Methyl Chloride → 2-(4-Methylbenzoxazolyl)-5-(hydroxylmethyl)-1,4-bis(hexyloxy)benzene

HRID 1528559ノート

反応式

HRID 1528559 の反応式
[NH2:1][C:2]1[C:7]([OH:8])=[CH:6][CH:5]=[CH:4][C:3]=1[CH3:9].[CH2:10]([O:16][C:17]1[CH:24]=[C:23]([CH2:25][OH:26])[C:22]([O:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH3:33])=[CH:21][C:18]=1[CH:19]=O)[CH2:11][CH2:12][CH2:13][CH2:14][CH3:15].ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl.C([O-])([O-])=O.[Na+].[Na+].CCl>C(Cl)Cl.CO>[CH3:9][C:3]1[C:2]2[N:1]=[C:19]([C:18]3[CH:21]=[C:22]([O:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH3:33])[C:23]([CH2:25][OH:26])=[CH:24][C:17]=3[O:16][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH3:15])[O:8][C:7]=2[CH:6]=[CH:5][CH:4]=1

参加物

8

反応物 5

HCID 6327Methyl ChlorideHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 10340Sodium CarbonateHCID 30141382-Amino-m-cresolHCID 867124922,5-Bis(hexyloxy)-4-(hydroxymethyl)benzaldehyde

生成物 1

HCID 867124912-(4-Methylbenzoxazolyl)-5-(hydroxylmethyl)-1,4-bis(hexyloxy)benzene

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 6344Dichloromethane溶媒

実験手順

Herein, the detailed synthetic procedure is described to illustrate the features related to the compound preparations, chemical synthesis, and spectroscopic properties. For the first reaction shown in Scheme 1, activated molecular sieves (5 Å) was added to 100 mL MeOH in 500 mL flask. Into this flask were charged 2-amino-m-cresol (2.39 g, 21.7 mmol) and 2,5-bis(hexyloxy)-4-(hydroxymethyl)benzaldehyde (2.54 g, 21.7 mmol). The resulting mixture solution was heated to reflux overnight. The solution was cooled to room temperature, filtered, and solvent was removed using a rotary evaporator. Then solution of DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) (4.85 g, 21.4 mmol) in 700 mL CH2Cl2 was added to the above residue. After stirring at room temperature for 2 h, the reaction mixture was treated with 400 mL saturated Na2CO3 and methyl chloride to remove the DDQH by-product, then washed with water and brine, and dried over Na2SO4. After evaporation of the solvent, the solid residues were collected and purified on a silica gel column by using an eluant (hexane:CH3COOEt=15:1). After recrystallization from methanol, the product 2-(4-methylbenzoxazolyl)-5-(hydroxylmethyl)-1,4-bis(hexyloxy)benzene was obtained as an off-white solid (7.8 g, 81.8%), which has the following spectral properties. 1H NMR (CDCl3, 300 MHz, δ): 7.58 (s, 1H), 7.39 (d, J=8.4 Hz, 1H), 7.32 (dd, J=8.4 Hz, J=8.1 Hz, 1H), 7.14 (d, J=7.5 Hz, 1H), 7.06 (s, 1H), 4.74 (d, J=6.6 Hz, 2H), 4.07 (tt, J=6.3 Hz, 4H), 2.68 (s, 3H), 1.83 (m, 4H), 1.58 (m, 4H), 1.34 (m, 8H), 0.89 (m, 6H). MS (EI): [M+H+]+=356.3, [M+Na+]+=462.3.

後処理

  1. customrelated to the compound preparations, chemical synthesis, and spectroscopic properties
  2. customFor the first reaction
  3. temperatureThe resulting mixture solution was heated
  4. temperatureto reflux overnight
  5. filtrationfiltered
  6. customsolvent was removed
  7. customa rotary evaporator
  8. customto remove the DDQH by-product
  9. washwashed with water and brine
  10. dry with materialdried over Na2SO4
  11. customAfter evaporation of the solvent
  12. customthe solid residues were collected
  13. custompurified on a silica gel column
  14. customAfter recrystallization from methanol

出典と根拠

ORDレコード
ord-dfa06ad61ef54d8b9b8cb78e6091c916
出典データセット
uspto-grants-2015_07
特許番号
US09090602B2

反応ノート

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