Binaphthyl compounds

Abstract

The present invention relates to binaphthyl compounds of the formula (I), which are suitable as monomers for preparing polycarbonate resins having beneficial optical properties and which can be used for producing optical lenses: Formula (I) where X is C.sub.2-C.sub.4-alkandiyl or C.sub.1-C.sub.4-alkandiyl-C(O)—, where C(O) is bound to the oxygen atom of the hydroxyl group and where C.sub.2-C.sub.4-alkandiyl or C.sub.1-C.sub.4-alkandiyl, respectively, are unsubstituted or carry a phenyl ring; R and R′ are identical or different and selected from mono or polycyclic aryl having from 6 to 36 carbon atoms and mono- or polycyclic hetaryl having a total of 5 to 36 atoms, which are ring members, where 1, 2, 3 or 4 of these atoms are selected from nitrogen, sulfur and oxygen, while the remainder of these atoms are carbon atoms, where mono- or polycyclic aryl and mono- or polycyclic hetaryl are unsubstituted or carry 1 or 2 radicals R.sup.a, which are selected from the group consisting of CN, CH.sub.3, OCH.sub.3, O-phenyl, O-naphthyl, S-phenyl, S-naphthyl, CI or F; and, if X is C.sub.1-C.sub.4-alkandiyl-C(O)—, the esters thereof, in particular the C.sub.1-C.sub.4-alkylesters thereof. ##STR00001##

Claims

1. A compound of the formula (I) ##STR00011## where X is C.sub.2-C.sub.4-alkandiyl or C.sub.1-C.sub.4-alkandiyl-C(O)—, where C(O) is bound to the oxygen atom of the hydroxyl group and where C.sub.2-C.sub.4-alkandiyl or C.sub.1-C.sub.4-alkandiyl, respectively, are unsubstituted or carry a phenyl ring; R and R′ are identical or different and selected from mono- or polycyclic aryl having from 6 to 36 carbon atoms and mono- or polycyclic hetaryl having a total of 5 to 36 atoms, which are ring members, where 1, 2, 3 or 4 of these atoms are selected from nitrogen, sulfur and oxygen, while the remainder of these atoms are carbon atoms, where mono- or polycyclic aryl and mono- or polycyclic hetaryl are unsubstituted or carry 1 or 2 radicals R.sup.a, which are selected from the group consisting of CN, CH.sub.3, OCH.sub.3, O-phenyl, O-naphthyl, S-phenyl, S-naphthyl and halogen, and, if X is C.sub.1-C.sub.4-alkandiyl-C(O)—, the esters thereof.

2. The compound of claim 1, where R and R′ are identical.

3. The compound of claim 1, where R and R′ are identical or different and selected from mono- or polycyclic aryl having from 6 to 36 carbon atoms and mono- or polycyclic hetaryl having a total of 5 to 36 atoms, which are ring members, where 1, 2, 3 or 4 of these atoms are selected from nitrogen, sulfur and oxygen, while the remainder of these atoms are carbon atoms, where mono- or polycyclic aryl and mono- or polycyclic hetaryl are unsubstituted.

4. The compound of claim 1, where R and R′ are selected from the group consisting of azulenyl, indenyl, which is unsubstituted or substituted by 1, 2, 3, 4 or 5 radicals selected from phenyl and polycyclic aryl bearing 2, 3 or 4 phenyl rings, which are linked to each other via a single bond, directly fused to each other and/or fused to a saturated or unsaturated 4- to 10-membered mono- or bicyclic hydrocarbon ring; phenyl, which is unsubstituted; phenyl, which is substituted by 1 or 2 CN radicals; phenyl, which is substituted by 1, 2, 3, 4 or 5 radicals selected from phenyl and polycyclic aryl bearing 2, 3 or 4 phenyl rings, which are linked to each other via a single bond, directly fused to each other and/or fused to a saturated or unsaturated 4- to 10-membered mono- or bicyclic hydrocarbon ring; and polycyclic aryl bearing 2, 3 or 4 phenyl rings, which are directly fused to each other and/or fused to a saturated or unsaturated 4- to 10-membered mono- or bicyclic hydrocarbon ring, where polycyclic aryl is unsubstituted or substituted by 1 or 2 radicals selected from phenyl and polycyclic aryl bearing 2 or 3 phenyl rings, which are linked to each other via a single bond, directly fused to each other and/or fused to a saturated 4- to 10-membered mono- or bicyclic hydrocarbon ring, where the phenyl rings of polycyclic aryl are unsubstituted or carry 1 or 2 radicals R.sup.a.

5. The compound of claim 1, where R and R′ are selected from the group consisting of phenyl, which is unsubstituted or substituted by 1, 2, 3, 4 or 5 phenyl radicals, phenyl, which is substituted by 1 or 2 CN radicals, phenyl, which is substituted by 1 or 2 polycyclic aryl radicals selected from biphenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl and pyrenyl and optionally by 1 further phenyl radical; naphthyl, which is unsubstituted or substituted by 1 or 2 radicals selected from CN, phenyl and polycyclic aryl selected from biphenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl and pyrenyl; biphenylenyl; triphenylenyl; tetraphenylenyl; phenanthryl; pyrenyl; 9H-fluorenyl; dibenzo[a,e][8]annulenyl; perylenyl; and 9,9′-spirobi[9H-fluoren]yl.

6. The compound of claim 5, where R and R′ are selected from the group consisting of phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-naphthyl, 1-naphthyl, and 9-phenanthryl.

7. The compound of claim 1, where R and R′ are selected from the group consisting of heteroaromatic monocyclic radicals having 5 or 6 ring atoms, which comprise 1, 2, 3 or 4 nitrogen atoms or 1 oxygen atom and 0, 1, 2 or 3 nitrogen atoms or 1 sulfur atom and 0, 1, 2 or 3 nitrogen atoms, where the remainder of the ring atoms are carbon atoms, heteroaromatic polycyclic radicals, which bear a heteroaromatic monocycle as defined above and 1, 2, 3, 4 or 5 further aromatic rings selected from phenyl and heteroaromatic monocycles, where the (hetero)aromatic rings of polycyclic hetaryl are linked to each other by a covalent bond or fused to each other directly and/or fused to a saturated or unsaturated 4 to 10-membered mono- or bicyclic hydrocarbon ring; and heteroaromatic polycyclic radicals, which bear at least one saturated or partially unsaturated 5- or 6-membered heterocyclic ring bearing 1 or 2 heteroatoms selected from oxygen, sulfur and nitrogen as ring atoms, and 1, 2, 3, 4 or 5 further aromatic rings selected from phenyl and heteroaromatic monocycles as defined above, where at least one of the further aromatic rings is directly fused to the saturated or partially unsaturated 5- or 6-membered heterocyclic radical and where the remainder of further aromatic rings of polycyclic hetaryl are linked to each other by a covalent bond or fused to each other directly and/or fused to a saturated or unsaturated 4 to 10-membered mono- or bicyclic hydrocarbon ring.

8. The compound of claim 7, where R and R′ are selected from the group consisting of furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, oxazolyl, isoxazolyl, 1,3,4-oxadiazolyl, 1,2,4-oxadiazolyl, pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, benzofuryl, dibenzofuranyl, benzothienyl, dibenzothienyl, thianthrenyl, naphthofuryl, furo[3,2-b]furanyl, furo[2,3-b]furanyl, furo[3,4-b]furanyl, oxanthrenyl, indolyl, isoindolyl, carbazolyl, indolizinyl, benzopyrazolyl, benzimidazolyl, benzoxazolyl, benzo[cd]indolyl, 1H-benzo[g]indolyl, quinolinyl, isoquinolinyl, acridinyl, phenazinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, benzo[b][1,5]naphthyridinyl, cinnolinyl, 1,5-naphthyridinyl, 1,8-naphthyridinyl, phenylpyrrolyl, naphthylpyrrolyl, dipyridyl, phenylpyridyl, naphthylpyridyl, pyrido[4,3-b]indolyl, pyrido[3,2-b]indolyl, pyrido[3,2-g]quinolinyl, pyrido[2,3-b][1,8]naphthyridinyl, pyrrolo[3,2-b]pyridinyl, pteridinyl, puryl, 9H-xanthenyl, 2H-chromenyl, phenanthridinyl, phenanthrolinyl, furo[3,2-f][1]benzofuranyl, furo[2,3-f][1]benzofuranyl, furo[3,2-g]quinolinyl, furo[2,3-g]quinolinyl, furo[2,3-g]quinoxalinyl, benzo[g]chromenyl, pyrrolo[3,2,1-hi]indolyl, benzo[g]quinoxalinyl, benzo[f]quinoxalinyl, and benzo[h]isoquinolinyl.

9. The compound of claim 1, where X is C.sub.2-C.sub.4-alkandiyl.

10. The compound of claim 1, where X is C.sub.1-C.sub.4-alkandiyl-C(O)—.

11. The compound of claim 1, which is selected from the group consisting of 6,6′-diphenyl-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl, 6,6′-di-(1-naphthyl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl, 6,6′-di-(2-naphthyl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl 6,6′-di-(9-phenanthryl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl, 6,6′-di-(3-cyanophenyl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl, 6,6′-di-(dibenzo[b,d]furan-4-yl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl and 6,6′-di-(dibenzo[b,d]thien-4-yl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl.

12. The compound of claim 1, which is selected from the group consisting of 2,2′-{(6,6′-diphenyl[1,1′-binaphthalene]-2,2′-diyl)bis(oxy)}diacetic, 2,2′-{(6,6′-bis(1-naphthyl)phenyl[1,1′-binaphthalene]-2,2′-diyl)bis(oxy)}diacetic acid, 2,2′-{(6,6′-bis(2-naphthyl)phenyl[1,1′-binaphthalene]-2,2′-diyl)bis(oxy)}diacetic acid, 2,2′-{(6,6′-bis(9-phenanthryl)phenyl[1,1′-binaphthalene]-2,2′-diyl)bis(oxy)}diacetic acid, 2,2′-{(6,6′-bis(3-cyanophenyl)phenyl[1,1′-binaphthalene]-2,2′-diyl)bis(oxy)}diacetic acid, 2,2′-{(6,6′-bis(dibenzo[b,d]furan-4-yl)phenyl[1,1′-binaphthalene]-2,2′-diyl)bis(oxy)}diacetic acid, 2,2′-{(6,6′-bis(dibenzo[b,d]thien-4-yl)phenyl[1,1′-binaphthalene]-2,2′-diyl)bis(oxy)}diacetic acid, the corresponding methyl esters and the corresponding ethyl esters.

13. The compound of claim 1 having a purity of at least 95%, calculated as non-volatile organic matter.

14. The compound of claim 1, which is crystalline.

15. The compound of claim 1, where X is 1,2-ethandiyl.

16. The compound of claim 1, where X is CH.sub.2—C(O)—.

17. The compound of claim 10, where the esters are C.sub.1-C.sub.4-alkylesters.

Description

PREPARATION EXAMPLES

Example 1: Preparation of 6,6′-diphenyl-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (Compound of Formula (Ia.1)—Procedure 1

1.1: Preparation of 6,6′-dibromo-1,1′-bi-2-naphthol (Compound III

(1) 155 g (541.34 mmol) of 1,1′-bi-2-naphthol (compound II) was suspended in 2.6 L DCM under argon atmosphere and the suspension was cooled to a temperature of −78° C. 2.3 to 2.5 equivalents of bromine, either neat or as a solution in DCM, was then added dropwise over a period of about 2 hours to the suspension. After continued stirring for about 1 hour at 22° C., TLC analysis (mobile phase: MTBE/n-heptane 2:1 (v/v)) revealed approximately complete consumption of the starting material and the reaction was then quenched by the addition of 1.16 kg of a saturated aqueous solution of sodium metabisulfite. Following phase separation the organic phase was washed with brine, dried over sodium sulfate and concentrated with a rotary evaporator until the product started to precipitate. After the precipitation was completed, the obtained solids were filtered off, washed with ice-cold toluene and dried. By concentrating the mother liqueur further product was obtained, which was also filtered off, washed with ice-cold toluene and dried. Combining the product fractions resulted in 205-210 g (ca. 85.3%-87.3%) of the raw title compound.

1.2: Alternative Preparation of 6,6′-dibromo-1,1′-bi-2-naphthol (Compound III) Via Oxidative Coupling

(2) To a solution of 6-bromo-2-naphthol (750 g; 3.36 mol) in methanol (750 g) was added 5.5 g copper(II) chloride and 7.5 g TMEDA. The mixture was heated to 35° C. and a stream of air is passed through the mixture for 36 h under stirring. The mixture was cooled to 20° C. and the solid product was filtered off, washed with methanol and dried to yield 529 g (1.19 mol) of the title compound (71%) having a chemical purity of about 97% (UPLC). The mother liquor was concentrated, the precipitate filtered off and the obtained filter cake washed and dried to yield another 164 g with a chemical purity of about 90% (UPLC).

(3) The obtained product could be further purified by recrystallization from toluene.

1.3: Alternative Preparation of 6,6′-dibromo-1,1′-bi-2-naphthol (Compound III

(4) 44.87 g of 1,1′-bi-2-naphthol was suspended in 350 mL (305 g) isopropyl acetate under an atmosphere of argon and the mixture was cooled to 0° C. Bromine (76.71 g) was then slowly added over a period of about 1 h in such a manner that the temperature did not rise above 5° C. Following the addition of bromine the reaction mixture was allowed to warm to room temperature. After the conversion was complete (approximately 2 h), the now homogeneous mixture was cooled down to 0° C. and a solution of Na.sub.2S.sub.2O.sub.5 (25 g) in water (100 mL) was added to remove remaining bromine. The phases were separated and the organic phase was washed consecutively with water (60 mL), with a saturated aqueous solution of Na.sub.2CO.sub.3 (120 mL) until the pH value of the aqueous phase remained above 7, and with brine (50 mL). The organic phase was then dried over Na.sub.2SO.sub.4 and the solvent was removed in vacuo to yield 78.4 g of 6,6′-dibromo-1,1′-bi-2-naphthol as a brownish solid having a chemical purity of 91% (UPLC). This raw product was crystallized from a 2.5- to 3.5-fold volume of toluene and thoroughly washed with pentane to afford 58.3 g of the title compound (yellowish to white crystals) with a chemical purity of 98.8% (UPLC). Recrystallization from a 4.2- to 4.6-fold volume of toluene followed by thoroughly washing with pentane resulted in 54.4 g of the title compound (white crystals) having a chemical purity of 99.5% (UPLC).

1.4: Preparation of 6,6′-diphenyl-1,1′-bi-2-naphthol (Compound VII, with Ar=Phenyl

(5) 222.06 g (500 mmol) of 6,6′-dibromo-1,1′-bi-2-naphthol (compound III) obtained according to protocol 1.1, 152.41 g (1.25 mol) of phenylboronic acid (2.5 equivalents) and 7.61 g (25 mmol) of tri(o-tolyl)phosphine (3 mol-%) were charged to the reaction vessel under argon, and then 500 mL of a 2.0 M aqueous solution of potassium carbonate, 1350 mL (1.17 kg) of toluene and 1350 mL (1.07 kg) Ethanol [a toluene/EtOH mixture (1:1, v/v)] were added. The mixture was degassed and, after the addition of 1.13 g (5 mmol) of palladium(II) acetate (1 mol-%), was stirred under inert gas for about 1 to 3 hours at a temperature of 90° C. until TLC analysis (mobile phase: DCM/MTBE/n-heptane 20:1:5 (v/v/v)) revealed approximately complete consumption of the starting material. Reaction mixture was cooled down to RT and then diluted with 500 mL saturated K.sub.2CO.sub.3 aqueous solution/1 L water/1 L MEK, and mixture was stirred for 1 h. After aqueous phase separation, the organic phase was separated, washed with brine, mixed with MEK and the homogeneous solution was purified with activated charcoal, filtered through Celite® in order to remove traces of palladium. The filtrate was concentrated with a rotary evaporator (at 60° C. and up to 180 mbar) until solid precipitates. Suspension was cooled down to RT and stirred at this temperature for 1-2 hours. The precipitated solids were filtered off, washed with ice-cold toluene and dried to yield 167-202 g of the raw title compound (ca. 77-92%). Purification of a crude product by slurry wash in toluene at 80-90° C. for 3-4 hours gave 160-165 g of the purified product (ca. 73-75%).

1.5: 6,6′-diphenyl-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (Compound Ia.1

(6) 150.0 g (342 mmol) of 6,6′-diphenyl-1,1′-bi-2-naphthol, 90.37 g (1.026 mol) of ethylene carbonate (3 equiv.) and 14.18 g (102.6 mmol) of potassium carbonate (30 mol-%) in 900 g (1.04 L) toluene were heated under reflux for at least 5 hours (Caution: CO.sub.2 gas evolution!), while monitoring the reaction progress by TLC (mobile phase: acetyl acetate or MTBE). Then mixture was cooled down to 70° C., addition amount of toluene (300-400 mL) was added and 150 mL water was then slowly added to the mixture. Caution: CO.sub.2 gas evolution! After completion of a gas evolution and phase separation, the organic phase was washed successively twice with 5% aqueous solution of sodium hydroxide and twice or more with water until aqueous wash solution is neutral (pH=7). The organic phase was then concentrated with a rotary evaporator until the product started to precipitate. Following complete precipitation at RT, obtained solids were filtered off, washed with toluene and dried to afford 149-158 g of the raw title compound (yield: 82.7-87.7% and purity of ca. 87-90%). Two consecutive recrystallizations from toluene or from MEK gave 110-124 g of the purified title compound (ca. 61-69%) with a purity of >99% (UPLC).

(7) Melting point: 162 to 164° C.

Example 2: Preparation of 6,6′-diphenyl-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (Compound of Formula (Ia.1)—Procedure 2

2.1: 6,6′-dibromo-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (compound IV, with X=1,2-ethandiyl

(8) 71.1 g (160 mmol) of 6,6′-dibromo-1,1′-bi-2-naphthol (compound III) obtained according to protocol 1.1, 42.27 g (480 mmol) of ethylene carbonate (3 equiv.) and 6.634 g (48 mmol) of potassium carbonate (30 mol-%) in 360 g (415 mL) toluene were heated under reflux for at least 5 hours (caution: CO.sub.2 gas evolution!), while monitoring the reaction progress by TLC (mobile phase: acetyl acetate or MTBE). Afterwards the reaction mixture was cooled to 80° C., additional 300 mL MEK was added to dissolve precipitated solids and obtain a clear solution. Then 150 mL of water were slowly added to the reaction mixture (caution: gas evolution!). After completion of the gas evolution and phase separation, the organic phase was washed successively twice with 5% or 10% aqueous solution of sodium hydroxide and twice or more with water until the aqueous wash solution was neutral (pH=7). The organic phase was then concentrated with a rotary evaporator until the product started to precipitate. Following complete precipitation the obtained solids were filtered off, washed with toluene and dried to afford 17.1 g of the raw title compound (ca. 80.3%).

2.2: Alternative preparation of 6,6′-dibromo-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (Compound IV, with X=1,2-ethandiyl

(9) To a mixture of 70 g (157 mmol) of 6,6′-dibromo-1,1′-bi-2-naphthol, 452 g anisole and 6.5 g (47 mmol) of potassium carbonate (30 mol-%) was added 41.6 g (473 mmol) of ethylene carbonate (3 equiv.) and the mixture was heated under reflux for at least 1 h (caution: CO.sub.2 gas evolution!), while monitoring the reaction progress by TLC (mobile phase: MTBE). Afterwards the reaction mixture was cooled to 80° C. and 50 mL of water and 19 g of brine were slowly added (caution: gas evolution!). After completion of the gas evolution and phase separation, the organic phase was treated with a 15% aqueous solution of sodium hydroxide for 1 h. After separation of the aqueous phase the organic phase was washed twice or more with a diluted aqueous solution of NaCl until the aqueous wash solution was neutral (pH=7). The organic phase was used directly for the next reaction step (see protocol 2.4 below).

2.3: 6,6′-diphenyl-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (Compound Ia.1

(10) 212.89 g (400 mmol) of 6,6′-dibromo-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl, 121.93 g (1 mol) of phenylboronic acid (2.5 equivalents) and 6.087 g (20 mmol) of tri(o-tolyl)-phosphine (5 mol-%) were charged to the reaction vessel under argon, and then 400 mL of a 2.0 M aqueous solution of potassium carbonate and 2.16 L of a toluene/EtOH mixture (1:1, v/v) were added. The mixture was degassed and, after the addition of 900 mg (4 mmol) of palladium(II) acetate (1 mol-%), was stirred under inert gas for 1 to 3 hours at a temperature of 90° C. until TLC analysis (mobile phase: MeOH/H.sub.2O=7:3 (v/v)) revealed approximately complete consumption of the starting material. The reaction mixture was cooled down to RT and then diluted with 500 mL saturated aqueous solution of K.sub.2CO.sub.3, 1 L water and 1 L MEK, and the obtained mixture was stirred for 1 h. The organic phase was separated, washed subsequently with 500 mL of a 2 M aqueous solution of HCl, 500 mL brine, and the resulting homogeneous solution was purified with activated charcoal (ca. 10 g) and filtered through Celite® in order to remove traces of palladium. Solvent was removed with a rotary evaporator to obtain a viscous oil, which was dried in vacuo to remove volatiles. Toluene (ca. 180-200 g) was then added and the mixture was homogenized under reflux. The obtained solution was slowly cooled down to RT, while solid material precipitated. The suspension was stirred at RT for more than 12 hours, while the product very slowly crystalized. The precipitated solids were then filtered off, washed with ice-cold toluene and dried to yield 161-185 g of the raw title compound (ca. 76-88% with a purity of 81-87%). The crude product was purified by slurry wash in MeOH followed by recrystallization from MEK to give 145-150 g of the purified product (ca. 69-71%) having a purity of >99.5% (UPLC).

2.4: Alternative preparation of 6,6′-diphenyl-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (Compound Ia.1

(11) To the organic phase obtained according to protocol 2.2 40.4 g of phenylboronic acid, 73.6 g of K.sub.3PO.sub.4, 163.5 g of water and 192 mg of tri(o-tolyl)-phosphine were added. The mixture was heated to 60° C. and 35 mg of palladium(II) acetate (0.1 mol-%) were added. The exothermic reaction effected a temperature increase to 95° C. The mixture was then heated to reflux for 15 min and afterwards cooled to 70° C. The organic phase was washed successively with a diluted aqueous solution of NaOH (5%; 200 mL), with a 4 M aqueous solution of HCl (63 mL) and with brine (200 mL). The organic phase was then treated with activated charcoal, dried over Na.sub.2SO.sub.4 (40 g) and filtered through Celite®. The solvent was removed under reduced pressure and the residue was taken up in a hot mixture of toluene and methanol (3:7 (v/v); 85 g). The resulting mixture was cooled to RT and stirred overnight. The formed crystals were collected by filtration, washed with pentane and dried at 60° C. to yield 70.8 g of the title compound with a chemical purity of 96.7% (UPLC).

Example 3: Preparation of 6,6′-diphenyl-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (Compound of Formula (Ia.1)—Procedure 3

3.1: 2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (compound VIII, with X=1,2-ethandiyl

(12) 150.0 g (523.88 mmol) of 1,1′-bi-2-naphthol (compound II), 138.37 g (1571.3 mmol) of ethylene carbonate (3 equiv.) and 21.75 g (157.13 mmol) of potassium carbonate (30 mol-%) in 1 L toluene were heated under reflux for at least 5 to 6 hours, by maintaining argon atmosphere. During the reaction gas evolves. The reaction is monitored by TLC using TBME as solvent. When TLC indicates complete reaction the slightly yellow reaction mixture is cooled to 70° C. and mixed with 100 g of water (Caution: CO.sub.2 gas evolution!) The reaction mixture is then stirred for further 10-15 min at 70° C. to dissolve potassium carbonate. The stirrer is stopped and phases are separated at about 70° C. The organic phase is washed with 100 g of 5% w/w aqueous solution of NaOH at 80-90° C. for at least 1 h (Caution: CO.sub.2 gas evolution!), followed by washing with water (each 100 mL) at 70° C., until the pH of the washing water is neutral (pH 7). 15 g of charcoal is optionally added to the organic phase and the mixture is stirred at 70° C. for 30 min. Then the warm solution is filtered through Celite®. The clear and slightly yellowish filtrate is cooled to RT and product crystallizes in the form of thin platelets. The solid is filtered off, washed with toluene and dried. 142-170 g (72.4-86.7%) of the title compound are obtained as a white, dry solid.

3.2: 6,6′-dibromo-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (Compound IV, with X=1,2-ethandiyl

(13) A suspension of 37.44 g (100 mmol) of 2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl in 485 mL DCM was cooled to a temperature of −10° C. 40 g Bromine (2.3 to 2.5 equivalents) as a solution in DCM (120 mL) were then added dropwise over a period of between 1 and 2 hours to the suspension. After continued stirring for about 1 to 2 hours at RT, TLC analysis (mobile phase: MTBE/n-heptane 2:1 (v/v) or MeOH/water 7:3 (v/v)) revealed approximately complete consumption of the starting material and the reaction was then quenched by the addition of aqueous solution of sodium metabisulfite (12 g of Na.sub.2S.sub.2O.sub.5 dissolved in 50 g water). Since product slowly precipitates, additionally 2.35 L MEK and 750 mL water were added in order to homogenize both organic and aqueous layers and to obtain two clear phases. Following phase separation the organic phase was successively washed with water (500 g), then saturated Na.sub.2CO.sub.3-solution (80 mL) [gas evolution] and brine (500 mL), dried over magnesium sulfate. The dried organic phase was filtered through Celite® and concentrated with a rotary evaporator until the product started to precipitate. After the precipitation was completed the obtained solids were filtered off, washed with ice-cold toluene and dried. By concentrating the mother liqueur further product was obtained, which was also filtered off, washed with ice-cold toluene and dried. Combined the product fractions were suspended in MTBE and purified twice by slurry wash at 45-50° C. for 2 hours, finally resulting in 44.5 g g of the purified title compound (83%), which was used without additional recrystallization for the next step.

3.3: Alternative preparation of 6,6′-dibromo-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (Compound IV, with X=1,2-ethandiyl

(14) 44.9 g of 2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl were suspended under argon or nitrogen in 250 mL MEK at a temperature of 20-22° C. To the suspension were added 100 mg of ammonium acetate (about 1.5 mol-%) as catalyst and a suspension of 48.1 g of N-bromosuccinimide (2.1-2.2 equiv.) in 500 mL of MEK. The reaction mixture turned into a reddish solution and was stirred for another 1 to 2 hours until TLC analysis showed approximately complete consumption of the starting material. The reaction was then quenched by the addition of 25 mL of a saturated aqueous solution of sodium metabisulfite. Following phase separation the organic phase was washed successively with water and brine, dried over sodium sulfate and concentrated with a rotary evaporator until the product started to precipitate. Then 300 mL of water were added and the residual MEK was removed in the rotary evaporator at a temperature of 60° C. The obtained solids were slurried in the remaining water at a temperature of 60° C. and filtered off. The solids were slurried again in 300 mL of water at 60° C., filtered off and washed with water and dried in an oven at a temperature of 60° C. overnight. Further washing was achieved by slurrying the solids in 337 mL of MTBE at a temperature of 45° C. After cooling the slurry to RT the solids were filtered off, washed with MTBE and dried to afford 40.0 g of the title compound (63%) with a chemical purity of 77.25% (UPLC).

3.4: Alternative preparation of 6,6′-dibromo-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (Compound IV, with X=1,2-ethandiyl

(15) In a reaction vessel, which had previously been dried and flushed with nitrogen or argon, 44.9 g of 2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl were suspended under argon or nitrogen in 337 mL of dry THF (peroxides-free and stabilized) at a temperature of 20-22° C. To the suspension were added 43.5 g of N-bromosuccinimide (2.1-2.2 equiv.) as a solid in four portions over 1.5 h. The reaction mixture turned into a yellow solution and was stirred overnight after which TLC analysis showed approximately complete consumption of the starting material. The reaction was then quenched by the addition of 25 mL of a saturated aqueous solution of sodium metabisulfite. Following phase separation the organic phase was washed successively with water and brine, dried over sodium sulfate and concentrated with a rotary evaporator until the product started to precipitate. Then 300 mL of water were added and the residual THF was removed in the rotary evaporator at a temperature of 60° C. The obtained solids were slurried in the remaining water at a temperature of 60° C., filtered off, washed with water and dried in an oven at a temperature of 60° C. and filtered off. The solids were slurried again in 300 mL of water at 60° C., filtered off and washed with water and dried in an oven at a temperature of 60° C. overnight. Further washing was achieved by slurrying the solids in 337 mL of MTBE at a temperature of 45° C. After cooling the slurry to RT the solids were filtered off, washed with MTBE and dried to afford 57.2 g of the title compound (90%) with a chemical purity of 91.34% (UPLC).

3.5: 6,6′-diphenyl-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (Compound Ia.1

(16) 212.89 g (400 mmol) of 6,6′-dibromo-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl, 121.93 g (1 mol) of phenylboronic acid (2.5 equivalents) and 6.087 g (20 mmol) of tri(o-tolyl)phosphine (5 mol-%) were charged to the reaction vessel under argon, and then 400 mL of a 2.0 M aqueous solution of potassium carbonate and 2.16 L of a toluene/EtOH mixture (1:1, v/v) were added. The mixture was degassed and, after the addition of 900 mg (4 mmol) of palladium(II) acetate (1 mol-%), was stirred under inert gas for 1 to 3 hours at a temperature of 90° C. until TLC analysis (mobile phase: MeOH/H.sub.2O=7:3 (v/v)) revealed approximately complete consumption of the starting material. The reaction mixture was cooled to RT and then diluted with 500 mL saturated K.sub.2CO.sub.3 aqueous solution, 1 L water and 1 L MEK, and the mixture was then stirred for 1 h. After phase separation the organic phase was isolated, washed successively with 500 mL of 2M HCl, 500 mL of brine, and the resulting homogeneous solution was purified with activated charcoal (about 10 g) and filtered through Celite® in order to remove traces of palladium. Solvent was removed with a rotary evaporator to obtain a viscous oil, which was dried in vacuo to remove volatiles. Toluene (ca. 180-200 g) was then added and the mixture was homogenized under reflux. The obtained solution was slowly cooled to RT, while solid precipitated. The thus obtained suspension was stirred at RT for more than 12 hours, while the product very slowly crystalized. The precipitated solids were then filtered off, washed with ice-cold toluene and dried to yield 161-185 g of the raw title compound (ca. 76-88%) with a purity of 81-87% (UPLC). The crude product was purified by slurry wash in MeOH followed by recrystallization from MEK to give 145-150 g of the purified title compound (ca. 69-71%) having purity of >99.5% (UPLC).

(17) .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.12 (d, J=1.7 Hz, 2H), 8.06 (d, J=9.0 Hz, 2H), 7.75-7.65 (m, 4H), 7.60-7.43 (m, 8H), 7.40-7.32 (m, 2H), 7.31-7.23 (m, 2H), 4.27 (ddd, J=10.0, 6.6, 2.7 Hz, 2H), 4.07 (ddd, J=10.3, 5.4, 2.7 Hz, 2H), 3.66 (ddd, J=12.4, 5.4, 2.7 Hz, 2H), 3.59 (ddd, J=12.4, 6.6, 2.7 Hz, 2H), 2.44 (br s, 2H) ppm.

(18) IR [cm.sup.−1]: 819.77, 825.56, 835.21, 850.64, 864.14, 885.36, 896.93, 941.29, 983.73, 1037.74, 1053.17, 1082.10, 1149.61, 1201.69, 1217.12, 1247.99, 1282.71, 1340.57, 1361.79, 1375.29, 1442.80, 1492.95, 1575.89, 1595.18, 1622.19, 2870.17, 2933.83, 2972.40, 3319.60.

(19) Melting point: 164° C.

Example 4: Preparation of 6,6′-di-(1-naphthyl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (Compound Ia.2

(20) 6,6′-dibromo-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (compound IV, with X=1,2-ethandiyl) and 1-naphthylboronic acid (2.5 equivalents) were reacted in accordance with the protocol of example 2.3. Workup of the reaction mixture and recrystallization of the raw product gave the title compound in 74% yield. The purity of the obtained product was >99% (UPLC).

(21) .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.11-8.03 (m, 4H), 7.99 (d, J=8.4 Hz, 2H), 7.93 (d, J=8.1 Hz, 2H), 7.89 (d, J=7.4 Hz, 2H), 7.60-7.46 (m, 10H), 7.46-7.40 (m, 2H), 7.37 (d, J=8.7 Hz, 2H), 4.38-4.28 (m, 2H), 4.21-4.09 (m, 2H), 3.88-3.54 (m, 4H), 2.50 (t, J=6.4, 2H) ppm.

(22) IR [cm.sup.−1]: 802.41, 831.35, 864.14, 889.21, 937.44, 962.51, 987.59, 1018.45, 1049.31, 1082.1, 1095.60, 1112.96, 1145.75, 1207.48, 1238.34, 1251.84, 1280.78, 1334.78, 1394.58, 1454.38, 1483.31, 1575.89, 1591.33, 1624.12, 2874.03, 2920.32, 3045.70, 3383.26.

(23) Melting point: 220° C.

Example 5: Preparation of 6,6′-di-(2-naphthyl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (Compound Ia.3

(24) 6,6′-dibromo-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (compound IV, with X=1,2-ethandiyl) and 1-naphthylboronic acid (2.5 equivalents) were reacted in accordance with the protocol of example 2.3. Workup of the reaction mixture and recrystallization of the raw product from acetone gave the title compound in 86% yield. The purity of the obtained product was >99% (UPLC).

(25) .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.25 (d, J=1.8 Hz, 2H), 8.13 (d, J=1.3 Hz, 2H), 8.10 (d, J=9.0 Hz, 2H), 7.98-7.81 (m, 8H), 7.68 (dd, J=8.8, 1.9 Hz, 1H), 7.60-7.42 (m, 6H), 7.32 (d, J=8.8 Hz, 2H), 4.29 (ddd, J=10.3, 6.6, 2.8 Hz, 2H) 4.10 (ddd, J=10.4, 5.4, 2.7 Hz, 2H), 3.68 (ddd, J=12.4, 5.4, 2.7 Hz, 2H), 3.61 (ddd, J=12.4, 6.6, 2.7 Hz, 2H), 2.11 (br s, 2H) ppm.

(26) IR [cm.sup.−1]: 800.49, 815.92, 835.21, 864.14, 879.57, 931.65, 952.87, 1014.59, 1028.09, 1049.31, 1097.53, 1143.83, 1201.69, 1228.70, 1246.06, 1296.21, 1329.00, 1359.86, 1394.58, 1435.09, 1460.16, 1479.45, 1572.04, 1585.54, 1618.33, 1979.03, 2955.04, 3053.42, 3495.13, 3574.21.

(27) Melting point: 199° C.

Example 6: Preparation of 6,6′-di-(9-phenanthryl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (Compound Ia.4

(28) 6,6′-dibromo-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (compound IV, with X=1,2-ethandiyl) and 9-phenanthrylboronic acid (2.5 equivalents) were reacted in accordance with the protocol of example 2.3. Workup of the reaction mixture and recrystallization of the raw product from tetrahydrofurane gave the title compound in 88% yield. The purity of the obtained product was >99% (UPLC).

(29) .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.79 (d, J=8.2 Hz, 2H), 8.74 (d, J=8.2 Hz, 2H), 8.10 (d, J=1.5 Hz, 2H), 8.08 (d, J=9.0 Hz, 2H), 8.01 (d, J=7.5 Hz, 2H), 7.91 (dd, J=7.8, 1.2 Hz, 2H), 7.80 (s, 2H), 7.72-7.58 (m, 6H), 7.58-7.50 (m, 6H), 7.40 (d, J=8.7 Hz, 2H), 4.34 (ddd, J=10.1, 6.2, 2.8, 2H), 4.17 (ddd, J=10.3, 5.4, 2.7 Hz, 2H), 3.83-3.64 (m, 4H), 2.09 (br s, 2H) ppm.

(30) IR [cm.sup.−1]: 702.11, 725.26, 750.33, 767.69, 792.77, 808.20, 831.35, 854.49, 889.21, 929.72, 954.80, 968.30, 995.30, 1051.24, 1087.89, 1128.39, 1166.97, 1192.05, 1247.99, 1271.13, 1307.78, 1334.78, 1423.51, 1450.52, 1481.38, 1591.33, 2872.10, 2933.83, 3400.62.

(31) Melting point: 257° C.

Example 7: Preparation of 6,6′-di-(3-cyanophenyl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (Compound Ia.5

(32) 87.3 g (160 mmol) of 6,6′-dibromo-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (compound IV, with X=1,2-ethandiyl), 49.4 g (336 mmol) of 3-cyanophenyl-boronic acid (2.1 equivalents), 74.7 g of K.sub.3PO.sub.4 (352 mmol), 165 g of water, 472 mL of toluene, 472 mL of ethanol and 390 mg of tri(o-tolyl)-phosphine (1.3 mmol) were charged to the reaction flask under argon. The mixture was heated to 60° C. and following the addition of 72 mg (0.32 mmol) of palladium(II) acetate (0.2 mol-%) was stirred under reflux for 2.5 hours until TLC analysis (mobile phase: methanol/water=3:1 (v/v)) showed complete conversion. The reaction mixture was then cooled down to 60° C. and the organic phase was separated, mixed with 400 mL of MEK and 200 mL of water, and the resulting mixture was stirred for 5 min. The water phase was removed and the organic phase was successively washed with a 8% aqueous solution of NaOH (200 mL), with a 4 M aqueous HCl (100 mL) and with brine (100 mL). The organic phase was cooled to 20° C. and stirred overnight. The formed precipitate was collected by filtration, washed with pentane and dried (at 60° C.) to yield 84.6 g of the raw title compound (88%) having a chemical purity of 96.2% (UPLC). This material was further purified by recrystallization from toluene/acetonitrile (1:1 (v/v); 514 g) to yield 72.2 g of crystalline title compound with a chemical purity of 97.7% (UPLC).

(33) .sup.1H NMR (400 MHz, DMSO-d.sub.6): δ=8.40 (d, J=1.9 Hz, 2H), 8.25 (t, J=1.8 Hz, 2H), 8.20-8.14 (m, 2H), 8.11 (ddd, J=8.0, 1.9, 1.1 Hz, 2H), 7.83 (dt, J=7.7, 1.3 Hz, 2H), 7.74-7.60 (m, 6H), 7.03 (d, J=8.9 Hz, 2H), 4.64 (t, J=5.3 Hz, 2H), 4.13-4.03 (m, 4H), 3.44 (q, J=5.4 Hz, 4H).

(34) Melting point: 208 to 209° C.

Example 8: Preparation of 6,6′-di-(dibenzo[b,d]thien-4-yl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (Compound Ia.7

(35) 43.8 g (80 mmol) of 6,6′-dibromo-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (compound IV, with X=1,2-ethandiyl), 40.33 g (168 mmol) of dibenzothiophene-4-boronic acid (2.1 equivalents), 37.4 g of K.sub.3PO.sub.4 (176 mmol), 83 g of water, 236 mL of toluene, 236 mL of ethanol and 97.4 mg of tri(o-tolyl) phosphine (0.32 mmol) were charged to the reaction vessel under argon. The mixture was heated to 60° C. and, after the addition of 18 mg (0.08 mmol) of palladium(II) acetate (0.1 mol-%), was stirred under reflux for 6 hours until TLC analysis (mobile phase: ethyl acetate/dichloromethane=1:1 (v/v)) showed complete conversion. The reaction mixture was cooled down to 60° C. and the aqueous phase was removed. The organic phase was cooled to room temperature and the formed precipitate was collected by filtration. The mother liquor was concentrated and additional precipitate was collected by filtration. The combined filter cakes were washed successively with water (200 mL), with a 20% aqueous solution of NaOH (200 mL) and again two times with water (2×200 g) to yield the 42 g of the title compound (70%) with a chemical purity of 98.2% (UPLC).

(36) .sup.1H NMR (400 MHz, DMSO-d.sub.6): δ=8.45-8.35 (m, 6H), 8.20 (d, J=9.0 Hz, 2H), 8.04-7.95 (m 2H), 7.75 (d, J=9.2 Hz, 2H), 7.69-7.60 (m 6H), 7.58-7.47 (m 4H), 7.18 (d, J=8.8 Hz, 2H), 4.68 (t, J=5.3 Hz, 2H), 4.14 (td, J=5.5, 1.9 Hz, 4H), 3.51 (q, J=5.7 Hz, 4H).

(37) Melting point: 214 to 216° C.

Example 9: Preparation of 6,6′-di-(dibenzo[b,d]furan-4-yl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (Compound Ia.6

(38) 89 g (160 mmol) of 6,6′-dibromo-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (compound IV, with X=1,2-ethandiyl), 75 g (336 mmol) of dibenzofuran-4-boronic acid (2.1 equivalents), 74.7 g of K.sub.3PO.sub.4 (352 mmol), 166 g of water, 472 mL of toluene, 472 mL of ethanol and 194.8 mg of tri(o-tolyl) phosphine (0.64 mmol) were charged to the reaction vessel under argon. The mixture was heated to 60° C. and, after the addition of 36 mg (0.16 mmol) of palladium(II) acetate (0.1 mol-%), was stirred under reflux for 0.5 hours until TLC analysis (mobile phase: ethyl acetate/dichloromethane=1:1 (v/v)) showed complete conversion. The reaction mixture was cooled down to 60° C. and the aqueous phase was removed. The organic phase was cooled to room temperature and precipitate was collected by filtration. The filter cake was washed with water (200 mL) and dried to yield 99.8 g of the title compound with a chemical purity of 95% (UPLC).

(39) .sup.1H NMR (400 MHz, DMSO-d.sub.6): δ=8.52 (d, J=1.9 Hz, 2H), 8.26-8.10 (m, 6H), 7.85-7.75 (m, 4H), 7.77-7.70 (m, 4H), 7.58-7.47 (m, 4H), 7.42 (td, J=7.5, 1.0 Hz, 2H), 7.16 (d, J=8.9 Hz, 2H), 4.66 (t, J=5.3 Hz, 2H), 4.12 (td, J=5.3, 2.5 Hz, 4H), 3.50 (q, J=5.4 Hz, 4H).

(40) Melting point range: 230 to 235° C.

Example 10: Preparation of diethyl 2,2′-{(6,6′-diphenyl[1,1′-binaphthalene]-2,2′-diyl)bis(oxy)}diacetate (Compound Id.1

(41) 6,6′-Diphenyl-1,1′-bi-2-naphthol (48.24 g, 110 mmol) and ethyl α-chloroacetate (40.31 g, 328.9 mmol) were dissolved in 1.2 L of dry acetone and anhydrous K.sub.2CO.sub.3 (37.85 g, 273.9 mmol) was added to the solution. The mixture was refluxed for 8-12 h and the conversion was monitored by TLC. After completion, the reaction mixture was cooled to RT and K.sub.2CO.sub.3 was filtered off. After evaporation of the solvent, water was added to the residue, and the mixture was then extracted with 3×20 mL methyl ethyl ketone or a mixture of toluene and methyl ethyl ketone (20:80%.sub.v/v). The organic layers were collected, dried over anhydrous Na.sub.2SO.sub.4 or MgSO.sub.4, and the solvent was evaporated. Yield of the title compound was 59.79 g (89%).

Example 11: Preparation of 2,2′-{(6,6′-diphenyl[1,1′-binaphthalene]-2,2′-diyl)bis(oxy)}diacetic Acid (Compound Ib.1

(42) 58.0 g (95 mmol) of compound Id.1 was mixed with 1 L of a 20% solution of KOH in ethanol-water (80:20%.sub.v/v). The mixture was refluxed for 2-3 h and the reaction was monitored by TLC. After completion of the reaction, ethanol was evaporated, deionized water was added and the pH was finally adjusted to pH=1-2 with concentrated HCl. The precipitated solid was filtered off and dissolved in toluene and methyl ethyl ketone (20:80%.sub.2/2). The solution dried over anhydrous Na.sub.2SO.sub.4 or MgSO.sub.4 and then concentrated until the title compound crystallized. Precipitated solid was filtered off, washed with toluene and dried at 60-70° C. to yield 47.42 g of the title compound Ib.1 (yield 90%; chemical purity (UPLC): 98.7%)

(43) .sup.1H NMR (400 MHz, DMSO-d.sub.6) δ 9.42 (br s, 2H), 8.25 (s, 2H), 8.19-8.09 (m, 2H), 7.74 (t, J=8.3 Hz, 4H), 7.63-7.42 (m, 8H), 7.41-7.30 (m, 2H), 7.15-7.05 (m, 2H), 4.74-4.59 (m, 4H).