89-60-1Relevant articles and documents
Dehydroxyalkylative halogenation of C(aryl)-C bonds of aryl alcohols
Liu, Mingyang,Zhang, Zhanrong,Liu, Huizhen,Wu, Tianbin,Han, Buxing
supporting information, p. 7120 - 7123 (2020/07/14)
We herein report Cu mediated side-directed dehydroxyalkylative halogenation of aryl alcohols. C(aryl)-C bonds of aryl alcohols were effectively cleaved, affording the corresponding aryl chlorides, bromides and iodides in excellent yields. Aryl alcohols could serve as both aromatic electrophilic and radical synthetic equivalents during the reaction.
Inexpensive NaX (X = I, Br, Cl) as a halogen donor in the practical Ag/Cu-mediated decarboxylative halogenation of aryl carboxylic acids under aerobic conditions
Fu, Zhengjiang,Jiang, Ligao,Zuo, Qianming,Li, Zhaojie,Liu, Yanzhu,Wei, Zhenhong,Cai, Hu
supporting information, p. 5416 - 5421 (2018/08/12)
Versatile and practical Ag/Cu-mediated decarboxylative halogenation between readily available aryl carboxylic acids and abundant NaX (X = I, Br, Cl) has been achieved under aerobic conditions in moderate to good yields. The halodecarboxylation is shown to be an effective strategy for S-containing heteroaromatic carboxylic acid and benzoic acids with nitro, chloro and methoxyl substituents at the ortho position. A gram-scale reaction and a three-step procedure to synthesize iniparib have been performed to evaluate the practicality of this protocol. A preliminary mechanistic investigation indicates that Cu plays a vital role and a radical pathway is involved in the transformation.
Synthetic method of aryl halide taking aryl carboxylic acid as raw material
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Paragraph 0091, (2018/01/03)
A synthetic method of an aryl halide taking aryl carboxylic acid as a raw material is characterized in that a corresponding aryl halide is formed by carrying out substitution reaction on an aryl carboxylic acid compound and haloid salt MX in an organic solvent under the condition that oxygen, a silver catalyst, a copper additive and a bidentate nitrogen ligand exist, wherein M in MX represents alkali metal or alkaline earth metal, and X represents F, Cl, Br or I. Compared with a conventional aryl halide synthetic method, the synthetic method disclosed by the invention has the obvious advantages that reaction raw materials (comprising aryl carboxylic acid and MX) are cheap and easy to obtain, the using amount of a metal catalyst is small, pollution to the environment when the oxygen is used as an oxidant is the smallest, good tolerance to various functional groups on an aromatic ring is obtained, the yield is high, and the like. The synthetic method disclosed by the invention can be widely applied to synthesis in the fields of medicine, materials, natural products and the like in industry and academia.
Efficient transposition of the sandmeyer reaction from batch to continuous process
D'Attoma, Joseph,Camara, Titi,Brun, Pierre Louis,Robin, Yves,Bostyn, Stéphane,Buron, Frédéric,Routier, Sylvain
, p. 44 - 51 (2017/11/30)
The transposition of Sandmeyer chlorination from a batch to a safe continuous-flow process was investigated. Our initial approach was to develop a cascade method using flow chemistry which involved the generation of a diazonium salt and its quenching with copper chloride. To achieve this safe continuous process diazotation, a chemometric approach (Simplex method) was used and extrapolated to establish a fully continuous-flow method. The reaction scope was also examined via the synthesis of several (het)aryl chlorides. Validation and scale-up of the process were also performed. A higher productivity was obtained with increased safety.
Decarboxylative Halogenation and Cyanation of Electron-Deficient Aryl Carboxylic Acids via Cu Mediator as Well as Electron-Rich Ones through Pd Catalyst under Aerobic Conditions
Fu, Zhengjiang,Li, Zhaojie,Song, Yuanyuan,Yang, Ruchun,Liu, Yanzhu,Cai, Hu
, p. 2794 - 2803 (2016/04/26)
Simple strategies for decarboxylative functionalizations of electron-deficient benzoic acids via using Cu(I) as promoter and electron-rich ones by employing Pd(II) as catalyst under aerobic conditions have been established, which lead to smooth synthesis of aryl halides (-I, Br, and Cl) through the decarboxylative functionalization of benzoic acids with readily available halogen sources CuX (X = I, Br, Cl), and easy preparation of benzonitriles from decarboxylative cyanation of aryl carboxylic acids with nontoxic and low-cost K4Fe(CN)6 under an oxygen atmosphere for the first time.
Substituted tetrahydro-1H-pyrido[4,3-b]indoles as serotonin receptors agonists and antagonists
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Page/Page column 22, (2010/11/25)
The present application describes compounds, including all pharmaceutically acceptable salts, prodrugs, solvates and stereoisomers thereof, according to Formula I, pharmaceutical compositions, comprising at least one compound according to Formula I and optionally at least one additional therapeutic agent and methods of treating various diseases, conditions and disorders associated with modulation of serotonin receptors such as, for example: metabolic diseases, which includes but is not limited to obesity, diabetes, diabetic complications, atherosclerosis, impared glucose tolerance and dyslipidemia; central nervous system diseases which includes but is not limited to, anxiety, depression, obsessive compulsive disorder, panic disorder, psychosis, schizophrenia, sleep disorder, sexual disorder and social phobias; cephalic pain; migraine; and gastrointestinal disorders using compounds according to Formula I
Iron(III)-catalysed nitration of non-activated and moderately activated arenes with nitrogen dioxide-molecular oxygen under neutral conditions
Suzuki, Hitomi,Yonezawa, Shuji,Nonoyama, Nobuaki,Mori, Tadashi
, p. 2385 - 2389 (2007/10/03)
In the presence of molecular oxygen and a catalytic amount of tris(pentane-2,4-dionato)iron(III), non-activated and moderately activated arenes, which include alkylbenzenes, halogenobenzenes, phenolic ethers, naphthalene and derivatives, can be nitrated with nitrogen dioxide at ice-bath temperature or below to give the corresponding nitro derivatives in fair to good yields. An electron-transfer mechanism has been proposed, where an activated NO2-FeIII complex plays a key role in the cyclic process for converting arenes into nitroarenes.
Nitration of p-Chlorotoluene and p-Chloroisopropylbenzene
Khan, Iftikhar A.,Manglik, Ajay K.,Sangal, S. K.
, p. 415 - 416 (2007/10/02)
The nitrations of p-chlorotoluene and p-chloroisopropylbenzene with nitric acid in acetic anhydride have been studied.The product composition from the nitration of p-chlorotoluene in acetic anhydride when examined alongwith the previously known product compositions obtained from the nitrations of p-chlorotoluene in varying percentages of sulphuric acid gave information of the degree of attack by the nitronium ion at various positions in p-chlorotoluene.The relative rates of nitrations at various nuclear positions for chlorobenzene could then be calculated.Results from nitration of p-chloroisopropylbenzene were found to be in agreement with these values.
ipso Nitration. XXVIII. Nitration of 4-substituted toluenes: 1,2 adducts
Fisher, Alfred,Fyles, Deborah L.,Henderson, George, N.,Mahasay, Sumit Ray
, p. 1764 - 1770 (2007/10/02)
Nitration of 4-acetamido, 4-chloro, and 4-methoxy-toluene in acetic anhydride gives in each case a cis 1,2 nitronium acetate adduct in adition to the nitro substitution product(s).Nitration of 4-fluorotoluene gives a pair of diastereomeric 1,4 nitronium acetate adducts and the cis 1,2 adduct.
Electrophilic Aromatic Substitution. Part 30. The Kinetics and Products of the Solvolyses in Aqueous Sulphuric Acids of 5-Chloro-2-methyl-2-nitrocyclohexa-3,5-dienyl Acetate: the Occurence of AAC2 and AAl1 Solvolyses, and of an Acid-catalysed Elimination of Nitrous Acid, and the...
Bloomfield, Colin,Moodie, Roy B.,Schofield, Kenneth
, p. 1793 - 1802 (2007/10/02)
Good first order kinetics of solvolysis of the above-named diene in water and in 6.5-43.6percent H2SO4 at 25 deg C, and in water and in 15.2-58.8percent H2SO4 at 5 deg C have been observed.The yields of 4-chlorotoluene, 5-chloro-2-methylphenyl acetate, 5-chloro-2-methylphenol, 4-chloro-2-nitrotoluene, 4-chloro-3-nitrotoluene, and 4-methyl-2-nitrophenol produced in water and in 21.5-92.4percent H2SO4 at 25 deg C in the presence of sulphanilic acid or hydrazinium sulphate, and additionally of 2- and 4-nitroanisole when anisole was also added, have been measured.The solvolysis proceeds by an acid-catalysed elimination of nitrous acid (confirming a tentative conclusion in another case), which competes with AAC2 and AAL1 ester solvolyses.With increasing acidity the solvolyses become dominant, the AAL1 reaction increasingly so.The small yield of 4-chloro-3-nitrotoluene comes from a thermal reaction of the diene unrelated to the elimination and solvolyses.The AAL1 reaction generates the ipso-Wheland intermediate (WiMe) that is also formed in the nitration of 4-chlorotoluene.The intermediate reacts by return to 4-chlorotoluene and nitronium ion (which can be captured by anisole), by 1,2-and 1,4-nucleophilic capture by water (giving 5-chloro-2-methylphenol and 4-methyl-2-nitrophenol, respectively), and by 1,2-rearrangement to 4-chloro-2-nitrotoluene.The first of these reactions never accounts for more than about 12percent of the WiMe and competition between capture and rearrangement moves strongly in favour of the latter with increasing acidity.Re-examination of the nitration of 4-chlorotoluene has revealed products arising from 1,2- and 1,4-capture of WiMe, previously overlooked.An improved assessmentof positional reactivities shows 59percent of primary attack by nitronium ion to occur at C-Me in 63percent H2SO4.
