- Method for synthesizing α - isopropyl -3 and 4 -methoxyacetonitrile
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The invention belongs to the technical field of organic synthesis, and particularly discloses a synthesis method α - isopropyl -3 and 4 -methoxyacetonitrile. To 3, 4 - dimethoxyphenyl acetic acid as a raw material, 2 - (3, 4 - dimethoxyphenyl) acetamide is formed through acylation reaction, and 3, 4 -methoxyphenyl acetonitrile are obtained by dehydration, and α - isopropyl -3 and 4 -methoxyacetonitrile are formed by alkylation reaction. The starting materials are cheap and easily available. The method avoids the use of highly toxic crisis reagents, is mild in reaction conditions, simple in post-treatment, short in synthetic route and high in yield.
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- Nickel-Catalyzed Photodehalogenation of Aryl Bromides
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Herein, we describe a Ni-catalyzed photodehalogenation of aryl bromides under visible-light irradiation that utilizes tetrahydrofuran as hydrogen source. The protocol obviates the need for exogeneous amine reductants or photocatalysts and is characterized by its simplicity and broad scope, including challenging substrate combinations.
- Higginson, Bradley,Sanjosé-Orduna, Jesus,Gu, Yiting,Martin, Ruben
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supporting information
p. 1633 - 1636
(2021/04/23)
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- Decarboxylative Cyanation of Aliphatic Carboxylic Acids via Visible-Light Flavin Photocatalysis
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An operationally simple method is disclosed for the decarboxylative cyanation of aliphatic carboxylic acids at room temperature. Riboflavin tetraacetate, which is an inexpensive organic photocatalyst, promotes the oxidation of carboxylic acids upon visible-light activation. After decarboxylation, the generated radicals are trapped by TsCN, yielding the desired nitriles without any further additive, in a redox-neutral process. Importantly, this protocol can be adapted to flow conditions.
- Ramirez, Nieves P.,K?nig, Burkhard,Gonzalez-Gomez, Jose C.
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supporting information
(2019/03/08)
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- Production technology of 3,4-dimethoxy phenethylamine
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A production technology of 3,4-dimethoxyphenethylamine is disclosed, and characterized by using 3,4-dihydroxybenzyl chloride and dimethyl sulfate as raw materials; performing an etherification reaction to generate 3,4-dimethoxybenzyl chloride in the presence of sodium hydrate; performing an cyanation reaction on the 3,4-dimethoxybenzyl chloride and a cyanide compound to generate 3,4-dimethoxybenzyl cyanide; cooling the 3,4-dimethoxybenzyl cyanide in propanone for crystallization to obtain 3,4-dimethoxybenzyl cyanide crystals; subjecting 3,4-dimethoxybenzyl cyanide to catalytic ammoniation and hydrogenation in a solvent to generate 3,4-dimethoxyphenethylamine; and performing reduced-pressure distillation on the product obtained after ammoniation and hydrogenation to obtain an qualified product of 3,4-dimethoxyphenethylamine. The overall product yield is 86% or higher.
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Paragraph 0005; 0020
(2016/10/08)
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- Palladium-catalyzed cyanomethylation of aryl halides through domino Suzuki coupling-isoxazole fragmentation
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A one-pot protocol for the cyanomethylation of aryl halides through a palladium-catalyzed reaction with isoxazole-4-boronic acid pinacol ester was developed. Mechanistically, the reaction proceeds through (1) Suzuki coupling, (2) base-induced fragmentation, and (3) deformylation as shown by characterization of all postulated intermediates. Under optimized conditions (PdCl2dppf, KF, DMSO/H2O, 130 °C) a broad spectrum of aryl bromides could be converted into arylacetonitriles with up to 88% yield.
- Velcicky, Juraj,Soicke, Arne,Steiner, Roland,Schmalz, Hans-Guenther
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supporting information; experimental part
p. 6948 - 6951
(2011/06/19)
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- Novel hybrids from lamellarin D and combretastatin A 4 as cytotoxic agents
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A new series of hybrids of lamellarin D and combretastatin A 4, 1,2-diphenyl-5,6-dihydropyrrolo [2,1-a] isoquinolines, were designed as cytotoxic agents based on principles of combination in medicinal chemistry and taking the parent compounds' different anti-proliferative mechanisms into consideration. Twenty-two novel hybrids were synthesized through a convenient route, with a key step of core pyrrole formation and evaluated for their anti-proliferative activities in vitro against K-562, A-549, SMMC-7721, SGC-7901 and HCT-116 cancer cell lines. The results showed that some hybrids had good anti-proliferative activities in low IC50 ranges.
- Shen, Li,Yang, Xiaochun,Yang, Bo,He, Qiaojun,Hu, Yongzhou
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scheme or table
p. 11 - 18
(2010/03/03)
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- Synthesis and biological evaluation of 3,4-diaryl-5-aminoisoxazole derivatives
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A series of cis-restricted 3,4-diaryl-5-aminoisoxazoles have been synthesized and evaluated for their biological activities. Among them, compound 11a and 13a displayed potent cytotoxic activities in vitro against five human cancer cell lines with IC50 values in the low micromolar range and two compounds inhibited tubulin polymerization with IC50 value of 1.8, and 2.1 μM, respectively, similar to that of CA-4. Compound 13a could arrest at the G2/M phase of the cell cycle at the concentration of 0.1 and 1.0 μM and induce apoptosis at 0.1-1.0 μM.
- Liu, Tao,Dong, Xiaowu,Xue, Na,Wu, Rui,He, Qiaojun,Yang, Bo,Hu, Yongzhou
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scheme or table
p. 6279 - 6285
(2011/02/24)
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- Oxidative conversion of amines into their corresponding nitriles using o-iodoxybenzoic acid (IBX)/iodine: Selective oxidation of aminoalcohols to hydroxynitriles
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o-Iodoxybenzoic acid (IBX)/iodine in dimethyl sulfoxide at 65 °C oxidatively and efficiently converted various amines into the corresponding nitriles in good to excellent yields. Under the reaction conditions, amines were selectively oxidized to the nitrile in the presence of a primary hydroxy group within the same molecule. Thieme Stuttgart.
- Chiampanichayakul, Supanimit,Pohmakotr, Manat,Reutrakul, Vichai,Jaipetch, Thaworn,Kuhakarn, Chutima
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experimental part
p. 2045 - 2048
(2009/04/11)
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- A convenient new procedure for converting primary amides into nitriles
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An operationally simple and high-yielding procedure has been developed for the conversion of primary amides to the corresponding nitriles, using ethyl dichlorophosphate/DBU as the mild dehydrating agent. The Royal Society of Chemistry.
- Kuo, Chun-Wei,Zhu, Jia-Liang,Wu, Jen-Dar,Chu, Cheng-Ming,Yao, Ching-Fa,Shia, Kak-Shan
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p. 301 - 303
(2007/10/03)
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- Design, synthesis and antiproliferative activity of tripentones: A new series of antitubulin agents
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Structure-activity relationship studies of a new series of tripentones (thieno[2,3-b]pyrrolizin-8-ones), led us to prepare several derivatives with antiproliferative activities. The most promising 3-(3-hydroxy-4-methoxyphenyl)thieno[2,3-b]pyrrolizin-8-one 20 (leukemia L1210, IC50 = 15 nM) was shown to be a potent inhibitor of tubulin polymerization.
- Lisowski, Vincent,Enguehard, Cecile,Lancelot, Jean-Charles,Caignard, Daniel-Henri,Lambel, Stephanie,Leonce, Stephane,Pierre, Alain,Atassi, Ghanem,Renard, Pierre,Rault, Sylvain
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p. 2205 - 2208
(2007/10/03)
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- Design, synthesis, and structure - Activity relationship studies of ATP analogues as DNA gyrase inhibitors
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We report herein the design and synthesis of ATP-analogues, namely 4-amino-pyrazolo[3,4-d]pyrimidines and 4-amino-pyrazolo[1,5-a][1,3,5]triazines, with DNA gyrase inhibitory activity. Among these series, some compounds exhibited promising antibacterial activity. (C) 2000 Elsevier Science Ltd. All rights reserved.
- Luebbers, Thomas,Angehrn, Peter,Gmuender, Hans,Herzig, Silvia,Kulhanek, Josef
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p. 821 - 826
(2007/10/03)
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- Biosynthesis of the A/B/C/D-Ring System of the Rotenoid Amorphigenin by Amorpha fruticosa Seedlings
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With phenylalanine as the starting point, the biosynthesis of the characteristic rotenoid A/B/C/D-ring system of amorphigenin is studied using Amorpha fruticosa seedlings.The course of the biosynthesis can be divided into four phases represented by the bordered and interconnecting Schemes 1, 3, 6 and 7 which summarise the Chalcone-Flavanone Phase, the Flavanone-Isoflavone Phase, the Hydroxylation/Methoxylation Phase and the Rotenoid Phase.By using an INADEQUATE NMR experiment involving the administration of acetate, the type of folding forming ring-D isdemonstrated by 13C-13C coupling and is interpreted as involving a polyketide containing a glutaconate segment which cyclises by a Claisen condensation.The resulting chalcone is cyclised, enzymically and stereospecifically, to 4',7-dihydroxyflavanone.The latter flavanone undergoes aryl migration, in a manner similar to that found in isoflavone biosynthesis, to give 7-hydroxy-4'-methoxyisoflavone.Possible mechanisms for the flavanone-isoflavone rearrangement are discussed, including a proposal that the initiating step involves attack on ring-A and is similar to the first stage of the aromatic hydroxylation of tyrosine to dopa.Although possessing no 4'-hydroxy group in ring-A, the mechanism is also applicable to the recently discovered rotenoids of the Boerhaavia and Iris type, and it provides an explanation for the biogenesis of natural spirobenzocyclobutanes from dihydroeucominoids.Six suitably substituted isoflavonoids labelled with 13C or 3H are synthesized and are used to show that the next hydroxylation (and probably methylation) involves C-3' rather than C-2' in 7-hydroxy-4'-methoxyisoflavone.Whilst the methylations involveS-adenosylmethionine, the hydroxylating enzymes are probably very similar to the flavanone-isoflavone-rearranging enzyme.The closure of ring-B to form finally the rotenoid system probably involves conjugate addition of a methoxyl radical.Prenylation and oxidative modifications are characteristically late-stage processes.
- Bhandari, Prabha,Crombie, Leslie,Daniels, Peter,Holden, Ian,Bruggen, Nicholas Van,Whiting, Donald A.
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p. 839 - 850
(2007/10/02)
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- SYNTHESES BASED ON β-PHENYLETHYLAMINES. I. PREPARATION OF SUBSTITUTED β-PHENYLETHYLAMINES
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A comparative study has been made of methods of synthesizing substituted β-phenylethylamines via the corresponding nitriles and via nitrostyrenes, and a superiority of the latter method has been established.The possibility has been shown for the first time of reducing nitrostyrenes to saturated amines with diisobutylaluminum hydride (DIBAH).The use of DIBAH as reducing agent enables amines to be obtained in high yields.
- Vinogradova, V. I.,Yunusov, M. S.,Kuchin, A. V.,Tolstikov, G. A.,Sagandykov, R. T.,et al.
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- ARYNIC CONDENSATION OF NITRILE ANIONS IN THE PRESENCE OF THE COMPLEX BASE NaNH2-CH3CH2(OCH2CH2)2ONa
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Nitrile anions are easily condensed with aryl halides in the presence of Complex Base NaNH2-CH3CH2(OCH2CH2)2ONa via the intermediate arynes.
- Carre, M. C.,Ezzinadi, A. S.,Zouaoui, M. A.,Geoffroy, P.,Caubere, P.
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p. 3323 - 3330
(2007/10/02)
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- Substituted 5-Imino-3,3-pentamethylene-1,2,4-thiadiazolidines by Amination of Thiourea Derivatives
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N-Acylthioureas 2a-b and thiosemicarbazones of aldehydes, ketones, and esters 4a-g are aminated at the potential SH-group by 3,3-pentamethyleneoxaziridine yielding substituted 5-imino-3,3-pentamethylene-1,2,4-thiadiazolidines 3 and 6 the latter via the intermediates 5.The reaction of the thiosemicarbazones 4 is a very general one, but only two acylthioureas 2 could be converted into the title compounds.
- Andreae, Siegfried,Schmitz, Ernst
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p. 1008 - 1014
(2007/10/02)
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- Synthesis of 4-(1,5,9-Trimethyl-1-vinyl-4,8-decadienyl)catechol Dimethyl Ether
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Synthesis of 4-(1,5,9-trimethyl-1-vinyl-4,8-decadienyl)catechol dimethyl ether has been described utilizing Wittig reaction for the introduction of vinylic substituent at the quaternary carbon.
- Anand, Ramesh Chander,Ranjan, Harish
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p. 791 - 792
(2007/10/02)
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- A NEW SYNTHESIS OF SOME NON-STEROIDAL ANTI-INFLAMMATORY AGENTS VIA CYANOPHOSPHATES
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A simple and convenient procedure for the syntheses of some non-steroidal anti-inflammatory agents, ibuprofen, rac-naproxen, clidanac and loxoprofen, is described.
- Hurusawa, Shinya,Nakamura, Shuji,Yagi, Sayoko,Kurihara, Takushi,Hamada, Yasumasa,Shioiri, Takayuki
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p. 1365 - 1372
(2007/10/02)
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- REACTIONS OF OXIMES WITH TRIMETHYLSILYL IODIDE: DEHYDRATION AND BECKMANN REARRANGEMENT
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Aldoximes are dehydrated in good yields to nitriles and certain ketoximes undergo Beckmann rearrangement when treated with trimethylsilyl iodide.
- Jung, Michael E.,Long-Mei, Zeng
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p. 4533 - 4534
(2007/10/02)
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- A SIMPLE ONE-POT CONVERSION OF ARYL HALIDES INTO ARYLACETONITRILES
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When heated in hexamethylphosphoric triamide in the presence of copper(I) iodide, aryl iodides and bromides react with cyanoacetate anion to form arylcyanoacetates, which lose the ester group on hydrolysis, giving the corresponding arylacetonitriles in good to moderate yields.
- Suzuki, Hitomi,Kobayashi, Tsutomu,Yoshida, Yoshiki,Osuka, Atsuhiro
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p. 193 - 194
(2007/10/02)
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- Syntheses of Arylacetone and Arylacetonitrile by Friedel-Crafts Reaction with α-Chloro-α-(methylthio)-substituted Acetone and Acetonitrile
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Novel preparative methods for arylacetone and arylacetonitrile are described.Friedel-Crafts reactions of aromatic compounds with α-chloro-α-(methylthio)acetone (4) and α-chloro-α-(methylthio)acetonitrile (7) in the presence of Lewis acid afforded α-(methylthio)arylacetone (5) and α-(methylthio)arylacetonitrile (8), respectively.Compounds (5) and (8) were converted into the corresponding arylacetone (6) and arylacetonitrile (9) by reduction with zinc dust in acetic acid.Keywords: Friedel-Crafts reaction with α-chloro-α-(methylthio)acetone; Friedel-Crafts reaction with α-chloro-α-(methylthio)acetonitrile; α-(methylthio)arylacetone; α-(methylthio)arylacetonitrile; arylacetone; arylacetonitrile; reductive desulfurization; zinc dust-acetic acid
- Tamura, Yasumitsu,Choi, Hong Dae,Mizutani, Masako,Ueda, Yuko,Ishibashi, Hiroyuki
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p. 3574 - 3579
(2007/10/02)
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- A New Synthesis of Septicine, a Secophenanthroindolizine Alkaloid
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Septicine , an alkaloid isolated from Ficus septica and Tylophora asthmatica, has been synthesized using 2-(3',4'-dimethoxyphenacyl)pyrrolidine (6) and 3,4-dimethoxy-phenylacetyl chloride (11) as the essential intermediates.Condensation of 6 and 11 affords 2-(3',4'-dimethoxyphenacyl)-N-(3'',4''-dimethoxyphenylacetyl)pyrrolidine (12) which on treatment with potassium-t-butoxide furnishes 6,7-di-(3',4'-dimethoxyphenyl)-5-oxo-1,2,3,5,8,8a-hexahydroindolizine (13).LAH reduction of 13 affords septicine (1), identical (co-TLC, IR, PMR, m.m.p.) with a natural sample.
- Mangla, V. K.,Bhakuni, D. S.
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p. 748 - 749
(2007/10/02)
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