# US 11,078,218 B2 · Process for the production of triaryl organoborates

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- Number: US 11,078,218 B2
- Document ID: US11078218B2
- Status: Granted
- Kind: B2
- Application number: 16/348,262
- Filed: 2017-11-07
- Published: 2019-09-12
- Granted: 2021-08-03
- Earliest claimed: 2016-11-09
- Assignees: Covestro Deutschland AG
- Applicants: Covestro Deutschland AG
- Inventors: Thomas Rölle; Horst Berneth; Dennis Hönel; Friedrich-Karl Bruder
- Web page: https://patentgrep.com/patent/US11078218B2

## CPC

- C07F 5/025: {Boronic and borinic acid compounds}
- C07F 5/027: {Organoboranes and organoborohydrides}
- C08F 2/50: with sensitising agents
- G03F 7/001: {Phase modulating patterns, e.g. refractive index patterns}
- G03F 7/029: Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
- G03H 1/02: Details {of features involved during the holographic process; Replication of holograms without interference recording}
- G03H 2001/0264: {Organic recording material}
- G03H 2260/12: Photopolymer
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)
- G03H: HOLOGRAPHIC PROCESSES OR APPARATUS (holograms, e.g. point holograms, used as ordinary optical elements G02B5/32; producing stereoscopic or other three-dimensional effects G02B30/00; diffraction-grating systems G02B27/44; systems using moiré fringes G02B27/60; optical logic elements G02F3/00; stereo-photography G03B35/00; photosensitive materials or processes for photographic purposes G03C; {stereo-photographic or similar processes G03C9/00}; apparatus for processing exposed photographic materials G03D; analogue computers performing mathematical operations with the aid of optical elements G06E3/00; authentication by radiation, of concealed information carried by holograms or diffraction gratings G06K19/16; holographic storage G11B7/0065, G11C13/04; {stereoscopic or other three dimensional effects in television systems H04N13/00})

## 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 Kn+ to obtain 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, 3 equivalents of a haloaromatic R4—Y (III) are added, and optionally a second organic solvent water is added and the compound 1/n Kn+ R24B−—R1 (IV) is separated off with the organic phase, and to the use of these substances as co-initiator in photopolymer formulations.

## Claims

### Claim 1

Process for preparing triaryl organoborates of the formula 1/n Kn+R34B−—R1 (IV), where one equivalent of an 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 S, 3 equivalents of a haloaromatic R4—Y (III) are added, water and optionally a second organic solvent S is added and the compound 1/n Kn+ R34B−—R1 (IV) is separated off with the organic phase, and
R1 is an optionally hydroxyl- and/or alkoxy- and/or acyloxy- and/or halogen-substituted C1- to C22-alkyl, C3- to C22-alkenyl, C3- to C22-alkynyl, C5- to C7-cycloalkyl or C7- to C13-aralkyl radical and
R2 and R3 are independently an optionally branched C1- to C22-alkyl radical or an optionally alkyl-substituted C3- to C7-cycloalkyl radical or R2 and R3 together form a 2-8-membered carbon bridge which is optionally substituted by alkyl and/or interrupted by oxygen atoms, or R2 and R3 together form a 4-7-membered, optionally substituted carbocycle, and
R4 is a C6- to C10-aryl radical optionally substituted by at least one radical selected from halogen, C1- to C4-alkyl, trifluoromethyl, C1- to C4-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.

### Claim 2 (depends on 1)

Process for preparing compounds 1/n Kn+ R34B−—R1 of the formula (IV) according to claim 1, comprising the steps of
i) initially charging one equivalent of organoboronic ester B—R1(OR2)(OR3) (I) together with 1/n equivalents of salt Kn+ nX− (II) and 3 equivalents of metal M in a solvent or solvent mixture S,
ii) adding 3 equivalents of a haloaromatic R4—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 Kn+ R34B−—R1 (IV).

### Claim 3 (depends on 1)

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.

### Claim 4 (depends on 1)

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.

### Claim 5 (depends on 1)

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.

### Claim 6 (depends on 1)

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 C6- to C12-alkyl, C6- to C10-aryl, C7- to C12-arylalkyl or C5- to C6-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.

### Claim 7 (depends on 1)

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 C4- to C12-alkyl, C6- to C10-aryl, C7- to C12-arylalkyl or C5- to C6-cycloalkyl radicals and/or form oligomeric or polymeric repeating connecting units to give iodonium salts with 1≤n≤3, or are further polymeric cations.

### Claim 8 (depends on 1)

Process according to claim 1, characterized in that R1 is an optionally hydroxyl- and/or alkoxy- and/or acyloxy- and/or halogen-substituted C2- to C18-alkyl, C3- to C18-alkenyl, C3- to C18-alkynyl, C5- to C6-cycloalkyl or C7- to C13-aralkyl radical.

### Claim 9 (depends on 1)

Process according to claim 1, characterized in that R2 and R3 are independently an optionally branched C2- to C18-alkyl radical or R2 and R3 together form a 4-7-membered, optionally substituted carbocycle.

### Claim 10 (depends on 1)

Process according to claim 1, characterized in that R4 is a C6- to C10-aryl radical optionally substituted by at least one radical selected from halogen, C1- to C4-alkyl, trifluoromethyl, C1- to C4-alkoxy, trifluoromethoxy, phenyl and/or phenoxy.