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

Patent metadata

Field	Value
Publication number	US-9505688-B2
Application number	US-201615162805-A
Country	US
Kind code	B2
Filing date	May 24, 2016
Priority date	Dec 19, 2012
Publication date	Nov 29, 2016
Grant date	Nov 29, 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 norbornene methanol of formula (IB):

comprising:
reacting cyclopentadiene with allyl acetate, without any solvent, at a temperature of from about 130° C. to about 260° C. for a sufficient period of time to form norbornene methyl acetate of formula (IIIB):

distilling so formed norbornene methyl acetate of formula (IIIB); and
subjecting said distilled norbornene methyl acetate (IIIB) to trans-esterification reaction in the presence of methanol and a catalyst at a temperature of from about 40° C. to about 50° C. to form norbornene methanol (IB) of purity of at least 99 percent, which is essentially free of norbornane methanol.

2. The process of claim 1 , wherein cyclopentadiene is reacted with allyl acetate at a temperature of from about 180° C. to about 240° C. and said reaction is carried out in a closed tubular reactor.

3. The process of claim 1 , wherein cyclopentadiene is reacted with allyl acetate at a temperature of from about 200° C. to about 240° C.

4. The process of claim 1 , wherein cyclopentadiene is reacted with allyl acetate at a temperature of from about 210° C. to about 230° C.

5. The process of claim 1 , wherein cyclopentadiene is reacted with allyl acetate at a temperature of about 220° C.

6. The process of claim 1 , wherein the catalyst is a base.

7. The process of claim 6 , wherein the base is selected from the group consisting of lithium hydroxide, lithium methoxide, lithium ethoxide, lithium tert-butoxide, lithium carbonate, lithium bicarbonate, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, potassium carbonate, potassium bicarbonate, cesium hydroxide, cesium methoxide, cesium ethoxide, cesium tert-butoxide, cesium carbonate, cesium bicarbonate, calcium hydroxide, calcium methoxide, calcium ethoxide, calcium tert-butoxide, calcium carbonate, calcium bicarbonate, magnesium hydroxide, magnesium methoxide, magnesium ethoxide, magnesium tert-butoxide, magnesium carbonate, magnesium bicarbonate, ammonia, trimethylamine, triethylamine, imidazole, and a mixture in any combination thereof.

8. The process of claim 6 , wherein the base is sodium methoxide.

9. The process of claim 1 , wherein the catalyst is an acid.

10. The process of claim 9 , wherein the acid is selected from the group consisting of hydrochloric acid, hydrobromic acid, hydrofluoric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, 2-hydroxyethanesulfonic acid, p-toluenesulfonic acid, fumaric acid, maleic acid, hydroxymaleic acid, malic acid, ascorbic acid, succinic acid, glutaric acid, acetic acid, salicylic acid, cinnamic acid, 2-phenoxybenzoic acid, hydroxybenzoic acid, phenylacetic acid, benzoic acid, oxalic acid, citric acid, tartaric acid, glycolic acid, lactic acid, pyruvic acid, malonic acid, carbonic acid or phosphoric acid, and a mixture in any combination thereof.

11. The process of claim 1 , wherein the purity of norbornene methanol (IB) is at least 99.6 percent.

12. The process of claim 1 , wherein the purity of norbornene methanol (IB) is at least 99.8 percent.

13. A process for the preparation of (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)-diphenylsilane of formula (VB):

comprising:
reacting cyclopentadiene with allyl acetate, without any solvent, at a temperature of from about 200° C. to about 240° C. for a sufficient period of time to form norbornene methyl acetate of formula (IIIB):

subjecting norbornene methyl acetate (IIIB) to trans-esterification reaction in the presence of methanol and sodium methoxide at a temperature of from about 40° C. to about 50° C. to form norbornene methanol (IB), which is essentially free of norbornane methanol:

 and
reacting norbornene methanol (IB) with methyldiphenylsilane in the presence of a suitable solvent and a catalyst to obtain (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)diphenylsilane (VB) of at least 99 percent purity.

14. The process of claim 11 , wherein the solvent is tetrahydrofuran.

15. The process of claim 11 , wherein the catalyst is potassium tert-butoxide.

16. The process of claim 11 , wherein the purity of (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)diphenylsilane (VB) is at least 99.5 percent.

17. The process of claim 11 , wherein the purity of (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)diphenylsilane (VB) is at least 99.8 percent.

Assignees

• Promerus Llc

Inventors

• Bell Andrew
• Jablonski Dane

Classifications

• C07F7/1848

  Chemistry & Metallurgy · mapped topic

• C07C29/1285 Primary

  of esters of organic acids · CPC title

• B01J2531/004

  Ligands · CPC title

• C07C67/54

  by distillation · CPC title

• C07C2103/54

  Chemistry & Metallurgy · mapped topic