Process for the production of triaryl organoborates

Patent metadata

Field	Value
Publication number	US-11078218-B2
Application number	US-201716348262-A
Country	US
Kind code	B2
Filing date	Nov 7, 2017
Priority date	Nov 9, 2016
Publication date	Aug 3, 2021
Grant date	Aug 3, 2021

Abstract

Provided herein is a process for preparing triaryl organoborates proceeding from alkyl or cycloalkyl boronates in the presence of an n-valent cation 1/n K n+ to obtain organoborates of the formula 1/n K n+ R 3 4 B − —R 1 (IV), where one equivalent of organoboronic ester of the formula B—R 1 (OR 2 )(OR 3 ) (I) is initially charged together with 1/n equivalents of salt K n+ nX − (II) and 3 equivalents of metal M in a solvent or a solvent mixture, 3 equivalents of a haloaromatic R 4 —Y (III) are added, and optionally a second organic solvent water is added and the compound 1/n K n+ R 2 4 B − —R 1 (IV) is separated off with the organic phase, and to the use of these substances as co-initiator in photopolymer formulations.

First claim

The invention claimed is:

1. Process for preparing triaryl organoborates of the formula 1/n K n+ R 3 4 B − —R 1 (IV), where one equivalent of an organoboronic ester of the formula B—R 1 (OR 2 )(OR 3 ) (I) is initially charged together with 1/n equivalents of salt K n+ nX − (II) and 3 equivalents of metal M in a solvent or a solvent mixture S, 3 equivalents of a haloaromatic R 4 —Y (III) are added, water and optionally a second organic solvent S is added and the compound 1/n K n+ R 3 4 B − —R 1 (IV) is separated off with the organic phase, and
R 1 is an optionally hydroxyl- and/or alkoxy- and/or acyloxy- and/or halogen-substituted 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 13 -aralkyl radical and
R 2 and R 3 are independently an optionally branched C 1 - to C 22 -alkyl radical or an optionally alkyl-substituted C 3 - to C 7 -cycloalkyl radical or R 2 and R 3 together form a 2-8-membered carbon bridge which is optionally substituted by alkyl and/or interrupted by oxygen atoms, or R 2 and R 3 together form a 4-7-membered, optionally substituted carbocycle, and
R 4 is a C 6 - to C 10 -aryl radical optionally substituted by at least one radical selected from halogen, C 1 - to C 4 -alkyl, trifluoromethyl, C 1 - to C 4 -alkoxy, trifluoromethoxy, phenyl and phenoxy and
K is an organocation of valency n and having any substitution, based on nitrogen, phosphorus, oxygen, sulfur and/or iodine, and
M is any metal selected from the alkali metals, or from magnesium, calcium and aluminium and
X is a halide or alkoxide or alkyl sulphide and
Y is iodine or bromine or chlorine and
n is 1, 2 or 3 and
S is an aprotic organic solvent or a mixture of aprotic solvents.

2. Process for preparing compounds 1/n K n+ R 3 4 B − —R 1 of the formula (IV) according to claim 1 , comprising the steps of
i) initially charging one equivalent of organoboronic ester B—R 1 (OR 2 )(OR 3 ) (I) together with 1/n equivalents of salt K n+ nX − (II) and 3 equivalents of metal M in a solvent or solvent mixture S,
ii) adding 3 equivalents of a haloaromatic R 4 —Y (III), as a result of which
iii) an organometallic reagent generated in situ reacts with the initially charged substances (I) and (II) to give 1/n K n+ R 3 4 B − —R 1 (IV).

3. Process according to claim 1 , characterized in that the organocations K of valency n based on nitrogen are ammonium ions, pyridinium ions and imidazolium ions, which optionally bear further functional groups selected from the group consisting of ethers, esters, amides and carbamates in one or more side chains and which may also be in oligomeric or polymeric or bridging form.

4. Process according to claim 1 , characterized in that the organocations K of valency n based on phosphorus are tetraalkylphosphonium, trialkylarylphosphonium, dialkyldiarylphosphonium, alkyltriarylphosphonium or tetraarylphosphonium salts having any substitution, which optionally bear further functional groups selected from the group consisting of such as carbonyls, amides and/or carbamates in one or more side chains and which may also be in oligomeric or polymeric or bridging form.

5. Process according to claim 1 , characterized in that the organocation K of valency n based on oxygen is pyrylium having any substitution, including in fused form as in benzopyrylium, flavylium, naphthoxanthenium or polymeric cations.

6. Process according to claim 1 , characterized in that the organocations K of valency n based on sulfur are onium compounds of sulfur that bear identical or different optionally substituted C 6 - to C 12 -alkyl, C 6 - to C 10 -aryl, C 7 - to C 12 -arylalkyl or C 5 - to C 6 -cycloalkyl radicals and/or that form oligomeric or polymeric repeating connecting units to give sulfonium salts with 1≤n≤3, and thiopyrylium or polymeric cations.

7. Process according to claim 1 , characterized in that the organocations K of valency n based on iodine are onium compounds of iodine bearing identical or different optionally substituted C 4 - to C 12 -alkyl, C 6 - to C 10 -aryl, C 7 - to C 12 -arylalkyl or C 5 - to C 6 -cycloalkyl radicals and/or form oligomeric or polymeric repeating connecting units to give iodonium salts with 1≤n≤3, or are further polymeric cations.

8. Process according to claim 1 , characterized in that R 1 is an optionally hydroxyl- and/or alkoxy- and/or acyloxy- and/or halogen-substituted 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 radical.

9. Process according to claim 1 , characterized in that R 2 and R 3 are independently an optionally branched C 2 - to C 18 -alkyl radical or R 2 and R 3 together form a 4-7-membered, optionally substituted carbocycle.

10. Process according to claim 1 , characterized in that R 4 is a C 6 - to C 10 -aryl radical optionally substituted by at least one radical selected from halogen, C 1 - to C 4 -alkyl, trifluoromethyl, C 1 - to C 4 -alkoxy, trifluoromethoxy, phenyl and/or phenoxy.

Assignees

• Covestro Deutschland Ag

Inventors

• Rölle Thomas
• Berneth Horst
• Hönel Dennis
• Bruder Friedrich-Karl

Classifications

• C07F5/027 Primary

  Organoboranes and organoborohydrides · CPC title

• C08F2/50

  with sensitising agents · CPC title

• C07D347/00

  Heterocyclic compounds containing rings having halogen atoms as ring hetero atoms · CPC title

• G03F7/029

  Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur · CPC title

• C07F5/025 Primary

  Boronic and borinic acid compounds · CPC title