Methylene chloride ethylene reaction

Chlorine reacts with saturated hydrocarbons either by substitution or by addition to form chlorinated hydrocarbons and HCl. Thus methanol or methane is chlorinated to produce CH Cl, which can be further chlorinated to form methylene chloride, chloroform, and carbon tetrachloride. Reaction of CI2 with unsaturated hydrocarbons results in the destmction of the double or triple bond. This is a very important reaction during the production of ethylene dichloride, which is an intermediate in the manufacture of vinyl chloride ... 

The Nenitzescu process is presumed to involve an internal oxidation-reduction sequence. Since electron transfer processes, characterized by deep burgundy colored reaction mixtures, may be an important mechanistic aspect, the outcome should be sensitive to the reaction medium. Many solvents have been employed in the Nenitzescu reaction including acetone, methanol, ethanol, benzene, methylene chloride, chloroform, and ethylene chloride however, acetic acid and nitromethane are the most effective solvents for the process. The utility of acetic acid is likely the result of its ability to isomerize the olefinic intermediate (9) to the isomeric (10) capable of providing 5-hydroxyindole derivatives. The reaction of benzoquinone 4 with ethyl 3-aminocinnamate 35 illustrates this effect. ... 

This reaction can proceed by 1,1-proton abstraction to form a carbene radical anion, but can also occur by l,n-abstraction to form the negative ion of a diradical. Thus, reaction of O with methylene chloride results in the formation of CCI2 (Eq. S.Sa), reaction with ethylene gives vinylidene radical anion, H2CC (Eq. 5.8b), and the reaction with acetonitrile gives the radical anion of cyanomethylene, HCCN (Eq. 5.8c) Investigations of these ions have been used to determine the thermochemical properties of dichlorocarbene, CCI2, vinylidene, and cyanomethylene. ... 

Reactions in various alkyl halide solvents. A preliminary survey of polymerisations catalysed by titanium tetrachloride in various alkyl halide solvents was undertaken using highly purified materials and a vacuum technique. The most important qualitative result obtained was that in the solvents methylene dichloride, ethyl chloride, ethylene dichloride,... 

Thioetherification of PECH is feasibly performed in DA-solvents as already described in the patent (20J. For example, the highest substitution was obtained by the reaction of P(ECH-EO)(1 1 copolymer of epichloro-hydrin and ethylene oxide) and equimolar thiophenoxide in HMPA at 100°C for 10 h as DS 83% for sodium and 93% for potassium salts. The DS in our nucleophilic substitution was estimated by the elemental analysis as well as the titration of liberated chloride ion with mercuric nitrate (21). In the latter method, reacted medium was pretreated with hydrogen peroxide when the reductive nucleophiles which can react with mercuric ion were used. As described before for PVC, thiolation was also achieved conveniently with iso-thiuronium salt followed by alkaline hydrolysis without the direct use of ill-smelling thiolate. The thiolated PECH obtained are rubbery solids, soluble in toluene, methylene chloride, ethyl methyl ketone and DMF and insoluble in water, acetone, dioxane and methanol. 

Ethylene glycol in the presence of an acid catalyst readily reacts with aldehydes and ketones to form cyclic acetals and ketals (60). 1,3-Dioxolane [646-06-0] is the product of condensing formaldehyde and ethylene glycol. Applications for 1,3-dioxolane are as a solvent replacement for methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, and methyl ethyl ketone as a solvent for polymers as an inhibitor in 1,1,1-trichloroethane as a polymer or matrix interaction product for metal working and electroplating in lithium batteries and in the electronics industry (61). 1,3-Dioxolane can also be used in the formation of polyacetals, both for homopolymerization and as a comonomer with formaldehyde. Cyclic acetals and ketals are used as protecting groups for reaction-sensitive aldehydes and ketones in natural product synthesis and pharmaceuticals (62). 

Reaction of 1,2-dimethylcyclohexene with the ethylene glycol acetal of acrolein in methylene chloride in the presence of 25 mol % of BF3.0Et2 at -78 to -10°C for 2 hours gives a 70% yield of the cycloadduct 1 in a formal 2k + 2% intermolecular cycloaddition. All of the evidence for this and related reactions, however, indicates a stepwise mechanism for the formation of 1. 

This binuclear photooxidative addition reaction is general for a number of halocarbons (Figure 3). While DCE and 1,2-dibromoethane react cleanly to give the dihalide metal dimers and ethylene, substrates such as bromobenzene or methylene chloride react through an alkyl or aryl intermediate. This intermediate reacts further to yield the dihalide d2-d2 metal complexes. 

A solution of 460 mg of (+/-)-2a-(2-carboxy-2-formylethyl)-3p-hydroxy-5-oxo-ip-cyclopentaneheptanoic acid methyl ester 6-lactone, 5-cyclic ethylene acetal in 6 ml of methylene chloride and 4.4 ml of pyridine was treated with a 5% ozone-oxygen mixture at - 70°C until the mixture had persistent pale blue color. The excess of ozone was evaporated by bubbling nitrogen into reaction and the solvents were removed in vacuo. The residue was tirturaed with ether affording crystalline (+/-)-2a-(2-carboxy-2-oxoethyl)-3p-hydroxy-5-oxo-ip-cyclopentaneheptanoic acid methyl ester 6-lactone, 5-cyclic ethylene acetal, m.p. 114-116°C. 

B. Methyl (3, (3 -dibramoisnbutyrate. In a 200-mL, round-bottomed flask fitted with a reflux condenser are placed 61.5 g (0.25 mol) of (3,(3 -dibromoisobutyric acid, 25 g (0.78 mol) of commercial methanol, 75 mL of ethylene dichloride, and 0.2 mL of methanesulfonic acid (Notes ll4 and 12). The reaction mixture is heated under reflux for 24 hr. The solution is cooled to room temperature, diluted with about 200 mL of methylene chloride, and neutralized with dilute, cold sodium bicarbonate solution (Note 13). The organic layer is dried over anhydrous sodium sulfate and concentrated on a rotary evaporator to remove most of the methylene chloride. Fractional distillation of this residue under reduced pressure (the receiver is cooled with an ice-salt mixture) yields 48.8 g (75%) of product, bp 64-65°C (0.3 mm).3,5,6... 

Photolysis of the arene complexes in the presence of monodentate ligands, e.g. carbon monoxide, leads to new complexes of the type CpFe(L) whereas in pure aprotic solvents, ferrocene and iron salts are formed Investigation of the photo-lytic reaction of an iron arene complex with excess ethylene oxide in methylene chloride solution (Meier and Rhis ) showed that a crystalline crown ether complex (structure shown in Fig. 9) was obtained in high yield. Only traces of dioxane could be detected. 

Esterification is usually effected by refluxing the acid and alcohol with a small amount of sulfuric acid, hydrogen chloride, or arylsulfonic acid. The equilibrium is shifted to the right by an excess of one of the reactants or by removal of water either by azeotropic distillation or by means of a suitable drying agent. The necessity for continuous drying is eliminated when methylene or ethylene chlorides are used as solvents for the reaction. A small amount of an acid chloride such as thionyl chloride, acetyl chloride, or stearoyl chloride has proved superior to hydrogen chloride as a catalyst for certain esterifications at room temperature. ... 

We have already mentioned that Dorfman and collaborators have developed a versatile technique to observe ort-lived carbenium ions in solution generated by dissociative pulse radiolysis. This novel approach to the characterisation of transient species has also allowed this schod to measure the rate constants of many electrophilic reactions between carbenium ions (the benzylium ion in particular) and various nucleophiles. In the first paper of the series Jones and Dorfman reported the rate constants of the benzylium ion reaction with methanol, ethanol, the bromide and the iodide ions in ethylene chloride at 24 C. Values of about 5 x 10 sec were obtained for the halide ions and of around 10 sec for the alcohols. Later studies confirmed that the reaction of halide ions vrith benzylium, diphenyl-methylium and triphenylmethylium ions is at the limit of diffusion control. Reaction rate constants of these three carbenium ions with amines and alcdiols were also reported in the same paper. More recently, these studies have been extended to include cyclopropylphenylmetiiylium ion as electrophile, ammonia as nucleophile and methylene chloride and trichloroethane as solvents These results are extremely... 

The polymerisation of this monomer by stable carbenium salts was first reported by Sauvet et who only remarked that at —70°C in methylene chloride, about 30% yield was obtained in two hours with a 10 M concentration of trityl hexachloroanti-monate. In the same year, Higashimura et al. measured the rate of interaction between trityl pentachlorostannate and a-methylstyrene at 30-60°C in ethylene chloride and mixtures of this solvent with benzene. They monitored the disqipearance of the characteristic visible bands of the trityl ion as the reaction proceeded. Good first order plots were obtained and the external order in monomer was found to be unity so that kinetically the reaction was bimolecular with a kj of 1.3 min at 30°C in pure eth-... 

Addition reactions (1. 29). 1,5-Dichloropentanc-3-onc can be prepared by reaction of 3-chloropropionyl chloride with ethylene in methylene chloride in the presenee of anhydrous aluminum chloride. The yield of produci as a dark brown oil is 9.1 96%. 

Methyl esters. A convenient method for the conversion of acids into their methyl esters involves refluxing the acid (1 mole) with methanol (3 moles), ethylene dichloride (300 ml., methylene chloride can also be used), and sulfuric acid (3 ml. for an aliphatic acid, 15 ml. for aromatic) for 6-15 hrs. (overnight is convenient). The reaction mixture is diluted with water, and the organic layer is washed with sodium carbonate solution and dried, and the solvent is removed. A number of aliphatic and aromatic acids afford methyl esters in yields of 87-98°%. ... 

Engel and Rakhit found that selective ketalization of the 12-keto group of the 12,20-diketone (1) by reaction with ethylene glycol and boron trifluoride etherate proceeds best with methylene chloride present as co-solvent to provide a homogeneous medium. Without the cosolvent, the yield was 57%. 

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