- N-Heterocyclic phosphenium cations: Syntheses and cycloaddition reactions
-
A series of trifluoromethanesulfonate (OTf) salts of N-heterocyclic phospheniums (NHP) bearing phenyl (1a), para-methoxyphenyl (1b), 2,6-diisopropylphenyl (1c) and mesityl (1d) substituents is reported. The compounds 1b-d are made by a modification to a literature procedure that improves the overall yields for 1c and 1d by 15 and 23%, respectively. Two unwanted side-products in the synthesis of 1d, the diammonium salt, [(2,6-iPr-C6H3)N(H)2CH2CH 2N(H)2(2,6-iPr-C6H3)]Cl2 (4) and the bisphosphine (2,6-iPr-C6H3)N(PCl 2)CH2CH2N(PCl2)(2,6-iPr-C 6H3) (5), are crystallographically characterized, as is the intermediate cyclic chlorophosphine, C1PN(4-OMe-C6H 4)CH2CH2N(4-OMe-C6H4) (3b). The phenyl-substituted NHP 1a is fully characterized, including by X-ray crystallography, for the first time; this compound contains a short P-O contact of 2.1850(14) A Cycloaddition reactions of 1a-d with 2,3-dimethyl-1,3- butadiene give the expected spirocyclic phospholeniums, 7,8-dimethyl-1,4-diaryl- 1,4-diaza-5-phopshoniaspiro[4.4]non-7-ene, as their OTf salts (6a-d), while reactions with N,N′-dimesityl-1,4-diaza-1,3-butadiene give, except in the case of 1c, which is too bulky to react, the aza analogues, 1,4-dimesityl-6,9- diaryl-1,4,6,9-tetraaza-5-phosphoniaspiro[4.4]non-2-ene (7a, 7b and 7d). The sterically congested 7d is in thermal equilibrium with 1d and free diazadiene, and undergoes a substitution reaction with 2,3-dimethyl-1,3-butadiene to give 6d.
- Caputo, Christine A.,Price, Jacquelyn T.,Jennings, Michael C.,McDonald, Robert,Jones, Nathan D.
-
p. 3461 - 3469
(2008/09/21)
-
- A Novel Method for the Synthesis of Symmetrical Vicinal Tertiary and Secondary Diamines
-
A variety of symmetrical vicinal tertiary and secondary diamines are readily prepared in good to excellent yields by either Grignard reaction or reduction of the glyoxal bisproducts with benzotriazole and secondary or primary amines.
- Katritzky, Alan R.,Fan, Wei-Qiang,Fu, Cong
-
p. 3209 - 3213
(2007/10/02)
-