1,2-Dichloroethane → HCID 21848475, compound

HRID 618783Notes

Reaction equation

HRID 618783 reaction equation
[C:1](#[N:5])[CH2:2][C:3]#[N:4].[C:6]1([N:12]=[C:13]=S)[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.C(Cl)CCl.[CH3:19][CH:20]([CH3:24])[CH2:21][CH2:22][NH2:23].Cl>CN(C=O)C.C(N(CC)CC)C>[C:3]([C:2](=[C:13]([NH:23][CH2:22][CH2:21][CH:20]([CH3:24])[CH3:19])[NH:12][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)[C:1]#[N:5])#[N:4]

Participants

8

Reactant 5

HCID 111,2-DichloroethaneHCID 313Hydrochloric AcidHCID 7673Phenyl IsothiocyanateHCID 7894IsoamylamineHCID 8010Malononitrile

Product 1

HCID 21848475HCID 21848475, compoundYield 47%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 8471TriethylamineSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of malononitrile (0.34 g, 5.15 mmol) in DMF (5 mL) at 0° C. first phenylisothiocyanate (0.60 mL, 5.02 mmol) and then triethylamine (1.4 mL) were added. The resulting mixture was stirred at 0° C. for 25 min, and then a freshly prepared mixture of EDC (2.90 g, 15.1 mmol), 3-methylbutylamine (1.20 mL, 10.3 mmol) and DMF (10 mL) was added. After stirring at room temperature for 2 d the mixture was poured into a mixture of ice-water (50 mL) and conc. HCl (3.0 mL). The product was extracted (2×30 mL ethyl acetate), the combined organic extracts were washed (2×30 mL brine), dried (magnesium sulfate) and concentrated. The remaining oil was mixed with methanol (3 mL), whereby a solid precipitated. After 20 h the solid was filtered off and dried in vacuo. 0.60 g (47%) of the title compound was obtained as slightly yellow crystals. Recrystallization from ethyl acetate/heptane yielded 0.40 g of an analytically pure sample, mp. 183-185° C. LCMS: MH+ calcd.: 255, found: 255. 1H NMR (400 MHz, DMSO-d6): δ=0.83 (d, J=7 Hz, 6H), 1.40 (q, J=7 Hz, 2H), 1.57 (nonett, J=7 Hz, 1H), 3.18 (m, 2H), 7.10 (m, 3H), 7.33 (t, J=8 Hz, 2H), 7,87 (s, br, 1H), 9.33 (s, 1H); 13C NMR (100 MHz, DMSO-d6): δ=22.06, 24.90, 35.34, 37.38, 41.92, 118.11, 121.46, 124.16, 129.15, 138.81, 161.43. Anal. Calcd. for C15H18N4 (254.34): C, 70.84; H, 7.13; N, 22.03. Found: C, 70.88; H, 7.28; N, 21.90.

Workup

  1. additionwas added
  2. stirringAfter stirring at room temperature for 2 d the mixture
  3. extractionThe product was extracted (2×30 mL ethyl acetate)
  4. washthe combined organic extracts were washed (2×30 mL brine)
  5. dry with materialdried (magnesium sulfate)
  6. concentrationconcentrated
  7. additionThe remaining oil was mixed with methanol (3 mL), whereby a solid
  8. customprecipitated
  9. filtrationAfter 20 h the solid was filtered off
  10. customdried in vacuo

Sources & evidence

ORD record
ord-4dd89e5b5d7148c18203a70f696f6a4b
Source dataset
uspto-grants-1999_09
Patent number
US05955548

Reaction notes

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