133399-22-1Relevant articles and documents
Enabling the Use of Alkyl Thianthrenium Salts in Cross-Coupling Reactions by Copper Catalysis
Chen, Cheng,Wang, Minyan,Lu, Hongjian,Zhao, Binlin,Shi, Zhuangzhi
supporting information, p. 21756 - 21760 (2021/08/30)
Alkyl groups are one of the most widely used groups in organic synthesis. Here, a a series of thianthrenium salts have been synthesized that act as reliable alkylation reagents and readily engage in copper-catalyzed Sonogashira reactions to build C(sp3)?C(sp) bonds under mild photochemical conditions. Diverse alkyl thianthrenium salts, including methyl and disubstituted thianthrenium salts, are employed with great functional breadth, since sensitive Cl, Br, and I atoms, which are poorly tolerated in conventional approaches, are compatible. The generality of the developed alkyl reagents has also been demonstrated in copper-catalyzed Kumada reactions.
PROCESS FOR MAKING FORMIC ACID UTILIZING LOWER-BOILING FORMATE ESTERS
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Paragraph 00184; 00185, (2019/02/15)
Disclosed is a process for recovering formic acid from a formate ester of a C3 to C4 alcohol. Disclosed is also a process for producing formic acid by carbonylating a C3 to C4 alcohol, hydrolyzing the formate ester of the alcohol, and recovering a formic acid product. The alcohol may be dried and returned to the reactor. The process enables a more energy efficient production of formic acid than the carbonylation of methanol to produce methyl formate.
METHOD OF CONVERTING ALCOHOL TO HALIDE
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Page/Page column 53; 144; 145, (2017/01/02)
The present invention relates to a method of converting an alcohol into a corresponding halide. This method comprises reacting the alcohol with an optionally substituted aromatic carboxylic acid halide in presence of an N-substituted formamide to replace a hydroxyl group of the alcohol by a halogen atom. The present invention also relates to a method of converting an alcohol into a corresponding substitution product. The second method comprises: (a) performing the method of the invention of converting an alcohol into the corresponding halide; and (b) reacting the corresponding halide with a nucleophile to convert the halide into the nucleophilic substitution product.
Reactions of 5-(alkyl)thianthrenium and other sulfonium salts with nucleophiles
Liu, Bo,Shine, Henry J.
, p. 81 - 89 (2007/10/03)
A series of 5-(alkyl)thianthrenium triflates (3a-d, g-i) with alkyl (R) groups Me (a), Et (b), isoPr (c), 2-Bu (d), cyclopentyl (g), cyclohexyl (h) and cycloheptyl (i) were prepared by alkylation of thianthrene (Th) with alkyl formate and trifluoromethanesulfonic (triflic) acid. Benzylation (3f) was achieved with benzyl bromide and silver triflate. 5-(Neopentyl)thianthrenium perchlorate (3e) was prepared by reaction of thianthrene cation radical perchlorate with dineopentyl mercury. Methyl- (4a) and cyclohexyldiphenylsulfonium triflate (4b) were made by alkylation of diphenyl sulfide. Benzyldimethyl- (5a), dibenzylmethyl- (5b) and benzylmethylphenylsulfonium perchlorate (5c) were prepared in standard ways. Reactions of these sulfonium salts with iodide ion and thiophenoxide ion were studied for comparison with our earlier reported reactions of comparable 5-(alkoxy)thianthrenium and methoxydiphenylsulfonium salts. It is deduced that reactions of 3-5 with nucleophiles (Nu-) I- and PhS- follow traditional SN2 and E2C paths. Thus, the salts 3a-c, e and f gave virtually quantitative yields of RNu and Th, while small amounts of butene(s) were obtained from 3d. The cycloalkyl salts 3g-i gave amounts of cycloalkylNu and cycloalkene typical of competition of SN2 and E2C routes in the classical reactions of cycloalkyl halides and tosylates with I- and PhS- ions. Whereas 4a gave only SN2 products, 4b gave SN2 and E2C products typical of SN2/E2C competition. Among the salts 5a-c displacement of the benzyl group was dominant (5a) or exclusive (5b, c), thus exhibiting the preferential displacement of a benzyl group that has been fully documented in earlier studies of SN2 reactions. Qualitative comparison showed that 3a (methyl) reacted much faster than 3e (neopentyl) with PhS-. Unlike alkoxysulfonium salts, the salts 3-5 do not appear to undergo reactions at the sulfonium sulfur atom. Copyright
The preparation of esters of formic acid using boron oxide
Carlson, Charles G.,Hall, Judith E.,Huang, Yan Y.,Kotila, Sirpa,Rauk, Arvi,Tavares, Donald F.
, p. 2461 - 2463 (2007/10/02)
Boron oxide has been found to act as an efficient reagent in the preparation of a number of formate esters by the direct esterification of formic acid with the alcohol.The reaction is most appropriate for primary and secondery alcohols, including unsaturated alcohols.The formate ester so produced is free of contamination by unreacted alcohol.
