DD146041A1 - PROCESS FOR PREPARING CRYSTALLINE LIQUID 4-STROKE BRANCHES ON TRANS-4-N-ALKYLCYCLOHEXANOYLOXY SQUARE BRACKETS FOR TRANS-N-ALKYLCYCLOHEXANES BZW.4-SQUARE BRACKET ON TRANS-4-N-ALKYLCYCLOHEXANOYLOXY CORNER BRACKET CLOSED TO 3-SUBST. -BENZOYLOXY- SQUARE BRACKET ON TRANS-4-N-ALKYLCYCLOHEXANES SQUARE BRACKET CLOSED - Google Patents

Abstract

The invention relates to a process for the preparation of crystalline-liquid 4-trans-4-n-alkylcyclohexanoyloxy! -Trans-n-alkylcyclohexanes or 4-trans-4-n-alkylcyclohexanoyloxy! -3-subst.-benzoyloxy- & trans-4- n-alkylcyclohexanes !, which are suitable for use in electro-optical components. The aim of the invention is the preparation of new crystalline liquid substances. It was found that 4- & trans-4-n-alkylcyclohexanoyloxy! -Trans-n-alkylcyclohexanes and 4- & trans-4-n-alkylcyclohexanoyloxy! -3-subst.-benzoyloxy & trans-4-n-alkylcyclohexanes, respectively, can be prepared are by esterification of trans-4-n-Alkylcyclohexancarbonsaeurechloriden and 4- & trans-4-n-alkyl-cyclohexanoyloxy! -3-subst.-benzoesaeurechloriden with trans-4-n-alkylcyclohexanols in a dry organic base, preferably pyridine or quinoline , at temperatures between 0 and 60 degrees C, preferably room temperature, according to the general scheme (see back page).

Description

1-57 4

Method: 2. Preparation of Crystalline-liquid 4- / txans ^ 4-n-alkylcyclolexanoylos: yJ7-tl ⁿ -n-alkylC3ΓClo hexanes and 4~ / ~ trans-4 ~ n ~ alkylQyGlohexanoyloxy_7-3, respectively ~ subst ~ ~ ben2; oyloxy ~ ^ ~ trans ~ 4-n-alkyloyelohexaneiiJ7 ^r

Anjwenchingsgebiet the JBrfind ung

The invention "relates to a process for the preparation of crystalline-liquid. 4 -" "trans-4-n-alkyloyelohexanoyloxy-7-trans-n-alkyl-cyanohexanes or 4-tert-4-alkylcyclohexanoyloxy-7-3-subst. benaoyloxy- ^ trans-4 * -n ~ alkylcyolohexane__7 of the general formula

Ε ¹ - ^> - ί C00 - ^ - Vc00- / ff> -E ²

where R ¹ = ⁰ ^ _{2n +} I ^r3 = ^E f ^CH 3 » ^C 2 ^H 5» ^{Cli B} ' ^£

with 1 β 0, i

m, η = 1 to 10 * The substances are suitable for use in optoelectronic components because of their favorable properties . «

The compounds mentioned above are new. "Accordingly, there can be no known processes for their preparation"

'} /, o; -i -iQ 7 Q .j. Hello

Object of the invention

The aim of the invention is the preparation of new crystalline liquid substances. ,

Presentation of the essence s th e invention

The invention is based on the object, an entanglement for the preparation of new crystalline liquid 4-π ~ trans-4 ~ n-AlkylGyolohexanoyloxy ^ trans-n-alkyloyolohexanen "or 4-2r" trans-4 ~ n-AlkyloyololiexanoyloxyJ7 "~ 3-substbenzoyloxy- ^ ~ trans-4 ~ n ~ alkylcyolohexanen7 to find.

It was found that 4- / ~~ trans ~ 4 - n-Alkylcyclohexanoyloxy ^ trans-n-alkylcyclohexane or A - / _ trans-4-n-Alkyloyclohexanoyloxy.J ^ -3-s ubs t · benzoyloxy trans-4-n-alkylcyclohexanes can be prepared by esterifying trans ~ 4-n-alkylcyclohexanecarboxylic acid chlorides or 4 ~ / 3-trans-4-n-alkylcyclohexanoyloxy_ _< 7 ~ 3-substituted benzoyl chlorides rait trans-4- n-Alkylcyclohexanolen in a dry organic base, preferably pyridine or quinoline, at temperatures zviisohen 0 and 60 °, preferably room temperature, according to the general scheme:

COO-R

- C

Cl

+ HO-

⁵ '

"obel

^{E C} ra ^H 2rn-i-1 R ³ _B H, CH ₅ ,

Cl, - Br

With

1 «Ö, 1 m _s u « = 1 Ms 10

example 1

Dax position of the trans - ^ - n-alkylcyclohexanols The preparation is carried out by. Hydrogenation of the 4-n-alkylphenols and subsequent separation of the ice / trans isomer mixture * a) Hydrogenation of the 4-n-alkylphenols • 75 g (0.5 mmol) of 4-n-butylphenol in 200 ml of absolute ethanol. are shaken with 10 g of Raney® cocaine in an autoclave at 16O ⁰ C and 120 at hydrogen pressure (measured at room temperature) until the calculated Druokahfa.il has been reached within 1 h 1.5 h. After filtering off the catalyst and screening the solvent, the mixture is fractionated in a water-jet vacuum, removing unhydrogenated and partially hydrogenated constituents. Yield: $ 90 of theory. The remaining 4-n-alkylcyclohexanols are obtained by the same process.

R

Boiling point at mm Hg

₃ 173 745

Q ₄ H ₉ '114 11

C ₅ H ₁₁ 131 17

b) Separation of the Eis ™ and Txans ~ 4 ~ n ~ alkylcyclohexanols

78 g _(0? 5 mol) of the obtained at aer hydrogenation isomer mixture of 4-n-Butylcyclohexanols in pyridine under Rübren und'Eiskühlung with the equimolar amount of 3,5-Dinitrobeniaö.ylohlorid% ^r ersetato The batch is 1 1/2 h cooked on a water bath and left overnight. Then you pour. the mixture on ice and säv.ert with .. concentrated sulfuric acid on »The extracted product

U -4-

becomes

washed with dilute sodium bicarbonate solution, water, dilute hydrochloric acid, and again with water. The pure trans-4-n-alkyloylohexyl ester is obtained by recrystallization from a ^constant point of methanol (about 5 ×). 3.5 ~ dinitrobenzoic acid-trans-4 ~ methylcyclohe: xyl-ester F 141 ⁰ C.

3.5 ~ 3> ini tr tozoic acid e-trans -4-n-butylcyclohexyl ester F: 115 ⁰ C

NaOH saponification of trans-4-n-Alkyloyolohexylesters with 20 proz, met hanoiischer KOH v, the corresponding alcohol is isolated by steam distillation and fractionated. Yield: 25 # of the / ore ore.

Λ $ trans-4-methylcyclohexanoli Kp *. 78 ⁰ C / 12 mm Hg trans-4-n-Butylcyclohexanöl t Kp: 107 ⁰ C / 9 mm Hg

Variant 2

When in terms of yields the cheapest, most efficient method of isomer separation of 4-n ~ alkylcyclohexanols, the fractional distillation proved via a rotating band column. The column had 55 theoretical plates. At a reflux ratio of 1 ^Σ 250 and a column load of 1 ml / min, we took 50 drops per hour.

as

Compilation of boiling temperatures of the 4-n-alkylcyclohexanols in the distillation via the rotating band column

Temperature ( ⁰ )

Pressure assignment of stereoisomers (Torr) (by H NMR spectroscopy

^ -n- butylcyclohexanol; 61 0.35

64.5 0.3.8

69.5 to 70

0.45

4-n- amylcyclohexanol 10 77.5 0.8

80-80.5 0.7

85

0.85

isomer

approx. 50: 50 (estimated) trans

isomer

about 50 5 50 (estimated) trana

With this method of isomer separation, it was possible to produce larger amounts of pure trans compounds. The

Evidence for the purity of the stereoisomers was given by 1 H NMR spectroscopy.

EXAMPLE

Preparation of the 4 - / * trans - 4 - n-alkylcyclohexanoyloxy-3- J- 3-benzoic acid chlorides

The preparation of these compounds is carried out in three stages according to the scheme: 0

HO

Jr

CHO

3

a) Preparation of the 4 ~ / ~ trans ~ 4- ~ n ~ butyloyclohexanoyl ~ oxyJ7-bensaldehyde s

12.2 g (0.1 mol) of 4-hydroxybenzaldehyde is dissolved with 50 ml of 2N sodium hydroxide solution in 150 ml of acetone. * A solution of 20.3 g (0.1 mol) trans-4-n is added dropwise thereto at room temperature. Butylcyclohexanecarbonyl chloride in 50 ml of aoeton. After 2 hours, 350 ml of water are added, whereby the substituted benzaldehyde is precipitated. The resulting crude product is further worked up to the acid without purification.

b) Preparation of the A - / _ trans-4-n-butylcyciohexanoyloxy_7-benzoic acid

The resulting crude substituted benzaldehyde is dissolved in 70 ml of 90% ethanol. To this mixture, a solution of 19 g CrO ^ in 38 ml of 60 $ acetic acid is added dropwise at room temperature.

Then it is stirred for 12 hours at 40 ⁰ C, 200 ml of water are added, sucks off the precipitated substituted benzoic acid, trooknet and crystallized from a.Methanol / ethanol mixture to.

Yield? 80 ^c fa theory.

o) Preparation of the A - / 'tTau8 ~ A -' - u - 'B - atjlojolohexanojl oxy_7 - ben ζ oylchiorids

1.52 g (0.005 mol) of the 4 - ^, "trans-4-a-Butyloyclohexa- noyloxy__7-benzoic acid are added to 20 ml of pure thionyl chloride and 3 drops of pyridine and boiled for 5 hours on a water bath Excess thionyl chloride is completely stripped off on a water bath in vacuo.The residual acid chloride can be used for esterification without further purification.

The saturated benzotrichlorides with modified alkyl substituents are obtained according to the same procedure under a single reagent of corresponding t3-ans-4-n-alkyloyolohexanecarboxylic acid chlorides. «

-CGO - Ä-COOH R K N

CpH ₅ . 220-224 , 226-229 ^C 4 ^H _{9 e} 215-220 , 230-235 10 C ₆ H " ₁₃ : 212-215 , 227-232 K = crystalline solid-   .N » nematic at isotropic-liquid game 3

Preparation of 4- ^ "trans ~ Butylcyoloh.exanoyloxy _{j <} _7 ·" trans-n-butylcyclohexane

1.6 g (Ο, O1 mol) of trans ~ 4-n-butyloyclohexanol in 30 ml of dry pyridine are added dropwise with 2 g (O ₅ 01 mol) of tsans-4-n-butylcyclohexaricarboxylic acid 2X'echlo3: iä.

The solution is shaken until pyridinium hydrochloride precipitates. It is allowed to stand overnight and warmed on the next day for one hour on a water bath (60 ⁰ C) ₀ After cooling 'poured on ice and 20 ml of conc. Sulfuric acid ", the ester is added to Xther, with sodium bicarbonate solution," water "dilute Sal washed 3säure and Y / ater Then, or is dissolved in hot methanol and gently in an ice bath from GE for 01 ¹ ₅ Gn what else... 'twice' vjird

Yield! 65 % of the theory.

 - 8th -

Example 4

The 4- / 3-trans-alkylcyclohexanoyloxyj ^ -trans-n-alkylcyclohexanes can all be hexed, for example, after the first day in Example 3. Table 1 gives examples of these substances.

Example 5

4- £ ~ trans-4-n-butyl € _{yclohexanoyloxy>} J ⁷ -benzoic acid- / ftrans ^ -n-butylcyolohexylester ^ /

1.6 g (0.01 mol) trans-4-n-Butylcyolohexanol v / ground in 40 ml of dry pyridine was added to 3.3 g (0.01 mol) of 4- _/ / ~ '~ trans 4-n ~ ButyloyclohexaTioyloxy_7- The reaction is shaken until the solution is clear and pyridinium hydroxoxide precipitates and, after standing overnight, is heated on the water bath for one hour at 60 ° C. It is allowed to cool and then poured on ice and 13 ml of concentrated, sulfuric acid, d ± q solid products are filtered off with suction, washed several times with water and dried. The product is purified by recrystallizing three times from methanol.

Yield: 80 % of theory *

& V-3

Table 1

¹ _, # e |

C-O

Nx.

E ¹

5 1.1 HC ₄ H ₉ UC ₃ H ₇ . "€ 10 24th • 20 , 5 _β 5 - 38 1.2 UC ₅ H ₁₁ HC ₃ H ₇ , 23- • • 21st 37 - - 52 ₉ 5 3.1 C ₂ H ₅ HC ₄ H ₉ , 10 0. 18 , 5 - , 5 o 1.4 UC ₃ H ₇ HC ₄ H ₉ , 8-1 • 27th # 33 - , 0 - 39 1.5 HC ₄ E ₉ HC ₄ H ₉ , 26- 0 ♦ ft 48 -58- , 0 - O 1.6 UC ₅ H ₁₁ ^U " ^C 4 ^H 9 ♦ 25,  20th 57 60-61- 5 - 1 1.7 UC ₆ H ₁₃ HC ₄ H ₉ , 18- Ί6. 65-66- ? 5 - 1.8 UC ₇ H ₁₅ , 14- • , 69 1.9 UC ₈ H ₁₇ HC ₄ H ₉ , 32 , 20-21. 35 1.10 C ₂ H ₅ UC ₅ H ₁₁ , 24 51 5 1/11 Ti-C ₃ H ₇ UC ₅ H ₁₁ ♦ 20- 62 54 1 1/12 HC ₄ H ₉ UC ₅ H ₁₁ , 52 72 1/13 UC ₅ H ₁₁ UC ₅ H ₁₁ «26 75 1/14 UG ₆ H ₁₃ UC ₅ H ₁₁ , 27 78 1.15 HC ₇ H _{1 5} UC ₅ II ₁₁

Table 2

No. 3T ITK H

2.1 C ₂ H ₅ CH ₅ ♦ 78 , 129. 5 2.2 C ₂ H ₅ ^C 4 ^H 9 , 62 , 162. 2.3 ^C 2 ^H 5 S ^H 11 , 59 .163. 2.4 C ₄ H ₉ ^C 4 ^H 9 , 72 , 174. 2.5 C ₄ H ₉ C ₅ H ₁₁ , 68 .182.

The 4α / ^M trans-4-n-alkylcyololxyxyloxy _{> =} 7--3-subst. T3enEoyloxy- ~~ trans ~ 4-ri "" alkylcyololxane_7 are all prepared analogously to the procedure of Example 5 using the appropriately substituted alkylcyclohexanols and substituted benzoyl chlorides.

Table 2 shows examples of the substances thus obtained.

Claims (1)

Bx find r h h 1. Preparation of New Crystalline-Liquid 4 ~ £ ~ tran3 ~ 4 = n-Alkyloyclohexanoyloxy_7 ~ trans-n ~ alkyloyoclohexaw ta «. 4 - ^ "" trans-4-n-allyloxyhexanoyloxy ___ 7-3-subs t "-" benaoyloxy-ε "" trans-4-allyloxyhexane ^ of the general formula - I coo- iiobel R ^. C _n r = C ^ ^m
R β is H, CH _3, C ₂ H _5, Cl, Br rait 1 = 0, 1 .m, η = 1 "to 10", denote net d a.d, ui oh j that txans ^ -n-Alkyloycloiiexancarbonsaureolilide siibste-benzoesäureohloride with trans '' 4 ~ n ~ are alkyl cyclohexanols in a dry organic base, preferably pyridine or quinoline j, "at temperatures z ^ isoken 0 and 60 ⁰ C, Torzugsvieise room temperature, esterified ·