Déplacements homolytiques intramoléculaires. 2. Décomposition du perpentène-4 oate de tert-butyle dans les éthers

1984 ◽  
Vol 62 (11) ◽  
pp. 2385-2390 ◽  
Author(s):  
A. Kharrat ◽  
C. Gardrat ◽  
B. Maillard
Keyword(s):  
Double Bond ◽  
Main Product ◽  
Similar Reaction ◽  
Tert Butyl ◽  
Lower Temperature ◽  
Induced Decomposition

The thermolysis of tert-butyl perpent-4-enoate 1 in THF led to several compounds; the main product, 5-(2-tetrahydrofuryl)-4-pentanolide (yield 42%) comes from an induced decomposition of the perester occurring with the addition of 2-tetrahydrofuryl radical to the double bond. A similar reaction was performed at a lower temperature, using butyl perdicarbonate as initiator, but did not define the mechanism (concerted or two-step). The thermolysis of 1 in ethers (THP, oxepane, 1,4-dioxane, dipropyl ether) appears to be a useful synthetic tool: several new γ-lactones have been obtained in this way.

scholarly journals Chemoselective and metal-free reduction of α,β-unsaturated ketones by in situ produced benzeneselenol from O-(tert-butyl) Se-phenyl selenocarbonate

RSC Advances ◽  
2020 ◽  
Vol 10 (56) ◽  
pp. 33706-33717
Author(s):  
Andrea Temperini ◽  
Marco Ballarotto ◽  
Carlo Siciliano
Keyword(s):  
Double Bond ◽  
Hydrochloric Acid ◽  
Unsaturated Ketones ◽  
Metal Free ◽  
Tert Butyl ◽  
Carbon Double Bond

The carbon–carbon double bond of arylidene acetones and chalcones can be selectively reduced with benzeneselenol generated in situ by reacting O-(tert-butyl) Se-phenyl selenocarbonate with hydrochloric acid in ethanol.

Reaktionen koordinierter Liganden, III [1]. Stabilisierung von Dimenthyldiphosphen und Menthylphosphiniden als Brückenliganden in Metallcarbonylkomplexen / Reaction of Coordinated Ligands, III [1]. Stabilization of Dim enthyldiphosphene and Menthylphosphinidene as Bridging Ligands in Metal Carbonyl Complexes

1986 ◽  
Vol 41 (5) ◽  
pp. 629-639 ◽  
Author(s):  
Anna-Margarete Hinke ◽  
Axel Hinke ◽  
Wilhelm Kuchen ◽  
Wolfgang Hönle
Keyword(s):  
Crystal Structure ◽  
Double Bond ◽  
Complex Formation ◽  
Main Product ◽  
Metal Carbonyl ◽  
Crystal Structure Analysis ◽  
Carbonyl Complexes ◽  
Bridging Ligands ◽  
Metal Carbonyl Complexes ◽  
Chromium Compounds

Abstract Reduction of MentPBr2M(CO)5 1 (M = Cr, W) with magnesium in THF yields the diphos­phene complex (CO)5M(Ment)P=P(Ment)M(CO)5 2 as the main product. In addition, a phosphinidene complex, (CO)5M(Ment)PM(CO)5 (3) is also formed. The latter is obtained in larger amounts, if the reaction is carried out in the presence of M(CO)5THF. The proposed structures are confirmed by NMR and UV data as well as - in the case of the chromium compounds (2a, 3a) - by crystal structure analysis. Compound 2a is obtained only as the frans-isomer. The P-P distance in 2a (204.0 pm) indicates a double bond which does not participate in the complex formation. The P-Cr distance in 3a (average: 230.3 pm) is within the low est range found for this element combination. Reaction of 2a with LiAlH4 yields the diphosphane complex (CO)5CrMent(H)P-P(H)MentCr(CO)5 4 as a mixture of “meso” and “rac” diastereomers.

Cyclohexyneplatinum(0) Complexes Containing Di-t-butylphenylphosphine, t-butyldiphenylphosphine or Trimethylphosphine

1992 ◽  
Vol 45 (1) ◽  
pp. 135 ◽  
Author(s):  
MA Bennett ◽  
HG Fick ◽  
GF Warnock
Keyword(s):  
Pure State ◽  
Room Temperature ◽  
Main Product ◽  
Similar Reaction ◽  
Molar Proportion ◽  
Sodium Amalgam ◽  
Tertiary Phosphines

Cyclohexyneplatinum (0) complexes Pt(C6H8)L2 [L = PBut2Ph(4), PbutPh2(5)] analogous to the known complex (3) (L=PPh3) have been prepared by reaction of the two-coordinate complexes PtL2 with 1,2-dibromocyclohexene and 1% sodium amalgam. The corresponding tricyclohexylphosphine complex is formed by a similar reaction but it could not be isolated in a pure state. Attempts to prepare analogues of (4) and (5) containing cycloheptyne or cyclooctyne were unsuccessful, possibly because the bulky t-butyl groups of the tertiary phosphines hinder coordination of the larger rings. Bulky tertiary phosphines do not displace PPh3 from (3) but trimethylphosphine reacts with (3) to give successively Pt(C6H8)(PMe3)2(PPh3) (10) and Pt(C6H8)(PMe3)2 (11), as shown by 31P{1H) n.m.r. spectroscopy. The tertiary phosphines in these complexes equilibrate rapidly at room temperature in benzene and only (10) can be isolated as a solid from the reaction. Complexes (4) and (5) react with HCl (1 molar proportion) to give n1-cyclohexen-l-yl complexes trans- PtCl (C6H9)L2 [L= PBut2Ph(6), PButPh2 (7)]. In the absence of air, (4) reacts with methanol at 65°C to give the hydrido complex trans- PtH (C6H9)(PBut2Ph)2 (8). In the presence of oxygen from the air, however, the main product is the dioxygen complex Pt(O2)(Pbut2Ph)2 (9). This represents an unusual example of complete displacement of cyclohexyne from a platinum(0) complex by a π-acceptor ligand.

Di-tert-butyl nitroxide quenching of the photoaddition of olefins to the carbon-nitrogen double bond of 3-ethoxyisoindolenone

1977 ◽  
Vol 99 (19) ◽  
pp. 6332-6340 ◽  
Author(s):  
David R. Anderson ◽  
Joseph S. Keute ◽  
Tad H. Koch ◽  
Robert H. Moseley
Keyword(s):  
Double Bond ◽  
Tert Butyl ◽  
Nitrogen Double Bond

ChemInform Abstract: Induced Decomposition of Di(tert-butyl)trioxide

ChemInform ◽  
2010 ◽  
Vol 28 (42) ◽  
pp. no-no
Author(s):  
S. L. KHURSAN ◽  
A. F. KHALIZOV ◽  
V. V. SHERESHOVETS
Keyword(s):  
Tert Butyl ◽  
Induced Decomposition
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