B preparation

B) Preparation of the Cuprous Solution, Add 85 ml. of concentrated ammonia solution (d, o-o88) to a solution of 50 g. of crystalline copper sulphate in 200 ml. of water, and cool to 10 . Dissolve 14 5 g. of hydroxylamine hydrochloride (or 17-4 g. of the sulphate) in 50 ml. of water, cool to 10 , and add a solution of 9 g. of sodium hydroxide in 30 ml. of water. Without delay add this hydroxylamine solution with stirring to the copper solution, which will be immediately reduced, but will retain a blue colour. 

The o-nitrobenzyl and p-nitrobenzyl ethers can b prepared and cleaved by many of the methods described for benzyl ethers. The p-nitrobenzyl ether is also prepared from an alcohol and p-nitrobenzyl alcohol (trifluoroacetic anhydride, 2,6-lutidine, CH2CI2, 67% yield). In addition, the o-nitrobenzyl ether can be cleaved by irradiation (320 nm, 10 min, quant, yield of carbohydrate " 280 nm, 95% yield of nucleotide ). The p-nitrobenzyl ether has been cleaved by electrolytic reduction (—1.1 V, DMF, R4N X, 60% yield) and by reduction with Na2S204 (pH 8-9, 80-95% yield). These ethers can also be cleaved oxidatively (DDQ or electrolysis) after reduction to the aniline derivative. ... 

B. Preparation of B- and Z-Cirmamonitrile. A 1-L, three-necked, round-bottomed flask equipped with a mechanical stirrer, reflux condenser, and addition funnel is charged with potassium hydroxide pellets (33 g, 0.5 mol. Note 1) and acetonitrile (400 mL, Note 2), The mixture is brought to reflux under nitrogen and a solution of benzaldehyde (53 g, 0.5 mol. Note 4) in acetonitrile (100 mL) is added in a stream (1-2 min). After addition. 

B) Preparation of S-Trifluoromethyl-2,4-Disulfamylaniline—The 5-trifluoromethylaniline-2,4-disulfonyl chloride obtained in step (A) is taken up in ether and the ether solution dried with magnesium sulfate. The ether is removed from the solution by distillation, the residue is cooled to 0°C, and 60 ml of ice-cooled, concentrated ammonia water is added while stirring. The solution is then heated for one hour on a steam bath and evaporated... 

B Preparation of Benzyithiomethyi-6-Chioro-7-Suifamyi-3,4-Dihydrobenzothiadiazine-1,1-Dioxide—A. mixture of 3-(chloromethvl)-6-chloro-7-sulfamvl-3,4-dihydrobenzothiadiazine-1,1-dioxide (0.02 mol) and benzylmercaptan (0.024 mol) in 20 ml of 10% sodium hydroxide and 20 ml of dimethylformamide is stirred at room temperature for 6 hours. 

B) Preparation of 7-Chloro-3-Methoxycarbony/-5-Phenyl-2-0xo-2,3-Dihydro-iH-Benzo [fl-1,4-Diazepine (4347 CB) A solution of 9.2 g (0.04 mol) of compound 4356 CB in 20 ml of methanol is added dropwise, in the course of one hour and 30 minutes, to a boiling solution of 9.2 g (0.05 mol) of the hydrochloride of methyl aminomalonate in 30 ml of methanol. When this is completed, heating under reflux is continued for 30 minutes and the product then concentrated to dryness under reduced pressure. The residue is taken up in water and ether, the ethereal layer separated, the product washed with water and dried over sodium sulfate. The solvent is evaporated under reduced pressure. The residue, which consists of the methyl ester, could not be obtained in the crystalline state. It is dissolved in 25 ml of acetic acid, heated under reflux for 15 minutes, the product evaporated to dryness and the residual oil taken up in ether. A colorless solid separates which... 

B) Preparation of 1-0-D-Arabinofuranosylcytosine In a glass liner, a mixture of 1.16 g (3.0 mmol) of 1-(2,3,5-tri-0-acetyl-(3-D-arabinofuranosyl)-4-thiouracil prepared in (A) and about 60 ml of absolute methanol which had been saturated with anhydrous ammonia at 0°C was heated in a steel bomb at 98° to 105°C for 35 hours. After cooling to about 25°C and venting the bomb, the dark solution was filtered into a round-bottom flask. The methanol and excess ammonia were then removed under reduced pressure at about 25°C. The residual syrup was dissolved in absolute methanol, and the methanol was removed under reduced pressure at a bath temperature of about 40°C. This procedure of dissolving in absolute methanol and removing the solvent was repeated, and the residue was held under reduced pressure at a bath temperature of 45°C for 12 hours. 

Step B Preparation of 3-Methoxy-17a-Methyl-19-Nor-A ° -Pregn3diene-20-ol — 500 cc of ammonia and a solution of 20 grams of 3-methoxy-17a -methyl-19-nor-A , ( >-pregna-triene-20-one were admixed with 400 cc of THF, and 10 cc of ethanol were added. The temperature was lowered to -35°C. 2.150 grams of lithium were added under an inert atmosphere and the reaction mixture was agitated for 15 minutes, after which 10 cc of ethanol and... 

B) Preparation of Diphenyl-(N-Methyl-4-Plperidylidene)Methane The carbinol can be dehydrated with 60% sulfuric acid. In general, to one part of the carbinol there is added... 

Step B Preparation of 2,3-Dichioro-4-[2-(DimethyiaminomethyijButyryi]Phenoxyacetic Acid Hydrochioride — In a 100 ml round flask equipped with an outlet tube suitable for... 

B) Preparation of 7-Chloro-1,2,3,4-Tetrahydro-1-Methyl-6H-1,4-Bemodiazepin-5-one A mixture of 25.25 g (0.1 mol) of 4-acetyl-7-chloro-1,2,3,4-tetrahydro-1-methyl-5H-1,4-benzo-diazepin-5-one, 33.3 ml (0.1 mol) of 3 N sodium hydroxide and 350 ml of ethanol was heated under reflux for 15 minutes and then concentrated to dryness in vacuo. The residue was treated with 500 ml of water, collected and washed with ethanol to give 20.2 g... 

B) Preparation of Methyl p-Acetyiphenoxy-Acetate A mixture of 80 g of the acid obtained in (A) and 200 ml of methyl alcohol in 600 ml of dichloromethane is refluxed in the presence of sulfuric acid. The desired ester is isolated in accordance with a method known per se, and recrystallized. When the refluxing period is 12 hours, the ester is obtained with a yield of 70%. When the refluxing period is 18 hours, the yield for this ester is 85%. 

B) Preparation of o- 2-Thienyl-(2 )-Ethyl]Benzoic Acid 24.0 g of thenylidene-(2)-phthalide, 8.8 g of red pulverized phosphorus, 240 ml of hydrochloric acid (d = 1.7) and 240 ml of glacial acetic acid are heated to boiling under nitrogen and while stirring vigorously. 70 ml toluen are then added and 6.0 g of red phosphorus added in small portions over a period of 1 hour. It is then poured into 3 liters of ice water, stirred with 300 ml of chloroform and the phosphorus removed by filtration. 

B) Preparation of 4-Amino-2-Chloro-5-(Methylsulfamyl)Benzenesulfonamide The 5-sub-stituted-2,4-dlsulfamyl anilines may be prepared by procedures described in the literature, for example, the general procedures in Monatsch. Chem. vol. 48, p 87 (1927), which involves the treatment of a m-substituted aniline with from 10 to 20 parts by weight of chlorosulfonic acid followed by the gradual addition of from about 90 to 170 parts by weight of sodium chloride. The resultant mixture is heated at approximately 150°C for about 2 hours after which the reaction mixture is poured into water and the resultant 5-substituted aniline-2,4-disulfonyl chloride is filtered and is then treated with concentrated ammonium hydroxide or suitable amine by standard procedures to obtain the corresponding disulfonamide. 

B) Preparation of 2-(Hydroxyiminomethyl)-1-Methyl Pyridinium Chloride An aqueous solution of 15 ml of 1-methyl-2-picolinium chloride having a concentration of 477 mg/ml Is covered with 50 ml of benzene in an atmosphere of nitrogen and cooled to below 10°C. An aqueous solution of sodium hydroxide is added dropwise and the mixture is stirred for 5 minutes and allowed to stratify. The aqueous phase Is then drawn off and the benzene solution is added slowly to a solution of 3 ml of nitrosyl chloride in 175 ml of benzene containing 0.5 ml of dimethyl formamide at about 10°C in an atmosphere of nitrogen with good agitation. The mixture is then stirred for 1.5 hours and then extracted with four... 

Stage B Preparation of 17j -HydroxyEstra-4,9,11-Trien-3-one — 3 g of 17/3-benzoyloxy-estra-4,9,11 -trien-3-one, obtained as described in Stage A are dissolved in 15 cc of methanol. 0.03 g of hydroquinone is added, and the mixture Is taken to reflux while bubbling in nitrogen. Then 1.2 cc of 11% methanolic caustic potash is added and reflux is maintained for three hours, after which the reaction product Is acidified with 0.36 cc of acetic acid. 

B) Preparation of 7-A//y/oxy-4,8-Dimethylcoumarin 7-Hydroxy-4,8-dimethylcoumarin (191.3 g, 1.01 mols), anhydrous potassium carbonate (604 g, 4.37 mols), and allyl bromide (578 ml, 6.22 mols) were refluxed overnight in acetone (ca 3 liters) with mechanical stirring. The reaction mixture was concentrated nearly to dryness on a steam bath under re-... 

B. Preparation of Elastomer-Plastic Blend by Melt Mixing Without Vuicanization... 

B. Preparation of Allyl Cyanide.— In a i-l. round-bottom flask fitted with a condenser (Note 4) and a mechanical stirrer are placed 220 g. (1.83 moles) of allyl bromide (Note 5) and 170 g,... 

Procedure (b). Prepare the indicator by dissolving 0.05 g bromopyrogallol red in 100 mL of 50 per cent ethanol, and a buffer solution by mixing 100 mL of 1M ammonium chloride solution with 100 mL of 1M aqueous ammonia solution. 

---