trinitrophloroglucinol

     Trinitrophloroglucinol is a stable high explosive similar to TNT. Other names for this explosive include 1,3,5-trihydroxy-2,4,6-trinitrobenzene; 2,4,6-trinitro-1,3,5-benzenetriol; 2,4,6-trinitrophloroglucinol; and TNPG. Trinitrophloroglucinol has found a use in many explosive applications as well as use in percussion caps, detonators, and as an ingredient in the preparation of other explosives. The metallic salts of trinitrophloroglucinol are also useful.

CHEMICALS	APPARATUS
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     Synthesis 1: Prepare a solution of 8.0 g of sodium hydroxide and 27.6 g of sodium nitrite in 75 mL of water warmed to 30 C. Add 16.2 g of phloroglucinol to the solution. Carefully add 108 g of ice to 21 mL of 99% nitric acid and cool the acid solution to below 5 C. Slowly add the phloroglucinol solution dropwise to the cooled acid while maintaining the temperature below 5 C. Stir the mixture for 20 minutes, and then slowly add 100 mL of 65% nitric acid warmed to 50 C. Warm the mixture to 50 C and stir for 45 minutes. Allow the mixture to cool to room temperature. Filter to collect the precipitated product, wash it with 60 mL of 3M hydrochloric acid, and allow to dry. Yield of trinitrophloroglucinol is about 19.5 g or 70%. Synthesis 2: Prepare a solution of 5 g of phloroglucinol in 40 mL of 98% sulfuric acid and cool it to below -8 C. Prepare a second solution of 13 g of dinitrogen pentoxide in 86 mL of 98% sulfuric acid. Slowly add the second solution to the first while maintaining the temperature below -8 C. After the addition stir the solution for 4 hours while keeping the temperature between -8 C and 10 C. As the reaction progresses a yellow precipitate will form. Drown the acid mixture in a large volume of ice water and quickly filter to collect the crystals of trinitrophloroglucinol. Wash them with 50 mL of cold 3M hydrochloric acid, and allow to dry. Yield is almost 9 g or 83%. Synthesis 3: Prepare a solution of 2.21 g of 1,3,5-triacetoxybenzene in 5 mL of 98% sulfuric acid and cool it to below -5 C. Prepare a second solution of 3.28 g of dinitrogen pentoxide in 34 mL of 98% sulfuric acid. Slowly add the second solution to the first while maintaining the temperature below -5 C. After the addition stir the solution for 4 hours while keeping the temperature between -10 C and 10 C. As the reaction progresses a yellow precipitate will form. Drown the acid mixture in a large volume of ice water and quickly filter to collect the crystals of trinitrophloroglucinol. Extract the crystals with 500 mL of dichloromethane, add 100 mL of methyl alcohol, filter to remove any undissolved impurities, and heat the filtrate on a steam bath to drive off the solvent. Yield is a little over 2 g or 98%. Synthesis 4: Prepare a mixture of 38 mL of 71% nitric acid and 62 mL of 97% sulfuric acid. Prepare a second mixture of 25.22 g of phloroglucinol and 500 mL of 97% sulfuric acid, and cool it to 5 C in an ice bath. Slowly add, with stirring, the mixed acid to the second mixture while maintaining the temperature between 5 C and 8 C. Continue stirring for 9 minutes before pouring the reaction mixture into a large beaker containing 1800 g of crushed ice. A precipitate should form. After most of the ice has melted filter to collect the precipitate, wash it with two 125 mL portions of 3N hydrochloric acid, and dry the crystals at room temperature under vacuum. Final yield is around 36.5 g or 70%. The trinitrophloroglucinol may be purified by recrystallizing from dichloroethane. Synthesis 5: Prepare a solution of 16.2 g of phloroglucinol, 27.6 g of sodium nitrite, and 8 g of sodium hydroxide in 25 mL of warm water. Slowly, and with rapid stirring, add this solution to a beaker containing 21 mL of fuming nitric acid and 108 g of crushed ice. Maintain the temperature below 5 C during the addition. Continue stirring the mixture at 15 C for 20 minutes before dumping the whole works into a beaker with 100 mL of 65% nitric acid heated to 50 C. Cool the beaker to 0 C in an ice bath, and then filter to collect the crystals of trinitrophloroglucinol. The product is washed thoroughly with water and allowed to dry under vacuum. Final yield is 73%. Synthesis of sodium phloroglucinate: Prepare a solution of 40 g of phloroglucinol, 57.2 mL of glacial acetic acid, and 100 mL of ethyl ether in 800 mL of water; cool this solution to 7-9 C. Prepare a second solution of 67.6 g of sodium nitrite in 400 mL of water cooled to -2 C. Slowly add the nitrite solution to the phloroglucinol solution dropwise and with vigorous stirring while keeping the temperature around 5 C. Continue stirring for 1 hour, and then slowly add 110 g of sodium hydroxide at such a rate as to keep the temperature below 14 C. Allow the solution to cool back down to 5 C before filtering to collect the precipitate of sodium phloroglucinate. The salt can be purified by adding to 250 mL of water, heating while stirring to 60 C, and cooling the solution down to 5 C. The purified salt can be collected by filtering. Synthesis of lead phloroglucinate: Lead phloroglucinate is a sensitive high explosive similar to mercury fulminate in properties and uses. Prepare a solution of the above sodium salt in 1 L of water heated to 60 C. Slowly add a solution consisting of 160 g of lead nitrate dissolved in 700 mL of water to the phloroglucinate solution. Lead phloroglucinate will precipitate from the solution after cooling it in an ice bath. Filter to collect the salt and allow it to dry. Final yield of the lead salt is somewhat over 125 g. Synthesis of potassium phloroglucinate: Potassium phloroglucinate may be prepared exactly as sodium phloroglucinate except potassium hydroxide, or potassium nitrate, is used. Many other explosive metal salts of trinitrophloroglucinol are possible, however only the lead salt has found a commercial use.

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