- Synthesis and extraction properties of oxathiacrown compounds containing benzyl groups
-
8-Benzyl-1.4-dioxa-7,10-dithiacyclododecane and 11-benzyl-1,4,7-trioxa-10, 13-dithiacyclopentadecane were obtained by the interaction of (2,3-dibromo-1-propyl)benzene with 1,8-dimercapto-3,6-dioxaoctane and 1,11-dimercapto-3,6,9-trioxaundecane. The extrac
- Rezekina,Rakhmanov,Lukovskaya,Bobylyova,Abramov,Chertkov,Khoroshutin,Anisimov
-
-
Read Online
- Dibrominated addition and substitution of alkenes catalyzed by Mn2(CO)10
-
A practical method for the dibromination of alkenes without using molecular bromine is consistently appealing in organic synthesis. Herein, we report Mn-catalyzed dibrominated addition and substitution of alkenes only with N-bromosuccinimide, producing a variety of synthetically valuable dibrominated compounds in moderate to high yields. This journal is
- Chan, Albert S. C.,Jiang, Yi,Meng, Shanshui,Song, Xianheng,Zhang, Hong,Zou, Yong
-
supporting information
p. 13385 - 13388
(2021/12/17)
-
- Electrochemical bromofunctionalization of alkenes in a flow reactor
-
The bromination of organic molecules has been extensively studied to date, yet there is still a demand for safe and sustainable methodologies. Hazardous reagents, selectivity, low atom economy and waste production are the most persisting problems of brominating reagents. The electrochemical oxidation of bromide to bromine is a viable strategy to reduce waste by avoiding chemical oxidants. Furthermore, thein situgeneration of reactive intermediates minimizes the risk of hazardous reagents. In this work, we investigate the electrochemical generation of bromine from hydrobromic acid in a flow electrochemical reactor. Various alkenes could be converted to their corresponding dibromides, bromohydrines, bromohydrin ethers and cyclized products in good to excellent yields.
- Seitz, Jakob,Wirth, Thomas
-
supporting information
p. 6892 - 6896
(2021/08/20)
-
- A Highly Efficient Method for the Bromination of Alkenes, Alkynes and Ketones Using Dimethyl Sulfoxide and Oxalyl Bromide
-
The pairing of DMSO and oxalyl bromide is reported as a highly efficient brominating reagent for various alkenes, alkynes and ketones. This bromination approach demonstrates remarkable advantages, such as mild conditions, low cost, short reaction times, provides excellent yields in most cases and represents a very attractive alternative for the preparation of dibromides and α-bromoketones.
- Ding, Rui,Li, Jiaqi,Jiao, Wenyi,Han, Mengru,Liu, Yongguo,Tian, Hongyu,Sun, Baoguo
-
p. 4325 - 4335
(2018/11/21)
-
- Practical regio- and stereoselective azidation and amination of terminal alkenes
-
There is significant interest in developing more rapid and efficient production of nitrogen-containing allylic compounds, as widely used in various syntheses. This work reports a variety of allylic azides and allylic amines synthesized by an efficient, new one-pot protocol that employs readily available terminal alkenes as starting materials. This method is highly regio- and stereoselective, affording the linear (E)-isomer, under metal-free conditions. This process tolerates several functional groups including halogen-containing molecules; it is general for azides and amine nucleophiles; and, adducts were obtained in good yields.
- Ojo, Olatunji S.,Miranda, Octavio,Baumgardner, Kyle C.,Bugarin, Alejandro
-
supporting information
p. 9354 - 9358
(2019/01/03)
-
- Closing the Gap: Structural Evidence for the Missing Hexabromide Dianion [Br6]2?
-
The formation and experimental characterization of the first hexabromide dianion is presented. This dianion fills the last remaining gap in the series of polybromides from the tribromide [Br3]? to the undecabromide [Br11]
- Sonnenberg, Karsten,Pr?hm, Patrick,Müller, Carsten,Beckers, Helmut,Steinhauer, Simon,Lentz, Dieter,Riedel, Sebastian
-
supporting information
p. 1072 - 1075
(2018/01/15)
-
- Oxidative bromination reactions in aqueous media by using Bu4NBr/TFA/H2O2 system
-
Metal-free oxidative bromination reactions in aqueous media were performed using tetrabutylammonium bromide, trifluoroacetic acid, and hydrogen peroxide under mild conditions. Oxidative bromination reaction of alkenes was found to afford the corresponding vic-bromides. Furthermore, this oxidative bromination system is applicable to the oxidative bromination of alkynes, arenes, and 3,4-dihydronaphthalen-1(2H)-one. A gram-scale bromination reaction was also performed successfully.
- Moriuchi, Toshiyuki,Fukui, Yasuhiro,Sakuramoto, Takashi,Hirao, Toshikazu
-
supporting information
p. 1708 - 1710
(2017/11/23)
-
- Metal-free, regio- and stereoselective synthesis of linear (E)-allylic compounds using C, N, O, and S nucleophiles
-
A variety of allylic acetates and derivatives were synthesized by an efficient two-step protocol that employs readily available terminal alkenes as starting materials. This method is highly regio- and stereoselective, affording the linear (E)- isomer as the sole adduct. This process tolerates several functional groups including halogen-containing molecules, and it is general for weak oxygen, carbon, nitrogen, and sulfur nucleophiles. Furthermore, adducts were obtained in good to excellent yields.
- Huang, Xiaojun,Fulton, Brandon,White, Kana,Bugarin, Alejandro
-
supporting information
p. 2594 - 2597
(2015/06/16)
-
- Bromination of olefins with HBr and DMSO
-
A simple and inexpensive methodology is reported for the conversion of alkenes to 1,2-dibromo alkanes via oxidative bromination using HBr paired with dimethyl sulfoxide, which serves as the oxidant as well as cosolvent. The substrate scope includes 21 olefins brominated in good to excellent yields. Three of six styrene derivatives yielded bromohydrins under the reaction conditions.
- Karki, Megha,Magolan, Jakob
-
p. 3701 - 3707
(2015/04/22)
-
- Brominations with Pr4NBr9 as a solid reagent with high reactivity and selectivity
-
Tetrapropylammonium nonabromide (Pr4NBr9) is introduced as a room-temperature solid reagent for rapid bromination reactions of various substrates. The reagent exhibits reactivity similar to that of elemental bromine, but shows higher selectivity and it is easier and safer to store and to handle. Georg Thieme Verlag Stuttgart · New York.
- Beck, Thorsten M.,Haller, Heike,Streuff, Jan,Riedel, Sebastian
-
p. 740 - 747
(2014/04/03)
-
- Rasta resin-triphenylphosphine oxides and their use as recyclable heterogeneous reagent precursors in halogenation reactions
-
Heterogeneous polymer-supported triphenylphosphine oxides based on the rasta resin architecture have been synthesized, and applied as reagent precursors in a wide range of halogenation reactions. The rasta resin-triphenylphosphine oxides were reacted with either oxalyl chloride or oxalyl bromide to form the corresponding halophosphonium salts, and these in turn were reacted with alcohols, aldehydes, aziridines and epoxides to form halogenated products in high yields after simple purification. The polymersupported triphenylphosphine oxides formed as a byproduct during these reactions could be recovered and reused numerous times with no appreciable decrease in reactivity.
- Xia, Xuanshu,Toy, Patrick H.
-
p. 1397 - 1405
(2014/07/22)
-
- Synthesis of acetylenes via dehydrobromination using solid anhydrous potassium phosphate as the base under phase-transfer conditions
-
Phase-transfer catalyzed preparation of acetylenes from the corresponding vicinal dibromo compounds via double dehydrobromination using the mild solid base, anhydrous potassium phosphate, under very mild conditions is reported.
- Shenawi-Khalil, Sanaa,Sonavane, Sachin U.,Sasson, Yoel
-
experimental part
p. 2295 - 2297
(2012/07/27)
-
- Vanadium-catalyzed oxidative bromination promoted by Br?nsted acid or Lewis acid
-
The oxidative bromination of arenes was induced by a vanadium catalyst in the presence of a bromide salt and a Br?nsted acid or a Lewis acid under molecular oxygen, which provides an eco-friendly bromination method as compared with a conventional bromination one with bromine. This catalytic reaction could be applied to the bromination of alkenes and alkynes to give the corresponding vic-bromides. Use of aluminum halide as a Lewis acid in place of a Br?nsted acid was demonstrated to provide a more practical protocol for the oxidative bromination. From ketones, α-bromination products were obtained. AlBr3 was found to serve as both a bromide source and a Lewis acid to induce the bromination smoothly. 51V NMR experiment showed that this catalytic bromination is likely to depend on the redox cycle of a vanadium catalyst under molecular oxygen.
- Kikushima, Kotaro,Moriuchi, Toshiyuki,Hirao, Toshikazu
-
experimental part
p. 6906 - 6911
(2010/09/18)
-
- Oxidative bromination reaction using vanadium catalyst and aluminum halide under molecular oxygen
-
The vanadium-catalyzed oxidative bromination reaction of arenes, alkenes, and alkynes was performed in the presence of AlBr3 to provide an alternative method for conventional bromination using hazardous bromine. The catalytic cycle is formed under molecular oxygen, which is more advantageous to vanadium bromoperoxidase (VBrPO) requiring hydrogen peroxide as a terminal oxidant.
- Kikushima, Kotaro,Moriuchi, Toshiyuki,Hirao, Toshikazu
-
supporting information; experimental part
p. 340 - 342
(2010/03/04)
-
- Electrophilic bromination of alkenes, alkynes, and aromatic amines with iodic acid/potassium bromide under mild conditions
-
Bromination of alkenes, alkynes, and aromatic amines has efficiently been carried out at room temperature in short reaction times using HIO 3/KBr in CH2Cl2/H2O (1:1) to prepare corresponding brominated compounds in excellent yields.
- Khazaei, Ardeshir,Zolfigol, Mohammad Ali,Kolvari, Eskandar,Koukabi, Nadiya,Soltani, Hamid,Bayani, Leyla Sharaf
-
experimental part
p. 2954 - 2962
(2010/10/20)
-
- Elctrophilic bromination of alkenes, alkynes, and aromatic amines with potassium bromide/orthoperiodic acid under mild conditions
-
Bromination of alkenes, alkynes, and aromatic amines has efficiently been carried out at room temperature in short reaction times using potassium bromide/orthoperiodic acid in dichloromethane-water (1:1) to prepare the corresponding bromo compounds with excellent yields.
- Khazaei, Ardeshir,Zolfigol, Mohammad Ali,Kolvari, Eskandar,Koukabi, Nadiya,Soltani, Hamid,Komaki, Fatemeh
-
experimental part
p. 3672 - 3676
(2010/04/05)
-
- A bimetallic palladium(II) catalyzed synthesis of 1,2-dibromo compounds
-
A bimetallic palladium(II) catalyst containing a triketone ligand and a bridging dinitrogen ligand oxidizes aromatic and cyclic aliphatic olefins in bromide-containing aqueous-THF to 1,2-dibromo compounds and bromohydrins. With aromatic olefins, the 1,2-dibromo products were obtained in a 70-80% yield and the bromohydrins in a 10-15% yield; this observation is opposition to that obtained in chloride containing medium where the chlorohydrin product predominates. The oxidation of 2,3-dihydrofuran gave trans-2,3- dibromotetrahydrofuran, 3-oxotetrahydrofuran, and 3-bromo-2- hydroxytetrahydrofuran in relative yields of 75%, 15%, and 10%, respectively. On the other hand, the oxidation of cyclopentene and cyclohexene affords only trans-1,2-dibromo products in about 90% yield. The stereochemistry is consistent with an anti-at-tack of bromide followed by decomposition involving attack of bromide from the coordination sphere of the Pd(II). The procedure outlined here is a convenient method for the one step synthesis of 1,2-dibromides.
- Qaseer
-
-
- Effect of cyclodextrin complexation in bromine addition to unsymmetrical olefins: Evidence for participation of cyclodextrin hydroxyl groups
-
Multiple recognition by cyclodextrin in a bimolecular reaction, namely bromination of styrene, methyl cinnamate, phenylacetylene and allylbenzene, has been studied. Bromohydrin is obtained as a major product along with dibromide in the bromination of styrene and methyl cinnamate. The percentage of bromohydrin decreases as the cavity size increases. With phenylacetylene, bromophenylacetylene and phenacyl bromide are obtained in addition to the dibromides. In the bromination of cyclodextrin complexes of allylbenzene, the product distribution is the same as in solution bromination. The observed results demonstrate the efficiency of cyclodextrin in stabilizing the open carbocationic intermediate and thus provide chemical evidence for the participation of cyclodextrin hydroxyl groups. The Royal Society of Chemistry 2005.
- Manickam, Manickam C. Durai,Annalakshmi, Subramanian,Pitchumani, Kasi,Srinivasan, Chockalingam
-
p. 1008 - 1012
(2007/10/03)
-
- An efficient bromination of alkenes using cerium(IV) ammonium nitrate (CAN) and potassium bromide
-
Bromination of alkenes using a combination of potassium bromide and cerium(iv) ammonium nitrate (CAN) in a two phase system consisting of water and dichloromethane affords the corresponding dibromides in excellent yield. The reaction most likely involves the addition of the bromine radical generated from bromide ion by CAN and subsequent formation of the dibromide.
- Nair, Vijay,Panicker, Sreeletha B,Augustine, Anu,George, Tesmol G,Thomas, Siji,Vairamani
-
p. 7417 - 7422
(2007/10/03)
-
- Reaction of Aromatic and Unsaturated Compounds with the Potassium Permanganate/HCI (HBr) Acetonitrile Reagent
-
Addition of hydrochloric or hydrobromic acid to a solution of potassium permanganate in acetonitrile produced a homogeneous mixture, which is suitable for laboratory chlorination or bromination, respectively. Aromatic compounds more reactive than alkylbenzenes can be chlorinated or brominated without additional catalyst. Alkenes and alkynes give the corresponding vicinal dihaloalkanes and vinyl halides. All reactions complete within two hours under mild condition (25-60 °C) with excellent to moderate yields.
- Liu, Lilian Kao,Lin, Ching-Shan
-
-
- TETRABUTYLAMMONIUM DIHYDROGENTRIFLUORIDE: AN EFFECTIVE SOURCE OF FLUORIDE ION FOR HALOFLUORINATION OF ALKENES
-
Vicinal halofluorides have been prepared from the corresponding alkenes by reaction with a stoichiometric amount of Bu4N+H2F3- as a source of fluoride anion and an excess of an N-halosuccinimide (NXS).The reaction products are obtained in good yields, with a prevalent Markownikoff regiochemistry.Olefins containing hydroxy, epoxy, acetoxy and alkoxy groups do not undergo side reactions under these reaction conditions.
- Albanese, Domenico,Landini, Dario,Penso, Michele,Pratelli, Marco
-
p. 537 - 541
(2007/10/02)
-
- Solvation and steric effects on electrophilic reactivity of ethylenic compounds. 2. Kinetic criteria for nucleophilic assistance and return in bromination
-
Three kinetic criteria, mBr, R (kaqEtOH/kAcOH)Y, and KSIE (kinetic solvent isotope effect), are used to estimate the magnitude of the electrophilic and nucleophilic involvement of protic solvents and the occurre
- Ruasse, Marie-Fran?ois,Motallebi, Shahrokh,Galland, Bernard
-
p. 3440 - 3446
(2007/10/02)
-
- HALOFLUORINATION OF OLEFINS: ELUCIDATION OF REACTION CHARACTERISTICS AND APPLICATIONS IN LABELING WITH THE POSITRON-EMITTING RADIONUCLIDE FLUORINE-18
-
Olefin halofluorination involves the in situ generation of a halogen-fluoride reagent and subsequent addition to an olefin.The characteristics of this reaction were investigated with three model olefins (allylbenzene, 1-hexene and propene) in order to ass
- Chi, Dae Yoon,Kiesewetter, Dale O.,Katzenellenbogen, John A.
-
-
- REACTION OF t-BUTYL BROMIDE-DIMETHYL SULPHOXIDE: HALOGENATION AND MIXED HALOGENATION OF MULTIPLE BONDS
-
The "t-butyl bromide-Me2SO" reagent brominates alkenes versus alkynes efficiently and selectively.By adding calcium chloride or potassium iodide to the system it is possible to obtain the corresponding dichloro or diiodo derivatives.By adding benzyltriethylammonium chloride to the system, bromochloro derivatives are obtained in good yields.The mechanism of the reactions is discussed.
- Dossena, Arnaldo,Marchelli, Rosangela,Casnati, Giuseppe
-
-
- A CONVENIENT SYNTHESIS OF α-BROMOKETONES FROM OLEFINS
-
α-Bromoketones are prepared in good yields by the reaction of olefins with sodium bromite in aqueous acetic acid at room temperature.
- Kageyama, Toshifumi,Tobito, Yoshimichi,Katoh, Atsushi,Ueno, Yoshio,Okawara, Makoto
-
p. 1481 - 1482
(2007/10/02)
-