CN103360339B - Green method for catalytically synthesizing 2'-aminobenzothiazolyl-arylmethyl-2-naphthol - Google Patents
Green method for catalytically synthesizing 2'-aminobenzothiazolyl-arylmethyl-2-naphthol Download PDFInfo
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- CN103360339B CN103360339B CN201310350252.2A CN201310350252A CN103360339B CN 103360339 B CN103360339 B CN 103360339B CN 201310350252 A CN201310350252 A CN 201310350252A CN 103360339 B CN103360339 B CN 103360339B
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- aminobenzothiazole
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- arylmethyl
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- aromatic aldehyde
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- UNAZUCUHTAAOOS-UHFFFAOYSA-N Oc1c(C(C2C=CC=CC2)Nc2nc3ccccc3[s]2)c(cccc2)c2cc1 Chemical compound Oc1c(C(C2C=CC=CC2)Nc2nc3ccccc3[s]2)c(cccc2)c2cc1 UNAZUCUHTAAOOS-UHFFFAOYSA-N 0.000 description 1
- JWAZRIHNYRIHIV-UHFFFAOYSA-N Oc1ccc(cccc2)c2c1 Chemical compound Oc1ccc(cccc2)c2c1 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 1
- UHGULLIUJBCTEF-UHFFFAOYSA-O [NH3+]c1nc2ccccc2[s]1 Chemical compound [NH3+]c1nc2ccccc2[s]1 UHGULLIUJBCTEF-UHFFFAOYSA-O 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention provides a green method for catalytically synthesizing 2'-aminobenzothiazolyl-arylmethyl-2-naphthol, belonging to the field of organic chemical synthesis. The method comprises the following steps: carrying out synthetic reaction, wherein the aromatic aldehyde:2-aminobenzothiazole:beta-naphthol mol ratio is 1:1:1, the bissulfonate acidic ion liquid catalyst accounts for 5-8 mol% of the aromatic aldehyde, the reaction temperature is 80-95 DEG C, the reaction time is 3-10 minutes, and the volume (ml) of the reaction solvent water is 3-5 times of the molar weight (mmol) of the aromatic aldehyde; and after the reaction is finished, cooling to room temperature, carrying out vacuum filtration, recrystallizing the filter residue with 95% ethanol, and carrying out vacuum drying to obtain the 2'-aminobenzothiazolyl-arylmethyl-2-naphthol.Compared with other synthesis methods, the invention has the characteristics of high catalytic activity, low catalyst consumption, recyclable catalyst, low environmental pollution in the whole process, simple and convenient after-treatment and the like.
Description
Technical field
The invention belongs to organic chemical synthesis field, be specifically related to the method for a kind of green catalysis synthesis 2 '-aminobenzothiazole-arylmethyl-beta naphthal.
Background technology
Heterogeneous ring compound containing thiazole ring has broad-spectrum biological activity, can be used as local anesthetic, and there is anticonvulsion, antiviral, antibacterial, desinsection, the effect such as anti-inflammatory and antianaphylaxis, wherein containing aminothiazole cyclics, there is stronger physiologically active, can be used for treatment allergy, hypertension, osteoporosis, asthma, cancer, HIV virus, be also widely used in cytobiology simultaneously.In addition, it or the good intermediate of a class, can there is a series of reaction in amido functional group, the various compounds synthesized thus have a wide range of applications in medicine, agricultural chemicals, dyestuff etc.Therefore, receive the concern of Pharmaceutical Chemist containing aminothiazole lopps derivative, the medicine of this class formation of research and development synthesis has important theory significance and practical value always.
2 '-aminobenzothiazole-arylmethyl-beta naphthal is as containing the very important compound of one in aminothiazole lopps derivative, its preparation also becomes the focus that organic synthesis men are studied, the research of the catalyst system particularly adopted for aromatic aldehyde, 2-aminobenzothiazole and 2-Naphthol one-step synthesis method.Such as 2007, it is catalyzer that Shaabani etc. report with LiCl, by aromatic aldehyde in water medium, 2-aminobenzothiazole and 2-Naphthol have synthesized the method for 2 '-aminobenzothiazole-arylmethyl-beta naphthal, the method has the advantage of Green Chemistry, but there is long reaction time, catalyst levels is large, expensive, not easily shortcoming (Water promoted one-pot synthesis of2 '-aminobenzothiazolomethyl naphthols and5-(2 '-the aminobenzothiazolomethyl)-hydroxyquinolines such as recovery, Tetrahedron Letters, 2007, 48:7291-7294).Acidic ion liquid, particularly preparation simple, to all stable bronsted acid ionic liquid of water and air, because it has green non-pollution, to organicly having good solubility, the acidic site be evenly distributed with mineral compound, is easy to product and is separated and the advantage such as can recycles and be applied in as green catalyst in the synthesis of 2 '-aminobenzothiazole-arylmethyl-beta naphthal.Such as Guo Hong cloud etc. are with ionic liquid [Hnmp] HSO
4(N-Methyl pyrrolidone hydrosulfate) is as catalyzer, under condition of no solvent, catalysis aromatic aldehyde, 2-aminobenzothiazole and 2-Naphthol have synthesized a series of 2 '-aminobenzothiazole-arylmethyl-beta naphthal, the method reaction conditions is gentle, reaction times is shorter, and productive rate is higher and environmentally friendly.In addition, catalyzer can reclaim easily, and recycles four its catalytic activitys and significantly do not reduce (ionic liquid [Hnmp] HSO under condition of no solvent
4catalysis one pot process 2 '-aminobenzothiazole-arylmethyl-beta naphthal, organic chemistry, 2011,51 (1): 96-100).
The acidic ion liquid adopted above due to acidity more weak, in the process of catalyzing and condensing aromatic aldehyde, 2-aminobenzothiazole and 2-Naphthol synthesis 2 '-aminobenzothiazole-arylmethyl-beta naphthal, catalytic effect is still waited to improve, simultaneously the usage quantity of ionic liquid comparatively large (accounting for 10% of aromatic aldehyde molar weight used).In addition, the number of dropouts of ionic liquid in recycling is also comparatively large, can only recycle 4 times.All these make the technological process benefit of the method lower, in the suitability for industrialized production of 2 '-aminobenzothiazole-arylmethyl-beta naphthal, be difficult to large-scale use.
Summary of the invention
The object of the invention is to overcome the acidic ionic liquid catalysts usage quantity that exists in prior art and recycle all very large shortcoming of middle number of dropouts, and provide a kind of using water as reaction solvent, catalyzer is made, the method for green catalysis synthesis 2 '-aminobenzothiazole-arylmethyl-beta naphthal that product purity and productive rate are all very high with the disulfonic acid root acidic ion liquid that acidity is higher.
The structural formula of disulfonic acid root acidic ionic liquid catalysts used in the present invention is:
The method of a kind of green catalysis synthesis 2 '-aminobenzothiazole-arylmethyl-beta naphthal provided by the present invention, its reaction formula is:
Wherein aromatic aldehyde (I) in reaction, 2-aminobenzothiazole (II) is 1:1:1 with the mol ratio of 2-Naphthol (III), the molar weight of disulfonic acid root acidic ionic liquid catalysts is 5 ~ 8% of aromatic aldehyde used, temperature of reaction is 80 ~ 95 DEG C, reaction times is 3 ~ 10min, 3 ~ 5 times that the volume (ml) of reaction solvent water is aromatic aldehyde molar weight (mmol), reaction pressure is a normal atmosphere, room temperature is cooled to after reaction, suction filtration, filter residue 95% ethyl alcohol recrystallization, pure 2 '-aminobenzothiazole-arylmethyl-beta naphthal (IV) is obtained after vacuum-drying.The disulfonic acid root acidic ionic liquid catalysts contained in filtrate and the raw material that unreacted is complete on a small quantity, can not treatedly reuse.
The present invention's aromatic aldehyde (I) used is phenyl aldehyde, any one in 2-chlorobenzaldehyde, 4-chlorobenzaldehyde, 4-nitrobenzaldehyde, 4-tolyl aldehyde, 4-methoxybenzaldehyde, Benzaldehyde,2-hydroxy, 2-nitrobenzaldehyde, 2,4 dichloro benzene formaldehyde.
The preparation method of disulfonic acid root acidic ionic liquid catalysts used in the present invention, see pertinent literature (Diastereoselectivesynthesis of pyrazolines using a bifunctional Br nsted acidic ionic liquid under solvent-freeconditions.Advanced Synthesis & Catalysis, 354 (2012), 3095-3104).
Compared with the preparation method that the present invention and other acidic ion liquid make catalyzer, there is following characteristics:
1, the sour density containing disulfonic acid root acidic ion liquid is high, and catalytic activity is good, and catalysis productive rate is high;
2, catalyzer usage quantity is few and to recycle middle loss amount also less;
3, use water as reaction solvent, environmental pollution is little;
4, last handling process is easy, and catalyzer just can be recycled without any process.
Embodiment
In order to more clearly describe the present invention, now enumerate following examples, but the present invention is not limited to following embodiment, under the scope not departing from the described aim in front and back, any change all should be included within protection scope of the present invention.Embodiment reaction product nuclear magnetic resonance analyser and infrared spectrometer test characterize, wherein
1h NMR uses Bruker AVANCE-II500MHz, and what IR adopted is NEXUS670 Fourier infrared spectrograph.
Embodiment 1
1mmol phenyl aldehyde, 1mmol2-aminobenzothiazole, 1mmol 2-Naphthol, 3ml water and 0.05mmol disulfonic acid root acidic ion liquid are joined respectively 25ml with in the single port bottle of stirrer and reflux condensing tube.At 80 DEG C, vigorous stirring reaction 5min, TLC (thin plate chromatography) detects, and raw material point disappears, be cooled to room temperature, suction filtration, obtain straight product 2 '-aminobenzothiazole-phenyl methyl-beta naphthal after gained filter residue 95% aqueous ethanolic solution recrystallization, vacuum-drying, productive rate is 94%.Directly add phenyl aldehyde, 2-aminobenzothiazole and 2-Naphthol in filtrate to reuse.
2 '-aminobenzothiazole-phenyl methyl-beta naphthal:
1h NMR (500MHz, DMSO-d
6): δ=6.97 ~ 7.86 (m, 16H, ArH/CH), 8.80 (s, 1H ,-NH-), 10.13 (s, 1H ,-OH); IR (KBr): ν=3379,1623,1595,1544,1518,1445,1332,1270,814,750cm
-1
Embodiment 2
1mmol2-chlorobenzaldehyde, 1mmol2-aminobenzothiazole, 1mmol 2-Naphthol, 5ml water and 0.05mmol disulfonic acid root acidic ion liquid are joined respectively 25ml with in the single port bottle of stirrer and reflux condensing tube.Vigorous stirring reaction 4min at 80 DEG C, TLC (thin plate chromatography) detects, raw material point disappears, be cooled to room temperature, suction filtration, obtain straight product 2 '-aminobenzothiazole-(2-chloro-phenyl-) methyl-beta naphthal after gained filter residue 95% aqueous ethanolic solution recrystallization, vacuum-drying, productive rate is 95%.Directly add 2-chlorobenzaldehyde, 2-aminobenzothiazole and 2-Naphthol in filtrate to reuse.
2 '-aminobenzothiazole-(2-chloro-phenyl-) methyl-beta naphthal:
1h NMR (500MHz, DMSO-d
6): δ=6.96 ~ 8.04 (m, 15H, ArH/CH), 8.82 (s, 1H ,-NH-), 9.91 (s, 1H ,-OH); IR (KBr): ν=3384,1628,1597,1543,1440,1319,1271,815,754cm
-1
Embodiment 3
1mmol4-nitrobenzaldehyde, 1mmol2-aminobenzothiazole, 1mmol 2-Naphthol, 5ml water and 0.05mmol disulfonic acid root acidic ion liquid are joined respectively 25ml with in the single port bottle of stirrer and reflux condensing tube.Vigorous stirring reaction 3.5min at 85 DEG C, TLC (thin plate chromatography) detects, raw material point disappears, be cooled to room temperature, suction filtration, obtain straight product 2 '-aminobenzothiazole-(4-nitrophenyl) methyl-beta naphthal after gained filter residue 95% aqueous ethanolic solution recrystallization, vacuum-drying, productive rate is 96%.Directly add 4-nitrobenzaldehyde, 2-aminobenzothiazole and 2-Naphthol in filtrate to reuse.
2 '-aminobenzothiazole-(4-nitrophenyl) methyl-beta naphthal:
1h NMR (500MHz, DMSO-d
6): δ=7.06 ~ 8.14 (m, 15H, ArH/CH), 8.92 (s, 1H ,-NH-), 10.21 (s, 1H ,-OH); IR (KBr): ν=3393,1626,1599,1534,1443,1349,1270,813,753cm
-1
Embodiment 4
1mmol4-tolyl aldehyde, 1mmol2-aminobenzothiazole, 1mmol 2-Naphthol, 4ml water and 0.05mmol disulfonic acid root acidic ion liquid are joined respectively 25ml with in the single port bottle of stirrer and reflux condensing tube.Vigorous stirring reaction 3min at 80 DEG C, TLC (thin plate chromatography) detects, raw material point disappears, be cooled to room temperature, suction filtration, obtain straight product 2 '-aminobenzothiazole-(4-aminomethyl phenyl) methyl-beta naphthal after gained filter residue 95% aqueous ethanolic solution recrystallization, vacuum-drying, productive rate is 96%.Directly add 4-tolyl aldehyde, 2-aminobenzothiazole and 2-Naphthol in filtrate to reuse.
2 '-aminobenzothiazole-(4-aminomethyl phenyl) methyl-beta naphthal:
1h NMR (500MHz, DMSO-d
6): δ=2.22 (s, 3H ,-CH
3), 6.98 ~ 7.84 (m, 15H, ArH/CH), 8.76 (s, 1H ,-NH-), 10.11 (s, 1H ,-OH); IR (KBr): ν=3373,1629,1595,1541,1453,1336,1273,1204,815,750cm
-1
Embodiment 5
1mmol4-methoxybenzaldehyde, 1mmol2-aminobenzothiazole, 1mmol 2-Naphthol, 4ml water and 0.08mmol disulfonic acid root acidic ion liquid are joined respectively 25ml with in the single port bottle of stirrer and reflux condensing tube.Vigorous stirring reaction 5min at 90 DEG C, TLC (thin plate chromatography) detects, raw material point disappears, be cooled to room temperature, suction filtration, obtain straight product 2 '-aminobenzothiazole-(4-p-methoxy-phenyl) methyl-beta naphthal after gained filter residue 95% aqueous ethanolic solution recrystallization, vacuum-drying, productive rate is 95%.Directly add 4-methoxybenzaldehyde, 2-aminobenzothiazole and 2-Naphthol in filtrate to reuse.
2 '-aminobenzothiazole-(4-p-methoxy-phenyl) methyl-beta naphthal:
1h NMR (500MHz, DMSO-d
6): δ=3.67 (s, 3H ,-OCH
3), 6.85 ~ 7.92 (m, 15H, ArH/CH), 8.78 (s, 1H ,-NH-), 10.13 (s, 1H ,-OH); IR (KBr): ν=3374,1626,1598,1542,1510,1451,1256,1173,818,752cm
-1
Embodiment 6
1mmol2,4-dichlorobenzaldehyde, 1mmol2-aminobenzothiazole, 1mmol 2-Naphthol, 5ml water and 0.08mmol disulfonic acid root acidic ion liquid are joined respectively 25ml with in the single port bottle of stirrer and reflux condensing tube.Vigorous stirring reaction 10min at 90 DEG C, TLC (thin plate chromatography) detects, raw material point disappears, be cooled to room temperature, suction filtration, obtain straight product 2 '-aminobenzothiazole-(2,4 dichloro benzene base) methyl-beta naphthal after gained filter residue 95% aqueous ethanolic solution recrystallization, vacuum-drying, productive rate is 94%.Directly add 2,4 dichloro benzene formaldehyde, 2-aminobenzothiazole and 2-Naphthol in filtrate to reuse.
2 '-aminobenzothiazole-(2,4 dichloro benzene base) methyl-beta naphthal:
1h NMR (500MHz, DMSO-d
6): δ=6.98 ~ 8.04 (m, 14H, ArH/CH), 8.88 (s, 1H ,-NH-), 9.93 (s, 1H ,-OH); IR (KBr): ν=3379,1627,1596,1540,1470,1454,1268,816,751,687cm
-1
Embodiment 7
With embodiment 1 for probe reaction, make the active replica test of catalysts disulfonic acid root acidic ion liquid, ionic liquid reuses 5 times.The yield data of reaction is in table 1.
The catalyst activity replica test result that table 1 the present invention uses
| Disulfonic acid root acidic ion liquid access times | Productive rate (%) |
| 1 | 94 |
| 2 | 92 |
| 3 | 91 |
| 4 | 91 |
| 5 | 90 |
| 6 | 88 |
Such conclusion can be drawn: the productive rate that catalyzer is recycling 2 '-aminobenzothiazole in process-phenyl methyl-beta naphthal is in a slight decrease by table 1 data, but the amplitude of reduction is less, proves that it can recycle in preparation 2 '-aminobenzothiazole-arylmethyl-beta naphthal.
Claims (2)
1. the method for green catalysis synthesis 2 '-aminobenzothiazole-arylmethyl-beta naphthal, wherein synthesize aromatic aldehyde in the reaction of 2 '-aminobenzothiazole-arylmethyl-beta naphthal, the mol ratio of 2-aminobenzothiazole and 2-Naphthol is 1:1:1, the molar weight of disulfonic acid root acidic ionic liquid catalysts is 5 ~ 8% of aromatic aldehyde used, temperature of reaction is 80 ~ 95 DEG C, reaction times is 3 ~ 10min, be with 3 ~ 5 times of the aromatic aldehyde amount of mmole gauge in the volume of the reaction solvent water of milliliter, reaction pressure is a normal atmosphere, room temperature is cooled to after reaction, suction filtration, filter residue 95% ethyl alcohol recrystallization, pure 2 '-aminobenzothiazole-arylmethyl-beta naphthal is obtained after vacuum-drying,
Described aromatic aldehyde is any one in phenyl aldehyde, 2-chlorobenzaldehyde, 4-chlorobenzaldehyde, 4-nitrobenzaldehyde, 4-tolyl aldehyde, 4-methoxybenzaldehyde, Benzaldehyde,2-hydroxy, 2-nitrobenzaldehyde and 2,4 dichloro benzene formaldehyde;
The structural formula of described disulfonic acid root acidic ionic liquid catalysts is:
2. the method for a kind of green catalysis synthesis 2 '-aminobenzothiazole-arylmethyl-beta naphthal as claimed in claim 1, it is characterized in that, the disulfonic acid root acidic ionic liquid catalysts contained in filtrate after described suction filtration can not treatedly be reused.
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| CN113816973B (en) * | 2021-10-27 | 2022-07-12 | 江西力田维康科技有限公司 | Preparation method of medical intermediate benzothiazole [2, 3-b ] quinazolinedione derivative |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2868774A (en) * | 1957-04-15 | 1959-01-13 | Eastman Kodak Co | Metallizable azo dyes prepared from amino-benzothiazole derivatives and beta-naphthol derivatives |
| CN1065457A (en) * | 1991-04-04 | 1992-10-21 | 卫材株式会社 | Benzothiazole derivant |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2868774A (en) * | 1957-04-15 | 1959-01-13 | Eastman Kodak Co | Metallizable azo dyes prepared from amino-benzothiazole derivatives and beta-naphthol derivatives |
| CN1065457A (en) * | 1991-04-04 | 1992-10-21 | 卫材株式会社 | Benzothiazole derivant |
Non-Patent Citations (4)
| Title |
|---|
| Ahmad Shaabani,等.Water promoted one-pot synthesis of 2’-aminobenzothiazolomethyl naphthols and 5-(2’-aminobenzothiazolomethyl)-6-hydroxyquinolines.《Tetrahedron Letters》.2007,第48卷(第41期), * |
| Allen Ohanian,等.One-pot Synthesis of 2’-Aminobenzothiazolomethylnaphtols In water catalyzed by Wells-Dawson heteropolyacid.《International Electronic Conference on Synthetic Organic Chemistry》.2009,第13卷 * |
| Anil Kumar,等.Sodium Dodecyl Sulfate-assisted Synthesis of 1-(Benzothiazolylamino)methyl-2-naphthols in Water.《Aust.J.Chem》.2010,第63卷(第11期), * |
| 余意,等.无溶剂条件下离子液体[Hnmp]HS04催化一锅法合成2’-氨基苯并噻唑一芳甲基-2-萘酚.《有机化学》.2011,第31卷(第96-100期), * |
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