Sodium diformylamide

Sodium diformylamide [18197-26-7] M 95.0. Grind under dry tetrahydrofiiran (fumehood), filter and wash with this solvent then dry in vacuum. [IR and prepn Synthesis 122 7990 Chem Ber 100 355 1967, 102 4089 7969.]... 

A number of syntheses of primary amines from reagents other than potassium phthal-imide has been described (Review Reference 46). Sodium diformylamide is a convenient substitute. It is alkylated in DMF or acetonitrile by adding an alkyl halide or tosylate and the products are decomposed by adding dilute hydrochloric acid to give alkylamine hydrochlorides in excellent yields (equation 15)47. 

Sodium diformylamide [18197-26-7] M 95.0. Grind under dry tetrahydrofuran (fumehood), filter and... 

Other nucleophiles have been used in this reaction. For example, BINAP was shown to be the best ligand for the enantioselective allylic amination of 19 with sodium diformylamide, a protected ammonia equivalent, furnishing the desired product in good yield and excellent enantioselectivity [96]. Also, a P,N-ligand has been developed for the allylic sulfonylation with good ee but moderate yield [97]. 

Han, Y., Hu, H. A convenient synthesis of primary amines using sodium diformylamide as a modified Gabriel reagent. Synthesis 1990, 122-124. 

Sodium diformylamide 2. A mixture of formamide 1 (90 g, 2 mol) and NaOMe in MeOH (23.5 g Na in MeOH 200mL) was stirred at 20°C for 1 h, then was slowly evaporated on a Rotavap for 2 h at 80-90°C. The crystalline product after drying under vacuum for 3h afforded 95 g of 2 (100%) pure enough for the next step. 

Allylation of ammonia gives a mixture of products, and it is difficult to prepare primary amines from ammonia, and several ammonia surrogates are used. Allylation of sodium diformylamide (219) with the allyl acetate 218 proceeded smoothly by using DPPF as a ligand to afford 220, which was hydrolyzed to provide the primary allylamine 221. The reaction was sluggish when PPhs was used. The primary allylamine 224 with high ee (95.5 %) was obtained from 94 via 223 by the use of (5)-BINAP [81]. 

Figure IL New DALA synthesis from levulinic acid with sodium diformylamide as nucleophilic aminating agent (Reproduced from reference 58,)...

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