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Process for the Preparation of (3E, 7E)-Homofarnesol

Inactive Publication Date: 2013-10-17
BASF AG
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

The invention is a process for making a chemical called (3E,7E)-homofarnesol. This process involves combining two different building blocks in a chemical reaction called a Wittig reaction. The starting material for this process is a specific type of cyclopropylphosphonium salt, which is commercially available. The other building block, geranyl acetone, is a commonly available industrial product. The desired chemical form of the desired product can be obtained by distillation. This process can be applied to different homologs of geranyl acetone. The technical effect of this invention is a more efficient and cost-effective method for making a specific chemical compound.

Problems solved by technology

However, this synthesis is not a technically-economically sensible route to (E,E)-homofarnesol.
Disadvantages of this route are the moderate yields and the required flash chromatography for separating the stereoisomers.
Furthermore, the reaction takes place disadvantageously for the implementation at high CO pressures of ca.
Furthermore, expensive hydride reagents are required for reducing the homofarnesylic acid.
Process (4) is economically unattractive on account of the reagents required.

Method used

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  • Process for the Preparation of (3E, 7E)-Homofarnesol

Examples

Experimental program
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Effect test

preparation examples

B) Preparation Examples

Example 1

Wittig Reaction Starting from the Cyclopropylphosphonium Salt with Potassium Tert-Butylate

[0089]

Feed Materials:

[0090]

640 ml(7890.58 mmol)ITetrahydrofuran24.7 eq  598.96 gM = 72.11 g / mol122.6 g(320 mmol)IICyclo-1 eqpropylphosphonium saltM = 383.27 g / mol35.91 g(320 mmol)IIIPotassium tert-butylate1 eqM = 112.21 g / mol48.6 g(288 mmol)IVE-Geranyl acetone0.9 eq  M = 194.32 g / mol

The reactor is flushed with nitrogen. 500 ml of THF (I) are introduced as initial charge and cooled to 0° C. Cyclopropylphosphonium salt (II) comminuted in the mortar is added rinsed with the remaining amount (140 ml) of THF (I) and stirred at 0° C. for 8 min. Under an N2 atmosphere, potassium tert-butylate (III) is added, during which the internal temperature increases to 5° C. The suspension becomes immediately red-orange, and is then stirred at ca. 0° C. for 2 hours.

[0091]Geranyl acetone (IV) is added dropwise over the course of ca. 10 min (slight exothermyl), then stirring is carr...

example 2

Wittig Reaction Starting from the TPP-Bromopropane Salt with NaH

[0095]

Feed Materials:

[0096]

250 ml(3082.3 mmol)ITetrahydrofuran12.3 eq222.25 gM = 72.11 g / mol126.6 g(250 mmol)IIC4 salt HPLC - 91.67%  1 eqby weight22 g(550 mmol)IIISodium hydride in mineral 2.2 eqoil 60% strengthM = 24 g / mol48.6 g240.1 mmolIVGeranyl acetone0.96 eq90%(E) and 6%(Z)based on (E)M = 194.32 g / mol 0.9 eqand (Z)225 mmolbased on (E)

[0097]The C4 salt (II) is introduced as initial charge at room temperature in THF (I). The sodium hydride (III) is washed 3× with in each case 100 ml of n-hexane, dried in the nitrogen stream and added. The white suspension is then stirred for 4.5 h at room temperature (conversion check via HPLC). Geranyl acetone (IV) is then added and the mixture is heated at 35° C. for 21 h. 500 ml of n-heptane are then added to the yellowish suspension. THF is then removed on a rotary evaporator. The remaining suspension is admixed with 500 ml of water / methanol and the phases are separated. The aqu...

example 3

Ring Opening with BF3 Etherate and Glacial Acetic Acid

[0100]

Feed Materials:

[0101]

MolecularQuantitativeWeightAmountSubstancePurity %g / molMass gMolEqC16-90.3 (based218.38109.20.4521cyclopropaneon E & Z)Glacial acetic10060.05191431.87570.5acidBF3 etherate100141.939.050.06380.14Glacial acetic10060.052043.47.5acid

[0102]The C16-cyclopropane (I) is dissolved in glacial acetic acid (II) and produces a clear, yellow solution. The BF3 etherate is prediluted in glacial acetic acid and added over the course of 2 min at RT. The solution slowly becomes darker, no heat tonality. Stirring is carried out overnight at RT. A dark brown, clear solution (HPLC analysis) is obtained. After 27 h at RT, 2.5 l of water and 1 l of cyclohexane are added to the clear, dark brown solution, and the phases are separated. The aqueous phase is extracted twice with 0.5 l cyclohexane. The combined organic phases are washed in succession with 4×0.2 l of water, 0.25 l of saturated NaHCO3 solution and again 0.25 l of wat...

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Abstract

The present invention relates to new types of processes for the improved preparation of homofarnesol, in particular of (3E,7E)-homofarnesol and homofarnesol preparations with an increased content of (3E,7E)-homofarnesol (also referred to as all E-homofarnesol).

Description

[0001]The present invention relates to new types of processes for the improved preparation of homofarnesol, in particular of (3E,7E)-homofarnesol and homofarnesol preparations with an increased content of (3E,7E)-homofarnesol (also referred to as all E-homofarnesol).BACKGROUND OF THE INVENTION[0002]Ambrox® is the trade name of the enantiomerically pure compound (−)-ambrox (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan), a sought-after fragrance. Naturally occurring (−)-ambrox is the olfactory most important ingredient of ambergris, a digestion product of sperm whales.[0003]The different diastereomers of (−)-ambrox have a similar scent, but sometimes differ in their odor thresholds (G. Ohloff, W. Giersch, W. Pickenhagen, A. Furrer, B. Frei, Helv. Chim. Acta 68 (1985) 2022. G. Fráter, J. A. Bajgrowicz, P. Kraft, Tetrahedron 54 (1998) 7633). The odor threshold of 3a-epi-(−)-ambrox is higher than that of (−)-ambrox by a factor of 100. By contrast, 9b-epi-(−)-ambro...

Claims

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Application Information

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IPC IPC(8): C07C29/58C07D307/92
CPCC07C29/58C07D307/92C07C1/34C07C13/04C07C17/08C07C29/124C07C29/38C07C67/00C07C2601/02
Inventor BONNEKESSEL, MELANIEERNST, HANSGEORGSIEGEL, WOLFGANGWINTERFELDT, EKKEHARDHOFFMANN, REINHARD W.
Owner BASF AG
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