- Synthesis of 2,4-dihydroxyquinazolines using carbon dioxide in the presence of DBU under mild conditions
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Chemical fixation of carbon dioxide was performed under mild conditions. Carbon dioxide (1 atm) easily reacted with 2-aminobenzonitriles at 20°C, assisted by DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) to give 2,4- dihydroxyquinazolines in excellent yields.
- Mizuno, Takumi,Okamoto, Noriaki,Ito, Takatoshi,Miyata, Toshiyuki
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- [TBDH][HFIP] ionic liquid catalyzed synthesis of quinazoline-2,4(1H,3H)-diones in the presence of ambient temperature and pressure
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The utilization of carbon dioxide under mild reaction conditions is an important aspect of the sustainable chemistry point of view. Herein, we prepared three bifunctional protic ionic liquids having 1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) as a cation and an alcohol anions were prepared by simple neutralization of the super base TBD with proton donor alcohols such as hexafluoroisopropanol (HFIP), TFE (2,2,2-Trifluoroethanol) and TFA (2,2,2-Trifluoroacetic acid). These PILs were used as catalysts for chemical fixation of carbon dioxide into quinazoline-2,4(1H,3H)-diones. [TBDH+][HFIP-] protic ionic liquid (PIL) shows very good result compare to other PILs. As a bifunctional ionic liquid, it simultaneously activates 2-aminobenzonitrile as well as CO2 and shows excellent performance for the conversion of 2-aminobenzonitrile to quinazoline-2,4(1H,3H)-diones in presence of CO2 balloon pressure at 35 °C temperature. Moreover, the [TBDH+][HFIP-] PIL can be recycled up to six recycle run.
- Phatake, Vishal V.,Gokhale, Tejas A.,Bhanage, Bhalchandra M.
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- Proton type ionic liquid [HDBN] [2-PyOH] and preparation and application thereof
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The invention discloses proton type ionic liquid [HDBN] [2-PyOH] and preparation and application thereof, and belongs to the technical field of catalysts. The preparation method comprises the steps that 1, 5-diazabicyclo [4.3. 0] nonyl-5-ene reacts with 2-hydroxypyridine to prepare protonic ionic liquid [HDBN] [2-PyOH]; and as a catalyst, the ionic liquid can catalyze CO2 and o-aminobenzonitrile compounds to efficiently react under mild conditions to obtain a series of quinazoline-2, 4 (1H, 3H)-diketone compounds. The proton type ionic liquid catalyst has the advantages of simple synthesis process, excellent catalytic performance, good substrate expansion capability, easy product separation and the like, and has a good industrial application prospect.
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Paragraph 0021; 0025-0029; 0070-0074
(2021/11/21)
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- Alcohol amine-catalyzed CO2conversion for the synthesis of quinazoline-2,4-(1H,3H)-dione in water
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The conversion of CO2to high value-added chemicals in water using environment-friendly and cost-effective catalysts is a very significant topic. In this work, a green method for the conversion of CO2catalyzed by alcohol amines has been developed. Alcohol amines showed considerable activating ability to CO2in the cyclization with 2-aminobenzonitrile to quinazoline-2,4(1H,3H)-dione in water. Notably, when diethanolamine (DEA) was used as the catalyst, 94% yield of quinazoline-2,4-(1H,3H)-dione could be achieved. A plausible mechanism has been proposed based on the1H NMR, FT-IR analysis and DFT calculation. The excellent catalytic performance is attributed to the combined effect of both the secondary amine and hydroxyl groups on alcohol amines with the assistance of water in the formation of carbamate. Water plays a bi-functional role of solvent and co-catalyst in this catalytic process. Catalysts can be easily recovered and reused five times without significant loss of activity.
- Huang, Min-Min,Sheng, Zhi-Zheng,Wu, Hai-Hong,Xia, Fei,Xue, Teng
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p. 34910 - 34915
(2020/10/12)
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- Synthesis method of 2, 4-(1H, 3H)-quinazolinedione and derivatives thereof
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The invention discloses a synthesis method of 2, 4-(1H, 3H)-quinazolinedione and derivatives thereof. CO2 and aminobenzonitrile compounds are used as raw materials, and the 2, 4-(1H, 3H)-quinazolinedione and the derivatives thereof are obtained through a reaction by adopting a catalyst as shown in the formula I provided by the invention. Reagents used in the method are cheap and easy to obtain, the product can be synthesized through a one-step method, harsh conditions of high pressure and high temperature are not needed, no metal is left in the whole reaction system, and the used catalyst canbe recycled.
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Paragraph 0077-0078; 0085-0086
(2020/08/06)
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- Efficient transformation of CO2 into quinazoline-2,4(1: H,3 H)-diones at room temperature catalyzed by a ZnI2/NEt3 system
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The readily available ZnI2/NEt3 system was used firstly to catalyze the transformation of CO2 and 2-aminobenzonitriles into quinazoline-2,4(1H,3H)-diones at room temperature and low CO2 pressure in high yields. Further experiments indicated that this ZnI2/NEt3 system has excellent effects on activating both amino and cyano groups.
- Chen, Shangqing,Wang, Zheng,Hu, Jiayin,Guo, Yafei,Deng, Tianlong
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p. 16164 - 16168
(2019/11/03)
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- CO2 involved synthesis of quinazoline-2,4(1 H,3 H)-diones in water using melamine as a thermoregulated catalyst
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In this study, pharmaceutically relevant quinazoline-2,4(1H,3H)-diones were synthesized eco-efficiently by cycloaddition of CO2 and 2-aminobenzonitrile in water, catalyzed by melamine as a thermoregulated catalyst. Quinazoline-2,4(1H,3H)-dione was produced selectively with 92% yield at 120 °C, 4.2 MPa, and automatically separated from the hot catalytic aqueous solution, which was reused directly for several runs until its activity decreased in an obvious manner. Then, the catalyst melamine was recrystallized from the spent aqueous solution via simple cooling and reused for another several catalytic runs. The efficient valorization of CO2 and the straightforward stepwise recovery of the products and catalyst were important to save energy and minimize process waste for the practical industrial production.
- Zhao, Guo-Ying,Mu, Ling-Ling,Ullah, Latif,Wang, Meng,Li, Hong-Ping,Guan, Xin-Xin
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p. 212 - 218
(2019/03/06)
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- Facile and efficient synthesis of quinazoline-2,4(1H,3H)-diones through sequential hydrogenation condensation
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The heterocyclizations from various methyl (2-nitrobenzoyl)carbamates to substituted quinazoline-2,4(1H,3H)-diones under hydrogenation conditions were investigated in this study. In the presence of p-toluenesulfonic acid monohydrate in methanol, various q
- Wang, Peng-Xu,Wang, Ya-Nan,Lin, Zi-Yun,Li, Gang,Huang, Hai-Hong
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supporting information
p. 1183 - 1189
(2018/04/02)
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- Efficient synthesis of 2-oxazolidinones and quinazoline-2,4(1H,3H)-diones from CO2 catalyzed by tetrabutylammonium fluoride
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By employing tetrabutylammonium fluoride (TBAF) as a catalyst, the various carboxylative cyclizations of the propargylic amines having internal alkynes with CO2 proceeded to afford the corresponding 2-oxazolidinones. In this case, it was also found that the generated 2-oxazolidinones were tautomerized into the corresponding 2-oxazolones due to the basicity of TBAF. In addition, we performed the synthesis of quinazoline-2,4(1H,3H)-dione from 2-aminobenzonitrile and CO2 by using TBAF as a catalyst.
- Fujii, Akira,Matsuo, Hideaki,Choi, Jun-Chul,Fujitani, Tadahiro,Fujita, Ken-ichi
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p. 2914 - 2920
(2018/05/16)
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- Basic Salt-Lake Brine: An Efficient Catalyst for the Transformation of CO2 into Quinazoline-2,4(1 H,3 H)-diones
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The efficient transformation of CO2 into value-added chemicals with green, abundant, and cheap catalysts is an interesting and challenging topic in both green and sustainable chemistry. In this study, a series of salt-lake brines were used for the first time to catalyze the reaction of CO2 and a broad range of 2-aminobenzonitriles to form the corresponding quinazoline-2,4(1 H,3 H)-diones. It was found that the abundant, available, and inexpensive Zhabuye basic salt-lake brine could efficiently promote the reaction of 2-aminobenzonitriles under low pressure of CO2. Very high yields of value-added products were obtained. Further studies indicated that the basic carbonate and borate ions in the brine play key roles in accelerating the reactions.
- Hu, Jiayin,Chen, Shangqing,Guo, Yafei,Li, Long,Deng, Tianlong
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p. 4219 - 4225
(2018/12/11)
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- A 2, 4 - quinazoline dione compound preparation method
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The invention belongs to the field of organic chemistry, and concretely relates to a preparation method of benzoyleneurea compounds. The preparation method comprises the following steps: a 2-aminobenzonitrile compound and carbon dioxide are used as raw materials, preferably a reaction employs acylamino divalent rare earth metal amides and DBU as catalysts at 50-150 DEG C under a normal pressure, the reaction is carried out in an aprotic polar solvent for 4-40 hours, and the benzoyleneurea compounds are obtained with a high yield. The method has the advantages of mild reaction condition, few catalyst amount, simple separation and purification, high yield and wide substrate application range.
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Paragraph 0116; 0117
(2017/10/31)
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- Synthetic method of quinazoline-2,4(1H, 3H)-dione and derivatives thereof
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The invention discloses a synthetic method of quinazoline-2,4(1H, 3H)-dione and derivatives thereof. The method comprises the following steps: carrying out a carboxy cyclization on a substrate o-aminobenzontrile or 4,5-position substituted derivatives thereof in carbon dioxide with a diethanolamine-water solution as a catalyst, and filtering, washing and drying the obtained reaction solution to obtain the product quinazoline-2,4(1H, 3H)-dione and the derivatives thereof, wherein a molar ratio of the substrate to the diethanolamine-water solution is (3-8):(1-3); the reaction temperature of the carboxy cyclization is 60-140 DEG C, and the reaction time is 6-18 h; and the pressure of the carbon dioxide is 0.5-2 MPa. Compared with the prior art, the synthetic method has the advantages of low cost of the catalyst, high product yield and good selectivity, and is an environmentally-friendly method for homogeneous catalytic synthesis of the quinazoline-2,4(1H, 3H)-dione and the derivatives thereof.
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Paragraph 0030-0031
(2017/09/01)
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- Cyanuric Acid-Based Organocatalyst for Utilization of Carbon Dioxide at Atmospheric Pressure
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A organocatalytic system based on economical and readily available cyanuric acid has been developed for the synthesis of 2-oxazolidinones and quinazoline-2,4(1H,3H)-diones from propargylamines and 2-aminobenzonitriles under atmospheric pressure carbon dioxide. Notably, a low concentration of carbon dioxide in air was directly converted into 2-oxazolidinone in excellent yields without an external base. Through mechanistic investigation by in situ FTIR spectroscopy, cyanuric acid was demonstrated to be an efficient catalyst for carbon dioxide fixation.
- Yu, Bing,Kim, Daeun,Kim, Seoksun,Hong, Soon Hyeok
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p. 1080 - 1084
(2017/03/29)
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- SUBSTITUTED QUINAZOLINE COMPOUNDS AND PREPARATION AND USES THEREOF
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The present invention relates quinazolinone compounds of Formula (I), as well as their preparation and uses, and further relates pharmaceutical compositions comprising these compounds and their uses； wherein the compounds or pharmaceutical compositions disclosed herein can be used for antagonizing the orexin receptor. The present invention also relates to uses of the compounds or pharmaceutical compositions in treating or preventing neurological and psychiatric disorders and diseases of the central nervous system in mammals, especially in humans.
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Page/Page column 52; 71
(2017/03/08)
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- Carbon Dioxide Mediated Novel Synthesis of Quinazoline-2,4(1H,3H)-dione in Water
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A novel, efficient, and scalable CO2 mediated synthesis of quinazoline-2,4(1H,3H)-dione was developed by a simple cyclization of 2-aminobenzonitrile with DMF in water as the solvent. This is the first report of its kind. DMF was used as the necessary carbon source in the synthesis of quinazoline-2,4(1H,3H)-dione. This synthetic protocol is very efficient; it gives >99% conversion with excellent selectivity. The product was isolated by filtration because of the highly insoluble nature of quinazoline-2,4(1H,3H)-dione in water. The co-product, dimethyl amine, also has industrial importance, and the CO2 that is used can be recycled. This protocol has wide-spread applications in the syntheses of benzimidazole and benzothiazole.
- Rasal, Kalidas B.,Yadav, Ganapati D.
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p. 2067 - 2073
(2016/12/24)
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- Synthesis and Characterization of Amidato Divalent Lanthanide Complexes and Their Use in Forming 2,4-Quinazolidinones from CO2 and 2-Aminobenzonitriles
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Four amidato divalent lanthanide complexes, {LnLn[N(TMS)2]THF}2 [n = 1, Ln = Eu (1); n = 2, Ln = Eu (3), Yb (4); HL1 = tBuC6H4CONHC6H3(iPr)2; HL2 = C6H5CONHC6H3(iPr)2] and {L3Eu[N(TMS)2]THF}{L32Eu(THF)2} (2) [HL3 = ClC6H4CONHC6H3(iPr)2], were synthesized and extensively characterized. This is the first time that the amidato lanthanide amides 1-4 were used to catalyze the reactions of CO2 and 2-aminobenzonitriles to form quinazoline-2,4(1H,3H)-diones at atmospheric pressure. All the complexes efficiently catalyzed the transformation, with complex 3 showing the highest activity. This catalytic system gave good to excellent yields, and good functional group tolerance. Preliminary studies were conducted to investigate the reaction mechanism.
- Wang, Qianyu,Lu, Chengrong,Zhao, Bei,Yao, Yingming
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p. 2555 - 2559
(2016/06/01)
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- Azole-Anion-Based Aprotic Ionic Liquids: Functional Solvents for Atmospheric CO2 Transformation into Various Heterocyclic Compounds
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The chemical transformation of atmospheric CO2 is of great significance yet still poses a great challenge. Herein, azole-anion-based aprotic ionic liquids (ILs) were synthesized by the deprotonation of weak proton donors (e.g., 2-methylimidazole, 4-methylimidazole, and 2,4-dimethylimidazole) with tetrabutylphosphonium hydroxide, [Bu4P][OH]. We found that these ILs, such as [Bu4P][2-MIm], could activate atmospheric CO2 through the formation of carbamates. The resultant carbamate intermediates could further react with various types of substrate, including propargylic alcohols, 2-aminobenzonitriles, ortho-phenylenediamines, and 2-aminothiophenol, thereby producing α-alkylidene cyclic carbonates, quinazoline-2,4(1 H,3 H)-diones, benzimidazolones, and benzothiazoline, respectively, in moderate-to-good yields. Thus, we have achieved the transformation of CO2 at atmospheric pressure, and we expect this method to open up new routes for the synthesis of various oxygen-containing heterocyclic compounds under metal-free conditions.
- Zhao, Yanfei,Wu, Yunyan,Yuan, Guangfeng,Hao, Leiduan,Gao, Xiang,Yang, Zhenzhen,Yu, Bo,Zhang, Hongye,Liu, Zhimin
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p. 2735 - 2740
(2016/10/11)
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- La-Mg mixed oxide as a highly basic water resistant catalyst for utilization of CO2 in the synthesis of quinazoline-2,4(1H,3H)-dione
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The synthesis of quinazoline-2,4(1H,3H)-dione was done by direct utilization of CO2 in the cyclization of 2-aminobenzonitrile (2-ABN) using lanthanum magnesia mixed oxide (La-Mg MO) as a strong basic catalyst under mild reaction conditions in water. It gave a conversion of ～92% with 100% selectivity at 140 °C in 14 h. La-Mg MO was prepared by hydrothermal method using urea as homogeneous precipitating agent. The catalyst was characterized by different analytical techniques like BET, XRD, FT-IR, SEM, and TGA, and the basicity by CO2-TPD and acidity by NH3 TPD. Various reaction parameters were studied to predict the reaction mechanism and kinetics. The reaction follows the Langmuir-Hinshelwood-Hougen-Watson (LHHW) type kinetics model with an apparent activation energy of 23.3 kcal mol-1. The catalyst was recycled three times with an insignificant change in activity. The overall process is clean and green.
- Rasal,Yadav, Ganapati D.
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p. 111079 - 111089
(2016/12/03)
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- Ionic liquid catalyst and its preparation method and application
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The invention discloses an ionic liquid catalyst as well as a preparation method and an application of the ionic liquid catalyst. The ionic liquid catalyst is composed of negative ions as shown in a formula II and any one of positive ions as shown in formulas Ia to Ic. The ionic liquid catalyst is applicable to catalyzing a reaction system in which CO2 reacts with a series of aminobenzonitrile compounds to synthesize quinazoline-2,4(1H, 3H)-diketone compounds at a normal temperature and under normal pressure; the ionic liquid catalyst is easy to synthesize, green, efficient and easy to recovery, and also has high application value. The formulas are shown in the specification.
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Paragraph 0044; 0064-0065
(2017/02/17)
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- Function-oriented development of CXCR4 antagonists as selective human immunodeficiency virus (HIV)-1 entry inhibitors
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Motivated by the pivotal role of CXCR4 as an HIV entry co-receptor, we herein report a de novo hit-to-lead effort on the identification of subnanomolar purine-based CXCR4 antagonists against HIV-1 infection. Compound 24, with an EC50 of 0.5 nM against HIV-1 entry into host cells and an IC50 of 16.4 nM for inhibition of radioligand stromal-derived factor-1α (SDF-1α) binding to CXCR4, was also found to be highly selective against closely related chemokine receptors. We rationalized that compound 24 complementarily interacted with the critical CXCR4 residues that are essential for binding to HIV-1 gp120 V3 loop and subsequent viral entry. Compound 24 showed a 130-fold increase in anti-HIV activity compared to that of the marketed CXCR4 antagonist, AMD3100 (Plerixafor), whereas both compounds exhibited similar potency in mobilization of CXCR4+/CD34+ stem cells at a high dose. Our study offers insight into the design of anti-HIV therapeutics devoid of major interference with SDF-1α function.
- Wu, Chien-Huang,Wang, Chuan-Jen,Chang, Chun-Ping,Cheng, Yung-Chi,Song, Jen-Shin,Jan, Jiing-Jyh,Chou, Ming-Chen,Ke, Yi-Yu,Ma, Jing,Wong, Ying-Chieh,Hsieh, Tsung-Chih,Tien, Yun-Chen,Gullen, Elizabeth A.,Lo, Chen-Fu,Cheng, Chia-Yi,Liu, Yu-Wei,Sadani, Amit A.,Tsai, Chia-Hua,Hsieh, Hsin-Pang,Tsou, Lun K.,Shia, Kak-Shan
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supporting information
p. 1452 - 1465
(2015/03/04)
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- Efficient synthesis of quinazoline-2,4(1H,3H)-diones from CO2 catalyzed by N-heterocyclic carbene at atmospheric pressure
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Under atmospheric pressure, quinazoline-2,4(1H,3H)-diones were obtained from the reaction of 2-aminobenzonitriles with carbon dioxide (0.1 MPa) with a catalytic amount of N-heterocyclic carbene in DMSO. It was found that various electron-donating and electron-withdrawing groups such as -OMe, -F, -Cl, -Br, -CH3, -CF3 and -CN were well tolerated to give the products in almost quantitative yields.
- Xiao, Yunqing,Kong, Xianqiang,Xu, Zhicheng,Cao, Changsheng,Pang, Guangsheng,Shi, Yanhui
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p. 5032 - 5037
(2015/03/03)
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- Tetra-butylphosphonium arginine-based ionic liquid-promoted cyclization of 2-aminobenzonitrile with carbon dioxide
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An easily prepared amino acid ionic liquid (AAIL) i.e. [TBP][Arg] comprising a tetra-butylphosphonium cation and an arginine anion was found to be an efficient and recyclable catalyst for the synthesis of quinazoline-2,4(1H,3H)-diones from 2-aminobenzonitriles and CO2 under solvent-free conditions. As a result, various 2-aminobenzonitriles bearing electron-withdrawing or electron-donating substituents worked well to afford quinazoline-2,4(1H,3H)-diones in excellent yields. Notably, this type of AAIL showed good stability, and could be easily recovered and reused five times without significant loss of its catalytic activity. This process represents an alternative approach for greener chemical fixation of CO2 to afford valuable compounds. This journal is
- Lang, Xian-Dong,Zhang, Shuai,Song, Qing-Wen,He, Liang-Nian
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p. 15668 - 15673
(2015/02/19)
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- A highly efficient way to capture CX2 (O, S) mildly in reusable ReILs at atmospheric pressure
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The highly efficient transformation of CX2 (O, S) into valuable chemicals at atmospheric pressure is an attractive topic. A novel method of preparing quinazoline derivatives by capturing CX2 (O, S) in reusable, room-temperature, reversible ionic liquids (ReILs) with high yields (up to 98%) at 40 °C and atmospheric pressure was developed in this paper. The different reaction conditions were optimized and the products were easily separated from the ReILs which could be reused at least six times without considerable loss in yield. The plausible mechanism of capturing CX2 (O, S) in the ReILs was proposed and it provides a green, efficient protocol to capture CX2 (O, S) in ReILs to synthesize quinazoline derivatives. This journal is the Partner Organisations 2014.
- Zheng, Hui,Cao, Xianting,Du, Kui,Xu, Jun,Zhang, Pengfei
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p. 3142 - 3148
(2014/06/10)
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- Efficient synthesis of quinazoline-2,4(1H,3H)-diones from CO2 using ionic liquids as a dual solvent-catalyst at atmospheric pressure
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The highly efficient transformation of CO2 into value-added chemicals is an interesting topic in green chemistry. In this work, we studied the synthesis of quinazoline-2,4(1H,3H)-diones from CO2 and 2-aminobenzonitriles in a series of ionic liquids (ILs). It was found that 1-butyl-3-methylimidazolium acetate ([Bmim]Ac), a simple and easily prepared IL, could act as both solvent and catalyst, the reactions could be carried out very efficiently at atmospheric pressure of CO2, and a high yield of the products was obtained. Further study indicated that the IL was also very efficient for converting other 2-aminobenzonitriles into their corresponding quinazoline-2,4(1H,3H)-diones in high yields at atmospheric pressure. Moreover, the separation of the products from the IL was very easy, and the IL could be reused at least five times without considerable loss in catalytic activity.
- Lu, Wenjing,Ma, Jun,Hu, Jiayin,Song, Jinliang,Zhang, Zhaofu,Yang, Guanying,Han, Buxing
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p. 221 - 225
(2014/01/06)
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- Choline hydroxide promoted chemical fixation of CO2 to quinazoline-2,4(1H,3H)-diones in water
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The efficient conversion of CO2 to high value-added chemicals in water with cheap and non-toxic catalysts is a very attractive topic in green chemistry. In this work, the transformation of CO2 and 2-aminobenzonitriles to quinazoline-2,4(1H,3H)-diones in water promoted by choline hydroxide has been studied. The effect of temperature, pressure, reaction time, and amount of catalyst on the reaction were investigated and the reaction conditions were optimized. It was demonstrated that choline hydroxide showed supernormal catalytic activity to promote this reaction as a biodegradable, environmentally friendly, green and cheap material showed supernormal catalytic activity to promote this reaction. Furthermore, the reaction mechanism was discussed.
- Lu, Wenjing,Ma, Jun,Hu, Jiayin,Zhang, Zhaofu,Wu, Congyi,Han, Buxing
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p. 50993 - 50997
(2014/12/10)
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- A protic ionic liquid catalyzes CO2 conversion at atmospheric pressure and room temperature: Synthesis of quinazoline-2,4(1H,3H)-diones
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The chemical fixation of CO2 under mild reaction conditions is of significance from a sustainable chemistry viewpoint. Herein a CO 2-reactive protic ionic liquid (PIL), [HDBU+][TFE -], was designed by neutralization of the superbase 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) with a weak proton donor trifluoroethanol (TFE). As a bifunctional catalyst for simultaneously activating CO2 and the substrate, this PIL displayed excellent performance in catalyzing the reactions of CO2 with 2-aminobenzonitriles at atmospheric pressure and room temperature, thus producing a series of quinazoline-2,4(1H,3H)-diones in excellent yields. No pressure: The reaction of CO2 with various 2-aminobenzonitriles was achieved at atmospheric pressure and room temperature by using the bifunctional protic ionic liquid [HDBU+][TFE-], thus producing the title compounds in excellent yields. The ionic liquid serves as both the catalyst and solvent, and activates both CO2 and the substrates simultaneously. DBU=1,8-diazabicyclo[5.4.0]undec-7-ene, TFE=trifluoroethanol.
- Zhao, Yanfei,Yu, Bo,Yang, Zhenzhen,Zhang, Hongye,Hao, Leiduan,Gao, Xiang,Liu, Zhimin
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supporting information
p. 5922 - 5925
(2014/06/10)
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- Amine functionalized MCM-41: An efficient heterogeneous recyclable catalyst for the synthesis of quinazoline-2,4(1H,3H)-diones from carbon dioxide and 2-aminobenzonitriles in water
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A simple covalently linked amine functionalized MCM-41 compound was investigated using mesoporous catalytic protocols as a highly efficient, heterogeneous and recyclable catalyst for the synthesis of a wide variety of quinazoline-2,4(1H,3H)-dione derivatives from 2-aminobenzonitriles and carbon dioxide in aqueous reaction medium. This catalytic system represents a heterogeneous and environmentally benign protocol. The effect of various reaction parameters, such as the influences of solvent, temperature, CO 2 pressure, and time for the synthesis of quinazoline-2,4(1H,3H)- diones were studied. The developed protocol can be applied for the synthesis of the most important key intermediate 6,7-dimethoxyquinazoline-2,4(1H,3H)-dione and several biologically active derivatives such as Prazosin, Bunazosin and Doxazosin. Besides this, the developed catalyst could be reused for five consecutive recycles without any significant loss in its catalytic activity. The amine functionalized MCM-41 catalyst was characterized by various characterization techniques such as FT-IR, TGA/DTA, XRD, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), and solid state 29Si CP MAS NMR analysis. This journal is the Partner Organisations 2014.
- Nale, Deepak B.,Rana, Surjyakanta,Parida, Kulamani,Bhanage, Bhalchandra M.
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p. 1608 - 1614
(2014/06/09)
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- Novel 2-chloro-4-anilino-quinazoline derivatives as EGFR and VEGFR-2 dual inhibitors
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Novel 2-chloro-4-anilino-quinazolines designed as EGFR and VEGFR-2 dual inhibitors were synthesized and evaluated for inhibitory effects. EGFR and VEGFR-2 are validated targets in cancer therapy and combined inhibition might be synergistic for both antitumor activity and resistance prevention. The biological data obtained proved the potential of 2-chloro-4-anilino-quinazoline derivatives as EGFR and VEGFR-2 dual inhibitors, highlighting compound 8o, which was approximately 7-fold more potent on VEGFR-2 and approximately 11-fold more potent on EGFR compared to the prototype 7. SAR and docking studies allowed the identification of pharmacophoric groups for both kinases and demonstrated the importance of a hydrogen bond donor at the para position of the aniline moiety for interaction with conserved Glu and Asp amino acids in EGFR and VEGFR-2 binding sites.
- Barbosa, Maria Letícia De Castro,Lima, Lídia Moreira,Tesch, Roberta,Sant'Anna, Carlos Mauricio R.,Totzke, Frank,Kubbutat, Michael H.G.,Sch?chtele, Christoph,Laufer, Stefan A.,Barreiro, Eliezer J.
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- Efficient synthesis of quinazoline-2,4(1H,3H)-diones from CO2 and 2-aminobenzonitriles in water without any catalyst
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We discovered that the synthesis of quinazoline-2,4(1H,3H)-diones from CO2 and 2-aminobenzonitriles could proceed efficiently in water without any catalyst and excellent yields were obtained, while the reaction did not occur in organic solvents
- Ma, Jun,Han, Buxing,Song, Jinliang,Hu, Jiayin,Lu, Wenjing,Yang, Dezhong,Zhang, Zhaofu,Jiang, Tao,Hou, Minqiang
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p. 1485 - 1489
(2013/09/24)
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- Condensation reaction of ethyl 4-oxo-4h-benzo[d][1,3]-oxazine-2- carboxylates with potassium cyanate: 2,4(1H,3H)-quinazolinediones synthesis
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The condensation reaction of ethyl 4-oxo-4H-benzo[d][1,3]oxazine-2- carboxylates with acidic solution of potassium cyanate offers a novel and expedient route to the synthesis of 2,4(1H,3H)-quinazolinediones under mild reaction conditions..
- Nikpour, Farzad,Havasi, Forugh,Arzegar, Zeinab
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p. 2745 - 2748,4
(2020/09/16)
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- Synthesis and anti-proliferative activity of substituted- anilinoquinazolines and its relation to EGFR inhibition
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4-Anilinoquinazoline is a privileged scaffold in developing small molecule inhibitors of tyrosine kinases (TK) especially epidermal growth factor receptor (EGFR). 2 series belonging to 3'-substituted-4-anilinoquinazoline scaffold were synthesized and screened in vitro on isolated and a breast cancer cell line. The research aims at exploring the activity of compounds having diverse substituents at 3' position of the aniline moiety. Generally, the meta-substituted-anilinoquinazolines exhibited significant inhibitory activity against isolated enzyme as well as MCF-7 cancer cell line. For instance, compound 10b inhibited >99% of EGFR activities at 10 M concentration. 6 of the tested compounds exhibited range of anti-proliferative activity below 10 M potency. In particular, compounds 6e and 10b displayed the highest activity among the tested compounds with IC50 values equal to 8.6 and 4.84 M, respectively. Structure-based tools were utilized to rationalize EGFR-TK binding of compound 10b since it is the most active compound in the enzyme inhibition test. Georg Thieme Verlag KG Stuttgart.New York.
- El Ella,Saleh,Hassan,Hamdy,El-Araby,Abouzid
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p. 360 - 366
(2012/10/29)
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- Alkali metal cations control over nucleophilic substitutions on aromatic fused pyrimidine-2,4-[1H,3H]-diones: Towards new PNA monomers
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In this paper we report synthesis of a series of aromatic fused pyrimidine-2,4(3H)-dione-1-yl acetic acid and new PNA monomers containing these polycyclic nucleobase analogues. Introduction of a fused aromatic ring onto the 5,6-positions of the pyrimidine-2,4-[1H,3H]-diones brings about the steric effects and the charge delocalization, both weakening the nucleophilic substitutions on the 1- and 3-positions. We found that alkali metal cations play an important role in this alkylation reaction. LiOH brings out a much more efficient alkylation than NaOH does, while KOH nearly does not work on this reaction. Such influences from the alkali metal cations are probably due to that the charge-pairing interactions between the pyrimidine-2,4-dioxide anions and the alkali metal cations rearrange the charge distribution around the whole aromatic system and increase the negative charge distribution on the 1- and 3-nitrogen atoms, which then strengthens the nucleophilic reactivity on these positions.
- Li, Pengfa,Zhan, Chuanlang,Zhang, Shanlin,Ding, Xunlei,Guo, Fengqi,He, Shenggui,Yao, Jiannian
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p. 8908 - 8915
(2012/10/29)
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- Efficient [WO4]2--catalyzed chemical fixation of carbon dioxide with 2-aminobenzonitriles to quinazoline-2,4(1 H,3 H)-diones
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A simple monomeric tungstate, TBA2[WO4] (I, TBA = tetra-n-butylammonium), could act as an efficient homogeneous catalyst for chemical fixation of CO2 with 2-aminobenzonitriles to quinazoline-2,4(1H,3H)-diones. Various kinds of structurally diverse 2-aminobenzonitriles could be converted into the corresponding quinazoline-2,4(1H,3H)-diones in high yields at atmospheric pressure of CO 2. Reactions of inactive 2-amino-4-chlorobenzonitrile and 2-amino-5-nitrobenzonitrile at 2 MPa of CO2 also selectively proceeded. The present system was applicable to a g-scale reaction of 2-amino-5-fluorobenzonitrile (10 mmol scale) with CO2 and 1.69 g of analytically pure quinazoline-2,4(1H,3H)-dione could be isolated. In this case, the turnover number reached up to 938 and the value was the highest among those reported for base-mediated systems so far. NMR spectroscopies showed formation of the corresponding carbamic acid through the simultaneous activation of both 2-aminobenzonitirile and CO2 by I. Kinetic and computational studies revealed that I plays an important role in conversion of the carbamic acid into the product.
- Kimura, Toshihiro,Sunaba, Hanako,Kamata, Keigo,Mizuno, Noritaka
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p. 13001 - 13008
(2013/02/22)
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- Is CO2 fixation promoted through the formation of DBU bicarbonate salt?
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The bicyclic amidines, 1,8-diazabicyclo [5.4.0]undec-7-ene (DBU) and 1,5-diazabicyclo[4.3.0] non-5-ene (DBN), were used for the chemical fixation of carbon dioxide. The promotion for CO2 fixation is often reported through the formation of a thermally unstable DBU or DBN bicarbonate salt. To examine the effects of the DBU or DBN bicarbonate salt, reactions of 2-aminobenzonitrile with the DBU salt or DBN salt in dimethylformamide (DMF) were performed at 20°C for 24 h in argon or carbon dioxide (0.1 MPa). However, in all the cases, 1H-quinazoline-2,4-dione was not obtained completely. In contrast with room temperature reactions, 2-aminobenzonitriles and DBU bicarbonate salt in DMF reacted for 4 h under high temperature (80°C) and CO2 atmosphere (0.1 MPa) gave 1H-quinazoline-2,4-diones in good to excellent yields. At high-temperature conditions, DBU bicarbonate salt is decomposed to DBU and carbon dioxide. Also, the carbonylation of 2-aminobenzonitrile using DBU and carbon dioxide afforded 1H-quinazoline-2,4- dione in good yields under similar reaction conditions. These results suggest that the combination of DBU or DBN as a strong base and carbon dioxide is much more important than the in situ formation of DBU or DBN bicarbonate salt for the acceleration of CO2 fixation.
- Mizuno, Takumi,Nakai, Takeo,Mihara, Masatoshi
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experimental part
p. 276 - 280
(2012/07/28)
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- A facile and convenient approach for the one-pot synthesis of 2,4(1H,3H)-quinazolinediones
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A fast and efficient method is described for the one-pot synthesis of 2,4(1H,3H)-quinazolinediones by cyclization reaction of anthranilic acid derivatives with potassium cyanate and acetic acid in PEG. Good to high yields of the products obtain in short reaction times with simple work-up.
- Sharafi-Kolkeshvandi, Mahnaz,Nikpour, Farzad
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experimental part
p. 431 - 433
(2012/06/18)
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- Chemical fixation of CO2: efficient synthesis of quinazoline-2,4(1H, 3H)-diones catalyzed by guanidines under solvent-free conditions
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Guanidines were proved to be efficient catalysts for the chemical fixation of carbon dioxide with 2-aminobenzonitriles under solvent-free conditions. Notably, the catalysts with low loading worked well for a variety of 2-aminobenzonitriles. As a result, quinazoline-2,4(1H, 3H)-diones by employing present protocol were obtained in good yields under mild conditions. This process represents an alternative approach for the greener chemical fixation of CO2 to afford valuable compounds.
- Gao, Jian,He, Liang-Nian,Miao, Cheng-Xia,Chanfreau, Sébastien
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experimental part
p. 4063 - 4067
(2010/07/05)
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- Design, synthesis and in vitro antitumor activity of 4-aminoquinoline and 4-aminoquinazoline derivatives targeting EGFR tyrosine kinase
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Two series of new 6-alkoxy-4-substituted-aminoquinazolines (2-4f) and their bioisoteric quinoline congeners (5-7c) were designed and synthesized. Virtual screening was carried out through docking the designed compounds into the ATP binding site of epidermal growth factor receptor (EGFR) to predict if these compounds have analogous binding mode to the EGFR inhibitors. The newly synthesized compounds were tested in vitro on human breast carcinoma cell line (MCF-7) in which EGFR is highly expressed. Most of the tested compounds exploited potent antitumor activity with IC50 values in the nanomolar range in particular compound 3b which displayed the highest activity among the tested compounds with IC50 equal to 0.13 nmol.
- Abouzid, Khaled,Shouman, Samia
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p. 7543 - 7551
(2008/12/23)
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- Solvent-free synthesis of quinazoline-2,4(1H,3H)-diones using carbon dioxide and a catalytic amount of DBU
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An ideal reaction system, which is aimed at sustainable chemistry, was developed. Under solvent-free conditions, quinazoline-2,4(1H,3H)-diones were obtained in good to excellent yields from 2-aminobenzonitriles with only carbon dioxide (1 bar) and a catalytic amount of base (DBU or DBN). For example, 6,7-dimethoxyquinazoline-2,4(1H,3H)-dione, which is a key intermediate of several drugs (Prazosin, Bunazosin, and Doxazosin) was synthesized successfully in 97% yield [DBU (0.2 equiv), CO2 (1 bar), 120°C]. Georg Thieme Verlag Stuttgart.
- Mizuno, Takumi,Mihara, Masatoshi,Nakai, Takeo,Iwai, Toshiyuki,Ito, Takatoshi
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p. 2524 - 2528
(2008/03/11)
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- A green, facile, and one-pot synthesis of 2,4-(1H,3H)-quinazolinediones under microwave irradiations
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Quinazoline-2,4-diones are of considerable interest due to their wide pharmacological properties. Here, we have described an environmentally friendly method for the one-pot synthesis of 2,4-(1H,3H)-quinazolinediones from the reaction of anthranilic acid derivatives with urea in H2O media under microwave irradiations. This method is simple, safe, and fast which produces high yield of products without use of any catalyst. Copyright
- Nikpour, Farzad,Paibast, Touraj
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p. 1438 - 1439
(2007/10/03)
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- The simple solvent-free synthesis of 1H-quinazoline-2,4-diones using supercritical carbon dioxide and catalytic amount of base
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Using scCO2 as a reactant and a solvent, 1H-quinazoline-2,4- diones were synthesized in good to excellent yields.
- Mizuno, Takumi,Iwai, Toshiyuki,Ishino, Yoshio
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p. 7073 - 7075
(2007/10/03)
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- A modified synthesis of iodoazidoaryl prazosin.
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The antihypertension agent iodoazidoaryl prazosin (IAAP) has been made using a convergent route involving addition of an acylated piperazine 7 to 2-chloroquinazoline 5. IAAP has been shown to function as a multidrug resistance (MDR) reversal agent and bind to P-glycoprotein, a transmembrane transport protein. A study is also reported involving palladium-catalyzed substitution with amine heterocycles. With N,N-bis(2,6-diisopropyl)dihydroimidazolium chloride (10) as the ligand (2 mol %) for palladium(II) acetate (2 mol %) in THF at room temperature, morpholine added to 5 in 81% yield.
- Andrus, Merritt B,Mettath, Sashikumar N,Song, Chun
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p. 8284 - 8286
(2007/10/03)
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- Highly efficient synthesis of 1H-quinazoline-2,4-diones using carbon dioxide in the presence of catalytic amount of DBU
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The first example of chemical fixation of carbon dioxide in the presence of catalytic amount of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) or DBN (1,5-diazabicyclo[4.3.0]non-5-ene) was developed. Carbon dioxide easily reacted with 2-aminobenzonitriles under
- Mizuno, Takumi,Ishino, Yoshio
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p. 3155 - 3158
(2007/10/03)
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