CN114149385B - Synthesis method of 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene - Google Patents
Synthesis method of 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene Download PDFInfo
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- CN114149385B CN114149385B CN202111542655.8A CN202111542655A CN114149385B CN 114149385 B CN114149385 B CN 114149385B CN 202111542655 A CN202111542655 A CN 202111542655A CN 114149385 B CN114149385 B CN 114149385B
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- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000001308 synthesis method Methods 0.000 title claims abstract description 11
- BWAUVGNNSIBWFM-UHFFFAOYSA-N 4-[(4-butylphenyl)diazenyl]aniline Chemical compound C1=CC(CCCC)=CC=C1N=NC1=CC=C(N)C=C1 BWAUVGNNSIBWFM-UHFFFAOYSA-N 0.000 claims abstract description 23
- OFYGYNSYCAWHNF-UHFFFAOYSA-N (4-butylphenyl)-(4-nitrophenyl)diazene Chemical compound CCCCC1=CC=C(C=C1)N=NC2=CC=C(C=C2)[N+](=O)[O-] OFYGYNSYCAWHNF-UHFFFAOYSA-N 0.000 claims abstract description 20
- VDQQJMHXZCMNMU-UHFFFAOYSA-N 1-phenylpyrrolidine Chemical compound C1CCCN1C1=CC=CC=C1 VDQQJMHXZCMNMU-UHFFFAOYSA-N 0.000 claims abstract description 11
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 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 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000012065 filter cake Substances 0.000 claims description 16
- 229960000583 acetic acid Drugs 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 14
- IDZTUECABAHWLE-UHFFFAOYSA-N 1-nitro-4-nitrosobenzene Chemical compound [O-][N+](=O)C1=CC=C(N=O)C=C1 IDZTUECABAHWLE-UHFFFAOYSA-N 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000012362 glacial acetic acid Substances 0.000 claims description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- OGIQUQKNJJTLSZ-UHFFFAOYSA-N 4-butylaniline Chemical compound CCCCC1=CC=C(N)C=C1 OGIQUQKNJJTLSZ-UHFFFAOYSA-N 0.000 claims description 7
- 235000010288 sodium nitrite Nutrition 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 235000011056 potassium acetate Nutrition 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims 5
- 239000007864 aqueous solution Substances 0.000 claims 2
- 230000001276 controlling effect Effects 0.000 claims 2
- FYFDQJRXFWGIBS-UHFFFAOYSA-N 1,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C([N+]([O-])=O)C=C1 FYFDQJRXFWGIBS-UHFFFAOYSA-N 0.000 claims 1
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 239000013078 crystal Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- VSHTWPWTCXQLQN-UHFFFAOYSA-N n-butylaniline Chemical compound CCCCNC1=CC=CC=C1 VSHTWPWTCXQLQN-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 238000006193 diazotization reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- -1 p-nitronitronitroaniline Chemical compound 0.000 abstract 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- 239000007858 starting material Substances 0.000 description 5
- 239000000987 azo dye Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- OJJRABFYHOHGGU-UHFFFAOYSA-N 1,2,4-trinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C([N+]([O-])=O)C([N+]([O-])=O)=C1 OJJRABFYHOHGGU-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002761 liquid phase assay Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- FZZMDWLROBNSRG-UHFFFAOYSA-N n-phenyliminonitramide Chemical compound [O-][N+](=O)N=NC1=CC=CC=C1 FZZMDWLROBNSRG-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
Abstract
The invention relates to a synthetic method of 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene, which comprises the steps of preparing p-nitronitronitroaniline by oxidation reaction of p-nitroaniline and potassium hydrogen persulfate, preparing (4-butylphenyl) (4-nitrophenyl) diazene from the p-nitronitronitroaniline and the butylaniline, and reducing the (4-butylphenyl) (4-nitrophenyl) diazene by hydrazine hydrate to obtain (4-butylphenyl) (4-aminophenyl) diazene; diazotization of (4-butylphenyl) (4-aminophenyl) diazene and coupling with 1-phenylpyrrolidine gives 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene. The synthesis method of the 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene has the advantages of reasonable process design, low raw material cost, easy purification treatment, high yield, regular production equipment and easy realization of industrial production.
Description
Technical Field
The invention relates to a novel synthesis method of 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene, belonging to the technical field of organic synthesis.
Background
Azo dyes have become the dye which was first used in the "guest-host" effect due to their molecular structural properties and tailorability, and have found important applications in liquid crystal color displays. The azo dye has simple preparation method, good optical property, thermal stability, dissolubility and the like after being doped with liquid crystal, and has important significance for improving the quality and performance of liquid crystal display. Currently, research on azo dyes is focused on increasing the width of the absorption spectrum of azo dyes in liquid crystals; improving the dichroism and the order parameters of the dye; enhancing the solubility and photostability of the dye in the liquid crystal, etc.
The structure of 1-pyrrolidinyl- (4- (4 '-butylphenylazo)) azobenzene is a very important chemical in the liquid crystal display industry, but 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene has no document or patent report on its synthesis method at present, and the patent CN_112088323_A only refers to the synthesis method and does not describe the synthesis method. Therefore, it is of great value to develop a synthetic method suitable for the production of 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene.
Disclosure of Invention
The invention provides a novel synthesis method of 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene aiming at the defects existing in the prior art.
The technical scheme for solving the technical problems is as follows: a novel synthesis method of 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene, which comprises the following steps:
(1) Intermediate 1: preparation of 4-nitro-nitrosobenzene (M1):
adding potassium hydrogen persulfate and water into a reactor, cooling to 15 ℃ by stirring ice bath, adding 4-nitroaniline into the reactor, reacting for 2 hours at 40 ℃, detecting no raw material point by TLC, returning a suction filtration filter cake to the reactor, adding dichloromethane, stirring and washing for 30 minutes, suction filtration, and drying the filter cake to obtain yellow flaky solid 4-nitro-nitrosobenzene (M1), wherein the yield is 73-75.8%.
(2) Preparation of 4-n-butyl-4' -nitroazobenzene (M2):
m1 was added to the reactor, and a mixed solution of 4-n-butylaniline and acetic acid was added thereto, followed by stirring at 40℃overnight for reaction. TLC detected no starting material point and stopped the reaction. The reaction solution was poured into a reactor, water was added thereto, and brown solid powder was precipitated, stirred for 2 hours, and then filtered. Leaching the filter cake with ethanol, and drying to obtain the 4-n-butyl-4' -nitroazobenzene (M2) with the yield of 85-87%.
(3) 4-n-butyl-4' -aminoazobenzene (M3):
adding M2 and DMF into a reactor, stirring and dissolving, then dropwise adding hydrazine hydrate, and controlling the temperature to be not more than 40 ℃. The reaction is carried out for 3 hours at the temperature of 30-40 ℃. Cooling to 30deg.C after the reaction, filtering, pouring the filtrate into hydrochloric acid solution prepared in advance, stirring for 20min at below 40deg.C, stirring for 30min at 50deg.C, suction filtering, leaching the filter cake with water, adjusting pH to 6 with sodium hydroxide solution, suction filtering to obtain 4-n-butyl-4' -aminoazobenzene (M3) crude product with yield of 83-85%
In the synthesis process of 4-n-butyl-4' -aminoazobenzene, a hydrazine hydrate reduction method is used to avoid reduction of nitrogen-nitrogen double bonds.
(4) Synthesis of 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene (F)
M3 and concentrated hydrochloric acid are added into the reactor, water is stirred for 10 minutes, and when the temperature is cooled to 5 ℃, sodium nitrite solution is added dropwise, and the reaction is stirred for 0.5h at the temperature. Then 1-phenylpyrrolidine glacial acetic acid solution is added dropwise, and the stirring reaction is carried out for 1h at the temperature of 5-8 ℃ after the dripping is finished. The reaction mixture was quenched with aqueous potassium acetate to a pH of 3-4, then with aqueous sodium hydroxide to a pH of 6, the reaction product was filtered off, washed with water and dried. Separating and purifying the crude product by column chromatography (silica gel is used as a carrier, carbon tetrachloride is used as eluent), and recrystallizing to obtain a dark red crystalline product: 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene (F). Mp.234.5 ℃; the maximum absorption wavelength (in CHCl 3) was 492nm.
Preferably, in the step (1), the mass ratio of the 4-nitroaniline to the potassium hydrogen persulfate is 1: the mass ratio of the 3-4, 4-nitroaniline to the dichloromethane is 1:4-5.
Preferably, in the step (2), the mass ratio of the 4-nitro-nitrosyl and the butylaniline is 1:1-1.1; the mass ratio of the glacial acetic acid to the butylaniline is 20-40:1.
preferably, in the step (3), the mass ratio of the 4-n-butyl-4' -nitroazobenzene to the hydrazine hydrate is 1:0.8-1.0.
Preferably, in the step (4), the mass ratio of the 4-n-butyl-4' -aminoazobenzene to the 1-phenylpyrrolidine is 1:0.4-0.45.
The beneficial effects of the invention are as follows: the invention prepares p-nitronitronitrobenzene by oxidation reaction of p-nitroaniline and potassium hydrogen persulfate, prepares (4-butylphenyl) (4-nitrophenyl) diazene by the p-nitronitronitrobenzene and butylaniline, and then obtains (4-butylphenyl) (4-aminophenyl) diazene by reducing (4-butylphenyl) (4-nitrophenyl) diazene by hydrazine hydrate; diazotization of (4-butylphenyl) (4-aminophenyl) diazene and coupling with 1-phenylpyrrolidine gives 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene. The synthesis method has the advantages of reasonable process design, low raw material cost, easy purification treatment, high yield and suitability for small-batch production.
Drawings
FIG. 1 is a liquid phase assay of the 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene product of example 1;
FIG. 2 is a liquid mass spectrum of the 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene product of example 1;
FIG. 3 is an infrared spectrum of the 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene product of example 1;
FIG. 4 is a nuclear magnetic resonance spectrum of the 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene product of example 1.
Detailed Description
The following detailed description of the present invention will provide further details in order to make the above-mentioned objects, features and advantages of the present invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
(1) Intermediate 1: preparation of 4-nitro-nitrosobenzene (M1):
to a three-necked flask, 126g of potassium hydrogen persulfate and 1000g of water were added, followed by cooling to 15℃with stirring in an ice bath. To the flask was added 36g of 4-nitroaniline and the reaction was carried out at 40℃for 2 hours, and the absence of starting material was detected by TLC. And (3) returning the filter cake after suction filtration to a bottle, adding 126g of dichloromethane, stirring and washing for 30 minutes, suction filtering, and drying the filter cake to obtain yellow flaky solid 4-nitro-nitrosobenzene (M1) with the yield of 80%.
(2) Preparation of 4-n-butyl-4' -nitroazobenzene (M2):
to a three-necked flask, 25g of M1 was added, followed by a mixed solution of 26.2g of 4-n-butylaniline and 785g of acetic acid, and the mixture was stirred at 40℃overnight for reaction. TLC detected no starting material point and stopped the reaction. The reaction solution was poured into a three-necked flask, 1000g of water was added thereto, and brown solid powder was precipitated, stirred for 2 hours, and then filtered. Eluting the filter cake with ethanol, and drying to obtain 4-n-butyl-4'
The yield of nitroazobenzene (M2) was 88.5%.
(3) 4-n-butyl-4' -aminoazobenzene (M3):
28.3g M2 and 150g DMF are added into a three-mouth bottle, 25g hydrazine hydrate is added dropwise after stirring and dissolving, and the temperature is controlled to be not more than 40 ℃. The reaction is carried out for 3 hours at the temperature of 30-40 ℃. Cooling to 30deg.C after the reaction, filtering, pouring the filtrate into hydrochloric acid solution prepared in advance, stirring for 20min at below 40deg.C, stirring for 30min at 50deg.C, suction filtering, leaching the filter cake with water, pouring back into beaker, adjusting pH to 6 with sodium hydroxide solution, suction filtering to obtain 4-n-butyl-4' -aminoazobenzene (M3) crude product with 86.5% yield
(4) Synthesis of F
5.06g of M3 and 10ml of concentrated hydrochloric acid were added to a three-necked flask, stirred for 10 minutes with 40ml of water, cooled to 5℃and then sodium nitrite solution (1.52 g of sodium nitrite+6 g of water) was added dropwise thereto, and the reaction was stirred at this temperature for 0.5 hours. Then, a solution of 1-phenylpyrrolidine glacial acetic acid (2.1 g of 1-phenylpyrrolidine+4 g of glacial acetic acid) was added dropwise thereto, and the reaction was stirred at 5-8℃for 1 hour. The reaction mixture was quenched with aqueous potassium acetate to a pH of 3-4, then with aqueous sodium hydroxide to a pH of 6, the reaction product was filtered off, washed with water and dried. Separating and purifying the crude product by column chromatography (silica gel is used as a carrier, carbon tetrachloride is used as eluent), and recrystallizing to obtain a dark red crystalline product: 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene (F). Mp.234.5 ℃; the maximum absorption wavelength (in CHCl 3) was 492nm.
The data of the vapor phase detection pattern are shown in table 1 below. The relevant detection patterns of the 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene are shown in fig. 1-4.
Table 11 liquid phase detection pattern data of pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene
Example 2
(1) Intermediate 1: preparation of 4-nitro-nitrosobenzene (M1):
to a three-necked flask was added potassium hydrogen persulfate 189g and water 1500g, and the temperature was lowered to 15℃with stirring in an ice bath. 54g of 4-nitroaniline was added to the flask and reacted at 40℃for 2 hours, and the absence of starting material was detected by TLC. And (3) returning the filter cake after suction filtration to a bottle, adding 189g of dichloromethane, stirring and washing for 30 minutes, suction filtering, and drying the filter cake to obtain yellow flaky solid 4-nitro-nitrosobenzene (M1) with the yield of 80.5%.
(2) Preparation of 4-n-butyl-4' -nitroazobenzene (M2):
to the flask was added 37.5g of M1, and a mixed solution of 39.3g of 4-n-butylaniline and 1177g of acetic acid was added thereto, and the mixture was stirred at 40℃overnight for reaction. TLC detected no starting material point and stopped the reaction. The reaction solution was poured into a three-necked flask, 1500g of water was added thereto, and brown solid powder was precipitated, stirred for 2 hours, and then filtered. The filter cake is leached by ethanol and dried to obtain the 4-n-butyl-4' nitroazobenzene (M2) with the yield of 89 percent.
(3) 4-n-butyl-4' -aminoazobenzene (M3):
42.5g M2 and 225g DMF are added into a three-necked flask, and after stirring and dissolution, 37.5g hydrazine hydrate is added dropwise, and the temperature is controlled to be no more than 40 ℃. The reaction is carried out for 3 hours at the temperature of 30-40 ℃. Cooling to 30deg.C after the reaction, filtering, pouring the filtrate into hydrochloric acid solution prepared in advance, stirring for 20min below 40deg.C, stirring for 30min at 50deg.C, suction filtering, leaching the filter cake with water, pouring back into beaker, adjusting pH to 6 with sodium hydroxide solution, suction filtering to obtain 4-n-butyl-4' -aminoazobenzene (M3) crude product with yield of 87%
(4) Synthesis of F
10.1g of M3, 20ml of concentrated hydrochloric acid and 80ml of water are added into a three-necked flask, stirred for 10 minutes, cooled to 5 ℃, sodium nitrite solution (sodium nitrite 3 g+12 g of water) is added dropwise, and the reaction is stirred at this temperature for 0.5h. Then, a solution of 1-phenylpyrrolidine glacial acetic acid (4.2 g of 1-phenylpyrrolidine+8 g of glacial acetic acid) was added dropwise thereto, and the reaction was stirred at 5-8℃for 1 hour. The reaction mixture was quenched with aqueous potassium acetate to a pH of 3-4, then with aqueous sodium hydroxide to a pH of 6, the reaction product was filtered off, washed with water and dried. Separating and purifying the crude product by column chromatography (silica gel is used as a carrier, carbon tetrachloride is used as eluent), and recrystallizing to obtain a dark red crystalline product: 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene (F). Mp.234.5 ℃; the maximum absorption wavelength (in CHCl 3) was 492nm.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (6)
1. A synthesis method of 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene, which is characterized by comprising the following steps:
(1) Preparation of 4-nitro-nitrosyl benzene:
adding potassium hydrogen persulfate and water into a reactor, stirring, cooling, adding 4-nitroaniline into the reactor, heating for reaction, detecting no raw material point by TLC, carrying out suction filtration, returning a filter cake to the reactor, adding dichloromethane into the reactor, stirring for washing, carrying out suction filtration, and drying the filter cake to obtain yellow flaky solid 4-nitro-nitrosobenzene;
(2) Preparation of 4-n-butyl-4' -nitroazobenzene:
adding 4-nitro-nitrobenzene into a reactor, adding a mixed solution of 4-n-butylaniline and acetic acid, stirring at 40 ℃ for overnight reaction, detecting no raw material point by TLC, stopping the reaction, adding water into the reaction liquid, separating out brown solid powder, stirring, filtering, leaching a filter cake with ethanol, and drying to obtain 4-n-butyl-4' -nitroazobenzene;
(3) Preparation of 4-n-butyl-4' -aminoazobenzene:
adding 4-n-butyl-4 '-nitroazobenzene and DMF into a reactor, stirring and dissolving, then dropwise adding hydrazine hydrate, controlling the temperature to be not more than 40 ℃ when the hydrazine hydrate is dropwise added, keeping the temperature for reaction for 3 hours after the dropwise adding is finished, cooling to 30 ℃ after the reaction is finished, filtering, pouring filtrate into a hydrochloric acid solution prepared in advance, controlling the temperature to be below 40 ℃, stirring for 20min, then stirring for 30min at 50 ℃, carrying out suction filtration, leaching a filter cake with water, regulating the PH to 6 with a sodium hydroxide solution, and carrying out suction filtration to obtain a crude product of 4-n-butyl-4' -aminoazobenzene; wherein the mass ratio of the 4-n-butyl-4' -nitroazobenzene to the hydrazine hydrate is 1:0.8-1.0;
(4) Synthesis of 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene
Adding 4-n-butyl-4' -aminoazobenzene, concentrated hydrochloric acid and water into a reactor, stirring, cooling, dropwise adding sodium nitrite solution, stirring for reaction at a controlled temperature, dropwise adding glacial acetic acid solution of 1-phenylpyrrolidine, stirring for reaction at a controlled temperature after the completion of the dropwise adding, adjusting the pH to 3-4 with potassium acetate aqueous solution to terminate the reaction, adjusting the pH to 6 with sodium hydroxide aqueous solution, filtering out a reaction product, washing with water, drying, separating and purifying a crude product through column chromatography, and recrystallizing to obtain a dark red crystal product: 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene;
in the step (4), 4-n-butyl-4' -aminoazobenzene, concentrated hydrochloric acid and water are added into a reactor, stirred for 10 minutes, then sodium nitrite solution is added dropwise when the mixture is cooled to 5 ℃, stirred and reacted for 0.5 hours at the temperature, then glacial acetic acid solution of 1-phenylpyrrolidine is added dropwise, and the stirring and the reaction for 1 hour at the temperature of 5-8 ℃ are maintained after the dripping.
2. The method for synthesizing 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene according to claim 1, wherein in step (1), the mass ratio of 4-nitroaniline to potassium hydrogen persulfate is 1:3-4, wherein the mass ratio of the 4-nitroaniline to the dichloromethane is 1:4-5.
3. The method for synthesizing 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene according to claim 1, wherein in step (2), the mass ratio of 4-nitro-nitrosyl and 4-n-butylaniline is 1:1-1.1; the mass ratio of the acetic acid to the 4-n-butylaniline is 20-40:1.
4. the method for synthesizing 1-pyrrolidinyl- (4- (4 '-butylphenylazo)) azobenzene according to claim 1, wherein in the step (4), the mass ratio of 4-n-butyl-4' -aminoazobenzene to 1-phenylpyrrolidine is 1:0.4-0.45.
5. The method for synthesizing 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene according to claim 1, wherein in the step (1), potassium hydrogen persulfate and water are added into the reactor, stirred and cooled to 15 ℃, and then 4-nitroaniline is added into the reactor and reacted at 40 ℃ for 2 hours.
6. The method for synthesizing 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene according to claim 1, wherein in step (2), 4-nitro-nitrosyl is added to the reactor, and after adding a mixed solution of 4-n-butylaniline and acetic acid, the mixture is stirred at 40 ℃ for overnight reaction; in addition, water was added to the reaction solution, and the mixture was stirred for 2 hours and then filtered.
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