Solvent systems methylene

Thin-layer chromatography was carried out on DC-Fertigplatte Merck Kieselgel F254 supplied by Firma Merck AG, 61 Darmstadt, Germany. For the solvent system methylene chloride/methanol (97/3) the product has an Rf value of 0.45. 

CeUulose triacetate is insoluble in acetone, and other solvent systems are used for dry extmsion, such as chlorinated hydrocarbons (eg, methylene chloride), methyl acetate, acetic acid, dimethylformamide, and dimethyl sulfoxide. Methylene chloride containing 5—15% methanol or ethanol is most often employed. Concerns with the oral toxicity of methylene chloride have led to the recent termination of the only triacetate fiber preparation faciHty in the United States, although manufacture stiH exists elsewhere in the world (49). 

Aqueous salt solutions such as saturated 2inc chloride [7646-85-7] or calcium thiocyanate [2092-16-2] can dissolve limited amounts of cellulose (87). Two non-aqueous salt solutions are ammonium thiocyanate [1762-95-4]— uoamonia. and lithium chloride /744Z-4/A/—dimethyl acetamide [127-19-5]. Solutions up to about 15% can be made with these solvents. Trifluoroacetic acid [76-05-17—methylene chloride [75-09-2] and /V-methy1morpho1ine N-oxide [7529-22-8]—(92—94) are two other solvent systems that have been studied (95). 

Figure 2.15. HC HSQC experiment (contour plot) of a-pinene [ CDCI3, 5 % v/v, 25 °C, 125 MHz for C, 500 MHz for h, 4 scans, 256 experiments]. This experiment gives the same information as Fig. 2.14 within 8 minutes instead of two hours required for the CH-COSY in Fig. 2.14 due to higher sensitivity because of proton detection and stronger magnetic field. Deviations of proton shifts from those in Fig. 2.14 arise from the change of the solvent. The methylene protons collapsing in Fig. 2.14 at Sh = 2.19 (200 MHz) display in this experiment an AB system with = 2.17 and Sg = 2.21 (500 MHz)...

A recently discovered (2) oxidizing system promises to become very important for the oxidation of acid-sensitive compounds. The reagent is chromium trioxide-pyridine complex, which may be isolated after preparation and employed in nonaqueous solvents (usually methylene chloride). A remarkable feature of the reagent is that good yields of aldehydes are obtained by direct oxidation of primary alcohols. The preparation of the reagent and its use are given. 

Preparation of siloxane-carbonate segmented copolymers by interfacial polymerization involves the reaction of carboxypropyl-terminated siloxane oligomers with bisphenol-A and phosgene, in the presence of a strong base and a phase transfer catalyst, in water/methylene chloride solvent system l50 192), as shown in Reaction Scheme XIV. 

As previously discussed, solvents that dissolve cellulose by derivatization may be employed for further functionahzation, e.g., esterification. Thus, cellulose has been dissolved in paraformaldehyde/DMSO and esterified, e.g., by acetic, butyric, and phthalic anhydride, as well as by unsaturated methacrylic and maleic anhydride, in the presence of pyridine, or an acetate catalyst. DS values from 0.2 to 2.0 were obtained, being higher, 2.5 for cellulose acetate. H and NMR spectroscopy have indicated that the hydroxyl group of the methy-lol chains are preferably esterified with the anhydrides. Treatment of celliflose with this solvent system, at 90 °C, with methylene diacetate or ethylene diacetate, in the presence of potassium acetate, led to cellulose acetate with a DS of 1.5. Interestingly, the reaction with acetyl chloride or activated acid is less convenient DMAc or DMF can be substituted for DMSO [215-219]. In another set of experiments, polymer with high o -celliflose content was esterified with trimethylacetic anhydride, 1,2,4-benzenetricarboylic anhydride, trimellitic anhydride, phthalic anhydride, and a pyridine catalyst. The esters were isolated after 8h of reaction at 80-100°C, or Ih at room temperature (trimellitic anhydride). These are versatile compounds with interesting elastomeric and thermoplastic properties, and can be cast as films and membranes [220]. 

A similar technique, the so-called spontaneous emulsification solvent diffusion method, is derived from the solvent injection method to prepare liposomes [161]. Kawashima et al. [162] used a mixed-solvent system of methylene chloride and acetone to prepare PLGA nanoparticles. The addition of the water-miscible solvent acetone results in nanoparticles in the submicrometer range this is not possible with only the water-immiscible organic solvent. The addition of acetone decreases the interfacial tension between the organic and the aqueous phase and, in addition, results in the perturbation of the droplet interface because of the rapid diffusion of acetone into the aqueous phase. 

Different procedures of this dehydrogenation are thoroughly discussed in the monograph (4). It is only necessary to note here that the process is carried out mainly as halogenation-dehydrohalogenation. The intermediate hydroximoyl halide is frequently not isolated (Scheme 1.3). The reaction is convenient for both the generation of unstable nitrile oxides (in the presence of a dipolarophile) and the preparation of stable nitrile oxides. It is usually carried out in a two-phase water-organic solvent system with methylene dichloride as the preferred solvent. 

However, the effects on the rates in nonpolar solvent systems is dramatically larger and often of apparent contradiction. For example, the Hammett rho value for the oxidation of substituted methyl cinnamates and cinnamic acids by tetrabutylammonium permanganate in methylene chloride solutions is positive (33,49). See Figure lb. However, a rho value of converse sign (-0.6) is obtained from a Taft plot (Figure Ic) for the oxidation of vinyl ethers in aqueous tetrahydrofuran (33,50). For many other compounds the Hammett relationships are no longer linear, but concave upward ... 

The solvent system 70/30 methylene chloride/ hexafluorolsopropanol has been In use In our laboratory since 1977 as a solvent for poly(ethylene terephthalate) (PET) and other semlcrystalllne polar polymers. Some advantages of this solvent are It provides rapid room temperature solubilization It Is transparent at 254 nm (U.V.) It Is a solvent for polystyrene and It Is a minimum boiling azeotrope. Disadvantages are Its low boiling point (36 C) and the potential safety hazard It represents. The combination of appropriate HPGPC equipment and this solvent system reveals heretofore unrecognized features of the molecular weight distributions of polyesters ... 

Water is a possible axial ligand for the transient Ni(PP) in these systems and has been shown to form weak complexes with other nickel porphyrin species (18). While we cannot unequivocally rule out weak, transient ligation, the observation of similar transient behavior in Ni(OEP) and Ni(PPDME) in noncoordinating, nonaqueous, solvents (toluene, methylene chloride (9, unpublished results)) leads us to conclude that the transient behavior of the Ni(PP) in acetone/water is not predicated upon ligand binding. 

The furan products can be purified by flash chromatography and should be used at once. A mixture of ethyl acetate and methylene chloride is a good solvent system for flash chromatography. Small residues of silica tend to partly decompose these furans within two weeks. The products are hygroscopic. Diisopropyl ether-diethyl ether-hexane is a useful solvent system for recrystallization of solid furans. 

Methylene chloride was selected primarily on the basis of the following criteria (1) It is commonly referred to as the universal solvent or the one used most frequently in the extraction of semivolatile organics sorbed on polymeric sorbent media. Hence, the contaminant chemistry associated with this solvent system would be of the most use to resin users. (2) The physical and chemical properties of methylene chloride make it ideally suited for the extraction of semivolatile organics sorbed on polymeric sorbent media. 

A reconstructed ion chromatogram (GC-MS) containing extractable contaminants isolated from a typical lot of foam is shown in Figure 4. The qualitative composition of the extractable contaminants was provided by GC-MS. Contaminant profiles were identical for each of the two solvent systems employed, methylene chloride (1003 ) and ethyl ether/hexane (5/95). The contaminant chemistry shown here and again in Figure 5 in several instances is consistent with the manufacturing process data shown in the box, most notably the presence of residual toluene diisocyanate (starting materials, see Scheme II) and an aliphatic amine (possible reaction catalyst). 

When HPLC is used as part of the analysis, the mobile phase is typically a mixture of methanol and methyl-tert-butyl ether (i.e., 50 50, v/v), although other HPLC solvents for LC/MS using APCI (e.g., water, tetrahydrofuran) can be used. It is important to note that if combustible nonaqueous solvent systems are used, water or a halogenated solvent such as methylene chloride or chloroform should be added to the mobile phase postcolumn to suppress ignition in the ion source. In addition, the APCI source must be vented outside the laboratory and should not allow air into the ionization chamber. A scan range of m/z 300 to 1000 will include the known carotenoids and their most common esters. 

A systematic study has been developed by Christopoulou and Perkins (78). They employed three different types of detectors (differential refractometer, variable wavelength detector set at 205 or 232 nm, and infrared detector at 5.72 /zm) and three commercially packed columns (I, LC-Si, 250 X 4.6-mm ID, 5-/zm particle size II, LC-18, 250 X 4.6-mm ID, 5-/zm particle size III, LC-18, 150 X 4.6-mm ID, 5-/zm particle size). The various mobile phases used were system I, 1.5% isopropyl alcohol (IPA) in hexane system II, acetonitrile/acetone (1 1) system III, acetonitrile (spectra) system IV, acetonitrile/methylene chloride (3 1). Columns I and II were used with solvent systems I and II, respectively, and refractometry was the mode of detection. Column III was used with solvent system III and UV detection at 205 or 232 nm, as well as with solvent system IV and infrared detection at 5.72 /zm. 

The carbamate pesticides can also be determined by normal-phase chromatography on different columns. Silica (113-116), amine (51), and cyanopropyl (112) columns have been used for the determination of carbamate residues. These columns were used with different solvent systems, with isopropanol-heptane being the mobile phase producing generally better results and methylene chloride-heptane the preferred solvent system when nonpolar carbamates were present in the sample. Another mobile phase used was iso-octane-dioxane (113). Although normal-phase mode was for the most part satisfactory, reversed-phase mode gave generally superior results. 

The term oil and grease refers to a broad class of organic substances recovered from the sample matrices by extraction with an appropriate solvent. Such recovery, therefore, is characteristic of certain physical properties of the compounds, primarily the volatility of the compounds and their solubility in the extraction solvent. The solvent must be immiscible in water and volatile, as well as readily distilled on a water bath. Many solvents or mixed-solvent systems should be suitable for the extraction of oil and grease in aqueous and nonaqueous samples. These include petroleum ether, w-hexanc, methylene chloride, methyl ter/-butyl ether, and trichlorotrifhroroethan (freon). These solvents are listed in Table 1. 

A mixture of norcodeine hydrochloride (11.48 g, 27.8 mmol), (chloromethyl)cyclopropane (5.14 g, 55.6 mmol), sodium carbonate (14.73 g, 139.0 mmol), and potassium iodide (4.61 g, 27.8 mmol) in ethanol (250 ml) was heated at reflux for 20 hr, cooled, and evaporated in vacuo to dryness. The residue was basified with NH4OH, and extracted with methylene chloride. The extract was washed with water and evaporated in vacuo to dryness. The residue (11.7 g) was chromatographed on silica gel with a eluting solvent system of methanol/ethyl acetate (10/90) to give 17-cyclopropylmethylnorcodeine (10.68 g, 91% yield). 

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