Nucleophilic Addition of the Double Bond of 2,4,6-Trinitrostyrene and Transformations of Adducts.

8-Azabenzo[4,5]cyclohepta[1,2,3-de]naphthalene, a nitrogen analogue of one of the hypothetical hydrocarbons on which Pullman et al.1 have made a theoretical-study, has been synthesized. This compound has been found to undergo nucleophilic addition of water, methanol, or aniline to the carbon-nitrogen double bond with surprising ease, and a possible explanation for these reactions has been proposed.

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ChemInform Abstract: NUCLEOPHILIC ADDITION TO OLEFINS. 5. REACTION OF 1,1-DINITRO-2,2-DIPHENYLETHYLENE WITH WATER AND HYDROXIDE ION IN 50% DIMETHYL SULFOXIDE-50% WATER. COMPLETE KINETIC ANALYSIS OF HYDROLYTIC CLEAVAGE OF THE C:C DOUBLE BOND IN ACIDIC AND

Chemischer Informationsdienst ◽

10.1002/chin.198146105 ◽

1981 ◽

Vol 12 (46) ◽

Author(s):

C. F. BERNASCONI ◽

D. J. CARRE ◽

A. KANAVARIOTI

Keyword(s):

Double Bond ◽

Kinetic Analysis ◽

Dimethyl Sulfoxide ◽

Nucleophilic Addition ◽

Hydrolytic Cleavage ◽

Hydroxide Ion

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Nucleophilic addition to olefins. 5. Reaction of 1,1-dinitro-2,2-diphenylethylene with water and hydroxide ion in 50% dimethyl sulfoxide-50% water. Complete kinetic analysis of hydrolytic cleavage of the C:C double bond in acidic and basic solution

Journal of the American Chemical Society ◽

10.1021/ja00406a030 ◽

1981 ◽

Vol 103 (16) ◽

pp. 4850-4860 ◽

Cited By ~ 6

Author(s):

Claude F. Bernasconi ◽

David J. Carre ◽

Anastassia Kanavarioti

Keyword(s):

Double Bond ◽

Kinetic Analysis ◽

Dimethyl Sulfoxide ◽

Nucleophilic Addition ◽

Basic Solution ◽

Hydrolytic Cleavage ◽

Hydroxide Ion

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meso-Tetraphenylporphyrin-derived oxypyriporphyrin, oxypyrichlorin, and thiomorpholinochlorin, as their Ni(II) complexes

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s1088424612500654 ◽

2012 ◽

Vol 16 (05n06) ◽

pp. 576-588 ◽

Cited By ~ 15

Author(s):

Subhadeep Banerjee ◽

Matthias Zeller ◽

Christian Brückner

Keyword(s):

Double Bond ◽

Single Crystal ◽

Nucleophilic Addition ◽

Nickel Complex ◽

Aldol Condensation ◽

Trans Configuration ◽

Free Base ◽

X Ray ◽

Methylene Groups ◽

Lawesson's Reagent

trans-Diolchlorin was prepared by nucleophilic addition of methyl-Grignard bromide to meso-tetraphenyl-2,3-dioxoporphyrin, as its free base or Ni(II) complex. The trans-configuration of the vic-diol functionality was shown by single crystal X-ray diffractometry. The nickel complex of the trans-dimethyldiol proved susceptible to Pb(IV) acetate-induced, oxidative diol cleavage, generating a meso-tetraphenylsecochlorin bismethylketone Ni(II) complex, the first example of this chromophore class. Under Brønsted-basic conditions, this bisketone cyclized via an intramolecular aldol condensation to provide a meso-tetraphenyloxypyriporphyrin. Reduction of this porphyrin analog saturated the double bond in the pyridinone moiety, generating an oxypyrichlorin. Reaction of the meso-tetraphenylsecochlorin bismethylketone Ni(II) complex with Lawesson's reagent induced the formation of a thiomorpholinochlorin substituted with two methylene groups, the first example of any porphyrin analog containing a thiomorpholine moiety.

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