Chiral compounds

Abstract

Chiral compounds of formula I ##STR00001##
wherein the paramters have the meaning given in claim 1, liquid crystal mixtures comprising at least one chiral compound of formula I, to chiral linear or crosslinked liquid crystal polymers obtainable by polymerizing a polymerizable mixture comprising at least one chiral compound of formula I, to the use of chiral compound of formula I and mixtures and polymers obtained thereof in liquid crystal displays, active and passive optical elements, adhesives, synthetic resins with anisotropic mechanical properties, cosmetic and pharmaceutical compositions, diagnostics, liquid crystal pigments, for decorative and security applications, nonlinear optics, optical information storage or as chiral dopants, and a liquid crystal display comprising a mixture comprising at least one chiral compound of formula I.

Claims

1. A process comprising alkylating or acetalizing a compound of the formula ##STR00262## to produce a compound of the formula ##STR00263## wherein A.sup.11, A.sup.l2, A.sup.21, A.sup.22 each, identically or differently, denote 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2,6-diyl, it being possible for all these groups to be unsubstituted, mono- or polysubstituted with L.sup.31, R.sup.11, R.sup.21, R.sup.31 each, identically or differently, denote H, F, Cl, CN, straight chain or branched alkyl with up to 7 C atoms which may be unsubstituted, mono- or polysubstituted by F, Cl, or CN, it being also possible for one or more non-adjacent CH.sub.2 groups to be replaced, in each case independently from one another, by —O—, —CO—, —C(O)O—, —OC(O)—, —OCO—O—, —SC(O)—, —C(O)S—, —CH═CH— or —C≡C— in such a manner that —O— and/or —S— atoms are not linked directly to one another, or a polymerizable group, Z.sup.11, Z.sup.12, Z.sup.21 and Z.sup.22 each, identically or differently, denote —O—, —CO—, —C(O)O—, —OC(O)—, —O—C(O)O—, —OCH.sub.2—, —CH.sub.2O—, —CF.sub.2O—, —OCF.sub.2—, —CH.sub.2CH.sub.2—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —CF.sub.2CF.sub.2—, —CH═CH—, —CF═CH—, —CH═CF—, —CF═CF—, —C≡C—, or a single bond, Z.sup.31 denotes —O—, —OC(O)—, —OCH.sub.2—, —CH.sub.2CH.sub.2—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —CF.sub.2CF.sub.2— or a single bond, L.sup.11, L.sup.21, L.sup.31 each, identically or differently, denote F, Cl, or alkyl or alkoxy with 1 to 7 C atoms, wherein one or more H atoms may be substituted by F or Cl, m1, m2 each, identically or differently, is 0, 1, 2 or 3, r1, r2, s1 each, identically or differently, are 0, 1 or 2, and s denotes 0 or 1.

Description

EXAMPLES

(1) In the following examples the invention is described in grater detail without delimiting it in any way.

(2) Examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.

1. Synthesis

Example 1: 12,15-Di(naphthalen-2-yl)-5-(4-pentylcyclohexyl)-5,6-dihydro-4H-dinaphtho[2,1-f:1′,2′-h][1,5]dioxonine

1.1 7-Methoxy-2-trifluoromethanesulfonyloxy naphthalene

(3) ##STR00235##

(4) To a mixture of 7-methoxy-2-naphthol (25.0 g, 144 mmol) and DMAP (0.70 g, 5.7 mmol) in CH.sub.2Cl.sub.2 (400 mL), triethylamine (30 mL) is added. The yellow reaction mixture is cooled to 0° C. At this temperature trifluoromethane sulfonic acid anhydride (33 mL, 200 mmol) is added dropwise. The solution is allowed to warm to room temperature and stirred for 20 h. The resulting mixture is poured into ice water and extracted with CH.sub.2Cl.sub.2. The combined organic layers are washed with water (1×200 mL), dried with NaSO.sub.4 and concentrated under reduced pressure. The product is purified by column chromatography (heptane/toluene 1:1) and crystallized from heptane.

1.2 7-Methoxy-2,2′-binaphthyl

(5) ##STR00236##

(6) A flask is flushed with nitrogen and charged with a mixture of 7-methoxy-2-trifluoromethanesulfonyloxy naphthalene (60.0 g, 195.9 mmol), 2-naphthylboronic acid (41.70 g, 235.1 mmol) and THF (700 mL). Then NaBO.sub.2.4H.sub.2O (41.34 g, 293.9 mmol), 180 mL water, PdCl.sub.2(PPh.sub.3).sub.2 (2.75 g, 3.9 mmol) and 2-3 drops of hydrazinium hydroxide are added. The mixture is stirred at 60° C. for 20 h, cooled to room temperature, diluted with water (300 mL) and extracted with MTB ether (600 mL). The organic phases are washed with water (1×400 mL), dried with NaSO.sub.4 and concentrated under reduced pressure. The product is purified by column chromatography (heptane/toluene 1:1) and crystallized from heptane.

1.3 7-Hydroxy-2,2′-binaphthyl

(7) ##STR00237##

(8) To a solution of 7-methoxy-2,2′-binaphthyl (1.50 g, 5.2 mmol) in CH.sub.2Cl.sub.2 (30 mL) at 5° C. BBr.sub.3 (0.75 mL, 7.9 mmol) is added. The solution is allowed to warm to room temperature and stirred for 20 h. The excess of BBr.sub.3 is decomposed by the dropwise addition of water. The resulting mixture is diluted with water and extracted with CH.sub.2Cl.sub.2 (100 mL). The organic phase is washed with saturated NaHCO.sub.3 (2×50 mL), water (1×50 mL) and dried with NaSO.sub.4. The solvent is removed under reduced pressure and the product is purified by crystallization from toluene.

1.4 2,2′-Dihydroxy-7,7′-dinaphthyl-1,1′-binaphthyl

(9) ##STR00238##

(10) 7-Hydroxy-2,2′-binaphthyl (1.00 g, 3.7 mmol) is added to a mixture of CuCl(OH)-TMEDA (20 mg, 0.04 mmol) in CH.sub.2Cl.sub.2 (40 mL) and the whole is stirred at room temperature for 20 h exposed to air. The solvent is removed under reduced pressure and purified by column chromatography (toluene/ethylacetate 9:1). Crystallization from toluene gives 2,2′-dihydroxy-7,7′-dinaphthyl-1,1′-binaphthyl as a white solid.

1.5 12,15-Di(naphthalen-2-yl)-5-(4-pentylcyclohexyl)-5,6-dihydro-4H-dinaphtho[2,1-f:1′,2′-h][1,5]dioxonine

(11) ##STR00239##

(12) A mixture of 2,2′-dihydroxy-7,7′-dinaphthyl-1,1′-binaphthyl (1.50 g, 2.48 mmol) and K.sub.2CO.sub.3 (0.38 g, 2.73 mmol) in 30 mL DMF is stirred at 80° C. At this temperature a solution of 2-(4-n-pentylcyclohexyl)propane-1,3-diolditosylate (1.64 g, 2.97 mmol) in 20 mL DMF is added dropwise to the reaction mixture. The reaction is stirred for 20 h at 80° C. After cooling to room temperature, the reaction mixture is poured onto water and extracted with MTB ether (100 mL). The organic phase was washed with water (1×50 mL) and dried with NaSO.sub.4. The solvent is removed under reduced pressure and the product is purified by column chromatography (heptane/toluene 1:1). The racemic product is separated into enantiomers by chiral HPLC on ChiralPak IA. 12,15-Di(naphthalen-2-yl)-5-(4-pentylcyclohexyl)-5,6-dihydro-4H-dinaphtho[2,1-f:1′,2′-h][1,5]dioxonine is obtained as colorless solid, mp. 113° C.

(13) This standard procedure (SP-1) is also used for the reaction between 2,2′-Dihydroxy-7,7′-dinaphthyl-1,1′-binaphthyl and the following ditosylates to give Examples 2 to 5.

(14) ##STR00240##

(15) Example 5 (Not in Accordance with the Invention): 2,2′-Methylenedioxy-7,7′-bis-[4-(4-propyl-cyclohexyl)phenyl]-[1,1′]binaphthalene

5.1 7-(4-(4-propylcyclohexyl)phenyl)naphthalen-2-ol

(16) ##STR00241##

(17) A flask is flushed with nitrogen and charged with a mixture of 7-bromo-2-naphthol (10.5 g, 46.6 mmol), (4-(4-propylcyclohexyl)benzene)boronic acid (13.77 g, 55.92 mmol) and THF (100 mL). Then NaBO.sub.2.4H.sub.2O (9.83 g, 69.9 mmol), 30 mL water, PdCl.sub.2(PPh.sub.3).sub.2 (1.64 g, 2.33 mmol) and 2-3 drops of hydrazinium hydroxide are added. The mixture is stirred at 60° C. for 5 h. The mixture is cooled to room temperature, diluted with water (250 mL), extracted with MTB ether (300 mL) and filtered through a pad of celite. The organic phases are is washed with water (1×100 mL), dried with NaSO.sub.4 and concentrated under reduced pressure. The product is purified by crystallization from heptane/ethylacetate 10:1.

5.2 7,7′-bis(4-(4-propylcyclohexyl)phenyl)-[1,1′-binaphthalene]-2,2′-diol

(18) ##STR00242##

(19) 7-(4-(4-propylcyclohexyl)phenyl)naphthalen-2-ol (1.00 g, 2.9 mmol) is added to a mixture of CuCl(OH)-TMEDA (14 mg, 0.04 mmol) in CH.sub.2Cl.sub.2 (50 mL) and the reaction is stirred at room temperature for 4 h exposed to air. The solvent is removed under reduced pressure and purified by column chromatography (toluene/ethylacetate 95:5). Crystallization from a mixture of heptane/ethyl acetate/toluene 5:4:1 gives 7,7′-bis(4-(4-propyl-cyclohexyl)phenyl)-[1,1′-binaphthalene]-2,2′-diol as a white solid.

5.3 2,2′-Methylenedioxy-7,7′-bis-[4-(4-propyl-cyclohexyl)phenyl]-[1,1′]binaphthalene

(20) ##STR00243##

(21) A mixture of 7,7′-bis(4-(4-propylcyclohexyl)phenyl)-[1,1′-binaphthalene]-2,2′-diol (2.00 g, 2.90 mmol), diiodomethane (2.33 g, 8.71 mmol) and K.sub.2CO.sub.3 (1.73 g, 17.42 mmol) in 50 mL DMF is stirred at 80° C. under nitrogen for 20 h. After cooling to room temperature, the reaction mixture is poured onto water (100 mL) and extracted with MTB ether (200 mL). The organic phase is washed with water (1×100 mL) and dried with NaSO.sub.4. The solvent is removed under reduced pressure and the product is purified by column chromatography (toluene). The racemic product is separated into enantiomers by chiral HPLC on ChiralCel OD-H to give optically active 2,2′-Methylenedioxy-7,7′-bis-[4-(4-propyl-cyclohexyl)phenyl]-[1,1′]binaphthalene as colorless crystals, m.p 125° C.

Example 6: 5-(4-pentylcyclohexyl)-12,15-bis(4-(4-propylcyclohexyl)-phenyl)-5,6-dihydro-4H-dinaphtho[2,1-f:1′,2′-h][1,5]dioxonine

(22) ##STR00244##

(23) From 7,7′-bis(4-(4-propylcyclohexyl)phenyl)-[1,1′-binaphthalene]-2,2′-diol (step 5.2) example 6 is synthesized using the standard procedure SP-1 described above. The racemic product is separated into enantiomers by chiral HPLC on ChiralPak AD-H.

(24) Example 7 (Not in Accordance with the Invention): 2,2′-Methylenedioxy-7,7′-bis-[4-(4-propyl-cyclohexyl)phenyl]-[1,1′]binaphthalene

7.1 7-(4-(4-propylcyclohexyl)phenyl)naphthalen-2-ol

(25) ##STR00245##

(26) A flask is flushed with nitrogen and charged with a mixture of 7-bromo-2-naphthol (10.50 g, 46.6 mmol), (4-(4-propylcyclohexyl)phenyl)boronic acid (13.77 g, 55.92 mmol) and THF (100 mL). Then NaBO.sub.2. 4H.sub.2O (9.83 g, 69.9 mmol), 30 mL water, PdCl.sub.2(PPh.sub.3).sub.2 (1.64 g, 2.33 mmol) and 2-3 drops of hydrazinium hydroxide are added. The mixture is stirred at 60° C. for 5 h. The mixture is cooled to room temperature, diluted with water (250 mL), extracted with MTB ether (300 mL) and filtered through a pad of celite. The organic phases are washed with water (1×100 mL), dried with NaSO.sub.4 and concentrated under reduced pressure. The product is purified by crystallization from heptane/ethyl acetate (10:1).

7.2 7,7′-bis(4-(4-propylcyclohexyl)phenyl)-[1,1′-binaphthalene]-2,2′-diol

(27) ##STR00246##

(28) 7-(4-(4-propylcyclohexyl)phenyl)naphthalen-2-ol (1.00 g, 2.9 mmol) is added to a mixture of CuCl(OH)-TMEDA (14 mg, 0.04 mmol) in CH.sub.2Cl.sub.2 (50 mL) and the whole is stirred at room temperature for 4 h in open air. The solvent is removed under reduced pressure and purified by column chromatography (toluene/ethyl acetate 95:5). Crystallization from a mixture of heptane/ethyl acetate/toluene 5:4:1 gives 7,7′-bis(4-(4-propyl-cyclohexyl)phenyl)-[1,1′-binaphthalene]-2,2′-diol as a white solid.

7.3 2,2′-Methylenedioxy-7,7′-bis-[4-(4-propyl-cyclohexyl)phenyl]-[1,1′]binaphthalene

(29) ##STR00247##

(30) A mixture of 7,7′-bis(4-(4-propylcyclohexyl)phenyl)-[1,1′-binaphthalene]-2,2′-diol (2.00 g, 2.90 mmol), diiodomethane (2.33 g, 8.71 mmol), K.sub.2CO.sub.3 (1.73 g, 17.42 mmol) and 50 mL DMF is stirred at 80° C. under nitrogen for 20 h. After cooling to room temperature, the reaction mixture is poured into water (100 mL) and extracted with MTB ether (200 mL). The organic phase is washed with water (1×100 mL) and dried with NaSO.sub.4. The solvent is removed under reduced pressure and the product is purified by column chromatography (toluene). Crystallization from heptane gives 2,2′-methylenedioxy-7,7′-bis-[4-(4-propyl-cyclohexyl)phenyl]-[1,1′]binaphthalene as a colorless solid. The racemic product is separated into enantiomers by chiral HPLC on ChiralCel OD-H to give optically active 2,2′-Methylenedioxy-7,7′-bis-[4-(4-propyl-cyclohexyl)phenyl]-[1,1′]binaphthalene as colorless solid, mp. 113° C.

(31) From 7,7′-bis(4-(4-propylcyclohexyl)phenyl)-[1,1′-binaphthalene]-2,2′-diol (step 7.2) and according to general procedure SP-1 above, the following examples 8, 9 an 10 are obtained.

(32) ##STR00248##

(33) In analogy to example 1 the compounds of the formula

(34) ##STR00249##

(35) are obtained:

(36) TABLE-US-00007 Example R.sup.11 R.sup.21 R.sup.31 11 H H —CH.sub.3 12 H H —C.sub.2H.sub.5 13 H H n-C.sub.3H.sub.7 14 H H n-C.sub.4H.sub.9 1 H H n-C.sub.5H.sub.11 15 —CH.sub.3 —CH.sub.3 —CH.sub.3 16 —CH.sub.3 —CH.sub.3 —C.sub.2H.sub.5 17 —CH.sub.3 —CH.sub.3 n-C.sub.3H.sub.7 18 —CH.sub.3 —CH.sub.3 n-C.sub.4H.sub.9 19 —CH.sub.3 —CH.sub.3 n-C.sub.5H.sub.11 20 —C.sub.2H.sub.5 —C.sub.2H.sub.5 —CH.sub.3 21 —C.sub.2H.sub.5 —C.sub.2H.sub.5 —C.sub.2H.sub.5 22 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.3H.sub.7 23 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.4H.sub.9 24 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.5H.sub.11 25 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 —CH.sub.3 26 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 —C.sub.2H.sub.5 27 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 28 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.4H.sub.9 29 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.5H.sub.11 30 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 —CH.sub.3 31 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 —C.sub.2H.sub.5 32 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.3H.sub.7 33 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 34 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 35 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 —CH.sub.3 36 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 —C.sub.2H.sub.5 37 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.3H.sub.7 38 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.4H.sub.9 39 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11

(37) In analogy to example 2 the compounds of the formula

(38) ##STR00250##

(39) are obtained:

(40) TABLE-US-00008 Example R.sup.11 R.sup.21 R.sup.31 40 H H —CH.sub.3 41 H H —C.sub.2H.sub.5 2 H H n-C.sub.3H.sub.7 42 H H n-C.sub.4H.sub.9 43 H H n-C.sub.5H.sub.11 44 —CH.sub.3 —CH.sub.3 —CH.sub.3 45 —CH.sub.3 —CH.sub.3 —C.sub.2H.sub.5 46 —CH.sub.3 —CH.sub.3 n-C.sub.3H.sub.7 47 —CH.sub.3 —CH.sub.3 n-C.sub.4H.sub.9 48 —CH.sub.3 —CH.sub.3 n-C.sub.5H.sub.11 49 —C.sub.2H.sub.5 —C.sub.2H.sub.5 —CH.sub.3 50 —C.sub.2H.sub.5 —C.sub.2H.sub.5 —C.sub.2H.sub.5 51 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.3H.sub.7 52 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.4H.sub.9 53 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.5H.sub.11 54 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 —CH.sub.3 55 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 —C.sub.2H.sub.5 56 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 57 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.4H.sub.9 58 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.5H.sub.11 59 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 —CH.sub.3 60 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 —C.sub.2H.sub.5 61 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.3H.sub.7 62 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 63 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 64 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 —CH.sub.3 65 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 —C.sub.2H.sub.5 66 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.3H.sub.7 67 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.4H.sub.9 68 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11

(41) In analogy to example 3 the compounds of the formula

(42) ##STR00251##

(43) are obtained:

(44) TABLE-US-00009 Example R.sup.11 R.sup.21 R.sup.31 69 H H —CH.sub.3 70 H H —C.sub.2H.sub.5 3 H H n-C.sub.3H.sub.7 71 H H n-C.sub.4H.sub.9 72 H H n-C.sub.5H.sub.11 73 —CH.sub.3 —CH.sub.3 —CH.sub.3 74 —CH.sub.3 —CH.sub.3 —C.sub.2H.sub.5 75 —CH.sub.3 —CH.sub.3 n-C.sub.3H.sub.7 76 —CH.sub.3 —CH.sub.3 n-C.sub.4H.sub.9 77 —CH.sub.3 —CH.sub.3 n-C.sub.5H.sub.11 78 —C.sub.2H.sub.5 —C.sub.2H.sub.5 —CH.sub.3 79 —C.sub.2H.sub.5 —C.sub.2H.sub.5 —C.sub.2H.sub.5 80 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.3H.sub.7 81 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.4H.sub.9 82 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.5H.sub.11 83 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 —CH.sub.3 84 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 —C.sub.2H.sub.5 85 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 86 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.4H.sub.9 87 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.5H.sub.11 88 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 —CH.sub.3 89 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 —C.sub.2H.sub.5 90 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.3H.sub.7 91 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 92 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 93 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 —CH.sub.3 94 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 —C.sub.2H.sub.5 95 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.3H.sub.7 96 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.4H.sub.9 97 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11

(45) In analogy to example 4 the compounds of the formula

(46) ##STR00252##

(47) are obtained:

(48) TABLE-US-00010 Example R.sup.11 R.sup.21 R.sup.31 98 H H —CH.sub.3 99 H H —C.sub.2H.sub.5 4 H H n-C.sub.3H.sub.7 100 H H n-C.sub.4H.sub.9 101 H H n-C.sub.5H.sub.11 102 —CH.sub.3 —CH.sub.3 —CH.sub.3 103 —CH.sub.3 —CH.sub.3 —C.sub.2H.sub.5 104 —CH.sub.3 —CH.sub.3 n-C.sub.3H.sub.7 105 —CH.sub.3 —CH.sub.3 n-C.sub.4H.sub.9 106 —CH.sub.3 —CH.sub.3 n-C.sub.5H.sub.11 107 —C.sub.2H.sub.5 —C.sub.2H.sub.5 —CH.sub.3 108 —C.sub.2H.sub.5 —C.sub.2H.sub.5 —C.sub.2H.sub.5 109 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.3H.sub.7 110 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.4H.sub.9 111 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.5H.sub.11 112 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 —CH.sub.3 113 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 —C.sub.2H.sub.5 114 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 115 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.4H.sub.9 116 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.5H.sub.11 117 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 —CH.sub.3 118 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 —C.sub.2H.sub.5 119 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.3H.sub.7 120 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 121 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 122 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 —CH.sub.3 123 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 —C.sub.2H.sub.5 124 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.3H.sub.7 125 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.4H.sub.9 126 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11

(49) In analogy to example 5 the compounds of the formula

(50) ##STR00253##

(51) are obtained:

(52) TABLE-US-00011 Example R.sup.11 R.sup.21 R.sup.31 127 (Not in Accordance with the Invetion) H H H 128 (Not in Accordance with the Invetion) H H —CH.sub.3 129 (Not in Accordance with the Invetion) H H —C.sub.2H.sub.5 130 (Not in Accordance with the Invetion) H H n-C.sub.3H.sub.7 131 (Not in Accordance with the Invetion) H H n-C.sub.4H.sub.9 132 (Not in Accordance with the Invetion) H H n-C.sub.5H.sub.11 133 (Not in Accordance with the Invetion) —CH.sub.3 —CH.sub.3 H 134 (Not in Accordance with the Invetion) —CH.sub.3 —CH.sub.3 —CH.sub.3 135 (Not in Accordance with the Invetion) —CH.sub.3 —CH.sub.3 —C.sub.2H.sub.5 136 (Not in Accordance with the Invetion) —CH.sub.3 —CH.sub.3 n-C.sub.3H.sub.7 137 (Not in Accordance with the Invetion) —CH.sub.3 —CH.sub.3 n-C.sub.4H.sub.9 138 (Not in Accordance with the Invetion) —CH.sub.3 —CH.sub.3 n-C.sub.5H.sub.11 139 (Not in Accordance with the Invetion) —C.sub.2H.sub.5 —C.sub.2H.sub.5 H 140 (Not in Accordance with the Invetion) —C.sub.2H.sub.5 —C.sub.2H.sub.5 —CH.sub.3 141 (Not in Accordance with the Invetion) —C.sub.2H.sub.5 —C.sub.2H.sub.5 —C.sub.2H.sub.5 142 (Not in Accordance with the Invetion) —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.3H.sub.7 143 (Not in Accordance with the Invetion) —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.4H.sub.9 144 (Not in Accordance with the Invetion) —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.5H.sub.11  5 (Not in Accordance with the Invetion) n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 H 145 (Not in Accordance with the Invetion) n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 —CH.sub.3 146 (Not in Accordance with the Invetion) n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 —C.sub.2H.sub.5 147 (Not in Accordance with the Invetion) n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 148 (Not in Accordance with the Invetion) n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.4H.sub.9 149 (Not in Accordance with the Invetion) n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.5H.sub.11 150 (Not in Accordance with the Invetion) n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 H 151 (Not in Accordance with the Invetion) n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 —CH.sub.3 152 (Not in Accordance with the Invetion) n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 —C.sub.2H.sub.5 153 (Not in Accordance with the Invetion) n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.3H.sub.7 154 (Not in Accordance with the Invetion) n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 155 (Not in Accordance with the Invetion) n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 156 (Not in Accordance with the Invetion) n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 H 157 (Not in Accordance with the Invetion) n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 —CH.sub.3 158 (Not in Accordance with the Invetion) n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 —C.sub.2H.sub.5 159 (Not in Accordance with the Invetion) n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.3H.sub.7 160 (Not in Accordance with the Invetion) n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.4H.sub.9 161 (Not in Accordance with the Invetion) n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11

(53) In analogy to example 6 the compounds of the formula

(54) ##STR00254##

(55) are obtained:

(56) TABLE-US-00012 Example R.sup.11 R.sup.21 R.sup.31 162 H H —CH.sub.3 163 H H —C.sub.2H.sub.5 164 H H n-C.sub.3H.sub.7 165 H H n-C.sub.4H.sub.9 166 H H n-C.sub.5H.sub.11 167 —CH.sub.3 —CH.sub.3 —CH.sub.3 168 —CH.sub.3 —CH.sub.3 —C.sub.2H.sub.5 169 —CH.sub.3 —CH.sub.3 n-C.sub.3H.sub.7 170 —CH.sub.3 —CH.sub.3 n-C.sub.4H.sub.9 171 —CH.sub.3 —CH.sub.3 n-C.sub.5H.sub.11 172 —C.sub.2H.sub.5 —C.sub.2H.sub.5 —CH.sub.3 173 —C.sub.2H.sub.5 —C.sub.2H.sub.5 —C.sub.2H.sub.5 174 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.3H.sub.7 175 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.4H.sub.9 176 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.5H.sub.11 177 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 —CH.sub.3 178 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 —C.sub.2H.sub.5 179 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 180 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.4H.sub.9 6 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.5H.sub.11 181 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 —CH.sub.3 182 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 —C.sub.2H.sub.5 183 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.3H.sub.7 184 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 185 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 186 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 —CH.sub.3 187 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 —C.sub.2H.sub.5 188 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.3H.sub.7 189 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.4H.sub.9 190 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11

(57) In analogy to example 7 the compounds of the formula

(58) ##STR00255##

(59) are obtained:

(60) TABLE-US-00013 Example R.sup.11 R.sup.21 R.sup.31 191 (Not in Accordance with the Invetion) H H H 192 (Not in Accordance with the Invetion) H H —CH.sub.3 193 (Not in Accordance with the Invetion) H H —C.sub.2H.sub.5 194 (Not in Accordance with the Invetion) H H n-C.sub.3H.sub.7 195 (Not in Accordance with the Invetion) H H n-C.sub.4H.sub.9 196 (Not in Accordance with the Invetion) H H n-C.sub.5H.sub.11 197 (Not in Accordance with the Invetion) —CH.sub.3 —CH.sub.3 H 198 (Not in Accordance with the Invetion) —CH.sub.3 —CH.sub.3 —CH.sub.3 199 (Not in Accordance with the Invetion) —CH.sub.3 —CH.sub.3 —C.sub.2H.sub.5 200 (Not in Accordance with the Invetion) —CH.sub.3 —CH.sub.3 n-C.sub.3H.sub.7 201 (Not in Accordance with the Invetion) —CH.sub.3 —CH.sub.3 n-C.sub.4H.sub.9 202 (Not in Accordance with the Invetion) —CH.sub.3 —CH.sub.3 n-C.sub.5H.sub.11 203 (Not in Accordance with the Invetion) —C.sub.2H.sub.5 —C.sub.2H.sub.5 H 204 (Not in Accordance with the Invetion) —C.sub.2H.sub.5 —C.sub.2H.sub.5 —CH.sub.3 205 (Not in Accordance with the Invetion) —C.sub.2H.sub.5 —C.sub.2H.sub.5 —C.sub.2H.sub.5 206 (Not in Accordance with the Invetion) —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.3H.sub.7 207 (Not in Accordance with the Invetion) —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.4H.sub.9 208 (Not in Accordance with the Invetion) —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.5H.sub.11  7 (Not in Accordance with the Invetion) n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 H 209 (Not in Accordance with the Invetion) n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 —CH.sub.3 210 (Not in Accordance with the Invetion) n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 —C.sub.2H.sub.5 211 (Not in Accordance with the Invetion) n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 212 (Not in Accordance with the Invetion) n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.4H.sub.9 213 (Not in Accordance with the Invetion) n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.5H.sub.11 214 (Not in Accordance with the Invetion) n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 H 215 (Not in Accordance with the Invetion) n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 —CH.sub.3 216 (Not in Accordance with the Invetion) n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 —C.sub.2H.sub.5 217 (Not in Accordance with the Invetion) n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.3H.sub.7 218 (Not in Accordance with the Invetion) n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 219 (Not in Accordance with the Invetion) n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 220 (Not in Accordance with the Invetion) n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 H 221 (Not in Accordance with the Invetion) n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 —CH.sub.3 222 (Not in Accordance with the Invetion) n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 —C.sub.2H.sub.5 223 (Not in Accordance with the Invetion) n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.3H.sub.7 224 (Not in Accordance with the Invetion) n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.4H.sub.9 225 (Not in Accordance with the Invetion) n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11

(61) In analogy to example 8 the compounds of the formula

(62) ##STR00256##

(63) are obtained

(64) TABLE-US-00014 Example R.sup.11 R.sup.21 R.sup.31 226 H H —CH.sub.3 227 H H —C.sub.2H.sub.5 228 H H n-C.sub.3H.sub.7 229 H H n-C.sub.4H.sub.9 230 H H n-C.sub.5H.sub.11 231 —CH.sub.3 —CH.sub.3 H 232 —CH.sub.3 —CH.sub.3 —CH.sub.3 233 —CH.sub.3 —CH.sub.3 —C.sub.2H.sub.5 234 —CH.sub.3 —CH.sub.3 n-C.sub.3H.sub.7 235 —CH.sub.3 —CH.sub.3 n-C.sub.4H.sub.9 236 —CH.sub.3 —CH.sub.3 n-C.sub.5H.sub.11 237 —C.sub.2H.sub.5 —C.sub.2H.sub.5 H 238 —C.sub.2H.sub.5 —C.sub.2H.sub.5 —CH.sub.3 239 —C.sub.2H.sub.5 —C.sub.2H.sub.5 —C.sub.2H.sub.5 240 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.3H.sub.7 241 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.4H.sub.9 242 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.5H.sub.11 243 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 H 244 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 —CH.sub.3 245 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 —C.sub.2H.sub.5 8 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 246 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.4H.sub.9 247 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.5H.sub.11 248 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 H 249 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 —CH.sub.3 250 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 —C.sub.2H.sub.5 251 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.3H.sub.7 252 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 253 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 254 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 H 255 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 —CH.sub.3 256 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 —C.sub.2H.sub.5 257 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.3H.sub.7 258 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.4H.sub.9 259 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11

(65) In analogy to example 9 the compounds of the formula

(66) ##STR00257##

(67) are obtained.

(68) TABLE-US-00015 Example R.sup.11 R.sup.21 R.sup.31 260 H H —CH.sub.3 261 H H —C.sub.2H.sub.5 262 H H n-C.sub.3H.sub.7 263 H H n-C.sub.4H.sub.9 264 H H n-C.sub.5H.sub.11 265 —CH.sub.3 —CH.sub.3 H 266 —CH.sub.3 —CH.sub.3 —CH.sub.3 267 —CH.sub.3 —CH.sub.3 —C.sub.2H.sub.5 268 —CH.sub.3 —CH.sub.3 n-C.sub.3H.sub.7 269 —CH.sub.3 —CH.sub.3 n-C.sub.4H.sub.9 270 —CH.sub.3 —CH.sub.3 n-C.sub.5H.sub.11 271 —C.sub.2H.sub.5 —C.sub.2H.sub.5 H 272 —C.sub.2H.sub.5 —C.sub.2H.sub.5 —CH.sub.3 273 —C.sub.2H.sub.5 —C.sub.2H.sub.5 —C.sub.2H.sub.5 274 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.3H.sub.7 275 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.4H.sub.9 276 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.5H.sub.11 277 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 H 278 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 —CH.sub.3 279 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 —C.sub.2H.sub.5 9 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 280 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.4H.sub.9 281 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.5H.sub.11 282 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 H 283 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 —CH.sub.3 284 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 —C.sub.2H.sub.5 285 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.3H.sub.7 286 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 287 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 288 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 H 289 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 —CH.sub.3 290 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 —C.sub.2H.sub.5 291 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.3H.sub.7 292 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.4H.sub.9 293 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11

(69) In analogy to example 10 the compounds of the formula

(70) ##STR00258##

(71) are obtained:

(72) TABLE-US-00016 Example R.sup.11* R.sup.21* R.sup.31 294 H H —CH.sub.3 295 H H —C.sub.2H.sub.5 296 H H n-C.sub.3H.sub.7 297 H H n-C.sub.4H.sub.9 298 H H n-C.sub.5H.sub.11 299 —CH.sub.3 —CH.sub.3 H 300 —CH.sub.3 —CH.sub.3 —CH.sub.3 301 —CH.sub.3 —CH.sub.3 —C.sub.2H.sub.5 10 —CH.sub.3 —CH.sub.3 n-C.sub.3H.sub.7 302 —CH.sub.3 —CH.sub.3 n-C.sub.4H.sub.9 303 —CH.sub.3 —CH.sub.3 n-C.sub.5H.sub.11 304 —C.sub.2H.sub.5 —C.sub.2H.sub.5 H 305 —C.sub.2H.sub.5 —C.sub.2H.sub.5 —CH.sub.3 306 —C.sub.2H.sub.5 —C.sub.2H.sub.5 —C.sub.2H.sub.5 307 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.3H.sub.7 308 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.4H.sub.9 309 —C.sub.2H.sub.5 —C.sub.2H.sub.5 n-C.sub.5H.sub.11 310 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 H 311 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 —CH.sub.3 312 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 —C.sub.2H.sub.5 313 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 314 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.4H.sub.9 315 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 n-C.sub.5H.sub.11 316 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 H 317 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 —CH.sub.3 318 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 —C.sub.2H.sub.5 319 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.3H.sub.7 320 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 321 n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 322 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 H 323 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 —CH.sub.3 324 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 —C.sub.2H.sub.5 325 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.3H.sub.7 326 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.4H.sub.9 327 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11 n-C.sub.5H.sub.11

(73) Example 328 (Not in Accordance with the Invention): 2,2′-Methylenedioxy-7-[4-(4-propyl-cyclohexyl)phenyl]-[1,1′]binaphthalene

(74) The starting material, 2,2′-Methylenedioxy-7,7′-dibromo[1,1′]binaphthalene is described in the literature [CAS-No. 263339-97-5].

328.1 2,2′-Methylenedioxy-7-bromo-7′-[4-(4-propyl-cyclohexyl)phenyl]-[1,1′]binaphthalene

(75) ##STR00259##

(76) 7.00 g (15.3 mmol) 2,2′-methylenedioxy-7,7′-dibromo[1,1′]binaphthalene and 4-(4-propyl-cyclohexyl)benzene boronic acid are dissolved in 150 ml of THF and after addition of 3.24 g (23.0 mmol) sodium metaborate-tetrahydrate, 1.08 g (1.54 mmol) bis(triphenylphosphine) palladium(II)chloride and 7 μl of hydrazinium hydrate, the reaction is heated at reflux overnight. The reaction is poured onto water, the aqueous layer is extracted with ether and the combined org. layers are washed with brine and dried over sodium sulfate. The solvent is evaporated and the residue is purified by chromatography to give 2,2′-methylenedioxy-7-bromo-7′-[4-(4-propyl-cyclohexyl)phenyl]-[1,1′]binaphthalene as a colourless solid.

328.2 2,2′-Methylenedioxy-7-[4-(4-propyl-cyclohexyl)phenyl]-[1,1′]binaphthalene

(77) ##STR00260##

(78) 2,2′-Methylenedioxy-7-bromo-7′-[4-(4-propyl-cyclohexyl)phenyl]-[1,1′]binaphthalene is hydrogenated in THF on palladium-C (5%) catalyst until one equivalent of hydrogen is consumed. The catalyst is filtered off, the filtrate is evaporated and the residue is purified by chromatography to give 2,2′-Methylenedioxy-7-[4-(4-propyl-cyclohexyl)phenyl]-[1,1′]binaphthalene as colourless crystals, m.p. 152° C.

2. HTP Measurements

(79) A nematic Host N1 for HTP measurements is prepared as follows

(80) TABLE-US-00017 CPG-3-F 7.50% Clp. 60° C. CPG-5-F 7.50% PZG-2-F 9.50% PZG-2-F 10.00% PGP-2-3 8.00% PGU-2-F 9.00% PGU-3-F 9.00% PGUQU-3-F 9.50% PGUQU-4-F 9.50% PGUQU-5-F 9.50% PUQU-2-F 5.50% PUQU-3-F 5.50%

(81) The HTP values are measured as described above and are listed in table 1.

(82) TABLE-US-00018 TABLE 1 Compound Example HTP [μm.sup.−1] .sup.[1] HTP [μm.sup.−1] .sup.[2] R-5011 c.s. 95 145 1 1 119 N/A 2 2 103 N/A 3 3 100 N/A 4 4 120 N/A 5 5 128 200 6 6 146 271 7 7 141 201 8 8 124 204 9 9 137 220 10 10 129 208 c.s.: comparative substance 1 .sup.[1] measured in MLC-6260 .sup.[2] measured in N1

(83) As shown in table 1, compounds of examples 1 to 10 exhibit significantly higher HTP values than R-5011 from the state of the art.

3. Mixture Examples

Comparative Example 1

(84) A cholesteric mixture C1 contains 96.98% of a nematic component N2:

(85) TABLE-US-00019 TABLE 1 Nematic Host N2 CC-5-O1 7.0% Kp. 86 CCZC-3-3 3.0% CCZC-3-5 3.0% Δn 0.0645 CCZC-4-3 3.0% n.sub.e 1.5325 CCU-2-F 7.0% CCU-3-F 5.0% Δε +10.2 CCZU-2-F 6.0% CCZU-3-F 15.0% CCZU-5-F 6.0% CDU-2-F 9.0% CDU-3-F 9.0% CDU-5-F 16.0% CC-3-T 7.0% CC-5-T 8.0% CCZPC-3-4 3.0% CCZPC-3-3 3.0%

(86) and 3.02% of chiral dopant R-5011 of formula

(87) ##STR00261##

(88) The mixture C1 shows a reflection wavelength of λ=400 nm.

Mixture Example M1

(89) A cholesteric mixture M1 is prepared from nematic host N2 above and the compound of synthesis example 1.

(90) TABLE-US-00020 TABLE 2 Cholesteric mixture M1 Mass % N2 97.59 Example 1 2.41

Mixture Example M2

(91) A cholesteric mixture M2 is prepared from nematic host N2 above and the compound of synthesis example 6.

(92) TABLE-US-00021 TABLE 3 Cholesteric mixture M2 Mass % N2 98.19 Example 6 1.81

Mixture Example M3

(93) A nematic Host N3 is prepared as follows:

(94) TABLE-US-00022 TABLE 4 Nematic Host N3 GUQGU-3-F 8.00% Kp. 72.5 GUQGU-4-F 6.00% GUQGU-5-F 4.00% Δn 0.1929 GUUQU-3-N 6.00% n.sub.e 1.6811 GUQU-3-F 7.00% n.sub.o 1.4882 GUQU-4-F 6.00% GUQGU-2-T 12.00% Δε 202.1 GUQGU-3-T 12.00% ε.sub.∥ 213.6 GUQGU-4-T 12.00% ε.sub.⊥ 11.5 GUQGU-5-T 12.00% DPGU-4-F 8.00% PGU-5-T 3.00% PGU-4-T 4.00%

(95) A Blue Phase mixture M3 is prepared from the nematic host mixture N3 above and the compound of synthesis example 6:

(96) TABLE-US-00023 TABLE 5 Blue Phase mixture M3 Mass % N3 97.2 Example 6 2.8