Process for the manufacturing of triaryl-organo borates

Patent metadata

Field	Value
Publication number	US-11242360-B2
Application number	US-201716348333-A
Country	US
Kind code	B2
Filing date	Nov 7, 2017
Priority date	Nov 9, 2016
Publication date	Feb 8, 2022
Grant date	Feb 8, 2022

Abstract

The invention relates to a process for the preparation of triaryl-organo borates from boronic ester and the use of these substances in photo initiator systems, photopolymer compositions comprising such photo initiator systems, a holographic medium comprising said photopolymer composition and the respective hologram.

First claim

The invention claimed is:

1. Process for the production of triaryl-organo borates of the formula 1/m A m+ [R 1 BR 3 3 ] − (IX) obtainable or obtained by reacting a boronic ester of formula B(OR 2 ) 3 (I) with an organolithium- or Grignard-reagent of formula R 1 -E (II) in a solvent or solvent mixture S1, adding a previously formed organometallic reagent of the formula R 3 -M-X (V) in a solvent or solvent mixture S2, further adding a salt of the formula 1/m A m+ Y − (VIII) and isolating the precipitated triaryl-alkyl borate product of formula 1/m A m+ [R 1 BR 3 3 ] − (IX), wherein the triaryl-alkyl borate of 1/m A m+ [R 1 BR 3 3 ] − (IX) comprises less than 10.000 ppm of tetra aryl borate A m+ [BR 4 3 ] − ,
in which
A stands for a substituted organic cation with the charge m on the basis of nitrogen, phosphorus, oxygen, sulfur and/or iodine,
B stands for boron
E stands for lithium or magnesium-monohalide,
M stands for a metal selected from magnesium, calcium, aluminum, tin, zinc or cadmium,
X stands for chlorine, bromine or iodine,
Y stands for halide, alkoxide, or sulfide,
R 1 stands for a C 1 - to C 22 -alkyl-, C 3 - to C 22 -alkenyl-, C 3 - to C 22 -alkynyl-, C 5 - to C 7 -cycloalkyl- or C 7 - to C 15 -aralkyl-residue, which can be optionally substituted by oxygen or nitrogen or halogen,
R 2 stands for an optionally branched C 1 - to C 22 -alkyl-residue or an optionally alkyl-substituted C 3 - to C 7 -cycloalkyl-residue or an optionally aryl- or heteroaryl substituted C 2 - to C 22 -alkyl-residue or R 2 may form a 2-8-membered bicyclic ring optionally substituted by alkyl residues and/or by oxygen atoms or R 2 may form a 4-14-membered tricyclic ring an optionally substituted by alkyl residues and/or by oxygen atoms,
R 3 stands for a C 6 - to C 14 -aryl residue optionally substituted by at least one residue selected from halogen, C 1 -to C 4 -alkyl, trifluoromethyl, C 1 - to C 4 -alkoxy, trifluoromethoxy, phenyl and/or phenoxy,
m stands for 1, 2 or 3,
S1 and S2 independently from one another stand for an aprotic organic solvent or a mixture of aprotic organic solvents.

2. The process according to claim 1 comprising the steps of
i) reacting boronic ester of formula B(OR 2 ) 3 (I) in a solvent or solvent mixture S1 at a temperature or temperature range T1 with an organolithium- or Grignard-reagent of formula R 1 -E (II) to yield the salt of formula [R 1 B(OR 2 ) 3 ] − E + (III),
ii) reacting an organic halogen compound of formula R 3 -X (IV) in a solvent or solvent mixture S2 at a temperature or temperature range T2 with a metal M to yield an organometallic reagent of formula R 3 -M-X (V),
iii) reacting the compounds (III) and (V) in a combined solvent or solvent mixture S1 and S2 at a temperature or temperature range T3 to yield the salts of formula [R 1 BR 3 3 ] − E + (VI) and of formula R 2 O-M-X (VII),
iv) adding the salt of formula 1/m A m+ Y − (VIII) and water and
v) isolating the precipitated product of formula 1/m A m+ [R 1 BR 3 3 ] − (IX)
whereby
T1 stands for a temperature of −110° C. to −50° C.,
T2 stands for a temperature of −20° C. to 100° C., and
T3 stands for a temperature of 0° C. to 100° C.

3. Process according to claim 1 , characterized in that R 1 stands for an C 2 - to C 18 -alkyl-, C 3 - to C 18 -alkenyl-, C 3 - to C 18 -alkynyl-, C 5 - to C 6 -cycloalkyl- or C 7 - to C 13 -aralkyl residue optionally substituted by oxygen and/or halogen.

4. Process according to claim 1 , characterized in that R 2 stands for a branched C 2 - to C 18 -alkyl-residue or R 2 forms a 2-6-membered bicyclic ring optionally substituted by alkyl residues and/or by oxygen atoms or R 2 may form a 4-10-membered tricyclic ring optionally substituted by alkyl residues and/or by oxygen atoms.

5. Process according to claim 1 , characterized in that R 3 stands for a C 6 - to C 10 -aryl residue that may be optionally substituted by at least one of the residues selected from halogen, C 1 -to C 4 -alkyl, trifluoromethyl, C 1 - to C 4 -alkoxy, trifluormethoxy, phenyl and/or phenoxy.

6. Process according to claim 1 , characterized in that S1 and S2 independently from one another stand for alkanes, alkenes, benzene and aromatics with aliphatic and/or aromatic substituents, carboxylic acid esters, ethers or mixtures thereof.

7. Process according to claim 1 , characterized in that M stands for magnesium, calcium or aluminum.

Assignees

• Covestro Deutschland Ag

Inventors

• Rölle Thomas
• Satyanarayana Ganugapati
• Roychowdhury Sumana
• Patil Ravindra Mahadev
• Pillai Anup Krishnnan Appukuttan

Classifications

• G03F7/035

  the binders being polyurethanes · CPC title

• C07D233/58

  with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms · CPC title

• G03H1/02

  Details {of features involved during the holographic process; Replication of holograms without interference recording} · CPC title

• C07D233/02

  having no double bonds between ring members or between ring members and non-ring members · CPC title

• C07F5/027 Primary

  Organoboranes and organoborohydrides · CPC title