Solvent extraction dimethylformamide

The principal route for production of isoprene monomer outside of the CIS is recovery from ethylene by-product C streams. This route is most viable where ethylene is produced from naphtha or gas oil and where several ethylene plants are located in relatively close proximity to the isoprene plant. Although the yield of isoprene per mass of ethylene is quite low, there is enough ethylene produced to provide a large portion of demand. Because of the presence of / -pentane in these streams which a2eotropes with isoprene, extractive distillation must be used to recover pure isoprene. Acetonitrile is the most common solvent, but dimethylformamide is also used commercially. 

Table 2.3 as a completely worked out example using quantitative solvent extraction, ash content determination, TGA, FTIR, XRF, GC-MS, HS-GC-MS, PyFTIR, ICP, and s-NMR. Information on the cure and antidegradant systems was obtained (assigned species/possible origin), as follows cyclohexane thiol/CBS accelerator benzothiazole/MBT, MBTS or CBS accelerators N, A-dimethylformamide/TMTD accelerator phthalim-ide/Santoguard PVI and IV-phenylbenzene amine/possi-bly a diphenyl/acetone amine antioxidant. 

The transesterification of sucrose has been performed with a fatty acid ester of a volatile alcohol in the presence of an alkaline catalyst in a dipolar, aprotic solvent.142 The reaction of sucrose (293 mmoles) with methyl dodecanoate (293 mmoles) in A/,N-dimethylformamide in the presence of sodium methoxide in a pressure bomb for 8 h at 130° gave, after solvent extraction and crystallization, sucrose mono(dodecanoate) (m.p. 72-80° [a]D+52°) in 50% yield.142 Commercialization of these sucrose esters has so far been limited, in part because of the use of expensive solvents, and, in part, because solvent remaining in the product makes it unsuitable for use as a food emulsifier. In view of this situation, methods have been developed in which the use of toxic and expensive solvents has been avoided. 

A better method is to first add an equal volume of dimethylsulfoxide (DMSO) or dimethylformamide (DMF) to the aqueous sample. This breaks both biological and encapsulation membranes and pulls polar and nonpolar material into solution. The second step is to dilute the sample with 10 volumes of water. At this point, nonpolars can be removed by solvent extraction or with a Cig SFE. Charged molecules can be recovered with pH-controlled extraction or with ion pairing reagents. The DMSO or DMF stays with the water layer. Customers have told me they can achieve almost complete recovery of both fat-soluble and water-soluble vitamins from polymer-encapsulated mixtures. Vitamins are encapsulated to protect potency from air-oxidation. Water-soluble vitamins have nonpolar encapsulation fat-soluble vitamins have polar encapsulation. Either vitamin can be extracted by themselves, but they are difficult to extract under the same condition unless DMSO or DMF are used to break both capsules. 

Acylthiophenes. Manufacturing methods introducing the carboxaldehyde group into the 2- or 5-positions of thiophene and alkylthiophenes utilize the Vilsmeier-Haack reaction. To synthesize 2-thiophenecarboxaldehyde (Table 5), a controlled addition of phosphoms oxychloride to thiophene in A ,A-dimethylformamide is carried out, causing the temperature to rise. Completion of the reaction is followed by an aqueous quench, neutralization, and solvent extraction to isolate the product. 

Purification. For polymerization, butadiene that is at least 99 mol% pure is required. Although alkynes are the most troublesome impurities, separation of the butadiene from other C4 products is also necessary. Simple fractional distillation is effective for removing the light (C3) and heavy (C5) ends from butadiene, but not for removing the various C4 species because of the closeness of the boiling points to each other and to butadiene. Further complicating purification, butadiene forms azeotropes with re-butane and 2-butene. The most widely used recovery systems are extraction with aqueous cuprous ammonium acetate (CAA) and solvent extractions with furfural, acetonitrile, dimethylformamide, dimethylacetamide, or AT-methylpyrrolidinone (65,66). 

Solvent extraction. This purification method is based on the alteration of the relative volatilities of the C4 hydrocarbons by selective solvents. The volatilities follow the order of the boiling points. 1-Bntene (bp = —6.3°C), for example, is more volatile than butadiene (bp = —4.4°C) n-bntane (bp = —0.5°C) is less volatile. Selective solvents change this order, making the impurities more volatile than butadiene. Hence, separations become easier. Furfural (77), acetonitrile (78), A(//-dimethylformamide (79), A(,A(-dimethylacetamide (80), and iV-methylpyrolidinone (81) appear to be most widely used (82). y3-Methoxyproprionitrile (78), dimethylsulfoxide (83), and A(-acetylmorpholine (84) have also been studied. The commercial processes generally do not require prehydrogenation. They employ countercurrent extraction of the C4 stream where the butanes and butenes are removed at the top, and the butadiene-rich solvent at the bottom. The butadiene is stripped from the solvent and further purified by fractional distillation. The butadiene is at least 99% pure and contains a few ppm acetylenes. 

Solvent extraction utilizes organic solvents to absorb and separate the organic components (mainly isoprene) from the fermentor off-gas. Different from the polar solvents (e.g., acetonitrile, dimethylformamide, Af-methylpyrrolidone), which are often used in the industrial extraction of petroleum-based isoprene, isoparaffin [50], and isopropyl myristate [5] are required to extract bioisoprene. According to the patents of biotech companies, isoparaffin can efficiently extract isoprene from the fermentor off-gas, while isopropyl myristate can be used as a solvent for the in situ extraction of bioisoprene from its microbial host. An equal-weight mixture of sulfolane and methyl carbitol was also reported to selectively extract isoprene from isoprene-containing steam [51], but its application for the recovery of bioisoprene has not been examined yet. 

The experimental conditions for conducting the above reaction in the presence of dimethylformamide as a solvent are as follows. In a 250 ml. three-necked flask, equipped with a reflux condenser and a tantalum wire Hershberg-type stirrer, place 20 g. of o-chloronitrobenzene and 100 ml. of diinethylform-amide (dried over anhydrous calcium sulphate). Heat the solution to reflux and add 20 g. of activated copper bronze in one portion. Heat under reflux for 4 hours, add another 20 g. portion of copper powder, and continue refluxing for a second 4-hour period. Allow to cool, pour the reaction mixture into 2 litres of water, and filter with suction. Extract the solids with three 200 ml. portions of boiling ethanol alternatively, use 300 ml. of ethanol in a Soxhlet apparatus. Isolate the 2 2- dinitrodiphenyl from the alcoholic extracts as described above the 3ueld of product, m.p. 124-125°, is 11 - 5 g. 

In a lOOmL round-bottomed flask fitted with a magnetic stirrer is placed a mixture of palladium (II) chloride (89mg, O.Smmol), p-benzoquinone (5.94g, 55mmol) and 7 1 dimethylformamide/water (20mL). To the solution, t-decene [substitute safrole for this compound) (7.0g, 50mmc4) is added in 10 min and the mixture is stirred at room temperature for 7h. The solution is poured into cold 3 normal hydrochloric acid (lOOmL) and extracted with 5 portions of ether. The extracts are combined and washed with three portions of 10% aqueous sodium hydroxide solution and a portion of brine, and then dried After removal of the solvent, the residue is distilled to give 2-decanone [P2P] yield 6.1g (78%). 

Extraction of hemiceUulose is a complex process that alters or degrades hemiceUulose in some manner (11,138). Alkaline reagents that break hydrogen bonds are the most effective solvents but they de-estetify and initiate -elimination reactions. Polar solvents such as DMSO and dimethylformamide are more specific and are used to extract partiaUy acetylated polymers from milled wood or holoceUulose (11,139). Solvent mixtures of increasing solvent power are employed in a sequential manner (138) and advantage is taken of the different behavior of various alkaUes and alkaline complexes under different experimental conditions of extraction, concentration, and temperature (4,140). Some sequences for these elaborate extraction schemes have been summarized (138,139) and an experimenter should optimize them for the material involved and the desired end product (102). 

Liquid—hquid extraction can be used to obtain high purity linoleic acid from safflower fatty acids or linoleic acid from linseed fatty acids using furfural and hexane as solvents (18). High purity linoleic acid has been obtained from sunflower fatty acids using a dimethylformamide and hexane solvent system (19). 

A pressure safe glass bottle containing 7.4 g (0.05 mol) of potassium thio-phenoxide and 50 mL of dimethylformamide is placed under vacuum The bottle IS charged with 2 7 bars of bromotnfluoromethane and shaken for 3 h. The reaction is slightly exothermic. The mixture is poured in 100 inLof 17% hydrochloric acid The aqueous phase is extracted with hexane. The organic layer is washed with water and dried over potassium carbonate The solvent is evaporated, and the residue is distilled to give 5 5 g (62%) of trifluoromethylthiobenzene (bp, 77-78 C at 754 mm of Hg). 

Prepares solution of sodium methylate by dissolving 3.9 g of sodium metal in 500 ml of methanol. Add 39.0 g of 7-chloro-1,3-dihydro-5-phenyl-2H-1,4-benzodiazeplne-2-one. Evaporate the reaction mixture to a residue and dissolve the residue in 170 ml of dimethylformamide. Add 30 g of 2,2,2-trifluoroethyl Iodide and stir at room temperature for Vi hour, then heat to 60°C to 70°C for an additional 7 hours. Add 19 g of 2,2,2-trifluoroethyl iodide and resume the heating and stirring at 60°C to 70°C for an additional 16 hours. Filter off the solids and evaporate the filtrate to a residue in vacuo. Triturate the residue with water and extract with ethyl ether. Wash the ethereal extract with water, dry over anhydrous sodium sulfate and evaporate the solvent to a residue. 

IB) 21-Chloro-90i-fluoro- -pregnene-11 160l,170i-triol-3,2Q-d ane 16,17-acetonlde A solution of 200 mg of the acetonide 21-mesylate from part (A) and 900 mg of lithium chloride in 25 ml of dimethylformamide is kept at 100°C for 24 hours. The mixture is poured on ice, extracted with chloroform and the chloroform extract washed with water and dried over sodium sulfate. Evaporation of the solvent in vacuo furnishes the crystalline chloride, which after recrystallization from acetone-ethanol has a melting point about 276°C to 277°C. 

To a stirred and refluxing solution of 40 parts of benzene and 35 parts of dimethylformamide (both solvents previously dried azeotropically) are added successively 1.6 parts of sodium hydride and 7.7 parts of Ct-(2,4-dichlorophenyl)imidazole-1-ethanol, (coolingon ice is necessary). After the addition is complete, stirring and refluxing is continued for 30 minutes. Then there are added 7.8 parts of 2,6-dichlorobenzyl chloride and the whole is stirred at reflux for another 3 hours. The reaction mixture is poured onto water and the product 1-[2,4-dichloro-/3 (2,6-dichlorobenzyloxy)phenethyl] imidazole, is extracted with benzene. The extract is washed twice with water, dried, filtered and evaporated in vacuo. The bese residue is dissolved in a mixture of acetone and diisopropyl ether and to this solution is added an excess of concentrated nitric acid solution. The precipitated nitrate salt is filtered off and recrystallized from a mixture of methanol and diisopropyl ether, yielding 1-[2,4-dichloro- (2,6-dichlorobenzyl-oxv)phenethyl] imidazole nitrate melting point 179°C. 

Vat dyes (the best known are Tyrian purple, indigo and woad) are insoluble in water. Before dyeing, they must be reduced into water-soluble leucoforms. After impregnation of the textile, dyestuffs are again oxidized into colour forms. As far as their extraction is concerned, aprotic solvents are usually recommended, e.g. pyridine, dimethylformamide or dimethylsulfoxide. 

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