Volatile dichloromethane

Liquids examined by FAB are introduced into the mass spectrometer on the end of a probe inserted through a vacuum lock in such a way that the liquid lies in the target area of the fast atom or ion beam. There is a high vacuum in this region, and there would be little point in attempting to examine a solution of a sample in one of the commoner volatile solvents such as water or dichloromethane because it would evaporate extremely quickly, probably as a burst of vapor when introduced into the vacuum. Therefore it is necessary to use a high-boiling solvent as the matrix material, such as one of those listed in Table 13.1. 

Treatment of the Z-aldehyde 9 (R1 = R2 = H) with trifluoroacetic acid in dichloromethane at — 10 C, then with l,4-diazabicyclo[2.2.2]octane or /V,/V-diethylpyridin-4-amine, constitutes the first synthesis of 27/-azepine (10, R1 = R2 = H) which was isolated, with great difficulty and in very low yield (1 %), as a highly volatile, unstable oil, the structure of which was confirmed by high field H and 13CNMR spectroscopy.290 Similar treatment of the Z-alkenones 9a-d furnishes the thermally unstable (5)-2/7-azepines lOa-d in much higher yields.291... 

To avoid loss of the volatile epoxide, removal of the dichloromethane on a rotary evaporator is not recommended. 

The volatilities of both ferf-butylaminc and dichloromethane necessitate the use of an efficient condenser as a precaution, although the rate of reflux is generally not vigorous. In preparations where higher boiling amines are used, this precaution is less critical. 

Although these issues have already been briefly noted, they deserve a few additional comments. For freely water-soluble substrates that have low volatility, there are few difficulties in carrying out the appropriate experiments described above. There is, however, increasing interest in xenobiotics such as polycyclic aromatic hydrocarbons (PAHs) and highly chlorinated compounds including, for example, PCBs, which have only low water solubility. In addition, attention has been focused on volatile chlorinated aliphatic compounds such as the chloroethenes, dichloromethane, and carbon tetrachloride. All of these substrates present experimental difficulties of greater or lesser severity. 

There is an anomaly in the higher index value for dichloromethane compared with chloroform although dichloromethane is noted for being the less toxicity halogenous solvent. But this figure only reflects the extreme volatility of this substance since its LC50 is lower than the one for chloroform. There is probably a similar problem for acetonitrile, which is underestimated by this approach. 

Eluent components should be volatile. Solvents such as ethyl acetate, isopropyl ether, diethylketone, chloroform, dichloromethane, and toluene as modifiers and n-hexane as diluent are recommended for normal phase chromatography. For reversed-phase systems, methanol or acetonitrile are used as modifiers. Such components as acetic acid or buffers, as well as ion association reagents, should be avoided. 

After the identification of the suitable compound bands, silica gel is scraped off the plates, placed in short glass columns, Pasteur pipettes, or sintered filter funnels, and fractions are recovered with such volatile solvents as ethyl acetate or dichloromethane. 

To the acidic distillate in the 125-mL separatory funnel, add 5 mL of 50% sodium hydroxide and 15 mL of dichloromethane. Cap the separatory funnel tightly, and allow its contents to cool for 30 min. Heat created by the addition of caustic to the acidic distillate will cause some of the dichloromethane to volatilize, creating pressure in the funnel therefore, the cap must be secured tightly to the funnel. Escaping solvent will result in loss of analytes. Shake the funnel for 5 min on a mechanical shaker. Allow 15 min for phase separation after shaking the funnel. Drain the lower dichloromethane layer into a second 125-mL separatory funnel. Extract the aqueous layer a second time with 15 mL of dichloromethane. Following shaking of the funnel and phase separation, combine both dichloromethane layers in the same 125-mL separatory funnel. 

An explosion was experienced dining work up of an epoxide opening reaction involving acidified sodium azide in a dichloromethane/dimethyl sulfoxide solvent. The author ascribes this to diazidomethane formation from dichloromethane [1]. A second report of an analoguous accident, also attributed to diazidomethane, almost certainly involved hydrogen azide for the cold traps of a vacuum pump on a rotary evaporator were involved this implies an explosive more volatile than dichloromethane. It is recommended that halogenated solvents be not used for azide reactions [2]. 

The organic phase is washed with 150 mL of water and the combined aqueous phases are extracted with 300 mL of dichloromethane. The aqueous solution is then carefully treated with 300 mL of 2 N aqueous sodium hydroxide and the mixture is extracted 4 times with 150 mL of methylene chloride. The combined organic extracts are washed with brine, dried over anhydrous sodium sulfate, and filtered. Removal of volatile material under reduced pressure (water aspirator) gives 47-50 g (89-94%) of racemic diamine as a pale yellow solid, mp 81-82°C, lit.4 mp 82°C corr. (Note 10). 

Equivalent amounts of aldehydes and alkoxytrimethylsilanes react to form unsymmetrical ethers in near quantitative yields in the presence of either trimethylsilane or triethylsilane and catalytic amounts (ca. 10 mol%) of TMSI in dichloromethane.329,333,334,341 The procedure is particularly convenient experimentally when trimethylsilane is used with TMSI because the catalyst provides its own color indicator for the reduction step (color change from deep violet to vivid red-gold) and the only silicon-containing product following aqueous workup is the volatile hexamethyldisiloxane (bp 99-100°). It is possible to introduce trimethylsilane (bp 7°) either as a previously prepared solution in dichloromethane or by bubbling it directly into the reaction mixture. Cyclohexyloxytrimethylsilane and n-butanal react by this method to give a 93% isolated yield of n-butyl cyclohexyl ether (Eq. 183).334... 

This method was first reported by Vanderhoff [82] for the preparation of artificial latexes. The polymer and drug are dissolved or dispersed in a volatile water-immiscible organic solvent, such as dichloromethane, chloroform, or ethyl acetate. This is emulsified in an aqueous continuous phase containing a surfactant, such as poly(vinylalcohol), to form nanodroplets. The organic solvent diffuses out of the nanodroplets into the aqueous phase and evaporates at the air/water interface, as illustrated in Figure 6. The solvent is removed under reduced pressure. The nanodroplets solidify and can be separated, washed, and dried to form a free-flowing powder. 

Inorganic residue is rinsed with diethyl ether. The combined ethereal extracts are added to the filtered solution and the mixture is concentrated to ca. 10 mL by evaporation of the solvent under reduced pressure. The residue is treated with a saturated solution of potassium chloride (KCI) (50 mL), extracted with dichloromethane (3 x 50 mL), and the combined extracts are dried over anhydrous sodium sulfate (Note 21). Removal of volatile material under reduced pressure gives an oil that is flash Chromatographed (silica, diethyl ether - petroleum ether 1 1) to afford 1.77 g (62%) of 2-0-benzyl-3,4-isopropylidene-D-erythrose (Note 22). 

Volatile alkyl halogenides such as methyl iodide, methylene chloride etc., react quantitatively with the solid methylamine salt of 5-benzylidene- (39a) [32] and 5,5-diphenylthiohydantoin (37) to form the anticonvulsive solids 225 and 226 in quantitative yield [28] (Scheme 30). Unlike the solution reaction, only the S-alkylation occurs under gas-solid conditions. Furthermore, various dialkylamidodithiolate salts 228 react readily with dichloromethane at 80 °C. The salts with the quaternary cations react at room temperature and it is also possible to catalyze the reaction of the sodium salt by admixture of 10% of the corresponding phase transfer bromides [28]. These reactions have been tuned for removal of dichloromethane from loaded air streams [28]. 

C. 1- Butyl-3-methylimidazolium hexafluorophosphate. A 1-L, one-necked, round-bottomed flask (Note 13) is charged with 65.6 g (0.37 mol, 1 equiv) of 1- butyl-3-methylimidazolium chloride, and 69.3 g (0.37 mol, 1 equiv) of potassium hexafluorophosphate (Note 19) in 70 ml of distilled water. The reaction mixture is stirred at room temperature for 2 hr affording a two-phase system. The organic phase is washed with 3 X 50 mL of water and dried under reduced pressure (0.1 mbar, 0.001 mm). Then 100 ml of dichloromethane and 35 g of anhydrous magnesium sulfate are added. After 1 hr, the suspension is filtered and the volatile material is removed under reduced pressure (0.1 bar, 0. 1 mm) at 30°C for 2 hr to afford 86.4 g (0.29 mol, 81%) of 1- butyl-3-methylimidazolium hexafluorophosphate as alight yellow viscous liquid, mp 10°C (Notes 20 and 21). 

According to the vendor, this technology is capable of removing chlorinated hydrocarbons, aliphatic hydrocarbons, aromatics, benzene, toluene, xylene, carbon tetrachloride, vinyl chloride, dichloromethane, and trichloroethane. Polychlorinated biphenyls (PCBs), polyaromatic hydrocarbons (PAHs), and volatile inorganic solvents can also be removed. The technology is currently in use and is commercially available. 

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