CH619705A5 - Process for the preparation of N-formyl-7-oxocyclohexano- or -8-oxocycloheptano[b]thiophene-4-amines - Google Patents

Process for the preparation of N-formyl-7-oxocyclohexano- or -8-oxocycloheptano[b]thiophene-4-amines Download PDF

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Publication number
CH619705A5
CH619705A5 CH1016878A CH1016878A CH619705A5 CH 619705 A5 CH619705 A5 CH 619705A5 CH 1016878 A CH1016878 A CH 1016878A CH 1016878 A CH1016878 A CH 1016878A CH 619705 A5 CH619705 A5 CH 619705A5
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Switzerland
Prior art keywords
acid
formula
preparation
formyl
thiophene
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CH1016878A
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German (de)
Inventor
Goro Asato
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American Cyanamid Co
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Publication of CH619705A5 publication Critical patent/CH619705A5/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/116—Heterocyclic compounds
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/116—Heterocyclic compounds
    • A23K20/121—Heterocyclic compounds containing oxygen or sulfur as hetero atom
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/116—Heterocyclic compounds
    • A23K20/137—Heterocyclic compounds containing two hetero atoms, of which at least one is nitrogen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P3/00—Drugs for disorders of the metabolism
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/56—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/66—Nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C07D333/70—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/78—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
    • C07D333/80—Seven-membered rings

Abstract

The N-formyl-7-oxocyclohexano- or -8-oxocycloheptano[b]thiophene-4-amines correspond to the formula <IMAGE> in which R1, Y and Z have the meanings given in Claim 1. They are prepared by oxidising 1 mol equivalent of an appropriate compound, which contains a methylene group or a hydroxymethylene group in the ring instead of the carbonyl group, at a temperature from 0 to 100 DEG C using 2 to 8 mol equivalents of an oxidising agent. The oxidising agents used are (a) chromic anhydride in acetic anhydride or (b) cerium(IV) ammonium nitrate, silver oxide, chromic anhydride or sodium dichromate in the presence of an aqueous solution of acetic acid, acetonitrile, tetrahydrofuran, dioxane, dimethoxyethane or diethylene glycol dimethyl ether. The aqueous solution can contain nitric acid, phosphoric acid or perchloric acid. When using the oxidising agents (a), hydrolysis is additionally carried out subsequently. The formylamino compounds of the formula I or II thus prepared can be hydrolysed in dilute mineral acid. The acid salts of the corresponding amino compounds obtained in this process can be converted into the corresponding ureas or thioureas using an alkali metal cyanate or thiocyanate. These ureas and thioureas have a growth-promoting action in animals.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von N-Formyl-7-oxocyclohexano- oder -8-oxocycloheptano-25 [b]-thiophen-4-aminen der Formel: The invention relates to a process for the preparation of N-formyl-7-oxocyclohexano- or -8-oxocycloheptano-25 [b] -thiophene-4-amines of the formula:

R, R,

Worin Z für Wasserstoff oder Ci-Ct-Alkyl steht, Y Wasserstoff, Ci-Ci-Alkyl, Halogen, Cyano, Nitro, Acetyl, Acetylamino oder ein Rest der Formel Ri-NHCONH- ist und Ri Wasserstoff oder Ci-Ci-Alkyl bedeutet, dadurch gekennzeichnet, dass man ein Moläquivalent einer Verbindung der Formel: Where Z is hydrogen or Ci-Ct-alkyl, Y is hydrogen, Ci-Ci-alkyl, halogen, cyano, nitro, acetyl, acetylamino or a radical of the formula Ri-NHCONH- and Ri is hydrogen or Ci-Ci-alkyl , characterized in that one molar equivalent of a compound of the formula:

(Ia) (Ia)

oder or

(IIa) (IIa)

30 30th

N-CHO N-CHO

(i) (i)

bzw. respectively.

45 45

(II) (II)

55 55

60 60

worin Z für Wasserstoff oder Ci-Ct-Alkyl steht, Y Wasserstoff, Ci-C4-Alkyl, Halogen, Cyano, Nitro, Acetyl, Acetylamino oder ein Rest der Formel Ri-NHCONH- ist und Ri Wasserstoff oder Ci-Ci-Alkyl bedeutet. Das Verfahren ist dadurch gekennzeichnet, dass man ein Moläquivalent einer Verbindung der Formel: wherein Z is hydrogen or Ci-Ct-alkyl, Y is hydrogen, Ci-C4-alkyl, halogen, cyano, nitro, acetyl, acetylamino or a radical of the formula Ri-NHCONH- and Ri is hydrogen or Ci-Ci-alkyl . The process is characterized in that one molar equivalent of a compound of the formula:

worin U für-CH2— oder-CHOH— steht, bei einer Temperatur von 0 bis 100°C mit 2 bis 8 Moläquivalent a) Chromsäureanhydrid in Essigsäureanhydrid oder 65 where U is —CH2— or —CHOH— at a temperature of 0 to 100 ° C. with 2 to 8 molar equivalents a) chromic anhydride in acetic anhydride or 65

b) Cer(IV)ammoniumnitrat, Silberoxid, Chromsäureanhydrid oder Natriumdichromat in Gegenwart einer wässrigen Lösung von Essigsäure, Acetonitril, Tetrahydrofuran, Dioxan, b) cerium (IV) ammonium nitrate, silver oxide, chromic anhydride or sodium dichromate in the presence of an aqueous solution of acetic acid, acetonitrile, tetrahydrofuran, dioxane,

N-CHO N-CHO

(Ia) (Ia)

oder or

3 3rd

619 705 619 705

î1 î1

N-CHO N-CHO

worin U für-CHi- oder-CHOH- steht, bei einer Temperatur von 0 bis 1000 C mit 2 bis 8 Moläquivalent a) Chromsäureanhydrid in Essigsäureanhydrid oder 15 where U is -CHi or -CHOH-, at a temperature of 0 to 1000 C with 2 to 8 molar equivalents a) chromic anhydride in acetic anhydride or 15

b) Cer(IV)-ammoniumnitrat, Silberoxid, Chromsäureanhydrid oder Natriumdichromat in Gegenwart einer wässrigen Lösung von Essigsäure, Acetonitril, Tetrahydrofuran, Dioxan, Dimethoxyäthan oder Diäthylenglykoldimethyläther oxidiert und bei Verwendung von Chromsäureanhydrid in 20 Essigsäureanhydrid als Oxidationsmittel anschliessend hydro-lysiert. Die wässrige Lösung kann Salpetersäure, Phosphorsäure oder Perchlorsäure enthalten. b) Cerium (IV) ammonium nitrate, silver oxide, chromic anhydride or sodium dichromate oxidized in the presence of an aqueous solution of acetic acid, acetonitrile, tetrahydrofuran, dioxane, dimethoxyethane or diethylene glycol dimethyl ether, and when using chromic anhydride in 20 acetic anhydride as an oxidizing agent, oxidized as an oxidizing agent. The aqueous solution can contain nitric acid, phosphoric acid or perchloric acid.

Das erfindungsgemässe Verfahren wird vorzugsweise unter Verwendung von 4 bis 5 Moläquivalent eines Oxidationsmittels 2s der genannten Art sowie vorzugsweise bei einer Temperatur von 20 bis 60 °C durchgeführt. The process according to the invention is preferably carried out using 4 to 5 molar equivalents of an oxidizing agent 2s of the type mentioned and preferably at a temperature of 20 to 60 ° C.

Nach Beendigung der Oxidationsstufe können die erhaltenen Oxoverbindungen in verdünnter Mineralsäure hydrolysiert werden. Die auf diese Weise erhaltenen Säuresalze der Amine 30 können mit einem Alkalimetallcyanat oder -thiocyanat bei einem pH-Wert von 5 bis 7 umgesetzt werden, wodurch man die entsprechenden Harnstoffe oder Thioharnstoffe erhält, die sich durch eine wachstumsfördernde Wirkung insbesondere bei Tieren auszeichnen. Die erfindungsgemäss herstellbaren Ver- 35 After the oxidation stage has ended, the oxo compounds obtained can be hydrolyzed in dilute mineral acid. The acid salts of the amines 30 obtained in this way can be reacted with an alkali metal cyanate or thiocyanate at a pH of 5 to 7, which gives the corresponding ureas or thioureas which are distinguished by a growth-promoting effect, in particular in animals. The producible according to the invention 35

bindungen sind demzufolge wertvolle Zwischenprodukte zur Herstellung solcher Cycloalkano-[b]-thienylharnstoffe. Die Erfindung wird anhand der Beispiele weiter erläutert. Accordingly, bonds are valuable intermediates for the preparation of such cycloalkano- [b] thienylureas. The invention is further illustrated by the examples.

Beispiel 1 example 1

Herstellung von N-Formyl-4,5,6,7-tetrahydro-7-oxobenzo-[b]-thiophen-4-amin Man löst 6 g N-Formyl-4,5,6,7-tetrahydrobenzo-[b]-thiophen-4-amin in 375 ml 50%iger wässriger Essigsäure und gibt unter Rühren im Verlaufe von 10 Minuten bei einer Temperatur von 25 bis 35°C portionsweise 75 g Cer(IV)-ammo-niumnitrat zu. Die Lösung wird weitere 5 Minuten lang gerührt und dann mit 10 ml Wasser versetzt. Hierauf wird die Lösung zweimal mit Methylenchlorid (450 ml und 350 ml) extrahiert, worauf man die vereinigten Extrakte mit 100 ml Wasser wäscht. Der organische Extrakt wird im Vakuum zur Trockne eingedampft. Durch Umkristallisieren des dabei erhaltenen Rückstands erhält man N-Formyl-Tetrahydro-7-oxobenzo-[b]-thio-phen-4-amin mit einem Schmelzpunkt von 118 bis 120°C (Zersetzung). Preparation of N-formyl-4,5,6,7-tetrahydro-7-oxobenzo- [b] -thiophene-4-amine 6 g of N-formyl-4,5,6,7-tetrahydrobenzo- [b] are dissolved. -thiophene-4-amine in 375 ml of 50% aqueous acetic acid and added with stirring over a period of 10 minutes at a temperature of 25 to 35 ° C, 75 g of cerium (IV) ammonium nitrate. The solution is stirred for a further 5 minutes and then 10 ml of water are added. The solution is extracted twice with methylene chloride (450 ml and 350 ml) and the combined extracts are washed with 100 ml of water. The organic extract is evaporated to dryness in vacuo. By recrystallizing the residue obtained in this way, N-formyl-tetrahydro-7-oxobenzo- [b] -thio-phen-4-amine with a melting point of 118 to 120 ° C. (decomposition).

Wenn man Cer(IV)-ammoniumnitrat durch Silberoxid, Chromsäureanhydrid oder Natriumdichromat ersetzt, so erhält man ebenfalls die oben angegebene 7-Oxoverbindung. Auch die Umsetzung mit Chromsäureanhydrid in Essigsäureanhydrid ergibt die 7-Oxoverbindung. Die oben erwähnten 7-Oxover-bindungen kann man ferner in ähnlicher Weise durch Oxidation der entsprechenden 7-HydroxyVerbindungen herstellen. If cerium (IV) ammonium nitrate is replaced by silver oxide, chromic anhydride or sodium dichromate, the 7-oxo compound indicated above is also obtained. The reaction with chromic anhydride in acetic anhydride also gives the 7-oxo compound. The above-mentioned 7-oxo compounds can also be prepared in a similar manner by oxidation of the corresponding 7-hydroxy compounds.

Beispiel 2 Example 2

Herstellung von N-Formyl-8-oxocycloheptano-[b]-thiophen-4-amin Nach dem in Beispiel 1 beschriebenen Verfahren behandelt man N-Formylcycloheptano-[b]-thiophen-4-amin, das bei 164 bis 166 °C schmilzt, mit 4 Äquivalent Cer(IV)-ammonium-nitrat, wodurch man die im Titel genannte Verbindung erhält. Preparation of N-formyl-8-oxocycloheptano- [b] -thiophene-4-amine According to the procedure described in Example 1, N-formylcycloheptano- [b] -thiophene-4-amine is treated, which melts at 164 to 166 ° C , with 4 equivalents of cerium (IV) ammonium nitrate, whereby the compound mentioned in the title is obtained.

B B

Claims (3)

619705 619705 2 2nd PATENTANSPRÜCHE 1. Verfahren zur Herstellung von N-Formyl-7-oxo-cyclo-hexano- oder -8-oxocycloheptano-[b]-thiophen-4-aminen der Formel: PATENT CLAIMS 1. Process for the preparation of N-formyl-7-oxo-cyclo-hexano- or -8-oxocycloheptano- [b] -thiophene-4-amines of the formula: FL FL N-CHO N-CHO (I) (I) bzw. respectively. Dimethoxyäthan oder Diäthylenglykoldimethvläther oxidiert und bei Verwendung von Chromsäureanhydrid in Essigsäureanhydrid als Oxidationsmittel anschliessend hydroly-siert. Oxidized dimethoxyethane or diethylene glycol dimethyl ether and then hydrolyzed when using chromic acid anhydride in acetic anhydride as the oxidizing agent. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, 2. The method according to claim 1, characterized in that dass die wässrige Lösung Salpetersäure, Phosphorsäure oder Perchlorsäure enthält. that the aqueous solution contains nitric acid, phosphoric acid or perchloric acid. 3.Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass man 4 bis 5 Moläquivalent Oxidationsmittel verwendet und bei einer Temperatur im Bereich von 20 bis 60 °C arbeitet. 3. The method according to claim 1 or 2, characterized in that one uses 4 to 5 molar equivalents of oxidizing agent and works at a temperature in the range of 20 to 60 ° C. 4. Verfahren nach Anspruch 1 oder 2 zur Herstellung von Verbindungen der Formel I, worin Ri, Y und Z Wasserstoff bedeuten. 4. The method according to claim 1 or 2 for the preparation of compounds of formula I, wherein Ri, Y and Z are hydrogen. 15 15 (II) (II) 20 20th Die Herstellung von Tetrahydrobenzothiophenderivaten ist aus den US-PS Nr. 3 989 505, 3 776 924 und 3 998 959 bekannt. The preparation of tetrahydrobenzothiophene derivatives is known from U.S. Patent Nos. 3,989,505, 3,776,924 and 3,998,959.
CH1016878A 1974-01-25 1978-09-29 Process for the preparation of N-formyl-7-oxocyclohexano- or -8-oxocycloheptano[b]thiophene-4-amines CH619705A5 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US43682774A 1974-01-25 1974-01-25
US43682674A 1974-01-25 1974-01-25

Publications (1)

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CH619705A5 true CH619705A5 (en) 1980-10-15

Family

ID=27031116

Family Applications (4)

Application Number Title Priority Date Filing Date
CH87775A CH619703A5 (en) 1974-01-25 1975-01-24 Process for the preparation of novel optionally ring-substituted cycloalkano[b]thiophene ureas or thioureas and use thereof
CH1016678A CH619704A5 (en) 1974-01-25 1978-09-29 Process for the preparation of novel optionally ring-substituted cycloalkano[b]thiophene ureas or thioureas and use thereof
CH1016778A CH619949A5 (en) 1974-01-25 1978-09-29 Process for the preparation of novel 7- or 8-oxo-cycloalkano[b]thien-4-ylureas and use thereof
CH1016878A CH619705A5 (en) 1974-01-25 1978-09-29 Process for the preparation of N-formyl-7-oxocyclohexano- or -8-oxocycloheptano[b]thiophene-4-amines

Family Applications Before (3)

Application Number Title Priority Date Filing Date
CH87775A CH619703A5 (en) 1974-01-25 1975-01-24 Process for the preparation of novel optionally ring-substituted cycloalkano[b]thiophene ureas or thioureas and use thereof
CH1016678A CH619704A5 (en) 1974-01-25 1978-09-29 Process for the preparation of novel optionally ring-substituted cycloalkano[b]thiophene ureas or thioureas and use thereof
CH1016778A CH619949A5 (en) 1974-01-25 1978-09-29 Process for the preparation of novel 7- or 8-oxo-cycloalkano[b]thien-4-ylureas and use thereof

Country Status (21)

Country Link
JP (1) JPS51125069A (en)
AT (1) AT353590B (en)
CA (1) CA1060899A (en)
CH (4) CH619703A5 (en)
CS (1) CS195276B2 (en)
DD (4) DD125213A5 (en)
DE (1) DE2501788C2 (en)
DK (1) DK22775A (en)
ES (1) ES434095A1 (en)
FR (1) FR2333801A1 (en)
GB (1) GB1499582A (en)
IE (1) IE42039B1 (en)
IL (1) IL46375A (en)
IN (1) IN141050B (en)
IT (1) IT1035548B (en)
LU (1) LU71711A1 (en)
NL (1) NL7500845A (en)
PH (1) PH14544A (en)
SE (1) SE421617B (en)
TR (1) TR18381A (en)
YU (1) YU36721B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3994924A (en) * 1975-11-04 1976-11-30 American Cyanamid Company 4,5,6,7-Tetra hydro-7-oxobenzo(B)thien-4-yl isocyanate and isothiocyanate
FR2430231A1 (en) * 1978-07-04 1980-02-01 American Cyanamid Co 4,5,6,7-Tetra:hydro-benzo(b)thienyl-4 urea and 7-oxo deriv. compsn. - used for increasing growth of wool and ratio of sec. to prim. follicles in sheep, goats, llamas, rabbits and chinchilla
JPS6169772A (en) * 1984-12-04 1986-04-10 アメリカン　サイアナミッド　カンパニ− Tetrahydrobenzo(b)thiophene derivative, manufacture and animal growth acceleration
EP1801098A1 (en) 2005-12-16 2007-06-27 Merck Sante 2-Adamantylurea derivatives as selective 11B-HSD1 inhibitors

Also Published As

Publication number Publication date
SE7500793L (en) 1975-07-28
DD125212A5 (en) 1977-04-06
DK22775A (en) 1975-09-15
YU36721B (en) 1984-08-31
AT353590B (en) 1979-11-26
IT1035548B (en) 1979-10-20
YU17275A (en) 1982-06-18
IL46375A (en) 1982-04-30
CS195276B2 (en) 1980-01-31
TR18381A (en) 1977-05-01
ATA42675A (en) 1979-04-15
IN141050B (en) 1977-01-15
CH619949A5 (en) 1980-10-31
AU7691574A (en) 1976-07-01
SE421617B (en) 1982-01-18
IL46375A0 (en) 1975-04-25
DD125213A5 (en) 1977-04-06
DE2501788C2 (en) 1984-11-08
GB1499582A (en) 1978-02-01
PH14544A (en) 1981-09-24
ES434095A1 (en) 1977-05-16
CH619703A5 (en) 1980-10-15
JPS6133830B2 (en) 1986-08-04
CH619704A5 (en) 1980-10-15
CA1060899A (en) 1979-08-21
FR2333801B1 (en) 1982-07-09
FR2333801A1 (en) 1977-07-01
JPS51125069A (en) 1976-11-01
DD125211A5 (en) 1977-04-06
NL7500845A (en) 1975-07-29
IE42039B1 (en) 1980-05-21
LU71711A1 (en) 1975-06-24
DD119790A5 (en) 1976-05-12
IE42039L (en) 1975-07-25
DE2501788A1 (en) 1975-07-31

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