2167-39-7Relevant articles and documents
The reactions of 4-chloro-2-butanol and 3-chloro-1-butanol with aqueous sodium hydroxide, and 1-chloro-2-propanol and 2-chloro-1-propanol with isopropyl amine
Pihlaja, Kalevi,Aaljoki, Kari,Lyytinen, Maija-Riitta,Huusko, Marja-Liisa,Hotokka, Marjut
experimental part, p. 188 - 199 (2011/07/07)
The total reaction of 4-chloro-2-butanol 1 with NaOH(aq) is dominated (74%) by intramolecular substitution (SNi), besides which bimolecular substitution (SN2, 12%) and 1,4-elimination (i.e. fragmentation, contrary to earlier arguments) exhibit a significant contribution (11%). The total reaction of 3-chloro-1-butanol 2 instead is dominated by 1,4-(72%) and 1,2-elimination (25%), the substitution reactions being just observable (SNi 2% and SN2 1%). In 1 both the +I-effect and the conformational factors in the intermediate γ-chloroalkoxy anion favour the SNi-reaction, whereas in 2 the situation is opposite and the location of Cl on a secondary carbon also makes the SNi-reaction less favourable. The relative proportions of 1,4-and 1,2-eliminations for 2 can be explained by thermodynamic basis since the consequent products are more stable than the corresponding products from 1. 1-chloro-2-propanol 3 and 2-chloro-1-propanol 4 both react with isopropyl amine giving the same product, namely 1-isopropylamino-2-propanol, which indicates that the reaction proceeds through the propylene oxide intermediate. Compound 1 also reacted with isopropyl amine predominantly via SNi-reaction, giving first 2-methyloxetane which then further gave 4-isopropylamino-2-butanol, whereas 2 gave 3-isopropylamino-1-butanol through a direct S N2-reaction. ARKAT-USA, Inc.
OXYGEN YLIDES-I. REACTIONS OF CARBENES WITH OXETANE
Friedrich, Klaus,Jansen, Ulrich,Kirmse, Wolfgang
, p. 193 - 196 (2007/10/02)
The ylides generated from carbenes (:CH2, :CHCO2Et, :CHPh) and oxetane in the presence of methanol undergo Stevens rearrangement and protonation competitively, yielding tetrahydrofurans and 1,3-dialkoxycyclopropanes as major products.
Cadmium-photosensitized Reaction of γ-Valerolactone and α-Methyl-γ-butyrolactone
Yamamoto, Shunzo,Takahoso, Hiroshi,Sueishi, Yoshimi,Nishimura, Norio
, p. 2038 - 2042 (2007/10/02)
The cadmium-photosensitized reactions of γ-valerolactone and α-methyl-γ-butyrolactone have been investigated.The obtained products in both cases were carbon monoxide, ethylene, propylene, acetaldehyde, and 2-methyloxetane.The dependence of the yields of ethylene and propylene on the total pressure suggests the existence of a biradical and an energized intermediate.Possible mechanisms are discussed.
Chemical Activation Study of the Reactions of Methylene with Oxetan and 3,3-Dimethyloxetan
Frey, Henry M.,Pidgeon, Ivy M.
, p. 1237 - 1248 (2007/10/02)
Methylene (singlet) formed by the photolysis of ketene (313 nm) reacts with oxetan to yield 2-methyl- and 3-methyloxetans by insertion in the C-H bonds and probably also tetrahydrofuran.These products are formed chemically activated and undergo unimolecular decomposition unless collisionally stabilized.Using perfluoropropane as the bath gas, the results obtained with 2-methyloxetan have been interpreted using RRKM theory and a step-ladder model with a most probable step size of ca. 9 kJ mol-1.Using 206 nm radiation yields methylene with excess energy, some of which is still present when it reacts, and results in the production of 2-methyloxetan with an average lifetime approximately one-half that of the energised molecule produced when 313 nm radiation is used.Similarly methylene reacts with 3,3-dimethyloxetan to yield chemically activated 3-ethyl-3-methyloxetan and 2,3,3-trimethyloxetan.A third compound tentatively identified as 3,3-dimethyltetrahydrofuran is also formed.The decomposition of these 3 molecules has been followed and in the case of the ethylmethyloxetan the average energy transferred in collision with 3,3-dimethyloxetan has been found to be ca. 6.5 kJ mol-1.Some deductions can be made about the Arrhenius parameters for the thermal decomposition of the (as yet unreported) trimethyloxetan and the dimethyltetrahydrofuran.
