N,N,N',N'-Tetramethylethylenediamine → HCID 13146587, compound

HRID 1701936Notes

Reaction equation

HRID 1701936 reaction equation
[CH3:1][Si:2]([CH3:17])([CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16])[C:3]1[CH:4]=[C:5]([O:9][CH3:10])[CH:6]=[CH:7][CH:8]=1.CN(C)CCN(C)C.C([Li])CCC.[Li].C([Cu])#CCCCC.[C:39]1(=[O:45])[CH2:44][CH2:43][CH2:42][CH:41]=[CH:40]1.[Cl-].[NH4+].[OH-].[NH4+]>CCCCCC.O1CCCC1.C(OCC)C>[CH3:17][Si:2]([CH3:1])([CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16])[C:3]1[CH:8]=[CH:7][C:6]([CH:41]2[CH2:42][CH2:43][CH2:44][C:39](=[O:45])[CH2:40]2)=[C:5]([O:9][CH3:10])[CH:4]=1

Participants

11

Reactant 7

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 135942-Cyclohexen-1-oneHCID 14923Ammonium HydroxideHCID 25517Ammonium ChlorideHCID 13146586HCID 13146586, compoundHCID 178418339ButyllithiumHCID 178444234HCID 178444234, compound

Product 1

HCID 13146587HCID 13146587, compoundYield 36%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

To a 25° C. solution of 2.00 g. (8.0 mmole) of 3-(dimethyl-n-hexylsilyl)-1-methoxybenzene and 1.32 ml. (8.8 mmole) of N,N,N',N'-tetramethylethylenediamine in 8 ml. diethyl ether was added 3.2 ml. of 2.5 M n-butyllithium in hexane. The reaction solution was heated at reflux for 1 hr and then cooled to -78° C. To the -78° C. solution was added 9.68 mmole of 1-hexynyl copper lithium in 20 ml. tetrahydrofuran. The resultant yellow mixture was stirred 5 minute at -78° C. and then 768 mg. (8.0 mmole) of cyclohex-2-en-1-one was slowly added. The reaction mixture was stirred for 5 minute longer at -78° C. and then warmed to -20° C. and stirred for 5 minute. The reaction mixture was added to 500 ml. saturated aqueous ammonium chloride adjusted to pH 9 with saturated aqueous ammonium hydroxide. The quenched reaction was extracted five times with 500 ml. diethyl ether. The diethyl ether extracts were dried over magnesium sulfate and evaporated to an oil. The crude oil was purified by column chromatography on 200 g. of silica gel eluted with 10% diethyl ether-hexane to yield 1.0 g. (36%) of the title compound as an oil.

Workup

  1. customTo a 25° C.
  2. temperatureThe reaction solution was heated
  3. temperatureat reflux for 1 hr
  4. stirringThe reaction mixture was stirred for 5 minute longer at -78° C.
  5. temperaturewarmed to -20° C.
  6. stirringstirred for 5 minute
  7. additionThe reaction mixture was added to 500 ml
  8. customThe quenched reaction
  9. extractionwas extracted five times with 500 ml
  10. dry with materialThe diethyl ether extracts were dried over magnesium sulfate
  11. customevaporated to an oil
  12. customThe crude oil was purified by column chromatography on 200 g
  13. washof silica gel eluted with 10% diethyl ether-hexane
  14. customto yield 1.0 g

Sources & evidence

ORD record
ord-09d29270f69744d4841bc7745f8afc39
Source dataset
uspto-grants-1983_04
Patent number
US04379783

Reaction notes

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