(CAS NO.: ), which is also known as dihydrochloride, could be produced through the following synthetic routes.

A. Adipyl hydrazide (CAS NO.: ). A solution of 120 ml. of 85% aqueous hydrazine hydrate (105 g., 2.0 moles) and 25 ml. of absolute ethanol is brought to a gentle boil in a 500-ml. three-necked flask provided by means of ground glass joints with a ball joint-sealed mechanical stirrer, a reflux condenser, and a dropping funnel. One hundred and one grams (0.5 mole) of diethyl adipate2 is added dropwise to the boiling stirred solution at such a rate that a separate liquid phase does not accumulate in the reaction mixture. This operation requires 1–2 hours, at the end of which time the contents of the flask will have largely crystallized. The boiling is continued for 5 minutes after the completion of the addition, and the contents of the flask are then cooled to room temperature with running water. The crystals are washed onto a Büchner funnel with the aid of about 100 ml. of absolute ethanol used in several portions. The precipitate is dried by suction, and the product is washed once with 25 ml. of ether. After drying in air (or at 100°) the adipyl hydrazide weighs 77–80 g. (88–92%) and is of good quality, with a melting point about 170°. Concentration of the filtrate to a volume of about 25 ml. in an air stream on a steam bath yields an additional 2.5 g. of nearly pure material; total yield 91–95%.

B. Putrescine dihydrochloride (CAS NO.: ). A 2-l. wide-mouthed Erlenmeyer flask containing 200 ml. of concentrated hydrochloric acid and 400 g. of cracked ice is clamped in an ice-salt bath and provided with an efficient stirrer (inefficient stirring may lower the yield). The stirring is started, and 80 g. (0.46 mole) of adipyl hydrazide is added all at once, followed by 500 ml. of ether. While the temperature is maintained below 10°, a solution of 80 g. (1.15 moles) of sodium nitrite in 150 ml. of water is added over about 30 minutes through a dropping funnel whose stem reaches below the bottom of the ether layer, but not into the path of the stirrer. The operations in the next paragraph should be conducted without delay after the completion of the addition of the nitrite.

The cold reaction mixture, which may be freed from suspended solid by rapid filtration through a cotton plug, is transferred to a 2-l. or 3-l. separatory funnel, and the aqueous layer is drawn off into the original reaction flask. The ether layer is poured into a 2-l. Erlenmeyer flask containing about 50 g. of anhydrous calcium chloride, and this flask is placed in the ice bath in which the diazotization was run. The cold aqueous layer is then extracted with two 100-ml. portions of chilled ether, which are combined with the first ether extract. After 5 minutes with occasional swirling, the ether solution of adipyl azide is sufficiently dry, and it is poured into a 2-l. round-bottomed flask containing 350–400 ml. of benzene. The calcium chloride is rinsed with a 50-ml. portion of ether, which is added to the same flask.

The ether is distilled gently from a steam bath, preferably through a short fractionating column; nitrogen will be evolved at the same time. When the volume of the contents of the flask has reached about 400 ml., the flask is heated strongly on the steam bath for about 15 minutes to complete the decomposition of the azide. The flask is removed from the steam bath, and 200 ml. of concentrated hydrochloric acid is added cautiously to the hot solution. The flask is allowed to stand with occasional swirling until the carbon dioxide evolution has ceased (about 15 minutes). The mixture is heated strongly on a steam bath for about 15 minutes more, and the solvents are then distilled from a steam bath under aspirator vacuum. When the contents of the flask have become a crystalline paste, the vacuum is temporarily disconnected, and the inner walls of the flask are washed down with about 50 ml. of ethanol. The vacuum is renewed cautiously, and the mixture is distilled to dryness.

The residue of crystalline putrescine dihydrochloride is rinsed onto a Büchner funnel with the aid of 100–200 ml. of absolute ethanol used in several portions. The last portions of ethanol are used as wash liquid for the crystals. The crystals are finally pressed dry and washed with 25 ml. of ether. The air-dried product weighs 53–55 g. (72–74%) and melts above 275°. Analysis for chlorine indicates that the salt is anhydrous. Concentration of the filtrate to a volume of about 25 ml. yields an additional 1–2 g.; total yield 73–77%. The entire synthesis may be completed in one day.