Methanol → N-Dodecyl-4,5-dimethyl-benzene-1,2-diamine

HRID 217417

反応式

HRID 217417 の反応式
[CH3:1][C:2]1[CH:3]=[C:4]([NH2:10])[C:5]([NH2:9])=[CH:6][C:7]=1[CH3:8].Cl[CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH3:23].ClCCl.CO>C(N(CC)CC)C>[CH2:23]([NH:9][C:5]1[C:4]([NH2:10])=[CH:3][C:2]([CH3:1])=[C:7]([CH3:8])[CH:6]=1)[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18][CH2:17][CH2:16][CH2:15][CH2:14][CH2:13][CH3:12]

参加物

6

反応物 4

HCID 887MethanolHCID 6344DichloromethaneHCID 81921-ChlorododecaneHCID 766354,5-Dimethyl-1,2-phenylenediamine

生成物 1

HCID 86639203N-Dodecyl-4,5-dimethyl-benzene-1,2-diamine収率 60%

試薬・触媒・溶媒 1

HCID 8471Triethylamine溶媒

反応条件

温度
130 °C

実験手順

A mixture of 4.08 g (30 millimoles (mmol)) of 4,5-dimethyl-benzene-1,2-diamine (hereinafter compound “1”) and 2.04 grams (g) (10 mmol) of 1-chloro-dodecane in 20 milliliters (mL) of triethylamine was stirred at 130° C. for 6 hrs under argon. After cooling and addition of dichloromethane (100 mL), the organic solution was washed with aqueous Na2CO3 solution (10%, 40 mL). The aqueous layer was extracted twice with dichloromethane (2×100 mL). The combined organic extracts were dried over MgSO4 and rotary evaporated to dryness. The thin-layer chromatography retention factor (Rf) of the target compound (2) was 0.55 with dichloromethane (MC):methanol (MeOH) (95:5) mixture. Compound (2) was purified by flash chromatography on silica gel in MC:MeOH (95:5) to produce 1.8 g of reddish crystals (60% yield); mp 53-54° C.; 1H NMR (400 MHz, CDCl3) δ 6.56 (1H, s), 6.50 (1H, s), 3.20 (3H, broad s), 3.1 (2H, t, J=8 Hz), 2.26 (3H, s), 2.21 (3H, s), 1.68 (2H, q, J=7 Hz), 1.46 (2H, m), 1.34 (16H, s), 0.92 (3H, t, J=8 Hz); 13C NMR (100 MHz, CDCl3) δ 136.0, 131.8, 128.1, 125.9, 118.4, 113.93, 44.7, 31.9, 29.9, 29.69, 29.65, 29.5, 29.4; Anal. Calcd. for C20H36N2 (MW=304.51): C, 78.88; H, 11.92; N, 9.20. Found: C, 78.95; H, 12.16; N, 9.32.

後処理

  1. temperatureAfter cooling
  2. washthe organic solution was washed with aqueous Na2CO3 solution (10%, 40 mL)
  3. extractionThe aqueous layer was extracted twice with dichloromethane (2×100 mL)
  4. dry with materialThe combined organic extracts were dried over MgSO4
  5. customrotary evaporated to dryness
  6. customCompound (2) was purified by flash chromatography on silica gel in MC

出典と根拠

ORDレコード
ord-a1441b65920c45d8b388b09b851b2432
出典データセット
uspto-grants-2012_06
特許番号
US08193430B2

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