Methods for the synthesis of deuterated vinyl pyridine monomers
Methods for synthesizing deuterated vinylpyridine compounds of the Formula (1), wherein the method includes: (i) deuterating an acyl pyridine of the Formula (2) in the presence of a metal catalyst and D 2 O, wherein the metal catalyst is active for hydrogen exchange in water, to produce a deuterated acyl compound of Formula (3); (ii) reducing the compound of Formula (3) with a deuterated reducing agent to convert the acyl group to an alcohol group, and (iii) dehydrating the compound produced in step (ii) with a dehydrating agent to afford the vinylpyridine compound of Formula (1). The resulting deuterated vinylpyridine compounds are also described.
1. A compound having the following formula:
wherein one of A 2 , A 3 , A 4 , A 5 , and A 6 is a vinyl group of the formula:
wherein R 1 and R 2 are each independently either a deuterium atom or a perdeuterated alkyl group containing one to six carbon atoms;
the remainder of A 2 , A 3 , A 4 , A 5 , and A 6 are independently selected from hydrogen and deuterium atoms; and
the nitrogen atom of the pyridine ring is bound to a hydrogen atom, deuterium atom, or an alkyl group optionally substituted with one or more deuterium atoms;
provided that, when A 2 , A 4 , or A 6 is the vinyl group of Formula (1-a), and R 1 and R 2 are both deuterium atoms, then the remainder of A 2 , A 3 , A 4 , A 5 , and A 6 are not all hydrogen atoms; and when A 2 or A 6 is the vinyl group of Formula (1-a) and R 1 and R 2 are both deuterium atoms, then the remainder of A 2 , A 3 , A 4 , A 5 , and A 6 are not all deuterium atoms.
2. The compound of claim 1 , wherein A 2 is the vinyl group of Formula (1-a).
3. The compound of claim 1 , wherein A 3 is the vinyl group of Formula (1-a).
4. The compound of claim 1 , wherein A 4 is the vinyl group of Formula (1-a).
5. The compound of claim 1 , further provided that, when A 4 is the vinyl group of Formula (1-a), and R 1 and R 2 are both deuterium atoms, then A 2 , A 3 , A 5 , and A 6 are not all deuterium atoms.
6. The compound of claim 1 , wherein the remainder of A 2 , A 3 , A 4 , A 5 , and A 6 are hydrogen atoms.
7. The compound of claim 1 , wherein the remainder of A 2 , A 3 , A 4 , A 5 , and A 6 are deuterium atoms.
8. The compound of claim 1 , wherein at least one of A 2 , A 3 , A 4 , A 5 , and A 6 is a hydrogen atom and at least one of A 2 , A 3 , A 4 , A 5 , and A 6 is a deuterium atom.
9. The compound of claim 8 , wherein one of A 2 , A 3 , A 4 , A 5 , and A 6 is a deuterium atom.
10. The compound of claim 9 , wherein A 2 is the vinyl group of Formula (1-a) and A 6 is a deuterium atom.
11. The compound of claim 9 , wherein A 4 is the vinyl group of Formula (1-a), and A 2 or A 6 is a deuterium atom.
12. The compound of claim 8 , wherein two of A 2 , A 3 , A 4 , A 5 , and A 6 are deuterium atoms.
13. The compound of claim 12 , wherein A 2 and A 6 are deuterium atoms.
14. The compound of claim 12 , wherein A 4 is the vinyl group of Formula (1-a), and A 2 and A 6 are deuterium atoms.
15. The compound of claim 8 , wherein three of A 2 , A 3 , A 4 , A 5 , and A 6 are deuterium atoms.
16. The compound of claim 1 , wherein R 1 and R 2 are deuterium atoms.