Research output: Contribution to journal › Article › peer-review
Reactions of 3,3,3-Trihalogeno-1-nitropropenes with Arenes in the Superacid CF3SO3H: Synthesis of (Z)‑3,3,3-Trihalogeno-1,2- diarylpropan-1-one Oximes and Study on the Reaction Mechanism. / Васильев, Александр Викторович; Голушко, Андрей Алексеевич; Иванов, Александр Юльевич; Боярская, Ирина Алексеевна; Хорошилова, Олеся Валерьевна.
In: Journal of Organic Chemistry, Vol. 83, No. 17, 07.09.2018, p. 10142-10157.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Reactions of 3,3,3-Trihalogeno-1-nitropropenes with Arenes in the Superacid CF3SO3H: Synthesis of (Z)‑3,3,3-Trihalogeno-1,2- diarylpropan-1-one Oximes and Study on the Reaction Mechanism
AU - Васильев, Александр Викторович
AU - Голушко, Андрей Алексеевич
AU - Иванов, Александр Юльевич
AU - Боярская, Ирина Алексеевна
AU - Хорошилова, Олеся Валерьевна
PY - 2018/9/7
Y1 - 2018/9/7
N2 - 3,3,3-Trihalogeno-1-nitropropenes C(Hal 3)CH=CH(NO 2) (Hal = F, Cl, Br) in reaction with arenes in the superacid CF 3SO 3H (TfOH) at room temperature in 1 h afford 3,3,3-trihalogeno-1,2-diarylpropan-1-one oximes C(Hal 3)CH(Ar)-C(Ar)=NOH (CHal 3-oximes) in yields of 23-99%. Such CHal 3-oximes having one ortho-substituent in the aryl ring exist as atropoisomers in solutions at room temperature. Several cationic intermediates of this reaction were studied by means of NMR and DFT calculations, which proves the detailed reaction mechanism of the formation of CHal 3-oximes in TfOH. CHal 3-oximes (for Hal = Cl, Br) with DBU in DMF at microwave or thermal activation are cyclized into 5-halogeno-3,4-diarylisoxazoles in yields of 37-59%. CHal 3-oximes under the conditions of Beckmann rearrangement with PCl 5 in benzene at room temperature in 24 h are turned at first into imidoyl chlorides (yields of 94-96%), which undergo transformation into the corresponding benzamides PhCONHCHPh(CHal 3) on silica gel (yields of 46-47%).
AB - 3,3,3-Trihalogeno-1-nitropropenes C(Hal 3)CH=CH(NO 2) (Hal = F, Cl, Br) in reaction with arenes in the superacid CF 3SO 3H (TfOH) at room temperature in 1 h afford 3,3,3-trihalogeno-1,2-diarylpropan-1-one oximes C(Hal 3)CH(Ar)-C(Ar)=NOH (CHal 3-oximes) in yields of 23-99%. Such CHal 3-oximes having one ortho-substituent in the aryl ring exist as atropoisomers in solutions at room temperature. Several cationic intermediates of this reaction were studied by means of NMR and DFT calculations, which proves the detailed reaction mechanism of the formation of CHal 3-oximes in TfOH. CHal 3-oximes (for Hal = Cl, Br) with DBU in DMF at microwave or thermal activation are cyclized into 5-halogeno-3,4-diarylisoxazoles in yields of 37-59%. CHal 3-oximes under the conditions of Beckmann rearrangement with PCl 5 in benzene at room temperature in 24 h are turned at first into imidoyl chlorides (yields of 94-96%), which undergo transformation into the corresponding benzamides PhCONHCHPh(CHal 3) on silica gel (yields of 46-47%).
UR - http://www.scopus.com/inward/record.url?scp=85050020274&partnerID=8YFLogxK
U2 - 10.1021/acs.joc.8b01406
DO - 10.1021/acs.joc.8b01406
M3 - Article
VL - 83
SP - 10142
EP - 10157
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 17
ER -
ID: 34823400