M. Regitz: Diazoalkane, Eigenschaften und Synthesen. 339 Seiten, 5 Abb., 9 Schemata, 53 Tabellen, Georg Thieme Verlag, Stuttgart 1977. Preis: 148, ‐ DM.

Fritz, W.

doi:10.1002/food.19780220521

Cited by 13 publications

(15 citation statements)

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“…Compounds 7a-c were prepared by published methods. 19 Column chromatography was performed in water-cooled glass tubes under Ar. Silica gel was heated for 3 h in vacuo and then deactivated with 4% H 2 O (Brockmann activity II).…”

mentioning

confidence: 99%

Organophosphorus Compounds, Part 149. Preparation of 1,3-Oxaphospholes by Transition Metal-Catalyzed Reactions of α-Diazo-β-dicarbonyl Compounds with tert-Butylphosphaacetylene

Ruf¹,

Mack²,

Steinbach³

et al. 2000

Synthesis

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In the presence of Rh 2 (OAc) 4 as catalyst the cyclic a-diazo-b-dicarbonyl compounds 7a-c react with tert-butylphosphaacetylene 2 under elimination of nitrogen to furnish the 1,3-oxaphosphole derivatives 8a-c. The feasible competing reaction with formation of the 1,2,4-diazaphospholes 9a-c has not been observed.The class of the 1,3-oxaphospholes still constitutes a relatively unknown area in the fertile field of heterophosphole chemistry. 2 Currently, only two separate routes to nonbenzo-condensed 1,3-oxaphospholes have been described: Thus, 1,3-oxaphosphole derivatives can be obtained either by reaction of phosphaacetylenes with Fischer-type chromium carbene complexes or by 1,3-dipolar cycloaddition reactions of isomünchnones with the phosphaacetylenes. [3][4][5] Although the reaction of the isomünchnone 5 with the phosphaacetylene 2 furnishes the 1,3-oxophosphole derivative 6 in very good yield in a highly specific reaction, 3,4 the 1,3-oxaphosphole 3 prepared from the carbene complex 1 is isolated in merely 35% yield. 5 The reason for this low yield is the fact that the reaction is not specific for formation of the 1,3-oxaphosphole but is instead accompanied by a side reaction furnishing the phosphaarene species 4. 5 By use of catalytic amounts of rhodium(II) acetate we have now successfully realized reactions between the cyclic a-diazo-b-dicarbonyl compounds 7 and tert-bu- Scheme 1Downloaded by: National University of Singapore. Copyrighted material.

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mentioning

confidence: 99%

Organophosphorus Compounds, Part 149. Preparation of 1,3-Oxaphospholes by Transition Metal-Catalyzed Reactions of α-Diazo-β-dicarbonyl Compounds with tert-Butylphosphaacetylene

Ruf¹,

Mack²,

Steinbach³

et al. 2000

Synthesis

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“…The paleyellow color of 22 is no surprise; electron-attracting substituents have a hypsochromic effect on the light absorption of diazomethane [26]. The 19 F-NMR spectra offer the basic support.…”

Section: Methodsmentioning

confidence: 97%

Reactions of Methyl Diazoacetate with (E)‐ and (Z)‐1,2‐Bis(trifluoromethyl)ethene‐1,2‐dicarbonitrile: Novel and Unanticipated Pathways

Huisgen

Mlostoń

Pöchlauer

et al. 2007

Helvetica Chimica Acta

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Dedicated to Mordecai Rubin, Technion, Haifa, on the occasion of his 80th birthdayThe cycloadditions of methyl diazoacetate to 2,3-bis(trifluoromethyl)fumaronitrile ((E)-BTE) and 2,3-bis(trifluoromethyl)maleonitrile ((Z)-BTE) furnish the 4,5-dihydro-1H-pyrazoles 13. The retention of dipolarophile configuration proceeds for (E)-BTE with > 99.93% and for (Z)-BTE with > 99.8% (CDCl 3 , 258), suggesting concertedness. Base catalysis (1,4-diazabicyclo[2.2.2]octane (DABCO), proton sponge) converts the cycloadducts, trans-13 and cis-13, to a 94 : 6 equilibrium mixture (CDCl 3 , r.t.); the first step is N-deprotonation, since reaction with methyl fluorosulfonate affords the 4,5-dihydro-1-methyl-1H-pyrazoles. Competing with the cis/trans isomerization of 13 is the formation of a bis(dehydrofluoro) dimer (two diastereoisomers), 2 C 9 H 4 F 6 N 4 O 2 (13) ! C 18 H 6 F 10 N 8 O 4 (22) + 2 HF, the structure of which was elucidated by IR, 19 F-NMR, and 13 C-NMR spectroscopy. The reaction slows when DABCO is bound by HF, but F À as base keeps the conversion to 22 going and binds HF. The diazo group in 22 suggests a common intermediate for cis/trans isomerization of 13 and conversion to 22: reversible ring opening of N-deprotonated 13 provides 18, a derivative of methyl diazoacetate with a carban-A C H T U N G T R E N N U N G ionic substituent. Mechanistic comparison with the reaction of diazomethane and dimethyl 2,3-dicyanofumarate, a related tetra-acceptor-ethylene, brings to light unanticipated divergencies.

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“…0.60 g (100%) ockergelbe Nadeln, die bei 154°C verpuffen (aus Chloroform/Methanol bei nur vorsichtigem Erwarmen). ( 2 ) 1442 ( 3 ) 2205 (5) -227 ( 8 ) 932 ( 5 ) -89 ( 7 ) 2355 ( 5 ) 2113 (8) 3238 (6) -534 ( l o ) 2875 (7) -1465 (12) 3060 (5) 2001 ( 9 ) 2158 ( 5 ) 1084 ( 9 ) 4624 ( 7 ) 1525 (11) 5163 (8) 1483 (12) 6102 (8) 2442 (12) 6530 (8) 3505 (12) 6010 ( 7 ) 3598 (11) 6443 ( 7 ) 4672 (11) 5923 ( 7 ) 4726 (11) 4991 ( 7 ) 3753 (11) 4514 ( 7 ) 2731 ( l o ) 5046 ( 7 ) 2612 (11) 3668 ( 7 ) 557 (11) 3045 ( 7 ) 602 (11) 3516 ( 6 ) 1780 (11) 898 ( 7 ) 2988 (12) -66 ( 7 ) 2508 (12) -606 ( 7 ) 3749 (12) -134 (7) 5422 (12) 798 ( 8 ) 5903 (13) 1351 ( 7 ) 4667 (12) I 1415 ( 2 ) 4208 ( 3 ) -284 ( 8 ) 4290 ( 9 ) (2) 153 (14) 137 (13) 126 (17) 207 (21) 9 1 (14) 120 (16) 124 (20) 132 (21) 125 (20) (21) 147 (21) 133 (21) 127 (21) 9 1 ( 5 ) 9 1 (12) 84 …”

Section: I3-bis(diazo)-ih-phenalen-2(3h)-on (13)unclassified

Untersuchungen an Diazoverbindungen und Aziden, XL. 1,3‐Bis(diazo)‐1 H ‐phenalen‐2(3 H )‐on

et al. 1982

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Aus dem Triketonhydrat 8 und Tosylhydrazid im Molverhaltnis 1 : 1 erhalt man neben 6 als Hauptprodukt noch das 3-Diazo-1 ,2-diketon 9. Die gleiche Umsetzung liefert bei einem Reaktandenverhaltnis von 1 : 2 das 3-Diazo-l,2-diketon-tosylhydrazon 12, dessen Alkalispaltung zur Bildung der Titelsubstanz 13 fuhrt. Von (Bromphenylsulfony1)hydrazon 16 wurde eine Rontgenstrukturanalyse angefertigt. Investigations on Diazo Compounds and Azides, XL I) 1,3-Bis(diazo)-lH-phenalen-2(3H)-oneThe triketone hydrate 8 reacts with tosyl hydrazide in a molar ratio of 1 : 1 to form 6 as the main product besides the 3-diazo-1,2-diketone 9. At a molar ratio of 1 : 2 the same reaction yields the 3-diazo-l,2-diketone tosylhydrazone 12, the alkaline cleavage of which leads to the formation of the title compound 13. For the (bromopheny1sulfonyl)hydrazone 16, an X-ray structure analysis was performed.Die Photolyse von 1,3-Bis(diazo)-l,3-diphenyl-2-propanon liefert je nach den Bedingungen entweder Diphenylcyclopropenon oder das durch dessen Decarbonylierung entstandene Diphenylacetylen2). Ein vergleichbares Ergebnis erbrachte auch die Thermolyse von 2,4-Bis(diazo)-l,3,5-triketonen mit der Bildung von Diacylacetylenen; hierbei ist allerdings eine Cyclopropenon-Zwischenstufe nicht nachwei~bar~). Dem Versuch, diese Reaktionsfolge zur Erzeugung hochwinkelgespannter Cycloalkine heranzuziehen, blieb bisher der Erfolg versagt: Bestrahlt man das Bis(diazo)keton 1 in der Argonmatrix 1 2 H 2 C = C q 4 hv, [1,3s]-0 Verlag Chemie GmbH, D-

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M. Regitz: Diazoalkane, Eigenschaften und Synthesen. 339 Seiten, 5 Abb., 9 Schemata, 53 Tabellen, Georg Thieme Verlag, Stuttgart 1977. Preis: 148, ‐ DM.

Cited by 13 publications

References 0 publications

Organophosphorus Compounds, Part 149. Preparation of 1,3-Oxaphospholes by Transition Metal-Catalyzed Reactions of α-Diazo-β-dicarbonyl Compounds with tert-Butylphosphaacetylene

Organophosphorus Compounds, Part 149. Preparation of 1,3-Oxaphospholes by Transition Metal-Catalyzed Reactions of α-Diazo-β-dicarbonyl Compounds with tert-Butylphosphaacetylene

Reactions of Methyl Diazoacetate with (E)‐ and (Z)‐1,2‐Bis(trifluoromethyl)ethene‐1,2‐dicarbonitrile: Novel and Unanticipated Pathways

Untersuchungen an Diazoverbindungen und Aziden, XL. 1,3‐Bis(diazo)‐1 H ‐phenalen‐2(3 H )‐on

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