US 12,344,569 B2
Process for making a conjugated diene from an allyl alcohol
Fridtjof Schröder, Hettlingen (CH)
Assigned to Givaudan SA, Vernier (CH)
Appl. No. 17/998,531
Filed by Givaudan SA, Vernier (CH)
PCT Filed Jun. 15, 2021, PCT No. PCT/EP2021/066156
§ 371(c)(1), (2) Date Nov. 11, 2022,
PCT Pub. No. WO2021/255052, PCT Pub. Date Dec. 23, 2021.
Claims priority of application No. 2009189 (GB), filed on Jun. 17, 2020.
Prior Publication US 2023/0322645 A1, Oct. 12, 2023
Int. Cl. C07C 1/213 (2006.01); B01J 31/22 (2006.01); B01J 31/24 (2006.01)
CPC C07C 1/213 (2013.01) [B01J 31/2208 (2013.01); B01J 31/2409 (2013.01); B01J 31/2457 (2013.01); B01J 2231/005 (2013.01); B01J 2531/824 (2013.01); C07C 2523/44 (2013.01)] 16 Claims
 
1. A method for the in-situ formation of a conjugated diene of formula (III) from an allyl alcohol of formula (I), the method comprising converting the allyl alcohol of formula (I)

OG Complex Work Unit Chemistry
to an allyl carbonate, allyl ester, or allyl formate of formula (II)

OG Complex Work Unit Chemistry
in the presence of a base followed by converting the allyl carbonate, allyl ester, or allyl formate of formula (II) to the conjugated diene of formula (III)

OG Complex Work Unit Chemistry
using a palladium catalyst or palladium catalyst precursor and an organic phosphorous ligand,
wherein
each R1 is independently selected from H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aromatic hydrocarbon, and substituted aromatic hydrocarbon;
R2 is selected from H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aromatic hydrocarbon, and substituted aromatic hydrocarbon;
R3 is selected from H, alkyl, substituted alkyl, alkoxy, substituted alkoxy, phenyl, and substituted phenyl;
each R4 is independently selected from H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aromatic hydrocarbon, and substituted aromatic hydrocarbon; and
wherein at least one R1 bears a proton in a-position of the allylic C3 group which is deprotonated under basic reaction conditions thus forming a diene of formula (III) via 1,2 or 1,4 elimination and the at least one R1 is alkyl, substituted alkyl, alkenyl, substituted alkenyl, aromatic hydrocarbon, or substituted aromatic hydrocarbon.