- Palladium(II)-catalyzed oxidation of aldehydes and ketones. 1. Carbonylation of ketones with carbon monoxide catalyzed by palladium(II) chloride in methanol
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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.
- Hamed,El-Qisairi,Henry
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Read Online
- Rhenium complex as a useful catalyst for acylative cleavage of ethers
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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.
- Umeda, Rui,Kaiba, Kenta,Tanaka, Toshimasa,Takahashi, Yuuki,Nishimura, Takashi,Nishiyama, Yutaka
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Read Online
- Characterization of alkoxycarbonyl radicals by step-scan time-resolved infrared spectroscopy
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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.
- Bucher, G?tz,Halupka, Martin,Kolano, Christoph,Schade, Olaf,Sander, Wolfram
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- Halide exchange: Preparation of alkyl chlorides
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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.
- Peyrat, Jean-Francois,Figadere, Bruno,Cave, Andre
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Read Online
- Taking compact NMR to monitoring real reactions in large-scale chemical industries—General considerations and learnings from a lab-scale test case
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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.
- Nestle, Nikolaus,Lim, Zi Jian,B?hringer, Tobias,Abtmeyer, Sarah,Arenz, Sven,Leinweber, Felix C.,Wei?, Thomas,von Harbou, Erik
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Read Online
- Catalytic C-O bond cleavage of ethers using group 5 or 6 metal halide/acid chloride systems
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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.
- Guo,Miyaji,Gao,Hara,Takahashi
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Read Online
- Method for synthesizing 1-chloro-n-octane
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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.
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Paragraph 0032-0041
(2020/01/14)
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- Method for synthesizing chlorinated n-octane by using UV-0 waste acid
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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.
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Paragraph 0020-0025
(2021/01/15)
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- METHOD FOR PRODUCING REDUCED HALIDE COMPOUND HAVING UNDERGONE REDUCTION OF CARBON-CARBON UNSATURATED BOND
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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.
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Paragraph 0166-0171; 0208-0213
(2019/11/05)
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- Ferric(III) Chloride Catalyzed Halogenation Reaction of Alcohols and Carboxylic Acids Using α,α-Dichlorodiphenylmethane
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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.
- Lee, Chang-Hee,Lee, Soo-Min,Min, Byul-Hana,Kim, Dong-Su,Jun, Chul-Ho
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supporting information
p. 2468 - 2471
(2018/04/25)
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- RECYCLABLE CATALYSTS FOR CHLORINATION OF ORGANIC ACIDS AND ALCOHOLS
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The present invention discloses recyclable polymeric catalyst of Formula I, for chlorination of organic acids and alcohols using chlorinating agents such as carbonyl chloride, oxalyl chloride or thionyl chloride, wherein, ‘m’ on the pendent groups on polystyrene backbone can have values from 1 to 5 and R is the alkyl group ranging from C1 to C5.
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Paragraph 0106
(2017/10/10)
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- Catalytic halodefluorination of aliphatic carbon-fluorine bonds
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A variety of halosilanes, in conjunction with aluminum catalysts, convert fluorocarbons into higher halocarbons. Bromination and iodination of fluorocarbons are more effective than chlorination in terms of yield and activity. The mechanism for the reaction is investigated utilizing experimental and computational evidence and preliminary results suggest an alternate mechanism to that reported for the related hydrodefluorination reaction.
- Goh, Kelvin K.K.,Sinha, Arup,Fraser, Craig,Young, Rowan D.
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p. 42708 - 42712
(2016/05/19)
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- METHOD OF CONVERTING ALCOHOL TO HALIDE
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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.
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Page/Page column 53; 132; 134; 135
(2017/01/02)
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- Formamides as Lewis Base Catalysts in SNReactions—Efficient Transformation of Alcohols into Chlorides, Amines, and Ethers
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A simple formamide catalyst facilitates the efficient transformation of alcohols into alkyl chlorides with benzoyl chloride as the sole reagent. These nucleophilic substitutions proceed through iminium-activated alcohols as intermediates. The novel method, which can be even performed under solvent-free conditions, is distinguished by an excellent functional group tolerance, scalability (>100 g) and waste-balance (E-factor down to 2). Chiral substrates are converted with excellent levels of stereochemical inversion (99 %→≥95 % ee). In a practical one-pot procedure, the primary formed chlorides can be further transformed into amines, azides, ethers, sulfides, and nitriles. The value of the method was demonstrated in straightforward syntheses of the drugs rac-Clopidogrel and S-Fendiline.
- Huy, Peter H.,Motsch, Sebastian,Kappler, Sarah M.
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supporting information
p. 10145 - 10149
(2016/08/16)
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- Method of manufacturing imidoyl diazidosulfochloride compd. various compd. and manufacturing method of using the same
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PROBLEM TO BE SOLVED: To provide a new production method for synthesizing an imidoyl chloride compound dispensing with chlorination agents having poor handleability, to provide a method for producing various compounds in high yield and purity by using the imidoyl chloride compound, and to provide a method for isolating the imidoyl chloride compound in high efficiency and purity from a mixture of the imidoyl chloride compound and a phthalic anhydride compound.SOLUTION: The method for producing the imidoyl chloride compound comprises reaction of a specific amide compound with a specific phthaloyl chloride compound to produce a specific imidoyl chloride compound.
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Paragraph 0070
(2016/12/16)
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- Halogen Exchange Reaction of Aliphatic Fluorine Compounds with Organic Halides as Halogen Source
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The halogen exchange reaction of aliphatic fluorine compounds with organic halides as the halogen source was achieved. Treatment of alkyl fluorides (primary, secondary, or tertiary fluorides) with a catalytic amount of titanocene dihalides, trialkyl aluminum, and polyhalomethanes (chloro or bromo methanes) as the halogen source gave the corresponding alkyl halides in excellent yields under mild conditions. In the case of a fluorine/iodine exchange, no titanocene catalyst is needed. Only C-F bonds are selectively activated under these conditions, whereas alkyl chlorides, bromides, and iodides are tolerant to these reactions.
- Mizukami, Yuki,Song, Zhiyi,Takahashi, Tamotsu
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supporting information
p. 5942 - 5945
(2016/01/09)
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- Trichloroisocynuric acid/DMF as efficient reagent for chlorodehydration of alcohols under conventional and ultrasonic conditions
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A new and efficient method for the chlorodehydration of alcohols utilizing TCCA/DMF is described. Various alcohols can be converted smoothly into their corresponding alkyl chlorides in high yields under mild conditions with short reaction times. Taylor & Francis Group, LLC.
- Venkana, Purugula,Kumar, Mukka Satish,Rajanna, Kamatala Chinna,Ali, Mir Moazzam
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- SYNTHETIC METHOD FOR THE PREPARATION OF 1, 2-BENZISOTHIAZOLIN-3-ONE
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The present invention relates to a method for producing a 1,2-benzisothiazolin-3-one compound (I) by reacting a 2-halobenzonitrile compound (II) with a thiol compound (III) to form an intermediate (IV) and subsequently reacting the intermediate (IV) with a halogenation agent in the presence of water to form a reaction mixture (RM), comprising the 1,2-benzisothiazolin-3-one compound (I) and a halide compound (V).
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Paragraph 0266; 0267
(2015/12/05)
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- Synthetic method for the preparation of 1,2-Benzisothiazolin-3-one
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The present invention relates to a method for producing a 1,2-benzisothiazolin-3-one compound (I) by reacting a 2-halobenzonitrile compound (II) with a thiol compound (III) to form an intermediate (IV) and subsequently reacting the intermediate (IV) with a halogenation agent in the presence of water to form a reaction mixture (RM), comprising the 1,2-benzisothiazolin-3-one compound (I) and a halide compound (V). R3-SH (III), R3_X1(V),
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Paragraph 0159; 0160; 0161
(2015/12/18)
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- Cross-coupling of alkyl halides with aryl or alkyl Grignards catalyzed by dinuclear Ni(ii) complexes containing functionalized tripodal amine-pyrazolyl ligands
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Structurally distinctive dinuclear Ni(ii) complexes with furan or thiophene tethered amine-pyrazolyl tripodal hybrid ligands have been synthesized and crystallographically characterized. All complexes are catalytically active towards cross-coupling of aryl/alkyl Grignard reagents with β-H containing alkyl halides at room temperature in the presence of N,N,N',N'- tetramethylethylenediamine (TMEDA). The catalytic efficacy of the complexes is dependent on the tether substituent at the central amine. Two species, Ni(ii) TMEDA and Mg(ii) TMEDA complexes, have been isolated from the catalytic reaction mixtures under different conditions. Some ligand-stabilized Ni(ii) and Mg(ii) bimetallic species have also been identified in the ESI-MS spectra.
- Xue, Fei,Zhao, Jin,Hor, T. S. Andy
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p. 5150 - 5158
(2013/04/10)
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- A facile and green protocol for nucleophilic substitution reactions of sulfonate esters by recyclable ionic liquids [bmim][X]
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Ionic liquids [bmim][X] (X = Cl, Br, I, OAc, SCN) are highly efficient reagents for nucleophilic substitution reactions of sulfonate esters derived from primary and secondary alcohols. The counter anions (X-) of the ionic liquids, [bmim][X], effectively replace the sufonates affording the corresponding substitution products such as alkyl halides, acetates, and thiocyanides in excellent yields. The newly developed protocol is very environmentally attractive because the reactions use stoichiometric amounts of ionic liquids as sole reagents in most cases and do not require additional solvents, any other activating reagents, non-conventional equipment, or special precautions. Moreover, these ionic liquids can be readily recycled without loss of reactivity, making the whole process greener.
- Liu, Yajun,Xu, Yongnan,Jung, Sun Ho,Chae, Junghyun
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p. 2692 - 2698,7
(2012/12/12)
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- A facile and green protocol for nucleophilic substitution reactions of sulfonate esters by recyclable ionic liquids [bmim][X]
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Ionic liquids [bmim][X] (X = Cl, Br, I, OAc, SCN) are highly efficient reagents for nucleophilic substitution reactions of sulfonate esters derived from primary and secondary alcohols. The counter anions (X-) of the ionic liquids, [bmim][X], effectively replace the sufonates affording the corresponding substitution products such as alkyl halides, acetates, and thiocyanides in excellent yields. The newly developed protocol is very environmentally attractive because the reactions use stoichiometric amounts of ionic liquids as sole reagents in most cases and do not require additional solvents, any other activating reagents, non-conventional equipment, or special precautions. Moreover, these ionic liquids can be readily recycled without loss of reactivity, making the whole process greener. Georg Thieme Verlag KG Stuttgart · New York.
- Liu, Yajun,Xu, Yongnan,Jung, Sun Ho,Chae, Junghyun
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p. 2692 - 2698
(2013/01/15)
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- Synthesis of functionalized dialkyl ketones from carboxylic acid derivatives and alkyl halides
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Unsymmetrical dialkyl ketones can be directly prepared by the nickel-catalyzed reductive coupling of carboxylic acid chlorides or (2-pyridyl)thioesters with alkyl iodides or benzylic chlorides. A wide variety of functional groups are tolerated by this process, including common nitrogen protecting groups and C-B bonds. Even hindered ketones flanked by tertiary and secondary centers can be formed. The mechanism is proposed to involve the reaction of a (L)Ni(alkyl)2 intermediate with the carboxylic acid derivative.
- Wotal, Alexander C.,Weix, Daniel J.
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supporting information; experimental part
p. 1476 - 1479
(2012/05/21)
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- Differentiating C-Br and C-Cl bond activation by using solvent polarity: Applications to orthogonal alkyl-alkyl negishi reactions
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A pot to share: A Calkyl-Cl bond can be rendered "dormant" or "active" in the Negishi alkyl-alkyl cross-coupling by a simple solvent polarity "switch" (see scheme). Adjustment from a 1:2 to a 2:1 solvent ratio of dimethylimidazolidinone: tetrahydrofuran enables orthogonal alkyl-alkyl Negishi cross-coupling strategies to be carried out on bifunctional bromochloroalkanes in one pot at room temperature.
- Hadei, Niloufar,Achonduh, George T.,Valente, Cory,O'Brien, Christopher J.,Organ, Michael G.
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supporting information; experimental part
p. 3896 - 3899
(2011/06/24)
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- C-F bond-cleavage reactions of fluoroalkanes with magnesium reagents and without metal catalysts
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An unexpected C-F bond-cleavage reaction of unactlvated fluoroalkanes with the well-known Grlgnard reagents without using metal catalysts has been discovered. For example, a reaction between 1-fluorooctane and phenyl magnesium chloride gave n-octylbenzene In moderate yield. This coupling reaction via the activation of an unactlvated alkyl carbon-fluorine bond proceeds with phenylmagneslum chloride, whereas methylmagneslum chloride did not give the C-C cross-coupling product but rather a halogen exchange product.
- Matsubara, Kouki,Ishibashi, Tomoka,Koga, Yuji
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supporting information; body text
p. 1765 - 1768
(2009/09/06)
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- A new and more efficient synthesis of methylene acetals
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A new and efficient synthesis of benzyl chlorides and methylene acetals by use of 2,4-dichloro-6-methoxy[l,3,5]triazine (MeOTCT) and dimethyl sulfoxide has been developed. Chlorides are the major products for benzyl alcohols, while methylene acetals are the major products for secondary alcohols. This procedure provides the highest yields so far for methylene acetals of steroids. A plausible mechanism is proposed on the basis of the experiments. Georg Thieme Verlag Stuttgart.
- Chu, Guobiao,Zhang, Yanqiao,Li, Chunbao,Zhang, Yuqing
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experimental part
p. 3828 - 3832
(2010/03/03)
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- Reactivity of anionic nucleophiles in ionic liquids and molecular solvents
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The nucleophilic reactivity of a representative series of anions has been measured in [hmim][ClO4] 3i, [hm2im][ClO4] 3′i, and [hmim][PF6] 3l ILs in the reaction with n-alkyl methanesulfonates and compared with that found in common molecular solvents (MeOH, DMSO, PhCl). The reactivity is found to depend on both the imidazolium cation-anion interaction and the specific solvation by water present in the IL, the water playing the main effect, in particular with hydrophilic anions. Removal of the largest quantity of water remarkably increases the ion pair reactivity in the IL up to rate constant value k comparable with those obtained in DMSO and in low polarity media (PhCl).
- Betti, Cecilia,Landini, Dario,Maia, Angelamaria
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p. 1689 - 1695
(2008/09/18)
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- Conversion of a (sp3)C-F bond of alkyl fluorides to (sp 3)C-X (X = Cl, C, H, O, S, Se, Te, N) bonds using organoaluminium reagents
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A simple method for the conversion of (sp3)C-F bonds of alkyl fluorides to (sp3)C-X (X = Cl, C, H, O, S, Se, Te, N) bonds has been achieved by the use of a hexane solution of organoaluminum reagents having Al-X bonds. The Royal Society of Chemistry.
- Terao, Jun,Begum, Shameem Ara,Shinohara, Yoshiaki,Tomita, Masahiro,Naitoh, Yoshitaka,Kambe, Nobuaki
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p. 855 - 857
(2007/10/03)
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- An efficient method for chlorination of alcohols using PPh3/Cl3CCONH2
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A new and convenient method for the chlorination of alcohols utilizing PPh3/Cl3CCONH2 is addressed. Various alcohols could smoothly be converted into their corresponding alkyl chlorides in high yield under mild conditions with short reaction times. A mechanism is disclosed with the evidence of inversion of configuration of the analogous alkyl chloride derived from R-(-)-2-octanol.
- Pluempanupat, Wanchai,Chavasiri, Warinthorn
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p. 6821 - 6823
(2007/10/03)
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- Process for preparing alkyl chlorides
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The invention relates to a process for preparing alkyl chlorides by reacting alcohols with gaseous hydrogen chloride in the presence of a catalyst, wherein the catalyst comprises at least one compound of the structure: wherein R1 is a linear alkyl group having from 1 to 20 carbon atoms, R2, R3, and R4 is selected from a hydrogen, an alkyl, an alkenyl, an aralkyl or an alkylaryl group from 1 to 20 carbon atoms, wherein the substituents of R2, R3, and R4 are all identical, are all different or two of the substituents of R2, R3, and R4 type are identical.
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Page/Page column 5
(2008/06/13)
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- Synthesis of chlorothioformates from xanthates
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The Vilsmeier reagent derived from N-formylmorpholine produces chlorothioformates from primary and secondary alkyl xanthates. The major side products are the corresponding alkyl chlorides. Secondary alkyl chlorothioformates give lower yields due to their instability. Treating xanthates with other common chlorinating agents (oxalyl chloride, thionyl chloride) gives only dialkyl thiodicarbonates. Georg Thieme Verlag Stuttgart.
- Fikse, Megan A.,Bylund, William E.,Holubowitch, Nicolas E.,Abelt, Christopher J.
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p. 4118 - 4120
(2008/03/13)
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- Process to convert alkanes into primary alcohols
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This invention provides a process to convert alkanes to primary alcohols of the same carbon number. Carbon numbers of particular interest are C8 to C18. The process comprises the steps of: a) halogenating a linear or branched (or mixture of linear and branched) alkane to produce a mixture of primary mono-haloalkanes, internal mono-haloalkanes, unreacted alkanes, hydrogen halide, and possibly multi-haloalkanes in the presence of a catalyst and/or by heating the reaction mixture; b) separating the hydrogen halide from the mixture and optionally neutralizing it with a metal oxide to produce a partially halogenated metal oxide and/or metal halide which may be regenerated; c) separating the primary mono-haloalkanes from the mixture; d) reacting the separated primary mono-haloalkanes in a reactor with a metal oxide or combination of metal oxides and water to convert the aforesaid primary mono-haloalkane to a mixture of products that contains primary alcohols, unconverted primary mono-haloalkanes, and possibly other reaction products, and a partially halogenated metal oxide and/or metal halide which may be regenerated; e) regenerating the partially halogenated metal oxide and/or metal halide to halogen (such as Cl2) and/or acid and a metal oxide for recycle by reaction with air or oxygen; and f) removing the unreacted primary mono-haloalkane from the reaction mixture and then purifying the primary alcohol.
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Page/Page column 7
(2008/06/13)
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- Process to convert linear alkanes into alpha olefins
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This invention provides for a process to convert branched or linear alkanes to branched or linear alpha olefins (AO) of the same carbon number. The process comprises the steps of: a) halogenating linear alkanes, branched alkanes, or a mixture of linear and branched alkane to produce a mixture containing primary mono-haloalkanes and hydrogen halide; b) separating the hydrogen halide from the mixture and optionally neutralizing it with a metal oxide to produce a partially halogenated metal oxide and/or metal halide which may be regenerated; c) separating the primary mono-haloalkanes from the mixture; d) reacting the separated primary mono-haloalkanes with a metal oxide to produce a mixture of products that contains alpha olefins, unconverted primary mono-haloalkanes, possibly other reaction products, and a partially halogenated metal oxide and/or metal halide which may be regenerated; e) regenerating the partially halogenated metal oxide and/or metal halide to halogen and/or acid and a metal oxide (such as Cl2) for recycle by reaction with air or oxygen ; and f) removing the unreacted primary mono-haloalkane from the reaction mixture and then purifying the alpha olefin.
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Page/Page column 7
(2008/06/13)
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- Anion nucleophilicity in ionic liquids: A comparison with traditional molecular solvents of different polarity
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The nucleophilic reactivity of a homogeneous series of anions (halides, pseudohalides and organic anions) in the ionic liquids [hexmim] [ClO 4] and [hexmim] [PF6] has been measured in their reaction with n-alkyl methanesulfonates, and compared with that found in traditional molecular solvents of different polarity, that is, chlorobenzene, DMSO, and MeOH.
- Landini, Dario,Maia, Angelamaria
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p. 3961 - 3963
(2007/10/03)
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- Indium-catalyzed direct chlorination of alcohols using chlorodimethylsilane-benzil as a selective and mild system
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The InCl3-catalyzed reaction of alcohols with chlorodimethylsilane (HSiMe2Cl) in the presence of benzil gave the corresponding organic chlorides under mild conditions. Benzil significantly changes the reaction course because the reducing product through dehydroxyhydration was obtained in the absence of benzil. The secondary or tertiary alcohols were effectively chlorinated. The substrates bearing acid-sensitive functional groups were also applied to this system. The highly selective chlorination of the tertiary site was observed in the competitive reaction between tertiary and primary alcohols. The highly coordinated hydrosilane generated from benzil and HSiMe2Cl is an important intermediate. Copyright
- Yasuda, Makoto,Yamasaki, Satoshi,Onishi, Yoshiyuki,Baba, Akio
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p. 7186 - 7187
(2007/10/03)
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- Ionic liquids as reagents and solvents in conjunction with microwave heating: Rapid synthesis of alkyl halides from alcohols and nitriles from aryl halides
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We show that using ionic liquids as reagents in conjunction with microwave heating it is possible to prepare primary alkyl halides from the corresponding alcohols rapidly. Using ionic liquids as solvents in conjunction with microwave heating it is possible to prepare aryl nitriles from the corresponding aryl bromides or iodides. The scope and limitations of using microwave-promotion as a tool in these reactions is discussed.
- Leadbeater, Nicholas E.,Torenius, Hanna M.,Tye, Heather
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p. 2253 - 2258
(2007/10/03)
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- Pd-Catalyzed Cross-Coupling Reaction of Alkyl Tosylates and Bromides with Grignard Reagents in the Presence of 1,3-Butadiene
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A new method for cross-coupling reaction of alkyl tosylates and bromides with Grignard reagents has been developed by the use of Pd(acac)2 or PdCl2 as the catalyst. Addition of 1,3-butadiene is essential to afford good yields of coupling products. This reaction proceeds efficiently at room temperature using primary and secondary alkyl and aryl Grignard reagents.
- Terao, Jun,Naitoh, Yoshitaka,Kuniyasu, Hitoshi,Kambe, Nobuaki
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p. 890 - 891
(2007/10/03)
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- Conversion of alcohols into alkyl chlorides using trichloroisocyanuric acid with triphenylphosphine
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Trichloroisocyanuric acid with triphenylphosphine in anhydrous acetonitrile will convert alcohols into alkyl halides.
- Hiegel, Gene A.,Rubino, Mark
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p. 2691 - 2694
(2007/10/03)
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- The fragmentation of alkoxychlorocarbenes in hydrocarbon solvents and in low temperature argon matrixes
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Alkoxychlorocarbenes (ROCCl, R = benzyl, cyclohexyl, and 1-octyl) were generated from the corresponding diazirines in acetonitrile, dichloroethane, benzene, cyclohexane, and pentane solutions at 25°C, and the fragmentations of these carbenes were studied. A prominent product was phenacyl chloride (PhCH2CoCl), a formal rearrangement product of the carbene. In polar solvents, the two fragmentation transition states for CH3OCCl and C2H5OCCl were stabilized to the point where cis-trans isomerization, loss of CO, and concerted loss of CO + Cl all have similar activation energies. In less polar solvents, such as dichloroethane, heterolytic cleavage was probably not competitive.
- Moss, Robert A.,Ma, Yan,Zheng, Fengmei,Sauers, Ronald R.,Bally, Thomas,Maltsev, Alexander,Toscano, John P.,Showalter, Brett M.
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p. 12280 - 12291
(2007/10/03)
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- Generation of alkyl hypochlorites in oxidation of alcohols with carbon tetrachloride catalyzed by vanadium and manganese compounds
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Primary alcohols and diols with various structures were subjected to transformations into esters, aldehydes, ketones, and lactones under the action of carbon tetrachloride in the presence of manganese compounds (MnCl 2, MnO2, Mn(OAc)2, Mn(acac)3) and vanadium compounds (VCl5, V2O5, VO(acac) 2) as catalysts. These transformation proceeded with the involvement of alkyl hypochlorites, which were generated in the course of oxidation of alcohols with carbon tetrachloride catalyzed by manganese or vanadium compounds. The optimum molar ratios between the catalyst and reagents were determined, and the reaction conditions for the highly selective synthesis of esters, aldehydes, ketones, and lactones from alcohols were found.
- Khusnutdinov,Shchadneva,Baiguzina,Lavrentieva,Dzhemilev
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p. 2074 - 2079
(2007/10/03)
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- Group 5 and group 6 metal halides as very efficient catalysts for acylative cleavage of ethers
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Group 5 and 6 metal chlorides such as MoCl5, WCl6, NbCl5 and TaCl5 were found as very efficient catalysts for acylative cleavage of the C-O bond of ethers. Compared with conventional Lewis acid catalysts such as ZnCl2, AlCl3, SnCl4 and TiCl4, group 5 and 6 metal chlorides showed better results in the catalytic C-O bond cleavage of dibutyl ether with benzoyl chloride.
- Guo, Qiaoxia,Miyaji, Taichi,Hara, Ryuichiro,Shen, Baojian,Takahashi, Tamotsu
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p. 7327 - 7334
(2007/10/03)
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- Mild conversion of alcohols to alkyl halides using halide-based ionic liquids at room temperature
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Formula presented Alcohols were efficiently converted to alkyl halides using 1-n-butyl-3-methylylimidazolium halides (ionic liquids) in the presence of Bronsted acids at room temperature. The alkyl halide products were easily isolated from the reaction mixture via simple decantation or extraction, and the 1-n-butyl-3-methylimidazolium cation could be recycled for further uses.
- Ren, Rex X.,Wu, Jeff Xin
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p. 3727 - 3728
(2007/10/03)
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- Nitrogen-based halogenating agents and process for preparing halogen-containing compounds
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Disclosed are a fluorinating agent represented by the general formula (1): wherein R1to R4are a substituted or unsubstituted, saturated or unsaturated alkyl group or a substituted or unsubstituted aryl group, and can be the same or different; R1and R2or R3and R4can bond to form a ring including a nitrogen atom or a nitrogen atom and other hetero atoms; or R1and R3can bond to form a ring including a nitrogen atom or a nitrogen atom and other hetero atoms, for example: a preparation process of the fluorinating agent and a process for preparing fluorine compounds by reacting various compounds with the fluorinating agent. The invention has also disclosed that the fluorinating agent is very effective for fluorinating oxygen containing functional compounds.
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- 2-chloro-1,3-dimethylimidazolinium chloride. 3. Utility for chlorination, oxidation, reduction, and rearrangement reactions
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2-Chloro-1,3-dimethylimidazolinium chloride (1), which can act as a powerful dehydrating equivalent to DCC (2), is also applicable to chlorination, oxidation, reduction, and rearrangement under nearly neutral conditions. The utility of 1 for these reactions is described.
- Isobe, Toshio,Ishikawa, Tsutomu
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p. 5832 - 5835
(2007/10/03)
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- Thionyl chloride-benzotriazole in methylene chloride: A convenient solution for conversion of alcohols and carboxylic acids expeditiously into alkyl chlorides and acid chlorides by simple titration
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A solution of 1:1 equivalent of thionyl chloride and benzotriazole in dry methylene chloride efficiently transforms alcohols and carboxylic acids into the corresponding alkyl chlorides and acid chlorides respectively at room temperature, with excellent yields by simple titration.
- Chaudhari, Sachin S.,Akamanchi, Krishnacharya G.
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p. 1763 - 1765
(2007/10/03)
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- Influence of Haloalkanes on the Selectivity of Radical Chlorination of Saturated Hydrocarbons
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The selectivity of radical chlorination of alkanes with molecular chlorine increases when the reaction is carried out in halogenated hydrocarbons. The relations of the observed selectivity to the concentrations of the solvent and the substrate suggest formation of a complex between chlorine atom and haloalkane molecule.
- Dneprovskii,Eliseenkov,Kuznetsov
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p. 637 - 641
(2007/10/03)
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- Catalytic decomposition of alkyl chloroformates by hexabutylguanidinium chloride
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Hexabutylguanidinium chloride (0.5 molar %) efficiently decomposes alkyl chloroformates into chlorides, with low alkenes formation, via a S(N)2 mechanism as demonstrated from substituents effects and asymmetric chloride synthesis.
- Foulon, Frederique,Fixari, Bernard,Picq, Dominique,Le Perchec, Pierre
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p. 3387 - 3390
(2007/10/03)
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- CYCLOPHOSPHAZENIC POLYPODANDS AS POWERFUL CATION COMPLEXING AGENTS, EFFICIENT PHASE-TRANSFER CATALYSTS AND ANION ACTIVATORS
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A survey dealing with cyclophosphazenic polypodands 3a-c, a new class of "octopus-like" molecules is reported.These many-armed ligands are powerful complexing agents of alkali metal salts and hence behave as very efficient catalysts in many reations (nucleophilic substitutions, eliminations, alkylations, oxidations, reductions) under solid-liquid and liquid-liquid phase-transfer catalysis conditions.Their catalytic activity is much better than that of the open-chain analogues PEGs 4, 5 and TRIDENT-1, 6.Moreover, anion activation realized by cyclophosphazenic polypodands, both of homogeneous and heterogeneous systems, is comparable with that obtained with the more sophisticated and expensive crown ethers.
- Landini, Dario,Maia, Angelamaria,Podda, Gianni
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p. 583 - 588
(2007/10/03)
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