2H-Pyran, tetrahydro-2-(11-tetradecyn-1-yloxy)- → HCID 13280696, compound

HRID 1768893Notes

Reaction equation

HRID 1768893 reaction equation
[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][C:18]#[C:19][CH2:20][CH3:21]>[Ni]>[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17]/[CH:18]=[CH:19]\[CH2:20][CH3:21]

Participants

3

Reactant 1

HCID 1167412H-Pyran, tetrahydro-2-(11-tetradecyn-1-yloxy)-

Product 1

HCID 13280696HCID 13280696, compound

Reagents, catalysts & solvents 1

HCID 935NickelCatalyst

Procedure

The compounds in the composition are available commercially or can be prepared synthetically in accordance with the procedure described by S. Voerman in Agric. Ecosystems Environ. 21 31-41 (1988). The synthesis of I is shown in FIG. 1. In brief, 1,10-decanediol (III) is reacted with concentrated hydrochloric acid. Continuous extraction of the reaction mixture with petroleum ether (b.p. 100°-140° C.) gives 10-chlorodecan-1-ol (IV) free of dichloride. IV is reacted with an equimolar quantity of dihydropyran, catalysed by 1 drop of concentrated hydrochloric acid to produce 1-chloro-10-[(tetrahydro-2H-pyran-2-yl)oxy]decane (V). Butyne gas is bubbled into a solution of n-butyl lithium under nitrogen and then V is added dropwise to produce 14-[(tetrahydro-2H-pyran-2-yl)oxy]-3-tetradecyne (VI). VI is hydrogenated with a P2-nickel catalyst (H. C. Brown and V. K. Ahiya, J. Chem. Soc. Chem. Comm., pp. 553-554 (1973)) to produce the Z olefin, 14-[(tetrahydro-2H-pyran-2-yl)oxy]-(Z)-3-tetradecene (VII), with less than 1% of the E isomer. The pheromone component, I, is generated by heating VII for 15 minutes in methanol containing a few drops of hydrochloric acid. II is prepared according to the scheme shown in FIG. 2. The conversions of 1,8-octanediol (VIII) to (Z)-9-dodecen-1-ol (XIII) is carried out the same as III to I except that VIII is substituted for III. XIII is converted to the pheromone component, II, by reaction with acetic anhydride in pyridine.

Workup

  1. customButyne gas is bubbled into a solution of n-butyl lithium under nitrogen
  2. additionV is added dropwise
  3. customto produce 14-[(tetrahydro-2H-pyran-2-yl)oxy]-3-tetradecyne (VI)

Sources & evidence

ORD record
ord-15e3ac68a7034b6a8238fe2281572c85
Source dataset
uspto-grants-1995_01
Patent number
US05380524

Reaction notes

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