78-87-5Relevant academic research and scientific papers
METHODS AND SYSTEMS TO FORM PROPYLENE CHLOROHYDRIN AND PROPYLENE OXIDE
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Paragraph 164, (2019/01/05)
There are provided methods and systems to form propylene chlorohydrin by hydrolysis of 1,2-dichloropropane and to further form propylene oxide from propylene chlorohydrin.
ELECTROCHEMICAL HYDROXIDE SYSTEMS AND METHODS USING METAL OXIDATION
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Paragraph 0293, (2015/02/19)
There are provided methods and systems for an electrochemical cell including an anode and a cathode where the anode is contacted with a metal ion that converts the metal ion from a lower oxidation state to a higher oxidation state. The metal ion in the higher oxidation state is reacted with an unsaturated hydrocarbon and/or a saturated hydrocarbon to form products. Separation and/or purification of the products as well as of the metal ions in the lower oxidation state and the higher oxidation state, is provided herein.
Electrochemical hydroxide systems and methods using metal oxidation
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Page/Page column 98, (2015/12/04)
There are provided methods and systems for an electrochemical cell including an anode and a cathode where the anode is contacted with a metal ion that converts the metal ion from a lower oxidation state to a higher oxidation state. The metal ion in the higher oxidation state is reacted with hydrogen gas, an unsaturated hydrocarbon, and/or a saturated hydrocarbon to form products.
Propane chlorination over ruthenium oxychloride catalysts
Testova,Shalygin,Maksimov,Paukshtis,Parmon
, p. 428 - 433 (2015/08/04)
The gas-phase chlorination of propane over different catalysts, including those containing ruthenium oxychlorides as the active component, has been investigated. The propylene and chlorine-containing product formation selectivities in propane chlorination at 150-450°C in a fixed-bed flow reactor have been determined.
A systematic study on the activation of simple polyethers by MoCl 5 and WCl6
Dolci, Sara,Marchetti, Fabio,Pampaloni, Guido,Zacchini, Stefano
experimental part, p. 5367 - 5376 (2010/08/04)
MoCl5, 1a, and WCl6, 1b, activate 1,3-dioxolane at room temperature in chlorinated solvents: the compound [MoOCl 3{OC(H)OCH2CH2Cl}]2, 2, has been isolated from MoCl5/dioxolane. The mixed oxo-chloro species WOCl 4, 1c, reacts with 1,3-dioxolane, selectively giving the coordination adduct WOCl4(κ1-C3H6O 2), 3. Dimethoxymethane, CH2(OMe)2, undergoes activation including C-H bond cleavage when reacted with 1a to give the molybdenum complexes [MoOCl3{OC(H)OMe}]2, 4, and Mo 2Cl5(OMe)5, 5. The reactions of 1b with CH 2(OR)2 (R = Me, Et) proceed via O-abstraction with formation of the oxo-derivatives WOCl4[O(R)CH2Cl] (R = Me, 6a; R = Et, 6b) in admixture with equimolar amounts of RCl. The reactions of 1a,b with CMe2(OMe)2 lead to mesityl oxide, MeC(O)CHC(Me)2. A series of simple diethers of general formula ROCH2(CHR′)OR′′ are activated by 1a,b in CDCl 3, usually via cleavage of C-O bonds at high temperature. The complex WCl5(OCH2CH2OMe), 7, has been detected in solution as an intermediate species in the course of the degradation of 1,2-dimethoxyethane (dme) by 1b. The activation of CH(OMe)3 by 1 is limited to C-O bonds and selectively gives methyl chloride and methylformate, which has been found coordinated in WOCl4[OC(H)OMe], 8. The organic fragments produced in the reactions have been detected by GC-MS and NMR analyses, upon hydrolysis of the reaction mixtures. Compounds 2 and 5, which have had their molecular structures ascertained by X-ray diffraction, represent rare examples of crystallographically-characterized dinuclear Mo(v) species containing both halides and oxygen ligands.
METHOD OF PREPARING DICHLOROPROPANOL FROM GLYCEROL USING HETEROPOLYACID CATALYSTS
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Page/Page column 6-7; 8, (2009/07/17)
Provided is a method of preparing dichloropropanol from glycerol. According to the method, glycerol is reacted with a chlorinating agent using a heteropolyacid catalyst to prepare dichloropropanol. Accordingly, dichloropropanol can be directly prepared from glycerol by using heteropolyacid catalysts, and conventional problems such as recovery of the catalyst and separation of an azeotropic mixture including the catalyst and the products can be overcome. In addition, since the catalyst can be easily recovered and reused, the manufacturing process can be simplified and expensive dichloropropanol can be produced at high yield from inexpensive glycerol.
MANUFACTURE OF DICHLOROPROPANOL
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Page/Page column 19-21, (2009/03/07)
Manufacture of dichloropropanol Process for manufacturing dichloropropa nol wherein a glycerol-based product comprising at least one diol containi ng at least 3 carbon atoms other than 1,2- propanediol, is reacted with a chlorinati ng agent, and of products derived from dichloropropanol such as ep ichlorohydrin and epoxy resins. No figure.
Determination of the hydrogen-bond basicity of weak and multifunctional bases: The case of lindane (γ-hexachlorocyclohexane)
Ouvrard, Carole,Lucon, Maryvonne,Graton, Jerome,Berthelot, Michel,Laurence, Christian
, p. 56 - 64 (2007/10/03)
We made use of four methods for determining the hydrogen-bond (HB) basicity of lindane (λ-hexachlorocyclohexane): (i) experimental Fourier transform IR measurement of a sum of individual 1:1 equilibrium constants for the formation of 1:1 4-fluorophenol-lindane hydrogen-bonded complexes in CCl4; (ii) calculation of the overall HB basicity from octanol-water partition coefficients; (iii) correlation of the HB basicity of chloroalkanes with the electrostatic potentials around chlorine atoms; and (iv) correlation of the HB basicity of chloroalkanes with the computed enthalpy of their complexes with hydrogen fluoride. It is consistently found that lindane remains a weak HB base because multifunctionality cannot fully compensate for the electron-withdrawing inductive effects that chlorine atoms exert over one another. Actually, only five chlorine atoms behave as HB acceptors, one axial chlorine being deactivated by inductive effects. Stereoelectronic effects lead to the formation of three-centered hydrogen bonds. Copyright
Flash vacuum pyrolysis over magnesium. Part 1 - Pyrolysis of benzylic, other aryl/alkyl and aliphatic halides
Aitken, R. Alan,Hodgson, Philip K.G.,Morrison, John J.,Oyewale, Adebayo O.
, p. 402 - 415 (2007/10/03)
Flash vacuum pyrolysis over a bed of freshly sublimed magnesium on glass wool results in efficient coupling of benzyl halides to give the corresponding bibenzyls. Where an ortho halogen substituent is present further dehalogenation gives some dihydroanthracene and anthracene. Efficient coupling is also observed for halomethylnaphthalenes and halodiphenylmethanes while chlorotriphenylmethane gives 4,4′-bis(diphenylmethyl)biphenyl. By using α,α′-dihalo-o-xylenes, benzocyclobutenes are obtained in good yield, while the isomeric α,α′-dihalo-p-xylenes give a range of high thermal stability polymers by polymerisation of the initially formed p-xylylenes. Other haloalkylbenzenes undergo largely dehydrohalogenation where this is possible, in some cases resulting in cyclisation. Deoxygenation is also observed with haloalkyl phenyl ketones to give phenylalkynes as well as other products. With simple alkyl halides there is efficient elimination of HCl or HBr to give alkenes. For aliphatic dihalides this also occurs to give dienes but there is also cyclisation to give cycloalkanes and dehalogenation with hydrogen atom transfer to give alkenes in some cases. For 5-bromopent-1-ene the products are those expected from a radical pathway but for 6-bromohex-1-ene they are clearly not. For 2,2-dichloropropane and 1,1-dichloropropane elimination of HCl occurs but for 1,1-dichlorobutane, -pentane and -hexane partial hydrolysis followed by elimination of HCl gives E, E-, E,Z- and Z,Z- isomers of the dialk-1-enyl ethers and fully assigned 13C NMR data are presented for these. With 6-chlorohex-1-yne and 7-chlorohept-1-yne there is cyclisation to give methylenecycloalkanes and -cycloalkynes. The behaviour of 1,2-dibromocyclohexane and 1,2-dichlorocyclooctane under these conditions is also examined. Various pieces of evidence are presented that suggest that these processes do not involve generation of free gas-phase radicals but rather surface-adsorbed organometallic species.
Pressure dependence of the reaction Cl + C3H6
Kaiser,Wallington
, p. 9788 - 9793 (2007/10/03)
The rate constant for the reaction Cl + C3H6 (k1) has been measured relative to that of Cl + C2H6 over the range 0.3-700 Torr in N2 at 298 K. UV irradiation was used to generate Cl atoms in mixtures of C3H6, C2H6, Cl2, and N2 in two different reactors using FTIR or GC analysis. The yields of the two major products, allyl chloride (3-C3H5Cl) and 1,2-dichloropropane were measured. k1 decreases by a factor of 5 between 700 and 1 Torr. Below 1 Torr, the rate constant becomes independent of pressure. The results indicate that k1 is a composite of three reaction channels, each having a different pressure dependence. Measurement of the yield of 1,2-dichloropropane, the final product formed from the addition of Cl to C3H6, at each pressure allows a determination of the rate constant (k1a) for the addition of Cl to C3H6. Assuming a typical center broadening factor (Fc = 0.6), the high- and low-pressure limiting constants are calculated to be k1a(∞) = (2.7 ± 0.4) × 10-10 cm3 molecule-1 s-1 and k1a(0) = (4.0 ± 0.4) × 10-28 cm6 molecule-2 s-1. The pressure dependence of the yield of 3-C3H5Cl indicates that the allyl radical is likely formed by both abstraction and addition-elimination channels. The rate constant of the abstraction reaction from the methyl radical in C3H6 is (2.3 ± 0.3) × 10-11 cm3 molecule-1 s-1. At pressures below 10 Torr, the rate constant for formation of the allyl radical increases by 50%, and this is ascribed to an addition-elimination process. Relative rate constant ratios were also measured for Cl atom reactions with allyl chloride (k6) and 1,2-dichloropropane (k7) relative to C3H6, C2H5Cl, or CH3Cl to correct the product yield experiments for secondary consumption. The observed values of k6/k1 are 0.75 for total pressures of 10-700 Torr, 0.44 at 1 Torr, and 0.33 at 0.4 Torr. On the basis of the relative rate measurements k7 = (3.9 ± 0.6) × 10-12 cm3 molecule-1 s-1 over the range 1-700 Torr.
