Malonic Acid → N,N'-Dicyclohexylurea

HRID 1786657Notes

Reaction equation

HRID 1786657 reaction equation
C(O)(=O)CC(O)=[O:4].[CH2:8]1[CH2:13][CH2:12][CH:11]([N:14]=[C:15]=[N:16][CH:17]2[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]2)[CH2:10][CH2:9]1>C(Cl)Cl.CN(C1C=CN=CC=1)C>[CH:17]1([NH:16][C:15]([NH:14][CH:11]2[CH2:10][CH2:9][CH2:8][CH2:13][CH2:12]2)=[O:4])[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]1

Participants

5

Reactant 2

HCID 867Malonic AcidHCID 10868Dicyclohexylcarbodiimide

Product 1

HCID 4277N,N'-DicyclohexylureaYield 60%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

104 mg (1 mmol) of malonic acid and 1.23 g (2.2 mmol) of alcohol 7 were dissolved in dry CH2Cl2 under N2 protection and the solution cooled in an ice bath. 41.0 mg (0.20 mmol) DMAP (10 mol %) and 454 mg (2.20 mmol) DCC were added subsequently. After stirring under N2-protection for 15 min at 0° C. and 2 h at RT, TLC control showed complete conversion of the starting material. Dicyclohexyl urea formed during the reaction precipitated and was filtered off. Traces of urea were subsequently removed by repeated precipitation from ethyl acetate. After evaporation of the solvent and purification by FC on silica (CH2Cl2:EtOH=94:6) 714 mg of a white solid was obtained (yield 60%).—1H NMR (400 MHz, RT, CDCl3): δ=6.22, 4.97 (2br, 4H), 4.11 (t, 3J=6.8 Hz, 4H), 3.66-3.48 (3m, 12H), 3.34 (s, 2H), 3.33 (dt, 4H), 3.20 (dt, 4H), 2.11 (t, 3J=7.6 Hz, 4H), 1.74 (m, 4H), 1.60 (m, 4H), 1.41 (s, 18H), 1.35-1.19 (m, 40H).—13C NMR (100.5 MHz, RT, CDCl3): δ=172.9 (2C), 166.4 (2C), 155.8 (2C), 78.9 (2C), 70.5, 70.5, 70.2, 70.1, 70.1, 69.5 (12C), 65.6 (2C), 41.7 (1C), 38.6, 37.9 (4C), 36.9 (2C), 29.7, 29.7, 29.6, 29.6, 29.5, 29.4, 29.3, 29.1 (20C), 28.5 (6C), 25.9, 25.8 (4C).—IR (Film/KBr): ν=3312, 3082, 2919, 2851, 1747, 1719, 1685, 1640, 1543, 1468, 1390, 1366, 1347, 1251, 1182, 1127, 1021, 997, 867, 720, 694, 603 cm−1.—MS (FAB): m/z=1322 [M+Cs]+, 1212 [M+Na]+, 1190 [M]+, 1190, 990, 443.

Workup

  1. temperaturethe solution cooled in an ice bath
  2. custom2 h
  3. customat RT

Sources & evidence

ORD record
ord-a72737089aaa4ad48c4a57342ae8adb2
Source dataset
uspto-grants-2009_03
Patent number
US07507764B2

Reaction notes

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