Naphthalene → 2-Chloronaphthalene

HRID 2280048

Reaktionsgleichung

Reaktionsgleichung von HRID 2280048
C(NCC(O)=O)C(O)=O.[CH:10]1[C:19]2[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=2)[CH:13]=[CH:12][CH:11]=1.[Cl:20][C:21]1[CH:28]=[CH:27][C:24]([CH:25]=[CH2:26])=[CH:23][CH:22]=1.[Cl:29]C1C=CC=CC=1C=C.ClC1C=C(C=CC=1)C=C>[Pd]>[Cl:20][C:21]1[CH:28]=[CH:27][C:24]([CH:25]=[CH2:26])=[CH:23][CH:22]=1.[Cl:29][C:17]1[CH:18]=[C:19]2[C:14]([CH:13]=[CH:12][CH:11]=[CH:10]2)=[CH:15][CH:16]=1

Komponenten

8

Edukt 5

HCID 931NaphthaleneHCID 8897Iminodiacetic acidHCID 140854-ChlorostyreneHCID 14905m-ChlorostyreneHCID 149062-Chlorostyrene

Produkt 2

HCID 70562-ChloronaphthaleneHCID 140854-Chlorostyrene

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 23938PalladiumKatalysator

Versuchsvorschrift

Microwave irradiation of styrene 5 in either 1,2-dichloroethane (DCE) at 180° C. for 30 min or 1,1,1-trifluorotoluene at 180° C. for 180 minutes afforded the cyclopenta-naphthalene derivative 6 in nearly quantitative yield with no additional purification required of the final product (entries 1 and 2, Table 1). With conditions for an efficient and high yielding IMDA reaction utilizing a lower boiling solvent in hand, scope and limitations investigations were initiated. First, substitution on the aryl group was examined; exchanging a hydrogen atom for a chlorine atom was deemed valuable, enabling access to a wide-range of naphthalene derivatives via palladium-catalyzed cross coupling reactions. Moreover, a chlorine atom is more stable and accessible than other halides or groups used for coupling, such as triflates. Styrenyl derivatives 5b, 5c, and 5d were prepared and subjected to microwave irradiation. The para-chlorostyrene 5b gave 7-chloronaphthalene 6b in quantitative yield after 200 min (entry 3). The ortho-chlorostyrene 5c also produced only one product, the 5-chloronaphthalene 6c in 86% yield, even though two products are possible (entry 4). The meta-chlorostyrene 5d gave an inseparable 1.4:1 mixture of the 6-chloro- and 8-chloronaphthalenes, 6d and 6d′ in 79% yield (entry 5).

Aufarbeitung

  1. customwith no additional purification
  2. customWith conditions for an efficient and high yielding
  3. customwere prepared
  4. customirradiation

Quellen und Nachweise

ORD-Eintrag
ord-c7e96ac9e5074cd5b9667f738dced6c1
Quelldatensatz
uspto-grants-2015_09
Patentnummer
US09133234B2

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