54-20-6Relevant articles and documents
Catalyst-free and visible light promoted trifluoromethylation and perfluoroalkylation of uracils and cytosines
Huang, Yang,Lei, Yun-Yun,Zhao, Liang,Gu, Jiwei,Yao, Qiuli,Wang, Ze,Li, Xiao-Fei,Zhang, Xingang,He, Chun-Yang
, p. 13662 - 13665 (2018)
Fluoroalkylated enaminones, such as trifluridine and 5-trifluoromethyluracil, have widespread applications in pharmaceuticals and agrochemicals. Although these kinds of pharmaceutical agent often bear CF3 and perfluoroalkyl motifs in the core structure, access to such analogues typically requires multi-step synthesis. Here, we report a mild, metal-free and operationally simple strategy for the direct perfluoroalkylation of uracils, cytosines and pyridinones through a visible-light induced pathway from perfluoroalkyl iodides. This photochemical transformation features synthetic simplicity, mild reaction conditions without any photoredox catalyst, and high functional group tolerance, providing a facile route for applications in medicinal chemistry.
Facile perfluoroalkylation of uracils and uridines at the C-5 position
Nishida, Masakazu,Fujii, Shozo,Kimoto, Hiroshi,Hayakawa, Yoshio,Sawada, Hideo,Cohen, Louis A.
, p. 43 - 52 (1993)
Perfluoroalkylation at the C-5 position of uracil has been achieved in yields of 38-56percent by the reaction of its bis(trimethylsilyl) derivative with bis(perfluoroalkanoyl) peroxides and the hydrolytic deprotection of the silylated products.A substituent or nitrogen replacement at C-6 does not interfere with perfluoroalkylation at C-5, but no significant reaction occurs at C-6 when C-5 is blocked.
Au@ZnO Core-Shell: Scalable Photocatalytic Trifluoromethylation Using CF3CO2Na as an Inexpensive Reagent under Visible Light Irradiation
Bazyar, Zahra,Hosseini-Sarvari, Mona
supporting information, p. 2345 - 2353 (2019/10/16)
Trifluoromethylation is of significant importance for the synthesis of many small molecules vital for medicinal and agrochemical research. The importance of the CF3 group as well as the related synthetic challenges is so evident that many reagents have been reported for the synthesis of trifluoromethylated compounds, but these typical reagents are expensive and the methods for preparing them are difficult. Here, we report a new scalable and operationally simple trifluoromethylation reaction using sodium trifluoroacetate as a reagent and Au-modified ZnO as a photocatalyst under visible light irradiation. The reaction proceeds via trifluoromethylation of a broad range of aryl halides, arylboronic acids, and arene and heteroarene substrates. Some pharmaceutical and agrochemical compounds have been trifluoromethylated directly to demonstrate the applicability of the method.
Method for preparing 5-trifluoromethyl uracil
-
Paragraph 0038-0039, (2019/06/05)
The invention belongs to the field of organic synthesis, and specifically relates to a method for preparing 5-trifluoromethyl uracil. The method comprises the following steps: firstly, carrying out chlorination reaction on 5-iodouracil and phosphorus oxychloride, thus obtaining 2,4-dichloro-5-iodopyrimidine; secondly, carrying out trifluoromethylation reaction on the 2,4-dichloro-5-iodopyrimidineand a trifluoromethylating reagent, thus obtaining 2,4-dichloro-5-trifluoromethylpyrimidine; finally, enabling the 2,4-dichloro-5-trifluoromethylpyrimidine to react with acetic acid, thus obtaining aproduct. According to the method disclosed by the invention, since chlorination reaction, trifluoromethylation reaction and hydrolysis reaction are adopted, a key intermediate-trifluoromethyl uracil of trifluorothymidine is synthesized in high yield, low cost and low pollution.
Organic semiconductor photocatalyst can bifunctionalize arenes and heteroarenes
Ghosh, Indrajit,Khamrai, Jagadish,Savateev, Aleksandr,Shlapakov, Nikita,Antonietti, Markus,K?nig, Burkhard
, p. 360 - 366 (2019/08/15)
Photoexcited electron-hole pairs on a semiconductor surface can engage in redox reactions with two different substrates. Similar to conventional electrosynthesis, the primary redox intermediates afford only separate oxidized and reduced products or, more rarely, combine to one addition product. Here, we report that a stable organic semiconductor material, mesoporous graphitic carbon nitride (mpg-CN), can act as a visible-light photoredox catalyst to orchestrate oxidative and reductive interfacial electron transfers to two different substrates in a two- or three-component system for direct twofold carbon–hydrogen functionalization of arenes and heteroarenes. The mpg-CN catalyst tolerates reactive radicals and strong nucleophiles, is straightforwardly recoverable by simple centrifugation of reaction mixtures, and is reusable for at least four catalytic transformations with conserved activity.
Synthesis method of fluoropyrimidine-containing medical intermediate 2,4-dichloro-5-trifluoromethylpyrimidine
-
Page/Page column 3-6, (2018/09/28)
The invention relates to a synthesis method of a fluoropyrimidine-containing medical intermediate 2,4-dichloro-5-trifluoromethylpyrimidine. The method comprises steps as follows: (1) uracil, sodium trifluoromethanesulfonate, persulfate and water are added to a reaction container, the reaction temperature is controlled, and 5-(trifluoromethyl)uracil is obtained after the reaction; (2) 5-(trifluoromethyl)uracil, phosphorus oxychloride and diisopropylethylamine are added to a pressure reaction container and react at the reaction temperature of 150-220 DEG C, and a product is obtained after the reaction. In the preparation process of 5-(trifluoromethyl)uracil, only water is taken as a solvent, no other organic solvents or organic free radical initiators are used, aftertreatment is simple, theproduct purity is high, the next reaction can be directly performed, operation is simple, pollution is low, and the cost is low; through the pressure reaction container, the reaction temperature is increased, the dosage of phosphorus oxychloride is greatly reduced, three wastes are reduced, and the atom economy is met.
Synthetic method of 5-trifluoromethyl uracil
-
Paragraph 0023; 0026; 0029; 0032; 0033; 0034; 0035; 0038, (2018/09/21)
The invention discloses a synthetic method of 5-trifluoromethyl uracil prepared under simple and convenient conditions. The synthetic method is characterized in that starting from uracil and trifluoroiodomethane, after alkali is added, the 5-trifluoromethyl uracil is efficiently obtained under the irradiation of visible light. Some of products obtained are listed drug molecules or important pharmaceutical intermediates. The synthetic method has the benefits that the uracil and the trifluoroiodomethane which are cheap and easy to obtain are used as raw materials; in the reaction process, only the illumination is required, and the cheap alkali is added without the use of a catalyst; during the mass production, a solvent can be recovered through a vacuum distillation method; the synthetic method is green, economic and efficient in the whole production process and has very significant advantages compared with an existing production process.
A 5-trifluoro methyl uracil method for the synthesis of
-
Paragraph 0013-0019, (2017/06/08)
The invention discloses a synthetic method of 5-trifluoromethyl uracil. According to the method, uracil and sodium trifluoromethanesulfonate are used as raw materials, a mixed solvent of dichloromethane and water is used as a reaction solvent, tert-butyl hydroperoxide is used as a catalyst, and the target product namely 5-trifluoromethyl uracil is obtained with a relatively high yield in a micro-reduction system. The synthetic method is simple in synthetic step, mild in reaction condition and high in product yield, and can be used for industrial production.
Condensed-phase, halogen-bonded CF3I and C2F5I adducts for perfluoroalkylation reactions
Sladojevich, Filippo,McNeill, Eric,B?rgel, Jonas,Zheng, Shao-Liang,Ritter, Tobias
supporting information, p. 3712 - 3716 (2015/03/18)
A family of practical, liquid trifluoromethylation and pentafluoroethylation reagents is described. We show how halogen bonding can be used to obtain easily handled liquid reagents from gaseous CF3I and CF3CF2I. The synthetic utility of the new reagents is exemplified by a novel direct arene trifluoromethylation reaction as well as adaptations of other perfluoroalkylation reactions. Its (no longer) a gas! A family of practical, liquid trifluoromethylation and pentafluoroethylation reagents enabled by halogen bonding is described. The synthetic utility of these reagents is exemplified by a novel direct arene trifluoromethylation reaction as well as adaptations of other perfluoroalkylation reactions.
FLUOROALKYLATION REAGENTS AND USES THEREOF
-
Paragraph 00234; 00235, (2015/11/23)
Provided herein are halogen-bonded complexes of Formula (I), wherein is a halogen bond; R1 is unsubstituted C1-3 fluoroalkyl; D is N(R2)3, ((R2)2N)2C=NR2, 0=S(R2)2, substituted or unsubstituted heterocyclyl, or substituted or unsubstituted heteroaryl, and wherein R2 and y are as defined herein. D----(I??R1)y (I) Further provided are methods of preparing compounds of Formula (I), compositions, reagents, and kits comprising a compound of Formula (I), and methods for fluoroalkylating an organic compound using a compound of Formula (I).
