Xi:Irritant;
78-83-1Relevant academic research and scientific papers
Pitfalls in the toxicological analysis of an isobutyl nitrite-adulterated coffee drink
Seto, Yasuo,Kataoka, Mieko,Tsuge, Kouichiro,Takaesu, Hajime
, p. 5187 - 5192 (2000)
A forensic investigation was carried out on one poisoning case, where cyanide was first detected in an evidence sample of a canned coffee drink. A more complete study revealed that it had been adulterated with isobutyl nitrite (IBN) and not cyanide. We examined the detectivity of IBN and related compounds by headspace gas chromatography and capillary electrophoresis. IBN decomposes to isobutyl alcohol (iBuOH) and nitrite in aqueous solution, and under higher temperature and more acidic conditions, the rate of this reaction becomes more rapid. IBN was also produced by the esterification of iBuOH with nitrite below pH 5. Cyanide was produced in a coffee solution by the addition of nitrite below pH 6. An IBN-spiked canned coffee drink solution was stored at 4 °C and periodically analyzed for IBN, iBuOH, nitrite, nitrate, and cyanide. Since the IBN level decreased rapidly, 1BuOH was produced in an almost 90% molar yield. Nitrite production reached a maximum of 40% molar recovery on the first day and then gradually disappeared. The nitrate level reached a plateau of ～60% molar recovery. Cyanide was also detected, and its level at the 14th day was ～0.26% molar recovery. These findings suggest that, in a coffee drink solution, IBN undergoes hydrolysis to produce iBuOH and nitric acid, which is oxidized to nitrate and also produces cyanide through the nonspecific oxidation of organic compounds under acidic conditions.
Manganese-Catalyzed Selective Upgrading of Ethanol with Methanol into Isobutanol
Liu, Yaqian,Shao, Zhihui,Wang, Yujie,Xu, Lijin,Yu, Zhiyong,Liu, Qiang
, p. 3069 - 3072 (2019)
Isobutanol serves as an ideal gasoline additive owing to its good compatibility with current engine technology, high energy density, and high octane number. Herein, an efficient and selective Mn-catalyzed upgrading of ethanol with methanol into isobutanol is reported. This is the first example of deoxygenative coupling of lower alcohols to isobutanol by using a homogeneous non-noble-metal catalyst. This transformation proceeded at very low catalyst loading with a high turnover number (9233) and up to 96 % isobutanol selectivity.
METHOD FOR PRODUCING BIO ALCOHOL FROM INTERMEDIATE PRODUCTS OF ANAEROBIC DIGESTION TANK
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Paragraph 0057-0060; 0063; 0065-0066; 0068-0069; 0071, (2021/05/25)
The present invention relates to a method for producing a bio-alcohol by reacting a mixture of volatile fatty acid with methanol in 2 through 11 in a reactor in the presence of a 280 °C-membered alkaline earth metal catalyst or 400 °C transition metal catalyst formed based on a support.
(Hexamethylbenzene)Ru catalysts for the Aldehyde-Water Shift reaction
Phearman, Alexander S.,Moore, Jewelianna M.,Bhagwandin, Dayanni D.,Goldberg, Jonathan M.,Heinekey, D. Michael,Goldberg, Karen I.
supporting information, p. 1609 - 1615 (2021/03/09)
The Aldehyde-Water Shift (AWS) reaction uses H2O as a benign oxidant to convert aldehydes to carboxylic acids, producing H2, a valuable reagent and fuel, as its sole byproduct. (Hexamethylbenzene)RuIIcomplexes are demonstrated to have higher activity and selectivity (up to 95%) for AWS over disproportionation than previously reported catalysts.
Efficient and chemoselective hydrogenation of aldehydes catalyzed by well-defined PN3-pincer manganese(ii) catalyst precursors: An application in furfural conversion
Gholap, Sandeep Suryabhan,Dakhil, Abdullah Al,Chakraborty, Priyanka,Li, Huaifeng,Dutta, Indranil,Das, Pradip K.,Huang, Kuo-Wei
supporting information, p. 11815 - 11818 (2021/11/30)
Well-defined and air-stable PN3-pincer manganese(ii) complexes were synthesized and used for the hydrogenation of aldehydes into alcohols under mild conditions using MeOH as a solvent. This protocol is applicable for a wide range of aldehydes containing various functional groups. Importantly, α,β-unsaturated aldehydes, including ynals, are hydrogenated with the CC double bond/CC triple bond intact. Our methodology was demonstrated for the conversion of biomass derived feedstocks such as furfural and 5-formylfurfural to furfuryl alcohol and 5-(hydroxymethyl)furfuryl alcohol respectively.
Disproportionation of aliphatic and aromatic aldehydes through Cannizzaro, Tishchenko, and Meerwein–Ponndorf–Verley reactions
Sharifi, Sina,Sharifi, Hannah,Koza, Darrell,Aminkhani, Ali
, p. 803 - 808 (2021/07/20)
Disproportionation of aldehydes through Cannizzaro, Tishchenko, and Meerwein–Ponndorf–Verley reactions often requires the application of high temperatures, equimolar or excess quantities of strong bases, and is mostly limited to the aldehydes with no CH2 or CH3 adjacent to the carbonyl group. Herein, we developed an efficient, mild, and multifunctional catalytic system consisting AlCl3/Et3N in CH2Cl2, that can selectively convert a wide range of not only aliphatic, but also aromatic aldehydes to the corresponding alcohols, acids, and dimerized esters at room temperature, and in high yields, without formation of the side products that are generally observed. We have also shown that higher AlCl3 content favors the reaction towards Cannizzaro reaction, yet lower content favors Tishchenko reaction. Moreover, the presence of hydride donor alcohols in the reaction mixture completely directs the reaction towards the Meerwein–Ponndorf–Verley reaction. Graphic abstract: [Figure not available: see fulltext.].
Highly efficient NHC-iridium-catalyzed β-methylation of alcohols with methanol at low catalyst loadings
Lu, Zeye,Zheng, Qingshu,Zeng, Guangkuo,Kuang, Yunyan,Clark, James H.,Tu, Tao
, p. 1361 - 1366 (2021/06/30)
The methylation of alcohols is of great importance since a broad number of bioactive and pharmaceutical alcohols contain methyl groups. Here, a highly efficient β-methylation of primary and secondary alcohols with methanol has been achieved by using bis-N-heterocyclic carbene iridium (bis-NHC-Ir) complexes. Broad substrate scope and up to quantitative yields were achieved at low catalyst loadings with only hydrogen and water as by-products. The protocol was readily extended to the β-alkylation of alcohols with several primary alcohols. Control experiments, along with DFT calculations and crystallographic studies, revealed that the ligand effect is critical to their excellent catalytic performance, shedding light on more challenging Guerbet reactions with simple alcohols. [Figure not available: see fulltext.].
METHOD FOR PREPARING ISOBUTENOL
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Paragraph 0070-0071; 0078-0079; 0083, (2021/06/15)
The present invention provides a method for preparing isobutanol, which comprises a step of selectively hydrogenating methacrolein in the presence of a catalyst and additives. The preparation method according to the present invention can increase the selectivity of the isobutanol.
METHOD FOR PREPARING ISOBUTENOL
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Paragraph 0052-0053; 0068-0069, (2021/06/15)
The present invention provides a method for preparing isobutanol, which comprises a step of selectively hydrogenating methacrolein in the presence of a pincer ligand catalyst. The preparation method according to the present invention can increase the selectivity of the isobutanol.
METHOD FOR PREPARING ISOBUTENOL
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Paragraph 0077; 0092-0096, (2021/06/15)
The present invention provides a method for manufacturing isobutenol comprising a step of selectively hydrogenating methacrolein in the presence of an additive. A manufacturing method according to the present invention can increase the selectivity of isobutenol. In the manufacturing method according to an exemplary embodiment of the present invention, the additive represented by the chemical formula 1 is added to provide isobutenol with high selectivity, and the selective hydrogenation reaction is predominant, so that the amount of a catalyst can be reduced.
