111-85-3Relevant articles and documents
Palladium(II)-catalyzed oxidation of aldehydes and ketones. 1. Carbonylation of ketones with carbon monoxide catalyzed by palladium(II) chloride in methanol
Hamed,El-Qisairi,Henry
, p. 180 - 185 (2001)
Unsubstituted or alkyl-substituted cyclic ketones react with PdCl2 in methanol under a CO atmosphere to give mainly acyclic diesters along with some acyclic chloro-substituted monoesters. The monosubstituted cyclic ketones, 2-hydroxy- and 2-methoxycyclohexanone, do not give ring cleavage but rather produce 2-(carbomethoxy)cyclohex-2-en-1-one. 13CO labeling experiments indicate one CO is inserted in forming the diester product so the second ester group must arise from the original ketone group. Two mechanisms are possible for the diester reaction. One involves initial Pd(II)-CO2CH3 insertion across the double bond of the enol form of the ketone while the second involves initial addition of Pd(II)-OCH3 followed by CO insertion into the new Pd(II) carbon bond formed. Pd(II) elimination and acid-catalyzed ring cleavage produce the second methyl ester group in both routes. The chloro-substituted monoester is formed by initial Pd(II)-Cl insertion across the double bond followed by the acid-catalyzed ring cleavage. The 2-(carbomethoxy)cyclohex-2-en-1-one must result from elimination of water or methanol from the α-ketoester product formed by the initial methoxycarbonylation of the enol form of the ketone. As expected, the acyclic ketone 2-decanone, formed methyl acetate and a mixture of methyl nonanoate and products.
Rhenium complex as a useful catalyst for acylative cleavage of ethers
Umeda, Rui,Kaiba, Kenta,Tanaka, Toshimasa,Takahashi, Yuuki,Nishimura, Takashi,Nishiyama, Yutaka
, p. 3089 - 3091 (2010)
It was found that a rhenium complex such as ReBr(CO)5 acts as an efficient catalyst for the acylative cleavage of the carbon-oxygen bond of ethers with acyl chloride, giving the corresponding esters in moderate to good yields.
Characterization of alkoxycarbonyl radicals by step-scan time-resolved infrared spectroscopy
Bucher, G?tz,Halupka, Martin,Kolano, Christoph,Schade, Olaf,Sander, Wolfram
, p. 545 - 552 (2001)
A series of alkoxycarbonyl radicals has been generated by laser flash photolysis (355 nm) of fluorenone oxime alkyl oxalates in carbon tetrachloride and characterized by time-resolved infrared spectroscopy using the step-scan technique. The alkoxycarbonyl radicals (v?C=O = 1802 cm-1 for R = ethyl) generally have a lifetime of several microseconds, decaying by reaction with the solvent to yield esters of chloroformic acid. In some cases, decarboxylation yielding alkyl radicals has also been observed. Thus, photolysis of fluorenone oxime tert-butyl oxalate results in the formation of tert-butoxycarbonyl radicals, which subsequently decay, mainly yielding CO2 and tert-butyl radicals. The benzyloxycarbonyl radical and the acetoneiminoxycarbonyl radical both decarboxylate too rapidly to be detected with our spectrometer (25 ns rise-time). Upon purging the solution with oxygen, the alkoxycarbonyl radicals were efficiently quenched, to yield alkoxycarbonylperoxy radicals (v?C=O = 1845 cm-1 for R = ethyl), which again had a lifetime of the order of several microseconds. A short-lived transient (v? = 1768 cm-1, τ ? 200 ns) is assigned as the carbonyloxy radical 4a on the basis of comparison with time-resolved UV/Vis data. A further product of the photolysis of fluorenone oxime oxalates can be tentatively assigned as the 9-fluorenylideneiminoxy radical 3 (v? = 1670 cm-1), which according to our DFT calculations should show a very intense v?C=N-O,as. = 1665 cm-1. Fluorenone oxime oxalates are compounds well suited as precursors for alkoxycarbonyl radicals, since they are easily synthesized as crystalline solids, show a convenient absorption at λ = 355 nm, and exhibit a high degree of thermal stability.
Halide exchange: Preparation of alkyl chlorides
Peyrat, Jean-Francois,Figadere, Bruno,Cave, Andre
, p. 4563 - 4567 (1996)
Primary alkyl bromides can be quantitatively converted into the corresponding chlorides under very mild reaction conditions. The neutral conditions required for such bromide displacements allow the presence of other functions on the substrate.
Taking compact NMR to monitoring real reactions in large-scale chemical industries—General considerations and learnings from a lab-scale test case
Nestle, Nikolaus,Lim, Zi Jian,B?hringer, Tobias,Abtmeyer, Sarah,Arenz, Sven,Leinweber, Felix C.,Wei?, Thomas,von Harbou, Erik
, p. 1213 - 1221 (2020)
The considerations for use of compact nuclear magnetic resonance in a large-scale industrial environment clearly differ from those in academic and educational settings and even from those in smaller companies. In the first part of this article, these differences will be discussed along with the additional requirements that need to be fulfilled for successful applicability in different use cases. In the second part of the article, outcomes from different research activities aiming to fulfill these requirements will be presented with a focus on an online reaction-monitoring study on a lab-scale nucleophilic chlorination reaction.
Catalytic C-O bond cleavage of ethers using group 5 or 6 metal halide/acid chloride systems
Guo,Miyaji,Gao,Hara,Takahashi
, p. 1018 - 1019 (2001)
Ethers reacted with acid chlorides in the presence of a catalytic amount of MCl5/6 (M = Mo, W, Nb or Ta) to give esters in 75-98% yield; a stoichiometric reaction of dioctyl ether with MoCl5 afforded 1-chlorooctane in 93% yield and addition of benzoyl chloride to the resulting mixture gave octyl benzoate in 49% yield.
Method for synthesizing 1-chloro-n-octane
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Paragraph 0032-0041, (2020/01/14)
The invention discloses a method for synthesizing 1-chloro-n-octane. The method comprises the following steps: taking n-octanol and a chlorination reagent as raw materials, and reacting for 1-6 hoursin the presence of a formamide catalyst to obtain the product 1-chloro-n-octane. According to the method, n-octyl alcohol and a chlorination reagent are used as initial raw materials, formamide is used as a catalyst, the catalytic efficiency is high, the operation is simple, the reaction conditions are mild, the selectivity and the yield of the product are relatively high, and the method has a wide industrial application prospect.
Method for synthesizing chlorinated n-octane by using UV-0 waste acid
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Paragraph 0020-0025, (2021/01/15)
The invention discloses a method for synthesizing chlorinated n-octane by using UV-0 waste acid. According to the method, waste acid generated in the synthesis process of UV-0 (2,4-dihydroxybenzophenone) is used as a raw material to react with n-octanol to generate chlorinated n-octane. According to the synthesis method, a complex waste acid post-treatment process is omitted, the production process is simplified, the production energy consumption is reduced, the waste is utilized, the production cost is reduced, the reaction conditions are mild, the production operation is convenient, the post-treatment is simple, and the synthesis method is suitable for industrial production.
METHOD FOR PRODUCING REDUCED HALIDE COMPOUND HAVING UNDERGONE REDUCTION OF CARBON-CARBON UNSATURATED BOND
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Paragraph 0166-0171; 0208-0213, (2019/11/05)
A halide compound having one or more carbon-carbon unsaturated bonds is catalytically reduced with substantially no dehalogenation to produce a reduced halide compound in which at least one of the one or more unsaturated bonds is reduced. Specifically provided is a method for producing a reduced halide compound including steps of: reacting a nickel compound, a zinc compound, and a borohydride compound in a solvent to obtain a reduction catalyst; and subjecting a halide compound having one or more carbon-carbon unsaturated bonds to catalytic reduction in the presence of the reduction catalyst to reduce at least one of the one or more carbon-carbon unsaturated bonds to thereby obtain a reduced halide compound.
Ferric(III) Chloride Catalyzed Halogenation Reaction of Alcohols and Carboxylic Acids Using α,α-Dichlorodiphenylmethane
Lee, Chang-Hee,Lee, Soo-Min,Min, Byul-Hana,Kim, Dong-Su,Jun, Chul-Ho
supporting information, p. 2468 - 2471 (2018/04/25)
A new method for chlorination of alcohols and carboxylic acids, using α,α-dichlorodiphenylmethane as the chlorinating agent and FeCl3 as the catalyst, was developed. The method enables conversions of various alcohols and carboxylic acids to their corresponding alkyl and acyl chlorides in high yields under mild conditions. Particulary interesting is the observation that the respective alkyl bromides and iodides can be generated from alcohols when either LiBr or LiI are present in the reaction mixtures.
