IL50310A - Dimethyl ketophosphonates - Google Patents

Dimethyl ketophosphonates

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Publication number
IL50310A
IL50310A IL50310A IL5031073A IL50310A IL 50310 A IL50310 A IL 50310A IL 50310 A IL50310 A IL 50310A IL 5031073 A IL5031073 A IL 5031073A IL 50310 A IL50310 A IL 50310A
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dimethyl
oxo
indanyl
minutes
solution
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IL50310A
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Pfizer
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/93—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems condensed with a ring other than six-membered
    • C07D307/935—Not further condensed cyclopenta [b] furans or hydrogenated cyclopenta [b] furans
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P43/00—Drugs for specific purposes, not provided for in groups A61P1/00-A61P41/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C405/00—Compounds containing a five-membered ring having two side-chains in ortho position to each other, and having oxygen atoms directly attached to the ring in ortho position to one of the side-chains, one side-chain containing, not directly attached to the ring, a carbon atom having three bonds to hetero atoms with at the most one bond to halogen, and the other side-chain having oxygen atoms attached in gamma-position to the ring, e.g. prostaglandins ; Analogues or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C405/00—Compounds containing a five-membered ring having two side-chains in ortho position to each other, and having oxygen atoms directly attached to the ring in ortho position to one of the side-chains, one side-chain containing, not directly attached to the ring, a carbon atom having three bonds to hetero atoms with at the most one bond to halogen, and the other side-chain having oxygen atoms attached in gamma-position to the ring, e.g. prostaglandins ; Analogues or derivatives thereof
    • C07C405/0008—Analogues having the carboxyl group in the side-chains replaced by other functional groups
    • C07C405/0025—Analogues having the carboxyl group in the side-chains replaced by other functional groups containing keto groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/30—Compounds having groups
    • C07C43/315—Compounds having groups containing oxygen atoms singly bound to carbon atoms not being acetal carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C62/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C62/30—Unsaturated compounds
    • C07C62/34—Unsaturated compounds containing ether groups, groups, groups, or groups
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members 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 ring carbon atoms
    • C07D309/10—Oxygen atoms
    • C07D309/12—Oxygen atoms only hydrogen atoms and one oxygen atom directly attached to ring carbon atoms, e.g. tetrahydropyranyl ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4018—Esters of cycloaliphatic acids
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5407—Acyclic saturated phosphonium compounds

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Abstract

1456838 Silylated prostaglandins PFIZER Inc 8 Nov 1973 [8 Nov 1972] 51997/73 Heading C3S [Also in Division C2] N - Methansulphonyl - 15 - (5,6 - dimethoxy- 2 - indanyl) - 9α,11α,15# - tris - (dimethylisopropylsilyloxy) - 16,17,18,19,20 - pentanor - 13 - trans-prostenamide is prepared by hydrogenating N-methanesulphonyl-15-(5,6-dimethoxy-2- indanyl) - 9α,11α,15# - tris - (dimethylisopropylsilyloxy) - 16,17,18,19,20 - pentanor - 5 - cis, 13- trans-prostadienamide, resulting from the reaction between dimethylisopropylchlorosilane and N - methanesulphonyl - 9α,11α,15# - trihydroxy - 16,17,18,19,20 - pentanor - 5 - cis, 13- trans - prostadienamide. 16 - (2 - Indonyl)- 11α,15α - bis - (dimethylisopropylsilyloxy) - 9- oxo - 17,18,19,20 - tetranor - 13 - trans - prostenoic acid and 16-(2-indanyl)-11α,15α-bis-(dimethylisopropylsilyloxy) - 9 - oxo - 17,18.19,20- tetranor-5-cis, 13-trans-prostadienoic acid are obtained in a similar manner. [GB1456838A]

Description

50310/2 D»C7n 0*93 Q01S1QP V*H0*1 l¾w©l dimethyl S-etophosphoaates a.47722 50310 2 This invention relates to certain novel ketophosphonate intermediates useful in the preparation of the analogs of the naturally occurring prostaglandins, described in Israel Patent Specification No. 43571. The novel ketophosphonate intermediates are useful, in particular, in the preparation of novel 15-substituted-ω-pentanorprostaglandins .
The present invention comprises a compound of the structure: wherein A is cycloalkyl from three to ten carbon atoms, 1-ada antyl, 2-norbornyl, 2- ( 3. , 2 , 3 , 4-tetrahydron.ap.hthyl ) wherein said group is rac.emic or optically active, 2-indanyl or substituted 2-indanyl wherein said substituent is lower alkoxy; and n is an integer from 0 to 5.
These compounds are prepared be reacting a lower alkyl ester of the formula: O i! A - (CI-2 ) n - C - O - lower alkyl wherein A and n are as defined above, with dimethyl methylnhosDhonate ; and wherein lower signifies a chain of 1-4 carbon atoms.
The starting material for the various novel com-pounds of this invention are available commercially or are ^ made by methods well known to those skilled in the art. For example, to make dimethyl 2-oxo-2- (2-indanyl) ethylphosphon-ate, one cools a solution of dimethyl methylphosphonate in tetrahydrof ran to -78° in a dry nitrogen atmosphere and then adds n-butyllithium in hexane dropwise, slowly. After stirring, ethyl indane-2-carboxylate is added dropwise.
After 3 to 4 hours at -78° the reaction mixture is warmed to ambient temperature, neutralized with acetic acid and rotary evaporated to a white gel. The gelatinous material is taken up in' water, the aqueous phase is extracted in chloroform and the combined organic extracts are backwashed, dried, and concentrated to give the desired product.
SCHEME A A- (CH2)n-COOCH3 ) 2 1 2 As shown in Scheme A, the first step (1 — 2) is the condensation of the appropriate ester with a dialkyl methylphosphonate to produce ketophosphonate 2. Typically, the desired methyl ester is condensed with dimethyl methyl phosphonate.
The following examples are merely illustrative, and in no way limit the scope of the appended claims. In these examples it will be appreciated that all temperatures are expressed in Centigrade, all melting and boiling points are uncorrected.
EXAMPLE 1 Dimethyl 2-oxo°2- ( 2-indanyl ) ethylphosphonate A solution of 20.4 g. (164 mmoles) dimethyl methyl phosphonate (Aldrich) in 200 ml. dry tetrahydrofuran was cooled to -78° in a dry nitrogen atmosphere. To the stirred phosphonate solution was added 82.6 ml. of 2.25M n-butyl-lithium in hexane solution (Alfa Inorganics, Inc.) dropwise over a period of 20 minutes at such a rate that the reaction temperature never rose above -65° . After an additional 5 minutes stirring at -78°, 14.0 g. (73.5 mmole) methyl indane 2-carboxylate was added dropwise at a rate that kept the reaction temperature less than -70° (20 minutes). After 1.0 hour at -78° the reaction mixture was allowed to warm to ambient temperature, neutralized with. 20 ml. acetic acid and rotary evaporated to a white gel. The gelatinous material was taken up in 50 ml. water, the aqueous phase extracted with 75 ml. portions of methylene chloride (4x) , the combined organic extracts were backwashed (75 ml. H2O, dried (MgS04) , and concentrated (water aspirator) to a crude residue and distilled, b.p. 150-160° (0.1 mm) to give 17.0 g (86.4%) dimethyl 2-oxo-2- (2-indanyl) ethylphosphonate.
The nmr spectrum (CDCI3) of the distilled product exhibited a singlet at 7.15 6 for the aromatic protons, a doublet at 3.76 δ (J = 11 cps) for the OCH3, a singlet at 3.25 δ for the the benzylic protons, a doublet at 3.18 6 (J = 23 cps) for the and a deformed triplet at 3.13 δ (J = 2 cps) for the CHCO.
Additional Compound of the Structure ( eO) -JPCCHHLJC" (CH_) A n zb.p. n nmr Dat 0 240-243° (0.2 mm) 6.73(s) 1 160-162° (0.2 mm) 3.77(d) 1 209-212° (0.02 mm) 3.70(d) 2 195-200° (0.02 mm) 3.75(d) 1 138-141° (0.3 mm) 3.78(d a) distinct resonances.
EXAMPLE 2 Dimethyl 2-oxo-3- ( 2-indanyl) ropylphosphonate : A solution of 20.4 g. (164 mmoles) dimethyl meth IV: phosphonate (Aldrich) in 200 ml. dry tetrahydrofuran is cooled to -78° in a dry nitrogen atmosphere. To the stirred phosphorate solution is added 82.6 ml. of 2.25M n-butyllithium in hexane solution (Alfa Inorganics, Inc.) dropwise over a period of 20 minutes at such a rate that the reaction temperature never rises above -65°. After an additional 5 minutes stirring at -78°, 14.0 g. (73.5 mmole) methyl (2-indanyl) -acetate is added dropwise at a rate that keeps the reaction temperature less than -70° (20 minutes). ■ After 1.0 hour at -78° the reaction mixture is allowed to warm to ambient temperature, neutralized with 20 ml. acetic acid and rotary evaporated to a white gel. The gelatinous material is taken up in 50 ml. water, the aqueous phase extracted with 75 ml. portions of methylene chloride (4x) , the combined organic extracts are back-washed (75 ml. H20) , dried (MgS(_>4) , and concentrated (water aspirator) to a crude residue and distilled, dimethyl 2-oxo-3- (2-indanyl) propylphosphonate .
EXAMPLE 3 Dimethyl 2-oxo-2- (2- (1 , 2 , 3 , 4-tetrahydronaphthyl)ethylphosphonate A solution of 20.4 g. (164 mmoles) dimethyl methylphosphonate (Aldrich) in 200 ml. dry tetrahydrofuran is cooled to -78° in a dry nitrogen atmosphere. To the stirred phosphonate solution is added 82.6 ml. of 2.25M n-butyllithium in hexane solution (Alfa Inorganics, Inc.) dropwise over a period of 20 minutes at such a rate that the reaction temperature never rises above -65°. After an additional 5 minutes stirring at -78°, 14.0 g. (73.5 mmole) methyl 2- (1 , 2 , 3 , 4-tetrahyronaphthylcarboxylate) is added dropwise at a rate that keeps the reaction temperature less ^ than -70° (20 minutes). After 1.0 hour at -78° the reaction mixture is allowed to warm to ambient temperature, neutralized with 20 ml. acetic acid and rotary evaporated to a white gel. The gelatinous material is taken up in 50 ml. water, the aqueous phase extracted with 75 ml. portions of methylene chloride (4x) , the combined organic extracts are backwashed (75 ml. H2O) , dried (MgSO^) , and concentrated (water aspirator) to a crude residue and distilled to give dimethyl 2-oxo-2- (1/2,3, 4-tetrahydronaphthyl) ethylphosphonate.
EXAMPLE 4 Dimethyl 2-oxo-2- (2- (R-l , 2 , 3 , 4-tetrahydronaphthyl) ) -ethylphosphonate A solution of 20.4 g. (164 mmoles) dimethyl methyl-phosphonate (Aldrich) in 200 ml. dry tetrahydrofuran is cooled to -78° in a dry nitrogen atmosphere. To the stirred phospho-nate solution is added 82.6 ml. of 2.25M n-butyllithium in hexane solution (Alfa Inorganics, Inc.) dropwise over a period of 20 minutes at such a rate that the reaction temperature never rises above -65°. After an additional 5 minutes stirring at -78°, 14.0 g. (73.5 mmole)methyl 2- (R-l , 2 , 3 , 4-tetrahydronaphthylcarboxylate) is added dropwise at a rate that keeps the reaction temperature less than -70° (20 minutes) . After 1.0 hour at -78° the reaction mixture is allowed to warm to ambient temperature, neutralized with 20 ml. acetic acid and rotary evaporated to a white gel. The gelatinous material is taken up in 50 ml. water, the aqueous phase extracted with 75 ml. portions of methylene chloride (4x) , the combined organic extracts are backwashed (75 ml. H20) , dried (MgSO^) , and concentrated (water aspirator) to a crude residue which is purified by column chromatography to give '* dimethyl 2-oxo-2- (2- (R-l , 2 , 3 , -tetrahydronaphthyl) )ethyl-phosphonate.
EXAMPLE 5 Dimethyl 2-oxo-2- (2- (S-l, 2 , 3 , 4-tetrahydronaphthyl) ) ethyl- phosphonate : A solution of 20.4 g. (164 mmoles) dimethyl methyl-phosphonate -(Aldrich) in 200 ml. dry tetrahydrofuran is cooled to -78° in a dry nitrogen atmosphere. To the stirred phosphonate solution is added 82.6 ml. of 2.25M n-butyllithium in hexane solution (Alfa Inorganics, Inc.) dropwise over a period of 20 minutes at such a rate that the reaction temperature never rises above -65°. After an additional 5 minutes stirring at -78° , 14.0 g. (73.5 mmole) methyl 2-(S- 1 , 2 , 3 , 4-tetrahydronaphthyl) is added dropwise at a rate that keeps the reaction temperature less than -70° (20 minutes) .
After 1.0 hour at -78° the reaction mixture is allowed to warm to ambient temperature, neutralized with 20 ml. acetic acid and rotary evaporated to a white gel. The gelatinous material is taken up in 50 ml. water, the aqueous phase extracted with 75 ml. portions of methylene chloride (4x) , the combined organic extracts are backwashed (75 ml. H2O) , dried (MgSC>4) , and concentrated (water aspirator) to a crude residue which is purified by column chromatography to give dimethyl 2-oxo-2- (2- (S-l , 2 , 3 , -tetrahydronaphthyl) ) -ethylphosphonate .
EXAMPLE 6 Dimethyl 2-oxo-7-cyclopentylheptylphosphonate : A solution of 20.4 g. (164 mmoles) dimethyl methyl-phosphonate (Aldrich) in 200 ml. dry tetrahydrofuran is cooled to -78° in a dry nitrogen atmosphere. To the stirred phosphonate solution is added 82.6 ml. of 2.25M n-butyllithiui^ in hexane solution (Alfa Inorganics, Inc.) dropwise over a period of 20 minutes at such a rate that the reaction temper-ature never rises above -65°. After an additional 5 minutes stirring at -78° , 14.5 g. (73.5 mmole) methyl 6-cyclopentyl-hexanoate is added dropwise at a rate that keeps the reaction temperature less than -70° (20 minutes). After 1.0 hour at -78° the reaction mixture is allowed to warm to ambient temperature/ neutralized with 20 ml. acetic acid and rotary evaporated to a white gel. The gelatinous- material is taken up in 50 ml. water, the aqueous phase extracted with 75 ml. portions of methylene chloride (4x) , the combined organic extracts are backwashed (75 ml. H2O) , dried (MgSO/j) , and concentrated (water aspirator) to a crude residue and distilled to give dimethyl 2-oxo-7-cyclopentylheptylphosphonate .
EXAMPLE 7 Dimethyl 2-oxo-2-cyclodecylethylphosphonate ; A solution of 20.4 g. (164 mmoles) dimethyl methyl-phosphonate (Aldrich) in 200 ml. dry tetrahydrofuran is cooled to -78° in a dry nitrogen atmosphere. To the stirred phosphonate solution is added 82.6 ml. of 2.25M n-butyllithium in hexane solution (Alfa Inorganics, Inc.) dropwise over a period of 20 minutes at such a rate that the reaction temper-ature never rises above -65°. After an additional 5 minutes stirring at -78°, 14.5 g. (73.5 mmole) methyl cyclodecancarb-oxylate is added dropwise at a rate that kept the reaction temperature less than -70° (20 minutes). After 1.0 hour at -78° the reaction mixture is allowed to warm to ambient temperature, neutralized with 20 ml. acetic acid and rotar evaporated to a white gel. The gelatinous material is taken up in 50 ml. water, the aqueous phase extracted with 75 ml. portions of methylene chloride (4x) , the combined organic extracts are backwashed (75 ml. H2O) , dried ( gS04) , and concentrated (water aspirator) to a crude residue and distilled to give dimethyl 2-oxo-2-cyclodecylethylphosphonate .
EXAMPLE 8 Dimethyl 2-oxo-6-cyclopropylhexylphosphonate : A solution of 20.4 g. (164 mmoles) dimethyl methyl-phosphonate (Aldrich) in 200 ml. dry tetrahydrofuran is cooled to -78° in a dry nitrogen atmosphere. To the stirred phosphonate solution is added 82.6 ml. of 2.25M n-butyllithium in hexane solution (Alfa Inorganics, Inc.)' dropwise over a period of 20 minutes at such a rate that the reaction temper-ature never rises above -65°. After an additional 5 minutes stirring at -78° , 11.5 g. (73.5 mmole) methyl 5-cyclopropyl-valerate is added dropwise at a rate that keeps the reaction temperature less than -70° (20 minutes). After 1.0 hour at -78° the reaction mixture is allowed to warm to ambient temperature, neutralized with 20 ml. acetic acid and rotary evaporated to a white gel. The gelatinous material is taken up in 50 ml. water, the aqueous phase extracted with 75 ml. portions of methylene chloride (4x) , the combined organic extracts are backwashed (75 ml. H2O) , dried (MgS04) , and con-centrated (water aspirator) to a crude residue and distilled to give dimethyl 2-oxo-6-cyclopropylhexylphosphonate .

Claims (2)

P.C. 5446Α - Div. I What we claim is
1. A compound of the structure wherein A is cycloalkyl of from three to 10 carbon November 5, 1973 except com- atoms, 1-adamantyl, 2-norbornyl, 2- (1 , 2 , 3 , 4-tetrahydronaphthyl) , pounds of claim 2 2-indanyl or substituted 2-indanyl wherein said substituent is lower alkoxy n is an integer from 0 to 5.
2. A compound of Formula I wherein A is cycloalkyl November 8, 1972 of from three to 10 carbon atoms, 1-adamantyl, 2-indanyl or 2-norbornyl; n is an integer from 0 to 5.
IL50310A 1972-11-08 1973-11-05 Dimethyl ketophosphonates IL50310A (en)

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GB1431561A (en) * 1973-01-31 1976-04-07 Ici Ltd Cyclopentane derivatives
US3929862A (en) * 1974-01-08 1975-12-30 Upjohn Co Substituted tolylesters of PGF{HD 2{B {60
JPS5823393B2 (en) * 1974-03-14 1983-05-14 オノヤクヒンコウギヨウ カブシキガイシヤ prostaglandin
US4028396A (en) * 1975-07-02 1977-06-07 American Cyanamid Company 16,16-Spirocycloalkyl prostaglandin derivatives
NZ183136A (en) * 1976-02-11 1978-11-13 Miles Lab Monospiroalkyl derivatives of prostaclandis and pharmaceutical compositions
US4074063A (en) * 1976-02-11 1978-02-14 Miles Laboratories, Inc. Bicycloalkyl derivatives of prostaglandins
US4404372A (en) * 1977-06-13 1983-09-13 Pfizer Inc. 15-Substituted-ω-pentanorprostaglandin derivatives
DE2753995A1 (en) * 1977-12-03 1979-06-07 Bayer Ag NEW BICYCLOALKENYL PROSTAGLANDINS AND THE METHOD OF MANUFACTURING THEM
US6048895A (en) * 1997-09-09 2000-04-11 The Procter & Gamble Company Aromatic C16-C20 substituted tetrahydro prostaglandins useful as FP agonists
US5977173A (en) * 1997-09-09 1999-11-02 Wos; John August Aromatic C16 -C20 -substituted tetrahydro prostaglandins useful as FP agonists
IL134792A0 (en) * 1997-09-09 2001-04-30 Procter & Gamble Aromatic c16-c20-substituted tetrahydro prostaglandins useful as fp agonists
EP1159266B1 (en) * 1999-03-05 2004-11-03 Duke University C-16 unsaturated fp-selective prostaglandins analogs
US20020013294A1 (en) 2000-03-31 2002-01-31 Delong Mitchell Anthony Cosmetic and pharmaceutical compositions and methods using 2-decarboxy-2-phosphinico derivatives
US20020172693A1 (en) 2000-03-31 2002-11-21 Delong Michell Anthony Compositions and methods for treating hair loss using non-naturally occurring prostaglandins
US20020037914A1 (en) 2000-03-31 2002-03-28 Delong Mitchell Anthony Compositions and methods for treating hair loss using C16-C20 aromatic tetrahydro prostaglandins
ATE432910T1 (en) * 2007-11-28 2009-06-15 Bauer Maschinen Gmbh WINDS
US8623918B2 (en) 2008-10-29 2014-01-07 Novaer Holdings, Inc. Amino acid salts of prostaglandins
US8722739B2 (en) 2008-10-29 2014-05-13 Novaer Holdings, Inc. Amino acid salts of prostaglandins
US20230097470A1 (en) * 2021-08-23 2023-03-30 Chirogate International Inc. Processes and intermediates for the preparations of carboprost and carboprost tromethamine, and carboprost tromethamine prepared therefrom

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SE7612262L (en) 1976-11-03
SU667131A3 (en) 1979-06-05
ES456279A1 (en) 1978-11-01
SU704456A3 (en) 1979-12-15
IL43571A (en) 1977-08-31
DE2355731B2 (en) 1980-04-30
BE807046A (en) 1974-05-08
NO144385C (en) 1981-08-19
NO144385B (en) 1981-05-11
FR2291200B1 (en) 1979-01-05
CA1033727A (en) 1978-06-27
FR2286147A1 (en) 1976-04-23

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