NL8700357A - CHEMICAL METHOD. - Google Patents
CHEMICAL METHOD. Download PDFInfo
- Publication number
- NL8700357A NL8700357A NL8700357A NL8700357A NL8700357A NL 8700357 A NL8700357 A NL 8700357A NL 8700357 A NL8700357 A NL 8700357A NL 8700357 A NL8700357 A NL 8700357A NL 8700357 A NL8700357 A NL 8700357A
- Authority
- NL
- Netherlands
- Prior art keywords
- methyl
- methoxy
- lithium
- naphthyl
- process according
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 14
- 239000000126 substance Substances 0.000 title description 2
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- BLXXJMDCKKHMKV-UHFFFAOYSA-N Nabumetone Chemical compound C1=C(CCC(C)=O)C=CC2=CC(OC)=CC=C21 BLXXJMDCKKHMKV-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- -1 alkali metal salt Chemical class 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims 2
- 239000003960 organic solvent Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229960004270 nabumetone Drugs 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- LWOTXBQKJLOAOZ-UHFFFAOYSA-N 1-(6-methoxynaphthalen-2-yl)propan-1-one Chemical compound C1=C(OC)C=CC2=CC(C(=O)CC)=CC=C21 LWOTXBQKJLOAOZ-UHFFFAOYSA-N 0.000 description 1
- LUZDYPLAQQGJEA-UHFFFAOYSA-N 2-Methoxynaphthalene Chemical compound C1=CC=CC2=CC(OC)=CC=C21 LUZDYPLAQQGJEA-UHFFFAOYSA-N 0.000 description 1
- GWCHVJBOXKCOLG-UHFFFAOYSA-N C[Li].C(CC)(=O)O Chemical compound C[Li].C(CC)(=O)O GWCHVJBOXKCOLG-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 208000025747 Rheumatic disease Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005672 Willgerodt-Kindler rearrangement reaction Methods 0.000 description 1
- 230000002917 arthritic effect Effects 0.000 description 1
- 229940045348 brown mixture Drugs 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- 230000000552 rheumatic effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/004—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with organometalhalides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/255—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
% - Chemische werkwijze - -% - Chemical method - -
De uitvinding heeft betrekking op een werkwijze voor de bereiding van 4-(6-methoxy-2-nafty1)butan-2-on.The invention relates to a process for the preparation of 4- (6-methoxy-2-naphthyl) butan-2-one.
Het Amerikaanse octrooischrift 4.061.779 beschrijft 4-(6-methoxy-2-naftyl)-butan-2-on (nabumeton) en 3 het gebruik daarvan bij de behandeling van rheumatische en artritische aandoeningen. Een aantal werkwijzen voor de bereiding van de verbinding worden eveneens beschreven. De Amerikaanse octrooischriften 4.221.741 en 4.247.709 beschrijven andere werkwijzen voor de bereiding van nabumeton.U.S. Patent 4,061,779 describes 4- (6-methoxy-2-naphthyl) -butan-2-one (nabumetone) and its use in the treatment of rheumatic and arthritic conditions. A number of methods for the preparation of the compound are also described. U.S. Patents 4,221,741 and 4,247,709 describe other processes for the preparation of nabumetone.
. ^ Een nieuwe werkwijze voor de bereiding van nabumeton is nu gevonden, welke werkwijze gekenmerkt wordt door de reaktie van een carbonzuur met een methyImetaalderivaat.. A new process for the preparation of nabumetone has now been found, which process is characterized by the reaction of a carboxylic acid with a methyl metal derivative.
Dienovereenkomstig verschaft de uitvinding een werkwijze voor de bereiding van 4-(6-methoxy-2-naftyl)-^ butan-2-on , bij welke werkwijze men een verbinding met formule 1 of een alkalimetaalzout daarvan laat reageren met een methy Imetaalderivaat .Accordingly, the invention provides a process for the preparation of 4- (6-methoxy-2-naphthyl) -butan-2-one, wherein a compound of formula 1 or an alkali metal salt thereof is reacted with a methyl metal derivative.
De verbinding met formule 1 is bij voorkeur een alkalimetaalzout van het zuur , bij voorkeur het lithiumzout.The compound of formula 1 is preferably an alkali metal salt of the acid, preferably the lithium salt.
^0 Geschikte methylmetaalderivaten zijn bijvoorbeeld CHgMgHal waarin Hal halogeen zoals jodium is, of methyllithium. Bij voorkeur is het methylmetaalderivaat methyl-lithium.Suitable methyl metal derivatives are, for example, CHgMgHal wherein Hal is halogen such as iodine, or methyl lithium. Preferably, the methyl metal derivative is methyl lithium.
De reaktie heeft plaats in een inert oplos-^ middel zoals droge diethylether of tetrahydrofuran, bij voorkeur tetrahydrofuran, bij terugvloeitemperaturen wanneer het methylmetaalderivaat CH^MgHal is,of bij 0-50°C wanneer methyllithium gebruikt wordt.The reaction takes place in an inert solvent such as dry diethyl ether or tetrahydrofuran, preferably tetrahydrofuran, at reflux temperatures when the methyl metal derivative is CH 2 MgHal, or at 0-50 ° C when methyl lithium is used.
De verbinding met formule 1 is een bekende verbinding.The compound of formula 1 is a known compound.
Het volgende voorbeeld licht de uitvinding toe.The following example illustrates the invention.
5700357 * ^5700357 * ^
JJ
- 2 -- 2 -
Voorbeeld (zie reaktieschema A).Example (see reaction scheme A).
1. Friedel-Crafts-reaktie1. Friedel-Crafts reaction
AlCl^ (40,5 g) werd in porties onder roeren en afkoelen tot +2°C toegevoegd aan nitroethaan (225 ml) , waarna in de loop van 10 min 2-methoxynaftaleen ( 45 g) toegevoegd werd. De temperatuur daalde tot -5°C en het roodbruine mengsel werd met propionylchloride (28,2 ml) dat in 10 min toegevoegd werd , behandeld. Het mengsel werd 40 min bij +2° geroerd en vervolgens 6| uur tot +35 °C op gewarmd. Water 10 (250 ml) werd in 15 min toegevoegd en de organische produkten werden met MDC geextraheerd, waarna de oplosmiddelen verdampt werden onder verkrijging van het ruwe produkt( 46 g ). Het produkt werd in warme heptaan (+85°C)in aanwezigheid van Celite (10 g) opgelost, heet gefiltreerd en vervolgens afgekoeld onder 15 verkrijging van een lichtgele vaste stof ( 28 g, 45% opbrengst).AlCl 2 (40.5 g) was added portionwise with stirring and cooling to + 2 ° C to nitroethane (225 ml) and 2-methoxynaphthalene (45 g) was added over 10 min. The temperature dropped to -5 ° C and the reddish brown mixture was treated with propionyl chloride (28.2 ml) added over 10 min. The mixture was stirred at + 2 ° for 40 min and then 6 | hours to +35 ° C warmed up. Water 10 (250 ml) was added over 15 min and the organics were extracted with MDC and the solvents evaporated to give the crude product (46 g). The product was dissolved in warm heptane (+ 85 ° C) in the presence of Celite (10 g), filtered hot, then cooled to give a light yellow solid (28 g, 45% yield).
2. Willgerodt-reaktie 2-Methoxy-6-propionylnaftaleen ( 21,4 g ), zwavel ( 4,8 g )en morfoline ( 13 ml) werden 16 uur bij 125° 20 verhit. Natriumhydroxyde ( 10,6 g ) in methanol ( 50 ml) werd vervolgens toegevoegd en het mengsel werd onder terugvloeiing gedurende nog eens· 6 uur verwannd en daarna in HCl/water uitgegoten tot de pH gelijk aan 2 was. De organische produkten werden geextraheerd. Uit normale fase LC (Hexaan: IPA:MDC= 25 92:4:4) bleek dat het produkt twee hoofdbestanddelen bevatte met tR 4,01 min en tR 4,25 min (zuiver 3-(6'-methoxy-2'-naftyl)-propionzuur heeft t„ 4,20 min ). Hét smeltpunt van het produkt was 143° (vergelijk 154° voor het vereiste zuur ).2. Willgerodt reaction 2-Methoxy-6-propionylnaphthalene (21.4 g), sulfur (4.8 g) and morpholine (13 ml) were heated at 125 ° for 16 hours. Sodium hydroxide (10.6 g) in methanol (50 ml) was then added and the mixture was refluxed for an additional 6 hours and then poured into HCl / water until the pH was equal to 2. The organic products were extracted. Normal phase LC (Hexane: IPA: MDC = 25 92: 4: 4) showed that the product contained two main components with tR 4.01 min and tR 4.25 min (pure 3- (6'-methoxy-2'- naphthyl) propionic acid has 4,20 min. The melting point of the product was 143 ° (compare 154 ° for the required acid).
30 . ...30. ...
3. Propionzuur -methyllithium-reaktie3. Propionic acid methyl lithium reaction
Een suspensie van het lithiumzout v.an 3—(6'-methoxy-2'-naftyl)propionzuur ( 5,0 g ) in THF (150 ml) werd geroerd en tot ongeveer -10°C afgekoeld. Methyllithium ( 28 ml 1,6 M oplossing in diethylether) werd in de loop van 10 min 35A suspension of the lithium salt of 3- (6'-methoxy-2'-naphthyl) propionic acid (5.0g) in THF (150ml) was stirred and cooled to about -10 ° C. Methyllithium (28 ml 1.6 M solution in diethyl ether) became 35 over 10 min
via een spuit toegevoegd . Het verkregen mengsel werd bij -10°Cadded via a syringe. The resulting mixture was at -10 ° C
8700357 - -I* Λ η - 3 - gedurende nog eens 15 mln geroerd en daarna 6 uur tot +25°C verwarmd. De produkten werden in ijs/water (150 ml) afgeschrikt en met MDC geextraheerd, waarna het oplosmiddel verdampt werd onder verkrij ging van ongeveer 4,2 g ruw prodükt.8700357 - -I * Λ η - 3 - stirred for another 15 ml and then heated to + 25 ° C for 6 hours. The products were quenched in ice / water (150 ml) and extracted with MDC, after which the solvent was evaporated to obtain about 4.2 g of crude product.
87003578700357
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8603777 | 1986-02-15 | ||
| GB868603777A GB8603777D0 (en) | 1986-02-15 | 1986-02-15 | Chemical process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NL8700357A true NL8700357A (en) | 1987-09-01 |
Family
ID=10593133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NL8700357A NL8700357A (en) | 1986-02-15 | 1987-02-13 | CHEMICAL METHOD. |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPH0733345B2 (en) |
| CH (1) | CH670082A5 (en) |
| DK (1) | DK75387A (en) |
| ES (1) | ES2004224A6 (en) |
| GB (1) | GB8603777D0 (en) |
| GR (1) | GR870257B (en) |
| NL (1) | NL8700357A (en) |
| SE (1) | SE8700593L (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5756851A (en) * | 1996-10-21 | 1998-05-26 | Albemarle Corporation | Production of nabumetone or precursors thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT338257B (en) * | 1975-01-08 | 1977-08-10 | Beecham Group Ltd | PROCESS FOR PRODUCING NEW NAPHTHALIN DERIVATIVES |
-
1986
- 1986-02-15 GB GB868603777A patent/GB8603777D0/en active Pending
-
1987
- 1987-02-13 GR GR870257A patent/GR870257B/en unknown
- 1987-02-13 ES ES8700374A patent/ES2004224A6/en not_active Expired
- 1987-02-13 SE SE8700593A patent/SE8700593L/en not_active Application Discontinuation
- 1987-02-13 NL NL8700357A patent/NL8700357A/en not_active Application Discontinuation
- 1987-02-13 DK DK75387A patent/DK75387A/en not_active Application Discontinuation
- 1987-02-13 CH CH53787A patent/CH670082A5/en not_active IP Right Cessation
- 1987-02-14 JP JP3229487A patent/JPH0733345B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT338257B (en) * | 1975-01-08 | 1977-08-10 | Beecham Group Ltd | PROCESS FOR PRODUCING NEW NAPHTHALIN DERIVATIVES |
Non-Patent Citations (2)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 090, no. 1, 1 January 1979, Columbus, Ohio, US; abstract no. 000223, GOUDIE A C ET AL: "4-(6-Methoxy-2-naphthyl)butan-2-one and related analogs, a novel structural class of antiinflammatory compounds" * |
| J. MED. CHEM. (JMCMAR,00222623);78; VOL.21 (12); PP.1260-4, BEECHAM PHARM.;MED. RES. CENT.; HARLOW/ESSEX; ENGL. * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5756851A (en) * | 1996-10-21 | 1998-05-26 | Albemarle Corporation | Production of nabumetone or precursors thereof |
| US5907069A (en) * | 1996-10-21 | 1999-05-25 | Albemarle Corporation | Production of nabumetone or precursors thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8603777D0 (en) | 1986-03-19 |
| JPH0733345B2 (en) | 1995-04-12 |
| SE8700593D0 (en) | 1987-02-13 |
| CH670082A5 (en) | 1989-05-12 |
| GR870257B (en) | 1987-06-16 |
| DK75387A (en) | 1987-08-16 |
| DK75387D0 (en) | 1987-02-13 |
| SE8700593L (en) | 1987-08-16 |
| JPS62195343A (en) | 1987-08-28 |
| ES2004224A6 (en) | 1988-12-16 |
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| BA | A request for search or an international-type search has been filed | ||
| BB | A search report has been drawn up | ||
| BV | The patent application has lapsed |