594-20-7Relevant articles and documents
Far infra-red absorption of disubstituted propanes in rotator, solid and liquid phases
Haffmans,Larkin
, p. 1729 - 1741 (1972)
Experimental observations of the far infra-red (f.i.-r.) absorption spectra of three polar di-substituted propanes (2,2-dichloro-, 2-chloro-2-nitro-, 2-methyl-2-nitro-propane) over the temperature range 133-303 K in the liquid, rotator and non-rotator solid phases are reported. The spectra in both the liquid and rotator phases are discussed in terms of two simple theoretical models of librational and relaxational motions: an acceptable fit to the experimental spectra is obtained on the basis of reasonable barriers and other parameters of the molecular motion. One of the models indicates that the molecular librational potential wells may become narrower with decreasing temperature and that there may be a distribution of potential well depths or shapes. The variation of potential barrier height with group substitution is also discussed.
The interaction of molybdenum pentachloride with carbonyl compounds
Marchetti, Fabio,Pampaloni, Guido,Zacchini, Stefano
, p. 2477 - 2487 (2013/03/29)
The reactions of MoCl5, 1, with small amounts of a series of carbonyl compounds in a chlorinated solvent were investigated. The chloroiminium salts [ClCHNEt2][Mo(O)Cl4{OC(H)NEt2}], 2a, and [ClCNH(CH2)4CH2][Mo(O)Cl 4{OCNH(CH2)4CH2}], 2b, were obtained by a selective 1:2 molar reaction of 1 with, respectively, N,N-diethylformamide or ε-caprolactam. Otherwise 1 reacted with tetra-N-alkyl ureas in a 1:2 ratio to give the Mo(iv) mononuclear complexes MoCl4(urea) 2 [urea = (Me2N)2CO, 3a; urea = (Et 2N)2CO, 3b; urea = (EtPhN)2CO, 3c] in high yields. Addition of 2 equiv. of ketones to 1 resulted in clean formation of equimolar amounts of MoOCl3(OCR2) (R = Me, 4a; R = Et, 4b; R = Ph, 4c) and R2CCl2. Analogously 1,2-C 6H4(Me)(CHCl2) was produced from MoCl 5 and ortho-tolyaldehyde. The reactions of 1 with 1H-indole-2,3-dione (isatin) took place with selective chlorination of the carbonyl function non-adjacent to the nitrogen: the complexes MoOCl3(3,3-dichloro-2,3- dihydro-1H-indol-2-one)2, 5a, and MoOCl3(isatin)(3,3- dichloro-2,3-dihydro-1H-indol-2-one), 5b, were isolated depending on the stoichiometry employed. The X-ray molecular structures of 2b, 3b, 4b, 5a and 5b were ascertained.
ROLE OF INTERMOLECULAR INTERACTIONS IN THE SELECTIVE EFECT OF THE MEDIUM ON FREE-RADICAL CHLORINATION
Aver'yanow, V. A.,Golubev, V. E.,Semenov, A. O.,Kostylev, I. M.
, p. 1759 - 1764 (2007/10/02)
The effect of noncomplexing solvents on the selectivity of the free-radical chlorination of 2-chloropropane was studied.It was shown that the relative reactivity of C-H bonds in 2-chloropropane correlates with the solubility parameter and with the Kirkwood function.The obtained data are treated as a result of solvation of the chlorine atoms in solution.It was concluded that it is necessary to include the contribution from the substrates to the overall effect of the medium during interpretation of the selective action of the complexing solvents.
