Dinaphthothiophene compounds

Patent metadata

Field	Value
Publication number	US-2018362493-A1
Application number	US-201816013432-A
Country	US
Kind code	A1
Filing date	Jun 20, 2018
Priority date	Jun 20, 2017
Publication date	Dec 20, 2018
Grant date	—

Abstract

The present invention generally relates to various dinaphthothiophene compounds and processes for preparing these compounds.

First claim

1 . A process for preparing a dinaphthothiophene compound, the process comprising:
reacting, in the presence of a catalyst comprising palladium, a base, and organic solvent, 2,4-dibromothiophene with a phenylethenyl boronic acid compound of Formula A-1:

to form a 4-bromo-2-styrylthiophene compound of Formula A-2:

reacting, in the presence of a catalyst comprising palladium, a base, and organic solvent, the 4-bromo-2-styrylthiophene compound of Formula A-2 with a phenylethenyl boronic acid compound of Formula A-3:

to form a 2,4-distryrylthiophene compound of Formula A-4:

irradiating the compound of Formula A-4 with UV light in the presence of iodine and propylene oxide to form a dinaphthothiophene compound of Formula I-A:

wherein R 1 is hydrogen, hydroxy, substituted or unsubstituted C 1 -C 20 alkyl, or substituted or unsubstituted aryl; and R 2 is hydrogen, hydroxy, or substituted or unsubstituted C 1 -C 20 alkyl.

2 - 9 . (canceled)

10 . A dinaphthothiophene compound of
(a) Formula I:

wherein R 1 is hydrogen, hydroxy, substituted or unsubstituted C 1 -C 20 alkyl, or substituted or unsubstituted aryl; R 2 is hydrogen, hydroxy, or substituted or unsubstituted C 1 -C 20 alkyl; and n is 0, 1, or 2;
(b) Formula II:

wherein R is hydrogen, hydroxy, substituted or unsubstituted C 1 -C 20 alkyl, or substituted or unsubstituted aryl and n is 0, 1, or 2; or
(c) Formula III:

wherein R 3 is hydrogen hydroxy, substituted or unsubstituted C 1 -C 20 alkyl, or substituted or unsubstituted aryl; R 4 is hydrogen, hydroxy, substituted or unsubstituted C 1 -C 20 alkyl, or substituted or unsubstituted aryl; and n is 0, 1, or 2.

11 . The compound of claim 10 wherein R 1 is hydrogen, hydroxy, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkyl, C 1 -C 20 haloalkoxy, aryl, alkyl-substituted aryl, halo-substituted aryl, or hydroxy-substituted aryl.

12 . The compound of claim 10 wherein R 1 is hydrogen, hydroxy, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkyl, C 1 -C 10 haloalkoxy, aryl, alkyl-substituted aryl, halo-substituted aryl, or hydroxy-substituted aryl.

13 . The compound of claim 10 wherein R 1 is hydrogen, hydroxy, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, trifluoromethyl, phenyl, hydroxyphenyl, ethylphenyl, carboxyphenyl, naphthyl, anthracenyl, biphenyl, tolyl, cumyl, styryl, ortho-xylyl, meta-xylyl, para-xylyl, fluorophenyl, chlorophenyl, bromobenzyl, or iodobenzyl.

14 . The compound of claim 10 wherein R 2 is hydrogen, hydroxy, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkyl, C 1 -C 20 haloalkoxy, aryl, alkyl-substituted aryl, halo-substituted aryl, or hydroxy-substituted aryl.

15 . The compound of claim 10 wherein R 2 is hydrogen, hydroxy, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkyl, C 1 -C 10 haloalkoxy, aryl, alkyl-substituted aryl, halo-substituted aryl, or hydroxy-substituted aryl.

16 . The compound of claim 10 wherein R 2 is hydrogen, hydroxy, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, trifluoromethyl, phenyl, hydroxyphenyl, ethylphenyl, carboxyphenyl, naphthyl, anthracenyl, biphenyl, tolyl, cumyl, styryl, ortho-xylyl, meta-xylyl, para-xylyl, fluorophenyl, chlorophenyl, bromobenzyl, or iodobenzyl.

17 . The compound of claim 10 wherein R 1 and R 2 are different.

18 . A process for preparing a dinaphthothiophene compound, the process comprising:
reacting 2-bromthiophene with trans-2-(4-phenyl)vinylboronic acid in the presence of a catalyst comprising palladium, a base, and organic solvent to form (E)-2-styrylthiophene; formylating (E)-2-styrylthiophene to form (E)-5-styrylthiophene-2-carbaldehyde; reacting, in the presence of sodium hydride, (E)-5-styrylthiophene-2-carbaldehyde with a 4-substituted phosphonic acid diethyl ester compound of Formula B-1:

to form a compound of Formula B-2:

irradiating the compound of Formula B-2 with UV light in the presence of iodine and propylene oxide to form the dinaphthothiophene compound of Formula II-A:

wherein R is hydrogen, hydroxy, substituted or unsubstituted C 1 -C 20 alkyl, or substituted or unsubstituted aryl.

19 - 23 . (canceled)

24 . The compound of claim 10 wherein R is hydrogen, hydroxy, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkyl, C 1 -C 20 haloalkoxy, aryl, alkyl-substituted aryl, halo-substituted aryl, or hydroxy-substituted aryl.

25 . The compound of claim 10 wherein R is hydrogen, hydroxy, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkyl, C 1 -C 10 haloalkoxy, aryl, alkyl-substituted aryl, halo-substituted aryl, or hydroxy-substituted aryl.

26 . The compound of claim 10 wherein R is hydrogen, hydroxy, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, trifluoromethyl, phenyl, hydroxyphenyl, ethylphenyl, carboxyphenyl, naphthyl, anthracenyl, biphenyl, tolyl, cumyl, styryl, ortho-xylyl, meta-xylyl, para-xylyl, fluorophenyl, chlorophenyl, bromobenzyl, or iodobenzyl.

27 . A process for preparing a dinaphthothiophene compound, the process comprising:
formylating 3,4-dibromothiophene to form 4-bromothiophene-3-carbaldehyde; reacting, in the presence of a catalyst comprising palladium, a base, and organic solvent, 4-bromothiophene-3-carbaldehyde with a phenylethenyl boronic compound of Formula C-1:

to form a 3-formyl-4-styrylthiophene compound of Formula C-2:

reacting, in the presence of sodium hydride, the 3-formyl-4-styrylthiophene compound of Formula C-2 with a 4-substituted phosphonic acid diethyl ester compound of Formula C-3:

to form a compound of Formula C-4:

irradiating the compound of Formula C-4 with UV light in the presence of iodine and propylene oxide to form the dinaphthothiophene compound of Formula III-A:

wherein R 3 is hydrogen, hydroxy, substituted or unsubstituted C 1 -C 20 alkyl, or substituted or unsubstituted aryl and R 4 is hy

Assignees

• Univ Saint Louis

Inventors

• Mcculla Ryan D
• Petroff Ii John T
• Chintala Satyanarayana M
• Throgmorton John C

Classifications

• C07D333/50 Primary

  condensed with carbocyclic rings or ring systems · CPC title

• C07D333/74

  Naphthothiophenes · CPC title