CN1824646A - Aryl or aryl amine substuted quinone kind compound and its preparation method - Google Patents

Aryl or aryl amine substuted quinone kind compound and its preparation method Download PDF

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CN1824646A
CN1824646A CN 200510009538 CN200510009538A CN1824646A CN 1824646 A CN1824646 A CN 1824646A CN 200510009538 CN200510009538 CN 200510009538 CN 200510009538 A CN200510009538 A CN 200510009538A CN 1824646 A CN1824646 A CN 1824646A
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aryl
dimethylamine base
compound
phenyl
quinones
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王东
张海波
刘利
陈拥军
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Institute of Chemistry CAS
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Abstract

The present invention relates to a kind of aryl-group or arylamino-group substituted quinines compound and preparation method. It is characterized by that in the pure water the amino-group or methoxy-group substituted aromatic compound and p-benzoquinone or naphthoquinone compound are reacted under the catalysis of acid so as to form the aryl-group or arylamino-group substituted p-benzoquinone or naphthoquinone compound.

Description

Quinones and preparation method that a kind of aryl or aryl amine replace
Technical field
The present invention relates to a kind of quinones, relate in particular to para benzoquinone or naphthoquinone compound that a kind of aryl or aryl amine replace.
The invention still further relates to the preparation method of above-claimed cpd.
Background technology
Along with people to the pay attention to day by day of environment protection with to the requirement of the strategy of sustainable development, Green Chemistry is becoming the research focus of sciemtifec and technical sphere.The organic reaction that with water is medium is an important research content in the Green Chemistry.Compare with conventional organic solvents; water has many advantages as reaction medium, as easy and simple to handle, and safety; with low cost; do not pollute the environment, can omit synthesis steps such as a lot of protections and deprotection, utilize the peculiar property of water; as hydrogen bond; hydrophobic lipophilic effect, solvation, the easy accent of soda acid etc. can be realized than better reactive behavior of organic phase and selectivity.
Quinones has a wide range of applications in dyestuff, chemical sensor, medicine and other fields.Along with the deep development of natural product chemistry research, many biologically actives, for example antitumor, antiviral quinones is found, as: in sponge, found Nakijiquinone compound as receptor tyrosine kinase inhibitors; In Chinese medicine blackberry lily (Belamcanda Chinesis L), found Belamcandaquinone compound as lipoxidase inhibitor; Found to have the active asterriquinone compound of anti-hiv reverse transcriptase at Aspergillus terreus.These are naturally occurring to have unique bioactive compounds and all has the structure that alkyl or aryl replaces quinone.
In general, the method of the quinones that synthesizing aryl replaces mainly contains following several: 1, based on the method for oxidation of aromatic ring or hetero-aromatic ring, the normal transiting metal oxidation that adopts, consume a large amount of oxygenants, compare costliness and restive (the Tetrahedron Lett.1985 of reaction conditions, 26,819-822); 2, the Meerwein arylation of quinone and diazonium salt reaction (Chem.Lett.1994,465-468), productive rate is lower, obtains mixture; 3, the catalytic linked reaction of palladium reagent, substrate limitation big (J.Org.Chem.1985,50,5546-5550; Syn.Commun.2000,30,4563-4572); 4, the cyclization of alkynes and carbonyl compound under the illumination condition obtains aryl and replaces quinones, but by product many (Bull.Chem.Soc.Jpn.1979,52,1877-1878).
Quinone can be used as the Michael acceptor and nucleophilic reagent takes place 1, and the 4-addition reaction (TetrahedronLett.2003,44,9121-9124).But as nucleophilic reagent, to 1, the conjugate addition reaction productive rate of 4-benzoquinones is very low, the not even reaction that has with aromatic compound.We find, when being reaction medium with water, and 1,4-benzoquinones and amido or methoxyl group substituted aromatics can react smoothly under Lewis acid or protonic acid catalysis and obtain 1 of para benzoquinone, the 4-adduct.
Summary of the invention
The quinones that the object of the present invention is to provide a kind of aryl or aryl amine to replace.
Another purpose of the present invention is to provide a kind of method for preparing above-claimed cpd.Preparation method provided by the invention reacts simply, and safety is easy and simple to handle, with low cost, is and an eco-friendly class organic synthesis, can realize in the organic phase the reaction that can not carry out.
For achieving the above object, the quinones that aryl provided by the invention or aryl amine replace, its structure as shown in the formula
Figure A20051000953800041
R is hydrogen, methoxyl group, methyl, chlorine or naphthalene in the formula;
Ar is 4-(N, N dimethylamine base) phenyl, 4-(N, N dimethylamine base)-2-p-methoxy-phenyl, 4-(N, the N dimethylamine base)-and 2-aminomethyl phenyl, 2,4-Dimethoxyphenyl, 2,4,6-2,4,5-trimethoxyphenyl, 1-(N, N dimethylamine base) naphthyl, methylphenylamine or 2-methyl furan.
The method for preparing above-claimed cpd provided by the invention is in the pure water medium aromatic compound and para benzoquinone or naphthoquinone compound to be reacted under acid catalysis, generates para benzoquinone or naphthoquinone compound that aryl or aryl amine replace.
Reaction process as shown in the formula:
Figure A20051000953800042
R is hydrogen, methoxyl group, methyl, chlorine or naphthalene in the formula;
Ar is amido or methoxyl group substituted aromatics: 4-(N, the N dimethylamine base) phenyl, 4-(N, the N dimethylamine base)-2-p-methoxy-phenyl, 4-(N, the N dimethylamine base)-2-aminomethyl phenyl, 2,4-Dimethoxyphenyl, 2,4,6-2,4,5-trimethoxyphenyl, 1-(N, N dimethylamine base) naphthyl, methylphenylamine or 2-methyl furan;
Its main preparation process is:
A) with reactant N, accelerine derivative or methyl-phenoxide derivative and benzoquinones or naphthoquinone derivatives are 1 by feed ratio at room temperature: the 1-2 equivalent adds in the aqueous solvent;
B) add the acid catalyst that is equivalent to the normal 5mol% of aromatic compound, stirred 30 minutes-24 hours;
C) with dichloromethane extraction water react liquid, merge organic phase and use anhydrous sodium sulfate drying, filter, concentrate, obtain target compound through the silicagel column purifying.
Productive rate of the present invention can reach 69-93%.
Acid catalyst of the present invention comprises: trifluoromethanesulfonic acid indium, trifluoromethanesulfonic acid scandium, acid catalysts such as trifluoromethanesulfonic acid.
Embodiment
Reagent of the present invention is commodity and obtains.
When the used aromatic compound of the present invention was 1-(N, N dimethylamine base) naphthalene, reaction obtained the para benzoquinone that 4-(N, N dimethylamine base) naphthalene replaces.
The present invention is with furan derivatives or pyrroles and 1, and 4-benzoquinones and derivative thereof carry out above water react, generates the para benzoquinone compounds that furyl or pyrryl replace.
When the used aromatic compound of the present invention is the methylphenylamine derivative, obtain nitrogen as the nucleophilic species carry out 1, the 4-addition reaction generates the para benzoquinone compounds that the p-aryl amine replaces, reaction process as shown in the formula:
Figure A20051000953800051
R in the formula 1: hydrogen, methoxyl group;
Change the feed ratio to 1 of amido or methoxyl group substituted aromatics and para benzoquinone derivative: 1, then obtain 2, the para benzoquinone compounds that the 6-diaryl replaces, as shown in the formula
Figure A20051000953800061
R 4Be hydrogen, methoxyl group;
R 5Be methoxyl group, N, N dimethylamine base.
Change the feed ratio to 1 of methylphenylamine derivative and para benzoquinone derivative: 1, then obtain 2, the para benzoquinone compounds that 5-diaryl-amine base replaces.
Figure A20051000953800062
Embodiment 1:
In the 5mL round-bottomed flask, add 1, the 4-benzoquinones (21.6mg, 0.2mmol), N, N-dimethyl-3-anisidine (15.1mg, 0.1mmol) and the trifluoromethanesulfonic acid indium (2.8mg, 0.005mmol), and 2mL water.Stirred 2 hours under the room temperature.With dichloromethane extraction reaction solution (10mL * 3), organic phase is with anhydrous sodium sulfate drying.Filter, rotary evaporation is removed organic solvent and is obtained crude product.Crude product is through quick purification by silica gel column chromatography (eluent: petrol ether/ethyl acetate=6: 1) obtain blue solid, 2-(4 '-N, N dimethylamine base-2 '-p-methoxy-phenyl)-1,4-benzoquinones 24mg (productive rate: 93%).
Figure A20051000953800063
The physical and chemical index of product: mp:130-131 ℃ .IR (KBr): 2923,1648,1617,1603,1576,1549,1369,1268,796cm -1. 1HNMR (CDCl 3): δ 3.03 (s, 6H), 3.79 (s, 3H), 6.23 (d, J=2.3Hz, 1H), 6.34 (dd, J=8.6,2.3Hz, 1H), 6.74 (dd, J=10.1,2.5Hz, 1H), 6.82 (d, J=10.1Hz, 1H), 6.86 (d, J=2.5Hz, 1H), 7.10 (d, J=8.6Hz, 1H). 13CNMR (CDCl 3): δ 40.3,55.4,95.4,104.4,110.1,132.1,132.2,136.1,137.1,145.3,153.1,158.9,186.9,188.2.Anal Calcd for C 15H 15NO 3: C, 70.02; H, 5.88; N, 5.44.Found:C, 69.92; H, 5.92; N, 5.40.EIMS:m/z (%)=257 (M +, 100).
Embodiment 2:
Add 2-methoxyl group-1 in the 5mL round-bottomed flask, the 4-benzoquinones (55.3mg, 0.4mmol), methylphenylamine (21.4mg, 0.2mmol) and the trifluoromethanesulfonic acid indium (5.6mg, 0.01mmol), and 2mL water.Stirred 40 minutes under the room temperature.With dichloromethane extraction reaction solution (10mL * 3), organic phase is with anhydrous sodium sulfate drying.Filter, rotary evaporation is removed organic solvent and is obtained crude product.Crude product is through quick purification by silica gel column chromatography (eluent: petrol ether/ethyl acetate=3: 1) obtain red solid, 2-methoxyl group-5-(N, N-aminomethyl phenyl amido)-1,4-benzoquinones 43mg (productive rate: 89%).
Figure A20051000953800071
The physical and chemical index of product: mp:242-243 ℃ .IR (KBr): 3057,2980,1664,1618,1570,1494,1238,1043,703cm -1. 1HNMR (CDCl 3): 63.38 (s, 3H), 3.80 (s, 3H), 5.65 (s, 1H), 5.71 (s, 1H), 7.08 (dd, J=7.6,1.2Hz, 2H), 7.26-7.29 (m, 1H), 7.35-7.41 (m, 2H). 13CNMR (CDCl 3): δ 43.2,56.2,105.5,106.4,125.4,126.7,129.7,147.6,151.1,160.0,179.9,183.7.Anal Calcd for C 14H 13NO 3: C, 69.12; H, 5.39; N, 5.76.Found:C, 68.65; H, 5.48; N, 5.72.EIMS:m/z (%)=243 (M +, 100).
Embodiment 3
In the 5mL round-bottomed flask, add 2-methoxyl group-1, the 4-benzoquinones (55.3mg, 0.4mmol), N, accelerine (24.2mg, 0.2mmol) and the trifluoromethanesulfonic acid indium (5.6mg, 0.01mmol), and 2mL water.Stirred 24 hours under the room temperature.With dichloromethane extraction reaction solution (6mL * 3), organic phase is with anhydrous sodium sulfate drying.Filter, rotary evaporation is removed organic solvent and is obtained crude product.Crude product is through quick purification by silica gel column chromatography (eluent: petrol ether/ethyl acetate=6: 1) obtain blue solid, 2-methoxyl group-6-(4 '-N, N dimethylamine base phenyl)-1,4-benzoquinones 39mg (productive rate: 76%).
Figure A20051000953800072
The physical and chemical index of product: mp:240-241 ℃ .IR (KBr): cm -1. 1HNMR (CDCl 3): δ 3.04 (s, 6H), 3.85 (s, 3H), 5.97 (s, 1H), 6.72 (dd, J=7.1,1.9Hz, 2H), 6.73 (s, 1H), 7.51 (dd, J=7.1,1.9Hz, 2H). 13CNMR (CDCl 3): δ 40.1,56.2,107.9,111.8,120.0,126.5,131.2,145.9,151.9,158.8,182.1,187.9.Anal Calcd for C 15H 15NO 3: C, 70.02; H, 5.88; N, 5.44.Found:C, 69.71, H, 5.73, N, 5.42.
Embodiment 4
The ratio that changes reactant in the example 1 obtains disubstituted product.In the 5mL round-bottomed flask, add 1, the 4-benzoquinones (21.6mg, 0.2mmol), N, N-dimethyl-3-anisidine (30.2mg, 0.2mmol) and the trifluoromethanesulfonic acid indium (5.6mg, 0.01mmol), and 2mL water.Stirred 24 hours under the room temperature.With dichloromethane extraction reaction solution (6mL * 3), organic phase is with anhydrous sodium sulfate drying.Filter, rotary evaporation is removed organic solvent and is obtained crude product.The quick purification by silica gel column chromatography of crude product warp (eluent: petrol ether/ethyl acetate=6: 1) obtain red solid, 2, two (4 '-N, the N dimethylamine bases-2 '-p-methoxy-phenyl)-1 of 6-, 4-benzoquinones 32mg (productive rate: 79%).
Figure A20051000953800081
The physical and chemical index of product: mp:181-182 ℃ .IR (KBr): 2926,1668,1635,1608,1366,1242,1091,811cm -1. 1HNMR (CDCl 3): δ 3.02 (s, 12H), 3.83 (s, 6H), 6.24 (d, J=2.1Hz, 2H), 6.34 (dd, J=8.6,2.1Hz, 2H), 6.87 (s, 2H), 7.14 (d, J=8.6Hz, 2H). 13CNMR (CDCl 3): δ 40.4,55.5,95.6,104.5,111.6,131.2,132.2,146.6,152.9,159.0,187.2,188.6.Anal Calcd for C 24H 26N 2O 4: C, 70.92; H, 6.45; N, 6.89.Found:C, 70.65; H, 6.38; N, 6.99.EIMS:m/z (%)=406 (M +, 100).

Claims (3)

1. the quinones that replaces of aryl or aryl amine, its structure as shown in the formula
Figure A2005100095380002C1
R is hydrogen, methoxyl group, methyl, chlorine or naphthalene in the formula;
Ar is 4-(N, N dimethylamine base) phenyl, 4-(N, N dimethylamine base)-2-p-methoxy-phenyl, 4-(N, the N dimethylamine base)-and 2-aminomethyl phenyl, 2,4-Dimethoxyphenyl, 2,4,6-2,4,5-trimethoxyphenyl, 1-(N, N dimethylamine base) naphthyl, methylphenylamine or 2-methyl furan.
2. the method for preparing the described compound of claim 1 is reacted aromatic compound and quinones in water medium under acid catalysis, generate para benzoquinone or naphthoquinone compound that aryl or aryl amine replace; Its key step is:
A) be 1 by feed ratio at room temperature with aromatic compound and quinones: the 1-2 equivalent adds in the entry;
B) add the catalyzer that is equivalent to the normal 5mol% of aromatic compound, stirred 30 minutes-24 hours;
C) with dichloromethane extraction water react liquid, merge organic phase and use anhydrous sodium sulfate drying, filter, concentrate, obtain target compound through the silicagel column purifying;
Wherein aromatic compound is amido or methoxyl group substituted aromatics: 4-(N, the N dimethylamine base) phenyl, 4-(N, the N dimethylamine base)-2-p-methoxy-phenyl, 4-(N, the N dimethylamine base)-2-aminomethyl phenyl, 2,4-Dimethoxyphenyl, 2,4,6-2,4,5-trimethoxyphenyl, 1-(N, N dimethylamine base) naphthyl, methylphenylamine or 2-methyl furan;
Quinones is para benzoquinone or naphthoquinone compound;
3. the preparation method of claim 2 is characterized in that, acid catalyst comprises: trifluoromethanesulfonic acid indium, trifluoromethanesulfonic acid scandium or trifluoromethanesulfonic acid.
CN 200510009538 2005-02-21 2005-02-21 Aryl or aryl amine substuted quinone kind compound and its preparation method Pending CN1824646A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102503799A (en) * 2011-10-10 2012-06-20 山东轻工业学院 Structure, preparation and property of p-benzoquinone novel arene derivative
CN104193603A (en) * 2014-08-12 2014-12-10 齐鲁工业大学 Structure, preparation and application of aryl benzoquinone compound
CN113683524A (en) * 2021-07-23 2021-11-23 北京师范大学-香港浸会大学联合国际学院 Preparation method of isotope-labeled N- (1, 3-dimethylbutyl) -N' -phenyl p-benzoquinone
CN113735723A (en) * 2021-07-23 2021-12-03 北京师范大学-香港浸会大学联合国际学院 Preparation method of N- (1, 3-dimethylbutyl) -N' -phenyl-p-benzoquinone

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102503799A (en) * 2011-10-10 2012-06-20 山东轻工业学院 Structure, preparation and property of p-benzoquinone novel arene derivative
CN104193603A (en) * 2014-08-12 2014-12-10 齐鲁工业大学 Structure, preparation and application of aryl benzoquinone compound
CN113683524A (en) * 2021-07-23 2021-11-23 北京师范大学-香港浸会大学联合国际学院 Preparation method of isotope-labeled N- (1, 3-dimethylbutyl) -N' -phenyl p-benzoquinone
CN113735723A (en) * 2021-07-23 2021-12-03 北京师范大学-香港浸会大学联合国际学院 Preparation method of N- (1, 3-dimethylbutyl) -N' -phenyl-p-benzoquinone
CN113683524B (en) * 2021-07-23 2022-05-17 北京师范大学-香港浸会大学联合国际学院 Preparation method of isotope-labeled N- (1, 3-dimethylbutyl) -N' -phenyl p-benzoquinone

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