Über Tertiäre Oxoniumsalze, I

Meerwein, Hans; Hinz, Gerhard; Hofmann, Paul; Kroning, Erwin; Pfeil, E.

doi:10.1002/prac.19371471001

Cited by 348 publications

(98 citation statements)

References 15 publications

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“…It had been shown by Muxfeldt and Rogalski in their impressive synthesis of a tetracycline (22) that the benzoyl group of an amide could be removed under mild conditions using Meerwein's reagent (23) and hydrolysis of the resultant benzimidate in 5 % acetic acid. We therefore examined the possibility of using the acetyl group present in 3 as the blocking group.…”

Section: Synt/zesis Ofmentioning

confidence: 99%

Synthesis of 7-azabicyclo[2.2.1]heptane, exo-2-chloro-7-azabicyclo[2.2.1]heptane, and derivatives

Fraser¹,

Swingle²

1970

Can. J. Chem.

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A synthesis of 7-azabicyclo[2.2.1]heptane (1) in five steps and an overall yield of 18 % has beenachieved. An alternative five-step route which gives 1 in 36% yield but which requires large amounts of platinum oxide has also been developed. In comparison, the only previous synthesis of this con~pound gave less than a 1 % overall yield of an impure product. Several N-acyl derivatives and the N-n~troso derivative have been prepared, and the barriers to rotation about the N-CO bond of the acetyl derivative and the N-NO bond of the nitroso derivative have been determined. The barriers were found to be 1.2 and 6.5 kcal less, respectively, than in their unstrained analogs. exo-2-Chloro-7-azabicyclo[2.2.l]heptane has also been synthesized.Canadian Journal of Chemistry, 48,2065Chemistry, 48, (1970 Considerable interest has recently developed in the nitrogen analogs of bicyclo [2.2.1 Iheptane. Reports on the synthesis and reactions of compounds containing nitrogen in the 1-position (1,2) and in the 2-position (3,4) have appeared. The 7-azabicyclo[2.2.1]heptane system has perhaps received more attention. In particular, many highly substituted derivatives have been produced by the Diels-Alder reactions of N-alkyl and N-acyl pyrroles with dimethylacetylene dicarboxylate (5-12). In contrast the parent 7-azabicyclo [2.2.1 Iheptane (1) was reported as synthesized only in impure form and was characterized by conversion to a picrate and a 7,7-dimethiodide derivative (12). Its synthesis from hydroquinone involved seven steps and gave 1 in an overall yield of less than 1 %. We wish to report an improvement in the synthesis of 1, which allows its preparation in yields of up to 36 %. The proof of structure of 1 is supported by its conversion to five derivatives, two of which are the subject of a temperature-dependent nuclear magnetic resonance (n.m.r.) investigation. In addition the exo-2-chloro derivative of 1 was synthesized and preliminary studies of its reactivity are reported.

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Section: Synt/zesis Ofmentioning

confidence: 99%

Synthesis of 7-azabicyclo[2.2.1]heptane, exo-2-chloro-7-azabicyclo[2.2.1]heptane, and derivatives

Fraser¹,

Swingle²

1970

Can. J. Chem.

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“…Die Synthese der Metallcarbonyle l a und l b erfolgte nach [4g]. E t3OBF4 wurde nach der M ethode von H. M eer wein synthetisiert [25]. Alle übrigen Chemikalien waren handelsüblich, wobei die Oxalsäurehaloge nide und P(O M e)3 vor dem Gebrauch destilliert wurden.…”

Section: Experimenteller Teilunclassified

“…C21H 250 3Re (511,63). EI-MS (70 eV), m /z (%)'■ 512, 3 (27,7) [Cp*(CO)2R eC (O E t)Ph]+, 484,3 (17,1) [C p*(C O )R eC (O Et)Ph]+, 456,3 (1,7) [Cp*ReC(OEt)Ph]+, 427,1 (13,7) [Cp*(CO)RePh]+, 399,0 (45,9) [Cp*RePh]+, 350,1 (4,6) [Cp*Re(CO)]+, 322,1 (1,4) (1,2) [Cp*3TcCl]+, 404,0 (3,3) [Cp*2TcCl]+, 368, 2 (6 ,8) [Cp*2Tc]+, 367,2 (27,3) [Cp*(CO)2TcPh]+, 339,2 (3,8) [Cp*(CO)TcPh]+, 324,1 (2,9) [Cp*(CO)2TcCl]+, 322,1 (100,0) [Cp*TcCl2(O H )]+, 318,1 (25,2) [Cp*Tc(CO)3]+, 307,1 (15,8) [Cp*Tc(CO)2(O H )]+, 290,1 (8,9) [Cp*Tc(CO)2]+, 268,5 (68,7) [Cp*TcCl]+, 262,1 (22,9) [Cp*Tc(CO)]+, 234,1 (22,1) …”

Section: Icarbonylf(ethoxy) (Phenyl)carbenj(rf-pentam Ethylcyclopenmentioning

confidence: 99%

Carben- und Carbin-Komplexe des Technetiums und Rheniums - Synthese, Struktur und Reaktionen / Carbene and Carbyne Complexes of Technetium and Rhenium - Synthesis, Structure and Reactions

Fischer

Apostolidis²,

Dornberger³

et al. 1995

Zeitschrift Für Naturforschung B

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“…Reaktionen von [(C 5 H5)(CO)2MnCC 6 H5]BCl4 mit anderen Nucleophilen (Alkoholate, Phenolate [8], Cyanat [9], Cyanid, Isothiocyanat [10]) hatten uns bereits früher zu den entsprechenden Carben-Komplexen geführt. Ungewöhnlich an der jetzt durchgeführten Reaktion ist, daß sich die Fluorid-Addition bei 5 rückgängig machen läßt, wenn man BF3 in eine Lösung von 5 einleitet.…”

Section: 3unclassified

Übergangsmetall-Garben-Komplexe, CXXI [1] Fluorcarbenkomplexe des Mangans / Transition Metal Carbene Complexes, CXXI [1] Fluorocarbene Complexes of Manganese

Univ¹,

Kleine

Schambeck

et al. 1981

Zeitschrift Für Naturforschung B

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Abstract The reaction between CH3Cs5H4Mn(CO)3 and LiN(C2H5)2 and subsequent alkylation with [(C2H5)3O]BF4 affords CH3C5H4(CO)2MnC(OC2H5)N(C2H5)2. This carbene complex reacts with borontrihalides BX3 (X = F, Cl) to yield [CH3C5H4(CO)2MnCN(C2H5)2]BX4. Ad-dition of [(C4H9)4N]F to this cationic carbyne complex results in the formation of CH3C5H4(CO)2MnC(F)N(C2H5)2 . In the same way C5H5(CO)2MnC(F)C6H5 is prepared from [C5H5(CO)2MnCC6H5]SbCl6. Fluoride addition can be reversed by reaction of the latter carbene complex with BF3 to give [C5H5(CO)2MnCC6H5]BF4. In the X-ray structure of C5H5(CO)2MnC(F)C6H5 unusual bonding parameters are found, which are consistent with the easy cleavage of the C(carbene)-F bond.

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Über Tertiäre Oxoniumsalze, I

Cited by 348 publications

References 15 publications

Synthesis of 7-azabicyclo[2.2.1]heptane, exo-2-chloro-7-azabicyclo[2.2.1]heptane, and derivatives

Synthesis of 7-azabicyclo[2.2.1]heptane, exo-2-chloro-7-azabicyclo[2.2.1]heptane, and derivatives

Carben- und Carbin-Komplexe des Technetiums und Rheniums - Synthese, Struktur und Reaktionen / Carbene and Carbyne Complexes of Technetium and Rhenium - Synthesis, Structure and Reactions

Übergangsmetall-Garben-Komplexe, CXXI [1] Fluorcarbenkomplexe des Mangans / Transition Metal Carbene Complexes, CXXI [1] Fluorocarbene Complexes of Manganese

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