103281-94-3Relevant academic research and scientific papers
One-pot solvent-free synthesis of triaryl- and triheteroarylmethanes by Bi(OTf)3-catalyzed Friedel-Crafts reaction of arenes/heteroarenes with trialkyl orthoformates
Tuengpanya, Surisa,Chantana, Chayamon,Sirion, Uthaiwan,Siritanyong, Wipada,Srisook, Klaokwan,Jaratjaroonphong, Jaray
, p. 4373 - 4380 (2018)
A convenient, practical and highly efficient one-pot method has been developed for the synthesis of triaryl- and triheteroarylmethane derivatives by Bi(OTf)3-catalyzed Friedel-Crafts alkylation of trialkyl orthoformates in combination with a wide variety of arenes/heteroarenes at room temperature under solvent-free conditions and in an air atmosphere. The methodology offers an operational simplicity, high atom economy and environmentally benign procedure. Furthermore, selected compound 3k showed promising anti-inflammatory activity with inhibition nitric oxide and did not exhibit significant cytotoxic effects on macrophage cells.
Orthoamides, LXVII [1]. Bis(diformylamino)methane - A new efficient formylating reagent for aromatic compounds
Kantlehner, Willi,Anders, Ernst,Mezger, Jochen,Stoyanov, Edmont V.,Kre?, Ralf,Wermann, Kurt,Frey, Wolfgang,G?rls, Helmar
experimental part, p. 395 - 406 (2009/01/31)
Formaldehyde reacts with diformamide (10) to give N-(hydroxymethyl) diformamide (11), which upon treatment with thionylchloride yields N-(chlormethyl)diformamide (12) together with small amounts of oxydimethylenebis(diformamide) (13). Various diformylamine derivatives, such as diformylaminomethyl formiate (14), diformylaminomethylisothiocyanate (15) and the N-diformylaminomethylated guanidinium salt 16, can be prepared from 12. Bis(diformylamino) methane (7) can be obtained by the reaction of sodium diformamide (8) with either 1-(chloromethyl)pyridinium chloride (9) or N-(chloromethyl)diformamide (12) in acetonitrile. The action of tris(chloromethyl) amine (18) on sodium diformamide (8) affords tris(diformylaminomethyl)amine (19). The constitution of the compounds 7,11 and 19 was confirmed by crystal structure determination. The nature of the products from the reactions of aromatic compounds with 12 depends on the Lewis acid which is used as activator. Thus the N-benzylformamides 20a, b can be obtained from toluene and mesitylene and 12/BF3-ether, whereas 1,2,4- trimethoxybenzene is formylated by 12/AlCl3 to give the aldehyde 22. Interestingly enough, a novel and efficient formylating reagent resulted from these investigations: bis(diformylamino)methane (7), which can be activated by Lewis acids, e. g. AlCl3. The scope of this procedure is comparable with that of the Olah-formylation method (formylfluoride/BF3).
Unusual Stabilities and Reactivities of Tris- and Bis(2,4,6-trimethoxyphenyl)carbenium Salts
Wada, Masanori,Konishi, Hideki,Kirishima, Katsuhiko,Takeuchi, Hiroshi,Natsume, Satoko,Erabi, Tatsuo
, p. 2737 - 2741 (2007/10/03)
2,4,6-Trimethoxyphenyllithium, Φ + ′Li[Φ + ′=2,4,6-(MeO)3C6H2], reacted with diphenyl carbonate and with ethyl formate to give tris(2,4,6-trimethoxyphenyl)methanol, Φ + ′3COH (1), and bis(2,4,6-trimethoxyphenyl)methanol, Φ + ′2CHOH (2), respectively. Compound 1 reacted with a slight excess of perchloric acid in 2-propanol to give very dark-purple crystals of the triarylcarbenium salt, [Φ + ′3C]X (3, X=ClO4), which were inert even in hot ethanol. However, a treatment of 3 (X=Cl), prepared in situ in 1 M (1 M=1 moldm-3) hydrochloric acid, with 1 M sodium hydroxide resulted to give 4-bis(2,4,6-trimethoxyphenyl)methylene-3,5-dimethoxy-2,5-cyclohexadienone. Compound 2 also reacted with a slight excess of perchloric acid in methanol to give dark-red crystals of the diarylcarbenium salt, [Φ + ′2CH]X (5, X=ClO4). Compound 5 was considerably inert even in hot methanol, but was easily reduced in primary and secondary alcohols to give bis(2,4,6-trimethoxyphenyl)methane, Φ + ′2CH2. Measurements of the half-lives of 5 in these alcohols showed that 5 was more labile in secondary alcohols, such as 2-propanol and 2-butanol, than in primary alcohols. When a suspension of 5 (X=Cl), prepared in situ in 1 M hydrochloric acid, was heated, tris(2,4,6-trimetrioxyphenyl)methane, Φ + ′3CH (7), was obtained. Analogous reactions to give 7 were observed in methanol containing a slight excess of hydrochloric acid or nitric acid in place of perchloric acid. The possible paths of these reactions are discussed.
