Iodine → (2R,6R)-(+)-1-tert. Butoxy-2,6,10-trimethylundecane

HRID 1701239ノート

反応式

HRID 1701239 の反応式
[Mg].II.Br[CH2:5][CH2:6][C@H:7]([CH3:14])[CH2:8][CH2:9][CH2:10][CH:11]([CH3:13])[CH3:12].C1(C)C=CC(S(O[CH2:25][C@@H:26]([CH3:33])[CH2:27][O:28][C:29]([CH3:32])([CH3:31])[CH3:30])(=O)=O)=CC=1.OS(O)(=O)=O>O1CCCC1>[C:29]([O:28][CH2:27][C@H:26]([CH3:33])[CH2:25][CH2:5][CH2:6][C@H:7]([CH3:14])[CH2:8][CH2:9][CH2:10][CH:11]([CH3:13])[CH3:12])([CH3:32])([CH3:31])[CH3:30]

参加物

7

反応物 5

HCID 807IodineHCID 1118Sulfuric AcidHCID 5462224MagnesiumHCID 12801557(R)-1-bromo-3,7-dimethyloctaneHCID 86735106(S)-(+)-3-tert. butoxy-2-methyl-1-propyl p-toluenesulfonate

生成物 1

HCID 12923314(2R,6R)-(+)-1-tert. Butoxy-2,6,10-trimethylundecane

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒4 回

実験手順

A mixture of 2.33 g. (0.097 mole) of powdered magnesium and a few iodine crystals in 23 ml. of dry tetrahydrofuran was stirred at reflux temperature while a solution of 17.9 g. (0.08 mole) of (R)-(-)-1-bromo-3,7-dimethyloctane in 51 ml. of dry tetrahydrofuran was added dropwise over 1 hour. The mixture was stirred at reflux for an additional 1 hour then cooled to room temperature. To a solution of 19.5 g. (0.065 mole) of (S)-(+)-3-tert. butoxy-2-methyl-1-propyl p-toluenesulfonate in 56 ml. of dry tetrahydrofuran, stirring at -78° C. was added the R-3,7-dimethyl-1-octyl magnesium bromide solution dropwise, followed by 3.3 ml. of a 0.1 M Li2CuCl4 solution in dry tetrahydrofuran. The resulting mixture was stirred at -78° C. for 10 minutes, for 2 hours at 0°-5° C. (ice bath) and finally for 18 hours at room temperature. At the end of this time, the reaction mixture was treated with 1 N aqueous H2SO4 and work up was carried out by extraction with ether in the manner of Example 1. The crude product was chromatographed on 450 g. of silica gel. Elution with 19:1 parts by volume hexane-ether gave the desired product which was distilled under high vacuum yielding 12.5 g. of (2R,6R)-(+)-1-tert. butoxy-2,6,10-trimethylundecane as a colorless oil, b.p. 91°-95° C. (0.3 mm Hg); [α]25D+0.94° (c 2.01, hexane).

後処理

  1. additionA mixture of 2.33 g
  2. temperatureat reflux temperature while a solution of 17.9 g
  3. temperatureat reflux for an additional 1 hour
  4. stirringThe resulting mixture was stirred at -78° C. for 10 minutes, for 2 hours at 0°-5° C. (ice bath)
  5. extractionup was carried out by extraction with ether in the manner of Example 1
  6. customThe crude product was chromatographed on 450 g
  7. washElution with 19:1 parts by volume hexane-ether

出典と根拠

ORDレコード
ord-34e94312258449aeba66cb6a79ff15db
出典データセット
uspto-grants-1980_03
特許番号
US04191842

反応ノート

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