Toluene solution

During this period hydrogen chloride continues to be liberally evolved, and the product darkens considerably in colour. Now pour the product cautiously into 500 ml. of dilute hydrochloric acid and 100 g. of chipped ice in a separating-funnel, and shake the mixture thoroughly this operation removes the dark colour, and the toluene solution becomes yellow. Run off the lower acid layer, and extract the toluene three times with water. Finally dry the toluene solution over calcium chloride. 

The toluene solution from the previous step was treated with an ethanol solution of NaOEt (0.1 mol in 100 ml) at O C. When about a quarter of the solution had been added a thick precipitate formed and ether (100 ml) was added to maintain a fluid slurry. The remainder of the NaOEt was added and the slurry was stirred overnight. The solid was collected and w ashed with ether. It was then mixed with ether (200 ml) and 2NHC1 (75 ml) and shaken in a separatory funnel until the solid dissolved. The ether layer was washed with 2NHHC1 (2 X 50ml) and water and dried over MgS04. The solution was decolorized with Magnesol and evaporated to give the a-nitro ester as a red oil. 

Potassium Amides. The strong, extremely soluble, stable, and nonnucleophilic potassium amide base (42), potassium hexamethyldisilazane [40949-94-8] (KHMDS), KN [Si(CH2]2, pX = 28, has been developed and commercialized. KHMDS, ideal for regio/stereospecific deprotonation and enolization reactions for less acidic compounds, is available in both THF and toluene solutions. It has demonstrated benefits for reactions involving kinetic enolates (43), alkylation and acylation (44), Wittig reaction (45), epoxidation (46), Ireland-Claison rearrangement (47,48), isomerization (49,50), Darzen reaction (51), Dieckmann condensation (52), cyclization (53), chain and ring expansion (54,55), and elimination (56). 

The most recent, and probably most elegant, process for the asymmetric synthesis of (+)-estrone appHes a tandem Claisen rearrangement and intramolecular ene-reaction (Eig. 23). StereochemicaHy pure (185) is synthesized from (2R)-l,2-0-isopropyhdene-3-butanone in an overall yield of 86% in four chemical steps. Heating a toluene solution of (185), enol ether (187), and 2,6-dimethylphenol to 180°C in a sealed tube for 60 h produces (190) in 76% yield after purification. Ozonolysis of (190) followed by base-catalyzed epimerization of the C8a-hydrogen to a C8P-hydrogen (again similar to conversion of (175) to (176)) produces (184) in 46% yield from (190). Aldehyde (184) was converted to 9,11-dehydroestrone methyl ether (177) as discussed above. The overall yield of 9,11-dehydroestrone methyl ether (177) was 17% in five steps from 6-methoxy-l-tetralone (186) and (185) (201). 

Dibismuthines are very sensitive to oxidation. Thus tetramethyldibismuthine fumes ia air, and tetraphenyldibismuthine ia toluene solution rapidly absorbs oxygen. Under controlled conditions, dibismuthines react with chalcogens resulting ia cleavage of the bismuth—bismuth bond and iasertion of a chalcogen atom (105,138,140—142) ... 

Poly(phenylene ether) Alloys. Poly(phenylene ether) resins (91), composed of phenoHc monomers, have a very high T. The commercial resins are based on 2,6-dimethylphenol. The resin is produced by oxidative polymerization in toluene solution over an amine catalyst (see also PoLYETPiERS, aromatic). 

Homoallyl alcohol (3) Metalation of (E) butene (1 05 equiv) with n BuLI (t equiv) and KOtBu (1 equiv) in THF at SO C for 15 mm followed by treatment of (E)-crotyl potassum salt with B(OiPr)3 at 79°C gave after quenching with 1 N HCI and extraction with EtjO containing 1 equiv of diisopropyl tartarate. the crotyl boronate 2 A solution of decanall (156 mg 1 mmol) was added to a toluene solution of 2 (1 1 15 equiv) (0 2 M) at 78 C containing 4A molecular sieves (15-20 mg/L) After 3 h at -78°1 N NaOH was added, followed by extraction and chromatography to afford 208 mg of 3 (90%), anti syn 99 1... 

Hydroxy-1,2,3,4-tetrahydrocrysene (2) A mixture of 4-keto-1,2 3 4-tetrahydrocrysene 1 (2 75 g, 11 mmol) and aluminium isopropoxide (8 2 g, 40 mmol) in PhMe (25 mL) was refluxed for 1 h After cooling, iPrOH (25 mL) was added and the formed acetone was distilled slowly maintaining the volume constant by addition of iPrOH After all acelone was distilled, the solution was acidified with 0% H2SO4 The separated toluene solution was evaporated to gwe 2 1 g of 2 (76%), mp 156-158 C... 

The submitters used trimethylalane available in a cylinder from Ethyl Corporation. Both neat trimethylalane and its 2 M solution in toluene gave comparable results. The toluene solution of trimethylalane is also available from Aldrich Chemical Company. 

Nitrophenyl isocyanate has been prepared by heating -nitrophenyl carbamyl chloride. The latter has been obtained by the action of phosgene on -nitroaniline in benzene-toluene solutions, and by the action of phosphorus pentachloride on methyl jii-nitrophenylcarbamate. The preparation given above is based upon recent publications of the authors. ... 

Physical properties of Fullerene C q. It does not melt below 360°, and starts to sublime at 300° in vacuo. It is a mustard coloured solid that appears brown or black with increasing film thickness. It is soluble in common organic solvents, particularly aromatic hydrocarbons which give a beautiful magenta colour. Toluene solutions are purple in colour. Sol in (5mg/mL), but dissolves slowly. Crysts of C o are both needles and plates. 

Wash the green solid with H2O, dry in a vacuum desiccator and recrystallise from MeOH. [J Phys Chem 62 440 1958.] The complex can be conveniently dehydrated by azeotropic distn with toluene and the crystals may be isolated by concentrating the toluene solution. [J Am Chem Soc 76 1970 1954.]... 

If material free from all traces of ethyl adipate is desired, time and material can be saved by omitting the first distillation (observation of the checkers). The toluene solution of the crude 2-carbethoxycyclopentanone is cooled to 0° and added slowly with stirring to 300 cc. of 10 per cent potassium hydroxide solution maintained below r°. Cold water is added until the... 

Reinhoudt, Gray, Smit and Veenstra prepared a number of monomer and dimer crowns based on a variety of substituted xylylene units. They first conducted the reaction of 1,2-dibromomethylbenzene and a polyethylene glycol with sodium hydride or potassium Z-butoxide in toluene solution. Mixtures of the 1 1 and 2 2 (monomer and dimer) products were isolated and some polymer was formed . The reaction was conducted at temperatures from 30—60° and appeared to be complete in a maximum of one hour. The authors noted that the highest yield of 1 1 cyclic product was obtained with disodium tetraethylene glycolate instead of dipotassium hexaethylene gly-colate (see also Chap. 2) . Chloromethylation of 1,3-benzodioxole followed by reaction with disodium tetraethylene glycolate afforded the macrocycle (29% yield) illustrated in Eq. (3.20). 

The position of the free hydroxyl group in these two alkaloids is either C or C , since Spath has shown that the OiV-diacetyl derivative of -5-hydroxy-3 4-dimethoxyphenylethylamine, when heated in toluene solution with phosphoric oxide, yields a product which must be either 6-acetoxy-7 8-dimethoxy-, or 8-acetoxy-6 7-dimethoxy-l-methyl-3 4-dihydrowoquinoline. On reduction with tin and hydrochloric acid t is converted into anhalonidine, which must therefore be 6-hydroxy-7 8-dimethoxy- (or 8-hydroxy-6 7-dimethoxy-)-l-methyl-l 2 3 4-tetrahydrofsoquinoline. Similarly the methiodide of the acetoxy-com-pound on reduction yields, by loss of acetic acid and addition of two hydrogen atoms, pellotine, proving the latter to be A -methylanhalonidine. The position of the free hydroxyl group was finally shown by Spath to... 

The corresponding tellurium diimide BuNTe( -N Bu)2TeN Bu (10.7) may be obtained in good yields from the reaction of lithium tert-butylamide with TeCU in THE (Eq. 10.3). °" In toluene solution this reaction also produces the cyclic tellurium(II) imide (TcN Bu)3. The dimer 10.7 is obtained as an orange solid, which can be purified by vacuum sublimation at ca. 90°C. 

The crucial experiment suggesting that the H2 molecule might act as a dihapto ligand to transition metals was the dramatic observation that toluene solutions of the deep purple coordinatively unsaturated 16-electron complexes [Mo(CO)3(PCy3)2] and [W(CO)3-(PCy3)2l (where Cy = cyclohexyl) react readily and cleanly with Ha (I atm) at low temperatures to precipitate yellow crystals of [M(CO)3H2(PCy3)2] in 85-95% yield. The... 

Attempts to prepare the mono(cyclopenta-dienyl) derivatives are sometimes frustrated by a Schlenk-type equilibrium (see p. 132), but judicious choice of ligands, solvent etc. occasionally permits the isolation of such compounds, e.g. the centrosymmetric halogen-bridged dimer (t - -C5Me5)Ca(/i-l)(lhf)2 2] which cry.stallizes from toluene solution. The complex is isostruc-tural with the dimeric organosamarium(ll) analogue. - ... 

The yields of Skraup/Doebner-von Miller reaction can be dramatically improved by running the reaction as a two-phase mixture. Reaction of crotonaldehyde with 30 in acidic ethanol provides only 10% of quinoline 31. However, when a toluene solution of crotonaldehyde is reacted with 30 (starting as the acetanilide) in 6M HCI at 100 °C for 2 h, quinoline 31 is isolated in 80% yield on 5kg scale. 

On refluxing a toluene solution of benzoisotellurazole and Fe3(CO)L2, cleavage of the Te—N bond occurs, resulting in formation of the metal chelate complex 11 whose structure was determined by X-ray (97MI1). 

Refluxing a toluene solution of 2-methylbenzotellurazole 12b with Fc3(CO)l2 leads to detelluration of the heterocycle and formation of the iron clusters (97MI1). 

Vilsmeyer-Haack formylation of 7-hydroxy-2,3,6,7-tetrahydro-l//,5//-pyrido[3,2,l-y]quinazoline-l,3-dione with POCI3/DMF gave 7-chloro-6-formyl-2,3-dihydro-l//,5// derivative. Boiling a toluene solution of the aforementioned 7-hydroxy derivative in the presence of pTSA yielded dehydrated 2,3-dihydro derivative (01MI28). 

For many reactions, the enamine may be used without distillation. The cooled toluene solution is washed with bicarbonate followed by water. After drying, toluene is removed (rotary evaporator) and the crude enamine employed directly. 

Azeotropic drying of organic substances is also effective, providing the material is relatively nonvolatile. A benzene or toluene solution of the compound is distilled (in a Dean-Stark trap, if available) until the distillate is free of water droplets. The remaining solution is essentially dry. 

IB.2 grams of a-phenylbutyric acid chloride are dissolved in 25 ml of toluene. To this solution, there is slowly added a solution of 16.1 grams of diethylaminoethoxyethanol in 25 ml of toluene, the reaction mixture thereby becoming hot. It is then heated for B hr under reflux. The reaction mixture, after cooling, is carefully poured onto 75 grams of ice and made alkaline with dilute ammonia. After thorough shaking of the solution, the toluene layer is removed and washed until neutral with water. The toluene solution is treated with carbon and dried over sodium sulfate. The toluene is distilled off from the filtered solution. 

A mixture of iron, ferric chloride and water is added to the toluene solution. The mixture is heated to reflux and concentrated hydrochloric acid is added dropwise at a rate calculated to keep the mixture refluxing vigorously. After the hydrochloric acid Is all added, the refluxing is continued by the application of heat for several hours. A siliceous filter aid is then added to the cooled reaction mixture and the material is removed by filtration. The filter cake is washed four times, each time with 90 ml of benzene. The organic layer is then separated from the filtrate. The water layer is acidified to a pH of 2 and extracted three times with 90 ml portions of benzene. 

To a solution of 35.3 parts of phenylacetonitrile and 47.6 parts of 2-bromopyridine in 175 parts of dry toluene is added 53.4 parts of sodamide slowly with stirring over a period of 45 minutes. The resultant mixture is stirred at 100 C for 2 hours before it is cooled and the excess sodamide is decomposed by the addition of water. The toluene layer is separated and washed with water to remove excess alkali. The toluene solution is extracted with 6N hydrochloric acid and the acid extract is made alkaline and then extracted with toluene. The toluene solution is dried over sodium sulfate and the solvent is evaporated. Recrystal-lization of the residue from alcohol-hexane gives a-phenvl-2-pyridineacetonitrile melting at about 87°-88°C. 

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