Common use of Palladium Clause in Contracts

Palladium. charcoal (5%) until the reaction was complete. The catalyst and solvent were removed and the residue was crystallised from ethanol-diethyl ether (1:1 v/v) to give 4.7 g. 6-(4- aminobenzoylamino)-hexanoic acid; m.p. 132 - 134 degrees C. c) A solution of 2.5 g. 6-(4-aminobenzoylamino)-hexanoic acid in 15 ml. 2N hydrochloric acid was cooled to -5 degrees C. and treated dropwise, while stirring, with 8 ml. of a 10% aqueous solution of sodium nitrite. The reaction mixture was stirred for 30 minutes and then added at -5 degrees C. to salicylic acid in 20 ml. of water containing 2 g. sodium hydroxide and 1 g. sodium carbonate. After 3 hours, the reaction mixture was acidified and the precipitate obtained was isolated by centrifuging, dissolved in ethyl acetate, washed, dried and concentrated to a small volume. Upon cooling, there were obtained 2.7 g. 5- (4-carboxypentylcarbamoylphenylazo)-salicylic acid; m.p. 238 - 239 degrees C. Example 10. ----------- a) A solution of 13 g. copper sulphate in 60 ml. water and a solution of 2 g. sodium hydroxide in 30 ml. water were added simultaneously to a solution of 7.5 g. lysine in 50 ml. water, followed by the addition of 50 ml. of 10% aqueous sodium bicarbonate solution. The precipitated salt was filtered off and the blue filtrate was added, with vigorous stirring, to a solution of 7 g. 4-nitrobenzoyl chloride in 50 ml. acetone. The reaction mixture was stirred for 20 hours and the precipitate obtained was filtered off, washed with water, methanol and diethyl ether and dried in a vacuum at 50 degrees C. to give the copper salt of (E)-(4- nitrobenzoyl)-lysine. b) A suspension of 7 g. of the copper salt of (E)-(4-nitrobenzoyl)-lysine in 30 ml. water was stirred with 6 ml. hydrochloric acid until dissolution was complete. Hydrogen sulphide was passed in for 1 hour and precipitated copper sulphide then filtered off. The filtrate was evaporated to dryness and the residue was taken up in 20 ml. methanolic hydrogen chloride and heated under reflux for 3 hours. The cooled reaction mixture was diluted with water, rendered alkaline with sodium carbonate and extracted with ethyl acetate to give 4.8 g. (E)-(4-nitrobenzoyl)-lysine methyl ester in the form of a yellow oil.

Palladium. charcoal (5%) until the reaction was complete. The catalyst and solvent were removed and the residue was crystallised from ethanol-diethyl ether (1:1 v/v) to give 4.7 g. 6-(4- 6-(4-aminobenzoylamino)-hexanoic acid; m.p. 132 - 134 degrees 134deg.C. c) A solution of 2.5 g. 6-(4-aminobenzoylamino)-hexanoic aminobenzoylamino). hexanoic acid in 15 ml. 2N hydrochloric acid was cooled to -5 degrees -5deg.C. and treated dropwise, while stirring, with 8 ml. of a 10% aqueous solution of sodium nitrite. The reaction mixture was stirred for 30 minutes and then added at -5 degrees -5deg.C. to salicylic acid in 20 ml. of water containing 2 g. sodium hydroxide and 1 g. sodium carbonate. After 3 hours, the reaction mixture was acidified and the precipitate obtained was isolated by centrifuging, dissolved in ethyl acetate, washed, dried and concentrated to a small volume. Upon cooling, there were obtained 2.7 g. 5- (45-(4-carboxypentylcarbamoylphenylazo)-salicylic acid; : m.p. 238 - 239 degrees C. Example 10. ------------239deg.C. a) A solution of 13 g. copper sulphate in 60 ml. water and a solution of 2 g. sodium hydroxide in 30 ml. water were added simultaneously to a solution of 7.5 g. lysine in 50 ml. water, followed by the addition of 50 ml. of 10% aqueous sodium bicarbonate solution. (Distribution Schedule 1 cont...) The precipitated salt was filtered off and the blue filtrate was added, with vigorous stirring, to a solution of 7 g. 4-nitrobenzoyl chloride in 50 ml. acetone. The reaction mixture was stirred for 20 hours and the precipitate obtained was filtered off, washed with water, methanol and diethyl ether and dried in a vacuum at 50 degrees 50deg.C. to give the copper salt of (E)-(4- E-(4-nitrobenzoyl)-lysine. b) A suspension of 7 g. of the copper salt of (E)-(4E-(4-nitrobenzoyl)-lysine in 30 ml. water was stirred with 6 ml. hydrochloric acid until dissolution was complete. Hydrogen sulphide was passed in for 1 hour and precipitated copper sulphide then filtered off. The filtrate was evaporated to dryness and the residue was taken up in 20 ml. , methanolic hydrogen chloride and heated under reflux for 3 hours. The cooled reaction mixture was diluted with water, rendered alkaline with sodium carbonate and extracted with ethyl acetate to give 4.8 g. (E)-(4E-(4-nitrobenzoyl)-lysine methyl ester in the form of a yellow oil. c) A solution of 1 g. E -(4-nitrobenzoyl)-lysine methyl ester in 2 ml. methyl iodide and 0.2 ml. acetone was left to stand for 20 hours at ambient temperature, whereafter the NMR showed the reaction to be complete. The volatile materials were evaporated off to leave E:-(4-nitrobenzoyl)-a,a- dimethyllysine methyl ester in the form of an oil. (Distribution Schedule 1 cont...)