2,3-dihydrobenzothiophene derivatives

Abstract

The present invention relates to 2,3-dihydrobenzothiophene derivatives of the general formula I ##STR00001## In which the occurring groups and parameters have the meanings indicated in claim 1, to the use thereof in liquid-crystalline or mesogenic media, to liquid-crystalline or mesogenic media comprising these derivatives, and to electro-optical display elements containing these liquid-crystalline or mesogenic media.

Claims

1. A compound of formula I ##STR01047## in which R.sup.11, R.sup.21 and R.sup.22 each, identically or differently, denote H, F, Cl, Br, I, CN, SCN, OH, SF.sub.5, straight chain or branched alkyl with up to 15 C atoms which may be unsubstituted, mono- or polysubstituted by F, Cl, Br, I or CN, one or more non-adjacent CH.sub.2 groups optionally being replaced, in each case independently of one another, by ##STR01048## —O—, —S—, —NH—, —NR.sup.0—, —C(O)—, —C(O)O—, —OC(O)—, —OC(O)O—, —S—C(O)—, —CO—S—, —CH═CH— or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, A.sup.11, A.sup.12 A.sup.21 and A.sup.22 each, independently of one another, denote: a) trans-1,4-cyclohexylene, 1,4-cyclohexenylene, or decaline-2,6-diyl, in which one or more non-adjacent CH.sub.2 groups are optionally replaced by —O— and/or —S— and in which one or more H atoms are optionally replaced by F, b) 1,4-phenylene or 2,6-naphthylene, in which one or two CH groups are optionally replaced by N and in which, in addition, one or more H atoms are optionally replaced by L, c) 1,3-dioxane-2,5-diyl, tetrahydrofuran-2,5-diyl, cyclobutane-1,3-diyl, thiophene-2,5-diyl, selenophene-2,5-diyl, or 1,2,3,4-tetrahydronanaphthaline-2,6-diyl, each of which is optionally mono- or polysubstituted by L, d) bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, or spiro[3.3]heptane-2,6-diyl, in which one or more H atoms is optionally replaced by F L each, identically or differently, denote halogen, cyano, alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl group with 1 to 7 C atoms, wherein one or more H atoms is optionally substituted by F or Cl, Z.sup.11 and Z.sup.12 independently of one another, denote a single bond, —CF.sub.2O—, —OCF.sub.2—, —CH.sub.2CH.sub.2—, —CF.sub.2CF.sub.2—, —C(O)O—, —OC(O)—, —CH.sub.2O—, —OCH.sub.2—, —CF═CH—, —CH═CF—, —CF═CF—, —CH═CH— or —C≡C—, Y denotes H, F, Cl, CF.sub.3, or OCF.sub.3, and m and n are, independently of one another, 0, 1 or 2, with the proviso that at least one of m and n denotes 0.

2. The compound of formula I according to claim 1, wherein the compound is a compound of the sub-formula Ia ##STR01049## in which R.sup.11, A.sup.11, Z.sup.12, R.sup.21, R.sup.22, A.sup.21 and A.sup.22 are as defined in claim 1, and ##STR01050## is trans-1,4-cyclohexylene, 1,4-cyclohexenylene, or decaline-2,6-diyl, in which one or more non-adjacent CH.sub.2 groups is optionally replaced by —O— and/or —S— and in which one or more H atoms is optionally replaced by F.

3. The compound of formula I according to claim 1, where the compound is selected a compound of the sub-formula Ib ##STR01051## in which R.sup.11, A.sup.11, Z.sup.12, R.sup.21, R.sup.22, A.sup.21 and A.sup.22 are as defined in claim 1, and ##STR01052## is 1,4-phenylene or 2,6-naphthylene, in which one or two CH groups are optionally replaced by N and in which, in addition, one or more H atoms are optionally replaced by F, Cl or CF.sub.3.

4. The compound of formula I according to claim 1, wherein Z.sup.11 and Z.sup.12 denote a single bond.

5. The compound of formula I according to claim 1, of the sub-formulae ##STR01053## ##STR01054## ##STR01055## wherein R.sup.11, R.sup.21, R.sup.22, Y, A.sup.21 and A.sup.22 have the meanings indicated in claim 1.

6. The compound of formula I according to claim 1, of the sub-formulae ##STR01056## ##STR01057## ##STR01058## ##STR01059## ##STR01060## ##STR01061## wherein R.sup.11, R.sup.21, R.sup.22, Y, A.sup.21 and A.sup.22 have the meanings indicated in claim 1.

7. The compound of formula I according to claim 1 wherein ##STR01062## independently of one another, are 1,4-phenylene or 2,6-naphthylene, in which one or two CH groups are optionally replaced by N and in which, in addition, one or more H atoms may be replaced by F, Cl or CF.sub.3.

8. The compound according to claim 1, wherein Y denotes F.

9. The compound according to claim 1, wherein R.sup.11 denotes H, alkyl, alkenyl or alkoxy having up to 7 C atoms, and in which one or more H atoms is optionally replaced by fluorine, and R.sup.21 and R.sup.22, independently of one another, denote H, alkyl, alkenyl or alkoxy having up to 7 C atoms, F, Cl, CN, SCN, SF.sub.5, CF.sub.3, OCF.sub.3, OCF.sub.2H, OCHF.sub.2, or —OCH═CF.sub.2.

10. A process for the preparation of compounds of formula I according to claim 1, comprising hydrogenating in the presence of a catalyst a compound of formula II ##STR01063## in which R.sup.11, A.sup.11, Z.sup.12, R.sup.21, R.sup.22, A.sup.21 and A.sup.22 are as defined in claim 1.

11. A liquid-crystalline medium comprising two or more liquid-crystalline compounds, comprising one or more compounds according to claim 1.

12. An electro-optical display element containing a liquid-crystalline medium according to claim 11.

Description

EXAMPLES

Example 1: 7-Fluoro-6-butoxy-2-(4-propylcyclohexyl)-2,3-dihydrobenzothiophene

(1) Step 1:

(2) ##STR00034##

(3) A solution of BuLi (15% in hexane, 140 mL, 0.219 mol) is added dropwise to a stirred solution of 1-butoxy-2,3-difluorobenzene (40.0 g, 0.215 mol) in THF (160 mL) at −70° C. The mixture is stirred for 30 min at the same temperature before it is treated with a solution of N-formylpiperidine (24.5 mL, 0.221 mol) in THF (80 mL). The reaction mixture is allowed to warm to −30° C., treated with water and conc. HCl (until pH 6). The aqueous phase is separated and extracted with MTB ether (2 times). The combined organic phase is washed with water, dried over Na.sub.2SO.sub.4, filtered and concentrated in vacuo. The residue was purified by flash chromatography (heptane/ethyl acetate) to give 4-butoxy-2,3-difluoro-benzaldehyde as a colorless oil

(4) Step 2:

(5) ##STR00035##

(6) A solution of methyl mercaptoacetate (12.2 mL, 133.2 mmol) in trimethylamine (60 mL, 433.0 mmol) is added to a stirred solution of 4-butoxy-2,3-difluoro-benzaldehyde (26.0 g, 121.4 mmol) in DMSO (200 mL) at room temperature. The reaction mixture is stirred for 2 h at 80° C. before it is cooled to ambient temperature, quenched with ice water and stirred for 1 h. The precipitate is filtered off and washed with cold water to give methyl 6-butoxy-7-fluoro-benzothiophene-2-carboxylate as yellow crystals.

(7) Step 3:

(8) ##STR00036##

(9) A suspension of methyl 7-fluoro-6-methyl-benzothiophene-2-carboxylate (31.0 g, 109.8 mmol) in methanol (200 mL) and THF (100 mL) is treated with NaOH solution (2 N, 150 mL, 300 mmol). The reaction mixture is stirred at 40° C. for 4 h, poured onto ice and acidified with aq. HCl (2N, until pH 3). The precipitate is filtered off and washed with water to give 6-butoxy-7-fluoro-benzothiophene-2-carboxylic acid as colourless crystals.

(10) Step 4:

(11) ##STR00037##

(12) A suspension of 6-butoxy-7-fluoro-benzothiophene-2-carboxylic acid (30.0 g, 111.8 mmol) and copper powder (2.3 g, 36.9 mmol) in Quinoline (130 mL) is stirred for 2 h at 185° C. The resulted mixture is treated with 2N HCl solution (until pH 2), and extracted with ethyl acetate. The organic phase is dried over Na.sub.2SO.sub.4, filtered and concentrated under reduced pressure. The residue is filtered through a short pad of silica with n-heptane and concentrated under reduced pressure to give 6-butoxy-7-fluoro-benzothiophene as a colorless oil.

(13) Step 5:

(14) ##STR00038##

(15) A solution of BuLi (15% in hexane, 30.8 mL, 49.0 mmol) is added dropwise to a solution of 6-butoxy-7-fluoro-benzothiophene (10.0 g, 44.5 mmol) in THF (40 mL) at −70° C. The mixture is stirred for 1 h at the same temperature before a solution of 4-propylcyclohexanone (7.5 g, 53.5 mmol) in THF (10 mL) is added. The reaction mixture is stirred for 1 h at −70° C. before it is allowed to warm to room temperature, quenched with sat. ammonium chloride solution, extracted with MTB ether, dried over Na.sub.2SO.sub.4, filtered and concentrated under reduced pressure.

(16) The residue is purified by flash-chromatography to give the intermediate adduct as a brownish oil, which was dissolved in toluene (270 mL) and was heated under reflux in a Dean-Stark condenser in the presence of p-toluene sulfonic acid (0.6 g, 3.2 mmol). After 3 h, the reaction mixture is concentrated under reduced pressure and purified by flash chromatography to give 6-butoxy-7-fluoro-2-(4-propylcyclohexen-1-yl)benzothiophene as colourless crystals.

(17) .sup.1H NMR: 0.91 (t, J=7.1 Hz, 3H), 0.98 (t, J=7.4 Hz, 3H), 1.66-1.24 (m, 8H), 1.95-1.74 (m, 4H), 2.58-2.26 (m, 3H), 4.08 (t, J=6.5 Hz, 2H), 6.21 (dt, J=5.1, 2.4 Hz, 1H), 7.01-6.94 (m, 2H), 7.29 (dd, J=8.6, 0.8 Hz, 1H); EI-MS: 346.3

(18) Phase sequence: K 78 SmX 79 N 100.5 I

(19) Δε: −3.6

(20) Δn: 0.1858

(21) CIp.: 140° C.

(22) Step 6:

(23) ##STR00039##

(24) A solution of 6-butoxy-7-fluoro-2-(4-propylcyclohexen-1-yl)benzothiophene (4.0 g, 11.5 mmol) in toluene (40 mL) is catalytically hydrogenated (110° C., 147 bar) for 18 h. The reaction mixture is concentrated under reduced pressure and purified by flash chromatography, followed by crystallization from ethanol to give 6-butoxy-7-fluoro-2-(4-propylcyclohexyl)benzothiophene as colourless crystals.

(25) .sup.1H NMR: 0.84 (t, J=6.8 Hz, 3H), 0.92 (t, J=7.4 Hz, 3H), 1.30-1.18 (m, 4H), 1.62-1.38 (m, 7H), 1.90-1.69 (m, 6H), 2.98 (dtd, J=7.6, 4.9, 4.2, 2.8 Hz, 1H), 4.04 (t, J=6.6 Hz, 2H), 6.88 (dd, J=3.8, 1.3 Hz, 1H), 6.97 (dd, J=8.5, 7.6 Hz, 1H), 7.26 (dd, J=8.5, 0.8 Hz, 1H); .sup.19F NMR: −136.5 (m, 1F); EI-MS: 348.2.

(26) Phase sequence: K 37 N 84.9 I

(27) Δε: −3.3

(28) Δn: 0.1327

(29) CIp.: 106° C.

(30) Step 7:

(31) ##STR00040##

(32) In a 35 mL Schlenk tube, equipped with a magnetic stir bar, is placed [Ru(cod)(2-methylallyl).sub.2] (24.0 mg, 0.07 mmol), 1,3-dicyclohexylimidazolium chloride (45.0 mg, 0.15 mmol) and dry potassium tert-butylate (25.1 mg, 0.22 mmol). The mixture is dissolved in toluene (20 mL) and stirred at 70° C. for 16 h under argon atmosphere. Then the solution is transferred under argon to an autoclave containing the 6-butoxy-7-fluoro-2-(4-propylcyclohexyl)-2,3-dihydrobenzothiophene (0.26 g, 0.75 mmol) and a magnetic stirring bar. The autoclave is carefully pressurized/depressurized with hydrogen gas three times before the reaction pressure of 90 bar hydrogen is adjusted. The hydrogenation is performed at 70° C. for 20 h. The reaction mixture is concentrated under reduced pressure and purified by flash chromatography (heptane/chlorobutane), followed by recrystallization from heptane to give 6-butoxy-7-fluoro-2-(4-propylcyclohexyl)-2,3-dihydrobenzothiophene as colourless crystals.

(33) .sup.1H NMR: 1.24-0.83 (m, 13H), 1.30 (h, J=7.2 Hz, 2H), 1.63-1.42 (m, 3H), 1.89-1.71 (m, 6H), 3.03 (ddd, J=15.3, 9.0, 1.2 Hz, 1H), 3.27 (dd, J=15.2, 7.7 Hz, 1H), 3.80 (dt, J=9.1, 7.8 Hz, 1H), 3.98 (t, J=6.5 Hz, 2H), 6.58 (t, J=7.9 Hz, 1H), 6.77 (dd, J=8.1, 1.1 Hz, 1H); .sup.19F NMR: -135.0 (d, J=7.7 Hz, 1F); EI-MS: 350.2.

(34) Phase sequence: K 84 SmA (72) I

(35) Δε: −6.3

(36) Δn: 0.1131

(37) CIp: 75.4° C.

Example 2

(38) ##STR00041##

(39) Phase sequence: Tg −24 K 58 I

(40) Δε: −3.9

(41) Δn: 0.0349

(42) CIp.: −170° C.

(43) γ.sub.1: 85 mPas

Example 3

(44) ##STR00042##

(45) Phase sequence: Tg −73 K 33 I

(46) Δε: −4.6

(47) Δn: 0.0353

(48) CIp.: −119° C.

(49) γ.sub.1: 34 mPas

Example 4

(50) ##STR00043##

(51) Phase sequence: K 106 I

(52) Δε: −6.8

(53) Δn: 0.0651

(54) CIp.: −25.6° C.

(55) γ.sub.1: 255 mPa s

(56) (extrapolated from 5% in ZLI-4792 or ZLI-2857)

Example 5

(57) ##STR00044##

(58) Phase sequence: K 93 I

Example 6

(59) ##STR00045##

(60) Phase sequence: K 49 I

(61) Δε: −6.6

(62) Δn: 0.1110

(63) CIp.: −1.7° C.

(64) γ.sub.1: 467 mPa s

(65) (extrapolated from 5% in ZLI-4792 or ZLI-2857)

(66) In analogy to example 1 are obtained

(67) ##STR00046##

(68) TABLE-US-00001 No. R.sup.11 A.sup.11 A.sup.12 Y R.sup.21 R.sup.22 1 C.sub.2H.sub.5— — F —OCH.sub.3 H 2 C.sub.2H.sub.5— — F —OC.sub.2H.sub.5 H 3 C.sub.2H.sub.5— — F —OC.sub.3H.sub.9 H 4 C.sub.2H.sub.5— — 0 F —OC.sub.4H.sub.12 H 5 C.sub.3H.sub.7— — F —OCH.sub.3 H 6 C.sub.3H.sub.7— — F —OC.sub.2H.sub.5 H 7 C.sub.3H.sub.7— — F —OC.sub.3H.sub.7 H 8 C.sub.3H.sub.7— — F —OC.sub.4H.sub.9 H 9 C.sub.4H.sub.9— — F —OCH.sub.3 H 10 C.sub.4H.sub.9— — F —OC.sub.2H.sub.5 H 11 C.sub.4H.sub.9— — F —OC.sub.3H.sub.7 H 12 C.sub.4H.sub.9— — F —OC.sub.4H.sub.9 H 13 C.sub.5H.sub.12— — F —OCH.sub.3 H 14 C.sub.5H.sub.12— — 0 F —OC.sub.2H.sub.5 H 15 C.sub.5H.sub.12— — F —OC.sub.3H.sub.7 H 16 C.sub.5H.sub.12— — F —OC.sub.4H.sub.9 H 17 C.sub.2H.sub.5— — F —OCH.sub.3 H 18 C.sub.2H.sub.5— — F —OC.sub.2H.sub.5 H 19 C.sub.2H.sub.5— — F —OC.sub.3H.sub.9 H 20 C.sub.2H.sub.5— — F —OC.sub.4H.sub.12 H 21 C.sub.3H.sub.7— — F —OCH.sub.3 H 22 C.sub.3H.sub.7— — F —OC.sub.2H.sub.5 H 23 C.sub.3H.sub.7— — F —OC.sub.3H.sub.7 H 24 C.sub.3H.sub.7— — 0 F —OC.sub.4H.sub.9 H 25 C.sub.4H.sub.9— — F —OCH.sub.3 H 26 C.sub.4H.sub.9— — F —OC.sub.2H.sub.5 H 27 C.sub.4H.sub.9— — F —OC.sub.3H.sub.7 H 28 C.sub.4H.sub.9— — F —OC.sub.4H.sub.9 H 29 C.sub.5H.sub.12— — F —OCH.sub.3 H 30 C.sub.5H.sub.12— — F —OC.sub.2H.sub.5 H 31 C.sub.5H.sub.12— — F —OC.sub.3H.sub.7 H 32 C.sub.5H.sub.12— — F —OC.sub.4H.sub.9 H 33 C.sub.2H.sub.5— 0 F —OCH.sub.3 H 34 C.sub.2H.sub.5— F —OC.sub.2H.sub.5 H 35 C.sub.2H.sub.5— F —OC.sub.3H.sub.9 H 36 C.sub.2H.sub.5— F —OC.sub.4H.sub.12 H 37 C.sub.3H.sub.7— F —OCH.sub.3 H 38 C.sub.3H.sub.7— 0 F —OC.sub.2H.sub.5 H 39 C.sub.3H.sub.7— F —OC.sub.3H.sub.7 H 40 C.sub.3H.sub.7— F —OC.sub.4H.sub.9 H 41 C.sub.4H.sub.9— F —OCH.sub.3 H 42 C.sub.4H.sub.9— F —OC.sub.2H.sub.5 H 43 C.sub.4H.sub.9— 00 F —OC.sub.3H.sub.7 H 44 C.sub.4H.sub.9— 01 02 F —C.sub.4H.sub.9 H 45 C.sub.5H.sub.12— 03 04 F —OCH.sub.3 H 46 C.sub.5H.sub.12— 05 06 F —OC.sub.2H.sub.5 H 47 C.sub.5H.sub.12— 07 08 F —OC.sub.3H.sub.7 H 48 C.sub.5H.sub.12— 09 0 F —OC.sub.4H.sub.9 H 49 C.sub.2H.sub.5— F —OCH.sub.3 H 50 C.sub.2H.sub.5— F —OC.sub.2H.sub.5 H 51 C.sub.2H.sub.5— F —OC.sub.3H.sub.9 H 52 C.sub.2H.sub.5— F —OC.sub.4H.sub.12 H 53 C.sub.3H.sub.7— 0 F —OCH.sub.3 H 54 C.sub.3H.sub.7— F —OC.sub.2H.sub.5 H 55 C.sub.3H.sub.7— F —OC.sub.3H.sub.7 H 56 C.sub.3H.sub.7— F —OC.sub.4H.sub.9 H 57 C.sub.4H.sub.9— F —OCH.sub.3 H 58 C.sub.4H.sub.9— 0 F —OC.sub.2H.sub.5 H 59 C.sub.4H.sub.9— F —OC.sub.3H.sub.7 H 60 C.sub.4H.sub.9— F —OC.sub.4H.sub.9 H 61 C.sub.5H.sub.12— F —OCH.sub.3 H 62 C.sub.5H.sub.12— F —OC.sub.2H.sub.5 H 63 C.sub.5H.sub.12— 0 F —OC.sub.3H.sub.7 H 64 C.sub.5H.sub.12— F —OC.sub.4H.sub.9 H 65 C.sub.2H.sub.5— — F F H 66 C.sub.2H.sub.5— — F F F 67 C.sub.2H.sub.5— — F F —CH.sub.3 68 C.sub.2H.sub.5— — F F —C.sub.2H.sub.5 69 C.sub.2H.sub.5— — F F —C.sub.3H.sub.7 70 C.sub.2H.sub.5— — F F —OCH.sub.3 71 C.sub.2H.sub.5— — F F —OC.sub.2H.sub.5 72 C.sub.2H.sub.5— — 0 F F —OC.sub.3H.sub.7 73 C.sub.2H.sub.5— — F F —OC.sub.4H.sub.9 74 C.sub.3H.sub.7— — F F H 75 C.sub.3H.sub.7— — F F F 76 C.sub.3H.sub.7— — F F —CH.sub.3 77 C.sub.3H.sub.7— — F F —C.sub.2H.sub.5 78 C.sub.3H.sub.7— — F F —C.sub.3H.sub.7 79 C.sub.3H.sub.7— — F F —OCH.sub.3 80 C.sub.3H.sub.7— — F F —OC.sub.2H.sub.5 81 C.sub.3H.sub.7— — F F —OC.sub.3H.sub.7 82 C.sub.3H.sub.7— — 0 F F —OC.sub.4H.sub.9 83 C.sub.4H.sub.9— — F F H 84 C.sub.4H.sub.9— — F F F 85 C.sub.4H.sub.9— — F F —CH.sub.3 86 C.sub.4H.sub.9— — F F —C.sub.2H.sub.5 87 C.sub.4H.sub.9— — F F —C.sub.3H.sub.7 88 C.sub.4H.sub.9— — F F —OCH.sub.3 89 C.sub.4H.sub.9— — F F —OC.sub.2H.sub.5 90 C.sub.4H.sub.9— — F F —OC.sub.3H.sub.7 91 C.sub.4H.sub.9— — F F —OC.sub.4H.sub.9 92 C.sub.5H.sub.12— — 0 F F H 93 C.sub.5H.sub.12— — F F F 94 C.sub.5H.sub.12— — F F —CH.sub.3 95 C.sub.5H.sub.12— — F F —C.sub.2H.sub.5 96 C.sub.5H.sub.12— — F F —C.sub.3H.sub.7 97 C.sub.5H.sub.12— — F F —OCH.sub.3 98 C.sub.5H.sub.12— — F F —OC.sub.2H.sub.5 99 C.sub.5H.sub.12— — F F —OC.sub.3H.sub.7 100 C.sub.5H.sub.12— — F F —OC.sub.4H.sub.9 101 C.sub.2H.sub.5— — F F H 102 C.sub.2H.sub.5— — 0 F F F 103 C.sub.2H.sub.5— — F F —CH.sub.3 104 C.sub.2H.sub.5— — F F —C.sub.2H.sub.5 105 C.sub.2H.sub.5— — F F —C.sub.3H.sub.7 106 C.sub.2H.sub.5— — F F —OCH.sub.3 107 C.sub.2H.sub.5— — F F —OC.sub.2H.sub.5 108 C.sub.2H.sub.5— — F F —OC.sub.3H.sub.7 109 C.sub.2H.sub.5— — F F —OC.sub.4H.sub.9 110 C.sub.3H.sub.7— — F F H 111 C.sub.3H.sub.7— — F F F 112 C.sub.3H.sub.7— — 0 F F —CH.sub.3 113 C.sub.3H.sub.7— — F F —C.sub.2H.sub.5 114 C.sub.3H.sub.7— — F F —C.sub.3H.sub.7 115 C.sub.3H.sub.7— — F F —OCH.sub.3 116 C.sub.3H.sub.7— — F F —OC.sub.2H.sub.5 117 C.sub.3H.sub.7— — F F —OC.sub.3H.sub.7 118 C.sub.3H.sub.7— — F F —OC.sub.4H.sub.9 119 C.sub.4H.sub.9— — F F H 120 C.sub.4H.sub.9— — F F F 121 C.sub.4H.sub.9— — F F —CH.sub.3 122 C.sub.4H.sub.9— — 00 F F —C.sub.2H.sub.5 123 C.sub.4H.sub.9— — 01 F F —C.sub.3H.sub.7 124 C.sub.4H.sub.9— — 02 F F —OCH.sub.3 125 C.sub.4H.sub.9— — 03 F F —OC.sub.2H.sub.5 126 C.sub.4H.sub.9— — 04 F F —OC.sub.3H.sub.7 127 C.sub.4H.sub.9— — 05 F F —OC.sub.4H.sub.9 128 C.sub.5H.sub.12— — 06 F F H 129 C.sub.5H.sub.12— — 07 F F F 130 C.sub.5H.sub.12— — 08 F F —CH.sub.3 131 C.sub.5H.sub.12— — 09 F F —C.sub.2H.sub.5 132 C.sub.5H.sub.12— — 0 F F —C.sub.3H.sub.7 133 C.sub.5H.sub.12— — F F —OCH.sub.3 134 C.sub.5H.sub.12— — F F —OC.sub.2H.sub.5 135 C.sub.5H.sub.12— — F F —OC.sub.3H.sub.7 136 C.sub.5H.sub.12— — F F —OC.sub.4H.sub.9 137 C.sub.2H.sub.5— F F H 138 C.sub.2H.sub.5— F F F 139 C.sub.2H.sub.5— 0 F F —CH.sub.3 140 C.sub.2H.sub.5— F F —C.sub.2H.sub.5 141 C.sub.2H.sub.5— F F —C.sub.3H.sub.7 142 C.sub.2H.sub.5— F F —OCH.sub.3 143 C.sub.2H.sub.5— F F —OC.sub.2H.sub.5 144 C.sub.2H.sub.5— 0 F F —OC.sub.3H.sub.7 145 C.sub.2H.sub.5— F F —OC.sub.4H.sub.9 146 C.sub.3H.sub.7— F F H 147 C.sub.3H.sub.7— F F F 148 C.sub.3H.sub.7— F F —CH.sub.3 149 C.sub.3H.sub.7— 0 F F —C.sub.2H.sub.5 150 C.sub.3H.sub.7— F F —C.sub.3H.sub.7 151 C.sub.3H.sub.7— F F —OCH.sub.3 152 C.sub.3H.sub.7— F F —OC.sub.2H.sub.5 153 C.sub.3H.sub.7— F F —OC.sub.3H.sub.7 154 C.sub.3H.sub.7— 0 F F —OC.sub.4H.sub.9 155 C.sub.4H.sub.9— F F H 156 C.sub.4H.sub.9— F F F 157 C.sub.4H.sub.9— F F —CH.sub.3 158 C.sub.4H.sub.9— F F —C.sub.2H.sub.5 159 C.sub.4H.sub.9— 0 F F —C.sub.3H.sub.7 160 C.sub.4H.sub.9— F F —OCH.sub.3 161 C.sub.4H.sub.9— F F —OC.sub.2H.sub.5 162 C.sub.4H.sub.9— F F —OC.sub.3H.sub.7 163 C.sub.4H.sub.9— F F —OC.sub.4H.sub.9 164 C.sub.5H.sub.12— 0 F F H 165 C.sub.5H.sub.12— F F F 166 C.sub.5H.sub.12— F F —CH.sub.3 167 C.sub.5H.sub.12— F F —C.sub.2H.sub.5 168 C.sub.5H.sub.12— F F —C.sub.3H.sub.7 169 C.sub.5H.sub.12— 0 F F —OCH.sub.3 170 C.sub.5H.sub.12— F F —OC.sub.2H.sub.5 171 C.sub.5H.sub.12— F F —OC.sub.3H.sub.7 172 C.sub.5H.sub.12— F F —OC.sub.4H.sub.9 173 C.sub.2H.sub.5— F F H 174 C.sub.2H.sub.5— 0 F F F 175 C.sub.2H.sub.5— F F —CH.sub.3 176 C.sub.2H.sub.5— F F —C.sub.2H.sub.5 177 C.sub.2H.sub.5— F F —C.sub.3H.sub.7 178 C.sub.2H.sub.5— F F —OCH.sub.3 179 C.sub.2H.sub.5— 00 F F —OC.sub.2H.sub.5 180 C.sub.2H.sub.5— 01 02 F F —OC.sub.3H.sub.7 181 C.sub.2H.sub.5— 03 04 F F —OC.sub.4H.sub.9 182 C.sub.3H.sub.7— 05 06 F F H 183 C.sub.3H.sub.7— 07 08 F F F 184 C.sub.3H.sub.7— 09 0 F F —CH.sub.3 185 C.sub.3H.sub.7— F F —C.sub.2H.sub.5 186 C.sub.3H.sub.7— F F —C.sub.3H.sub.7 187 C.sub.3H.sub.7— F F —OCH.sub.3 188 C.sub.3H.sub.7— F F —OC.sub.2H.sub.5 189 C.sub.3H.sub.7— 0 F F —OC.sub.3H.sub.7 190 C.sub.3H.sub.7— F F —OC.sub.4H.sub.9 191 C.sub.4H.sub.9— F F H 192 C.sub.4H.sub.9— F F F 193 C.sub.4H.sub.9— F F —CH.sub.3 194 C.sub.4H.sub.9— 0 F F —C.sub.2H.sub.5 195 C.sub.4H.sub.9— F F —C.sub.3H.sub.7 196 C.sub.4H.sub.9— F F —OCH.sub.3 197 C.sub.4H.sub.9— F F —OC.sub.2H.sub.5 198 C.sub.4H.sub.9— F F —OC.sub.3H.sub.7 199 C.sub.4H.sub.9— 0 F F —OC.sub.4H.sub.9 200 C.sub.5H.sub.12— F F H 201 C.sub.5H.sub.12— F F F 202 C.sub.5H.sub.12— F F —CH.sub.3 203 C.sub.5H.sub.12— F F —C.sub.2H.sub.5 204 C.sub.5H.sub.12— 0 F F —C.sub.3H.sub.7 205 C.sub.5H.sub.12— F F —OCH.sub.3 206 C.sub.5H.sub.12— F F —OC.sub.2H.sub.5 207 C.sub.5H.sub.12— F F —OC.sub.3H.sub.7 208 C.sub.5H.sub.12— F F —OC.sub.4H.sub.9 209 C.sub.2H.sub.5— — F —OCH.sub.3 H 210 C.sub.2H.sub.5— — 0 F —OC.sub.2H.sub.5 H 211 C.sub.2H.sub.5— — F —OC.sub.3H.sub.9 H 212 C.sub.2H.sub.5— — F —OC.sub.4H.sub.12 H 213 C.sub.3H.sub.7— — F —OCH.sub.3 H 214 C.sub.3H.sub.7— — F —OC.sub.2H.sub.5 H 215 C.sub.3H.sub.7— — F —OC.sub.3H.sub.7 H 216 C.sub.3H.sub.7— — F —OC.sub.4H.sub.9 H 217 C.sub.4H.sub.9— — F —OCH.sub.3 H 218 C.sub.4H.sub.9— — F —OC.sub.2H.sub.5 H 219 C.sub.4H.sub.9— — F —OC.sub.3H.sub.7 H 220 C.sub.4H.sub.9— — 0 F —OC.sub.4H.sub.9 H 221 C.sub.5H.sub.12— — F —OCH.sub.3 H 222 C.sub.5H.sub.12— — F —OC.sub.2H.sub.5 H 223 C.sub.5H.sub.12— — F —OC.sub.3H.sub.7 H 224 C.sub.5H.sub.12— — F —OC.sub.4H.sub.9 H 225 C.sub.2H.sub.5— — F —OCH.sub.3 H 226 C.sub.2H.sub.5— — F —OC.sub.2H.sub.5 H 227 C.sub.2H.sub.5— — F —OC.sub.3H.sub.9 H 228 C.sub.2H.sub.5— — F —OC.sub.4H.sub.12 H 229 C.sub.3H.sub.7— — F —OCH.sub.3 H 230 C.sub.3H.sub.7— — 0 F —OC.sub.2H.sub.5 H 231 C.sub.3H.sub.7— — F —OC.sub.3H.sub.7 H 232 C.sub.3H.sub.7— — F —OC.sub.4H.sub.9 H 233 C.sub.4H.sub.9— — F —OCH.sub.3 H 234 C.sub.4H.sub.9— — F —OC.sub.2H.sub.5 H 235 C.sub.4H.sub.9— — F —OC.sub.3H.sub.7 H 236 C.sub.4H.sub.9— — F —OC.sub.4H.sub.9 H 237 C.sub.5H.sub.12— — F —OCH.sub.3 H 238 C.sub.5H.sub.12— — F —OC.sub.2H.sub.5 H 239 C.sub.5H.sub.12— — F —OC.sub.3H.sub.7 H 240 C.sub.5H.sub.12— — 0 F —OC.sub.4H.sub.9 H 241 C.sub.2H.sub.5— — F —OCH.sub.3 H 242 C.sub.2H.sub.5— — F —OC.sub.2H.sub.5 H 243 C.sub.2H.sub.5— — F —OC.sub.3H.sub.9 H 244 C.sub.2H.sub.5— — F —OC.sub.4H.sub.12 H 245 C.sub.3H.sub.7— — F —OCH.sub.3 H 246 C.sub.3H.sub.7— — F —OC.sub.2H.sub.5 H 247 C.sub.3H.sub.7— — F —OC.sub.3H.sub.7 H 248 C.sub.3H.sub.7— — F —OC.sub.4H.sub.9 H 249 C.sub.4H.sub.9— — F —OCH.sub.3 H 250 C.sub.4H.sub.9— — 00 F —OC.sub.2H.sub.5 H 251 C.sub.4H.sub.9— — 01 F —OC.sub.3H.sub.7 H 252 C.sub.4H.sub.9— — 02 F —OC.sub.4H.sub.9 H 253 C.sub.5H.sub.12— — 03 F —OCH.sub.3 H 254 C.sub.5H.sub.12— — 04 F —OC.sub.2H.sub.5 H 255 C.sub.5H.sub.12— — 05 F —OC.sub.3H.sub.7 H 256 C.sub.5H.sub.12— — 06 F —OC.sub.4H.sub.9 H 257 C.sub.2H.sub.5— — 07 F —OCH.sub.3 H 258 C.sub.2H.sub.5— — 08 F —OC.sub.2H.sub.5 H 259 C.sub.2H.sub.5— — 09 F —OC.sub.3H.sub.9 H 260 C.sub.2H.sub.5— — 0 F —OC.sub.4H.sub.12 H 261 C.sub.3H.sub.7— — F —OCH.sub.3 H 262 C.sub.3H.sub.7— — F —OC.sub.2H.sub.5 H 263 C.sub.3H.sub.7— — F —OC.sub.3H.sub.7 H 264 C.sub.3H.sub.7— — F —OC.sub.4H.sub.9 H 265 C.sub.4H.sub.9— — F —OCH.sub.3 H 266 C.sub.4H.sub.9— — F —OC.sub.2H.sub.5 H 267 C.sub.4H.sub.9— — F —OC.sub.3H.sub.7 H 268 C.sub.4H.sub.9— — F —OC.sub.4H.sub.9 H 269 C.sub.5H.sub.12— — F —OCH.sub.3 H 270 C.sub.5H.sub.12— — 0 F —OC.sub.2H.sub.5 H 271 C.sub.5H.sub.12— — F —OC.sub.3H.sub.7 H 272 C.sub.5H.sub.12— — F —OC.sub.4H.sub.9 H 273 C.sub.2H.sub.5— — F —OCH.sub.3 H 274 C.sub.2H.sub.5— — F —OC.sub.2H.sub.5 H 275 C.sub.2H.sub.5— — F —OC.sub.3H.sub.9 H 276 C.sub.2H.sub.5— — F —OC.sub.4H.sub.12 H 277 C.sub.3H.sub.7— — F —OCH.sub.3 H 278 C.sub.3H.sub.7— — F —OC.sub.2H.sub.5 H 279 C.sub.3H.sub.7— — F —OC.sub.3H.sub.7 H 280 C.sub.3H.sub.7— — 0 F —OC.sub.4H.sub.9 H 281 C.sub.4H.sub.9— — F —OCH.sub.3 H 282 C.sub.4H.sub.9— — F —OC.sub.2H.sub.5 H 283 C.sub.4H.sub.9— — F —OC.sub.3H.sub.7 H 284 C.sub.4H.sub.9— — F —OC.sub.4H.sub.9 H 285 C.sub.5H.sub.12— — F —OCH.sub.3 H 286 C.sub.5H.sub.12— — F —OC.sub.2H.sub.5 H 287 C.sub.5H.sub.12— — F —OC.sub.3H.sub.7 H 288 C.sub.5H.sub.12— — F —OC.sub.4H.sub.9 H 289 C.sub.2H.sub.5— — F —OCH.sub.3 H 290 C.sub.2H.sub.5— — 0 F —OC.sub.2H.sub.5 H 291 C.sub.2H.sub.5— — F —OC.sub.3H.sub.9 H 292 C.sub.2H.sub.5— — F —OC.sub.4H.sub.12 H 293 C.sub.3H.sub.7— — F —OCH.sub.3 H 294 C.sub.3H.sub.7— — F —OC.sub.2H.sub.5 H 295 C.sub.3H.sub.7— — F —OC.sub.3H.sub.7 H 296 C.sub.3H.sub.7— — F —OC.sub.4H.sub.9 H 297 C.sub.4H.sub.9— — F —OCH.sub.3 H 298 C.sub.4H.sub.9— — F —OC.sub.2H.sub.5 H 299 C.sub.4H.sub.9— — F —OC.sub.3H.sub.7 H 300 C.sub.4H.sub.9— — 0 F —OC.sub.4H.sub.9 H 301 C.sub.5H.sub.12— — F —OCH.sub.3 H 302 C.sub.5H.sub.12— — F —OC.sub.2H.sub.5 H 303 C.sub.5H.sub.12— — F —OC.sub.3H.sub.7 H 304 C.sub.5H.sub.12— — F —OC.sub.4H.sub.9 H 305 C.sub.2H.sub.5— — F —OCH.sub.3 H 306 C.sub.2H.sub.5— — F —OC.sub.2H.sub.5 H 307 C.sub.2H.sub.5— — F —OC.sub.3H.sub.9 H 308 C.sub.2H.sub.5— — F —OC.sub.4H.sub.12 H 309 C.sub.3H.sub.7— — F —OCH.sub.3 H 310 C.sub.3H.sub.7— — 0 F —OC.sub.2H.sub.5 H 311 C.sub.3H.sub.7— — F —OC.sub.3H.sub.7 H 312 C.sub.3H.sub.7— — F —OC.sub.4H.sub.9 H 313 C.sub.4H.sub.9— — F —OCH.sub.3 H 314 C.sub.4H.sub.9— — F —OC.sub.2H.sub.5 H 315 C.sub.4H.sub.9— — F —OC.sub.3H.sub.7 H 316 C.sub.4H.sub.9— — F —OC.sub.4H.sub.9 H 317 C.sub.5H.sub.12— — F —OCH.sub.3 H 318 C.sub.5H.sub.12— — F —OC.sub.2H.sub.5 H 319 C.sub.5H.sub.12— — F —OC.sub.3H.sub.7 H 320 C.sub.5H.sub.12— — 0 F —OC.sub.4H.sub.9 H 321 C.sub.2H.sub.5— F —OCH.sub.3 H 322 C.sub.2H.sub.5— F —OC.sub.2H.sub.5 H 323 C.sub.2H.sub.5— F —OC.sub.3H.sub.9 H 324 C.sub.2H.sub.5— F —OC.sub.4H.sub.12 H 325 C.sub.3H.sub.7— 0 F —OCH.sub.3 H 326 C.sub.3H.sub.7— F —OC.sub.2H.sub.5 H 327 C.sub.3H.sub.7— F —OC.sub.3H.sub.7 H 328 C.sub.3H.sub.7— F —OC.sub.4H.sub.9 H 329 C.sub.4H.sub.9— F —OCH.sub.3 H 330 C.sub.4H.sub.9— 0 F —OC.sub.2H.sub.5 H 331 C.sub.4H.sub.9— F —OC.sub.3H.sub.7 H 332 C.sub.4H.sub.9— F —OC.sub.4H.sub.9 H 333 C.sub.5H.sub.12— F —OCH.sub.3 H 334 C.sub.5H.sub.12— F —OC.sub.2H.sub.5 H 335 C.sub.5H.sub.12— 00 F —OC.sub.3H.sub.7 H 336 C.sub.5H.sub.12— 01 02 F —OC.sub.4H.sub.9 H 337 C.sub.2H.sub.5— 03 04 F —OCH.sub.3 H 338 C.sub.2H.sub.5— 05 06 F —OC.sub.2H.sub.5 H 339 C.sub.2H.sub.5— 07 08 F —OC.sub.3H.sub.9 H 340 C.sub.2H.sub.5— 09 0 F —OC.sub.4H.sub.12 H 341 C.sub.3H.sub.7— F —OCH.sub.3 H 342 C.sub.3H.sub.7— F —OC.sub.2H.sub.5 H 343 C.sub.3H.sub.7— F —OC.sub.3H.sub.7 H 344 C.sub.3H.sub.7— F —OC.sub.4H.sub.9 H 345 C.sub.4H.sub.9— 0 F —OCH.sub.3 H 346 C.sub.4H.sub.9— F —OC.sub.2H.sub.5 H 347 C.sub.4H.sub.9— F —OC.sub.3H.sub.7 H 348 C.sub.4H.sub.9— F —OC.sub.4H.sub.9 H 349 C.sub.5H.sub.12— F —OCH.sub.3 H 350 C.sub.5H.sub.12— 0 F —OC.sub.2H.sub.5 H 351 C.sub.5H.sub.12— F —OC.sub.3H.sub.7 H 352 C.sub.5H.sub.12— F —OC.sub.4H.sub.9 H 353 C.sub.2H.sub.5— F —OCH.sub.3 H 354 C.sub.2H.sub.5— F —OC.sub.2H.sub.5 H 355 C.sub.2H.sub.5— 0 F —OC.sub.3H.sub.9 H 356 C.sub.2H.sub.5— F —OC.sub.4H.sub.12 H 357 C.sub.3H.sub.7— F —OCH.sub.3 H 358 C.sub.3H.sub.7— F —OC.sub.2H.sub.5 H 359 C.sub.3H.sub.7— F —OC.sub.3H.sub.7 H 360 C.sub.3H.sub.7— 0 F —OC.sub.4H.sub.9 H 361 C.sub.4H.sub.9— F —OCH.sub.3 H 362 C.sub.4H.sub.9— F —OC.sub.2H.sub.5 H 363 C.sub.4H.sub.9— F —OC.sub.3H.sub.7 H 364 C.sub.4H.sub.9— F —OC.sub.4H.sub.9 H 365 C.sub.5H.sub.12— 0 F —OCH.sub.3 H 366 C.sub.5H.sub.12— F —OC.sub.2H.sub.5 H 367 C.sub.5H.sub.12— F —OC.sub.3H.sub.7 H 368 C.sub.5H.sub.12— F —OC.sub.4H.sub.9 H 369 C.sub.2H.sub.5— F —OCH.sub.3 H 370 C.sub.2H.sub.5— 0 F —OC.sub.2H.sub.5 H 371 C.sub.2H.sub.5— F —OC.sub.3H.sub.9 H 372 C.sub.2H.sub.5— F —OC.sub.4H.sub.12 H 373 C.sub.3H.sub.7— F —OCH.sub.3 H 374 C.sub.3H.sub.7— F —OC.sub.2H.sub.5 H 375 C.sub.3H.sub.7— 0 F —OC.sub.3H.sub.7 H 376 C.sub.3H.sub.7— F —OC.sub.4H.sub.9 H 377 C.sub.4H.sub.9— F —OCH.sub.3 H 378 C.sub.4H.sub.9— F —OC.sub.2H.sub.5 H 379 C.sub.4H.sub.9— F —OC.sub.3H.sub.7 H 380 C.sub.4H.sub.9— 0 F —OC.sub.4H.sub.9 H 381 C.sub.5H.sub.12— F —OCH.sub.3 H 382 C.sub.5H.sub.12— F —OC.sub.2H.sub.5 H 383 C.sub.5H.sub.12— F —OC.sub.3H.sub.7 H 384 C.sub.5H.sub.12— F —OC.sub.4H.sub.9 H 385 C.sub.2H.sub.5— 00 F —OCH.sub.3 H 386 C.sub.2H.sub.5— 01 02 F —OC.sub.2H.sub.5 H 387 C.sub.2H.sub.5— 03 04 F —OC.sub.3H.sub.9 H 388 C.sub.2H.sub.5— 05 06 F —OC.sub.4H.sub.12 H 389 C.sub.3H.sub.7— 07 08 F —OCH.sub.3 H 390 C.sub.3H.sub.7— 09 0 F —OC.sub.2H.sub.5 H 391 C.sub.3H.sub.7— F —OC.sub.3H.sub.7 H 392 C.sub.3H.sub.7— F —OC.sub.4H.sub.9 H 393 C.sub.4H.sub.9— F —OCH.sub.3 H 394 C.sub.4H.sub.9— F —OC.sub.2H.sub.5 H 395 C.sub.4H.sub.9— 0 F —OC.sub.3H.sub.7 H 396 C.sub.4H.sub.9— F —OC.sub.4H.sub.9 H 397 C.sub.5H.sub.12— F —OCH.sub.3 H 398 C.sub.5H.sub.12— F —OC.sub.2H.sub.5 H 399 C.sub.5H.sub.12— F —OC.sub.3H.sub.7 H 400 C.sub.5H.sub.12— 0 F —OC.sub.4H.sub.9 H 401 C.sub.2H.sub.5— F —OCH.sub.3 H 402 C.sub.2H.sub.5— F —OC.sub.2H.sub.5 H 403 C.sub.2H.sub.5— F —OC.sub.3H.sub.9 H 404 C.sub.2H.sub.5— F —OC.sub.4H.sub.12 H 405 C.sub.3H.sub.7— 0 F —OCH.sub.3 H 406 C.sub.3H.sub.7— F —OC.sub.2H.sub.5 H 407 C.sub.3H.sub.7— F —OC.sub.3H.sub.7 H 408 C.sub.3H.sub.7— F —OC.sub.4H.sub.9 H 409 C.sub.4H.sub.9— F —OCH.sub.3 H 410 C.sub.4H.sub.9— 0 F —OC.sub.2H.sub.5 H 411 C.sub.4H.sub.9— F —OC.sub.3H.sub.7 H 412 C.sub.4H.sub.9— F —OC.sub.4H.sub.9 H 413 C.sub.5H.sub.12— F —OCH.sub.3 H 414 C.sub.5H.sub.12— F —OC.sub.2H.sub.5 H 415 C.sub.5H.sub.12— 0 F —OC.sub.3H.sub.7 H 416 C.sub.5H.sub.12— F —OC.sub.4H.sub.9 H 417 C.sub.2H.sub.5— F —OCH.sub.3 H 418 C.sub.2H.sub.5— F —OC.sub.2H.sub.5 H 419 C.sub.2H.sub.5— F —OC.sub.3H.sub.9 H 420 C.sub.2H.sub.5— 0 F —OC.sub.4H.sub.12 H 421 C.sub.3H.sub.7— F —OCH.sub.3 H 422 C.sub.3H.sub.7— F —OC.sub.2H.sub.5 H 423 C.sub.3H.sub.7— F —OC.sub.3H.sub.7 H 424 C.sub.3H.sub.7— F —OC.sub.4H.sub.9 H 425 C.sub.4H.sub.9— 0 F —OCH.sub.3 H 426 C.sub.4H.sub.9— F —OC.sub.2H.sub.5 H 427 C.sub.4H.sub.9— F —OC.sub.3H.sub.7 H 428 C.sub.4H.sub.9— F —OC.sub.4H.sub.9 H 429 C.sub.5H.sub.12— F —OCH.sub.3 H 430 C.sub.5H.sub.12— 0 F —OC.sub.2H.sub.5 H 431 C.sub.5H.sub.12— F —OC.sub.3H.sub.7 H 432 C.sub.5H.sub.12— F —OC.sub.4H.sub.9 H 433 C.sub.2H.sub.5— F —OCH.sub.3 H 434 C.sub.2H.sub.5— F —OC.sub.2H.sub.5 H 435 C.sub.2H.sub.5— 00 F —OC.sub.3H.sub.9 H 436 C.sub.2H.sub.5— 01 02 F —OC.sub.4H.sub.12 H 437 C.sub.3H.sub.7— 03 04 F —OCH.sub.3 H 438 C.sub.3H.sub.7— 05 06 F —OC.sub.2H.sub.5 H 439 C.sub.3H.sub.7— 07 08 F —OC.sub.3H.sub.7 H 440 C.sub.3H.sub.7— 09 0 F —OC.sub.4H.sub.9 H 441 C.sub.4H.sub.9— F —OCH.sub.3 H 442 C.sub.4H.sub.9— F —OC.sub.2H.sub.5 H 443 C.sub.4H.sub.9— F —OC.sub.3H.sub.7 H 444 C.sub.4H.sub.9— F —OC.sub.4H.sub.9 H 445 C.sub.5H.sub.12— 0 F —OCH.sub.3 H 446 C.sub.5H.sub.12— F —OC.sub.2H.sub.5 H 447 C.sub.5H.sub.12— F —OC.sub.3H.sub.7 H 448 C.sub.5H.sub.12— F —OC.sub.4H.sub.9 H 449 C.sub.2H.sub.5— F —OCH.sub.3 H 450 C.sub.2H.sub.5— 0 F —OC.sub.2H.sub.5 H 451 C.sub.2H.sub.5— F —OC.sub.3H.sub.9 H 452 C.sub.2H.sub.5— F —OC.sub.4H.sub.12 H 453 C.sub.3H.sub.7— F —OCH.sub.3 H 454 C.sub.3H.sub.7— F —OC.sub.2H.sub.5 H 455 C.sub.3H.sub.7— 0 F —OC.sub.3H.sub.7 H 456 C.sub.3H.sub.7— F —OC.sub.4H.sub.9 H 457 C.sub.4H.sub.9— F —OCH.sub.3 H 458 C.sub.4H.sub.9— F —OC.sub.2H.sub.5 H 459 C.sub.4H.sub.9— F —OC.sub.3H.sub.7 H 460 C.sub.4H.sub.9— 0 F —OC.sub.4H.sub.9 H 461 C.sub.5H.sub.12— F —OCH.sub.3 H 462 C.sub.5H.sub.12— F —OC.sub.2H.sub.5 H 463 C.sub.5H.sub.12— F —OC.sub.3H.sub.7 H 464 C.sub.5H.sub.12— F —OC.sub.4H.sub.9 H 465 C.sub.2H.sub.5— 0 F —OCH.sub.3 H 466 C.sub.2H.sub.5— F —OC.sub.2H.sub.5 H 467 C.sub.2H.sub.5— F —OC.sub.3H.sub.9 H 468 C.sub.2H.sub.5— F —OC.sub.4H.sub.12 H 469 C.sub.3H.sub.7— F —OCH.sub.3 H 470 C.sub.3H.sub.7— 0 F —OC.sub.2H.sub.5 H 471 C.sub.3H.sub.7— F —OC.sub.3H.sub.7 H 472 C.sub.3H.sub.7— F —OC.sub.4H.sub.9 H 473 C.sub.4H.sub.9— F —OCH.sub.3 H 474 C.sub.4H.sub.9— F —OC.sub.2H.sub.5 H 475 C.sub.4H.sub.9— 0 F —OC.sub.3H.sub.7 H 476 C.sub.4H.sub.9— F —OC.sub.4H.sub.9 H 477 C.sub.5H.sub.12— F —OCH.sub.3 H 478 C.sub.5H.sub.12— F —OC.sub.2H.sub.5 H 479 C.sub.5H.sub.12— F —OC.sub.3H.sub.7 H 480 C.sub.5H.sub.12— 0 F —OC.sub.4H.sub.9 H 481 C.sub.2H.sub.5— F —OCH.sub.3 H 482 C.sub.2H.sub.5— F —OC.sub.2H.sub.5 H 483 C.sub.2H.sub.5— F —OC.sub.3H.sub.9 H 484 C.sub.2H.sub.5— F —OC.sub.4H.sub.12 H 485 C.sub.3H.sub.7— 00 F —OCH.sub.3 H 486 C.sub.3H.sub.7— 01 02 F —OC.sub.2H.sub.5 H 487 C.sub.3H.sub.7— 03 04 F —OC.sub.3H.sub.7 H 488 C.sub.3H.sub.7— 05 06 F —OC.sub.4H.sub.9 H 489 C.sub.4H.sub.9— 07 08 F —OCH.sub.3 H 490 C.sub.4H.sub.9— 09 0 F —OC.sub.2H.sub.5 H 491 C.sub.4H.sub.9— F —OC.sub.3H.sub.7 H 492 C.sub.4H.sub.9— F —OC.sub.4H.sub.9 H 493 C.sub.5H.sub.12— F —OCH.sub.3 H 494 C.sub.5H.sub.12— F —OC.sub.2H.sub.5 H 495 C.sub.5H.sub.12— 0 F —OC.sub.3H.sub.7 H 496 C.sub.5H.sub.12— F —OC.sub.4H.sub.9 H 497 C.sub.2H.sub.5— F —OCH.sub.3 H 498 C.sub.2H.sub.5— F —OC.sub.2H.sub.5 H 499 C.sub.2H.sub.5— F —OC.sub.3H.sub.9 H 500 C.sub.2H.sub.5— 0 F —OC.sub.4H.sub.12 H 501 C.sub.3H.sub.7— F —OCH.sub.3 H 502 C.sub.3H.sub.7— F —OC.sub.2H.sub.5 H 503 C.sub.3H.sub.7— F —OC.sub.3H.sub.7 H 504 C.sub.3H.sub.7— F —OC.sub.4H.sub.9 H 505 C.sub.4H.sub.9— 0 F —OCH.sub.3 H 506 C.sub.4H.sub.9— F —OC.sub.2H.sub.5 H 507 C.sub.4H.sub.9— F —OC.sub.3H.sub.7 H 508 C.sub.4H.sub.9— F —OC.sub.4H.sub.9 H 509 C.sub.5H.sub.12— F —OCH.sub.3 H 510 C.sub.5H.sub.12— 0 F —OC.sub.2H.sub.5 H 511 C.sub.5H.sub.12— F —OC.sub.3H.sub.7 H 512 C.sub.5H.sub.12— F —OC.sub.4H.sub.9 H 513 C.sub.2H.sub.5— F —OCH.sub.3 H 514 C.sub.2H.sub.5— F —OC.sub.2H.sub.5 H 515 C.sub.2H.sub.5— 0 F —OC.sub.3H.sub.9 H 516 C.sub.2H.sub.5— F —OC.sub.4H.sub.12 H 517 C.sub.3H.sub.7— F —OCH.sub.3 H 518 C.sub.3H.sub.7— F —OC.sub.2H.sub.5 H 519 C.sub.3H.sub.7— F —OC.sub.3H.sub.7 H 520 C.sub.3H.sub.7— 0 F —OC.sub.4H.sub.9 H 521 C.sub.4H.sub.9— F —OCH.sub.3 H 522 C.sub.4H.sub.9— F —OC.sub.2H.sub.5 H 523 C.sub.4H.sub.9— F —OC.sub.3H.sub.7 H 524 C.sub.4H.sub.9— F —OC.sub.4H.sub.9 H 525 C.sub.5H.sub.12— 0 F —OCH.sub.3 H 526 C.sub.5H.sub.12— F —OC.sub.2H.sub.5 H 527 C.sub.5H.sub.12— F —OC.sub.3H.sub.7 H 528 C.sub.5H.sub.12— F —OC.sub.4H.sub.9 H 529 C.sub.2H.sub.5— F —OCH.sub.3 H 530 C.sub.2H.sub.5— 0 F —OC.sub.2H.sub.5 H 531 C.sub.2H.sub.5— F —OC.sub.3H.sub.9 H 532 C.sub.2H.sub.5— F —OC.sub.4H.sub.12 H 533 C.sub.3H.sub.7— F —OCH.sub.3 H 534 C.sub.3H.sub.7— F —OC.sub.2H.sub.5 H 535 C.sub.3H.sub.7— 00 F —OC.sub.3H.sub.7 H 536 C.sub.3H.sub.7— 01 02 F —OC.sub.4H.sub.9 H 537 C.sub.4H.sub.9— 03 04 F —OCH.sub.3 H 538 C.sub.4H.sub.9— 05 06 F —OC.sub.2H.sub.5 H 539 C.sub.4H.sub.9— 07 08 F —OC.sub.3H.sub.7 H 540 C.sub.4H.sub.9— 09 0 F —OC.sub.4H.sub.9 H 541 C.sub.5H.sub.12— F —OCH.sub.3 H 542 C.sub.5H.sub.12— F —OC.sub.2H.sub.5 H 543 C.sub.5H.sub.12— F —OC.sub.3H.sub.7 H 544 C.sub.5H.sub.12— F —OC.sub.4H.sub.9 H 545 C.sub.2H.sub.5— 0 F —OCH.sub.3 H 546 C.sub.2H.sub.5— F —OC.sub.2H.sub.5 H 547 C.sub.2H.sub.5— F —OC.sub.3H.sub.9 H 548 C.sub.2H.sub.5— F —OC.sub.4H.sub.12 H 549 C.sub.3H.sub.7— F —OCH.sub.3 H 550 C.sub.3H.sub.7— 0 F —OC.sub.2H.sub.5 H 551 C.sub.3H.sub.7— F —OC.sub.3H.sub.7 H 552 C.sub.3H.sub.7— F —OC.sub.4H.sub.9 H 553 C.sub.4H.sub.9— F —OCH.sub.3 H 554 C.sub.4H.sub.9— F —OC.sub.2H.sub.5 H 555 C.sub.4H.sub.9— 0 F —OC.sub.3H.sub.7 H 556 C.sub.4H.sub.9— F —OC.sub.4H.sub.9 H 557 C.sub.5H.sub.12— F —OCH.sub.3 H 558 C.sub.5H.sub.12— F —OC.sub.2H.sub.5 H 559 C.sub.5H.sub.12— F —OC.sub.3H.sub.7 H 560 C.sub.5H.sub.12— 0 F —OC.sub.4H.sub.9 H 561 C.sub.2H.sub.5— F —OCH.sub.3 H 562 C.sub.2H.sub.5— F —OC.sub.2H.sub.5 H 563 C.sub.2H.sub.5— F —OC.sub.3H.sub.9 H 564 C.sub.2H.sub.5— F —OC.sub.4H.sub.12 H 565 C.sub.3H.sub.7— 0 F —OCH.sub.3 H 566 C.sub.3H.sub.7— F —OC.sub.2H.sub.5 H 567 C.sub.3H.sub.7— F —OC.sub.3H.sub.7 H 568 C.sub.3H.sub.7— F —OC.sub.4H.sub.9 H 569 C.sub.4H.sub.9— F —OCH.sub.3 H 570 C.sub.4H.sub.9— 0 F —OC.sub.2H.sub.5 H 571 C.sub.4H.sub.9— F —OC.sub.3H.sub.7 H 572 C.sub.4H.sub.9— F —OC.sub.4H.sub.9 H 573 C.sub.5H.sub.12— F —OCH.sub.3 H 574 C.sub.5H.sub.12— F —OC.sub.2H.sub.5 H 575 C.sub.5H.sub.12— 0 F —OC.sub.3H.sub.7 H 576 C.sub.5H.sub.12— F —OC.sub.4H.sub.9 H 577 C.sub.2H.sub.5— F —OCH.sub.3 H 578 C.sub.2H.sub.5— F —OC.sub.2H.sub.5 H 579 C.sub.2H.sub.5— F —OC.sub.3H.sub.9 H 580 C.sub.2H.sub.5— 0 F —OC.sub.4H.sub.12 H 581 C.sub.3H.sub.7— F —OCH.sub.3 H 582 C.sub.3H.sub.7— F —OC.sub.2H.sub.5 H 583 C.sub.3H.sub.7— F —OC.sub.3H.sub.7 H 584 C.sub.3H.sub.7— F —OC.sub.4H.sub.9 H 585 C.sub.4H.sub.9— 000 F —OCH.sub.3 H 586 C.sub.4H.sub.9— 001 002 F —OC.sub.2H.sub.5 H 587 C.sub.4H.sub.9— 003 004 F —OC.sub.3H.sub.7 H 588 C.sub.4H.sub.9— 005 006 F —OC.sub.4H.sub.9 H 589 C.sub.5H.sub.12— 007 008 F —OCH.sub.3 H 590 C.sub.5H.sub.12— 009 010 F —OC.sub.2H.sub.5 H 591 C.sub.5H.sub.12— 011 012 F —OC.sub.3H.sub.7 H 592 C.sub.5H.sub.12— 013 014 F —OC.sub.4H.sub.9 H 593 C.sub.2H.sub.5— 015 016 F —OCH.sub.3 H 594 C.sub.2H.sub.5— 017 018 F —OC.sub.2H.sub.5 H 595 C.sub.2H.sub.5— 019 020 F —OC.sub.3H.sub.9 H 596 C.sub.2H.sub.5— 021 022 F —OC.sub.4H.sub.12 H 597 C.sub.3H.sub.7— 023 024 F —OCH.sub.3 H 598 C.sub.3H.sub.7— 025 026 F —OC.sub.2H.sub.5 H 599 C.sub.3H.sub.7— 027 028 F —OC.sub.3H.sub.7 H 600 C.sub.3H.sub.7— 029 030 F —OC.sub.4H.sub.9 H 601 C.sub.4H.sub.9— 031 032 F —OCH.sub.3 H 602 C.sub.4H.sub.9— 033 034 F —OC.sub.2H.sub.5 H 603 C.sub.4H.sub.9— 035 036 F —OC.sub.3H.sub.7 H 604 C.sub.4H.sub.9— 037 038 F —OC.sub.4H.sub.9 H 605 C.sub.5H.sub.12— 039 040 F —OCH.sub.3 H 606 C.sub.5H.sub.12— 041 042 F —OC.sub.2H.sub.5 H 607 C.sub.5H.sub.12— 043 044 F —OC.sub.3H.sub.7 H 608 C.sub.5H.sub.12— 045 046 F —OC.sub.4H.sub.9 H

(69) The compounds are distinguished by a high negative dielectric anisotropy and high clearing temperatures which makes them very suitable for applications in liquid crystalline media for VA, IPS and FFS displays.