Sodium Hydroxide → Ethyl acetate methanol ammonia

HRID 890909Notes

Reaction equation

HRID 890909 reaction equation
[N:1]([O-])=O.[Na+].N(O)=[O:6].Cl.Cl.[C:10]1(N[CH2:21][CH2:22]N)C2C(=CC=CC=2)C=CC=1.N[C:25]1[C:33]2N=NNC=2C=CC=1.[OH-:34].[Na+]>Cl.C([O-])(=O)C.[Na+].CC(C)=O>[CH3:33][CH2:25][O:34][C:21]([CH3:22])=[O:6].[CH3:10][OH:34].[NH3:1]

Participants

9

Reactant 5

HCID 14798Sodium HydroxideHCID 15106N-1-Naphthylethylenediamine dihydrochlorideHCID 24529Nitrous AcidHCID 23668193Sodium Nitrite2×HCID 178507462HCID 178507462, compound

Product 1

HCID 21873639Ethyl acetate methanol ammoniaYield 66%

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 313Hydrochloric AcidSolventHCID 517045Sodium AcetateSolvent

Procedure

In more detail, to provide N1-[4-(5-Azobenzotriazoyl)phenyl]-ethane-1,2-diamine (=Compound 1), 5-Aminobenzotriazole (0.854 g, 1.1 eq, 6.37 mmol) was dissolved in HCl (5ml, 50% v/v) and diazotised by dropwise addition of sodium nitrite (0.484 g, 1.2 eq, in 5 ml H2O) at 0° C. An excess of sodium nitrite was detected using starch iodide paper. A dark blue colour indicated excess nitrous acid which inferred the formation of the diazonium salt. Separately N-(1-Naphthyl) ethylenediamine dihydrochloride (1.500 g, 5.79 mmol) was dissolved in sodium acetate buffer (1.0M, 60 ml, pH 6.0) and acetone (80 ml). Diazotised aminobenzotriazole (1.1 eq) was added to this solution dropwise at 0° C. with stirring over 1 hour after which the solution was neutralised by addition of sodium hydroxide (2M). The solid produced was isolated by filtration and washed with sat. KCl (3×50 ml) prior to purification by trituration using methanol and diethyl ether to produce the title compound as an orange solid in 66% yield Rf (EtOAc/CH3OH/NH3 5/1/1) 0.14; dH (270 MHz, CD3OH) 3.00 (2H, t, CH2) 3.48 (2H, t, CH2) 6.69 (1H, dd, arH) 7.51 (1H, t, arH) 7.63 (1H, t, arH) 7.87 (1H, d, arH) 7.94 (2H, m, arHs) 8.13 (1H, d, arH) 8.34 (1H, s, arH) 9.02 (1H, d, arH); dc(270 MHz, CD3OD) 41.40 (CH2) 47.01 (CH2) 104.26 (CH) 114.93 (CH) 115.13 (CH) 116.67 (CH) 117.47 (CH) 122.20 (CH) 124.26 (C) 124.73 (CH) 126.03 (CH) 127.91 (CH) 134.62 (C) 139.91 (C) 146.12 (C) 146.76 (C) 148.98 (C) 151 28 (C); FAB ms m/z 332.1621 [C18H18N7 (M+1) <0.1 ppm].

Workup

  1. customThe solid produced
  2. customwas isolated by filtration
  3. washwashed with sat. KCl (3×50 ml)
  4. customto purification by trituration

Sources & evidence

ORD record
ord-06ec18926999491cb25f99b65b58f0b3
Source dataset
uspto-grants-2006_02
Patent number
US07001721B1

Reaction notes

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