US 12,116,328 B2
11-halo-3-undecene compound and a process for preparing the same and a process for preparing 9-dodecenal compound
Yuki Miyake, Niigata (JP); Takeshi Kinsho, Niigata (JP); and Ryo Komatsu, Niigata (JP)
Assigned to Shin-Etsu Chemical Co., Ltd., Tokyo (JP)
Filed by Shin-Etsu Chemical Co., Ltd., Tokyo (JP)
Filed on Jul. 7, 2020, as Appl. No. 16/922,679.
Claims priority of application No. 2019-127829 (JP), filed on Jul. 9, 2019.
Prior Publication US 2021/0009489 A1, Jan. 14, 2021
Int. Cl. C07C 17/263 (2006.01); A01N 29/02 (2006.01); C07C 17/275 (2006.01); C07C 41/50 (2006.01); C07C 45/42 (2006.01); C07C 21/02 (2006.01); C07C 21/04 (2006.01)
CPC C07C 17/2632 (2013.01) [A01N 29/02 (2013.01); C07C 17/275 (2013.01); C07C 41/50 (2013.01); C07C 45/42 (2013.01); C07C 21/02 (2013.01); C07C 21/04 (2013.01)] 4 Claims
 
1. A process for preparing a (9Z)- or (9E)-9-dodecenal compound of the following formula (4):
CH3CH2CH═CH(CH2)7CHO  (4)
the process comprising steps of
subjecting a nucleophilic reagent, a (3Z)- or (3E)-3-hexenyl compound, of the following general formula (5):
CH3CH2CH═CH(CH2)2M2  (5)
in which M2 represents Li or MgZ2, wherein Z2 represents a halogen atom or a 3-hexenyl group, to a coupling reaction with a 1-halo-5-halopentane compound of the general formula (6):
X3(CH2)5X4  (6)
in which X3 represents a chlorine atom and X4 represents a bromine atom,
in the presence of a cuprous halide and a trialkyl phosphite compound having 3 to 9 carbon atoms to produce a (3Z)- or (3E)-11-halo-3-undecene compound of the following general formula (7):
CH3CH2CH═CH(CH2)7X1  (7)
in which X1 represents a chlorine atom; and
preparing the nucleophilic reagent, (8Z)- or (8E)-8-undecenyl compound of the following general formula (1);
CH3CH2CH═CH(CH2)7M1  (1)
in which M1 represents Li or MgZ1, wherein Z1 represents a halogen atom or an 8-undecenyl group,
from the (3Z)- or (3E)-11-chloro-3-undecene compound (7) thus obtained, respectively;
subjecting the nucleophilic reagent, (8Z)- or (8E)-8-undecenyl compound (1) thus obtained to a nucleophilic substitution reaction with an orthoformic ester compound of the following general formula (2):

OG Complex Work Unit Chemistry
in which R may be same with or different from each other and represents an alkyl group having 1 to 6 carbon atoms,
to produce a (9Z)- or (9E)-1,1-dialkoxy-9-dodecene compound of the following general formula (3):
CH3CH2CH═CH(CH2)7CH(OR)2  (3)
in which R is as defined above, respectively; and
hydrolyzing the (9Z)- or (9E)-1,1-dialkoxy-9-dodecene compound (3) thus obtained, in the presence of oxalic acid to produce the (9Z)- or (9E)-9-dodecenal compound (4), respectively.