Diisopropylethylamine → HCID 178464575, compound

HRID 1197811Notes

Reaction equation

HRID 1197811 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[N:10]=[C:11]=S)([O-:3])=[O:2].[N:13]#[C:14][NH2:15].[Na].C(N(C(C)C)CC)(C)C.[NH2:26][CH:27]([C:29]([CH3:32])([CH3:31])[CH3:30])[CH3:28].Cl.CN(C)CCCN=C=NCC>O1CCOCC1.CN(C)C=O>[C:14]([N:15]=[C:11]([NH:26][CH:27]([CH3:28])[C:29]([CH3:32])([CH3:31])[CH3:30])[NH:10][C:5]1[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=1[N+:1]([O-:3])=[O:2])#[N:13]

Participants

8

Reactant 5

HCID 81531DiisopropylethylamineHCID 1376902-Nitrophenyl isothiocyanateHCID 5209072-Butanamine, 3,3-dimethyl-HCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochlorideHCID 57375518Cyanamidnatrium

Product 1

HCID 178464575HCID 178464575, compoundYield 57.1%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
85 °C

Procedure

A mixture of 2-nitrophenyl isothiocyanate (6.00 g, 33 mmol) and monosodium cyanamide (1.92 g, 30 mmol) in dioxane (15 ml) was heated at 85° C. (oil bath) overnight under argon. The reaction was then diluted with dimethylformamide (15 ml). Diisopropylethylamine (2.76 ml, 33 mmol) and 2-amino-3,3-dimethyl butane (2.36 ml, 33 mmol) were added, and the resulting mixture was treated with 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (7.68 g, 44 mmol). After stirring for 1 hour, the reaction was partitioned between ethyl acetate and 1N hydrochloric acid. The organic phase was washed with water (four times) and saturated sodium chloride solution, dried over anhydrous magnesium sulfate, and evaporated. The crude product was flash chromatographed (4% EtOAc/CH2Cl2) over Merck silica (650 g). The fractions containing the desired product were combined and evaporated to give the title compound as a yellow oil (4.96 g) which was crystallized to give free-flowing yellow crystals (2.31 g), m.p. 116°-118° C. TLC (40% Acetone/Hexane) single spot, Rf =0.33. TLC (10% EtOAc/CH2Cl2) single spot, Rf =0.49.

Workup

  1. customthe reaction was partitioned between ethyl acetate and 1N hydrochloric acid
  2. washThe organic phase was washed with water (four times) and saturated sodium chloride solution
  3. dry with materialdried over anhydrous magnesium sulfate
  4. customevaporated
  5. customchromatographed (4% EtOAc/CH2Cl2) over Merck silica (650 g)
  6. additionThe fractions containing the desired product
  7. customevaporated

Sources & evidence

ORD record
ord-f50b91e1aedb409984158517934f98ee
Source dataset
uspto-grants-1994_01
Patent number
US05278169

Reaction notes

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