Crystal melting point

The excess reducing agent is then decomposed by means of a little water (foaming), the solution is filtered and about 300 ml of water are added while stirring. The 3-N-pyrrolidino-4-phenoxy-5-sulfamylbenzoic acid methyl ester which has crystallized out is recrystallized from methanol in the form of colorless crystals, melting point 191°C to 192°C. 

Preparation of 3-Amino-5-Methylisox3Zo/e 1.7 grams of ethyl 5-methylisoxa2ole-3-car-bamate was heated on a boiling water-bath with 5 cc of a 10% aqueous sodium hydroxide solution for 8 hours, then the reaction mixture was extracted several times with ether or benzene and the extract was cooled followed by the removal of the solvent and drying. The residue was solidified after a while and gave prismatic crystals, melting point 61° to 62°C, of 3-amino-5-methylisoxazole by recrystallization from benzene. 

The hydrogen sulfate was dissolved in water and the pH of the solution was adjusted to 5.6 (pH-meter) with 0.1 N sodium hydroxide solution. The water solution was evaporated to dryness and the residue dried with absolute ethanol/benzene and once more evaporated to dryness. The remaining crystal mixture was extracted in a Soxhiet extraction apparatus with absolute methanol. From the methanol phase the sulfate of 1-(3, 5 -dihydroxyphenyl)-2-(t-butylaminoj-ethanol crystallized. Melting point 246°C to 248°C. 

A solution of 18 g of 2-thienyl bromide in 30 ml of tetrahydrofuran Is gradually added to a mixture of 2.6 g of magnesium and 80 ml of tetrahydrofuran under stirring at 50°C. The mixture is stirred for 5 hours at room temperature until the magnesium is entirely dissolved in the solution. 6.2 g of methyl N-methyl-5-methoxy-nipecotinate are added to the mixture. Then, the mixture is refluxed for 4 hours. After the reaction Is completed, tetrahydrofuran is distilled off under reduced pressure. An aqueous ammonium chloride solution is added to the residue, and the solution is extracted with chloroform. The extract is dried and then evaporated to remove chloroform. The viscous oil thus obtained is recrystallired from a mixture of benzene and ether. 7 g of di-(2-thienyl) -(N-methyl-5-methoxy-3-piperidyl)-carbinol are obtained as crystals. Melting point 142°C to 146°C. 

B) 20 -cyano-4Q ,5Q -epoxandrostan-17(3-ol-3-one was prepared by treating 17(3-acetoxy-40 , 50 -epoxyandrostano [2,3-d] isoxazole with sodium methoxide, and was obtained in the form of tan crystals, melting point 257.8°C to 270.0°C (decomposition) (corrected) when recrystallized from a pyridine-dioxane mixture. 

A suspension of 30 g of sodium hydride in benzene (30 ml) was added dropwise to 52 g of 8-chlorodibenzo[b,f] thiepin-10(11 H)-one dissolved in dimethylformamide (800 ml), and the mixture was heated at 100°C for 2 hours. To this, there were added 68 g of 2-dimethylamino-ethyl chloride, and the mixture was heated at 60°C for 39 hours. The reaction mixture, after cooled, was poured into ice-water, and the solution was extracted with ethyl acetate. The ethyl acetate layer, after washed with water, was extracted with 10% hydrochloric acid, when oil was precipitated. The aqueous layer, in which oil was precipitated, was washed with ether, made neutral with concentrated sodium hydroxide solution and then extracted with ethyl acetate. The ethyl acetate layer was washed with water, dried over magnesium sulfate, and concentrated to give oil, which was allowed to stand to provide solid. The solid was washed with petroleum ether and recrystallized from cyclohexane to yield 42.5 g of 8melting point 90°C to 91°C. Male-ate as colorless needle, melting point 204°C to 204.5°C. 

For further purification the crystallised acid is boiled for a quarter of an hour under reflux with methylated spirit (one part by volume of spirit for each part by weight of acid), left over night without filtering, then collected again at the pump, washed with alcohol, and finally the almost colourless material is recrystallised from spirit, in which it is dissolved by boiling under reflux. The pure cholic acid separates on cooling in the form of transparent tetrahedral crystals. Melting point 196°. A further quantity of pure substance can be obtained from the mother liquor by concentration. If the acid, partially purified as described, is extracted in a thimble with ethyl acetate, a very fine preparation is obtained. The yield of pure acid amounts to fully 50 g. 

Two different types of crystals were obtained by cooling crystallization of qulzalofop-ethyl dissolved In ethyl alcohol at room temperature. As shown In Photograph 1, one type consists of plate-llke crystal of 20-50 jum In size and another one Is halrllke crystal of 1-2 pm In short axis size. As shown In Figure 1, different X-ray patterns were obtained for the two crystals. Melting points and heats of fusion were also measured for the two crystal types by DTA and DSC, which are listed In Table I. These results Indicate that the different shapes of the two crystal types are related to differences In crystal lattice. 

This crystalline ternary complex is obtained by treating the tert-butylammonium complex of dibenzo[18]crown-6 with DDQ (2,3-dichloro-5,6-dicyano-l,4-benzophe-none) in chloroform. The X-ray analysis of the red crystals, melting point 177... 

Polyacetylene prepared by the Shirakawa route pyrolyses on heating, before showing any detectable crystal melting point. At the same time, it is insoluble in all known solvents. For these reasons it is essentially unprocessable. Until recently it has seemed to be a general rule that all conducting polymers were insoluble, which follows naturally from the conjugation of the double bonds along the chain which results in chain stiffness. 

A mixture of phenacyl chloride 1 (0.46 g, 3 mmol), aldehyde 2 (0.64 g, 6 mmol), ammonium acetate (1.55 g, 20 mmol) and glacial acetic acid (10 ml) in w-PrOH (20 ml) in the presence of molecular sieves (4 A) was irradiated for 5-10 min in a self-tunable CEM microwave synthesizer at 90 °C (Scheme A.7). After the reaction had been cooled to room temperature, the solvent was removed under vacuum and the residue was crystallized from ethanol to give 2,4,6-triphenyl-3,5-diazabicyclo[3.1.0]hex-2-ene 3 as colorless crystals. Melting point 155-156°C. 

The whole is boiled for 1 h, is cooled to about 10°C and is added with 8% HCI to adjust the pH to 7. Benzene layer is dried and concentrated up to 2/3 of the volume. The 2-(l-methyl-5-nitro)imidazolyl-l-(2-hydroxy-5-tert-butylphenylcarbinol is allowed to crystallize, melting point 158°-160°C yield 0-60%. 

A suspension of 1.0 g of 9-fluoro-lip,16a,17,21-tetra-hydroxy-pregna-l,4-diene-3,20-dione in a mixture of 35 ml of dioxan, 15 ml of acrolein and 0.1 ml of perchloric acid was stirred for 3 h at room temperature. The clear solution thus obtained was poured into an aqueous saturated solution of sodium bicarbonate. The mixture was extracted twice with benzene, and the benzenic extract was concentrated to a small volume. The resulting crystals were collected and the 9-fluoro-lip,21-dihydroxy-16a,17-(2-propenylidenedioxy)-pregna-l,4-diene-3,20-dione was obtained as white crystals, melting point 200°-205°C. 

This 2-amino-5-methoxy-2,3-dihydro-lH-phenalene was converted to its hydrochloride salt in methanol with 1.5 N hydrogen chloride in diethyl ether solution to give 18.11 g of the 2-amino-5-methoxy-2,3-dihydro-lH-phenalene hydrochloride as colorless needle crystals, melting point 252°C (dec.). 

The 2-dimethylaminoethyl 1-adamantanecarboxylate was mixed with 1-bromodecan and allowed to stand for about 6 weeks. The resultant crystalline mass was washed with ether and dried to gave 2-(l -adamantanecarbonyloxy)ethyldimethyldecylammonium bromide as white crystals, melting point 183°-184.5°C (two recrystallizations from ethyl acetate). 

In 200 ml of methanol was dissolved 20.0 g of 5- l-hydroxy-2-[N-benzyl-2-(2-methoxyphenoxy)ethylamino]ethyl -2-methyl-benzenesulfonamide. After adding thereto 20 ml of ethanol containing about 10% hydrogen chloride and 1.0 g of 10% palladium charcoal, the mixture was shaken in hydrogen gas stream. When the absorption of hydrogen stopped, the catalyst was filtered away and the filtrate was distilled off under reduced pressure. The residue was dissolved in 100 ml of ethanol while it was hot and the solution was allowed to stand overnight in ice chamber, whereby 12.8 g of the a-type crystals of 5- 1-hydroxy-2-[2-(2-methoxyphenoxy)ethylamino]ethyl>-2-methylbenzenesulfonamide were obtained as the colorless crystals, melting point 169°-171°C. 

The reaction solution was stirred at room temperature for 4 h, and then condensed to a half volume in vacuo. The residual solution, added with 100 ml of water, was extracted with chloroform. The chloroform extract was washed with water, dried over anhydrous magnesium sulfate and evaporated in vacuo to give 4.8 g of 2-(3 -t-butylamino-2 -hydroxypropylthio)-4-(5 -carbamoyl-2 -thiophenyl)thiazole, as crystals, melting point 234°-235.5°C (dec., recrystallized from methanol/water). 

A solution of 2-(2-amino-5-chlorophenyl)-4-cyclopropyl-l,l,l-trifluoro-3-butyn-2-ol (15.00 g, 0.0518 mol) and 41.98 g (0.259 mol) of 1,1 -carbonyldiimidazole in 250 mL of dry THF was stirred under argon at 55°C for 24 hours. The solvent was removed on a rotary evaporator and the residue was partitioned between 500 mL of ethyl acetate and 400 mL of water. The layers were separated and the aqueous phase was extracted once more with ethyl acetate. The combined ethyl acetate extracts were washed with 2 times 200 mL of 2% aqueous HCI, saturated aqueous NaHC03, and brine. Drying over MgS04, filtration, and removal of the solvent in vacuo provided 16.42 g of the title compound as a solid. Recrystallization from ethyl acetate/hexane afforded 12.97 g of analytically pure ()-6-chloro-4-cyclopropylethynyl-4-trifluoromethyl-l,4-dihydro-2H-3,l-benzoxazin-2-one as a white crystals. Melting point 178°-180°C. 

The mother liquors from Step C above were purified by column chromatography on silica gel using 10% ethyl acetate in hexanes as eluant. The pure, undesired diastereomer (a colorless foam) was hydroylzed according to Step D. The enantiomeric benzoxazinone, (+)-6-chloro-4-cyclopropylethynyl-4-trifluoromethyl-l,4-dihydro-2H-3,l-benzoxazin-2-one, was obtained as white crystals. Melting point 131°-132°C [a]D20 =+84.4° (CHCI3, c=0.005 g/mL). 

The acetonitrile phase is evaporated to dryness under reduced pressure. The crystalline residue (42.1 g) is recrystallized from 80 ml of ethanol. This gives a further 24.1 g (19.7% of theory) of crystals. Melting point (after recrystallization from ethanol) 155°C. Total yield 84.2% of theory. 

To a solution of the ethyl 2-(3-methoxy-2,4,5-trifluorobenzoyl)-3-ethoxyacrylate (9.73 g) in ethanol (20 ml) cyclopropylamine (2.0 g) was added dropwise under cooling. After stirring for 2 h at room temperature, the reaction mixture was concentrated and the residue was purified by silica gel column chromatography eluting with n-hexane-ethyl acetate (5 1) to give ethyl 2-(3-methoxy-2,4,5-trifluorobenzoyl)-3-cyclopropylaminoacrylate (7.52 g) as yellowish white crystals, melting point 56°-58°C. 

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