Methanethiol → 1-Butanone, 3-(methylthio)-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-

HRID 262354

Reaktionsgleichung

Reaktionsgleichung von HRID 262354
[CH3:1]/[CH:2]=[CH:3]/[C:4]([C:6]1[C:11]([CH3:13])([CH3:12])[CH2:10][CH:9]=[CH:8][C:7]=1[CH3:14])=[O:5].C(N(CC)CC)C.[CH3:22][SH:23]>CCOCC>[CH3:22][S:23][CH:2]([CH3:1])[CH2:3][C:4]([C:6]1[C:11]([CH3:13])([CH3:12])[CH2:10][CH:9]=[CH:8][C:7]=1[CH3:14])=[O:5]

Komponenten

5

Edukt 3

HCID 878MethanethiolHCID 8471TriethylamineHCID 5366074beta-Damascenone

Produkt 1

HCID 30853881-Butanone, 3-(methylthio)-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 3283Diethyl EtherLösungsmittel

Reaktionsbedingungen

Temperatur
10 °C

Versuchsvorschrift

In a 50 ml, three-necked, round-bottom flask equipped with a magnetic stirring assembly, a tube submerged for the introduction of gas, an immersion thermometer and a dry ice isopropanol condenser, the outlet of which leads through a 50% alkali trap to the hood sink, is placed 8.3 grams of beta-damascenone and approximately 1 gram of triethylamine. Gaseous methyl mercaptan is introduced into the stirred reaction mixture which is maintained at 10° C. Addition is continued for approximately one hour and then stopped. The stirred reaction mix is allowed to attain room temperature, and the reaction mix is stirred overnight at room temperature. The next morning the light yellow reaction mix is transferred to 50 ml of ether in a separatory funnel and washed twice with dilute sulfuric acid, twice with saturated sodium bicarbonate solution, and then with saturated saline solution until the wash is neutral. The dried ether layer is stripped of solvent on a `rotovap` and GLC of the residue on an 1/8'×10" stainless steel, 5% carbowax 20 M column isothermally at 190° C. shows one major late eluting peak which is trapped for infra-red and nuclear magnetic resonance/mass spectral analyses. Infra-red analysis suggests that the cyclohexadienyl ring structure is intact and in conjugation with the side chain ketone which is, however, now out of cross conjugation. Therefore, reaction appears to have occurred at the side chain olefinic site. Mass spectral analysis shows a molecular weight of 238, and the proper fragmentation for the proposed structure. The mass spectral analysis also is a satisfactory match with the scan for peak "A" as set forth in Example I. This peak has an IE on SE-30 of 13.00. A trap of the synthetic material is run for IE and the IE on SE-30 is 13.08.

Aufarbeitung

  1. customIn a 50 ml, three-necked, round-bottom flask equipped with
  2. customa tube submerged for the introduction of gas
  3. additionAddition
  4. customThe stirred reaction
  5. additionmix
  6. customto attain room temperature
  7. additionthe reaction mix
  8. stirringis stirred overnight at room temperature
  9. customThe next morning the light yellow reaction
  10. additionmix
  11. washwashed twice with dilute sulfuric acid, twice with saturated sodium bicarbonate solution
  12. customisothermally at 190° C.
  13. customTherefore, reaction
  14. customA trap of the synthetic material is run for IE

Quellen und Nachweise

ORD-Eintrag
ord-1afa6ee77ac64595b3a53e8c58827363
Quelldatensatz
uspto-grants-1979_05
Patentnummer
US04154693

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