Process for the preparation of high purity norbornene alkanols and derivatives thereof

Patent metadata

Field	Value
Publication number	US-9382271-B2
Application number	US-201314439182-A
Country	US
Kind code	B2
Filing date	Dec 11, 2013
Priority date	Dec 19, 2012
Publication date	Jul 5, 2016
Grant date	Jul 5, 2016

Abstract

A process for the preparation of a variety of high purity norbornene alkanol monomers and their derivatives is disclosed and claimed. Specifically, a process for the preparation of industrial scale high purity norbornene methanol and its silyl ether derivative is disclosed and claimed. The high purity monomers prepared in accordance with the process of this invention are useful in a variety of applications including but not limited to the preparation of high quality and high purity polynorbornenes having utility in a variety of electronic applications, among various other applications.

First claim

What is claimed is:

1. A process for the preparation of a compound of formula (I):

wherein
n is an integer from 1 to 10, inclusive, and where one or more of CH 2 is optionally substituted with C 1 -C 10 -alkyl or C 1 -C 10 -perfluoroalkyl;
m is an integer from 0 to 2, inclusive;
R 1 , R 2 and R 3 are the same or different and independently of each other selected from hydrogen, halogen, methyl, ethyl, linear or branched C 3 -C 12 -alkyl, C 3 -C 12 -cycloalkyl, C 6 -C 12 -bicycloalkyl, C 7 -C 14 -tricycloalkyl, C 6 -C 10 -aryl, C 6 -C 10 -aryl-C 1 -C 3 -alkyl, C 6 -C 10 -heteroaryl, C 6 -C 10 -heteroaryl-C 1 -C 3 -alkyl, C 1 -C 12 -alkoxy, C 3 -C 12 -cycloalkoxy, C 6 -C 12 -bicycloalkoxy, C 7 -C 14 -tricycloalkoxy, C 6 -C 10 -aryloxy-C 1 -C 3 -alkyl, C 6 -C 10 -heteroaryloxy-C 1 -C 3 -alkyl, C 6 -C 10 -aryloxy, C 6 -C 10 -heteroaryloxy and C 1 -C 6 -acyloxy;
comprising:
reacting cyclopentadiene with a compound of formula (II):
CR 2 R 3 ═CR 1 —(CH 2 ) n —R  (II)

wherein
R is —OCOC 1 -C 6 -alkyl;
at a suitable temperature and conditions, without any solvent, to form a compound of formula (III):

and
subjecting compound of formula (III) to suitable trans-esterification agent in the presence of a catalyst to form the compound of formula (I) wherein the compound of formula (I) is prepared in purity higher than 95 percent and essentially free of the corresponding hydrogenated compound of formula (I).

2. The process of claim 1 for the preparation of the compound of formula (I) in a purity of at least 99 percent.

3. The process of claim 1 for the preparation of the compound of formula (I) in a purity of at least 99.8 percent.

4. The process of claim 1 , wherein n is 1, R is CH 3 C(O)O and each of R 1 , R 2 and R 3 is hydrogen.

5. The process of claim 4 for the preparation of exo-/endo-norbornene methanol in a purity of at least 99 percent.

6. The process of claim 1 , wherein said trans-esterification agent is an alcohol and said catalyst is a base.

7. The process of claim 6 , wherein said alcohol is methanol and said base is sodium methoxide.

8. The process of claim 1 , wherein said trans-esterification agent is an alcohol and said catalyst is an acid.

9. The process of claim 8 , wherein said alcohol is methanol and said acid is sulfuric or alkanesulfonic acid.

10. The process of claim 1 , which further comprises:
reacting compound of formula (I) with a silane of formula (IV):
R 5 R 6 R 7 SiH  (IV)

wherein R 5 , R 6 and R 7 are each independently of one another methyl, ethyl or linear or branched C 3 -C 9 -alkyl or substituted or unsubstituted C 6 -C 14 -aryl; and
a suitable catalyst to obtain a compound of formula (V):

and
wherein said compound of formula (V) is in a purity of at least 99 percent.

11. The process of claim 10 , wherein n is 1, each of R 1 , R 2 and R 3 is hydrogen, R 5 is methyl, and each of R 6 and R 7 is phenyl.

12. The process of claim 10 , wherein the catalyst is a base.

13. The process of claim 12 , wherein the base catalyst is potassium tert-butoxide.

14. The process of claim 10 for the preparation of the compound of formula (V) in a purity of at least 99-99.5 percent.

15. The process of claim 10 for the preparation of the compound of formula (V) in a purity of at least 99.8 percent.

16. The process of claim 10 for the preparation of (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)diphenylsilane in a purity of at least 99.8 percent.

Assignees

• Promerus Llc

Inventors

• Bell Andrew
• Jablonski Dane

Classifications

• C07C2102/42

  Chemistry & Metallurgy · mapped topic

• C07C67/293

  by isomerisation; by change of size of the carbon skeleton · CPC title

• C07F7/188 Primary

  by reactions involving the formation of Si-O linkages · CPC title

• C07C2103/54

  Chemistry & Metallurgy · mapped topic

• C07F7/1848

  Chemistry & Metallurgy · mapped topic