Method for producing triarylorganoborates

Abstract

The invention relates to a process for preparing triaryl organoborates proceeding from organoboronic esters in the presence of an n-valent cation 1/n K.sup.n+, comprising the anhydrous workup of the reaction mixture and the use of the triaryl organoborates obtained as co-initiator in photopolymer formulations, holographic media and holograms.

Claims

1. Compounds of the formula (CC) ##STR00191## in which R.sup.301 and R.sup.301′ are each independently an optionally branched C.sub.14- to C.sub.22-alkyl radical or are additionally defined as R.sup.302, with the proviso that T.sup.301 and R.sup.331 together and T.sup.302 and R.sup.332 together each contain at least 12 carbon atoms, R.sup.302 is a radical of the formulae ##STR00192## T.sup.301 is a bridge having 2 to 16 carbon atoms, of which not more than one third may be replaced by O and/or NR.sup.400, where there must be at least 2 carbon atoms between O or NR.sup.200, and which may be arranged in the form of an optionally branched chain and/or a five- or six-membered ring, R.sup.331 is an optionally branched and/or optionally substituted C.sub.4- to C.sub.22-alkylene radical, a cyclopentylene, cyclohexylene or cycloheptylene radical, a C.sub.8- to C.sub.12-aryldialkylene radical, an arylene radical or heteroarylene radical optionally substituted by nonionic radicals, an optionally branched and/or optionally substituted C.sub.4- to C.sub.22-alkanedioxy radical, a cyclopentanedioxy, cyclohexanedioxy or cycloheptanedioxy radical, a C.sub.7- to C.sub.12-oxyarylalkoxy radical, C.sub.8- to C.sub.12-aryldi(alkyloxy) radical, a benzenedioxy radical or heteroaryldioxy radical optionally substituted by nonionic radicals, an optionally branched and/or optionally substituted C.sub.4- to C.sub.22-alkanediamino radical, a cyclopentanediamino, cyclohexanediamino or cycloheptanediamino radical, a C.sub.8- to C.sub.12-aminoarylalkylamino radical, a benzenediamino radical or heteroarylenediamino radical optionally substituted by nonionic radicals, an alkylene-cycloalkylene radical, alkanedicycloalkylene radical or alkanediarylene radical, T.sup.302 is a bridge having 1 to 16 carbon atoms which may be arranged in the form of an optionally branched chain and/or a five- or six-membered ring, R.sup.332 is an optionally branched and/or optionally substituted C.sub.1- to C.sub.22-alkylene radical, a cyclopentylene, cyclohexylene or cycloheptylene radical, a C.sub.8- to C.sub.12-aralkylene radical, an arylene or heteroarylene radical optionally substituted by nonionic radicals, A is NR.sup.401 or oxygen, R.sup.400 and R.sup.401 are independently hydrogen or C.sub.1- to C.sub.4-alkyl, R.sup.303, R.sup.304, R.sup.303′ and R.sup.304′ are independently an optionally branched and/or optionally substituted C.sub.1- to C.sub.5-alkyl radical, or R.sup.302 is a radical of the formulae ##STR00193## T.sup.301, R.sup.331, T.sup.302, R.sup.332, R.sup.400, R.sup.401 and A have the definition given above, with the proviso that T.sup.301 and R.sup.331 together and T.sup.302 and R.sup.332 together each contain at least 12 carbon atoms, R.sup.301, R.sup.303 and R.sup.304 together with the N.sup.+ atom form an imidazole or pyridine ring substituted at least by one radical selected from C.sub.1- to C.sub.8-alkyl, C.sub.1- to C.sub.8-alkoxy, C.sub.5- to C.sub.7-cycloalkyl, benzyl or phenyl, and/or R.sup.301′, R.sup.303′ and R.sup.304′ together with the N.sup.+ atom form an imidazole or pyridine ring substituted at least by one radical selected from C.sub.1- to C.sub.8-alkyl, C.sub.1- to C.sub.8-alkoxy, C.sub.5- to C.sub.7-cycloalkyl, benzyl or phenyl, or R.sup.301 and R.sup.301′ are each independently an optionally branched C.sub.14- to C.sub.22-alkyl radical or are additionally defined as R.sup.302, with the proviso that T.sup.301 and R.sup.331 together and T.sup.302 and R.sup.332 together each contain at least 12 carbon atoms, R.sup.302 is a radical of the formulae ##STR00194## and T.sup.301, R.sup.331, T.sup.302, R.sup.332, R.sup.400, R.sup.401 and A have the definition given above, R.sup.303 and R.sup.304 together form a —(CH.sub.2).sub.4—, —(CH.sub.2).sub.5— or —(CH.sub.2).sub.2—O—(CH.sub.2).sub.2— bridge, and/or R.sup.303′ and R.sup.304′ together form a —(CH.sub.2).sub.4—, —(CH.sub.2).sub.5— or —(CH.sub.2).sub.2—O—(CH.sub.2).sub.2— bridge, 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 and 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.

2. The compounds of claim 1, wherein R.sup.301 and R.sup.301′ are each independently an optionally branched C.sub.14- to C.sub.22-alkyl radical or are additionally defined as R.sup.302, with the proviso that T.sup.301 and R.sup.331 together and T.sup.302 and R.sup.332 together each contain at least 12 carbon atoms, R.sup.302 is a radical of the formulae ##STR00195## T.sup.301 is a bridge having 2 to 9 carbon atoms, of which not more than one third may be replaced by O and/or NR.sup.400, where there must be at least 2 carbon atoms between two O or NR.sup.400, and which may be arranged in the form of an optionally branched chain and/or a five-or six-membered ring, R.sup.331 is an optionally branched and/or optionally substituted C.sub.4- to C.sub.16-alkylene radical, a cyclopentylene or cyclohexylene radical, a xylylene, benzenediethylene or benzenedipropylene radical, an arylene radical or heteroarylene radical optionally substituted by nonionic radicals, an optionally branched and/or optionally substituted C.sub.4- to C.sub.16-alkanedioxy radical, a cyclopentanedioxy or cyclohexanedioxy radical, a benzenedi(methyloxy), benzenedi(ethyloxy) or benzenedi(propyloxy) radical, a benzenedioxy radical or heteroarylenedioxy radical optionally substituted by nonionic radicals, an optionally branched and/or optionally substituted C.sub.4- to C.sub.22-alkanediamino radical, a cyclopentanediamino or cyclohexanediamino radical, a benzenedi(methylamino), benzenedi(ethylamino) or benzenedi(propylamino) radical, a benzenediamino radical, methyldicyclohexylene radical, 4-methylenebis(4,1-phenylene) radical or heteroarylenediamino radical optionally substituted by nonionic radicals, T.sup.302 is a bridge having 1 to 9 carbon atoms which may be arranged in the form of an optionally branched chain and/or a five- or six-membered ring, R.sup.332 is an optionally branched and/or optionally substituted C.sub.1- to C.sub.16-alkylene radical, a cyclopentylene or cyclohexylene radical, xylylene, benzenediethylene or benzenedipropylene radical, an arylene or heteroarylene radical optionally substituted by nonionic radicals, A is NR.sup.401 or oxygen, R.sup.400 and R.sup.401 are independently hydrogen, methyl or ethyl, R.sup.303 and R.sup.304 are independently an optionally branched and/or optionally substituted C.sub.1- to C.sub.5-alkyl radical, and/or R.sup.303′ and R.sup.304′ are independently an optionally branched and/or optionally substituted C.sub.1- to C.sub.5-alkyl radical, or R.sup.302 is a radical of the formulae ##STR00196## T.sup.301, R.sup.331, T.sup.302, R.sup.332, R.sup.400, R.sup.401 and A have the definition given above, with the proviso that T.sup.301 and R.sup.331 together and T.sup.302 and R.sup.332 together each contain 12 carbon atoms, R.sup.301, R.sup.303 and R.sup.304 together with the N.sup.+ atom form an imidazole or pyridine ring substituted at least by one radical selected from C.sub.1- to C.sub.6-alkyl, C.sub.1- to C.sub.6-alkoxy, cyclopentyl, cyclohexyl, benzyl or phenyl, and/or R.sup.301′, R.sup.303′ and R.sup.304′ together with the N.sup.+ atom form an imidazole or pyridine ring substituted at least by one radical selected from C.sub.1- to C.sub.6-alkyl, C.sub.1- to C.sub.6-alkoxy, cyclopentyl, cyclohexyl, benzyl or phenyl, or R.sup.301 and R.sup.301 are each independently an optionally branched C.sub.14- to C.sub.22-alkyl radical or are additionally defined as R.sup.302, with the proviso that T.sup.301 and R.sup.331 together and T.sup.302 and R.sup.332 together each contain at least 12 carbon atoms, R.sup.302 is a radical of the formulae ##STR00197## and T.sup.301, R.sup.331, T.sup.302, R.sup.332, R.sup.400, R.sup.401 and A have the definition given above, R.sup.303 and R.sup.304 together form a —(CH.sub.2).sub.4—, —(CH.sub.2).sub.5— or —(CH.sub.2).sub.2—O—(CH.sub.2).sub.2— bridge, and/or R.sup.30 3′ and R.sup.304′ together form a —(CH.sub.2).sub.4—, —(CH.sub.2).sub.5— or —(CH.sub.2).sub.2—O—(CH.sub.2).sub.2— bridge and R.sup.1 and R.sup.4 are as defined above.

3. The compounds of claim 1, wherein R.sup.301 and R.sup.301′ are each independently an optionally branched C.sub.14- to C.sub.22-alkyl radical, R.sup.302 is a radical of the formulae ##STR00198## T.sup.301 is a bridge in the form of an optionally branched chain which has 2 to 8 carbon atoms and may contain 1 or 2 oxygen atoms, where there must be at least 2 carbon atoms between two oxygen atoms, or a bridge of the formulae ##STR00199## R.sup.331 is an optionally branched and/or optionally substituted C.sub.4- to C.sub.16-alkylene radical, a cyclopentylene or cyclohexylene radical, a xylylene radical, an arylene radical optionally substituted by nonionic radicals or a furylene, thienylene or pyridylene radical, an optionally branched and/or optionally substituted C.sub.4- to C.sub.16-alkanedioxy radical, a cyclopentanedioxy or cyclohexanedioxy radical, a benzenedi(methyloxy) radical, a benzenedioxy radical optionally substituted by nonionic radicals, an optionally branched and/or optionally substituted C.sub.4- to C.sub.22-alkanediamino radical, a cyclopentanediamino or cyclohexanediamino radical, a benzenedi(methylamino) radical, a benzenediamino radical or pyridinediamino radical optionally substituted by nonionic radicals, T.sup.302 is a bridge in the form of an optionally branched chain having 2 to 8 carbon atoms or is a bridge of the formulae ##STR00200## R.sup.332 is an optionally branched and/or optionally substituted C.sub.1- to C.sub.16-alkylene radical, a cyclopentylene or cyclohexylene radical, a xylylene radical, an arylene radical or pyridylene radical optionally substituted by nonionic radicals, A is NR.sup.401 or oxygen, R.sup.401 is hydrogen or methyl, R.sup.303 and R.sup.304 are independently an optionally branched and/or optionally substituted C.sub.1- to C.sub.5-alkyl radical, and/or R.sup.303′ and R.sup.304′ are independently an optionally branched and/or optionally substituted C.sub.1- to C.sub.5-alkyl radical or R.sup.302 is a radical of the formulae ##STR00201## T.sup.301, R.sup.331, T.sup.302, R.sup.332, R.sup.400, R.sup.401 and A have the definition given above, with the proviso that T.sup.301 and R.sup.331 together and T.sup.302 and R.sup.332 together each contain at least 12 carbon atoms, R.sup.301, R.sup.303 and R.sup.304 together with the N.sup.+ atom form an imidazole or pyridine ring substituted at least by one radical selected from C.sub.1- to C.sub.4-alkyl, C.sub.1- to C.sub.4-alkoxy, cyclopentyl, cyclohexyl, benzyl or phenyl, and/or R.sup.301′, R.sup.303′ and R.sup.304′ together with the N.sup.+ atom form an imidazole or pyridine ring substituted at least by one radical selected from C.sub.1- to C.sub.4-alkyl, C.sub.1- to C.sub.4-alkoxy, cyclopentyl, cyclohexyl, benzyl or phenyl or R.sup.301 and R.sup.301′ are each independently an optionally branched C.sub.14- to C.sub.22-alkyl radical, R.sup.302 is a radical of the formulae ##STR00202## and T.sup.301, R.sup.331, T.sup.302, R.sup.332, R.sup.400, R.sup.401 and A have the definition given above, R.sup.303 and R.sup.304 together form a —(CH.sub.2).sub.4—, —(CH.sub.2).sub.5— or —(CH.sub.2).sub.2—O—(CH.sub.2).sub.2— bridge, and/or R.sup.303′ and R.sup.304′ together form a —(CH.sub.2).sub.4—, —(CH.sub.2).sub.5— or —(CH.sub.2).sub.2—O—(CH.sub.2).sub.2— bridge and R.sup.1 and R.sup.4 are as defined above.

4. The compounds of claim 1, wherein R.sup.301 and R.sup.301′, R.sup.302 and R.sup.302′, and R.sup.303 and R.sup.303′ as pairs are the same, and the other radicals have the definitions given above.

5. The compounds of claim 1, wherein R.sup.331 and R.sup.332 in the formulae ##STR00203## are attached via three or more bonds to the groups of the formulae ##STR00204##

6. The compounds of claim 5, wherein R.sup.331 is one of —(CH.sub.2).sub.4—, —NH—(CH.sub.2).sub.6—NH—, ##STR00205##

7. The compounds of claim 5, wherein R.sup.332 is one of —(CH.sub.2).sub.2—, —(CH.sub.2).sub.4—, —(CH.sub.2).sub.2—O—(CH.sub.2).sub.2—, ##STR00206##

8. The compounds of claim 5, wherein T.sup.301 is one of —(CH.sub.2).sub.2—, —(CH.sub.2).sub.3—, —(CH.sub.2).sub.4—, —CH.sub.2CH(CH.sub.3)—, —(CH.sub.2).sub.2—O—(CH.sub.2).sub.2—, —[(CH.sub.2).sub.2—O-].sub.2(CH.sub.2).sub.2—, —(CH.sub.2).sub.4—O—CH.sub.2—CH.sub.2—, ##STR00207##

9. The compounds of claim 5, wherein T.sup.302 is one of —CH.sub.2—, —(CH.sub.2).sub.2—, —(CH.sub.2).sub.3—, —(CH.sub.2).sub.4—, —CH.sub.2CH(CH.sub.3)—, —(CH.sub.2).sub.5—, —(CH.sub.2).sub.6—, ##STR00208##

10. A holographic media or hologram comprising a photopolymer composition comprising the triaryl organoborates according to claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1: shows a Δn of the holographic media determined by means of twin-beam interference.

EXAMPLES

(2) Test Methods:

(3) 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

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

(5) TABLE-US-00001 Ethylboronic acid [82954-89-0] is available from TCI Europe N.V., Zwijndrecht, Belgium. pinacol ester Isopropylboronic acid [76347-13-2] is available from ABCR GmbH & Co. KG, Karlsruhe, Germany. pinacol ester 2-Isopropenylboronic [126726-62-3] is available from ABCR GmbH & Co. KG, Karlsruhe, Germany. acid pinacol ester 1-Dodecylboronic [177035-82-4] is available from ABCR GmbH & Co. KG, Karlsruhe, Germany. acid pinacol ester 3-Phenyl-1-propyl [329685-40-7] is available from ABCR GmbH & Co. KG, Karlsruhe, Germany. boronic acid pinacol ester Diisopropyl [51851-79-7] is available from ABCR GmbH & Co. KG, Karlsruhe, Germany. allyl boronate (1,3,2-Dioxaborinan- [30169-75-6] is available from ABCR GmbH & Co. KG, Karlsruhe, Germany. 2-yl)cyclohexane Dibromoborane-dimethyl [55671-55-1] is available from Aldrich Chemie, Steinheim, Germany. sulfide 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.

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

(7) 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.

(8) 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.

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

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

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

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

(13) 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.

(14) Origin of the 1/n K.sup.n+ Cations Used

(15) 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.

(16) TABLE-US-00002 TABLE 1 Overview of the cations of the formula (II) used Index Name Structure CAS Source K-1 Tetramethyl- Me.sub.4NBr [64-20-0] 426296, Aldrich ammonium bromide K-2 Tetrabutylammonium Bu.sub.4NBr [1643-19-2] 426288, Aldrich bromide K-3 Benzyldimethyl- BnMe.sub.2HexadecylNCl [122-18-9] AB252026, abcr hexadecylammonium GmbH chloride K-4 Hexadecyltrimethyl- ammonium 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] AB289681, 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- hexadecylpyridinium chloride [1702465-32-4] WO 2015055576 A1 K-14 1,1′-[1,3- Phenylenebis (methylene)]bis (pyridinium) dichloride 0 [84002-71-1] Zhurnal Neorganich- eskoi 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- Dioctadecyl- piperidinium 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′- Hexabutylhexa- methylene- diammonium 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) oxylethyl)-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) oxylethyl)-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- For preparation method see below diazahexadecane- 1,16-diaminium dibromide K-26 N-(2-((((5-(((2- (Hexadecyldimethyl- ammonio)ethoxy) carbonyl)amino)- 1,3,3- trimethylcyclohexyl) methyl)carbamoyl) For preparation method see below oxy)ethyl)-N,N- dimethylhexadecane- 1-aminium dibromide 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- For preparation method see below dimethylhexadecane- 1-aminium bromide K-31 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- 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-2,1-diyl)) bis(N,N- dimethylhexadecane- 1-aminium) For preparation method see below dibromide 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(azanediyl))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- benzenetrimethan- aminium triiodide [88888-13-5] Chem. Ber. 117, 1487-1496 (1984). K-37 N-[2-[2-[2- (Benzyloxy)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-oxazoildinyl] triethyl]-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 Tributyltetradecyl- phosphonium 0 [81741-28-8] P444 (14) Cl, Ionic Liquids chloride Technologies GmbH K-101 Trihexyltetradecyl- phosphonium [258864-54-9] P666 (14) Cl, Ionic Liquids chloride Technologies GmbH K-102 Methyltriphenyl- phosphonium chloride [1031-15-8] AB349191, abcr GmbH K-103 Triphenylbenzyl- phosphonium chloride [1100-88-5] AB113982, abcr GmbH K-104 Tetraphenyl- phosphonium chloride [2001-45-8] AB119018, abcr GmbH K-105 Allyltriphenyl- phosphonium bromide [1560-54-9] AB121395, abcr GmbH K-106 (2-Oxo-2- phenylethyl) triphenyl- phosphonium 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 [104558-95-4] BASF SE, K-300 + K-301 Ludwigshafen, (Cyracure Germany UVI 6990) K-304 Tris[4-[(4- acetylphenyl)thio] phenyl]sulfoniumtris [(trifluoromethyl) sulfonyl] methanide [953084-20-3] BASF SE, Ludwigshafen, Germany K-305 2,4,6- Triphenylthio- pyrylium 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 Diphenylene- iodonium 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)

(17) 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.

(18) 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)

(19) 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.

(20) 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-(Benzoyloxy)-N,N-dimethyl-N-(2-(palmitoyloxy)ethyl)ethane-1-aminium Bromide (K-22)

(21) 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.

(22) 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)

(23) 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)

(24) 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.

(25) 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)

(26) 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.

(27) 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)

(28) 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.

(29) 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)

(30) 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.

(31) 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)

(32) 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.

(33) 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.

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, 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 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-diaminium 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-dimethylhexadecane-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(ethane-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 Substituents of formula (IV) K.sup.+ preparation method a) 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 amor- phous 8 diisopropyl allyl boronate 1-bromo-3- chloro-4- methylbenzene K-1 allyl 07 −10.6 amor- phous 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- dodecylboronic acid pinacol ester 1-bromo-4- fluorobenzene K-2 n- dodecyl −10.4 amor- phous 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- dodecylboronic acid pinacol ester 1-bromo-4- chlorobenzene K-2 n- dodecyl −10.3 amor- phous 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- propylboronic 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- trifluorometh- oxybenzene 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 amor- phous 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 amor- phous 29 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-6 n-hexyl −10.6 amor- phous 30 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-7 n-hexyl −10.6 amor- phous 31 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-8 n-hexyl 0 −10.6 amor- phous 32 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-9 n-hexyl −10.6 amor- phous 33 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-10 n-hexyl −10.6 amor- phous 34 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-11 n-hexyl −10.6 amor- phous 35 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-12 n-hexyl −10.6 amor- phous 36 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-13 n-hexyl −10.6 amor- phous 37 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-16 n-hexyl −10.6 amor- phous 38 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-17 n-hexyl −10.6 amor- phous 39 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-19 n-hexyl −10.6 amor- phous 40 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-20 n-hexyl −10.6 amor- phous 41 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-21 n-hexyl 0 −10.6 amor- phous 42 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-22 n-hexyl −10.6 amor- phous 43 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-23 n-hexyl −10.6 amor- phous 44 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-24 n-hexyl −10.6 amor- phous 45 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-30 n-hexyl −10.6 amor- phous 46 1- dodecylboronic acid pinacol ester 1-bromo-4- chlorobenzene K-2 n-dodecyl −10.3 oil 47 1- dodecylboronic acid pinacol ester 1-bromo-4- methoxybenzene K-2 n-dodecyl −10.4 oil 48 1- dodecylboronic acid pinacol ester 1-bromo- 3,4,5- trifluorobenzene K-2 n-dodecyl −10.1 oil 49 1- dodecylboronic acid pinacol ester 1-bromo-3- methyl-4- fluorobenzene K-2 n-dodecyl −10.6 oil 50 1- dodecylboronic acid pinacol ester 1-bromo-4- trifluorometh- oxybenzene 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 amor- phous 59 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-201 n-hexyl −10.4 amor- phous 60 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-202 n-hexyl −10.4 amor- phous 61 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-300 n-hexyl 0 −10.6 amor- phous 62 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-303 n-hexyl −10.6 amor- phous 63 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-303 n-hexyl −10.6 amor- phous 64 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-304 n-hexyl −10.6 amor- phous 65 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-305 n-hexyl −10.6 amor- phous 66 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-400 n-hexyl −10.5 amor- phous 67 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-401 n-hexyl −10.5 amor- phous 68 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-402 n-hexyl −10.5 amor- phous 69 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-403 n-hexyl −10.5 amor- phous 86 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-37 n-hexyl −10.5 amor- phous 87 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-38 n-hexyl 0 −10.5 amor- phous 88 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-39 n-hexyl −10.5 amor- phous 89 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-40 n-hexyl −10.5 amor- phous 90 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-41 n-hexyl −10.5 amor- phous 91 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-42 n-hexyl −10.5 amor- phous 92 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-43 n-hexyl −10.5 amor- phous
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 amor- phous 94 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-15 n-hexyl −10.6 amor- phous 95 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-18 n-hexyl −10.6 amor- phous 96 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-25 n-hexyl −10.6 amor- phous 97 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-26 n-hexyl 0 −10.6 amor- phous 98 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-27 n-hexyl −10.6 amor- phous 99 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-28 n-hexyl −10.6 amor- phous 100 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-29 n-hexyl −10.6 amor- phous 101 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-31 n-hexyl −10.6 amor- phous 102 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-32 n-hexyl −10.6 amor- phous 103 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-33 n-hexyl −10.6 amor- phous 104 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-34 n-hexyl −10.6 amor- phous 105 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-35 n-hexyl −10.6 amor- phous 106 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-203 n-hexyl −10.4 amor- phous 107 2-hexyl- 1,3,2- dioxaborinane 1-bromo-3- chloro-4- methylbenzene K-301 n-hexyl 0 −10.6 amor- phous

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′=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′=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 Example of medium 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 XIII 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.