US 12,454,526 B2
Method for producing pyrrole-imidazole (poly)amide
Takahiko Murata, Takasago (JP); Shohei Yamamoto, Takasago (JP); and Akira Nishiyama, Takasago (JP)
Assigned to KANEKA CORPORATION, Osaka (JP)
Appl. No. 17/442,306
Filed by KANEKA CORPORATION, Osaka (JP)
PCT Filed Mar. 12, 2020, PCT No. PCT/JP2020/010792
§ 371(c)(1), (2) Date Sep. 23, 2021,
PCT Pub. No. WO2020/195889, PCT Pub. Date Oct. 1, 2020.
Claims priority of application No. 2019-063936 (JP), filed on Mar. 28, 2019.
Prior Publication US 2022/0153727 A1, May 19, 2022
Int. Cl. C07D 403/12 (2006.01)
CPC C07D 403/12 (2013.01) 6 Claims
OG exemplary drawing
 
1. A method for producing a pyrrole-imidazole (poly)amide, comprising the steps of reacting a compound represented by the following formula (1):

OG Complex Work Unit Chemistry
wherein in the formula (1),
Ra is a (poly)amide organic group having 1 or more and 3 or less kinds of a unit selected from the units represented by the formulas (2a), (2b), and (2c) as a constituent unit, wherein a total number of the constituent unit is 1 or more and 30 or less,
Q1 is a carrier, or an amino group optionally having a hydroxy group, an organic group, or a substituent,
wherein the carrier is either a solid-phase carrier or a soluble carrier, the solid-phase carrier is a resin solid-phase carrier, and the soluble carrier is at least one selected from the group consisting of 3,4,5-tri(n-octadecyloxy)benzyl alcohol, 3,5-di(docosyloxy)benzyl alcohol, 2,4-di(docosyloxy)benzyl alcohol, and 2-[12-(docosyloxy) dodecyloxy]-9-(3-fluorophenyl)-9-bromofluorene,
and wherein the organic group is a C1-12 alkoxy group optionally having a substituent, a C2-12 alkenyloxy group optionally having a substituent, a C6-12 aryloxy group optionally having a substituent, or a C7-12 aralkyloxy group optionally having a substituent,
m is 0 or 1,
R1 to R3 independently represent a C1-12 alkyl group,
when the compound represented by the formula (1) has a plurality of units represented by the formula (2a), a plurality of R2 may be the same as or different from each other,
when the compound represented by the formula (1) has a plurality of units represented by the formula (2b), a plurality of R3 may be the same as or different from each other,
Rb represents a C1-10 alkylene group wherein the alkylene group may be bonded with one or more groups selected from an amino group having a substituent, a C1-12 alkoxy group optionally having a substituent, a C2-12 alkenyloxy group optionally having a substituent, a C6-12 aryloxy group optionally having a substituent, and a C7-12 aralkyloxy group optionally having a substituent,
when the compound represented by the formula (1) has a plurality of units represented by the formula (2c), a plurality of Rb may be the same as or different from each other,
wherein the substituent that may be present in the C1-12 alkoxy group, C2-12 alkenyloxy group, C6-12 aryloxy group, and C7-12 aralkyloxy group is a nitro group, a nitrile group, or a halogen atom,
and wherein the substituent that may be present in the amino group is a C1-12 alkyl group, a C2-12 alkenyl group, a C7-12 aralkyl group, or a C6-12 aryl group, wherein the alkyl group, alkenyl group, aralkyl group, and aryl group may optionally have a C1-12 alkylamino group bonded thereto,
represents a bond,
with a compound represented by the following formula (3):

OG Complex Work Unit Chemistry
wherein in the formula (3),
Rc is a (poly)amide organic group having 1 or more and 3 or less kinds of the unit selected from the units represented by the formulas (4a), (4b), and (4c) as a constituent unit and the total number of the constituent unit is 1 or more and 30 or less,
Q2 is a protective group of an amino group, or a group represented by the formulas (5a), (5b), (5c) or (5d),
E is a leaving group,
n is 0 or 1,
R4 to R8 each independently represents a C1-12 alkyl group,
when the compound represented by the formula (3) has a plurality of units represented by the formula (4a), a plurality of R5 may be the same as or different from each other,
when a compound represented by the formula (3) has a plurality of units represented by the formula (4b), a plurality of R6 may be the same as or different from each other,
Rd represents a C1-10 alkylene group wherein the alkylene group may be bonded with one or more groups selected from an amino group having a substituent, a C1-12 alkoxy group optionally having a substituent, a C2-12 alkenyloxy group optionally having a substituent, and a C6-12 aryloxy group optionally having a substituent, and a C7-12 aralkyloxy group optionally having a substituent,
when a compound represented by the formula (3) has a plurality of units represented by the formula (4c), a plurality of Rd may be the same as or different from each other,
Re represents a C1-10 alkyl group wherein the alkyl group may be bonded with one or more groups selected from an amino group having a substituent, a C1-12 alkoxy group optionally having a substituent, a C2-12 alkenyloxy group optionally having a substituent, a C6-12 aryloxy group optionally having a substituent, and a C7-12 aralkyloxy group optionally having a substituent,
wherein the substituent that may be present in the C1-12 alkoxy group, C2-12 alkenyloxy group, C6-12 aryloxy group, and C7-12 aralkyloxy group is a nitro group, a nitrile group, or a halogen atom,
and wherein the substituent that may be present in the amino group is a C1-12 alkyl group, a C2-12 alkenyl group, a C7-12 aralkyl group, or a C6-12 aryl group, wherein the alkyl group, alkenyl group, aralkyl group, and aryl group may optionally have a C1-12 alkylamino group bonded thereto,
represents a bond,
in the presence of a heterocyclic aromatic compound as a solvent to produce the pyrrole-imidazole (poly)amide represented by the following formula (6):

OG Complex Work Unit Chemistry
wherein in the formula (6), Ra, Rc, Q1, Q2, R1, R4, m and n are the same as described above,
wherein the reaction between the compound represented by the formula (1) and the compound represented by the formula (3) is carried out in the presence of a tertiary amine.