38697-07-3Relevant articles and documents
Concurrent Formation of N-H Imines and Carbonyl Compounds by Ruthenium-Catalyzed C-C Bond Cleavage of β-Hydroxy Azides
Lee, Jeong Min,Bae, Dae Young,Park, Jin Yong,Jo, Hwi Yul,Lee, Eunsung,Rhee, Young Ho,Park, Jaiwook
supporting information, p. 4608 - 4613 (2020/06/05)
A commercial cyclopentadienylrutenium dicarbonyl dimer ([CpRu(CO)2]2) efficiently catalyzes the formation of N-H imines and carbonyl compounds simultaneously from β-hydroxy azides via C-C bond cleavage under visible light. Density functional theory calculations for the cleavage reaction support the mechanism involving chelation of alkoxy azide species and liberation of nitrogen as the driving force. The synthetic utility of the reaction was demonstrated by a new amine synthesis promoted by chemoselective allylation of imine and synthesis of isoquinoline.
Thermal decomposition of O-benzyl ketoximes; role of reverse radical disproportionation
Blake, Jessie A.,Ingold, Keith U.,Lin, Shuqiong,Mulder, Peter,Pratt, Derek A.,Sheeller, Brad,Walton, John C.
, p. 415 - 420 (2007/10/03)
Thermolyses of seven dialkyl, two alkyl-aryl and two diaryl O-benzyl ketoxime ethers, R1R2C=NOCH2Ph, have been examined in three hydrogen donor solvents: tetralin, 9,10-dihydrophenanthrene, and 9,10-dihydroanthracene. All the oxime ethers gave the products expected from homolytic scission of both the O-C bond (viz., R1R2C=NOH and PhCH3) and N-O bond (viz., R1R2C=NH and PhCH2OH). The yields of these products depended on which solvent was used and the rates of decomposition of the O-benzyl oxime ethers were greater in 9,10-dihydrophenanthrene and 9,10-dihydroanthracene than in tetralin. These results indicated that a reverse radical disproportionation reaction in which a hydrogen atom was transferred from the solvent to the oxime ether, followed by β-scission of the resultant aminoalkyl radical, must be important in the latter two solvents. Benzaldehyde was found to be an additional product from thermolyses conducted in tetralin. This, and other evidence, indicated that another induced decomposition mode involving abstraction of a benzylic hydrogen atom, followed by β-scission of the resulting benzyl radical, became important for some substrates. Participation by minor amounts of enamine tautomers of the oxime ethers was shown to be negligible by comparison of thermolysis data for the O-benzyloxime of bicyclo[3.3.1]nonan-9-one, which cannot give an enamine tautomer, with that of the O-benzyloxime of cyclohexanone.
Reactions of N, N-dichloroalkylamines with solid base as studied by FTIR combined with DFT calculations
Egawa,Ito,Konaka
, p. 337 - 344 (2007/10/03)
Products of vacuum gas-solid reactions of N, N-dichloroalkylamines with KOH have been identified by FTIR spectroscopy and DFT calculations. It has been found that the reactions consist of elimination of two Cl atoms accompanied with migration of an H atom, a ring carbon or a methyl group from the α-carbon to the N atom and unstable imines with a C=N double bond are formed.
Catalysed aerobic dehydrogenation of amines and an X-ray crystal structure of a bis(benzylamine) ruthenium(II) porphyrin species
Bailey, Alan J.,James, Brian R.
, p. 2343 - 2344 (2007/10/03)
The complex trans-[RuVI(tmp)(O)2] 1 (tmp = dianion of 5,10,15,20-tetramesitylporphyrin) catalytically dehydrogenates primary and secondary amines in the presence of air; possible reaction steps involve a disproportionation reaction that generates a RuII intermediate, as evidenced by the isolated bis(benzylamine) complex [RuII(tmp)-(PhCH2NH2)2] 2 which is characterised crystallographically.
REACTIONS RETRODIENIQUES-IX. SYNTHESE PAR THERMOLYSE ECLAIR ET ETUDE D'ENAMINES PRIMAIRES INSTABLES
Ripoll, J. L.,Lebrun, H.,Thuillier, A.
, p. 2497 - 2504 (2007/10/02)
Etheneamine 1 and its methyl derivatives 2-7 have been synthesized from the adducts 8-14 by a retro-Diels-Alder reaction under flash thermolytic conditions.The primary enamines 1-4 have been identified (IR, (1)H and (13)C NMR in a pure state at -80 deg C; at the same temperature, the enamines 5-7, less stable, are already accompanied by their tautomeric imines 33 or 34.When warmed up to room temperature, the enamines 1-7 lead, following to their substitution, either to nitrogen heterocycles (30, 42) or to acyclic azadienes (35-37, 39, 40).
