- Electrochemical Nitration with Nitrite
-
Aromatic nitration has tremendous importance in organic chemistry as nitroaromatic compounds serve as versatile building blocks. This study represents the electrochemical aromatic nitration with NBu4NO2, which serves a dual role as supporting electrolyte and as a safe, readily available, and easy-to-handle nitro source. Stoichiometric amounts of 1,1,1-3,3,3-hexafluoroisopropan-2-ol (HFIP) in MeCN significantly increase the yield by solvent control. The reaction mechanism is based on electrochemical oxidation of nitrite to NO2, which initiates the nitration reaction in a divided electrolysis cell with inexpensive graphite electrodes. Overall, the reaction is demonstrated for 20 examples with yields of up to 88 %. Scalability is demonstrated by a 13-fold scale-up.
- Blum, Stephan P.,Nickel, Christean,Sch?ffer, Lukas,Karakaya, Tarik,Waldvogel, Siegfried R.
-
p. 4936 - 4940
(2021/10/25)
-
- Dehydroxyalkylative halogenation of C(aryl)-C bonds of aryl alcohols
-
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.
- Liu, Mingyang,Zhang, Zhanrong,Liu, Huizhen,Wu, Tianbin,Han, Buxing
-
p. 7120 - 7123
(2020/07/14)
-
- 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
-
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.
- Fu, Zhengjiang,Jiang, Ligao,Zuo, Qianming,Li, Zhaojie,Liu, Yanzhu,Wei, Zhenhong,Cai, Hu
-
supporting information
p. 5416 - 5421
(2018/08/12)
-
- Synthetic method of aryl halide taking aryl carboxylic acid as raw material
-
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.
- -
-
Paragraph 0133
(2018/01/03)
-
- 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
-
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.
- Fu, Zhengjiang,Li, Zhaojie,Song, Yuanyuan,Yang, Ruchun,Liu, Yanzhu,Cai, Hu
-
p. 2794 - 2803
(2016/04/26)
-
- Diastereoselective synthesis of rotationally restricted chiral phenylpyridines via intramolecular cascade cyclization of n-acyliminium ions containing α-amino acid residues
-
A series of chiral phenylpyridines possessing a fused chiral bridge were synthesized diastereoselectively via cascade cyclizations, where N-acyliminium ions including an enantiopure α-amino acid residue were involved. The absolute configuration of the synthesized phenylpyridines was identified unambiguously by using nuclear Overhauser effect difference and circular dichroism (CD) measurements on the basis of literature methods. Taylor & Francis Group, LLC.
- Li, Jin-Ling,Zhao, Hong-Wu,Qin, Xiao,Cui, Jin,Su, Shi,Li, Hai-Long,Yue, Yuan-Yuan,Song, Xiu-Qing
-
supporting information
p. 3175 - 3180
(2014/01/06)
-
- DIHYDROPYRIDONE UREAS AS P2X7 MODULATORS
-
Compounds of the formula I: or pharmaceutically acceptable salts thereof, wherein m, n, R1, R2, R3, R4 and R5 are as defined herein. Also disclosed are methods of making the compounds and using the compounds for treatment of diseases associated with the P2X7 purinergic receptor.
- -
-
Page/Page column 65
(2010/07/04)
-
- Silver-catalyzed decarboxylative halogenation of carboxylic acids
-
Decarboxylative halogenation of carboxylic acids catalyzed by silver carbonate is reported. ortho-Nitrobenzoic acids react with copper(II) chloride or bromide in DMF/DMSO at 130-140 °C leading to the corresponding aryl halides in moderate to good yields.
- Luo, Yong,Pan, Xiaolin,Wu, Jie
-
supporting information; experimental part
p. 6646 - 6648
(2011/02/21)
-
- NEW PHARMACEUTICAL COMPOUNDS
-
Compounds of formula (I), wherein R1-R4, X, Y and Z are as defined in claims, exhibit COMT enzyme inhibiting activity and are thus useful as COMT inhibitors.
- -
-
Page/Page column 25-26
(2008/06/13)
-
- Crown-containing spironaphthoxazines and spiropyrans 3. Synthesis and investigation of the merocyanine form of crown-containing spirobenzothiazolinonaphthoxazine
-
A method for the synthesis of the spirobenzothiazolinonaphthoxazine, stable in the merocyanine form and containing a crown-ether fragment was developed. The complexing properties of the prepared merocyanine compound and the spectroscopic and photochromic characteristics of its complexes with alkaline earth metal cations were studied by NMR and UV spectroscopy. The results were analyzed using quantum-chemical calculations. The addition of alkaline earth metal perchlorates to a solution of a crown ether-containing merocyanine dye in MeCN results in the coordination of metal cations to two binding centers, namely, the crown-ether fragment and the merocyanine oxygen atom. This gives rise to two types of complexes, which differ substantially in their structurally. The complexation induces changes in the UV spectra and influences on the photochromic behavior of the prepared compound.
- Fedorova,Koshkin,Gromov,Avakyan,Nazarov,Brichkin,Vershinnikova,Nikolaeva,Chernych,Alfimov
-
p. 1441 - 1450
(2007/10/03)
-
- An annulative approach to highly substituted indoles: Unusual effect of phenolic additives on the success of the arylation of ketone enolates
-
A novel palladium-catalyzed arylation of ketone enolates with o-nitrohaloarenes was achieved through the addition of phenol additives. The mild reaction conditions employed allowed for the inclusion of a wide variety of functional groups in both substrates to be tolerated. The products of this reaction were then readily reductively cyclized to give highly substituted indoles in moderate to excellent overall yields. Copyright
- Rutherford, Jennifer L.,Rainka, Matthew P.,Buchwald, Stephen L.
-
p. 15168 - 15169
(2007/10/03)
-
- Heterocyclic cytotoxic agents
-
The invention provides compounds of formula I: wherein R1-R8 and X and Y have any of the meanings defined in the specification and their pharmaceutically acceptable salts. The invention also provides pharmaceutical compositions comprising a compound of formula I, processes for preparing compounds of formula I, intermediates useful for preparing compounds of formula I, and therapeutic methods for treating cancer using compounds of formula I.
- -
-
-
- Pharmaceutical composition and method for treating cardiovascular diseases using substituted anilides and sulfonamides
-
A novel pharmaceutical composition and method is disclosed for the treatment of cardiovascular diseases, e.g. myocardial ischemia and/or arrhythmia. The method and composition include an effective amount of a compound of the formula STR1 wherein X, Y, R, R1, A, A', m, n, p, p' and B are as defined herein.
- -
-
-
- Synthesis and blood pressure lowering activity of 3-(substituted-amino)-1,2,4-benzothiadazine 1-oxide derivatives
-
A series of (substituted amino)-1,2,4-benzothiadiazine 1-oxides has been synthesized and most members of the series have been shown to have blood-pressure lowering effects in normotensive rabbits and in spontaneously hypertensive rats. The most active member of the series was 3-[4-(2-furoyl)-1-piperazinyl]-6,7-dimethoxy-1-methyl-1H-1,2,4-benzothiadiazine 1-oxide hydrochloride. This compound in animal tests was equipotent to the known antihypertensive Prazosin.
- Dillard,Yen,Stark,Pavey
-
p. 717 - 722
(2007/10/02)
-
- 1,3-Dialkyl-6,7-methoxy-1H-1,2,4-benzothiadiazine-1-oxides
-
1,3-Dialkyl-6,7-methoxy-1H-1,2,4-benzothiadiazine-1-oxides, useful as hypotensive agents.
- -
-
-