The Experts below are selected from a list of 36 Experts worldwide ranked by ideXlab platform
Hideyuki Hara - One of the best experts on this subject based on the ideXlab platform.
-
direct observation of aminyl radical intermediate during single crystal to single crystal photoinduced Orton Rearrangement
Journal of Physical Chemistry B, 2007Co-Authors: Pance Naumov, Kenji Sakurai, Masahiko Tanaka, Hideyuki HaraAbstract:A photoinduced analogue of the thermal Orton Rearrangement reaction by which an N-chlorine atom from a side amino group is transferred to a phenyl ring was studied in the solid state. Contrary to the mixture of products obtained in solution, in the N-chloro-N-acetylaminobenzene crystals the photoreaction proceeds with complete preservation of crystallinity, affording selectively and quantitatively the para isomer of chloroacetanilide. Study of the reaction mechanism by in situ steady-state photodiffraction, a combination of photoexcitation by UV light and single-crystal X-ray diffraction analysis, provided evidence for creation of N-acetyl-N-phenylaminyl (AcPhN•) radical as a metastable reaction intermediate. The structure of the aminyl radical produced in 9.2% yield from the major disordered component in the statically 85.6:14.4 disordered crystal was directly observed for the first time. The unprecedented stability of the radical is prescribed to the solid-state cage effect, the reactive center of the r...
Yoichiro Isoda - One of the best experts on this subject based on the ideXlab platform.
-
Orton Rearrangement of n chlorobenzanilides using iron iii chloride hydrogen chloride complex
Journal of Japan Oil Chemists Society, 1999Co-Authors: Jiro Yamamoto, Munehiro Tada, Yoichiro IsodaAbstract:After N-chlorobenzanilide (1) was had stood in ether solution containing iron (III) chloride-hydrogen chloride complex (FeCl3-HCl) at room temperature, 2-chloro and 4-chlorobenzanilides were obtained as the Rearrangement products. Remarkable differences in reaction rates and product distribution were noted for the Orton rearrangenment of 4'-methylbenzanilide (2), 4', N-dichlorobenzanilide (3) and 4'-nitrobenzanilide (4) using FeCl3-HCl. The order of the reaction rates was as follows; 4>2>1>3, the yields of Rearrangement products; 2>1>3>4, and yields of dechloronated products; 4>3>2=1=0. Reaction of 1 with iron (III) bromide-hydrogen bromide complex (FeBr3-HCl) gave 4-bromobenzanilide as the sole product. The Orton Rearrangement of 1 apparently proceeds via an intermolecular pathway in para-position, while ortho-chlorination of 1 may occure via both inter- and intramolecular pathways.
-
Orton Rearrangement of n chloroacetanilides with the iron iii chloride hydrogen chloride complex
Journal of Japan Oil Chemists Society, 1999Co-Authors: Jiro Yamamoto, Munehiro Tada, Hidekazu Kojima, Yoichiro IsodaAbstract:After an ether solution of N-chloroacetanilide (1) and iron (III) chloride-hydrogen chloride complex (FeCl3-HCl) had stood at room temperature, the reaction was noted to have proceeded essentially to completion within 0.5h, and o- (10) and p-chloroacetanilide (11) were obtained as Rearrangement products in various ortho-para ratios (10/11), depending on the particular concentration of FeCl3-HCl. The corresponding o- and p-chloroacetanilides were also produced by reaction of N-chloro-2-methylacetanilide with FeCl3-HCl. Two o-chloroacetanilides and a p-chloroacetanilide were obtained from N-chloro-3-methylacetanilide under the same reaction conditions. Some N-chloroacetanilides having chlorine in the parent aromatic nucleus failed to undergo Orton Rearrangement under any conditions or; so that the corresponding acetanilides were obtained in lower yields. The Rearrangement products, o- and p-chloroacylanilides, were obtained from N-chloro-2-methylpropionylanilide and N-chloro-2-methylbutyrylanilide under the same conditions.
Pance Naumov - One of the best experts on this subject based on the ideXlab platform.
-
direct observation of aminyl radical intermediate during single crystal to single crystal photoinduced Orton Rearrangement
Journal of Physical Chemistry B, 2007Co-Authors: Pance Naumov, Kenji Sakurai, Masahiko Tanaka, Hideyuki HaraAbstract:A photoinduced analogue of the thermal Orton Rearrangement reaction by which an N-chlorine atom from a side amino group is transferred to a phenyl ring was studied in the solid state. Contrary to the mixture of products obtained in solution, in the N-chloro-N-acetylaminobenzene crystals the photoreaction proceeds with complete preservation of crystallinity, affording selectively and quantitatively the para isomer of chloroacetanilide. Study of the reaction mechanism by in situ steady-state photodiffraction, a combination of photoexcitation by UV light and single-crystal X-ray diffraction analysis, provided evidence for creation of N-acetyl-N-phenylaminyl (AcPhN•) radical as a metastable reaction intermediate. The structure of the aminyl radical produced in 9.2% yield from the major disordered component in the statically 85.6:14.4 disordered crystal was directly observed for the first time. The unprecedented stability of the radical is prescribed to the solid-state cage effect, the reactive center of the r...
Kenji Sakurai - One of the best experts on this subject based on the ideXlab platform.
-
direct observation of aminyl radical intermediate during single crystal to single crystal photoinduced Orton Rearrangement
Journal of Physical Chemistry B, 2007Co-Authors: Pance Naumov, Kenji Sakurai, Masahiko Tanaka, Hideyuki HaraAbstract:A photoinduced analogue of the thermal Orton Rearrangement reaction by which an N-chlorine atom from a side amino group is transferred to a phenyl ring was studied in the solid state. Contrary to the mixture of products obtained in solution, in the N-chloro-N-acetylaminobenzene crystals the photoreaction proceeds with complete preservation of crystallinity, affording selectively and quantitatively the para isomer of chloroacetanilide. Study of the reaction mechanism by in situ steady-state photodiffraction, a combination of photoexcitation by UV light and single-crystal X-ray diffraction analysis, provided evidence for creation of N-acetyl-N-phenylaminyl (AcPhN•) radical as a metastable reaction intermediate. The structure of the aminyl radical produced in 9.2% yield from the major disordered component in the statically 85.6:14.4 disordered crystal was directly observed for the first time. The unprecedented stability of the radical is prescribed to the solid-state cage effect, the reactive center of the r...
Masahiko Tanaka - One of the best experts on this subject based on the ideXlab platform.
-
direct observation of aminyl radical intermediate during single crystal to single crystal photoinduced Orton Rearrangement
Journal of Physical Chemistry B, 2007Co-Authors: Pance Naumov, Kenji Sakurai, Masahiko Tanaka, Hideyuki HaraAbstract:A photoinduced analogue of the thermal Orton Rearrangement reaction by which an N-chlorine atom from a side amino group is transferred to a phenyl ring was studied in the solid state. Contrary to the mixture of products obtained in solution, in the N-chloro-N-acetylaminobenzene crystals the photoreaction proceeds with complete preservation of crystallinity, affording selectively and quantitatively the para isomer of chloroacetanilide. Study of the reaction mechanism by in situ steady-state photodiffraction, a combination of photoexcitation by UV light and single-crystal X-ray diffraction analysis, provided evidence for creation of N-acetyl-N-phenylaminyl (AcPhN•) radical as a metastable reaction intermediate. The structure of the aminyl radical produced in 9.2% yield from the major disordered component in the statically 85.6:14.4 disordered crystal was directly observed for the first time. The unprecedented stability of the radical is prescribed to the solid-state cage effect, the reactive center of the r...