Ferric nitrate, preparation

A suspension of sodium amide2 (0.1 mole) in liquid ammonia is prepared in a 500-ml. three-necked, round-bottomed flask fitted with a West condenser, a ball and socket glass mechanical stirrer (Note 1), and a dropping funnel. In the preparation of this reagent a small piece of clean sodium metal is added to 350 ml. of commercial anhydrous liquid ammonia. After the appearance of a blue color, a few crystals of hydrated ferric nitrate are added, whereupon the blue color is discharged. The remainder of the 2.3 g. (0.1 mole) of sodium (Note 2) is then rapidly added as small pieces. After all the sodium has been converted to sodium amide (Note 3), a solution of 16.4 g. (0.1 mole) of ethyl phenyl-acetate (Note 4) in 35 ml. of anhydrous ethyl ether is added dropwise over a 2-minute period, and the mixture is stirred for 20 minutes. To the dark green suspension is added over an 8-minute period a solution of 18.5 g. (0.1 mole) of (2-bromo-... 

Eerrocene (1) was the first sandwich complex to be discovered, thereby opening a wide and competitive field of organometallic chemistry. The formation of ferrocene was found at almost the same time in two independent studies on July 11, 1951, Miller, Tebboth, and Tremaine reported that on the passage of N2 and cyclopenta-diene over a freshly prepared mixture of reduced Ee (90%), alumina (8%), potassium oxide (1%), and molybdenum oxide (1%) at 300°C, yellow crystals identified as Cp2Ee (Eig. 1) were obtained [1]. Due to the low yields obtained (3 g starting from 650 g ferric nitrate), doubts remain as to whether Ee(0) was the... 

A suspension of sodium amide (0.275 mole) (Note 1) in liquid ammonia is prepared in the following manner in a 1-1. threenecked flask equipped with an air condenser (Note 2), a sealed mechanical stirrer, and a dropping funnel. Commercial anhydrous liquid ammonia (600 ml.) is introduced by pouring from an Erlenmeyer flask (Note 3). To the stirred liquid ammonia is added a small piece of sodium. After the appearance of a permanent blue color (Note 4) a few crystals of ferric nitrate hydrate (ica. 0.1 g.) are added, followed by small pieces of freshly cut sodium (Note 5) until 6.32 g. (0.275 g. atom) has been added. After all the sodium is converted to the amide (Note 6), 42.0 g. (0.250 mole) of diphenylmethane (Note 7) in 20 ml. of anhydrous ether is added (Note 8). The deep red suspension is stirred for 15 minutes. n-Butyl bromide (37.6 g., 0.274 mole) (Note 7) in... 

B. 2-Methylbenzyldimethylamine. Caution This preparation should he conducted in a good hood to avoid exposure to ammonia.) To 800 ml. of liquid ammonia contained in a 2-1. three-necked flask fitted with a rubber slip-sleeve-sealed wire stirrer and an aircooled reflux condenser, sodium is added in small pieces until the blue color persists (Note 6). At this point 0.5 g. of granulated ferric nitrate is added, and then 27.8 g. (1.2 gram atom) of sodium (cut into approximately 0.5-g. pieces), is introduced at such a rate that stirring is not hindered. After all the sodium is added (about 15 minutes), the mixture is stirred until the blue color disappears and the grayish-black suspension of sodium amide remains (15-20 minutes). Stirring is discontinued, and the mixture is swirled to wash down the mirror of sodium which forms on the upper walls of the flask (Note 7). 

Ferric nitrate/KlO bentonite clay (Clayfen). The reagent is prepared by addition of the clay to Fe(N03)3 in acetone followed by evaporation of the solvent at temperatures below 50°. Warning An unstable reagent is formed at higher temperatures.1... 

Approximately 3.8 grams of sodamide is freshly prepared from 2.25 grams of sodium, 90 grams of liquid ammonia and a catalytic trace of ferric nitrate. The ammonia is allowed to evaporate. A solution of 19.1 grams of 2-... 

In the case of the very dilute acid of density less than 1 034, solution is not accompanied by evolution of gas, but with the formation of ferrous nitrate and ammonium nitrate.2 If acid of density ranging from 1 034 upwards to 1 115 be employed, the resulting solution consists of a mixture of ferrous nitrate and ferric nitrate, the proportion of the latter increasing with the density of the acid. With acid of greater density than 1 115, ferric nitrate is the main product, and acid of density 1 33 is therefore recommended for the preparation of this salt.2... 

Preparation. Thompson et al. recommend that the salt be prepared by sodium hypochlorite oxidation of ferric nitrate. A somewhat tedious purification procedure is nece.ssary to obtain material of 92 96% purity in yields of 44-76%. 

Potassium ferrate, K2Fe04, which is prepared from ferric nitrate and alkaline hypochlorites [916], is a selective oxidant for the conversion of primary alcohols into aldehydes (not acids), of secondary alcohols into ketones, and of primary amines into aldehydes [917, 918]. 

Generation of reactive anions. In a typical alkylation of a ketone, Vanderwerf and Lemmerman prepared a grey suspension of sodium amide under nitrogen (1.5 I. of ammonia, a trace of ferric nitrate, and 2.05 g. atoms of sodium), added 1.2 1. of ether as rapidly as vaporization of ammonia permitted, warmed the mixture... 

---