Compositions and methods of promoting organic photocatalysis

Patent metadata

Field	Value
Publication number	US-10975171-B2
Application number	US-201815960086-A
Country	US
Kind code	B2
Filing date	Apr 23, 2018
Priority date	Oct 23, 2015
Publication date	Apr 13, 2021
Grant date	Apr 13, 2021

Abstract

The invention provides novel compounds and methods that are useful in promoting reactions that proceed through an oxidative quenching pathway. In certain embodiments, the reactions comprise atom transfer radical polymerization.

First claim

What is claimed is:

1. A compound, or a salt or solvate thereof, selected from the group consisting of:

wherein:
each occurrence of R is independently selected from the group consisting of H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted phenyl, —OH, —O(C 1 -C 6 alkyl), —NO 2 , —CN, —C(═O)OH, —C(═O)O(C 1 -C 6 alkyl), —C(═O)O-phenyl, —C(═O)(C 1 -C 6 alkyl), —C(═O)-phenyl, —S(O) 2 NH 2 , —S(O) 2 NH(C 1 -C 6 alkyl), —S(O) 2 N(C 1 -C 6 alkyl)(C 1 -C 6 alkyl), —S(C 1 -C 6 alkyl), —S(O) (C 1 -C 6 alkyl), —S(O) 2 (C 1 -C 6 alkyl), —S(phenyl), —S(O)(phenyl), and —S(O)2(phenyl),
each occurrence of R 1 is independently selected from the group consisting of phenyl, 1-naphthyl, and 2-naphthyl, each of which is independently substituted with at least one R;
each occurrence of R 2 and R 3 is independently selected from the group consisting of phenyl and 4-phenyl-phenyl, each of which is independently substituted with at least one R; and
each occurrence of R 4 , R 5 R 6 , and R 7 is independently selected from the group consisting of phenyl, 4-phenyl-phenyl, 1-naphthyl, 2-naphthyl, triphenylamino, phenanthrenyl, and pyrenyl, each of which is independently substituted with at least one R,

wherein:
if the compound is

then
each occurrence of R is independently selected from the group consisting of C 2 -C 6 alkyl, C 1 -C 6 haloalkyl, substituted phenyl, —O(C 2 -C 6 alkyl), —NO 2 , —C(═O)OH, —C(═O)O(C 2 -C 6 alkyl), —C(═O)O-phenyl, —C(═O)(C 1 -C 6 alkyl), —C(═O)-phenyl, —S(O) 2 NH 2 , —S(O) 2 NH(C 1 -C 6 alkyl), —S(O) 2 N(C 1 -C 6 alkyl)(C 1 -C 6 alkyl), —S(C 1 -C 6 alkyl), —S(O)(C 1 -C 6 alkyl), —S(O) 2 (C 1 -C 6 alkyl), —S(phenyl), —S(O)(phenyl), and —S(O) 2 (phenyl);
if the compound is

then
each occurrence of R is independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted phenyl, —OH, —O(C 2 -C 6 alkyl), —NO 2 , —CN, —C(═O)OH, —C(═O)O(C 1 -C 6 alkyl), —C(═O)O-phenyl, —C(═O)(C 1 -C 6 alkyl), —C(═O)-phenyl, —S(O) 2 NH 2 , —S(O) 2 NH(C 1 -C 6 alkyl), —S(O) 2 N(C 1 -C 6 alkyl)(C 1 -C 6 alkyl), —S(C 1 -C 6 alkyl), —S(O)(C 1 -C 6 alkyl), —S(O) 2 (C 1 -C 6 alkyl), —S(phenyl), —S(O)(phenyl), and —S(O) 2 (phenyl);
if the compound is

then
each occurrence of R 1 is independently selected from the group consisting of 1-naphthyl and 2-naphthyl, each of which is independently substituted with at least one R.

2. The compound of claim 1 , wherein R 1 is 1-naphthyl or R 1 is phenyl substituted by at least one substituent selected from the group consisting of CF 3 and C(═O)OH.

3. The compound of claim 2 , wherein the compound is selected from the group consisting of:

4. The compound of claim 1 , having the structure of

wherein
R 1 is independently selected from the group consisting of 1-naphthyl and 2-naphthyl, each of which is independently substituted with at least one R; and
R 2 and R 3 are independently selected from the group consisting of phenyl and 4-phenyl-phenyl, each of which is independently substituted with at least one R.

5. The compound of claim 1 , wherein if the compound is

wherein R 2 and R 3 are independently selected from the group consisting of phenyl and 4-phenyl-phenyl, each of which is independently substituted with at least one R,

then R 1 is 1-naphthyl.

6. The compound of claim 5 , having the structure:

7. The compound of claim 1 , wherein the compound has the structure:

wherein
each occurrence of R 1 is independently selected from the group consisting of phenyl, 1-naphthyl, and 2-naphthyl, each of which is independently substituted with at least one R;
each occurrence of R 2 and R 3 is independently selected from the group consisting of phenyl and 4-phenyl-phenyl, each of which is independently substituted with at least one R; and
each occurrence of R 4 , R 5 R 6 , and R 7 is independently selected from the group consisting of phenyl, 4-phenyl-phenyl, 1-naphthyl, 2-naphthyl, triphenylamino, phenanthrenyl, and pyrenyl, each of which is independently substituted with at least one R; and
each occurrence of R is independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted phenyl, —OH, —O(C 2 -C 6 alkyl), —NO 2 , —CN, —C(═O)OH, —C(═O)O(C 1 -C 6 alkyl), —C(═O)O-phenyl, —C(═O)(C 1 -C 6 alkyl), —C(═O)-phenyl, —S(O) 2 NH 2 , —S(O) 2 NH(C 1 -C 6 alkyl), —S(O) 2 N(C 1 -C 6 alkyl)(C 1 -C 6 alkyl), —S(C 1 -C 6 alkyl), —S(O)(C 1 -C 6 alkyl), —S(O) 2 (C 1 -C 6 alkyl), —S(phenyl), —S(O)(phenyl), and —S(O) 2 (phenyl).

8. The compound of claim 7 , wherein the compound is

9. A compound, or a salt or solvate thereof, having a structure selected from the group consisting of:

wherein:
each occurrence of R is independently selected from the group consisting of H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted phenyl, —OH, —O(C 1 -C 6 alkyl), —NO 2 , —CN, —C(═O)OH, —C(═O)O(C 1 -C 6 alkyl), —C(═O)O-phenyl, —C(═O)(C 1 -C 6 alkyl), —C(═O)-phenyl, —S(O) 2 NH 2 , —S(O) 2 NH(C 1 -C 6 alkyl), —S(O) 2 N(C 1 -C 6 alkyl)(C 1 -C 6 alkyl), —S(C 1 -C 6 alkyl), —S(O) (C 1 -C 6 alkyl), —S(O) 2 (C 1 -C 6 alkyl), —S(phenyl), —S(O)(phenyl), and —S(O) 2 (phenyl),
each occurrence of R 1 is independently selected from the group consisting of phenyl, 1-naphthyl, and 2-naphthyl, each of which is independently substituted with at least one R;
each occurrence of R 2 and R 3 is independently selected from the group consisting of phenyl and 4-phenyl-phenyl, each of which is independently substituted with at least one R; and
each occurrence of R 4 , R 5 R 6 , and R 7 is independently selected from the group consisting of phenyl, 4-phenyl-phenyl, 1-naphthyl, 2-naphthyl, triphenylamino, phenanthrenyl, and pyrenyl, each of which is independently substituted with at least one R.

10. The compound of claim 9 , having the structure

wherein
each occurrence of R 1 is independently select

Assignees

• Univ Colorado Regents
• Univ Colorado State Res Found

Inventors

• Miyake Garret
• Theriot Jordan Corinne
• Ryan Matthew D
• Pearson Ryan Michael
• French Tracy Allen
• Yang Haishen
• Lockwood Andrew
• Musgrave Charles
• Lim Chern-Hooi
• Du Ya
• Mccarthy Blaine

Classifications

• C08F2/50 Primary

  with sensitising agents · CPC title

• C08F220/1807

  C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate · CPC title

• C08F220/1811 Primary

  C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate · CPC title

• C08F230/085

  the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes · CPC title

• C08F220/1804

  C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate · CPC title