Method for producing triarylorganoborates

Patent metadata

Field	Value
Publication number	US-11098066-B2
Application number	US-201716348309-A
Country	US
Kind code	B2
Filing date	Nov 7, 2017
Priority date	Nov 9, 2016
Publication date	Aug 24, 2021
Grant date	Aug 24, 2021

Abstract

Provided herein is a process for preparing triaryl organoborates of the formula 1/n Kn+R34B−—R1 (IV), where one equivalent of organoboronic ester of the formula B—R1(OR2)(OR3) (I) is initially charged together with 1/n equivalents of salt Kn+ nX− (II) and 3 equivalents of metal M in a solvent or a solvent mixture S1, 3 equivalents of a haloaromatic R4—Y (III) are added, an auxiliary L and optionally a second organic solvent or solvent mixture S2 is added and the compound 1/n Kn+ R34B−—R1 (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 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 S1, 3 equivalents of a haloaromatic R 4 —Y (III) are added, an auxiliary L and optionally a second organic solvent or solvent mixture S2 is added and the compound 1/n K n+ R 3 4B 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,
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,
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,
K is an organocation of valency n and having any substitution, based on nitrogen, phosphorus, oxygen, sulfur and/or iodine, and
L is an auxiliary that forms a complex of sparing solubility in S1 and/or S2 with M salts MY(OR 2 ), MY(OR 3 ) and MXY, where L is a Lewis-basic compound, selected from the group consisting of open chain or cyclic or polycyclic ethers or polyethers or (poly)ether polyols, amine-functionalized and/or alkanolamine-functionalized alcohols or polyols or (poly)ether polyols, weakly basic organic compounds, weakly acidic macroporous cation exchangers and weakly alkaline macroporous cation exchangers,
M is any metal selected from the alkali metals, or from magnesium, calcium and aluminium,
X is a halide or alkoxide or alkyl sulfide,
Y is iodine or bromine or chlorine,
n is 1, 2 or 3,
S1 is an aprotic organic solvent or a mixture of aprotic solvents and
S2 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 S1,
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),
iv) adding an auxiliary L and
v) optionally a second organic solvent S2, where the compound (IV) remains in the organic phase, and
vi) the metal salts MY(OR 2 ), MY(OR 3 ) and MXY are separated off as precipitated solid complexes MY(OR 2 )L, MY(OR 3 )L and MXYL.

3. Process according to claim 1 , characterized in that the auxiliary L comprises Lewis-basic compounds having at least one freely available coordination site or mixtures thereof, selected from the group consisting of open-chain or cyclic or polycyclic ethers or polyethers or (poly)ether polyols, amine- and/or alkylamine-functionalized alcohols or polyols or (poly)ether polyols, weakly basic organic compounds, weakly acidic macroporous cation exchangers and weakly alkaline macroporous cation exchangers.

4. Process according to claim 1 , characterized in that the solvent or solvent mixtures S1 and S2 are independently anhydrous aprotic organic solvents or mixtures thereof.

5. Process according to claim 1 , characterized in that the organocations K of valency n based on nitrogen are ammonium ions, pyridinium ions, pyridazinium ions, pyrimidinium ions, pyrazinium ions, imidazolium ions, pyrrolidinium 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.

6. 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 carbonyls, amides and carbamates in one or more side chains and which may also be in oligomeric or polymeric or bridging form.

7. 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.

8. 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 4 - to C 14 -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.

9. 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 1 - to C 22 -alkyl, C 6 - to C 14 -aryl, C 7 - to C 15 -arylalkyl or C 5 - to C 7 -cycloalkyl radicals and/or form oligomeric or polymeric repeating connecting units to give iodonium salts with 1≤n≤3, or are further polymeric cations.

10. 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.

11. 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.

12. 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
• Kintrup Jürgen

Classifications

• C07D347/00

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

• C07D233/02

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

• C07D247/00

  Heterocyclic compounds containing rings having two nitrogen atoms as the only ring hetero atoms, according to more than one of groups C07D229/00 - C07D245/00 · CPC title

• C07D309/34

  having three or more double bonds between ring members or between ring members and non-ring members · CPC title

• C07C271/28

  to a carbon atom of a non-condensed six-membered aromatic ring · CPC title