Method for producing triarylorganoborates

Abstract

Provided herein is a process for preparing triaryl organoborates of the formula 1/n K.sup.n+R.sub.3.sup.4B.sup.−—R.sup.1 (IV), where one equivalent of organoboronic ester of the formula B—R.sup.1(OR.sup.2)(OR.sup.3) (I) is initially charged together with 1/n equivalents of salt K.sup.n+ nX.sup.− (II) and 3 equivalents of metal M in a solvent or a solvent mixture S1, 3 equivalents of a haloaromatic R.sup.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.sup.n+ R.sub.3.sup.4B.sup.−—R.sup.1 (IV) is separated off with the organic phase, and to the use of these substances as co-initiator in photopolymer formulations.

Claims

1. Process for preparing triaryl organoborates of the formula 1/n K.sup.n+R.sub.3.sup.4B.sup.−—R.sup.1 (IV), where one equivalent of organoboronic ester of the formula B—R.sup.1(OR.sup.2)(OR.sup.3) (I) is initially charged together with 1/n equivalents of salt K.sup.n+ nX.sup.− (II) and 3 equivalents of metal M in a solvent or a solvent mixture S1, 3 equivalents of a haloaromatic R.sup.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.sup.n+ R.sub.3.sup.4BB.sup.−—R.sup.1 (IV) is separated off with the organic phase and R.sup.1 is an optionally hydroxyl- and/or alkoxy- and/or acyloxy- and/or halogen-substituted C.sub.1- to C.sub.22-alkyl, C.sub.3- to C.sub.22-alkenyl, C.sub.3- to C.sub.22-alkynyl, C.sub.5- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.13-aralkyl radical, R.sup.2 and R.sup.3 are independently an optionally branched C.sub.1- to C.sub.22-alkyl radical or an optionally alkyl-substituted C.sub.3- to C.sub.7-cycloalkyl radical or R.sup.2 and R.sup.3 together form a 2-8-membered carbon bridge which is optionally substituted by alkyl and/or interrupted by oxygen atoms, or R.sup.2 and R.sup.3 together form a 4-7-membered, optionally substituted, carbocycle, R.sup.4 is a C.sub.6- to C.sub.10-aryl radical optionally substituted by at least one radical selected from halogen, C.sub.1- to C.sub.4-alkyl, trifluoromethyl, C.sub.1- to C.sub.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.sup.2), MY(OR.sup.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.sup.n+ R.sub.3.sup.4B.sup.−—R.sup.1 of the formula IV according to claim 1, comprising the steps of i) initially charging one equivalent of organoboronic ester B—R.sup.1(OR.sup.2)(OR.sup.3) (I) together with 1/n equivalents of salt K.sup.n+ nX.sup.− (II) and 3 equivalents of metal M in a solvent or solvent mixture S1, ii) adding 3 equivalents of a haloaromatic R.sup.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.sup.n+ R.sub.3.sup.4B.sup.−—R.sup.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.sup.2), MY(OR.sup.3) and MXY are separated off as precipitated solid complexes MY(OR.sup.2)L, MY(OR.sup.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.sub.4- to C.sub.14-alkyl, C.sub.6- to C.sub.10-aryl, C.sub.7- to C.sub.12-arylalkyl or C.sub.5- to C.sub.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.sub.1- to C.sub.22-alkyl, C.sub.6- to C.sub.14-aryl, C.sub.7- to C.sub.15-arylalkyl or C.sub.5- to C.sub.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.sup.1 is an optionally hydroxyl- and/or alkoxy- and/or acyloxy- and/or halogen-substituted C.sub.2- to C.sub.18-alkyl, C.sub.3- to C.sub.18-alkenyl, C.sub.3- to C.sub.18-alkynyl, C.sub.5- to C.sub.6-cycloalkyl or C.sub.7- to C.sub.13-aralkyl radical.

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

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

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows the holographic properties Δn of the holographic media determined by means of twin-beam interference in reflection arrangement as described in WO2015091427.

EXAMPLES

(2) Test methods: OH number: The OH numbers reported were determined according to DIN 53240-2. NCO value: The NCO values (isocyanate contents) reported were determined according to DIN EN ISO 11909. Solids content: The solids contents reported were determined according to DIN EN ISO 3251. Refractive index modulation Δn: The holographic properties Δn of the holographic media were determined by means of twin-beam interference in reflection arrangement as described in WO2015091427; a representative result is shown in FIG. 1.
Substances

(3) The solvents, reagents and all bromoaromatics used were purchased from chemical suppliers. Anhydrous solvents contain <50 ppm of water.

(4) TABLE-US-00001 Ethylboronic acid [82954-89-0] is available from TCI Europe pinacol ester N.V., Zwijndrecht, Belgium. Isopropylboronic [76347-13-2] is available from ABCR acid pinacol ester GmbH & Co. KG, Karlsruhe, Germany. 2-Isopropenylboronic [126726-62-3] is available from ABCR acid pinacol ester GmbH & Co. KG, Karlsruhe, Germany. l-Dodecylboronic [177035-82-4] is available from ABCR acid pinacol ester GmbH & Co. KG, Karlsruhe, Germany. 3-Phenyl-1-propyl [329685-40-7] is available from ABCR boronic acid pinacol GmbH & Co. KG, Karlsruhe, Germany. ester Diisopropyl [51851-79-7] is available from ABCR allyl boronate GmbH & Co. KG, Karlsruhe, Germany. (1,3,2-Dioxaborinan- [30169-75-6] is available from ABCR 2-yl)cyclohexane GmbH & Co. KG, Karlsruhe, Germany. Dibromoborane- [55671-55-1] is available from Aldrich dimethyl sulfide Chemie, Steinheim, Germany. complex 1-Octadecene [112-41-4] is available from ABCR GmbH & Co. KG, Karlsruhe, Germany. Desmorapid Z dibutyltin dilaurate [77-58-7], product from Covestro AG, Leverkusen, Germany. Desmodur ® N 3900 product from Covestro AG, Leverkusen, DE, hexane diisocyanate-based polyisocyanate, proportion of iminooxadiazinedione at least 30%, NCO content: 23.5%. Fomrez UL 28 Urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, CT, USA.

(5) Lewatit® MDS TP 208 is available from Lanxess Deutschland GmbH, Cologne, Germany.

(6) 2-Hexyl-1,3,2-dioxaborinane [86290-24-6] was prepared as described in Organometallics 1983, 2 (10), p. 1311-16, DOI:10.1021/om5.0004a008 from 1-hexene, propane-1,3-diol and dibromoborane-dimethyl sulfide complex.

(7) 2-Octadecyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was prepared analogously to Organometallics 1983, 2 (10), p. 1311-16, DOI:10.1021/om5.0004a008 from 1-octadecene, propane-1,3-diol and dibromoborane-dimethyl sulfide complex.

(8) Dye 1 (3,7-bis(diethylamino)phenoxazin-5-ium bis(2-ethylhexyl)sulfosuccinate) was prepared as described in WO 2012062655.

(9) Polyol 1 was prepared as described in Polyol 1 in WO2015091427.

(10) Urethane acrylate 1 (phosphorothioyltris(oxybenzene-4,1-diylcarbamoyloxyethane-2,1-diyl) trisacrylate, [1072454-85-3]) was prepared as described in WO2015091427.

(11) Urethane acrylate 2 (2-({[3-(methylsulfanyl)phenyl]carbamoyl}oxy)ethyl prop-2-enoate, [1207339-61-4]) was prepared as described in WO2015091427.

(12) Additive 1, bis(2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl)-(2,2,4-trimethylhexane-1,6-diyl)biscarbamate [1799437-41-4] was prepared as described in WO2015091427.

(13) Origin of the 1/n K.sup.n+ cations used

(14) The 1/n K.sup.n+ cations specified in Table 1 were purchased from the chemical supplier mentioned or prepared according to the source mentioned or the preparation is described hereinafter.

(15) TABLE-US-00002 TABLE 1 Overview of the cations of the formula (II) used Index Name Structure CAS Source K-1 Tetramethylammonium bromide Me.sub.4NBr [64-20-0] 426296, Aldrich K-2 Tetrabutylammonium bromide Bu.sub.4NBr [1643-19-2] 426288, Aldrich K-3 Benzyldimethylhexadecyl- BnMe.sub.2HexadecylNCl [122-18-9] AB252026, abcr ammonium chloride GmbH K-4 Hexadecyltrimethylammonium bromide 0 [57-09-0] AB117004, abcr GmbH K-5 Benzethonium chloride [121-54-0] AB131627, abcr GmbH K-6 1-Hexadecyl-3-methylimidazolium chloride [61546-01-8] AB289677, abcr GmbH K-7 1-Methyl-3-octylimidazolium chloride [64697-40-1] AB289637, abcr GmbH K-8 1-Dodecyl-3-methylimidazolium chloride [114569-84-5] AB280681, abcr GmbH K-9 1-Ethyl-3-imidazolium chloride [81505-35-3] AB289800, abcr GmbH K-10 1-Benzyl-3-hexadecyl- imidazolium bromide [1224595-52-1] Fuel Processing Technology (2014), 118, 296-301. K-11 N-Hexadecylpyridinium chloride monohydrate [6004-24-6] AB117002, abcr GmbH K-12 N-Docosylpyridinium bromide [80039-83-4] J. Am. Chem. Soc. (2002), 124 (11), 2604-2613. K-13 4-tert-Butyl-1-hexadecyl- pyridinium chloride [1702465-32-4] WO 2015055576 A1 K-14 1,1′-[1,3-Phenylenebis (methylene)bis(pyridinium) dichloride 0 [84002-71-1] Zhurnal Neoganicheskoi Khimii (1978), 23, 825-6. K-15 N,N,N,N′,N′,N′-Hexaethyl-1,3- benzenedimethane aminium dibromide [66753-59-1P] Chemische Berichte (1984), 117 (4), 1487-96. K-16 N,N-Dioctadecylpiperidium chloride [61550-95-6] J. Am. Chem. Soc. (1955), 77, 485-6. K-17 N-Hexadecyl-N,N- dimethylanilinium bromide [17695-00-0] Taiwan Kexue (1959), 13, 95-8. K-18 N,N,N,N′,N′,N′-Hexabutyl- hexamethylenediammonium dibromide [745829-82-7P] Chemical Engineering Science, 69 (1), 483- 491. K-19 N-(2-(Benzoyloxy)ethyl)-N,N- dimethyloctadecane-1- aminium bromide [152167-30-1] U.S. Pat. No. 5,194,472 A K-20 N-(2-((2-Ethylhexanoyl) oxy)ethyl)-N,N- dimethylhexadecane-1- aminium bromide For preparation method see below K-21 N-Benzyl-N,N-dimethyl-2-(2- (palmitoyloxy)ethoxy)ethane- 1-aminium bromide For preparation method see below K-22 2-(Benzoyloxy)-N,N-dimethyl-N-(2- (palmitoyloxy)ethyl)ethane-1- aminium bromide For preparation method see below K-23 N-(3-((2-Ethylhexyl)oxy)- 3-oxopropyl)-N,N- dimethyloctadecane-1-aminium bromide For preparation method see below K-24 N-(2-((Hexylcarbamoyl)oxy) ethyl)-N,N- dimethylhexadecane-1-aminium bromide 0 For preparation method see below K-25 N.sup.1,N.sup.16-Dihexadecyl-N.sup.1,N.sup.1,N.sup.16, N.sup.16,7,7,10-heptamethyl- 4,13-dioxo-3,14-dioxa-5,12- diazahexadecane-1,16- diaminium dibromide For preparation method see below K-26 N-(2-((((5-(((2- (Hexadecyldimethylammonio) ethoxy)carbonyl)amino)- 1,3,3- trimethylcyclohexyl)methyl) carbamoyl)oxy)ethyl)- N,N-dimethylhexadecane-1- aminium dibromide For preparation method see below K-27 N,N′-(((((Methylenebis (cyclohexane-4,1- diyl))bis(azanediyl))bis(carbonyl)) bis(oxy))bis(ethane-2,1-diyl)) bis(N,N-dimethylhexadecane-1- aminium) dibromide For preparation method see below K-28 N,N′-(((((4-Methyl-1,3- phenylene)bis(azanediyl)) bis(carbonyl))bis(oxy))bis (ethane-2,1-diyl))bis(N,N- dimethylhexadecane-1- aminium) dibromide [1073535-73-5] For preparation method see below K-29 N,N′-(((((Methylenebis(4,1- phenylene))bis(azanediyl)) bis(carbonyl))bis(oxy))bis (ethane-2,1-diyl))bis(N,N- dimethylhexadecane-1- aminium) dibromide For preparation method see below K-30 N-(2-(2-((Hexylcarbamoyl) oxy)ethoxy)ethyl)-N,N- dimethylhexadecane-1-aminium bromide For preparation method see below K-31 N.sup.1,N.sup.22-Dihexadecyl- N.sup.1,N.sup.1,N.sup.22N.sup.22,10,10,13- heptamethyl-7,16-dioxo-3,6,17,20- tetraoxa-8,15-diazadocosane- 1,22-diaminium dibromide For preparation method see below K-32 N-(2-(2-(((3-(10,10-Dimethyl- 3-oxo-4,7-dioxa-2,10- diazahexacosan-10-ium-1-yl)-3,5,5- trimethylcyclohexyl)carbamoyl) oxy)ethoxy)ethyl)- N,N-dimethylhexadecane-1- aminium dibromide For preparation method see below K-33 N,N′-(((((((Methylenebis (cyclohexane-4,1- diyl))bis(azanediyl))bis(carbonyl)) bis(oxy))bis(ethane-2,1-diyl)) bis((oxy))bis(ethane-1,2-diyl))bis (N,N-dimethylhexadecane-1- aminium) dibromide For preparation method see below K-34 N,N′-(((((((4-Methyl-1,3-phenylene) bis(azanediyl))bis-(carbonyl))bis(oxy)) bis(ethane-2,1-diyl))bis(oxy)) bis(ethane-2,1-diyl))bis(N,N- dimethylhexadecane-1-aminium) dibromide 0 For preparation method see below K-35 N,N′-(((((((Methylenebis(4,1- phenylene))bis((azenediyl))bis (carbonyl)) bis(oxy))bis(ethane-2,1- diyl))bis(oxy)bis(ethane-2,1- diyl))bis(N,N-dimethylhexadecane- 1-aminium) dibromide For preparation method see below K-36 N.sup.1,N.sup.1,N.sup.1,N.sup.3,N.sup.3,N.sup.3,N.sup.5,N.sup.5,N.sup.5- Nonamethyl-1,3,5- benzenetrimethanaminium triiodide [88888-13-5] Chem. Ber. 177, 1487-1496 (1984). K-37 N-[2-[2-(Benzoyloxy)ethoxy] ethoxy]ethyl]-N,N- dimethyloctadecane-1-aminium bromide [215591-20-1] SK 278487 K-38 1-[3-[(2-Ethylhexyl)oxy]-3-oxopropyl]- 4-methylpyridinium chloride [110250-87-8] U.S. Pat. No. 2,857,310 K-39 4-Methyl-1-[2-[(1-oxotetradecyl) oxy]ethyl]pyridinium chloride [42936-94-7] Izvestiya Vysshikh Uchebnykh Zavedenii, Khimiyai Khimicheskaya Tekhnologiya (1973), 16(6), 891. K-40 1-[[3-(4-Methoxyphenyl)-2-oxo-5- oxazolidinyl]methyl]-4- phenyl-pyridinium bromide [121082-85-7] DE 3723797 K-41 4-Methyl-1-[2-[(1-oxododecyl) amino]ethyl]pyridinium chloride [15147-43-0] Chemicky-Prumysl (1967), 17(2), 67-9. K-42 4,5-Dihydro-1-methyl-3-[2- [(1-oxotetradecyl)oxy]ethyl]-2- pentadecyl-1H-imidazolium chloride [131625-89-3] U.S. Pat. No. 4,954,635 K-43 4,4-Bis[2-[[(9Z)-1-oxo-9-octadecen-1- yl]oxy]ethyl]morpholinium chloride [272462-96-1] WO2000030444 K-100 Tributyltetradecylphosphonium chloride 0 [81741-28-8] P444(14) Cl, Ionic Liquids Technologies GmbH K-101 Trihexyltetradecylphosphonium chloride [258864-54-9] P666(14) Cl, Ionic Liquids Technologies GmbH K-102 Methyltriphenylphosphonium chloride [1031-15-8] AB349191, abcr GmbH K-103 Triphenylbenzylphosphonium chloride [1100-88-5] AB113982, abcr GmbH K-104 Tetraphenylphosphonium chloride [2001-45-8] AB119018, abcr GmbH K-105 Allyltriphenylphosphonium bromide [1560-54-9] AB121395, abcr GmbH K-106 (2-Oxo-2-phenylethyl) triphenylphosphonium bromide [6048-29-9] AB233312, abcr GmbH K-200 4-Methyl-2,6-diphenylpyrylium tetrafluoroborate [2340-23-0] S919802, Aldrich K-201 2,4,6-Triphenylpyrylium tetrafluoroborate [448-61-3] AB119969, abcr GmbH K-202 2,4,6-Trimethylpyrylium tetrafluoroborate [773-01-3] AB177250, abcr GmbH K-203 4,4′-Bis(2,6-diphenylpyrylium tetrafluoroborate) 0 [42559-29-5] S873950, Aldrich K-300 Diphenyl[4-(phenylthio) phenyl]sulfonium hexafluorophosphate [75482-18-7] AB334122, abcr GmbH K-301 Bis(diphenylsulfonium)diphenyl thioether hexafluorophosphate [74227-35-3] AB134315, abcr GmbH K-302 Diphenyl[4-(phenylthio)phenyl] sulfonium triflate [111281-12-0] AB231614, abcr GmbH K-303 Mixture of K-300 + K-301 [104558-95-4] BASF SE, (Cyracure UVI 6990) Ludwigshafen, Germany K-304 Tris[4-[(4-acetylphenyl)thio]phenyl] sulfonium tris[(trifluoromethyl) sulfonyl]methanide [953084-20-3] BASF SE, Ludwigshafen, Germany K-305 2,4,6-Triphenylthiopyrylium perchlorate [2930-37-2] AKOS001017031, AKos GmbH Austr. 26 Steinen, D-79585 Germany K-400 (4-Methylphenyl)[4-(2-methylpropyl) phenyliodonium] hexafluorophosphate [344562-80-7] BASF SE, Ludwigshafen, Germany K-401 Diphenyliodonium chloride [1483-72-3] AB109613, abcr GmbH K-402 Bis(4-methylphenyl)iodonium hexafluorophosphate [60565-88-0] AB336755, abcr GmbH K-403 Diphenyleneiodonium chloride [4673-26-1] AB348986, abcr GmbH
Preparation of Commercially Unavailable Cations 1/n K.sup.n+

N-(2-((2-Ethylhexanoyl)oxy)ethyl)-N,N-dimethylhexadecane-1-aminium bromide (K-20)

(16) 5.00 g of N,N-dimethylethanolamine were initially charged in dry chloroform cooled with an ice bath, and 9.12 g of 2-ethylhexanoyl chloride were cautiously added dropwise and the mixture was stirred at room temperature for 30 min. 30 ml of saturated sodium hydrogencarbonate solution were added and the organic solution was extracted with saturated sodium hydrogencarbonate solution until it was chloride-free. Subsequently, the organic phase was washed with 30 ml of water, the solution was dried and the solvent was distilled off under reduced pressure. 10.99 g of amino ester were obtained.

(17) To a solution of 10.99 g of amino ester in 30 ml of acetonitrile were added 15.58 g of 1-bromohexadecane, and the mixture was heated at reflux for 6 h. The solvent was almost completely distilled off under reduced pressure, the precipitated solids were isolated, and 19.33 g of a colourless tacky resin were obtained.

N-Benzyl-N,N-dimethyl-2-(2-(palmitoyloxy)ethoxy)ethane-1-aminium bromide (K-21)

(18) 6.00 g of N,N-2-[2-(dimethylamino)ethoxy]ethanol were initially charged in dry chloroform cooled with an ice bath, and 12.38 g of hexadecanoyl chloride were cautiously added dropwise and the mixture was stirred at room temperature for 30 min. 30 ml of saturated sodium hydrogencarbonate solution were added and the organic solution was extracted with saturated sodium hydrogencarbonate solution until it was chloride-free. Subsequently, the organic phase was washed with 30 ml of water, the solution was dried and the solvent was distilled off under reduced pressure. 14.68 g of amino ester were obtained.

(19) To a solution of 14.68 g of amino ester in 30 ml of acetonitrile were added 6.77 g of benzyl bromide, and the mixture was heated at reflux for 6 h. The solvent was almost completely distilled off under reduced pressure, the precipitated solids were isolated, and 8.23 g of a colourless tacky resin were obtained.

2-(Benzyloxy)-N,N-dimethyl-N-(2-(palmitoyloxy)ethyl)ethane-1-aminium bromide (K-22)

(20) 6.00 g of N,N-2-[2-(dimethylamino)ethoxy]ethanol were initially charged in dry chloroform cooled with an ice bath, and 12.38 g of hexadecanoyl chloride were cautiously added dropwise and the mixture was stirred at room temperature for 30 min. 30 ml of saturated sodium hydrogencarbonate solution were added and the organic solution was extracted with saturated sodium hydrogencarbonate solution until it was chloride-free. Subsequently, the organic phase was washed with 30 ml of water, the solution was dried and the solvent was distilled off under reduced pressure. 14.68 g of amino ester were obtained.

(21) To a solution of 14.68 g of amino ester in 30 ml of acetonitrile were added 6.77 g of benzyl bromide, and the mixture was heated at reflux for 6 h. The solvent was almost completely distilled off under reduced pressure, the precipitated solids were isolated, and 8.23 g of a colourless tacky resin were obtained.

N-(3-((2-Ethylhexyl)oxy)-3-oxopropyl)-N,N-dimethyloctadecane-1-aminium bromide (K-23)

(22) To a solution of 10.0 g of N,N-dimethyl-β-alanine 2-ethylhexyl ester ([184244-48-2], prepared as described in U.S. Pat. No. 5,565,290 A) in 30 ml of acetonitrile were added 15.0 g of octadecyl bromide and the mixture was heated at reflux for 6 h. The solvent was almost completely distilled off under reduced pressure, and 24.50 g of a colourless oil were obtained.

N-(2-((Hexylcarbamoyl)oxy)ethyl)-N,N-dimethylhexadecane-1-aminium bromide (K-24)

(23) To a mixture of 29.4 g of hexyl isocyanate and 0.05 g of Desmorapid Z were added dropwise, at 60° C., 20.6 g of N,N-dimethylethanol, and the mixture was kept at this temperature for 8 h. After cooling to room temperature, 50.0 g of aminourethane were obtained.

(24) 50.0 g of aminourethane were dissolved in 120 ml of acetonitrile, 70.6 g of 1-bromohexadecane were added dropwise and the mixture was heated at reflux for 12 h. The precipitated solids were isolated, washed with cold ether and dried, and 115.0 g of a colourless tacky resin were obtained.

N.SUP.1.,N.SUP.16.-Dihexadecyl-N.SUP.1.,N.SUP.1.,N.SUP.16.,N.SUP.16.,7,7,10-heptamethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diaminium dibromide (K-25)

(25) To a mixture of 27.0 g of Vestanat TMDI (product from EVONIK Deutschland) and 0.05 g of Desmorapid Z were added dropwise, at 60° C., 22.9 g of N,N-dimethylethanol, and the mixture was kept at this temperature for 8 h. After cooling to room temperature, 50.0 g of aminourethane were obtained.

(26) 11.7 g of aminourethane were dissolved in 50 ml of acetonitrile, 18.3 g of 1-bromohexadecane were added dropwise and the mixture was heated at reflux for 12 h. The precipitated solids were isolated, washed with cold ether and dried, and 28.0 g of a colourless tacky resin were obtained.

N-(2-(((5-(((2-(Hexadecyldimethylammonio)ethoxy)carbonyl)amino)-1,3,3-trimethylcyclohexyl)methyl)carbamoyl)oxy)ethyl)-N,N-dimethylhexadecane-1-aminium dibromide (K-26)

(27) To a mixture of 27.7 g of Desmodur I (product from COVESTRO Deutschland) and 0.05 g of Desmorapid Z were added dropwise, at 60° C., 22.2 g of N,N-dimethylethanol, and the mixture was kept at this temperature for 8 h. After cooling to room temperature, 50.0 g of aminourethane were obtained.

(28) 11.9 g of aminourethane were dissolved in 50 ml of acetonitrile, 18.1 g of 1-bromohexadecane were added dropwise and the mixture was heated at reflux for 12 h. The precipitated solids were isolated, washed with cold ether and dried, and 29.3 g of a colourless tacky resin were obtained.

N,N′-(((((Methylenebis(cyclohexane-4,1-diyl))bis(azanediyl))bis(carbonyl))bis(oxy))bis(ethane-2,1-diyl))bis(N,N-dimethylhexadecane-1-aminium) dibromide (K-27)

(29) To a mixture of 29.7 g of Desmodur W (product from COVESTRO Deutschland) and 0.05 g of Desmorapid Z were added dropwise, at 60° C., 20.2 g of N,N-dimethylethanol, and the mixture was kept at this temperature for 8 h. After cooling to room temperature, 50.0 g of aminourethane were obtained.

(30) 12.6 g of aminourethane were dissolved in 50 ml of acetonitrile, 17.4 g of 1-bromohexadecane were added dropwise and the mixture was heated at reflux for 12 h. The precipitated solids were isolated, washed with cold ether and dried, and 28.9 g of a colourless tacky resin were obtained.

N,N′-(((((4-Methyl-1,3-phenylene)bis(azanediyl))bis(carbonyl))bis(oxy))bis(ethane-2,1-diyl))bis(N,N-dimethylhexadecane-1-aminium) dibromide (K-28)

(31) To a mixture of 24.7 g of Desmodur T80 (product from COVESTRO Deutschland) and 0.05 g of Desmorapid Z were added dropwise, at 10° C., 25.3 g of N,N-dimethylethanol, and, on completion of addition, the mixture was kept at 60° C. for 8 h. After cooling to room temperature, 50.0 g of aminourethane were obtained.

(32) 11.0 g of aminourethane were dissolved in 50 ml of acetonitrile, 19.0 g of 1-bromohexadecane were added dropwise and the mixture was heated at reflux for 12 h. The precipitated solids were isolated, washed with cold ether and dried, and 27.2 g of a colourless tacky resin were obtained.

(33) N,N′-(((((Methylenebis(4,1-phenylene))bis(azanediyl))bis(carbonyl))bis(oxy))bis(ethane-2,1-diyl))bis(N,N-dimethylhexadecane-1-aminium) dibromide (K-29)

(34) To a mixture of 29.2 g of Desmodur MDI (product from COVESTRO Deutschland) and 0.05 g of Desmorapid Z were added dropwise, at 10° C., 20.8 g of N,N-dimethylethanol, and, on completion of addition, the mixture was kept at 60° C. for 8 h. After cooling to room temperature, 50.0 g of aminourethane were obtained.

(35) 12.4 g of aminourethane were dissolved in 50 ml of acetonitrile, 17.6 g of 1-bromohexadecane were added dropwise and the mixture was heated at reflux for 12 h. The precipitated solids were isolated, washed with cold ether and dried, and 29.2 g of a colourless tacky resin were obtained.

N-(2-(2-((Hexylcarbamoyl)oxy)ethoxy)ethyl)-N,N-dimethylhexadecane-1-aminium bromide (K-30)

(36) To a mixture of 29.4 g of hexyl isocyanate and 0.05 g of Desmorapid Z were added dropwise, at 60° C., 25.6 g of 2-(2-dimethylaminoethoxy)ethanol, and the mixture was kept at this temperature for 8 h. After cooling to room temperature, 50.0 g of aminourethane were obtained.

(37) 13.8 g of aminourethane were dissolved in 50 ml of acetonitrile, 162 g of 1-bromohexadecane were added dropwise and the mixture was heated at reflux for 12 h. The precipitated solids were isolated, washed with cold ether and dried, and 25.0 g of colourless solid, m.p. 220-225° C., were obtained.

N.SUP.1.,N.SUP.22.-Dihexadecyl-N.SUP.1.,N.SUP.1.,N.SUP.22.,N.SUP.22.,10,10,13-heptamethyl-7,16-dioxo-3,6,17,20-tetraoxa-8,15-diazadocosane-1,22-diaminiuum dibromide (K-31)

(38) To a mixture of 23.0 g of Vestanat TMDI (product from EVONIK Deutschland) and 0.05 g of Desmorapid Z were added dropwise, at 60° C., 27.9 g of 2-(2-dimethylaminoethoxy)ethanol, and the mixture was kept at this temperature for 8 h. After cooling to room temperature, 50.0 g of aminourethane were obtained.

(39) 13.1 g of aminourethane were dissolved in 50 ml of acetonitrile, 16.9 g of 1-bromohexadecane were added dropwise and the mixture was heated at reflux for 12 h. The precipitated solids were isolated, washed with cold ether and dried, and 27.5 g of a colourless tacky resin were obtained.

N-(2-(2-(((3-(10,10-Dimethyl-3-oxo-4,7-dioxa-2,10-diazahexacosan-10-ium-1-yl)-3,5,5-trimethylcyclohexyl)carbamoyl)oxy)ethoxy)ethyl)-N,N-dimethylhexadecan-1-aminium dibromide (K-32)

(40) To a mixture of 22.7 g of Desmodur I (product from COVESTRO Deutschland) and 0.05 g of Desmorapid Z were added dropwise, at 60° C., 27.2 g of 2-(2-dimethylaminoethoxy)ethanol, and the mixture was kept at this temperature for 8 h. After cooling to room temperature, 50.0 g of aminourethane were obtained.

(41) 13.3 g of aminourethane were dissolved in 50 ml of acetonitrile, 16.7 g of 1-bromohexadecane were added dropwise and the mixture was heated at reflux for 12 h. The precipitated solids were isolated, washed with cold ether and dried, and 29.3 g of a colourless tacky resin were obtained.

N,N′-(((((((Methylenebis(cyclohexane-4,1-diyl))bis(azanediyl))bis(carbonyl))bis(oxy))bis(ethane-2,1-diyl))bis(oxy))bis(ethan-2,1-diyl))bis(N,N-dimethylhexadecane-1-aminium) dibromide (K-33)

(42) To a mixture of 24.8 g of Desmodur W (product from COVESTRO Deutschland) and 0.05 g of Desmorapid Z were added dropwise, at 60° C., 25.2 g of 2-(2-dimethylaminoethoxy)ethanol, and the mixture was kept at this temperature for 8 h. After cooling to room temperature, 50.0 g of aminourethane were obtained.

(43) 13.9 g of aminourethane were dissolved in 50 ml of acetonitrile, 16.1 g of 1-bromohexadecane were added dropwise and the mixture was heated at reflux for 12 h. The precipitated solids were isolated, washed with cold ether and dried, and 25.9 g of a colourless tacky resin were obtained.

N,N′-(((((((4-Methyl-1,3-phenylene)bis(azanediyl))bis-(carbonyl))bis(oxy))bis(ethane-2,1-diyl))bis(oxy))bis(ethane-2,1-diyl))bis(N,N-dimethylhexadecane-1-aminium) dibromide (K-34)

(44) To a mixture of 9.90 g of Desmodur T80 (product from COVESTRO Deutschland) and 0.05 g of Desmorapid Z were added dropwise, at 10° C., 15.1 g of 2-(2-dimethylaminoethoxy)ethanol, and, on completion of addition, the mixture was kept at 60° C. for 8 h. After cooling to room temperature, 25.0 g of aminourethane were obtained.

(45) 12.6 g of aminourethane were dissolved in 50 ml of acetonitrile, 17.4 g of 1-bromohexadecane were added dropwise and the mixture was heated at reflux for 12 h. The precipitated solids were isolated, washed with cold ether and dried, and 23.1 g of a colourless tacky resin were obtained.

N,N′-(((((((Methylenebis(4,1-phenylene))bis(azanediyl))bis(carbonyl))bis(oxy))bis(ethane-2,1-diyl))bis(oxy))bis(ethane-2,1-diyl))bis(N,N-dimethylhexadecane-1-aminium) dibromide (K-35)

(46) To a mixture of 12.1 g of Desmodur MDI (product from COVESTRO Deutschland) and 0.05 g of Desmorapid Z were added dropwise, at 10° C., 12.9 g of 2-(2-dimethylaminoethoxy)ethanol, and, on completion of addition, the mixture was kept at 60° C. for 8 h. After cooling to room temperature, 25.0 g of aminourethane were obtained.

(47) 13.8 g of aminourethane were dissolved in 50 ml of acetonitrile, 16.2 g of 1-bromohexadecane were added dropwise and the mixture was heated at reflux for 12 h. The precipitated solids were isolated, washed with cold ether and dried, and 29.4 g of a colourless tacky resin were obtained.

EXAMPLES

(48) Unless noted otherwise, all percentage FIGURES are based on percent by weight.

(49) Preparation Method a1) for Triaryl Organoborates with Cations of Valency n=1

(50) 10.0 mmol of the specified boronic ester (I; R.sup.1), 30.0 mmol of magnesium turnings and 10.0 mmol of the salt (II) were suspended in a mixture of 3.40 g of anhydrous toluene and 0.73 g of anhydrous tetrahydrofuran in a dry four-neck flask with a mechanical stirrer, thermometer, metal condenser and pressure-equalized dropping funnel under a nitrogen atmosphere, and stirred vigorously for 30 min. The appropriate haloaromatic (III, R.sup.4) was added to this solution, at first in undiluted form, until the onset of exothermicity signals the start of the reaction. The remaining total amount of 30.6 mmol of haloaromatic was diluted with 10.0 g of anhydrous toluene and 10.0 g of anhydrous tetrahydrofuran and added dropwise at such a rate that the internal temperature does not exceed 45° C. On completion of addition, the reaction mixture was heated at reflux for 1 h or until the dissolution of the magnesium was complete. The reaction mixture was cooled to room temperature and 100 g of 1,4-dioxane were added dropwise. After standing overnight, the voluminous crystals that had precipitated out were filtered off, the organic phase was concentrated to dryness and the residue was recrystallized from 100 ml of i-propanol. Examples 15, 18, 20 and 27 and 46-52 were isolated without recrystallization as oils with a purity of >90%. The isolated yield for Example 1 that was prepared by this method was 2.87 g (72% of theory), whereas Example 1 prepared according to DE 198 50 139 A1 was obtained in a yield of 47% of theory.

(51) Preparation Method a2) for Triaryl Organoborates with Cations of Valency n=1

(52) 10.0 mmol of the specified boronic ester (I; R.sup.1), 30.0 mmol of magnesium turnings and 10.0 mmol of the salt (II) were suspended in a mixture of 3.40 g of anhydrous toluene and 0.73 g of anhydrous tetrahydrofuran in a dry four-neck flask with a mechanical stirrer, thermometer, metal condenser and pressure-equalized dropping funnel under a nitrogen atmosphere, and stirred vigorously for 30 min. The appropriate haloaromatic (III, R.sup.4) was added to this solution, at first in undiluted form, until the onset of exothermicity signals the start of the reaction. The remaining total amount of 30.6 mmol of haloaromatic was diluted with 10.0 g of anhydrous toluene and 10.0 g of anhydrous tetrahydrofuran and added dropwise at such a rate that the internal temperature does not exceed 45° C. On completion of addition, the reaction mixture was heated at reflux for 1 h or until the dissolution of the magnesium was complete. The reaction mixture was cooled to room temperature and 100 g of Lewatit® MDS TP 208 were added. After 1 h, the resin was filtered off, the organic phase was concentrated to dryness and the residue was recrystallized from 100 ml of i-propanol. Examples 15, 18, 20 and 27 and 46-52 were isolated without recrystallization as oils with a purity of >90%. The isolated yield for Example 1 that was prepared by this method was 2.87 g (72% of theory), whereas Example 1 prepared according to DE 198 50 139 A1 was obtained in a yield of 47% of theory.

(53) The composition of Examples 1-92 and selected physical properties are summarized in Table 2.

(54) TABLE-US-00003 TABLE 2 Overview of the compounds of the formula (IV) with n = 1 Feedstocks according to preparation method a) Substituents of formula (IV) K.sup.+ and characterization Boronic ester Haloaromatic Salt .sup.11B M.p. Example (I) (III) (II) R.sup.1 R.sup.4 [δ/ppm] [° C.]  1 ethylboronic acid pinacol ester 1-bromo-4- fluorobenzene K-1  ethyl 00 −10.2 101-105  2 ethylboronic acid pinacol ester 1-bromo-4- fluorobenzene K-2  ethyl 01 −10.3 144-149  3 ethylboronic acid pinacol ester 1-bromo-3- chloro-4- methylbenzene K-1  ethyl 02 −10.3 88-91  4 ethylboronic acid pinacol ester 1-bromo-3- chloro-4- methylbenzene K-2  ethyl 03 −10.2 120-122  5 isopropylboronic acid pinacol ester 1-bromo-4- fluorobenzene K-2  i-propyl 04 −10.3 134-138  6 isopropylboronic acid pinacol ester 1-bromo-3- chloro-4- methylbenzene K-2  i-propyl 05  −8.3 115-118  7 2- isopropenyl- boronic acid pinacol ester 1-bromo-3- chloro-4- methylbenzene K-2  2- propenyl 06  −8.3 amorphous  8 diisopropyl allyl boronate 1-bromo-3- chloro-4- methylbenzene K-1  allyl 07 −10.6 amorphous  9 diisopropyl allyl boronate 1-bromo-3- chloro-4- methylbenzene K-2  allyl 08 −10.6 84-88 10 (1,3,2- dioxaborinan- 2- yl)cyclohexane 1-bromo-4- fluorobenzene K-1  cyclohexyl 09 −10.4 59-60 11 (1,3,2- dioxaborinan- 2- yl)cyclohexane 1-bromo-4- fluorobenzene K-2  cyclohexyl 0 −10.3 166-168 12 (1,3,2- dioxaborinan- 2- yl)cyclohexane 1-bromo-3- chloro-4- methylbenzene K-2  cyclohexyl  −8.7 175-177 13 2-hexyl- 1,3,2- dioxaborinane 1-bromo-4- fluorobenzene K-2  n-hexyl −10.3 59-60 14 1- dodecyl- boronic acid pinacol ester 1-bromo-4- fluorobenzene K-2  n-dodecyl −10.4 amorphous 15 2-octadecyl- 4,4,5,5- tetramethyl- 1,3,2- dioxaborolane 1-bromo-4- fluorobenzene K-2  n-octadecyl −10.2 oil 16 2-hexyl- 1,3,2-dioxaborinane 1-bromo-4- chlorobenzene K-2  n-hexyl −10.4 80-81 17 1- dodecyl- boronic acid pinacol ester 1-bromo-4- chlorobenzene K-2  n-dodecyl −10.3 amorphous 18 2-octadecyl- 4,4,5,5- tetramethyl- 1,3,2- dioxaborolane 1-bromo-4- chlorobenzene K-2  n- octadecyl −10.4 oil 19 2-hexyl- 1,3,2- dioxaborinane 1-bromo-4- trifluoromethyl- benzene K-2  n-hexyl  −9.8 80-82 20 2-octadecyl- 4,4,5,5- tetramethyl- 1,3,2- dioxaborolane 1-bromo-3- chloro-4- methylbenzene K-2  n-octadecyl −10.2 oil 21 3-phenyl-1- propyl- boronic acid pinacol ester 1-bromo-4- chlorobenzene K-2  3- phenyl propyl 0 −10.3 101-105 22 3-phenyl-1- propylboronic acid pinacol ester 1-bromo-4- methoxybenzene K-2  3- phenyl propyl −10.3 116-118 23 3-phenyl-1- propylboronic acid pinacol ester 1-bromo-3,4,5- trifluorobenzene K-2  3- phenyl propyl −10.1 78-86 24 3-phenyl-1- propylboronic acid pinacol ester 1-bromo-3- methyl-4- fluorobenzene K-2  3-phenyl propyl −13.6 85-87 25 3-phenyl-1- propylboronic acid pinacol ester 1-bromo-4- trifluoromethoxy- benzene K-2  3-phenyl propyl −10.2 101-108 26 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-3  n-hexyl −10.6 amorphous 27 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-4  n-hexyl −10.6 oil 28 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-5  n-hexyl −10.6 amorphous 29 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-6  n-hexyl −10.6 amorphous 30 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-7  n-hexyl −10.6 amorphous 31 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-8  n-hexyl 0 −10.6 amorphous 32 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-9  n-hexyl −10.6 amorphous 33 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-10  n-hexyl −10.6 amorphous 34 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-11  n-hexyl −10.6 amorphous 35 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-12  n-hexyl −10.6 amorphous 36 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-13  n-hexyl −10.6 amorphous 37 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-16  n-hexyl −10.6 amorphous 38 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-17  n-hexyl −10.6 amorphous 39 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-19  n-hexyl −10.6 amorphous 40 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-20  n-hexyl −10.6 amorphous 41 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-21  n-hexyl 0 −10.6 amorphous 42 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-22  n-hexyl −10.6 amorphous 43 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-23  n-hexyl −10.6 amorphous 44 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-24  n-hexyl −10.6 amorphous 45 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-30  n-hexyl −10.6 amorphous 46 1- dodecyl- boronic acid pinacol ester 1-bromo-4- chlorobenzene K-2  n- dodecyl −10.3 oil 47 1- dodecyl- boronic acid pinacol ester 1-bromo-4- methoxybenzene K-2  n- dodecyl −10.4 oil 48 1- dodecyl- boronic acid pinacol ester 1-bromo- 3,4,5- trifluorobenzene K-2  n- dodecyl −10.1 oil 49 1- dodecyl- boronic acid pinacol ester 1-bromo-3- methyl-4- fluorobenzene K-2  n- dodecyl −10.6 oil 50 1- dodecyl- boronic acid pinacol ester 1-bromo-4- trifluoromethoxy- benzene K-2  n- dodecyl −10.8 oil 51 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-100 n-hexyl 0 −10.6 oil 52 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-101 n-hexyl −10.6 oil 53 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-102 n-hexyl −10.6 decomp. 54 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-103 n-hexyl −10.6 102-105 55 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-104 n-hexyl −10.6 134-138 56 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-105 n-hexyl −10.6 145-146 57 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-106 n-hexyl −10.6 155-159 58 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-200 n-hexyl −10.4 amorphous 59 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-201 n-hexyl −10.4 amorphous 60 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-202 n-hexyl −10.4 amorphous 61 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-300 n-hexyl 0 −10.6 amorphous 62 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-303 n-hexyl −10.6 amorphous 63 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-303 n-hexyl −10.6 amorphous 64 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-304 n-hexyl −10.6 amorphous 65 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-305 n-hexyl −10.6 amorphous 66 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-400 n-hexyl −10.5 amorphous 67 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-401 n-hexyl −10.5 amorphous 68 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-402 n-hexyl −10.5 amorphous 69 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-403 n-hexyl −10.5 amorphous 86 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-37  n-hexyl −10.5 amorphous 87 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-38  n-hexyl 0 −10.5 amorphous 88 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-39  n-hexyl −10.5 amorphous 89 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-40  n-hexyl −10.5 amorphous 90 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-41  n-hexyl −10.5 amorphous 91 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-42  n-hexyl −10.5 amorphous 92 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-43  n-hexyl −10.5 amorphous
Preparation Method b1) for Triaryl Organoborates with Cations of Valency n=2

(55) 10.0 mmol of the specified boronic ester (I; R.sup.1), 30.0 mmol of magnesium turnings and 5.0 mmol of the salt (II) were suspended in a mixture of 3.40 g of anhydrous toluene and 0.73 g of anhydrous tetrahydrofuran in a dry four-neck flask with a mechanical stirrer, thermometer, metal condenser and pressure-equalized dropping funnel under a nitrogen atmosphere, and stirred vigorously for 30 min. The appropriate haloaromatic (III, R.sup.4) was added to this solution, at first in undiluted form, until the onset of exothermicity signals the start of the reaction. The remaining total amount of 30.6 mmol of haloaromatic was diluted with 10.0 g of anhydrous toluene and 10.0 g of anhydrous tetrahydrofuran and added dropwise at such a rate that the internal temperature does not exceed 45° C. On completion of addition, the reaction mixture was heated at reflux for 1 h or until the dissolution of the magnesium was complete. The reaction mixture was cooled to room temperature and 100 g of 1,4-dioxane were added dropwise. After standing overnight, the voluminous crystals that had precipitated out were filtered off, the organic phase was concentrated to dryness and the residue was recrystallized from 100 ml of i-propanol.

(56) Preparation Method b2) for Triaryl Organoborates with Cations of Valency n=2

(57) 10.0 mmol of the specified boronic ester (I; R.sup.1), 30.0 mmol of magnesium turnings and 5.0 mmol of the salt (II) were suspended in a mixture of 3.40 g of anhydrous toluene and 0.73 g of anhydrous tetrahydrofuran in a dry four-neck flask with a mechanical stirrer, thermometer, metal condenser and pressure-equalized dropping funnel under a nitrogen atmosphere, and stirred vigorously for 30 min. The appropriate haloaromatic (III, R.sup.4) was added to this solution, at first in undiluted form, until the onset of exothermicity signals the start of the reaction. The remaining total amount of 30.6 mmol of haloaromatic was diluted with 10.0 g of anhydrous toluene and 10.0 g of anhydrous tetrahydrofuran and added dropwise at such a rate that the internal temperature does not exceed 45° C. On completion of addition, the reaction mixture was heated at reflux for 1 h or until the dissolution of the magnesium was complete. The reaction mixture was cooled to room temperature and 100 g of Lewatit® MDS TP 208 were added. After 1 h, the resin was filtered off, the organic phase was concentrated to dryness and the residue was recrystallized from 100 ml of i-propanol.

(58) The composition of Examples 93-107 and selected physical properties are summarized in Table 3.

(59) TABLE-US-00004 TABLE 3 Overview of the compounds of the formula (IV) with n = 2 Feedstocks according to Substituents of formula (IV) K.sup.+ preparation method b1) & b2) and characterization Boronic ester Haloaromatic Salt .sup.11B M.p. Example (I) (III) (II) R.sup.1 R.sup.4 [δ/ppm] [° C.]  93 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-14  n-hexyl −10.6 amorphous  94 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-15  n-hexyl −10.6 amorphous  95 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-18  n-hexyl −10.6 amorphous  96 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-25  n-hexyl −10.6 amorphous  97 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-26  n-hexyl 0 −10.6 amorphous  98 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-27  n-hexyl −10.6 amorphous  99 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-28  n-hexyl −10.6 amorphous 100 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-29  n-hexyl −10.6 amorphous 101 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-31  n-hexyl −10.6 amorphous 102 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-32  n-hexyl −10.6 amorphous 103 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-33  n-hexyl −10.6 amorphous 104 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-34  n-hexyl −10.6 amorphous 105 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-35  n-hexyl −10.6 amorphous 106 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-203 n-hexyl −10.5 amorphous 107 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-301 n-hexyl 0 −10.6 amorphous

Example 108 (Cation of Valency n=3), Method c1

(60) 1.70 g of 2-hexyl-1,3,2-dioxaborinane (10.0 mmol; I; R.sup.1=n-hexyl), 0.73 g (30.0 mmol) of magnesium turnings and 2.25 g of N.sup.1,N.sup.1,N.sup.1,N.sup.3,N.sup.3,N.sup.3,N.sup.5,N.sup.5,N.sup.5-nonamethyl-1,3,5-benzentrimethanaminium triiodide (3.33 mmol; K-36; II) are suspended in a mixture of 3.40 g of anhydrous toluene and 0.73 g of anhydrous tetrahydrofuran in a dry four-neck flask having a mechanical stirrer, thermometer, metal condenser and pressure-equalized dropping funnel under a nitrogen atmosphere, and stirred vigorously for 30 min. 1-Bromo-3-chloro-4-methylbenzene (III, R.sup.4) is added to this solution, at first in undiluted form, until the onset of exothermicity signals the start of the reaction. The remaining total amount of 6.29 g (30.6 mmol) of 1-bromo-3-chloro-4-methylbenzene is diluted with 10.0 g of anhydrous toluene and 10.0 g of anhydrous tetrahydrofuran and added dropwise at such a rate that the internal temperature does not exceed 45° C. On completion of addition, the reaction mixture is heated at reflux for 1 h or until the dissolution of the magnesium was complete. The reaction mixture was cooled to room temperature and 100 g of 1,4-dioxane were added dropwise. After standing overnight, the voluminous crystals that had precipitated out were filtered off, the organic phase was concentrated to dryness and the residue was recrystallized from 100 ml of i-propanol.

(61) .sup.11B NMR [δ/ppm]−10.6.

Example 108 (Cation of Valency n=3), Method c2

(62) 1.70 g of 2-hexyl-1,3,2-dioxaborinane (10.0 mmol; I; R.sup.1=n-hexyl), 0.73 g (30.0 mmol) of magnesium turnings and 2.25 g of N.sup.1,N.sup.1,N.sup.1,N.sup.3,N.sup.3,N.sup.3,N.sup.5,N.sup.5,N.sup.5-nonamethyl-1,3,5-benzentrimethanaminium triiodide (3.33 mmol; K-36; II) are suspended in a mixture of 3.40 g of anhydrous toluene and 0.73 g of anhydrous tetrahydrofuran in a dry four-neck flask having a mechanical stirrer, thermometer, metal condenser and pressure-equalized dropping funnel under a nitrogen atmosphere, and stirred vigorously for 30 min. 1-Bromo-3-chloro-4-methylbenzene (III, R.sup.4) is added to this solution, at first in undiluted form, until the onset of exothermicity signals the start of the reaction. The remaining total amount of 6.29 g (30.6 mmol) of 1-bromo-3-chloro-4-methylbenzene is diluted with 10.0 g of anhydrous toluene and 10.0 g of anhydrous tetrahydrofuran and added dropwise at such a rate that the internal temperature does not exceed 45° C. On completion of addition, the reaction mixture is heated at reflux for 1 h or until the dissolution of the magnesium was complete. The reaction mixture was cooled to room temperature and 100 g of Lewatit® MDS TP 208 were added. After 1 h, the resin was filtered off, the organic phase was concentrated to dryness and the residue was recrystallized from 100 ml of i-propanol.

(63) .sup.11B NMR [δ/ppm]−10.6.

(64) Production of Media to Determine the Holographic Properties

Example Medium I

(65) 3.38 g of the polyol component 1 were mixed with 0.010 g of Example 1, 2.00 g of urethane acrylate 1, 2.00 g of urethane acrylate 2, 1.50 g of additive 1, 0.10 g of triaryl alkyl borate 1 of formula (IV), 0.010 g of dye 1 and 0.35 g of N-ethylpyrrolidone at 60° C., so as to obtain a clear solution. Subsequently, the mixture was cooled down to 30° C., 0.65 g of Desmodur® N3900 was added and the mixture was mixed again. Finally, 0.01 g of Fomrez UL 28 was added and the mixture was mixed briefly again. The fluid mass obtained was then applied to a glass plate and covered thereon with a second glass plate. This specimen was left to stand at room temperature for 12 hours and hardened.

Example Medium II-XX

(66) The procedure was as in Example medium I, except using 0.10 g of the specified triaryl organoborate of formula (IV) rather than 0.10 g of triaryl organoborate 1.

(67) The properties of Example media I-XX are summarized in Table 4.

(68) TABLE-US-00005 TABLE 4 Overview of the holographic properties of Example media I-XX Example medium Example of formula (IV) Δn I 1 0.033 II 13 0.029 III 16 0.029 IV 17 0.034 V 18 0.033 VI 19 0.032 VII 20 0.037 VIII 24 0.033 IX 29 0.034 X 45 0.039 XI 51 0.035 XII 52 0.034 χIII 57 0.037 XIV 66 0.038 XV 93 0.037 XVI 95 0.040 XVII 97 0.040 XVIII 101 0.037 XIX 102 0.035 XX 104 0.037

(69) The values found for Example media I to XX show that the compounds of the formula (IV) used in the photopolymer formulations are of very good suitability for use in holographic media.