GB1588734A

GB1588734A – Tetracarboxylic acid tetrachlorides
– Google Patents

GB1588734A – Tetracarboxylic acid tetrachlorides
– Google Patents
Tetracarboxylic acid tetrachlorides

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Publication number
GB1588734A

GB1588734A
GB7222/80A
GB722280A
GB1588734A
GB 1588734 A
GB1588734 A
GB 1588734A
GB 7222/80 A
GB7222/80 A
GB 7222/80A
GB 722280 A
GB722280 A
GB 722280A
GB 1588734 A
GB1588734 A
GB 1588734A
Authority
GB
United Kingdom
Prior art keywords
bis
chlorocarbonyl
general formula
compound
triiodo
Prior art date
1976-06-23
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)

Expired

Application number
GB7222/80A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Bayer Pharma AG

Original Assignee
Schering AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
1976-06-23
Filing date
1977-06-20
Publication date
1981-04-29

1977-06-20
Application filed by Schering AG
filed
Critical
Schering AG

1981-04-29
Publication of GB1588734A
publication
Critical
patent/GB1588734A/en

Status
Expired
legal-status
Critical
Current

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Classifications

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C233/00—Carboxylic acid amides

C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms

C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C233/00—Carboxylic acid amides

C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms

C07C233/12—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups

Description

PATENT SPECIFICATION ( 11) 1 588 734
e ( 21) Application No 7222/80 ( 22) Filed 20 June 1977 ( 62) Divided out of No 1588733 ( 31) Convention Application No2628517 1 t ( 32) Filed 23 June 1976 in ( 33) Federal Republic of Germany (DE) ( 44) Complete Specification published 29 April 1981 ( 51) INT CL 3 C 07 C 103/46 ( 52) Index at acceptance C 2 C 220 227 22 Y 281 315 316 31 Y 339 342 34 Y 364 366 36 Y 582 586 587 596 63 X 669 699 AA KW ( 54) NEW TETRACARBOXYLIC ACID TETRACHLORIDES ( 71) WE, SCHERING AKTIENGESELLSCHAFT, a Body Corporate organised according to the laws of the Federal Republic of Germany, of Berlin and Bergkamen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to
be performed to be particularly described in and by the following statement: 5
The present invention is concerned with new tetracarboxylic acid tetrachlorides suitable as intermediates for the manufacture of X-ray contrast agents, and with a process for their manufacture.
The present invention provides compounds of the general formula I cool cccl II I I -C 0-X-C 0-N CO R R 3 R 35 O in which R 3 represents a hydrogen atom or a C,-C 4-alkyl group and X represents a direct carbon to carbon bond or a straight chained alkylene group which may be interrupted by at least one oxygen atom and/or may be substituted by at least one substituent selected from hydroxyl groups and C,-C 6-alkyl groups.
When R 3 and a substituent in the alkylene group represented by X represent 15 alkyl groups, there are intended especially straight chained groups containing I to 4 carbon atoms, and preferably 1 or 2 carbon atoms, for example butyl, propyl, ethyl and especially methyl groups.
X may be an optionally C 1,-C 6 alkyl substituted straight chained alkylene group which may be interrupted by one or more oxygen atoms and may contain 1 20 to 6 carbon atoms Preferred is a straight chained alkylene group containing 1 to 6 carbon atoms, which may be interrupted by one or more, and preferably by I to 4, oxygen atoms Especially preferred is a straight chained alkylene group containing I to 4 carbon atoms, which may be interrupted by I or 2 oxygen atoms.
As examples there may be mentioned -CH 2-, -(CH 2)2-, -(CH 2)4-, 25 -CH 2-O-CH 2-, -(CH 2-CH 2-O-CH 2-CH 2)-, -(CH 2-O-CH 2)2-, and -(CH 2 O-CH 2)3 groups.
As C 1,-C 6 alkyl substituted straight chained alkylene groups represented by X there come into consideration, for example, -lC(CH 3)21-, -lCH 2C(CH 3)2-CH 21-, -lCH 2-CH(CH 3)-CH(CH 3)-CH 2 l and -lCH 2 30 CH(CH 3)-CH 2 l groups.
The present invention also provides a process for the manufacture of a compound of the general formula I, wherein a 2,4,6 triiodo isophthalic acid dichloride of the general formula II 2 1,588,734 Cool I W, (II) 0 l CO 1 C I ó in which R 3 has the meaning given above, is reacted with a dicarboxylic acid dichloride of the general formula III CICO-X-COCI (III), in which X has the meaning given above 5 The new compounds of the general formula I are prepared from the known 5 amino or 5 alkylamino 2,4,6 triiodo isophthalic acid dichloride by condensation with the dichloride of an aliphatic dicarboxylic acid of the general formula Cl-CO-X-CO-CI, in which X has the meaning given above, which condensation may be carried out in a manner known per se As reaction media 10 there are suitable organic solvents, for example aromatic hydrocarbons, for example toluene, chlorobenzene, and especially inert polar solvents, for example dimethylacetamide, N methyl pyrrolidone, dioxan and tetrahydrofuran.
Especially preferred solvents are, for example, dimethylacetamide, dioxan and tetrahydrofuran 15 The dimeric tetracarboxylic acid tetrachlorides of the general formula I formed by the reaction either crystallize out or are isolated by concentration of the solutions in vacuo.
The compounds of the general formula I of the present invention may be used for the manufacture of dicarboxylic acid bis ( 3,5 dicarbamoyl 2,4,6 20 triiodoanilides) of the general formula IV lo Co (It), IR 1 R 2 I 113 v), x R 3 R 2 2 R 3 “RR 2 in which R, and X have the meanings given above, R, represents a C 2 -Calkyl group substituted by at least one hydroxyl group and R 2 represents a hydrogen atom or a C,-C,-alkyl group or has the same meaning as the meaning represented 25 HN R, in which R 1 and R 2 have the meanings given above.
The dicarboxylic acid bis ( 3,5 dicarbamoyl 2,4,6 triiodoanilides) of the general formula IV are valuable X-ray contrast agents and they and their 30 manufacture, as outlined above, are described and claimed in our Specification No.
25644/77 (Serial No 1588733) The following Examples illustrate the invention:
1,588,734 3 1,588,734 3 Example 1
To a solution of 103 gms of 5 amino 2,4,6 triiodo isophthalic acid dichloride in 412 ml of dioxan in an oil bath at an internal temperature of 80-90 C were added dropwise during the course of 10 minutes, while stirring, 10 3 ml of oxalic acid dichloride After stirring for 2 hours in the heat the new compound 5 identified below crystallized out; this can be accelerated by inoculation After stirring the mixture overnight at room temperature the precipitate was filtered off with suction and dried with the exclusion of moisture.
The yield of crude oxalic acid bis ( 3,5 bis chlorocarbonyl 2,4,6 triiodoanilide) was 88 5 gms= 73 6 % of the theoretical yield taking into account a 10 dioxan content of 10 % by weight M p: No decomposition up to 320 C.
Example 2
To a solution of 110 gms of 5 methylamnino 2,4,6 triiodo isophthalic acid dichloride in 110 ml of dioxan were added dropwise while stirring at 80 C 18 5 gms of 2-oxaglutaric acid dichloride The mixture was then boiled under reflux for 15 5.5 hours, a precipitate separating out After stirring for 20 hours, the latter was filtered off with suction.
Yield: 60 5 gms= 51 % of the theoretical yield of oxaglutaric acid bis ( 3,5 bis chlorocarbonyl 2,4,6 triiodo N methyl anilide).
Decomposition at about 300 C Dioxan content: < 0 5 % 20 Calculated: Cl 10 76 %, I 57 79 %, Found: Cl 11 3 %, I 57 7 %. Example 3 To a solution of 30 5 gms of 5 methylamino 2,4,6 triiodo isophthalic acid dichloride in 45 ml of dioxan were slowly added under reflux 4 2 grams of 25 malonyl chloride and the mixture was further heated for 3 hours After cooling the mixture, the precipitate was filtered off with suction. Yield: 25 8 gms= 80 % of the theoretical yield of malonic acid bis ( 3,5 bis chlorocarbonyl 2,4,6 triiodo N methyl anilide). Dioxan content 0 8 % Melting point: above 300 C 30 Example 4 Into a solution of 221 gms of 5 amino 2,4,6 triiodo isophthalic acid dichloride in 320 ml of dioxan were introduced dropwise, while refluxing, 41 gms of adipic acid dichloride After heating the mixture for 3 hours and cooling overnight, the precipitate was filtered off with suction 35 Yield: 169 gms= 67 % of the theoretical yield of adipic acid bis ( 3,5 bis chlorocarbonyl 2,4,6 triiodoanilide) containing 6 % of dioxan. Decomposition from 292 C. Example 5 Into a solution of 119 gms of 5 amino 2,4,6 triiodo isophthalic acid 40 dichloride in 119 ml of dioxan were introduced dropwise, under reflux, 25 8 gms of 3,6 dioxasuberic acid dichloride After heating the mixture for 6 hours and cooling overnight, the precipitate was filtered off with suction. Yield: 75 gms= 52 % of the theoretical yield of 3,6 dioxa suberic acid bis ( 3,5 bis chlorocarbonyl 2,4,6 triiodoanilide) containing 6 8 % of dioxan; 45 decomposition at 260-262 C. Claims (1) WHAT WE CLAIM IS: 1 A tetracarboxylic acid tetrachloride of the general formula I Ciol,OC 1 I I C l C O N-CO-X-CO-N I C 1 I O W I R R 3 I in which R, represents a hydrogen atom or a C 1-C 4-alkyl group and X represents a 50 direct carbon-to-carbon bond or a straight chained alkylene group which may be 1,588,734 4 1,588,734 4 interrupted by at least one oxygen atom and/or may be substituted by at least one substituent selected from hydroxyl groups and C,-C 6-alkyl groups. 2 A compound as claimed in claim 1, wherein the alkyl group represented by R 3 contains 1 or 2 carbon atoms. 3 A compound as claimed in claim 1, wherein the alkyl group represented by 5 R 3 is a methyl group. 4 A compound as claimed in any one of claims I to 3, wherein X represents a straight chained alkylene group containing 1 to 6 carbon atoms which may be interrupted by I to 4 oxygen atoms. 5 A compound as claimed in any one of claims I to 3, wherein X represents a 10 straight chained alkylene group containing I to 4 carbon atoms which may be interrupted by 1 or 2 oxygen atoms. 6 A compound as claimed in any one of claims I to 3, wherein X represents a -CH 2-, (CH 2)2-, -(CH 2)4-, -CH 2-O-CH 2-, (CH 2-CH 2-O-CH 2CH 2)-, -(CH 2-O-CH 2)2 or (CH 2-O-CH 2)a group 15 7 Oxalic acid bis ( 3,5 bis chlorocarbonyl 2,4,6 triiodoanilide). 8 Oxaglutaric acid bis ( 3,5 bis chlorocarbonyl 2,4,6 triiodo N methyl anilide). 9 Malonic acid bis ( 3,5 bis chlorocarbonyl 2,4,6 triiodo N methyl anilide) 20 Adipic acid bis ( 3,5 bis chlorocarbonyl 2,4,6 triiodo anilide). 11 3,6 Dioxansuberic acid bis ( 3,5 bis chlorocarbonyl 2,4,6 triiodoanilide). 12 A process for the manufacture of a tetracarboxylic acid tetrachloride of the general formula I given in claim 1, in which R 3 and X have the meanings given in 25 claim 1, wherein a 2,4,6 triiodo isophthalic acid dichloride of the general formula II COO 1 C 1 C O 1 I R 3 in which R 3 has the meaning given above, is reacted with a dicarboxylic acid dichloride of the general formula III 30 CICO-X-COCI (III), in which X has the meaning given above. 13 A process as claimed in claim 12, conducted substantially as described herein. 14 A process as claimed in claim 12, conducted substantially as described in 35 Example I herein. A process as claimed in claim 12, conducted substantially as described in any one of Examples 2 to 5 herein. ABEL & IMRAY, Chartered Patent Agents, Northumberland House, 303-306 High Holborn, London, WCIV 7 LH. Printed for Her Maiesty's Stationery Office, by the Courier Press, Leamington Spa 1981 Published by The Patent Office 25 Southampton Buildings, London, WC 2 A l AY from which copies may be obtained. GB7222/80A 1976-06-23 1977-06-20 Tetracarboxylic acid tetrachlorides Expired GB1588734A (en) Applications Claiming Priority (1) Application Number Priority Date Filing Date Title DE2628517A DE2628517C2 (en) 1976-06-23 1976-06-23 Dicarboxylic acid bis (3,5-dicarbamoyl-2,4,6-triiodanilide) compounds, process for their preparation and X-ray contrast media Publications (1) Publication Number Publication Date GB1588734A true GB1588734A (en) 1981-04-29 Family ID=5981407 Family Applications (2) Application Number Title Priority Date Filing Date GB25644/77A Expired GB1588733A (en) 1976-06-23 1977-06-20 Dicarboxylic acid bis - (3,5 - dicarbamoyl - 2,4,6-triiodoanilides) GB7222/80A Expired GB1588734A (en) 1976-06-23 1977-06-20 Tetracarboxylic acid tetrachlorides Family Applications Before (1) Application Number Title Priority Date Filing Date GB25644/77A Expired GB1588733A (en) 1976-06-23 1977-06-20 Dicarboxylic acid bis - (3,5 - dicarbamoyl - 2,4,6-triiodoanilides) Country Status (28) Country Link US (1) US4239747A (en) JP (2) JPS537637A (en) AT (1) AT361117B (en) AU (1) AU512304B2 (en) BE (1) BE856039A (en) CA (2) CA1106400A (en) CH (1) CH629751A5 (en) CS (1) CS199680B2 (en) DD (1) DD131014A5 (en) DE (1) DE2628517C2 (en) DK (2) DK150505C (en) ES (1) ES460007A1 (en) FI (1) FI67540C (en) FR (1) FR2355808A1 (en) GB (2) GB1588733A (en) GR (1) GR71696B (en) HU (1) HU174228B (en) IE (2) IE45225B1 (en) IL (2) IL52356A (en) IT (1) IT1237314B (en) LU (2) LU77588A1 (en) NL (1) NL189510C (en) NO (2) NO147447C (en) PL (1) PL108102B1 (en) PT (1) PT66690B (en) SE (1) SE436871B (en) SU (1) SU917696A3 (en) ZA (1) ZA773782B (en) Families Citing this family (29) * Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title CH626873A5 (en) * 1977-03-28 1981-12-15 Bracco Ind Chimica Spa DK273280A (en) * 1979-06-28 1980-12-29 Schering Ag TRIODED 5-AMINOISOPHTHALIC ACID DERIVATIVES IT1193211B (en) * 1979-08-09 1988-06-15 Bracco Ind Chimica Spa 2,4,6-TRIIODE-ISOPHTHALIC ACID DERIVATIVES, METHOD FOR THEIR PREPARATION AND CONTRAST MEANS THAT CONTAIN THEM IT1207226B (en) * 1979-08-09 1989-05-17 Bracco Ind Chimica Spa 2,4,6-TRIIODE-ISOPHTHALIC ACID DERIVATIVES, METHOD FOR THEIR PREPARATION AND CONTRAST MEANS THAT CONTAIN THEM. JPS56127373A (en) * 1980-01-31 1981-10-06 Univ California Novel amino-dioxepane intermediate for synthesizing novel nonionic contrast agent US4341756A (en) * 1980-01-31 1982-07-27 The Regents Of The University Of California Novel amino-dioxepane intermediates for the synthesis of new non-ionic contrast media DE3038853A1 (en) * 1980-10-10 1982-05-27 Schering Ag, 1000 Berlin Und 4619 Bergkamen NEW N-HYDROXY-ALKYLATED DICARBONIC ACID-BIS- (3,5-DICARBAMOYL-2,4,6-TRIJODANILIDES), THEIR PRODUCTION AND THEIR CONTAINING X-RAY CONTRAST AGENTS (II) LU88639I2 (en) * 1982-11-08 1996-02-01 Nycomed Imaging S A Contrast agents for x-rays FR2541272A1 (en) * 1983-02-23 1984-08-24 Guerbet Sa BROMINE COMPOUNDS AND OPACIFIER PRODUCTS CONTAINING THEM US4650903A (en) * 1984-06-21 1987-03-17 The Bf Goodrich Company Oligomeric amides as synergists for antioxidants and UV stabilizers DE3731542A1 (en) * 1987-09-17 1989-03-30 Schering Ag NEW DICARBONIC ACID-BIS (3,5-DICARBAMOYL-2,4,6-TRIIOD-ANILIDE), METHOD FOR THE PRODUCTION THEREOF AND THESE CONTAINING X-RAY AGENTS DE3739098A1 (en) * 1987-11-16 1989-05-24 Schering Ag NEW SUBSTITUTED DICARBONIC ACID-BIS (3,5-DICARBAMOYL-2,4,6-TRIYOD ANILIDE), METHOD FOR THE PRODUCTION THEREOF AND THEIR CONTAINING X-RAY CONTRASTING AGENTS US5075502A (en) * 1989-12-13 1991-12-24 Mallinckrodt, Inc. Nonionic x-ray contrast agents, compositions and methods IT1252180B (en) * 1991-12-10 1995-06-05 Bracco Ind Chimica Spa 5,5 '- (1,3-PROPANDIIL) BIS (IMINO (2-BONE-2,1-ETANDIIL) ACETYLIMINE) -BIS (2,4,6-TRIIODE-1,3-BENZENDICARBOXY), THEIR METHOD OF PREPARATION AND ROENTGENOGRAPHIC CONTRAST MEANS THAT CONTAIN THEM CN1038725C (en) * 1993-12-04 1998-06-17 吉林省鹊源国际生物工程有限公司 Nutritious oral liquor US6149891A (en) * 1995-05-31 2000-11-21 Israel Humanitarian Foundation Ltd. X-ray contrast medium and method for protecting against harmful effects thereof IT1299202B1 (en) * 1998-05-08 2000-02-29 Dibra Spa PROCESS FOR THE PREPARATION OF S-N, N'-BIS (2-HYDROXY-1- (HYDROXIMETHYL) ETHYL) -5 - ((2-HYDROXY-1-OXOPROPYL) AMINO) -2,4,6-TRIIODE US7790141B2 (en) * 2003-08-11 2010-09-07 Pathak Holdings, Llc Radio-opaque compounds, compositions containing same and methods of their synthesis and use BRPI0814811A2 (en) 2007-07-12 2015-02-03 Ge Healthcare As COMPOUND, AGENT, METHOD, AND DIAGNOSTIC COMPOSITION, USE OF A COMPOUND, AND IMAGE FORMATION METHOD EP2200655B1 (en) 2007-10-12 2012-07-18 GE Healthcare AS Contrast agents US20100221191A1 (en) 2007-10-12 2010-09-02 Duncan George Wynn Contrast agents EP2200971B1 (en) 2007-10-12 2013-04-24 GE Healthcare AS Contrast agents US8202511B2 (en) 2007-10-12 2012-06-19 Ge Healthcare As Contrast agents EP2203190A1 (en) * 2007-10-30 2010-07-07 GE Healthcare AS Contrast agents JP2011509943A (en) * 2008-01-14 2011-03-31 マリンクロッド・インコーポレイテッド Process for preparing iosimenol WO2012136813A2 (en) 2011-04-07 2012-10-11 Universitetet I Oslo Agents for medical radar diagnosis WO2016079330A1 (en) 2014-11-21 2016-05-26 Technical University Of Denmark Gel formulations for local drug release KR102358040B1 (en) 2016-05-20 2022-01-28 테크니칼 유니버시티 오브 덴마크 Facilitable Marker Compositions US20220339285A1 (en) 2019-06-12 2022-10-27 Technical University Of Denmark Dissacharide formulations for controlled drug release Family Cites Families (12) * Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title US2853424A (en) * 1952-08-06 1958-09-23 Schering Ag X-ray contrast agents comprising symmetrical bifunctional analogs of nu-acyl derivatives of 2, 4, 6 triiodo-3-amino benzoic acid US3178473A (en) * 1962-03-02 1965-04-13 Nyegaard & Co As Process for the n-alkylation of acyl anilides halogen substituted in the nucleus US3290366A (en) * 1963-03-06 1966-12-06 Mallinckrodt Chemical Works 5-amino-nu-alkyl-2, 4, 6-triiodoisophthalamic acid derivatives GB1033777A (en) * 1963-06-06 1966-06-22 Sterling Drug Inc Bis-anilide derivatives US3732293A (en) * 1968-03-15 1973-05-08 Sterling Drug Inc Iodinated bis(aminobenzoic acids) and esters thereof CH502104A (en) * 1968-05-02 1971-01-31 Bracco Ind Chimica Spa New X-ray contrast media and processes for their production IE34927B1 (en) * 1969-06-27 1975-10-01 Nyegaard & Co As Non-ionic iodinated x-ray contrast agents US3660464A (en) * 1970-06-19 1972-05-02 Squibb & Sons Inc Tri-iodinated diaminobenzoic acid derivatives BE787669A (en) * 1971-08-17 1973-02-19 Schering Ag N-METHYL-DICARBOXYLIC ACID TRIIODS ANILIDES AND THEIR PREPARATION PROCESS DD104193A5 (en) * 1972-12-22 1974-03-05 DE2629228C2 (en) * 1976-06-25 1984-10-18 Schering AG, 1000 Berlin und 4709 Bergkamen Iodinated isophthalamic acid derivatives Process for their production and their use CH626873A5 (en) * 1977-03-28 1981-12-15 Bracco Ind Chimica Spa 1976 1976-06-23 DE DE2628517A patent/DE2628517C2/en not_active Expired 1977 1977-05-18 NL NLAANVRAGE7705509,A patent/NL189510C/en not_active IP Right Cessation 1977-06-16 DK DK266177A patent/DK150505C/en not_active IP Right Cessation 1977-06-16 FI FI771900A patent/FI67540C/en not_active IP Right Cessation 1977-06-20 PL PL1977199019A patent/PL108102B1/en not_active IP Right Cessation 1977-06-20 CS CS774059A patent/CS199680B2/en unknown 1977-06-20 IE IE1249/77A patent/IE45225B1/en not_active IP Right Cessation 1977-06-20 GB GB25644/77A patent/GB1588733A/en not_active Expired 1977-06-20 GB GB7222/80A patent/GB1588734A/en not_active Expired 1977-06-21 PT PT66690A patent/PT66690B/en unknown 1977-06-21 GR GR53760A patent/GR71696B/el unknown 1977-06-21 IL IL52356A patent/IL52356A/en unknown 1977-06-21 DD DD7700199616A patent/DD131014A5/en unknown 1977-06-21 CH CH761277A patent/CH629751A5/en not_active IP Right Cessation 1977-06-21 LU LU77588A patent/LU77588A1/xx unknown 1977-06-22 HU HU77SCHE611A patent/HU174228B/en unknown 1977-06-22 SE SE7707230A patent/SE436871B/en not_active IP Right Cessation 1977-06-22 CA CA281,184A patent/CA1106400A/en not_active Expired 1977-06-22 SU SU772498151A patent/SU917696A3/en active 1977-06-22 AU AU26325/77A patent/AU512304B2/en not_active Expired 1977-06-22 ES ES460007A patent/ES460007A1/en not_active Expired 1977-06-22 NO NO772202A patent/NO147447C/en unknown 1977-06-23 FR FR7719234A patent/FR2355808A1/en active Granted 1977-06-23 ZA ZA00773782A patent/ZA773782B/en unknown 1977-06-23 IT IT7724994A patent/IT1237314B/en active 1977-06-23 AT AT443777A patent/AT361117B/en not_active IP Right Cessation 1977-06-23 BE BE178719A patent/BE856039A/en not_active IP Right Cessation 1977-06-23 JP JP7489777A patent/JPS537637A/en active Granted 1979 1979-01-12 US US06/002,901 patent/US4239747A/en not_active Expired - Lifetime 1980 1980-03-21 CA CA348,166A patent/CA1106401A/en not_active Expired 1980-06-18 IL IL60344A patent/IL60344A0/en unknown 1981 1981-10-08 IE IE812351A patent/IE45226L/en not_active IP Right Cessation 1982 1982-08-04 NO NO822674A patent/NO148811C/en unknown 1984 1984-12-12 DK DK595284A patent/DK165973C/en not_active IP Right Cessation 1985 1985-07-09 JP JP60149408A patent/JPS61126059A/en active Granted 1993 1993-06-09 LU LU88292C patent/LU88292I2/en unknown Also Published As Publication number Publication date SU917696A3 (en) 1982-03-30 IE45225L (en) 1977-12-03 DK165973C (en) 1993-07-26 FI771900A (en) 1977-12-24 FR2355808B1 (en) 1979-03-09 CH629751A5 (en) 1982-05-14 NO148811B (en) 1983-09-12 JPS6111220B2 (en) 1986-04-01 DK266177A (en) 1977-12-24 PT66690B (en) 1978-11-17 DE2628517C2 (en) 1985-02-21 GR71696B (en) 1983-06-21 LU88292I2 (en) 1994-05-04 IL52356A (en) 1981-03-31 SE436871B (en) 1985-01-28 IT1237314B (en) 1993-05-29 GB1588733A (en) 1981-04-29 DK595284A (en) 1984-12-12 NO822674L (en) 1977-12-27 DK150505C (en) 1988-01-11 NO147447C (en) 1983-04-13 DE2628517A1 (en) 1978-01-05 SE7707230L (en) 1977-12-24 JPS61126059A (en) 1986-06-13 PL199019A1 (en) 1978-03-28 AU512304B2 (en) 1980-10-02 CA1106401A (en) 1981-08-04 CS199680B2 (en) 1980-07-31 CA1106400A (en) 1981-08-04 DK150505B (en) 1987-03-16 US4239747A (en) 1980-12-16 IE45225B1 (en) 1982-07-14 IE45226B1 (en) 1982-07-14 AT361117B (en) 1981-02-25 NO772202L (en) 1977-12-27 NL189510C (en) 1993-05-03 NL7705509A (en) 1977-12-28 AU2632577A (en) 1979-01-04 LU77588A1 (en) 1977-09-29 HU174228B (en) 1979-11-28 DK595284D0 (en) 1984-12-12 ZA773782B (en) 1978-05-30 IL52356A0 (en) 1977-08-31 IL60344A0 (en) 1980-09-16 JPS537637A (en) 1978-01-24 PT66690A (en) 1977-07-01 ATA443777A (en) 1980-07-15 NO147447B (en) 1983-01-03 FI67540B (en) 1984-12-31 DK165973B (en) 1993-02-22 NL189510B (en) 1992-12-01 IE45226L (en) 1982-07-14 DD131014A5 (en) 1978-05-24 BE856039A (en) 1977-12-23 NO148811C (en) 1983-12-21 PL108102B1 (en) 1980-03-31 JPS6232185B2 (en) 1987-07-13 FI67540C (en) 1985-04-10 FR2355808A1 (en) 1978-01-20 ES460007A1 (en) 1978-05-01 Similar Documents Publication Publication Date Title GB1588734A (en) 1981-04-29 Tetracarboxylic acid tetrachlorides FI72321C (en) 1987-05-11 FOERFARANDE FOER FRAMSTAELLNING AV NYA, VID BEHANDLING AV CANCER ANVAENDBARA PLATINA (IV) -DIAMINKOMPLEXER. CA1258865A (en) 1989-08-29 Platinum complexes GB2093845A (en) 1982-09-08 Platinum-diamine complexes useful for the treatment of cancer SU436494A3 (en) 1974-07-15 METHOD OF OBTAINING N, N'-DI [PYRIMIDYL- Baiocchi et al. 1963 Studies on methylglyoxal bis (guanylhydrazone) 1 analogs. II. Structural variations on methylglyoxal bis (guanylhydrazone) 2 DE3319992A1 (en) 1983-12-08 AMIDINE COMPOUNDS, METHOD FOR THEIR PRODUCTION AND PHARMACEUTICAL AGENTS Reinaud et al. 1994 [Hydrotris (3-isopropyl-5-methylpyrazolyl) borato] iodocobalt (II): Unusual Purification by" Inverse Recrystallization" DE2304977A1 (en) 1974-08-08 3-Aminoaryl-5-alkyl-4,5-dihydro-6(1H)-pyridazones - prepd. by reacting 2-alkyl-3-aminoaroyl-propionic acids with hydrazines US4389399A (en) 1983-06-21 Thiocarbamoyl heterocycle-anthraquinone derivatives US4658047A (en) 1987-04-14 Method of preparing 1,2-diaminocyclohexane tetrachloro platinum (IV) isomers EP0331093A1 (en) 1989-09-06 Benzimidazo[1,2-c]quinazolines, their preparation and use DE1232148B (en) 1967-01-12 Process for the preparation of substituted quinoline compounds DE2114884A1 (en) 1972-10-12 Basically substituted derivatives of 1 (2H) -phthalazinone US4233215A (en) 1980-11-11 Aziridinyl quinone antitumor agents Bubnov et al. 1991 A novel method of synthesis of 1-azaadamantane from 1-boraadamantane US3822261A (en) 1974-07-02 5,6-dihalo-2-fluoroalkyl-1h-imidazo(4,5-b)pyrazines HU194243B (en) 1988-01-28 Process for producing n-7-abov-amidino-substituted mitomycin c derivatives DE2918832A1 (en) 1980-11-20 5,6-DIHYDRO-11-ALKYLENE-MORPHANETRIDINE-6-ONE DE2219601A1 (en) 1972-11-16 beta-lactams and processes for their preparation Bruce et al. 1997 Reactions of RuCl (C= CHBut)(PPh3)(hC5Me5) with Tertiary Phosphites: Molecular Structure of RuCl {P (OPh) 3} 2 (h;-C5Me5) JPS594423B2 (en) 1984-01-30 Nyoso Yudo Tainoseihou JPH02501924A (en) 1990-06-28 Method for producing 9-(hydroxy-alkyl)-hypoxanthines US3249605A (en) 1966-05-03 Lower-alkyl esters of 8-chloro-6-nitro-2-oxo-2h-1, 4-benzoxazine-3-lower-alkanoic acids DE1018869B (en) 1957-11-07 Process for the preparation of aminoalkyl purine derivatives Legal Events Date Code Title Description 1981-07-15 PS Patent sealed [section 19, patents act 1949] 1997-07-09 PE20 Patent expired after termination of 20 years Effective date: 19970619
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