(4-Chlorobenzyl)triphenylphosphonium chloride → E-[4-(4-chloro-benzylidene)-2-(3-methoxy-phenyl)-cyclohex-2-enylmethyl]-dimethyl-amine

HRID 1838115ノート

反応式

HRID 1838115 の反応式
CC([O-])(C)C.[K+].[Cl-].[Cl:8][C:9]1[CH:34]=[CH:33][C:12]([CH2:13][P+](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=[CH:11][CH:10]=1.[CH3:35][N:36]([CH2:38][CH:39]1[CH2:44][CH2:43][C:42](=O)[CH:41]=[C:40]1[C:46]1[CH:51]=[CH:50][CH:49]=[C:48]([O:52][CH3:53])[CH:47]=1)[CH3:37]>C1(C)C=CC=CC=1>[Cl:8][C:9]1[CH:10]=[CH:11][C:12](/[CH:13]=[C:42]2/[CH:41]=[C:40]([C:46]3[CH:51]=[CH:50][CH:49]=[C:48]([O:52][CH3:53])[CH:47]=3)[CH:39]([CH2:38][N:36]([CH3:37])[CH3:35])[CH2:44][CH2:43]/2)=[CH:33][CH:34]=1

参加物

5

反応物 3

HCID 2733546(4-Chlorobenzyl)triphenylphosphonium chlorideHCID 155411074-Dimethylaminomethyl-3-(3-methoxy-phenyl)-cyclohex-2-enoneHCID 23665647Potassium tert-butoxide

生成物 1

HCID 59059227E-[4-(4-chloro-benzylidene)-2-(3-methoxy-phenyl)-cyclohex-2-enylmethyl]-dimethyl-amine収率 31.9%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒2 回

反応条件

温度
70 °C

実験手順

21.6 g potassium tert-butylate and 65 g 4-chlorobenzyltriphenylphosphonium chloride were suspended in 800 ml analytical grade toluene under a nitrogen atmosphere at room temperature and the suspension was then stirred at 70° C. for one hour. 11.5 g 4-dimethylaminomethyl-3-(3-methoxy-phenyl)-cyclohex-2-enone in 100 ml analytical grade toluene were added at this temperature and the mixture was stirred at 70° C. for 3 days. The mixture was quenched with 500 ml water. The phases were separated and the aqueous phase was washed 3 times with 200 ml ethyl acetate each time. The combined organic phases were dried over magnesium sulfate and then freed from the solvent in vacuo. The solid which had precipitated out was filtered off and washed with diiso-ether. The combined organic phases were freed from the solvent in vacuo. The residue was purified by column chromatography on silica gel with ethyl acetate/methanol=9/1. 5.2 g E-[4-(4-chloro-benzylidene)-2-(3-methoxy-phenyl)-cyclohex-2-enylmethyl]-dimethyl-amine base were obtained as the first product fraction. To prepare the hydrochloride, the base was dissolved in 50 ml acetone, and an equimolar amount of trimethylchlorosilane and water was added. 4.7 g (27.6% of theory) of the title compound 46 were obtained in this way in the form of white crystals. 3.5 g Z-[4-(4-chloro-benzylidene)-2-(3-methoxy-phenyl)-cyclohex-2-enylmethyl]-dimethyl-amine base were obtained as the second product fraction. To liberate the hydrochloride, the base was dissolved in 50 ml acetone, and an equimolar amount of trimethylchlorosilane and water was added. 3 g (17.6% of theory) of the title compound 41 were obtained in this way in the form of white crystals.

後処理

  1. stirringthe mixture was stirred at 70° C. for 3 days
  2. customThe mixture was quenched with 500 ml water
  3. customThe phases were separated
  4. washthe aqueous phase was washed 3 times with 200 ml ethyl acetate each time
  5. dry with materialThe combined organic phases were dried over magnesium sulfate
  6. customThe solid which had precipitated out
  7. filtrationwas filtered off
  8. washwashed with diiso-ether
  9. customThe residue was purified by column chromatography on silica gel with ethyl acetate/methanol=9/1

出典と根拠

ORDレコード
ord-9586356d533746159b15597ecd8d5bb3
出典データセット
uspto-grants-2004_01
特許番号
US06673794B2

反応ノート

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