DD210899A1 - PROCESS FOR PREPARING CRYSTALLINE-LIQUID 7-N-ALKYL-PERHYDROPHENANTHRENE-2-CARBOXYLIC ACID ESTERS - Google Patents
PROCESS FOR PREPARING CRYSTALLINE-LIQUID 7-N-ALKYL-PERHYDROPHENANTHRENE-2-CARBOXYLIC ACID ESTERS Download PDFInfo
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- DD210899A1 DD210899A1 DD24417982A DD24417982A DD210899A1 DD 210899 A1 DD210899 A1 DD 210899A1 DD 24417982 A DD24417982 A DD 24417982A DD 24417982 A DD24417982 A DD 24417982A DD 210899 A1 DD210899 A1 DD 210899A1
- Authority
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- German Democratic Republic
- Prior art keywords
- carboxylic acid
- alkyl
- liquid
- perhydrophenanthrene
- acid esters
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- 239000007788 liquid Substances 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 150000007513 acids Chemical class 0.000 claims 1
- 230000032050 esterification Effects 0.000 abstract description 3
- 238000005886 esterification reaction Methods 0.000 abstract description 3
- 238000001953 recrystallisation Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 2
- 230000005693 optoelectronics Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000007868 Raney catalyst Substances 0.000 abstract 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 abstract 1
- 229910000564 Raney nickel Inorganic materials 0.000 abstract 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GNMCGMFNBARSIY-UHFFFAOYSA-N 1,2,3,4,4a,4b,5,6,7,8,8a,9,10,10a-tetradecahydrophenanthrene Chemical class C1CCCC2C3CCCCC3CCC21 GNMCGMFNBARSIY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 125000001792 phenanthrenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- HTNCYKZTYXSRHL-DYKIIFRCSA-N 18-norabietane Chemical compound C[C@H]1CCC[C@]2(C)[C@H]3CC[C@H](C(C)C)C[C@@H]3CC[C@H]21 HTNCYKZTYXSRHL-DYKIIFRCSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- ZNPSUQQXTRRSBM-UHFFFAOYSA-N 4-n-Pentylphenol Chemical compound CCCCCC1=CC=C(O)C=C1 ZNPSUQQXTRRSBM-UHFFFAOYSA-N 0.000 description 1
- ASEDVNPKWGLIGT-UHFFFAOYSA-N 7-butyl-1,2,3,4,4a,4b,5,6,7,8,8a,9,10,10a-tetradecahydrophenanthrene-2-carbonyl chloride Chemical compound C1C(C(Cl)=O)CCC2C3CCC(CCCC)CC3CCC21 ASEDVNPKWGLIGT-UHFFFAOYSA-N 0.000 description 1
- HNDIXQACSOFWMI-UHFFFAOYSA-N 7-butyl-1,2,3,4,4a,4b,5,6,7,8,8a,9,10,10a-tetradecahydrophenanthrene-2-carboxylic acid Chemical compound C1C(C(O)=O)CCC2C3CCC(CCCC)CC3CCC21 HNDIXQACSOFWMI-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- HTNCYKZTYXSRHL-UHFFFAOYSA-N Fichtelite Natural products CC1CCCC2(C)C3CCC(C(C)C)CC3CCC21 HTNCYKZTYXSRHL-UHFFFAOYSA-N 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001243 acetic acids Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Die Erfindung betrifft ein Verfahren zur Herstellung neuer kristallin-fluessiger 7-Alkylperhydrophenanthren-2-carbonsaeureester der allgemeinen Formel. Das Ziel der Erfindung besteht in der Herstellg. neuer kristallin-fluessiger 7-Alkyl-perhydrophenantren-2-carbonsaeureester. Erfindungsgemaess werden neue kristallin-fluessige 7-Alkyl-perhydrophenanthren-2-carbonsaeureester in hoher Reinheit und guter Ausbeute hergestellt durch vollstaendige Hydrierung der 7-Alkyl-9, 10-dihydrophenantren-2-carbonsaeure unter Hochdruck (10-13 M Pa) in waessriger Alkalilauge bei Temperaturen von 200 bis 270 Grad C mit Katalysatoren, vorzugsweise Raney-Nickel, Umkristallisieren und Verestern der erhaltenen reinen Saeure nach an sich bekannten Verfahren. Die Erfindung kann in der chemischen Industrie zur Herstellung kristallin-fluessiger Verbindungen, die fuer den Einsatz in optoelektronischen Bauelementen geeignet sind, angewendet werden.The invention relates to a process for the preparation of novel crystalline liquid 7-Alkylperhydrophenanthren-2-carboxylic acid esters of the general formula. The aim of the invention is the Herstellg. new crystalline-liquid 7-alkyl-perhydrophenanthrene-2-carboxylic acid ester. According to the invention, new crystalline-liquid 7-alkyl-perhydrophenanthrene-2-carboxylic acid esters are prepared in high purity and good yield by complete hydrogenation of the 7-alkyl-9,10-dihydrophenantrene-2-carboxylic acid under high pressure (10-13 M Pa) in aqueous Alkali solution at temperatures of 200 to 270 degrees C with catalysts, preferably Raney nickel, recrystallization and esterification of the resulting pure acid according to known methods. The invention may be used in the chemical industry for the preparation of crystalline-liquid compounds suitable for use in optoelectronic devices.
Description
"/erfahren zur Herstellung von kristallin-flüssigen"/ learn about the production of crystalline-liquid
Die Erfindung betrifft ein Verfahren zur Herstellung neuer ' kristallin-flüssiger Y-Alkyl-perhydrophenanthren-S-carbonsäureester der allgemeinen FormelThe invention relates to a process for the preparation of novel 'crystalline liquid Y-alkyl-perhydrophenanthrene-S-carboxylic acid esters of the general formula
. ^^, ^^
-er, 24 2 -er, 24 2
-Gl, -Brr-J-Gl, -Br r -J
. > H2, R3=-H,— CH3,'-.-S, -Cl, -GF nit n, in = 1 bis 14, > H 2 , R 3 = -H, -CH 3 , '- - S, -Cl, -GF n, in = 1 to 14
L1IUsEinkristalle werden vorzugsweise in optoelektronischen Jauelenenten zur Darstellung von Ziffern, Zeichen und Abbildungen genutzt.L 1 IUs single crystals are preferably used in optoelectronic Jauelenenten to represent numbers, characters and figures.
21.0Kr. 1982*0^227321.0Kr. 1982 * 0 ^ 2273
Charakteristik, der bekannten technischen LösungenCharacteristic, the known technical solutions
Die bisher bekannten Methoden zur Herstellung von partiell oder vollständig hydrierten Phenanthrenderivaten gehen ent— weder von der Isolierung von Naturstoffen (Steroiden) aus, oder sie verlaufen über den Aufbau aus einfachen Ringsystemen rtiit Hilfe vieler Syntheseschritte. Deshalb sind die erhältlichen Ausbeuten gering und die ,'!Reinheit der hergestellten Verbindungen ist unbefriedigendThe previously known methods for the preparation of partially or fully hydrogenated phenanthrene derivatives are based either on the isolation of natural substances (steroids), or they proceed via the structure of simple ring systems with the aid of many synthetic steps. Therefore, the yields available are low and the purity of the compounds produced is unsatisfactory
Beispiele hierfür sind bei P.E. Shaw et. al. (US-Patente .-3.795.3C1 (1973) und 3.932.482 (1976)) enthalten, in denen PolyIiydro-2-phenanthrylidenessigsäuren beschrieben Werden. Douglass und Samir (J. Am. Chem. Soc. JO2, 9089 (1980)) stellten angular substituierte Perhydrophenanthrene (Fichtelit) . ' .. durch Diels-Alder-Reaktion her. Iiajjos, Parios und Goldberg erreichten durch Cyclisierungsreaktionen, Hydroborierung und Oxydation Okta- und Dodekahydrophenanthrene, die u.a. auch in 2- bzw, 7—Stellung substituiert waren. Examples are at P.E. Shaw et. al. (U.S. Patents 3,795,371 (1973) and 3,932,482 (1976)) which describe polyhydro-2-phenanthrylidene acetic acids. Douglass and Samir (J.Am.Chem.Soc.JO2, 9089 (1980)) provided angularly substituted perhydrophenanthrenes (Fichtelite). '.. by Diels-Alder reaction ago. Iiajjos, Parios and Goldberg achieved by cyclization reactions, hydroboration and oxidation octa and dodecahydrophenanthrenes, which i.a. were also substituted in 2- or 7-position.
.> R. !instead et.al. (J. Am. Ghem. Söc. 64, 2014 (1942)) erhielten "durch kätalytische Hydrierung substituierter Phenanthrene mit Edelmetallkatalysatoren vorwiegend cis-Isomere und unvollständig hydrierte Produkte, In keinem Jail gelang die Isolierung der trans-3Jlti-trans--Perh3' drophenanthren-2-carbonsäure.> R.! Instead of et.al. (J. Am. Ghem., Söc., 64, 2014 (1942)) obtained "predominantly cis isomers and incompletely hydrogenated products by catalytic hydrogenation of substituted phenanthrene with noble metal catalysts. In no jail was the isolation of trans-3Jlti-trans - Perh3 'successful. drophenanthren-2-carboxylic acid.
In Analogie zu Kenntnissen an anderen hydrierten Ringsystemen /Ϊ). Demus, II. Demus, H. Zaschkej Flüssige Kristalle in Tabellen, VEB Deutscher Verlag für Grundstoffindustrie, Leipzig 19747 In analogy to knowledge of other hydrogenated ring systems / Ϊ). Demus, II. Demus, H. Zaschkej Liquid crystals in tables, VEB German publishing house for primary industry, Leipzig 19747
war zu erwarten, daß nur die Produkte mit all-trans-Konfiguration bei den Perhydrophenanthrenderivaten die Ausbildung kristallin-flüssiger Phasen erlauben wurden. Deshalb waren die bisher bekannten Methoden zur Darstellung von kristallin-flüssigen Perhydrophenanthrenderivaten völlig unbrauchbar.It was expected that only the products with all-trans configuration in the perhydrophenanthrene derivatives would allow the formation of crystalline-liquid phases. Therefore, the previously known methods for the preparation of crystalline liquid perhydrophenanthrene derivatives were completely useless.
.·. . Ziel der Erfindung . ·. , Object of the invention
Ziel der Erfindung ist die Herstellung neuer kristallin-flüssiger 7-n-Alk3' -perhydrOphenanthren-2-carbonsäureester.The aim of the invention is the preparation of new crystalline liquid 7-n-Alk3 '-perhydrOphenanthren-2-carboxylic acid ester.
— 3 —- 3 -
Aufgabe der Erfindung ist ein Verfahren zur Herstellung neuer kristallin-flüssiger 7-Alkyl—perhydrophenanthren-2-carbon- säureester in der all-transHKonfiguration. <.The object of the invention is a process for preparing new crystalline liquid 7-alkyl-perhydrophenanthren-2-carboxylic acid ester in the all-transHKonfiguration. <.
: Es wurde gefunden, daß 7-AIkyl~perhydrophenanthren-2-carbonsäureester der allgemeinen Formel I in hoher Reinheit und guter Ausbeute hergestellt werden können durch vollständige Hydrierung der 7—Alkyl—9, 1.0-Klihydrophenanthren—2.-carbonsäure unter Hochdruck (10-13 MPa) in wäßriger Alkalilauge bei Temperaturen von 200 bis 270 0G mit Katalysatoren, vorzugsweise lianey-Nickel, mehrmaliges Umkristallisieren und Verestern der erhaltenen reinen Säure nach an sich bekannten Verfahren, z.3. der Einhorn- oder Schotten—Baümann—Variante, sowie anschließendes mehrfaches Umkristallisieren bis zur Konstanz der Um- wundlungstemperaturen. Die nach diesem Verfahren erhaltenen Produkte sind überraschenderweise die reinen all-trans-Isoineren, was an dem Auftreten kristallin-flüssiger Phasen sowie an den scharfen Umwandlungstemperaturen zu erkennen ist.It has been found that 7-alkyl-perhydrophenanthrene-2-carboxylic acid esters of the general formula I can be prepared in high purity and good yield by complete hydrogenation of the 7-alkyl-9, 1.0-Klihydrophenanthren-2-carboxylic acid under high pressure (10 -13 MPa) in aqueous alkali at temperatures of 200 to 270 0 G with catalysts, preferably lianey-nickel, repeated recrystallization and esterification of the resulting pure acid according to known methods, z.3. the unicorn or Schotten-Baümann variant, and subsequent multiple recrystallization to the constancy of the Umwetterlungstemperaturen. The products obtained by this process are, surprisingly, the pure all-trans iso-iners, which can be recognized by the appearance of crystalline-liquid phases and by the sharp transformation temperatures.
Beispiel 1 : ; Example 1 :;
Synthese der 7-n-Butyl-perhydrophenaxιthren-2-carbonsäure 20 g (0,075 KoI) 7-n-Butyi-g, tO-dihydrophenanthren-2-carbonsäure ' in 200 ml 10#Lg-er Wäßriger Kalilauge werden mit 30 g RaneyiCickel 100 h unter einem Wassers to ff druck von 15 MPa bei 260 bis 270 0C im Autoklaven geschüttelt. Each Entfernen des Katalysators wird das Rohprodukt mit konzentrierter Salzsäure erhitzt, um die freie Säure zu erhalten. Es wird mehrmals aus Ethanol umkriställisiert» Es werden 13,9 g weißer kristalliner Saure erhalten, die bie 16O 0C schmilzt und bis 219 0C nematisch ist, .Synthesis of 7-n-butyl-perhydrophenaxethrene-2-carboxylic acid 20 g (0.075 KoI) of 7-n-butyi-g, t-O-dihydrophenanthrene-2-carboxylic acid in 200 ml of 10% aqueous potassium hydroxide solution are mixed with 30 g of RaneyiCickel Shaken for 100 h under a water pressure of 15 MPa at 260 to 270 ° C. in an autoclave. Each removal of the catalyst, the crude product is heated with concentrated hydrochloric acid to obtain the free acid. It is recrystallised several times from ethanol »13.9 g of white crystalline acid are obtained, which melts as 16O 0 C and to 219 0 C is nematic,.
7-n—Butyl-perhydrophenanthren-2-carbonsäurechlorid 0,005 Mol der 7-n-Butyl--perhydrophenanthren-2-carbonsäure7-n-butyl-perhydrophenanthrene-2-carboxylic acid chloride 0.005 mole of 7-n-butyl-perhydrophenanthrene-2-carboxylic acid
— λ "«1.- λ "« 1.
werden mit der 4-bis 5-fachen Menge Thionylchlorid und einigen Tropfen Pyridin Versetzt. Hach mehrstündigem Erhitzen wird das überschüssige Reagens abdestilliert und das Säurechlorid ohne weitere Reinigung zur Veresterung nach Einhorn eingesetzt.are placed with 4 to 5 times the amount of thionyl chloride and a few drops of pyridine. After heating for several hours, the excess reagent is distilled off and the acid chloride used without further purification for esterification after unicorn.
7-n-Butyl-perhydrophenanthren-2-carbonsäure-4-n-pent ylphenylester7-n-Butyl-perhydrophenanthrene-2-carboxylic acid 4-n-pentyl phenylester
0,0C5 Mol 4-n-Pentylphenol werden mit der äquimolaren Menge 7-n-Butyl-perhydrophenanthren-"2-carbonsäurechlorid in 20 ml Pyridin verestert. Dabei wird der Ansatz über ITacht stehen gelassen und anschließend noch 30 Minuten auf 70 bis 80 0G erhitzt. Each dein Abkühlen wird in bekannter Weise das Reaktionsprodukt aufgearbeitet. Es v/ird mehrmals aus Methanol umkristcliisiert,· bis der Ester schmelz- und klärpunktrein erhalten wird.0,0C5 mole 4-n-pentylphenol be-n-butyl-7 perhydrophenanthren- "2-carboxylic acid chloride is esterified with an equimolar amount in 20 ml of pyridine. The approach over ITacht is allowed to stand and then 30 minutes at 70 to 80 0 Each time you cool it, the reaction product is worked up in a known manner, and it is recrystallized several times from methanol until the ester is obtained in a pure and pure state.
Ausbeute: 50 - 60 % . -i Yield: 50 - 60 % . -i
K 75 S 1Λ4 I 135 IK 75 S 1Λ4 I 135 I
Beinpiel 4Beinpiel 4
Sach dem in Beicpiel 1 bis 3 illustrierten Verfahren werden die folgender. Substanzen hergestellt, indem jeweils die be— stii.ir.ite phenolische Komponente bei der Synthese eingesetzt wird.The following are illustrated in the method illustrated in Examples 1 to 3. Substances are prepared by each of the bestii.ir.ite phenolic component is used in the synthesis.
— 5 —- 5 -
4. H4. H
CH2CH2CH ^CSiCH 2 CH 2 CH 3 CSi
=σ.= Σ.
CITCIT
... 160 - 219... 160 - 219
. 75 . 114 . 135, 75. 114. 135
. 76· .135-6 γ 143-4 . 79 . -, 76 · .135-6 γ 143-4. 79. -
. 105 -, 105 -
89 ... -89 ... -
. 184-5, 184-5
124124
187187
84 »114 V 25684 »114V 256
-C-C
64 V 148 . 19864V 148. 198
• 83 C. 64)• 83 C. 64)
110110
Claims (1)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD24417982A DD210899A1 (en) | 1982-10-21 | 1982-10-21 | PROCESS FOR PREPARING CRYSTALLINE-LIQUID 7-N-ALKYL-PERHYDROPHENANTHRENE-2-CARBOXYLIC ACID ESTERS |
| DE19843408041 DE3408041A1 (en) | 1982-10-21 | 1984-03-05 | CRYSTALLINE LIQUID NEMATIC MIXTURES |
| CH1182/84A CH660181A5 (en) | 1982-10-21 | 1984-03-09 | CRYSTALLINE-LIQUID, 7-ALKYL-PERHYDROPHENANTHRENE-2-CARBONIC ACID ESTER AND A METHOD FOR PRODUCING THESE COMPOUNDS. |
| JP59048277A JPS60193948A (en) | 1982-10-21 | 1984-03-15 | Novel 7-alkyl-perhydrophenanthrene-2-carboxylic acid ester, manufacture and use |
| GB08407550A GB2156375B (en) | 1982-10-21 | 1984-03-23 | Liquid crystal nematic mixtures |
| US06/602,832 US4585576A (en) | 1982-10-21 | 1984-04-23 | Liquid-crystal nematic substances |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD24417982A DD210899A1 (en) | 1982-10-21 | 1982-10-21 | PROCESS FOR PREPARING CRYSTALLINE-LIQUID 7-N-ALKYL-PERHYDROPHENANTHRENE-2-CARBOXYLIC ACID ESTERS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DD210899A1 true DD210899A1 (en) | 1984-06-27 |
Family
ID=5541909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DD24417982A DD210899A1 (en) | 1982-10-21 | 1982-10-21 | PROCESS FOR PREPARING CRYSTALLINE-LIQUID 7-N-ALKYL-PERHYDROPHENANTHRENE-2-CARBOXYLIC ACID ESTERS |
Country Status (1)
| Country | Link |
|---|---|
| DD (1) | DD210899A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4585576A (en) * | 1982-10-21 | 1986-04-29 | Veb Werk Fur Fernsehelektronik Im Veb Kombinat Mikroelektronik | Liquid-crystal nematic substances |
-
1982
- 1982-10-21 DD DD24417982A patent/DD210899A1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4585576A (en) * | 1982-10-21 | 1986-04-29 | Veb Werk Fur Fernsehelektronik Im Veb Kombinat Mikroelektronik | Liquid-crystal nematic substances |
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