DD153826A1 - PROCESS FOR PREPARING CRYSTALLINE-LIQUID 7-N-ALKYL-9,10-DIHYDROPHENANTHRENE-2 CARBOXYLIC ACID ESTERS - Google Patents

Abstract

The invention relates to a process for the preparation of novel crystalline 7-n-alkyl-9,10-dihydrophenanthrene-2-carboxylic acid esters. The object of the invention is the preparation of novel crystalline liquid 7-n-alkyl-9,10- dihydrophenanthrene-2-carbonsaeureestern. It was found that new 7-n-alkyl-9,10-dihydrophenanthrene-2-carboxylic acid esters by catalytic high-pressure hydrogenation of phenanthrene, Friedel-Crafts acylation of the resulting 9,10-Dihydrophenanthrens in the 2-position and reduction with hydrazine hydrate for 2 -n-alkyl-9,10-dihydrophenanthrene, acetylation according to Friedel-Crafts in nitrobenzene in the 7-position and oxidation in a haloform reaction to carboxylic acid, preparation of the acid chloride and reacting the equimolar amounts of acid chloride can be prepared with a hydroxy compound.

Description

Process for the preparation of crystalline-liquid 7-n-alkyl-9-, 10-dihydrophenanthren ~ 2-carboxylic acid esters

Field of application of the invention

The invention relates to a process for the preparation of 'novel crystalline liquid 7-n-alkyl-9,10-dihydrophenanthren-2-carboxylic acid esters of the general formula

HOR

where R ¹ . "

COO '

-R '

-CU; -

-cli,

-COO-Cl

^b "° a ^H 2n + 1

~ ^C n ^H 2n-M ⁰ '~

-CK ₂ -CH ₂ CN, -CH s C (CN) ₂ ', where η β is 1 to 10.

Liquid crystals are media with special optical and electrical characteristics and consequently for the production 'of optoelectronic devices, such as _e B "Ziffernansei- suitable gen _t. ,

Characteristic of the most ts technical solutions regard -Lö

In the literature so far as crystalline-liquid substances I 2 / ~ 4 nA] ic.yloxyber _{A aylidenarnino;} _7-phenantlirenes and some 9 _f 10-dihydrophenanthrenes with alkyl and acyl

- 2

Substituents £ ~ J * Canceill, J. Jaques, J. Billard: Chem. And Ind. (London) 1971, 625J J. Canceill, C. Gros, J. Billard, J. Jaques: Pramana Suppl. 1, 1975, 397.J7 described. The substances produced according to the invention are novel and processes for their preparation have not been described so far.

Aim_. the invention

The aim of the invention is the preparation of new crystalline lin-liquid 7-n-alkyl-9,1-dihydrophenanthrene "2-carboxylic acid esters.

Invention;

The object of the invention is a process for the preparation of crystalline liquid 7-n-alkyl-9,10-dihydrophenanthrene "2-carboxylic acid esters"

It has been found that new 7 ~ n ~ alkyl ^ 9,10 ~ dihydrophenanthrene ~ 2 carboxylic acid esters by catalytic high-pressure hydrogenation of pkenanthrene, Priedel-Crafts acylation of the resulting 9,1O-dihydrophenanthrene in the 2 ~ Positioning and reduction with hydrazine hydrate for 2 ~ n-alkyl-9 »10-dihydrophenanthrene, acetylation according to Friedel-Crafts in nitrobenzene at temperatures below 0 ⁰ C in 7" position and oxidation in a haloforin reaction to the carboxylic acid, preparation of the acid chloride by Heating with thionyl chloride and reacting the equimolar amounts of acid chloride with a hydroxy compound can be prepared according to the following reaction scheme:

.H ₉ O

"* ' η 2a + r

CH ₀ COCl

-C-CH,

1! 0

- 3

HaOBr

SOCl ₂

HOR ¹

where R ¹

-C-OR tt 0

  -R

-COO-

Cl

, V2n + 1

-CH ₂ -CH ₂ CN, - "CH = C (CN) ₂ , with η = 1 to 10.

The compounds are produced in good yield and high purity.

, Example 1: 2-acyl-9,10-dihydrophenanthrene £ 50 g (0.28 mol) of 9,10-dihydrophenanthrene 2 (by 30-40 ßtündige catalytic hydrogenation of 100 g phenanthrene j, abs in .300 ml of ethanol, and 11g. Copper-chromite catalyst / ♦ Policers, H. Adkine, J. Amer.Chem., Soc., 1138 (1932) / at 220 ⁰ C and 15 MPa hydrogen pressure in an autoclave are dissolved in 100 ml of nitrobenzene and then with 0.3 mol of corresponding acyl chloride. It is then cooled to -10 ⁰ C, with stirring 40 g (0.3 mol) of AlCl ₃ added ', stirred for a further 3 hours (-10 to ^{0 0} C) and allowed to stand overnight at ^{0 0} C. The reaction mixture is poured onto ice / HCl, allowed to stand for 24 hours, the organic phase separated, the solvent was distilled off and the residue was fractionally distilled. The yields are 70 to 80 % • d.Th ..

m a 3 bp .: 134 ° C / O, O7 kPa m a 4 bp .: 154 ° C / O, O5 kPa

Example 2: 2-n-alkyl-9,1-O-dihydrophenanthrene

0.2 mole 2 »24 g (0.6 mole) 80% U ₂ H ₄ .H ₂ O, 45 g (0.8 mole) finely powdered. Caustic potash and 200 ml of triglycol are refluxed for 4 hours with a strong evolution, then the flask is equipped with a distillation apparatus and the temperature is slowly raised to 240 ⁰ G and maintained until the evolution of N _{2 has} ceased (Hydrasin and water are removed by distillation) * Hach

After cooling, the reaction mixture is mixed with the same amount barrels, extracted with ether, chloroform or carbon tetrachloride and fractionated'distilled after drying the extract in vacuo. The yields are 60 % d ₀ Th _e * £ · · · η «4 Kp .: 120-123 ° C / 0.02 kPa i ^ 2 η - 5 Kp .: 13O-132 ° C / O _f O5 kPa

Example 3: 7-Acetyl-2-n-alkyl-9,1-O-dihydrophenanthrene

To 0.1 mol '4_ in 60 ml of nitrobenzene are slowly added dropwise 7 »9g (0.1 mol) of acetyl chloride and then 26.6 g (0.2 mol) of AlCl ~ added in portions at temperatures around -5 ⁰ C.

The reaction mixture is allowed to stand at ⁰ ° C. overnight,

then poured onto ice / HCl, the organic phase separated. and fractionally distilled in vacuo. The yields are 50 to 60 % d. Th. _Β £ j1 η a 4 bp .: 163 ⁰ O / 0.1 kPa

^ 2 η a 5 Kp *: 16O ° C / O, O3 kPa

Example 4: 7-n-Alkyl-9 »10-dihydrophenanthrene-2-carboxylic acid £

With vigorous stirring and cooling, 20 g (0.5 mol) of NaOH in 100 ml. HgO 12 g (0.15 mol) of bromine are added dropwise so that the temperature remains below 1O ⁰ O. The solution becomes O ⁰ C

cooled and 0.05 moles of j? added in 50 nil dicxane

Thereafter, the mixture is stirred for one hour at room temperature (ending the BEEN "of the reaction is indicated by the temperature rise), drives the bromoform with Y / asserdampf over and falls by introducing _S0?, The crude acid from. _6 is recrystallized from toluene or methanol. The Yield is 50 % d * Th. 6.1 η = 4 'K 221 H 230 I 6 * 2 n = 5 K 205 H-235 I

Example 5: 7-n-Aikyl-9,10-dihydrophenanthrene-2-carboxylic acid chloride 2

0.01 mol of 6, v / earth mixed with 15 to 25 ml of thionyl chloride and a few drops of pyridine and heated for 5 to 6 hours on a water bath. After distilling off the excess SOClp, J is esterified without further purification.

Example 6: T-n-Alkyl-SjiO-dihydrophenanthrene ^ -carbon- *

acid ester 8

0j01 mol χ (synthesized according to Example 5) in "20 - 40 ml of pyridine / with 0.01 mol of corresponding alcohol or

Phenol added and shaken vigorously. The batch is allowed to stand over water and then heated for 30 minutes in a boiling water bath. After cooling, Bis / conc. EUSO ,, (120 g / 26 ml), the precipitate was taken up in ether, the ether extract was washed successively with bicarbonate solution, water, dilute hydrochloric acid and water. It is then dried, the solvent distilled off and the residue umkrist.allisiert 4 to 5 times from methanol. The yields are 70 to 80 % of theory.

Table 1 :

Verb,

8 * 1

in the

8.2

8.8

8 * 12

⁰ to ₊ V

xl

4 4 4 4 4 4 4 5 5 5

q 5

-GOR ¹

S) - ⁰ A "

S> - ° 5 ^H 11 92- 93. 171 ♦ 94. 158 ♦. 82-83. 142. • 99-100. 202. , 108-109. 152. , 68-69. 116th ·

70 ♦ 144.

90. 169.

-OC ₇ H ₁ 5 .89-90. 165. = 0, Η _η . 74-75 · 140 «

-CN. 109-110. 198. -C ₂ H ₄ CH .94. 161 ο

Cl. , 88. 258.

Example ¹ J : . ·

Table 1 lists some of the compounds which can be prepared by the process according to the invention, with their melting and clearing points. It means: K = crystalline-solid

N = nematic

is β isotropic-liquid

Claims (1)

invention claim .1. A process for the preparation of novel crystalline liquid 7-n-alkyl-9 t 10-dihydrophenanthren ~ 2-oarbonsäureestern, characterized by catalytic high pressure hydrogenation of phenanthrene,. Friedel-Crafts acylation of the resulting 9 _s 1O-dihyarophenanthrene in the 2-step and reduction with hydrazine hydrate to 2-n-alkyl-9,10-aihydrophenanthrene, A. cetylation according to Priedel-Orafts in iTitrobenzen at temperatures under O ⁰ O in 7- split soxvie oxidation in a haloform reaction to the carboxylic acid _} Preparation of the acid chloride by heating with thionyl chloride and reacting the equimolar amounts of acid chloride with a Kydro ± yverbindungβ