Dimethylformamide dispersion

Carbamate nerve agents have been dissolved in both water and organic solvents to facilitate handling, enhance dispersal, or increase the ease of percutaneous penetration by the agents. Percutaneous enhancement solvents include dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylpalmitamide, N,N-dimethyldecanamide, and saponin. Color and other properties of these solutions may vary from the pure agent. Odors will be dependent on the characteristics of the solvent(s) used. 

A solution of the sodium salt of the cyclic 2,2-dimethyltrimethylene phosphite was prepared by the addition of a 57% mineral oil dispersion of sodium hydride (8.42 g, 0.2 mol) to a solution of the cyclic 2,2-dimethyltrimethylene phosphite (30 g, 0.2 mol) in dry dimethylforma-mide (150 ml) while the temperature was maintained below 30°C. To the resultant solution was added a solution of l,4-bis(chloromethyl)-2,5-dimethylbenzene (20.3 g, 0.1 mol) in dry dimethylformamide (150 ml). After the addition was complete and the exotherm subsided, the reaction mixture was heated at 60 to 65°C for 15 h. After the reaction mixture was cooled to room temperature, the solid that formed was... 

The 3M Company manufactures a continuous polycrystalline alumina—silica—boria fiber (Nextel) by a sol process (17). Aluminum acetate is dissolved in water and mixed with an aqueous dispersion of colloidal silica and dimethylformamide. This mixture is concentrated in a Rotavapor flask and centrifuged. The viscous mixture is then extruded through spinnerettes at 100 kPa (1 atm) the filaments are collected on a conveyor and heat-treated at 870°C to convert them to metallic oxides. Further heating at 1000°C produces the 10-pm diameter aluminum borosilicate fibers, which are suitable for... 

DMF as solvent pORMIC ACID AND DERIVATIVES - DIMETHYLFORMAMIDE] (Vol 11) Polyurethane dispersions... 

B. Orcinol Monomethyl Ether. In a 1-1. three-necked flask equipped with a magnetic stirrer, a condenser, a dropping funnel, and a nitrogen inlet are placed 250 ml. of dry dimethyl-formamide (Note 6) and 22 g. (0.55 mole) of sodium hydride (60% oil dispersion). The suspension is stirred under an atmosphere of dry nitrogen and cooled with an ice bath while a solution of 31 g. (37 ml., 0.50 mole) of ethanethiol (Note 7) in 150 ml. of dry dimethylformamide (Note 6) is added slowly from the dropping funnel over a period of 20 minutes. The ice bath is removed and stirring is continued for an additional 10 minutes. A solution of 38.0 g. (36.5 ml., 0.25 mole) of orcinol dimethyl ether in 100 ml. of dry dimethylformamide (Note 6) is added in one lot, and the mixture is refluxed under an atmosphere of dry nitrogen for 3 hours (Notes 8 and 9), The mixture... 

In the next step, 118 mg of sodium hydride (55% dispersion in mineral oil) was suspended in 20 ml of dimethoxyethane under argon. To the suspension was added a solution of 689 mg of dimethyl 3-methyl-2-oxohept-5-yne-phosphonate in 10 ml of dimethylformamide, and the mixture was stirred for 30 min at a room temperature. 

A solution of N-(4-pyridinyl)-lH-indol-l-amine (6 g) in 25 ml of dimethylformamide was slowly added to an ice-cooled suspension of NaH (1.3 g of 60% NaH dispersion in mineral oil was washed with hexanes, the liquid was decanted and the residual solid was dispersed in 5 ml of dimethylformamide). After anion formation, a solution of 1-bromopropane (4 g) in 5 ml of dimethylformamide was added. After one hour of stirring at ambient temperature, the reaction mixture was stirred with ice-water and extracted with dichloromethane. The organic extract was washed with water and saturated sodium chloride solution, was dried over anhydrous magnesium sulfate, filtered and concentrated to 8 g of oil. This oil was purified by HPLC (silica, ethyl acetate) and thereafter by column chromatography (alumina, ether) to give 6.4 g oil. This oil was converted to the maleate salt and recrystallized from methanol/ether to give 6.8 g of crystals, m.p. 115-116°C. 

A suspension of 29.8 mmol of sodium hydride (55 percent oil dispersion) in 40 ml of dry dimethylformamide is treated at 20-30°C with 27.1 mmol of (S)-6-bromo-1,2,3, lla-tetrahydro-5H-pyrrolo[2,l-c][l,4]benzodiazepine-5,11 (10H)-dione, the mixture is stirred in the above temperature range for 45 min and then at -35°C 27.1 mmol of diethylchlorophosphate are added dropwise thereto. 

To a stirred suspension containing 5.1 g of 57% sodium hydride dispersed in mineral oil and 150 ml of dimethylformamide was added in portions 32.6 g of ethyl l,4-dihydro-4-oxo-7-(4-pyridyl)-3-quinolinecarboxylate [tautomeric with ethyl 4-hydroxy-7-(4-pyridyl)-3-quinolinecarboxylate] followed by the addition of 18.7 g of ethyl iodide. The resulting reaction mixture was heated on a steam bath for three hours with stirring and then concentrated in vacuo to remove the solvent. The semisolid residue was shaken well with a mixture of chloroform and water, and a small quantity of amorphous brown solid was filtered off. The layers were separated and the chloroform layer was evaporated in vacuo to remove it. 

A mixture of 1.6 parts of 1H-1,2,4-triazole, 54 parts of N.N-dimethylformamide and 45 parts of benzene is stirred and refluxed for 2 h. After cooling, 0.78 parts of sodium hydride dispersion 78% are added and the whole is stirred for 30 min at room temperature. Then there are added 8.9 parts of cis-2-(bromomethyl)-2-(2,4-dichlorophenyl)-l,3-dioxolan-4-ylmethyl benzoate and stirring is continued overnight at 150°C. The reaction mixture is cooled and poured onto water. The product is extracted three times with benzene. The combined extracts are washed twice with water, dried, filtered and evaporated, yielding 8.5 parts of cis-[2-(2,4-dichlorophenyl)-2-(lH-l,2,4-triazol- l-ylmethyl)-l,3-dioxolan-4-ylmethyl]benzoate as a residue. 

To a stirred solution of 28.4 parts of 1H-1,2,4-triazole in 135 parts of N,N-dimethylformamide were added 11.4 parts of a sodium hydride dispersion 80% under nitrogen atmosphere. After stirring for 1 hour at room temperature, a solution of 40 parts of 6-[chloro(4-chlorophenyl)-methyl]-l-methyl-lH-benzotriazole in 90 parts of N,N-dimethylformamide was added to the mixture. The whole was stirred for 1 hour at 60°C. The reaction mixture was diluted with 50 parts of water and the whole was evaporated. The residue was extracted with ethyl acetate. The extract was washed with water, dried, filtered and evaporated. The residue was purified by column chromatography over silica gel using a mixture of dichloromethane and methanol (99 1 by volume) as eluent. The pure fractions were collected and the eluent was evaporated. The residue was crystallized from a mixture of 2-propanone and l,l -oxy-bis-ethane (ether). The product was filtered off and dried, yielding 13 parts (29.2%) of 6-[(4-chlorophenyl)-(lH-l,2,4-triazol-l-yl)methyl]-l-methyl-lH-benzotriazole MP 178.9°C. A resolution of enantiomers any usual method gave crystals from 2-propanol, MP 130-135°C. [a]D20 = 8.0° (plus or minus) (c = 10 in CH3OH). 

To a mixture of ethyl 4-oxo-3H-phthalazin-l-ylacetate (1 mole-equivalent) and sodium hydride (50% w/w dispersion in mineral oil) in dimethylformamide (150 ml) was added 2-bromomethyl-5-trifluoromethylbenzothiazole (1 mole-equivalent) and the resulting mixture stirred at room temperature for 1 hour. This reaction mixture was poured over ice-water (500 ml) sufficient 10% HCI was added to adjust the pH to about 4.0 and the precipitated crude solid was collected. This was chromatographed over silica gel to obtain the ethyl[4-oxo-3-(5-trifluoromethylbenzothiazol-2-yl)-3,4-dihydro-phthalazin-l-yl]acetate ... 

More important are the compounds formed by acidic hydrocarbons such as cyclopentadiene, indene, and acetylenes. These are obtained by reaction with sodium in liquid ammonia or, more conveniently, sodium dispersed in THF, glyme, diglyme, or dimethylformamide (DMF). 

Reduction of a,a -dibromo ketones. Reduction of 2,4-dibromo-2,4-dimethyl-pentane-3-one (1) with ultrasonically dispersed mercury in the presence of a ketone such as acetone leads to a 4-methylene-l,3-dioxolane (2) in about 50% yield. A similar reaction has been observed in the reduction of dibromo ketones with zinc in dimethylformamide (5, 221). 2-Oxyallyl cations such as a have been invoked as intermediates in reductions of dihalo ketones with various metals. 

A Some ambiguity must be attached to this statement in view of the conclusions reached by Luzzati el al. (1961) on the basis of small angle X-ray scattering studies from dilute solutions of polybenzyl-L-glutamate in dimethylformamide, pyridine, and TO-cresol. These authors conclude that the conformation of the polypeptide in these solutions is that of the 3io-helix (Donohue, 1953) and not that of the a-helix. The value of 6o = —630° in Eq. (13) was obtained from optical rotatory dispersion measurements with similar solutions, and therefore if the conclusions of Luzzati et al. are correct, this value characterizes the 3io-helix. It would then be necessary to determine whether the 6o value for the a-helix is significantly different. 

---