19935-75-2Relevant academic research and scientific papers
A New Method for Generating Trichlorotitanium(IV) Ester Homoenolates. Direct Tin-Titanium Exchange
Goswami, Ramanuj
, p. 5907 - 5909 (1985)
Treatment of the β-tri-n-butylstannyl derivatives of esters with titanium tetrachloride in dichloromethane effects tin-titanium exchange to generate trichlorotitanium(IV) homoenolate derivatives of the esters, which may then be used in further reaction with electrophiles.
Ferric chloride–catalyzed deoxygenative chlorination of carbonyl compounds: A comparison of chlorodimethylsilane and dichloromethylsilane system
Xing, Bing-Han,Zhao, Xuan-Xuan,Qin, Yu-Jun,Zhang, Pu,Guo, Zhi-Xin
, p. 667 - 675 (2020/05/22)
Deoxygenative chlorination of carbonyl compounds using the HMe2SiCl/FeCl3/EtOAc and HMeSiCl2/FeCl3/EtOAc systems has been systemically investigated. The HMe2SiCl-FeCl3 system showed the advantages of good substrate applicability, mild reaction conditions, simple operation, low cost, and easy availability of raw materials. Also, it provided a simple and efficient synthesis route for carbonyl deoxychlorination via a one-pot method. Using the HMeSiCl2/FeCl3/EtOAc system, the β-methylchalcone derivative could be obtained in good yields in addition to obtaining the chlorinated compound. Finally, two plausible reaction routes were proposed to describe the formation of the chlorinated compound and the β-methylchalcone derivative.
Thiourea-Mediated Halogenation of Alcohols
Mohite, Amar R.,Phatake, Ravindra S.,Dubey, Pooja,Agbaria, Mohamed,Shames, Alexander I.,Lemcoff, N. Gabriel,Reany, Ofer
supporting information, p. 12901 - 12911 (2020/11/26)
The halogenation of alcohols under mild conditions expedited by the presence of substoichiometric amounts of thiourea additives is presented. The amount of thiourea added dictates the pathway of the reaction, which may diverge from the desired halogenation reaction toward oxidation of the alcohol, in the absence of thiourea, or toward starting material recovery when excess thiourea is used. Both bromination and chlorination were highly efficient for primary, secondary, tertiary, and benzyl alcohols and tolerate a broad range of functional groups. Detailed electron paramagnetic resonance (EPR) studies, isotopic labeling, and other control experiments suggest a radical-based mechanism. The fact that the reaction is carried out at ambient conditions, uses ubiquitous and inexpensive reagents, boasts a wide scope, and can be made highly atom economic, makes this new methodology a very appealing option for this archetypical organic reaction.
Silver-Catalyzed C(sp3)-H Chlorination
Ozawa, Jun,Kanai, Motomu
supporting information, p. 1430 - 1433 (2017/03/23)
A silver-catalyzed chlorination of benzylic, tertiary, and secondary C(sp3)-H bonds was developed. The reaction proceeded with as low as 0.2 mol % catalyst loading at room temperature under air atmosphere with synthetically useful functional group compatibility. The regioselectivity and reactivity tendencies suggest that the chlorination proceeded through a radical pathway, but an intermediate alkylsilver species cannot be ruled out.
Regioselective Synthesis of Vinyl Halides, Vinyl Sulfones, and Alkynes: A Tandem Intermolecular Nucleophilic and Electrophilic Vinylation of Tosylhydrazones
Ojha, Devi Prasan,Prabhu, Kandikere Ramaiah
supporting information, p. 18 - 21 (2015/07/28)
A diazo species is trapped in an intermolecular fashion by two independent ion species in tandem at the carbene center to install an electrophile and a nucleophile on the same carbon. This metal-free concept, which is unprecedented, has been illustrated by regioselective synthesis of a variety of vinyl halides, vinyl sulfones, and alkyne derivatives. (Chemical Equation Presented).
Preparation of 4-nitrostyrene
Shultsev
, p. 1859 - 1863 (2014/01/06)
The interaction of D,L-1-(4-nitrophenyl)ethanol with SOCl2 and P4O10 has been studied. In the reaction of D,L-1-(4-nitrophenyl)ethanol with SOCl2 a mixture of 1-(4-nitrophenyl)-1-chloroethane, 1,1′-bis-(4-nitrop
CHEMICAL PROCESS
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Page 50-51, (2010/02/04)
A process for the preparation of pyrimidine derivatives, which are useful as VEGFR2 inhibitors is described herein. The described invention also includes pyrimidine derivatives as well as methods of using the same in the treatment of hyperproliferative diseases.
Direct conversion of carbonyl compounds into organic halides: Indium(III) hydroxide-catalyzed deoxygenative halogenation using chlorodimethylsilane
Onishi, Yoshiyuki,Ogawa, Daigo,Yasuda, Makoto,Baba, Akio
, p. 13690 - 13691 (2007/10/03)
The reaction of carbonyls and chlorodimethylsilane was effectively catalyzed by indium(III) hydroxide and afforded the corresponding deoxygenative chlorination products, in which the carbonyl carbon accepted two nucleophiles (H and Cl) with releasing oxygen. Only In(OH)3 catalyzed the reaction, and typical Lewis acids such as TiCl4, AlCl3, and BF3·OEt2 showed no catalytic activity. The reaction mechanism of this deoxygenative chlorination includes initial hydrosilylation followed by chlorination. Other nucleophiles such as allyl or iodine were available for this methodology. The moderate Lewis acidity of indium catalyst enabled chemoselective reaction, and therefore ester, nitro, cyano, or halogen groups were not affected during the reaction course. Copyright
Nickel-catalyzed benzylic oxidation with NaOCl
Yamazaki, Shigekazu
, p. 2211 - 2216 (2007/10/03)
Ni(bpy)2Cl2 has been found to be an efficient catalyst for the oxidation of various alkylbenzenes with hypochlorite. Substituted toluenes having electron withdrawing group at 4-position were oxidized to the corresponding substituted benzoic acids in excellent yields.
Nucleophilic Substitution Reaction of 1-Phenylethyl Chlorides in Methanol
Lee, Ikchoon,Lee, Won Heui,Lee, Hai Whang,Bentley, T. W.
, p. 141 - 146 (2007/10/02)
Nucleophilic substitution reactions of 1-(Y-phenyl)ethyl chlorides with X-anilines have been investigated in methanol at 65.0 deg C.An isokinetic point is obtained at ?Y+ = ca. -0.23 with ρX = 0; the sign of ρX changes at this point from positive for the relatively strong electron donating Y substituents to negative for the more electron withdrawing Y substituents. The magnitude of the cross-interaction constant, ρXY, between the substituents X and Y is unusually large with the relatively small magnitude of ρXo resulting in an observable isokinetic point at .These results are interpreted in terms of a transition state (TS) structure in which nearly complete bond formation between the nucleophile and cation formed in an ion-pair preequilibrium is coupled with a TS imbalance phenomenon.The results of kinetic isotope effect studies involving deuteriated anilines and methanol are also in line with this mechanism.
