CN107739342B - Method for synthesizing 5-diarylaminobenzimidazole ketone derivative in one step - Google Patents
Method for synthesizing 5-diarylaminobenzimidazole ketone derivative in one step Download PDFInfo
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- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles 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 in position 2
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Abstract
The invention belongs to the technical field of organic synthesis, and discloses a method for synthesizing a 5-diarylaminobenzimidazole ketone derivative in one step. Adding a compound 1, a compound 2, a metal catalyst, a ligand, an oxidant and a solvent into a reactor, stirring and reacting for 1-24 hours at 25-130 ℃, cooling to room temperature after the reaction is finished, carrying out reduced pressure rotary evaporation to remove the solvent to obtain a crude product, and carrying out column chromatography purification on the crude product to obtain the 5-diarylaminobenzimidazole derivative; the compound 1 refers to a compound with a structure shown in a formula (1); the compound 2 refers to a secondary amine or a tertiary amine with the structure of formula (2), or a corresponding acid salt thereof. The method has the advantages of simple synthesis steps, safe operation, nontoxic and cheap and easily-obtained raw materials, good compatibility of the synthesis method for functional groups and high atom economy.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing a 5-diarylaminobenzimidazole ketone derivative in one step.
Background
Benzimidazolone is a C-2 oxidized derivative of benzimidazole and is mainly applied to the dye industry. In recent years, related studies have found that a series of benzimidazolone compounds also exhibit a wide range of medical biological activities, such as antibacterial, antiviral, anti-inflammatory, antihypertensive, insecticidal, and antitumor activities (j.b. wright, chem.rev.,1951,48, 397-541; a.m. monforte, a.rao, p.logotea, s.ferro, l.d.luca, m.l.barreca, n.iraci, g.maga, e.d.clercq, c.pannecouque, a.chimicrri, Bioorgan Med chem.2008, 16, 7429-7435.).
The traditional method for preparing benzimidazolone is obtained by synthesizing o-dichlorobenzene, o-phenylenediamine or o-nitroaniline serving as starting raw materials. (1) Taking o-dichlorobenzene as a raw material: under the catalysis of copper powder or cuprous chloride, o-dichlorobenzene, ammonia water and sodium carbonate (or sodium bicarbonate, urea and ethylene carbonate) react at 210-215 ℃ under the pressure of 6.2-7.8MPa to prepare benzimidazolone. The synthesis method has the advantages that the raw materials are easy to obtain and low in price, but the synthesis method needs to be carried out under the conditions of high temperature and high pressure, and the requirements on equipment are high. (2) O-phenylenediamine is used as a raw material: the benzimidazolone is synthesized by condensing o-phenylenediamine with carbonylation reagents such as urea, phosgene, carbon monoxide and the like. The method has low requirement on equipment, is simple and convenient to operate, and is suitable for industrial production. However, since phosgene, carbon monoxide and other raw materials are toxic gases, they are not friendly to the environment and have high technical requirements, and thus are limited in practical application. (3) Taking o-nitroaniline as a raw material: the reaction of o-nitroaniline and reductive carbonylation reagent carbon monoxide under different catalytic systems is mainly researched. Although the traditional synthetic methods have the advantages of easily available raw materials and low price, the traditional synthetic methods need to be carried out under the conditions of high temperature and high pressure, have higher requirements on equipment, and have the obvious defects of low product quality, large amount of waste water and waste residue generated in the production process, serious environmental pollution and the like. (Shaownwei, Synthesis of 5-aminobenzimidazole ketone and benzimidazole Compounds [ D ]. university of California, 2008).
Among them, 5-aminobenzimidazole ketone is a main intermediate for synthesizing benzimidazolone structured pigments, and with the rapid development of industries such as plastics, printing ink, coatings and the like, the demand for benzimidazolone is increasing at home and abroad. Therefore, it is necessary to research a better synthesis process of benzimidazolone. (Shengejia. benzimidazolone pigments and their use [ J ] chemical engineering and science markets 2001,24(04): 7-11).
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a method for synthesizing a 5-diarylaminobenzimidazole ketone derivative in one step.
The purpose of the invention is realized by the following technical scheme:
a method for synthesizing 5-diarylaminobenzimidazole ketone derivatives in one step comprises the following steps:
adding a compound 1, a compound 2, a metal catalyst, a ligand, an oxidant and a solvent into a reactor, stirring and reacting for 1-24 hours at 25-130 ℃, cooling to room temperature after the reaction is finished, carrying out reduced pressure rotary evaporation to remove the solvent to obtain a crude product, and carrying out column chromatography purification on the crude product to obtain the 5-diarylaminobenzimidazole derivative;
the compound 1 refers to a compound with a structure shown in a formula (1); the compound 2 refers to a secondary amine or a tertiary amine with the structure of formula (2), or a corresponding acid salt thereof;
wherein R is1Represents one or more substituted methyl, phenyl, methoxy, nitro, nitrile, trifluoromethyl, ester, halogen substituents or hydrogen on the aromatic ring; r2、R3、R4Are identical or different alkyl, substituted alkyl or hydrogen, with the proviso that R2And R3Not hydrogen at the same time.
The reaction equation involved in the above synthesis method is shown as follows:
the reactor is preferably a schlenk tube (schlank tube).
The molar ratio of the compound 1 to the compound 2 is (1-20) to 1; preferably 2: 1.
The metal catalyst is one or the mixture of more than two of cupric acetate, cupric sulfate, cuprous chloride, cupric fluoride, cuprous iodide, cuprous bromide, cupric bromide and copper trifluoromethanesulfonate.
The ligand is a nitrogen-containing ligand, and pyridine or pyridine derivatives are preferred.
The oxidant is one or the mixture of more than two of metal oxide, peroxide, acid with oxidability, silver salt and oxygen, wherein the pressure of the oxygen is 1-30 atmospheric pressures.
The solvent is one or the mixture of more than two of acetonitrile, tetrahydrofuran, ethanol, tertiary amyl alcohol, isopropanol, isobutanol, N-dimethylformamide, dimethyl sulfoxide, toluene, p-xylene, methanol and water.
The eluent used for the column chromatography purification is a mixed solvent of petroleum ether, dichloromethane and ethyl acetate in a volume ratio of (0.5-50) to (0-20) to 1.
The synthesis method of the invention has the following advantages and beneficial effects:
the invention takes diphenylamine compounds and secondary or tertiary amine as raw materials to synthesize the 5-diarylaminobenzimidazole ketone derivative by one step, and has the advantages of simple synthesis steps, safe operation, nontoxic, cheap and easily obtained raw materials, good compatibility of the synthesis method to functional groups and high atom economy.
Drawings
FIGS. 1 and 2 are a hydrogen spectrum and a carbon spectrum, respectively, of the product obtained in example 1;
FIGS. 3 and 4 are a hydrogen spectrum and a carbon spectrum, respectively, of the product obtained in example 2;
FIGS. 5 and 6 are a hydrogen spectrum and a carbon spectrum, respectively, of the product obtained in example 3;
FIGS. 7 and 8 are a hydrogen spectrum and a carbon spectrum, respectively, of the product obtained in example 4;
FIGS. 9 and 10 are a hydrogen spectrum and a carbon spectrum, respectively, of the product obtained in example 5;
fig. 11 and 12 are a hydrogen spectrum and a carbon spectrum of the product obtained in example 6, respectively.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
To a schlenk tube were added 0.5 mmol of diphenylamine, 0.25 mmol of diethylamine, 0.05 mmol of copper chloride, 0.5 mmol of pyridine, 1.5 ml of isobutanol, and O was added at 100 deg.C2Stirring and reacting for 12 hours under the condition that the oxygen pressure is one atmosphere, stopping heating and stirring, cooling to room temperature, decompressing and rotary evaporating to remove the solvent, and then carrying out column chromatography separation and purification to obtain the target product, wherein the volume ratio of the eluent of the column chromatography is 20:5:1, and the mixed solvent of petroleum ether, dichloromethane and ethyl acetate is adopted, and the yield is 78%.
The hydrogen spectrogram and the carbon spectrogram of the obtained product are respectively shown in fig. 1 and fig. 2, and the structural characterization data are as follows:
1H NMR(400MHz,CDCl3)δ7.58–7.48(m,4H),7.37(t,J＝7.1Hz,1H),7.20–7.26(m,4H),7.08(d,J＝7.9Hz,4H),6.97(t,J＝7.6Hz,3H),6.87(s,1H),6.81(d,J＝8.3Hz,1H),3.90(q,J＝7.2Hz,2H),1.30(t,J＝7.2Hz,3H)。
13C NMR(101MHz,CDCl3)δ153.34,148.28,142.88,134.94,130.24,129.57,129.29,127.55,126.01,125.91,123.29,122.32,119.51,109.53,106.03,36.14,13.64。
IR(KBr):3058,3033,2974,2929,2855,1712,1592,1491,1400,1276,1234,1192,1082,1022,754,695,656cm-1。
MS(EI,m/z):405[M]+。
HRMS(ESI):Calcd.for C27H23N3ONa[M+Na]+:428.1733；found:428.1727。
the structure of the resulting product is deduced from the above data as shown in the following formula:
example 2
To a schlenk tube were added 0.5 mmol of diphenylamine, 0.25 mmol of N-ethylisopropylamine, 0.05 mmol of cuprous chloride, 0.5 mmol of pyridine, and 1.5 ml of isobutanol at 80 ℃ O2Stirring and reacting for 16 hours under the condition that the oxygen pressure is one atmosphere, stopping heating and stirring, cooling to room temperature, decompressing and rotary-distilling to remove the solvent, and separating and purifying by column chromatography to obtain the target product, wherein the volume ratio of the eluent of the column chromatography is 20:5:1, and the mixed solvent of petroleum ether, dichloromethane and ethyl acetate is used, and the yield is 34%.
The hydrogen spectrogram and the carbon spectrogram of the obtained product are respectively shown in fig. 3 and fig. 4, and the structural characterization data are as follows:
1H NMR(400MHz,CDCl3):δ7.48–7.55(m,4H),7.37(t,J＝6.7Hz,1H),7.23(d,J＝7.4Hz,3H),7.09(d,J＝7.8Hz,4H),6.97(d,J＝7.5Hz,4H),6.79(d,J＝7.9Hz,1H),4.66(dt,J＝13.8,6.9Hz,1H),1.49(d,J＝6.9Hz,6H)。
13C NMR(101MHz,CDCl3):δ153.06,148.28,142.54,134.89,129.56,129.43,129.29,127.59,126.11,123.29,122.32,119.12,109.43,107.38,45.42,20.23。
IR(KBr):3063,3042,2968,2929,2869,1712,1629,1593,1491,1388,1273,1236,1176,752,695,660cm-1。
MS(EI,m/z):419[M]+。
HRMS(ESI):Calcd.for C28H25N3ONa[M+Na]+:442.1890；found:442.1888。
the structure of the obtained product is deduced according to the data as shown in the following formula:
example 3
To a schlenk tube were added 0.5 mmol of diphenylamine, 0.25 mmol of triallylamine, 0.05 mmol of copper trifluoromethanesulfonate, 0.5 mmol of pyridine, 1.5 ml of isobutanol, and O was added at 100 ℃2Stirring and reacting for 12 hours under the condition that the oxygen pressure is one atmosphere, stopping heating and stirring, cooling to room temperature, decompressing and rotary evaporating to remove the solvent, and then carrying out column chromatography separation and purification to obtain the target product, wherein the volume ratio of the eluent of the column chromatography is 20:5:1, and the mixed solvent of petroleum ether, dichloromethane and ethyl acetate is used, and the yield is 37%.
The hydrogen spectrogram and the carbon spectrogram of the obtained product are respectively shown in fig. 5 and 6, and the structural characterization data are as follows:
1H NMR(400MHz,CDCl3):δ7.61–7.47(m,4H),7.35–7.41(m,1H),7.19–7.27(m,4H),7.02–7.11(m,4H),7.02–6.94(m,3H),6.85–6.80(m,2H),5.81–5.93(m,1H),5.12–5.22(m,2H),4.52–4.41(m,2H)。
13C NMR(101MHz,CDCl3):δ153.42,148.21,142.92,134.93,131.73,130.39,129.60,129.28,127.62,125.92,123.39,122.39,119.46,118.07,109.51,106.61,43.66。
IR(KBr):3066,3024,2959,2929,2852,1716,1635,1599,1489,1395,1273,1220,1177,752,696,655cm-1。
MS(EI,m/z):417[M]+。
HRMS(ESI):Calcd.for C28H23N3ONa[M+Na]+:440.1733；found:440.1729。
the structure of the obtained product is deduced according to the data as shown in the following formula:
example 4
To a schlenk tube were added 0.5 mmol of 4-bromodiphenylamine, 0.25 mmol of triethylamine, 0.05 mmol of cupric chloride, 0.5 mmol of pyridine, 0.5 mmol of di-t-butyl peroxide (DTBP), 1.5 ml of isobutanol at 100 ℃ C2Stirring and reacting for 12 hours under the condition that the oxygen pressure is one atmosphere, stopping heating and stirring, cooling to room temperature, decompressing and rotary-distilling to remove the solvent, and separating and purifying by column chromatography to obtain the target product, wherein the volume ratio of the eluent of the column chromatography is 20:5:1, and the mixed solvent of petroleum ether, dichloromethane and ethyl acetate is used, and the yield is 75%.
The hydrogen spectrogram and the carbon spectrogram of the obtained product are respectively shown in fig. 7 and fig. 8, and the structural characterization data are as follows:
1H NMR(400MHz,CDCl3):δ7.64(d,J＝7.2Hz,2H),7.44(d,J＝7.3Hz,2H),7.31(d,J＝7.4Hz,2H),7.24(d,J＝7.4Hz,2H),7.07(d,J＝7.9Hz,2H),7.04–6.96(m,2H),6.93(d,J＝7.4Hz,2H),6.84(s,1H),6.80(d,J＝8.4Hz,1H),3.89(q,J＝6.9Hz,2H),1.30(t,J＝6.9Hz,3H)。
13C NMR(101MHz,CDCl3):δ153.02,147.67,147.37,142.64,133.93,132.76,132.23,130.35,129.48,127.33,125.72,124.36,123.71,123.05,121.05,119.51,114.45,109.52,106.05,36.22,13.62。
IR(KBr):3039,2959,2925,2852,1708,1638,1490,1403,1307,1232,1072,810,748,700cm-1。
MS(EI,m/z):561[M]+。
HRMS(ESI):Calcd.for C27H21Br2N3ONa[M+Na]+:583.9944；found:583.9925。
the structure of the obtained product is deduced according to the data as shown in the following formula:
example 5
To a schlenk tube were added 0.5 mmol of diphenylamine, 0.25 mmol of di-n-hexylamine, 0.05 mmol of cupric chloride, 0.5 mmol of pyridine, 1.5 ml of t-amyl alcohol, and O was added at 100 deg.C2Stirring and reacting for 12 hours under the condition that the oxygen pressure is one atmosphere, stopping heating and stirring, cooling to room temperature, decompressing and rotary-distilling to remove the solvent, and separating and purifying by column chromatography to obtain the target product, wherein the volume ratio of the eluent of the column chromatography is 20:5:1, and the mixed solvent of petroleum ether, dichloromethane and ethyl acetate is adopted, and the yield is 68%.
The hydrogen spectrum and the carbon spectrum of the obtained product are respectively shown in fig. 9 and fig. 10, and the structural characterization data are as follows:
1H NMR(400MHz,CDCl3):δ7.46–7.60(m,4H),7.32–7.39(m,1H),7.23(t,J＝7.9Hz,4H),7.08(d,J＝7.7Hz,4H),6.98(dd,J＝11.6,5.4Hz,3H),6.86(d,J＝1.8Hz,1H),6.80(dd,J＝8.4,2.0Hz,1H),3.82(t,J＝7.2Hz,2H),1.741.66(m,2H),1.36–1.24(m,6H),0.85(t,J＝6.9Hz,3H)。
13C NMR(101MHz,CDCl3):δ153.58,148.24,142.80,134.96,130.67,129.52,129.26,127.47,125.90,125.85,123.25,122.29,119.39,109.45,106.20,41.37,31.51,28.31,26.54,22.55,14.12。
IR(KBr):3066,3033,2953,2928,2857,1715,1626,1594,1490,1398,1370,1274,1176,1092,753,695,657cm-1。
MS(EI,m/z):461[M]+。
HRMS(ESI):Calcd.for C31H31N3ONa[M+Na]+:484.2359；found:484.2363。
the structure of the obtained product is deduced according to the data as shown in the following formula:
example 6
To a schlenk tube were added 0.5 mmol of 4-methyldiphenylamine, 0.25 mmol of diethylamine, 0.05 mmol of copper chloride, 0.5 mmol of pyridine, 1.5 ml of isobutanol, and O was added at 80 deg.C2Stirring and reacting for 24 hours under the condition that the oxygen pressure is one atmosphere, stopping heating and stirring, cooling to room temperature, decompressing and rotary evaporating to remove the solvent, and then carrying out column chromatography separation and purification to obtain the target product, wherein the volume ratio of the eluent of the column chromatography is 20:5:1, and the mixed solvent of petroleum ether, dichloromethane and ethyl acetate is used, and the yield is 59%.
The hydrogen spectrum and the carbon spectrum of the obtained product are respectively shown in fig. 11 and fig. 12, and the structural characterization data are as follows:
1H NMR(400MHz,CDCl3):δ7.43–7.39(m,2H),7.30(d,J＝8.1Hz,2H),7.23–7.18(m,2H),7.07–6.99(m,6H),6.95–6.91(m,2H),6.85(d,J＝1.8Hz,1H),6.78(dd,J＝8.4,1.9Hz,1H),3.89(q,J＝7.2Hz,2H),2.40(s,3H),2.31(s,3H),1.30(t,J＝7.2Hz,3H)。
13C NMR(101MHz,CDCl3):δ153.45,148.60,145.71,142.96,137.46,132.32,132.28,130.17,130.15,129.97,129.18,126.04,125.83,124.07,122.55,121.70,119.14,109.41,105.68,36.10,21.28,20.90,13.68。
IR(KBr):3030,2968,2926,2855,1714,1627,1594,1508,1492,1401,1294,1234,811,750,696cm-1。
MS(EI,m/z):433[M]+。
HRMS(ESI):Calcd.for C29H27N3ONa[M+Na]+:456.2046；found:456.2047。
the structure of the obtained product is deduced according to the data as shown in the following formula:
the above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (5)
1. A method for synthesizing 5-diarylaminobenzimidazole derivatives in one step is characterized by comprising the following steps:
adding a compound 1, a compound 2, a metal catalyst, a ligand, an oxidant and a solvent into a reactor, stirring and reacting for 1-24 hours at 25-130 ℃, cooling to room temperature after the reaction is finished, carrying out reduced pressure rotary evaporation to remove the solvent to obtain a crude product, and carrying out column chromatography purification on the crude product to obtain the 5-diarylaminobenzimidazole derivative;
the compound 1 refers to a compound with a structure shown in a formula (1); the compound 2 is a secondary amine or a tertiary amine with a structure of formula (2), or a corresponding acid salt thereof; the 5-diarylaminobenzimidazole derivative is a compound with a structure shown in a formula (3);
wherein R is1Represents methyl, phenyl, methoxy, nitro, nitrile, trifluoromethyl, ester, halogen substituent or hydrogen; r2、R3、R4Are identical or different alkyl, substituted alkyl or hydrogen, with the proviso that R2And R3Not hydrogen at the same time; r is R2Or R3；
The metal catalyst is one or the mixture of more than two of cupric acetate, cupric sulfate, cuprous chloride, cupric fluoride, cuprous iodide, cuprous bromide, cupric bromide and copper trifluoromethanesulfonate;
the ligand is a nitrogen-containing ligand;
the oxidant is one or a mixture of more than two of metal oxide, peroxide, acid with oxidability, silver salt and oxygen, and the pressure of the oxygen is 1-30 atmospheric pressures;
the solvent is one or the mixture of more than two of acetonitrile, tetrahydrofuran, ethanol, tertiary amyl alcohol, isopropanol, isobutanol, N-dimethylformamide, dimethyl sulfoxide, toluene, p-xylene, methanol and water.
2. The method for synthesizing the 5-diarylaminobenzimidazole derivative in one step according to claim 1, wherein: the reactor is a schlenk tube.
3. The method for synthesizing the 5-diarylaminobenzimidazole derivative in one step according to claim 1, wherein: the molar ratio of the compound 1 to the compound 2 is (2-20): 1.
4. The method for synthesizing the 5-diarylaminobenzimidazole derivative in one step according to claim 1, wherein: the nitrogen-containing ligand is pyridine or a pyridine derivative.
5. The method for synthesizing the 5-diarylaminobenzimidazole derivative in one step according to claim 1, wherein: the eluent used for the column chromatography purification is a mixed solvent of petroleum ether, dichloromethane and ethyl acetate in a volume ratio of (0.5-50) to (0-20) to 1.
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| CN101321736A (en) * | 2005-09-30 | 2008-12-10 | 葛兰素集团有限公司 | Compounds which have activity at m1 receptor and their uses in medicine |
| EP2394997A1 (en) * | 2009-02-03 | 2011-12-14 | Mitsubishi Tanabe Pharma Corporation | Process for preparing 1-(4-piperidinyl)benzimidazolone derivatives |
| CN102295605A (en) * | 2011-06-22 | 2011-12-28 | 华东理工大学 | Method for preparing benzimidazolone derivative |
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| CN101321736A (en) * | 2005-09-30 | 2008-12-10 | 葛兰素集团有限公司 | Compounds which have activity at m1 receptor and their uses in medicine |
| EP2394997A1 (en) * | 2009-02-03 | 2011-12-14 | Mitsubishi Tanabe Pharma Corporation | Process for preparing 1-(4-piperidinyl)benzimidazolone derivatives |
| CN102295605A (en) * | 2011-06-22 | 2011-12-28 | 华东理工大学 | Method for preparing benzimidazolone derivative |
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