Product, dried yield

Add 5 g. of potassium hydrogen tartrate and 5 g. of antimony trioxide (each being finely powdered) to 30 ml. of water contained in a small flask, and boil the mixture under a reflux water-condenser for 15 minutes. Then filter hot, using a Buchner funnel and flask which have been preheated by the filtration of some boiling distilled water. Pour the clear filtrate into a beaker and allow to cool. Potassium antimonyl tartrate separates as colourless crystals. Filter, drain and dry. Yield, 5 g. The product can be recrystallised from hot water, but this is usually not necessary. 

Prepare a mixture of 30 ml, of aniline, 8 g. of o-chloro-benzoic acid, 8 g. of anhydrous potassium carbonate and 0 4 g. of copper oxide in a 500 ml. round-bottomed flask fitted with an air-condenser, and then boil the mixture under reflux for 1 5 hours the mixture tends to foam during the earlier part of the heating owing to the evolution of carbon dioxide, and hence the large flask is used. When the heating has been completed, fit the flask with a steam-distillation head, and stcam-distil the crude product until all the excess of aniline has been removed. The residual solution now contains the potassium. V-phenylanthrani-late add ca. 2 g. of animal charcoal to this solution, boil for about 5 minutes, and filter hot. Add dilute hydrochloric acid (1 1 by volume) to the filtrate until no further precipitation occurs, and then cool in ice-water with stirring. Filter otT the. V-phcnylanthranilic acid at the pump, wash with water, drain and dry. Yield, 9-9 5 g. I he acid may be recrystallised from aqueous ethanol, or methylated spirit, with addition of charcoal if necessary, and is obtained as colourless crystals, m.p. 185-186°. 

Steam-distil the ethereal solution and discard the distillate. The residue in the flask is triphenyl-carbinol and solidifies on cooling. Filter at the pump, wash with water, drain and dry. Yield of crude product 0 6 g. Recrystallise when dry from benzene to obtain colourless crystals m.p. 162°. 

N-Nitrosodiethylamine. Add 36-5 g. (51-5 ml.) of diethylamine slowly to the calculated quantity of carefully standardised 5A-hydra chloric acid cooled in ice (1). Introduce the solution of the hydi ochloride into a solution of 39 g. of sodium nitrite (assumed to be of 90 per cent, purity) in 45 ml. of water contained in a 250 ml. distilling flask. Distil the mixture rapidly to dryness. Separate the yellow upper layer of the nitrosamine from the distillate saturate the aqueous layer with soUd potassium carbonate and remove the nitroso compound which separates and add it to the main product. Dry over anhydrous potassium carbonate and distil. Collect the diethylnitrosamine at 172-173-5°, The yield is 41 g. 

Method 1. Dissolve 76 g. of thiourea in 200 ml. of warm water in a 750 ml. or 1 litre round-bottomed flask. Dilute the solution with 135 ml. of rectified spirit and add 126-5 g. of benzyl chloride. Heat the mixture under reflux on a water bath until the benzyl chloride dissolves (about 15 minutes) and for a further 30 minutes taking care that the mixture is well shaken from time to time. Cool the mixture in ice there is a tendency to supersaturation so that it is advisable to stir (or shake) the cold solution vigorously, when the substance crystallises suddenly. Filter off the sohd at the pump. Evaporate the filtrate to about half bulk in order to recover a further small quantity of product. Dry the compound upon filter paper in the air. The yield of hydrochloric acid filter off the sohd which separates on cooling. Concentrate the filtrate to recover a further small quantity. The yield of recrystalhsed salt, m.p. 175° is 185 g. some of the dimorphic form, m.p. 150°, may also separate. 

Commercial Sodium Acetylide A suspension (30 ml) of sodium acete-lide (20% in exylene) is centrifuged and the solid brown sodium acetylide is taken up in 25 ml of dimethyl sulfoxide. To this is added a solution of 5 g of 5a-hydroxy-6j5-methylandrostane-3-17,dione 3-ethylene ketal in 85 ml of dimethyl sulfoxide. After stirring at room temperature overnight, ice is added and the solution diluted to about 250 ml. The tan precipitate is collected, washed with water and dried yield 4.8 g mp 202-204°. Crystallization from ethyl acetate gives a product of mp 204-206°. 

Microwave chemistry has been found to be a useful method for accelerating reactions or catalyzing reactions that are difficult to carry out by other methods. A modification of the Hantzsch method to directly obtain pyridines has been communicated. A dry medium using ammonium nitrate bentonitic clay system with microwave irradiation affords pyridines 96 in a single pot within 5 minutes. When the pyridine is not the major product (> 75% yield), the dealkylated pyridine 97 becomes an... 

A 100 gallon lined jacketed kettle provided with cooling is charged with 100 lb of benzyl-amine and 150 liters of water. The mixture is cooled to 5°C and with stirring 119 lb of /3-chloropropionyl chloride and a solution of 45 lb of sodium hydroxide pellets in 40 liters of water are added simultaneously at such a rate that the temperature does not exceed 10°C. During this period the pH of the mixture should be on the alkaline side but below pH 9.5. When the addition is complete the pH should be about 8. The mixture is stirred overnight in the cold, and the solid product is filtered. The filter cake is reslurred with about BO gallons of water, filtered, and air-dried. Yield, 12B pounds. 

B) A mixture of 2.4 parts of 1 acetyl-4-(4-hydroxyphenyl)piperazine, 0.4 part of sodium hydride dispersion 78% 75 parts of dimethylsulfoxide and 22.5 parts of benzene is stirred for one hour at 40°C. Then there are added 4.2 parts of cis-2-(2,4-dichlorophenyl)-2-(1 H-imidazol-1 -ylmethyl)-1,3-dioxolan-4-ylmethyl methane sulfonate and stirring is continued overnight at 100°C. The reaction mixture Is cooled and diluted with water. The product is extracted with 1,1 -oxybisethane. The extract is dried, filtered and evaporated. The residue Is crystallized from 4-methyl-2-pentanone. The product is filtered off and dried, yielding 3.2 parts (59%) of cis-1-acetyl-4-[2-(2,4-dichlorophenyl)-2-(1 H-imidazol-1-ylmethyl)-13-di-oxolan-4-ylmethoxy] phenyl] piperazine MP 146°C. 

A mixture of 9.6 parts of 4-amino-3-nitrobenzophenone, 160 parts of methanol, 8 parts of concentrated hydrochloric acid and 1 part of palladium-on-charcoal catalyst 10% is hydrogenated at normal pressure and at room temperature. After the calculated amount of hydrogen is taken up, hydrogenation is stopped. The catalyst is filtered off and the solvent is evaporated. The solid residue is triturated in 2-propanol. The latter is partly evaporated and the solid product is filtered off, washed with 2-propanol and dried, yielding 3,4-diaminobenzophenone hydrochloride MP 207 C. 

The filtrate was then slowly treated with concentrated hydrochloric acid until mixture tested acid. Product was then filtered, washed with water and dried. Yield 103 g (71.0%), MP 245° to 249°C (dec.). 

A mixture of 3-phenoxyphthalonitrile (3 220 mg, 1.7 mmol), urea (180 mg, 3.0 mmol), Zn(OAc)2 (60 mg, 0.33 mmol), Na2S04 (280 mg, 2 mmol), and a catalytic amount of (NH4)2Mo04 was kept for 1 h at 160-170 C and 0.5 h at 180-190 C. After cooling, the solid formed was extracted with CHClj, the solvent evaporated, and the residue treated with coned HC1. The product was dissolved in acetone and then precipitated with dil NH3. The precipitate was washed with H20 andMeOH, and dried yield 60 mg (25%). 

Phthalonitrile (128 g. 1 mol) and difluorophenylboron (63 g, 0.5 mol) in anhyd quinoline (300 mL) under N2 were heated slowly to reflux temperature and refluxed for 4h. Oxygen had to be strictly excluded. The mixture wascooled to rt and allowed to stand for several hours. The product was filtered, reprecipitated from 1-chloronaphthalene, and dried yield 28 g ( 20%). 

---