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Volumn 2007, Issue 6, 2007, Pages 47-54

Does phenothiazine give a dianion on addition of two equivalents of strong base?

Author keywords

Mechanism; Organolithiums; ortho Lithiation reaction; Phenothiazine

Indexed keywords


EID: 33846235994     PISSN: 1551-7012     EISSN: 14246376     Source Type: Journal    
DOI: 10.3998/ark.5550190.0008.604     Document Type: Article
Times cited : (9)

References (49)
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    • In a recent publication, we put forward for consideration that in the crucial step of the lithiation reaction, the directing and accelerating effect of the substituents might be due to the stabilization of both the initial complex and the transition structure (respectively 7 and 8 in this work, Coordination might be stronger in the transition state than in the initial complex. As a result, complexation would increase the rate of the reaction by providing a new mechanism that has a smaller activation energy Ea, See ref. 21d
    • a). See ref. 21d.
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    • 3 could allow the formation of a dianion. See: Svensson, A.; Martin, A. Heterocycles 1985, 23, 357.
    • 3 could allow the formation of a dianion. See: Svensson, A.; Martin, A. Heterocycles 1985, 23, 357.
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    • An analogous anionic N → C migration of arylsulfonamides has been reported: (a) Hellwinkel, D, Supp, M. Angew. Chem, Int. Ed. 1970, 13, 270
    • An analogous anionic N → C migration of arylsulfonamides has been reported: (a) Hellwinkel, D.; Supp, M. Angew. Chem., Int. Ed. 1970, 13, 270.
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    • 2OLi group cannot be metalated further and acid hydrolysis leads to an α-aminoalcohol that decomposes to give 1 and formaldehyde. The implication of a diacetylated species (by reaction of 10 with a second molecule of RCOX) on the reaction coordinate to explain the formation of 4a-d can be ruled out since only one equivalent of amide is required to give a high yield of 4a-d. See ref. 5a.
    • 2OLi group cannot be metalated further and acid hydrolysis leads to an α-aminoalcohol that decomposes to give 1 and formaldehyde. The implication of a diacetylated species (by reaction of 10 with a second molecule of RCOX) on the reaction coordinate to explain the formation of 4a-d can be ruled out since only one equivalent of amide is required to give a high yield of 4a-d. See ref. 5a.
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    • methylformanilide are rapidly deprotonated under these conditions
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    • N-Methylacetanilide and N
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    • For recent work on ortho-lithiation reactions of unprotected benzoic acid derivatives, see: (a) Selectivities in reactions of organolithium reagents with unprotected 2-halobenzoic acids: Gohier, F.; Castanet, A.-S.; Mortier, J. Org. Lett. 2003, 5, 1919.
    • For recent work on ortho-lithiation reactions of unprotected benzoic acid derivatives, see: (a) Selectivities in reactions of organolithium reagents with unprotected 2-halobenzoic acids: Gohier, F.; Castanet, A.-S.; Mortier, J. Org. Lett. 2003, 5, 1919.
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    • Ortho-lithiation of unprotected 3-bromo and 3-chlorobenzoic acids with hindered bases: Gohier, F.; Mortier, J. J. Org. Chem. 2003, 68, 2030.
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    • Reactions of unprotected naphthalene-1-carboxylic acid with strong bases: Tilly, D.; Castanet, A.-S.; Mortier, J. Chem. Lett. 2005, 34, 446.
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    • (d) Mechanism of ortholithiation. Tuning of selectivities in the metalation of meta-anisic acid: Nguyen, T. H.; Chau, N. T. T.; Castanet, A.-S.; Nguyen, K. P. P.; Mortier, J. Org. Lett. 2005, 7, 2445.
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    • Novel 6-substituted-2-chlorobenzoic acid syntheses: Gohier, F.; Castanet, A.-S.; Mortier, J. Synth. Commun. 2005, 35, 799.
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    • (f) Regioselective synthesis of contiguously 3- and 6-substituted 2-methoxybenzoic acid building blocks: Nguyen, T. H.; Castanet, A.-S.; Mortier, J. Org. Lett. 2006, 8, 765.
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    • 2CN (if it exists) has proved difficult to isolate. The existence of QUADAC structures was demonstrated by means of X-ray crystal determinations. See: (a) Boche, G. Angew. Chem., Int. Ed. Engl. 1989, 28, 277.
    • 2CN (if it exists) has proved difficult to isolate. The existence of QUADAC structures was demonstrated by means of X-ray crystal determinations. See: (a) Boche, G. Angew. Chem., Int. Ed. Engl. 1989, 28, 277.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.