IE49389B1 - Process for the preparation of xanthone derivatives - Google Patents
Process for the preparation of xanthone derivativesInfo
- Publication number
- IE49389B1 IE49389B1 IE250/80A IE25080A IE49389B1 IE 49389 B1 IE49389 B1 IE 49389B1 IE 250/80 A IE250/80 A IE 250/80A IE 25080 A IE25080 A IE 25080A IE 49389 B1 IE49389 B1 IE 49389B1
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- IE
- Ireland
- Prior art keywords
- formula
- compound
- effected
- group
- hydrolysis
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
- C07D311/82—Xanthenes
- C07D311/84—Xanthenes 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 in position 9
- C07D311/86—Oxygen atoms, e.g. xanthones
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Pyrane Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Diaphragms For Electromechanical Transducers (AREA)
- Peptides Or Proteins (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
A process for the preparation of compounds of general formula I, <IMAGE> (wherein R represents a hydrogen atom or an alkyl radical containing from 1 to 9 carbon atoms and R1 represents an alkyl radical containing from 1 to 5 carbon atoms) which comprises cyclising a compound of formula II, <IMAGE> (wherein R and R1 are as defined above, Ar represents an aryl group and R2 and R3, which may be the same or different, each represents an esterifying group) followed if required, by hydrolysis to the free acid of formula I. The compounds of general formula I possess interesting anti-allergic activity.
Description
This invention relates to a novel process for preparing xanthone derivatives of interest in the treatment of allergic conditions.
According to the present invention, there is provided a process for the preparation of compounds of general formula I, COOH (I) (wherein R represents a hydrogen atom or an alkyl radical containing from 1 to 9 carbon atoms and R^ represents an alkyl radical containing from 1 to 5 carbon atoms) which comprises cyclising a compound of formula II, (wherein R and R^ are as defined above, Ar represents an aryl group and R2 and Rg, which may be the same or different, each represents an esterifying group) followed, if required, by hydrolysis to the free acid of formula I.
The compounds of general formula I are described in our Irish Patent Specification No. 42122.
As indicated therein they possess interesting anti10 allergic activity and are, in particular, of importance in the treatment of allergic asthma and bronchial asthma of allergic origin. According to the present invention, these compounds may be prepared in good yields, using relatively stable intermediates and avoiding the use of azides in the formation of the sulphonimidoyl groupings.In general, R preferably represents an n-hexyl radical and R^ preferably represents a methyl radical. Ar preferably represents a monocyclic aryl group having 6 to 10 carbon atoms, e.g. a phenyl group which may carry substituents such as alkyl groups e.g. methyl groups. The £-tolyl group is preferred.
In the compound of formula II, R2 and Rg may, for example, each represent an alkyl group containing from 1 to 3 carbon atoms; an aryl, e.g. nitrophenyl, group; an aralkyl, e.g. nitrobenzyl, group; or a dialkylaminoalkyl, e.g. dimethylaminoethyl, group. According to a preferred embodiment the esterifyirig groups I<2 and R^ are such as to enable the compound of formula II to be obtained in a crystallised form so as to facilitate the preparation of pure compound of formula II.
Cyclisation of the compound of formula II is conveniently effected by means of a strong acid such as, for example, polyphosphoric or concentrated sulphuric acid, in which case hydrolysis to the free acid of formula I generally takes place simultaneously or, for example, on addition of water.Where, however, a corresponding ester and/or arylsulphonimidoyl derivative is the final product of the cyclisation reaction, hydrolysis to the free acid of formula I may take place in a separate stage according to conventional methods, e.g. by heating in acidic or basic solution. Preferred temperatures for the cyclisation are from 100 to 150°C.
The compound of formula II may be obtained, if desired, by reaction of a compound of formula III, (wherein R, R^ and Ar are as hereinbefore defined) with a compound of formula IV, (III) r3oo Hal coor2 (IV) (wherein R2 and R3 are as hereinbefore defined and Hal represents a chlorine, bromine or iodine atom) in the presence of a weak base and of metallic copper or a copper oxide, preferably in the form of a powder.
The weak base may, for example, be an alkali metal carbonate e.g. sodium or potassium carbonate. The reaction is preferably effected under reflux.
The compound of formula III may be prepared, for 10 example, by hydrolysis of a compound of formula V, (wherein R, R^ and Ar are as hereinbefore defined and represents an acyl group, for example a group of formula -CO-X where X represents an alkyl group 15 containing from 1 to 3 carbon atoms or a phenyl group).
Hydrolysis is preferably effected by means of an aqueous solution of a weak base such as, for example, an alkali metal carbonate, e.g. sodium carbonate, and preferably at the boiling point of the reaction mixture.
The compound of formula V may be formed, if desired, by oxidation of a compound of formula VI, (wherein R, Rj,R^ and Ar are as hereinbefore defined) e.g. using a periodate such as sodium metaperiodate, preferably in the presence of ruthenium (IV) oxide, or a peroxide oxidising agent . The oxidation is preferably effected in the presence of an organic solvent for the compound of formula VI, such as, for example, a halogenated hydrocarbon e.g. dichloromethane. Periodates will normally be used in aqueous solution, in which case a 2-phase solvent system may be present.
The compound of formula VI may itself be obtained, if desired, by reaction of a compound of formula VII, RI-S 0-R, (VII) R (wherein R, R. and R are as hereinbefore defined) *· 4 cj15 with a reagent of the formula ArS02NC^M+ (where Ar has the above meaning and M represents an alkali metal atom) Cl- advantagously chloramine T (£-tolyl-S02N^^a+ ).
The reaction is preferably effected in the presence of an organic solvent, most preferably an alkanol such as e.g. isopropanol.
The compound of formula VII may in turn be prepared, for example, by reaction of a compound of formula VIII, R^-S OH (VIII) R (wherein R and R^ are as hereinbefore defined) with an appropriate acylating agent, for example an acid halide or anhydride. Thus, for example when R^ in the compound of formula VII represents a group of formula -CO-X (where X is as hereinbefore defined) the acylating agent may be a compound of formula Z-GO-X (where Z represents a chlorine or bromine atom) or a compound of formula (X-CO)2O. The reaction of the compound of formula VIII with the acylating agent is preferably effected in the presence of an anhydrous organic solvent such as, for example, pyridine.
The following non-limiting Examples serve to illustrate the invention.
Example 1 -Hexyl-7-(S-me thylsulphonomidoyl)xanthone-2-carboxylic acid Step A: 1-hexyl-4-(methylthi£)johenyl_benzoat e A solution of 2-hexyl-4-(methylthio)phenol (75 g) in pyridine (225 ml) was·.stirred with benzoyl chloride (100 g) at room temperature for two hours. Water (450 ml) was then added thereto and the resultant mixture was stirred for 1 hour. The product thus formed was filtered off, washed with water and dried to give 2-hexyl-4(methylthio)phenyl benzoate (110 g, 100 %) as a colourless, crystalline solid, m.p. 57-58°.
Step B Z-heicy^-^-^S-methjrl^N^tos^lsulphiraido^O £henyl_b£n£oate The 2-hexyl-4-(methylthio)phenyl benzoate obtained in step A (50 g) was added over 15 min. to a stirred solution of chloramine-T (43 g) in isopropanol (IL) at 50°. After stirring for 15 min. the suspension obtained was filtered, cooled to 0°C and crystallisation induced.
The product thus formed was filtered off and dried to give 2-hexyl-4-(S-methyl-N-tosylsulphinfi.doyIiphenyl benzoate (63 g, 83%) as a colourless crystalline solid, m.p. 111-112°.
Step C:_ 2-hexyl-4-£S£methyl-N-tosylsul£honimidoyl)^ phenyl benzoate A solution of the 2-hexyl-4-(S-methyl-N-tosylsulphimidoyl)phenyl benzoate obtained in step B (50 g) in dichloromethane (250 ml) was stirred vigorously 49388 with ruthenium (IV) oxide (100 mg) and aqueous sodium periodate (50 ml , 10% w/v). A pale green emulsion was formed which darkened considerably after a few minutes when the periodate had been consumed. The process was repeated with four successive quantities of aqueous sodium periodate (50 ml, 10% w/v), the time taken to reprecipitate the catalyst increasing on each occasion. The total weight of sodium periodate used was 25 g.
The organic layer was separated and the aqueous layer extracted with dichloromethane (100 ml). The combined organic solutions'· were washed with water, dried (MgSO^) and evaporated under reduced pressure to give a colourless oil which was used directly in the next step.
The catalyst may be recovered by filtering the reaction mixture. The oil can be crystallised if required by trituration in IMS to give a colourless, crystalline solid, m.p. 90-91°.
Step D: 2- hexyL·S-methyl - Nyto sylsulphonimidoyl2jshenol The oil from the previous step was dissolved in methanol (250 ml) and the solution obtained was mixed with aqueous sodium carbonate (10%, 500 ml) and heated with stirring at 60° for 3 hours, whereupon a clear solution was obtained. The solution was treated at room temperature with hydrochloric acid (20%, 100 ml) and the product thus formed extracted with chloroform. Evaporation of the solvent under reduced pressure and trituration of the residue with 40-60 petrol gave 2-hexyl-4-(S-methyl-N-tosylsulphonimidoyl)phenol (40 g, 97% over two steps) as a colourless crystalline solid, m.p. 109-110°.
Step E: dirne_thyl_4^[ 2-hexyl-4-_£S^me thy 1-N-tosyl5 sulphonimidoy;l^phenoxyjisaphthalate! A mixture of the 2-hexyl-4-(S-methyl-N-tosylsulphonimidoyl)phenol obtained in the previous Step (20 g), dimethyl 4-bromoisophthalate (15 g), potassium carbonate (LO g), copper powder (1 g), nitrobenzene (100 ml) and toluene (50 ml) was stirred under nitrogen and heated slowly to 160° while some of the toluene (approx. 25 ml) was distilled out to dry the mixture. The temperature was maintained at 160° for 2 hours and then the remainder of the solvent was distilled off under reduced pressure. The cooled residue was dissolved in dichloromethane (400 ml) and the solution obtained was filtered and evaporated under reduced pressure. The residue was dissolved in ether (250 ml) and induced to crystallise by cooling the solution obtained to 0°. The solid was filtered off, washed with ether and dried to give dimethyl· 4-[2-hexyl4-(S-methyl-N-tosylsulphonimidoyl)phenoxy]isophthalate (15.7 g, 53%), as a light brown crystalline solid, m.p. 124-126°. The filtrate was evaporated to dryness and the residue triturated in 40-60 petrol to give a second crop of crude product (6.8g) in need of further purification.
Step F: 5-hexyl-7-(S-methylsulphonimidoyl)xanthone2-carboxyHc_acid A solution of the dimethyl 4-[2-hexyl-4-(S-methyl10 N-tosylsulphonimidoyl)phenoxy]isophthalate obtained in the previous step (5 g) in concentrated sulphuric acid (25 ml) was heated at 120° for 1 hour, cooled a little and poured with vigorous stirring into water (250 ml).
The solid thus precipitated was filtered off, washed with water and recrystallised from methanol to give 5-hexyl-7-(S-methylsulphonimidoyl)xanthone-2-carboxylic acid (2.5 g, 74.9%).
Example 2 -Hexyl-7-(S-methylsulphonimidoyl)xanthone-2-carboxylic acid Step A: 2-hexyl-4-^methylthio)phenxl_acetate A,solution of 2-hexyl-4-(methylthio)phenol (6.6 g) in pyridine (36 ml) and acetic anhydride (18 ml) was stirred overnight at room temperature and then poured into water. The mixture obtained was extracted with ether. The organic extract was washed with dilute hydrochloric acid, sodium bicarbonate solution and finally with water then evaporated to dryness. 2-Hexyl-4-(methylthio)phenyl acetate was obtained as a pale yellow oil (7.45 g, 95%). step B; 2-lie2iyi_Ai.siin£tiiyi"ii-£.0^yisii1£llimid2yI)r. j>henyl_acetate_ A solution of the 2-hexyl-4-(methylthio)phenyl acetate obtained in the previous step (5 g) and chloramine-T trihydrate (6.5 g) in dioxan (250 ml) and water (125 ml) was stirred for five hours, then evaporated to dryness leaving ρ red viscous oil (11 g). 49388 The residue was chromatographed on a silica gel column eluting with chloroform and collecting 50 ml fractions. Fractions (3)-(6) gave pure 2-hexyl-4-(S-raethyl-Ntosylsulphimidoyl)phenyl acetate as a colourless viscous oil which solidified to a white crystalline solid upon triturating with ice-cold petrol (60-80°) (5 g, 61%, m.p. 62-5°).
Step: C: 2 - hexyl - 4-£S heethy1 -' N-1osy1sulphonjjnidoy1) 10 £henjrl_acetate A solution of the .2-hexyl-4-(S-methyl-N-tosyl-. sulphimidoyl)phenyl acetate obtained in the previous step (1 g) in dichloromethane (40 ml) was treated with a solution of sodium metaperiodate (1 g) in water and soluble ruthenium (IV) oxide (5 mg). The resultant mixture was stirred for 30 mins, then a further 5 mg of ruthenium oxide and 0.3 g metaperiodate were added thereto. Stirring was continued for a further 15 mins, then the organic layer was separated, filtered and evaporated to dryness. The residue was chromatographed on a silica gel column eluting with ethyl acetate. Fractions (2)-(3) gave pure 2-hexyl-4-(S-methyl-Ntosylsulphonimidoyl)phenyl acetate as a colourless viscous oil which solidified on cooling (0.88 g, 85%).
Step D: 2"hexyi’A"£S;Lmethy 1-N-1osylsulphonimidoy1)phenol A suspension of the oily 2-hexyl-4-(S-methyl-N30 tosylsulphonimidoyl) phenyl, acetate obtained in the previous step (0.8 g) in saturated sodium carbonate solution (30 ml) and ethanol (15 ml) was stirred at 50° for 15 mins, after which time all the oil had dissolved. The resultant solution was poured into water, acifified with cone, hydrochloric acid and extracted with ether. Evaporation of the solvent gave 2- hexyl-4-(S-methyl-N-tosylsulphoniraidoyl)phenol as a white oil which solidified to a white crystalline solid upon triturating with ether/petrol (60-80°) (0.65 g, 90% m.p. 107-9°).
Step E: dimethjrl_/r[ 2-hexyl-_4-r£S;met hyl-N-.t o^ylsulphert; ____^.imidqyljphenq^yj-jso^ht.halate A solution of the 2- hexyl-4-(S-methyl-N-tosyl15 sulphonimidoyl)phenol obtained in the previous step (0.4 g) and dimethyl bromoisophthalate (0.3g) in nitrobenzene (10 ml) was dried azeotropically by the addition and distillation of benzene. The resultant solution was treated with copper powder (50 mg) and anhydrous potassium carbonate (0.4 g) and stirred for 2 hours at 160° under a stream of dry nitrogen gas.
The mixture thus obtained was cooled, diluted with chloroform, filtered and the solvent was evaporated off under high vacuum leaving a red/brown viscous oil.
Trituration of the oil with petrol (60-80°) caused it to solidify to a buff crystalline solid which was the required dimethyl 4-f2-hqxyl-4-(S-methyl-N-tosylsulphonimidoyl)-phenoxy]-isophthalate (0.53 g, 90%). The product was obtained as a white crystalline solid after passage through a short silica gel column eluting with chloroform (m.p. 115-7°).
Step F: methy ly5^hexy ly7y(S^-methylsulphonimidoyO·' xanthone^ycarboxylate A solution of the dimethyl 4-[2-hexyl-4-(S-methylN-to sylsulphonimidoyl)-phenoxy]-isophthalate obtained in the previous step (0.2 g) in polyphosphoric acid (4ml) was stirred at 80° for ten minutes and the temperature gradually increased to 120°. The resultant dark red viscous reaction mixture was stirred a further 1¾ hours at 120° and then cooled and poured into water to give a yellow viscous oil which was extracted into ethyl acetate. The product thus obtained (0.11 g) was a mixture of methyl 5-hexyl-7-(S-methylsulphonimidoyl)xanthone-2-carboxylate and the corresponding acid (shown by tic and NMR spectra). The ester was obtained pure by column chromatography on silica gel eluting with ethyl acetate and collecting 50 ml fractions. Fractions (9)-(12) gave the pure methyl 5-hexyl-7(S-methylsulphonimidoyl)xanthone-2-carboxylate as a white crystalline solid.
Step G: 5-hexyi-i-iS^methylsu.lphonimi.doy 1^)xanthene^ 2-carboxylic_acid A solution of the· methyl 5-hexyl-7-(S-methylsulphonimidoyl)xanthone-2-carboxylate obtained in the previous step (0.1 g) in ethanol (5 ml) and water (1 ml) was treated with 0.2 N sodium hydroxide solution (2.7 ml) and the resultant mixture was refluxed for 1 hour. After cooling, the solution obtained was acidified with 2 N hydrochloric acid solution. -hexyl-7-(S-methylsulphonimidoyl)xanthone-2-carboxylic acid separated out as a white solid and was filtered off and washed well with water. (0.09 g, 93%, m.p. 193-4°).
Claims (35)
1.L. A process for the preparation of compounds of general formula I, (wherein R represents a hydrogen atom or an alkyl 5 radical containing from 1 to 9 carbon atoms and represents an alkyl radical containing from 1 to 5 carbon atoms) which comprises cyclising a compound of formula II, (wherein R and R^ are as defined above, Ar represents an 10 aryl group and R 2 and R^> which may be the same or different, each represents an esterifying group) followed if required, by hydrolysis to the free acid of formula I.
2. A process as claimed in claim 1 wherein R represents an n-hexyl radical. 15
3. A process as claimed in claim 1 or claim 2 wherein represents a methyl radical.
4. A process as claimed in any preceding claim wherein, in the compound of formula II, Ar represents a monocyclic aryl group having from 6 to 10 carbon atoms. 20
5. A process as claimed in claim 4 wherein, in the compound of formula II, Ar represents a phenyl group optionally substituted by one or more alkyl groups.
6. A process as claimed in claim 5 wherein, in the compound of formula XI, Ar represents a £-tolyl group.
7. A process as claimed in any preceding claim wherein 5 in the compound of formula II, R 2 and R^, which may be the same or different, each represents an alkyl group containing from 1 to 3 carbon atoms or an aryl, aralkyl or dialkylaminoalkyl group.
8. A process as claimed in claim 7 wherein, in the 10 compound of formula II, R 2 and R^, which may be the same or different, each represents a nitrophenyl, nitrobenzyl or dimethylaminoethyl group.
9. A process as claimed in any preceding claim wherein cyclisation is effected by means of a strong acid. 15
10. A process as claimed in claim 9 wherein the strong acid is polyphosphoric or concentrated sulphuric acid,
11. A process as claimed in any preceding claim wherein the cyclisation is effected at temperatures of from 100 to 150°C. 20
12. A process as claimed in any preceding claim in which the acid of formula I is formed by hydrolysis during the cyclisation Step or by addition of water.
13. A process as claimed in any of claims 1 to 11 in which the product of the cyclisation step is subjected to 25 hydrolysis in a separate stage.
14. A process as claimed in any preceding claim wherein the compound of formula II is obtained by reaction of a compound of formula III, 48389 (III) (wherein R, and Ar are as defined in claim 1) with a compound of formula IV, R-OOi ΧΙΓ (wherein R 2 and R^ are represents a chlorine, - coor 2 (IV) as defined in claim 1 and Hal bromine or iodine atom) in the presence of a weak base and of metallic copper or a copper oxide.
15. A process as claimed in claim 14 wherein the metallic copper or copper oxide is in the form of a powder.
16. A process as claimed in claim 14 or claim 15 wherein the weak base is an alkali metal carbonate.
17. A process as claimed in any one of claims 14 to 16 wherein the reaction of the compound of formula III with the compound of formula IV is effected under reflux.
18. A process as claimed in any one of claims 14 to 17 wherein the compound of formula III is obtained by hydrolysis of a compound of formula V, 49383 (wherein R, R^ and Ar are as defined in claim 1 and R^ represents an acyl group).
19. A process as claimed in claim 18 wherein, in the 5. Compound of formula V, R^ represents a group of formula -CO-X (where X represents an alkyl group containing from 1 to 3 carbon atoms or a phenyl group).
20. A process as claimed in claim 18 or claim 19 wherein hydrolysis of the compound of formula V is effected by 6. 10 means of an aqueous solution of a weak base.
21. A process as claimed in claim 20 wherein hydrolysis of the compound of formula V is effected by means of an aqueous solution of an alkali metal carbonate.
22. A process as chimed in any one of claims 13 to 21 15 wherein the hydrolysis of the compound <£formula V is effected at the boiling point of the reaction mixture.
23. A process as claimed in any one of claims 18 to 22 wherein the compound of formula V is obtained by oxidation of a compound of formula VI, (wherein R, R. and Ar are as defined in claim 1 and R i 4 is as defined in claim 18). 49388
24. A process as claimed in claim 23 wherein oxidation is effected by means of a periodate or a peroxide oxidising agent.
25. A process as claimed in claim 24 wherein oxidation is 5 effected by means of sodium metaperiodate in the presence of ruthenium (IV) oxide.
26. A process as claimed in any one of claims 23 to 25 wherein the oxidation is effected in the presence of a halogenated hydrocarbon as solvent. 10
27. A process as claimed in any one of claims 23 to 26 wherein the compound of formula VI is obtained by reaction of a compound of formula VII, o-r 4 (VII) R (wherein R and Rj are as defined in claim 1 and is as 15 defined in claim 18 ) with a reagent of formula CI ArSO 2 N (wherein Ar is as defined in claim 1 and M represents an alkali metal atom).
28. A process as claimed in claim 27 wherein the reagent 20 of formula ArSO^N^ is chloramine T.
29. A process as claimed in claim 27 ar cletim 28 wherein the reaction ot the compound of formula Vll with the 49388 Cl reagent of formula ArSC^N is effected in the presence of an alkanol as solvent.
30. A process as claimed in any one of claims 27 to 29 , wherein the compound of formula VII is obtained by reac5 tion of a compound of formula VIII, R -S OH (VIII) R (wherein R and R^ are as defined in claim 1) with an appropriate acylating agent.
31. A process as claimed in claim 30 wherein the 10 acylating agent is an acid halide or anhydride.
32. A process as claimed in claim 30 or claim 31 wherein the reaction of the compound of formula VIII with the acylating agent is effected in the presence of an anhydrous organic solvent.
33. 15 33. A process for the preparation of compounds of general formula I as defined and claimed in claim 1 substantially as herein described.
34. A process for the preparation of compounds of general formula I as claimed in claim 1 substantially as herein 8. 20 described in Example 1 or Example 2.
35. Compounds of general formula I as defined in claim 1 whenever prepared by a process as claimed in any one ot claims 1 to 34.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7904649 | 1979-02-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE800250L IE800250L (en) | 1980-08-09 |
| IE49389B1 true IE49389B1 (en) | 1985-10-02 |
Family
ID=10503083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE250/80A IE49389B1 (en) | 1979-02-09 | 1980-02-08 | Process for the preparation of xanthone derivatives |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0016665B1 (en) |
| JP (1) | JPS55108867A (en) |
| AT (1) | ATE967T1 (en) |
| AU (1) | AU531013B2 (en) |
| CA (1) | CA1146571A (en) |
| DE (1) | DE3060348D1 (en) |
| DK (1) | DK145948C (en) |
| ES (1) | ES8102115A1 (en) |
| FI (1) | FI800392A (en) |
| GB (1) | GB2042540B (en) |
| HU (1) | HU180552B (en) |
| IE (1) | IE49389B1 (en) |
| IL (1) | IL59046A (en) |
| PT (1) | PT70795B (en) |
| ZA (1) | ZA80141B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL47519A (en) * | 1974-07-09 | 1979-03-12 | Roussel Uclaf | 7-sulphinimidoyl(sulphimidoyl)-xanthone-2-carboxylic acid derivatives, their preparation and pharmaceutical compositions containing them |
| JPS5850225B2 (en) * | 1976-01-01 | 1983-11-09 | ルセル・ユクラフ | Novel xanthones, their salts and esters, and pharmaceuticals comprising these compounds |
| SE445346B (en) * | 1978-03-03 | 1986-06-16 | Roussel Uclaf | SET TO PREPARE 7-SULPHONIMIDOYL-XANTON-2-CARBOXYLIC ACID DERIVATIVE |
-
1979
- 1979-12-27 IL IL59046A patent/IL59046A/en unknown
-
1980
- 1980-01-08 HU HU808033A patent/HU180552B/en unknown
- 1980-01-10 ZA ZA00800141A patent/ZA80141B/en unknown
- 1980-01-30 AT AT80400146T patent/ATE967T1/en not_active IP Right Cessation
- 1980-01-30 EP EP80400146A patent/EP0016665B1/en not_active Expired
- 1980-01-30 DE DE8080400146T patent/DE3060348D1/en not_active Expired
- 1980-02-07 PT PT70795A patent/PT70795B/en not_active IP Right Cessation
- 1980-02-08 DK DK54180A patent/DK145948C/en not_active IP Right Cessation
- 1980-02-08 GB GB8004291A patent/GB2042540B/en not_active Expired
- 1980-02-08 FI FI800392A patent/FI800392A/en not_active Application Discontinuation
- 1980-02-08 IE IE250/80A patent/IE49389B1/en unknown
- 1980-02-08 AU AU55350/80A patent/AU531013B2/en not_active Ceased
- 1980-02-08 ES ES488385A patent/ES8102115A1/en not_active Expired
- 1980-02-08 CA CA000345339A patent/CA1146571A/en not_active Expired
- 1980-02-08 JP JP1376980A patent/JPS55108867A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| EP0016665A1 (en) | 1980-10-01 |
| IL59046A0 (en) | 1980-03-31 |
| HU180552B (en) | 1983-03-28 |
| ATE967T1 (en) | 1982-05-15 |
| IE800250L (en) | 1980-08-09 |
| ZA80141B (en) | 1981-02-25 |
| DE3060348D1 (en) | 1982-06-24 |
| AU531013B2 (en) | 1983-08-04 |
| DK145948B (en) | 1983-04-25 |
| ES488385A0 (en) | 1980-12-16 |
| DK145948C (en) | 1983-09-26 |
| PT70795B (en) | 1981-06-11 |
| GB2042540A (en) | 1980-09-24 |
| FI800392A (en) | 1980-08-10 |
| ES8102115A1 (en) | 1980-12-16 |
| DK54180A (en) | 1980-08-10 |
| PT70795A (en) | 1980-03-01 |
| GB2042540B (en) | 1982-11-24 |
| IL59046A (en) | 1985-03-31 |
| AU5535080A (en) | 1980-08-14 |
| EP0016665B1 (en) | 1982-05-05 |
| CA1146571A (en) | 1983-05-17 |
| JPH0144710B2 (en) | 1989-09-29 |
| JPS55108867A (en) | 1980-08-21 |
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