Norbornenylhydrocarbylene dihydrocarbylboranes and methods of making the same

Patent metadata

Field	Value
Publication number	US-9328126-B2
Application number	US-201414759063-A
Country	US
Kind code	B2
Filing date	Jan 31, 2014
Priority date	Jan 31, 2013
Publication date	May 3, 2016
Grant date	May 3, 2016

Abstract

Embodiments of norbornenylhydrocarbylene dihydrocarbylboranes represented by the Formula (I),

and methods of forming such norbornenylhydrocarbylene dihydrocarbylboranes are provided, where m is 0, 1 or 2, A is a C 2 to C 12 hydrocarbylene group; R 1 and R 2 are independently selected from a substituted or unsubstituted C 1 to C 12 hydrocarbyl, substituted or unsubstituted, monocyclic or bicyclic C 5 to C 7 rings, and R 1 and R 2 , taken together with the boron atom to which they are attached, can form a monocyclic or bicyclic ring; wherein the norbornenylhydrocarbylene dihydrocarbylboranes of Formula (I) are subject to the proviso that 9-norbornenylethyl-9-borabicyclo[3.3.1]nonane is not included.

First claim

We claim:

1. A borane compound of the Formula I:

where m is 0, 1 or 2 and A is a C 2 to C 12 hydrocarbylene group; R 1 and R 2 are independently selected from —CH 3 , —C 2 H 5 , a linear or branched C 3 to C 12 acyclic hydrocarbyl group, a substituted or unsubstituted C 5 to C 7 mono- or bicyclic hydrocarbyl group, or where R 1 and R 2 are taken together with the boron atom to which they are attached form a mono- or bicyclic structure having from 3 to 6 carbon atoms.

2. The compound of claim 1 , which is selected from:
norbornenylethylbis(2,5-dimethylhex-4-en-3-yl)borane,
norbornenylbutylbis(2,5-dimethylhex-4-en-3-yl)borane,
norbornenylhexylbis(2,5-dimethylhex-4-en-3-yl)borane,
norbornenylethyldicyclohexylborane,
norbornenylbutyldicyclohexylborane,
norbornenylhexyldicyclohexylborane,
norbornenylethyldimesitylborane,
norbornenylbutyldimesitylborane and
norbornenylhexyldimesitylborane.

3. A method of forming a compound of Formula Ia:

which comprises:
reacting a compound of Formula I:

with a suitable reagent, where m is 0, 1 or 2 and A is a C 2 to C 12 hydrocarbylene group; R 1 and R 2 are independently selected from —CH 3 , —C 2 H 5 , a linear or branched C 3 to C 12 acyclic hydrocarbyl group, a substituted or unsubstituted C 5 to C 7 mono- or bicyclic hydrocarbyl group, or where R 1 and R 2 are taken together with the boron atom to which they are attached form a mono- or bicyclic structure having from 3 to 6 carbon atoms; and
A-Y is an alkyl pendent group, an alcohol pendent group, an ether pendent group, an alkaryl pendent group, a carboxylic acid pendent group, a sulfonic acid ester pendent group or an alkyl halide pendent group.

4. The method of claim 3 , where the alkaryl pendent group is —(CH 2 ) n —Ar where n is 1 to 12 and Ar is an aromatic group.

5. The method of claim 3 , where the alcohol pendent group is one of —(CH 2 ) n —OH or —(CH 2 ) n —C(CF 3 ) 2 OH, where n is 1 to 12.

6. The method of claim 3 , where the carboxylic acid pendent group is inclusive of ester derivatives and is one of —(CH 2 ) n —C(O)OH or —(CH 2 ) n —C(O)O(CH 2 ) m CH 3 , where n is 1 to 12 and m is 0 to 5.

7. The method of claim 3 , where the alkyl halide pendent group is one of —(CH 2 ) n —Br or —(CH 2 ) n —I, where n is 1 to 12.

8. The method of claim 3 , where the sulfonic acid ester pendent group is —(CH 2 ) n —S(O) 2 O(CH 2 ) m CH 3 or —(CH 2 ) n —S(O) 2 O(CH 2 ) m —Ar where n is 1 to 12, m is 0 to 5 and Ar is an aromatic group.

9. A method of making the borane compound of claim 1 , comprising:
generating a dihydrocarbylborane represented by structural Formula A:

where R 1 and R 2 are independently selected from —CH 3 , —C 2 H 5 , a linear or branched C 3 to C 12 acyclic hydrocarbyl group, a substituted or unsubstituted C 5 to C 7 mono- or bicyclic hydrocarbyl group, or where if R 1 and R 2 are taken together with the boron atom to which they are attached, a mono- or bicyclic structure having from 3 to 6 carbon atom, with the proviso that the C—B—C bond angle formed by the boron and the carbon of each hydrocarbyl group directly bonded to the boron have a bond angle greater than 118°;
reacting the dihydrocarbylborane and an alkenylnorbornene to generate said borane compound.

10. The method of claim 9 where the dihydrocarbylborane of structural Formula A is a dialkylborane.

11. The method of claim 10 where the dialkylborane is selected from di(cyclooctyl)borane, di(2-methylcyclopentyl)borane, dicyclopentylborane, di(3,5-dimethylcyclopentyl)borane, diisopropylprenylborane, dicyclohexylborane, di(2-methylcyclohexyl)borane, di(3,6-dimethylcyclohexyl)borane, dinorbornylborane, di(siamyl)borane, di(isopinocampheyl)borane, 3,6-dimethylborepane, di(o-tolyl)borane, dimesitylborane, (cyclohexyl)(tert-butyl)borane, (cyclohexyl)(methyl)borane, diphenylborane, or dis(2,4,6,-triisopropylphenyl).

12. The method of claim 11 where the dihydrocarbylborane is complexed with a Lewis base selected from 2-picoline, quinoline, quinoxaline, 2,3-lutidine, 2,4-lutidine, 2,5-lutidine, 5-ethyl-2-methylpyridine, 4-ethyl-2-methylpyridine, 3-ethyl-2-methylpyridine, 2,5-diethylpyridine, 5-propyl-2-methylpyridine, 4-propyl-2-methylpyridine, 5-isopropyl-2-methylpyridine, 5-t-butyl-2-methylpyridine, 5-n-hexyl-2-methylpyridine, 4-isobutyl-2-methylpyridine, and 2,4-dipropylpyridine.

13. The method of claim 9 where the dihydrocarbylborane of structural Formula A is a diarylborane.

14. The method of claim 13 where the diarylborane is selected from (o-tol) 2 BH, (C 6 F 5 ) 2 BH, (2,6-Me 2 Ph) 2 BH, (Mes) 2 BH, (Trip) 2 BH, (Ph) 2 BH, (2,6-diisopropylPh) 2 BH.

15. A method for making an essentially pure exo-5-hydrocarbyl-2-norbornene monomer comprising
generating a dihydrocarbylborane selected from dicyclopentylborane, di(3,5-dimethylcyclopentyl)borane, diisopropylprenyl borane, dicyclohexylborane, di(2-methylcyclohexyl)borane, di(3,6-dimethylcyclohexyl)borane, di(siamyl)borane, di(isopinocampheyl)borane, dimesitylborane, and di(tri(isopropyl)phenyl)borane;
reacting the dihydrocarbylborane and an appropriate exo-hydrocarbylenenorbornene to generate at least one trihydrocarbylborane where the norbornenylhydrocarbylene-dihydrocarbylborane is at least 95 mol % of all trihydrocarbylboranes; and
converting the norbornenylhydrocarbylene-dihydrocarbylborane to said exo-5-hydrocarbyl-2-norbornene monomer where said monomer is at least 95 mol % of all converted trihydrocarbylboranes.

16. The method of claim 15 , where the norbornenylhydrocarbylene-dihydrocarbylborane is at least 97 mol % of all trihydrocarbylboranes.

17. The method of claim 15 , where the norbornenylhydrocarbylene-dihydrocarbylborane is at least 99 mol % of all trihydrocarbylboranes.

18. A method for making essentially pure endo-5-hydrocarbyl-2-norbornene monomer comprising
generating a dihydrocarbylborane selected from dicyclopentylborane, di(3,5-dimethylcyclopentyl)borane, diisopropylprenyl borane, dicyclohexylborane, di(2-methylcyclohexyl)borane, di(3,6-dimethylcyclohexyl)borane, di(siamyl)borane, di(isopinocampheyl)borane, dimesitylborane, and di(tri(isopropyl)phenyl)borane;
reacting the dihydrocarbylborane and an appropriate endo-hydrocarbylenenorbornene to generate at least one trihydrocarbylborane where the norbornenylhydrocarbylene-dihydrocarbylborane is at least 95 mol % of all trihydrocarbylboranes; and
converting the norbornenylhydrocarbylene-dihydrocarbylborane to said endo-5-hydrocarbyl-2-norbornene monomer, where said monomer is at least 95 mol % of all converted trihydrocarbylboranes.

19. The method of claim 18 , where the norbornenylhydrocarbylene-dihydrocarbylborane is at least 97 mol % of all trihydrocarbylboranes.

20. The method of claim 18 , where the norbornenylhydrocarbylene-dihydrocarbylborane is at least 99 mol % of all trihydrocarbylboranes.

21. A method for making essentially pure form of a compound of Formula I:

Assignees

• Promerus Llc

Inventors

• Bell Andrew
• Seto Keitaro
• Westcott Stephen
• Potter Robert G

Classifications

• C07F5/027 Primary

  Organoboranes and organoborohydrides · CPC title

• C07C51/15

  by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis · CPC title

• C07C41/03

  by reaction of oxirane rings with hydroxy groups · CPC title

• C07C17/361

  by reactions involving a decrease in the number of carbon atoms · CPC title

• C07C17/093

  by replacement by halogens · CPC title