hydrate 1.5mL(0.03mol), stirring reaction, TLC follows the tracks of detection, reacts completely in 9 hours, filter, get filtrate concentrating, get enriched material and use ethyl acetate and sherwood oil with volume ratio 1:2 blended mixed solvent recrystallization, get solid 1.88g, productive rate is 93%, and transformation efficiency 100%, the fusing point that records are 35 ~ 36 ℃.
Embodiment 7 N, the N-dimethyl-p-phenylenediamine's is synthetic
In the flask of 100mL, add to nitro-N accelerine 2.49g(0.015mol), methyl alcohol 30mL, CuO/C 0.23g is heated to 20 ℃, drips hydrazine hydrate 1.5mL(0.03mol), stirring reaction, TLC follows the tracks of detection, reacts completely in 20 hours, filter, get filtrate concentrating, get enriched material and use ethyl acetate and sherwood oil with volume ratio 1:2 blended mixed solvent recrystallization, get solid 1.62g, productive rate is 80%, and transformation efficiency 100%, the fusing point that records are 35 ~ 36 ℃.
Embodiment 8 N, the N-dimethyl-p-phenylenediamine's is synthetic
In the flask of 100mL, add to nitro-N accelerine 2.49g(0.015mol), ethanol 30mL, CuO/C 0.23g is heated to 40 ℃, drips hydrazine hydrate 3.75mL(0.075mol),, stirring reaction, TLC follows the tracks of detection, reacted completely in 16 hours, and filtered, get filtrate concentrating, get enriched material and use ethyl acetate and sherwood oil with volume ratio 1:2 blended mixed solvent recrystallization, get solid 1.72g, productive rate is 85%, transformation efficiency 100%, the fusing point that records are 35 ~ 36 ℃.
Embodiment 9 N, the N-dimethyl-p-phenylenediamine's is synthetic
In the flask of 100mL, add to nitro-N accelerine 2.49g(0.015mol), ethanol 30mL, CuO/C 0.5g is heated to 80 ℃, drips hydrazine hydrate 1.5mL(0.03mol), stirring reaction, TLC follows the tracks of detection, reacts completely in 6 hours, filter, get filtrate concentrating, get enriched material and use ethyl acetate and sherwood oil with volume ratio 1:2 blended mixed solvent recrystallization, get solid 1.90g, productive rate is 94%, and transformation efficiency 100%, the fusing point that records are 35 ~ 36 ℃.
Embodiment 10 N, the N-dimethyl-p-phenylenediamine's is synthetic
In the flask of 100mL, add to nitro-N accelerine 2.49g(0.015mol), water 40mL, CuO/C 0.17g is heated to 100 ℃, drips hydrazine hydrate 1.5mL(0.03mol), stirring reaction, TLC follows the tracks of detection, reacts completely in 8 hours, filter, get filtrate concentrating, get enriched material and use ethyl acetate and sherwood oil with volume ratio 1:2 blended mixed solvent recrystallization, get solid 1.84g, productive rate is 91%, and transformation efficiency 100%, the fusing point that records are 35 ~ 36 ℃.
Claims (7)
1. N shown in formula I, N-dimethyl-p-phenylenediamine's synthetic method, it is characterized in that described method is: in proton polar solvent, in the presence of Catalysts Cu O/C, shown in formula II to nitro-N, accelerine and hydrazine hydrate are at 20～100 ℃ of following stirring reactions, TLC tracks to and reacts completely, the aftertreatment of reaction end afterreaction liquid makes the N shown in formula I, N-dimethyl-p-phenylenediamine; Described shown in formula II to nitro-N, the amount of substance of accelerine, hydrazine hydrate is than for 1:1 ~ 5; The charge capacity of CuO is 8 ~ 10% among the described Catalysts Cu O/C;
2. the method for claim 1, it is characterized in that described Catalysts Cu O/C with to nitro-N, the ratio of the quality of accelerine is 1:5 ~ 15.
3. the method for claim 1 is characterized in that described proton polar solvent is the mixing of following one or more arbitrary proportions: water, methyl alcohol or ethanol.
4. the method for claim 1, the volumetric usage that it is characterized in that described proton polar solvent are with to nitro-N, and the amount of substance of accelerine is counted 1～10 mL/mmol.
5. the method for claim 1, it is characterized in that described reaction solution post-treating method is: after reaction finishes, reacting liquid filtering, getting filtrate concentrates except that desolvating, get enriched material and get product N, the N-dimethyl-p-phenylenediamine with volume ratio 1:2 blended mixed solvent recrystallization with ethyl acetate and sherwood oil.
6. the method for claim 1 is characterized in that describedly to nitro-N, and the amount of substance of accelerine, hydrazine hydrate is than being 1:2.
7. the method for claim 1, it is characterized in that described method carries out according to the following steps: in proton polar solvent, in the presence of Catalysts Cu O/C, shown in formula II to nitro-N, accelerine and hydrazine hydrate are at 20～100 ℃ of following stirring reactions, TLC tracks to and reacts completely, reaction finishes afterreaction liquid and filters, getting filtrate concentrates except that desolvating, get enriched material and get product N, the N-dimethyl-p-phenylenediamine with volume ratio 1:2 blended mixed solvent recrystallization with ethyl acetate and sherwood oil; Described shown in formula II to nitro-N, the amount of substance of accelerine, hydrazine hydrate is than for 1:1 ~ 5; The charge capacity of CuO is 8% among the described Catalysts Cu O/C, described Catalysts Cu O/C with to nitro-N, the mass ratio of accelerine is 1:5 ~ 15.
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Cited By (1)
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| CN103664645A (en) * | 2013-12-26 | 2014-03-26 | 常州市春港化工有限公司 | Industrialized preparation method of 1,8-diaminonaphthalene |
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| CN101665436A (en) * | 2009-09-27 | 2010-03-10 | 池州方达科技有限公司 | Synthesis method of p-phenylenediame |
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| CN101665436A (en) * | 2009-09-27 | 2010-03-10 | 池州方达科技有限公司 | Synthesis method of p-phenylenediame |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103664645A (en) * | 2013-12-26 | 2014-03-26 | 常州市春港化工有限公司 | Industrialized preparation method of 1,8-diaminonaphthalene |
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