ZA200306164B - Method for preparing compounds derived from thiazolidinedione, oxazolidinedione or hydantoin. - Google Patents

Method for preparing compounds derived from thiazolidinedione, oxazolidinedione or hydantoin. Download PDF

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ZA200306164B
ZA200306164B ZA200306164A ZA200306164A ZA200306164B ZA 200306164 B ZA200306164 B ZA 200306164B ZA 200306164 A ZA200306164 A ZA 200306164A ZA 200306164 A ZA200306164 A ZA 200306164A ZA 200306164 B ZA200306164 B ZA 200306164B
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South Africa
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formula
formic acid
pph
compound
hydrogen
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ZA200306164A
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Michel Bulliard
Yvon Derrien
Tony Pintus
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Ppg Sipsy
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Publication of ZA200306164B publication Critical patent/ZA200306164B/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three 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
    • C07D263/44—Two oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two 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
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • C07D233/76—Two oxygen atoms, e.g. hydantoin with substituted hydrocarbon radicals attached to the third ring carbon atom
    • C07D233/78—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/96—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three 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
    • C07D277/34—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

N } ° oo.
The present invention pertains to a new method for the preparation of thiazolidinedione, oxazolidinedione and hydantoin derivative compounds of formula (1) from compounds of formula (11 below:
R1 9 Ry py OL — SA n /) a
Qf 1
In which — Q represents an oxygen atom or a sulfur atom; — Q1 represents an oxygen atom or a sulfur atom, — R1 and R2, which can be identical or different, represent a hydrogen atom, a C.4 alkyl chain, a cycloalkyl, an alkylaryl, an arylalkyl; said alkyl, cycloalkyl, alkylaryl or arylalkyl groups being optionally substituted by an alkyl, an alkoxy or aryloxy, a halogen, a hydroxy, a sulfino, a sulfonyl, an amino such as NH,, NHR;, N(R3),, with R3 representing an alkyl, an alkoxy or an alkylcarbonyl.
The thiazolidinedione, oxazolidinedione and hydantoin derivative compounds of formula (I) are known as synthesis intermediaries for the preparation of active pharmaceutical principles or as active pharmaceutical agents such as, for example, pioglitazone, rosiglitazone, troglitazone and ciglitazone.
Known in the prior art are methods for the preparation of thiazolidinedione, oxazolidinedione, and hydantoin derivative compounds: — via reduction in the presence of a metal hydride as described in international patent application WO 98/37073, or — via reduction in the presence of a transition metal as described in European patent EP 257781, — or via reduction in the presence of magnesium and methanol as described in international patent application WO 98/37073.
These various methods present the disadvantages of generating large amounts of impurities, which can exceed 10% in the synthesis of pioglitazone, of using a large amount of catalyst or solvent, and of having a selectivity problem in the isolation of the resultant compound of formula (1).
The method according to the invention presents the advantages of preparing said compounds of formula (I) while generating low amounts of impurities, of obtaining a total transformation rate, of eliminating the use of large amounts of solvent, of being selective and of easily isolating the product of formula (I). The method according to the present invention thus makes it possible to reduce the economic costs of industrial production of compounds of formula (1).
The present invention thus has as its object a method for the preparation of a thiazolidinedione, oxazolidinedione or hydantoin derivative compound of formula (I) from a compound of formula (ll) below: 9 Ri QR w= EE aw SA (h /) oC
Qf / in which Q, Q1, R1 and R2 have the same meanings as above, characterized in that a compound of formula (ll) is brought to react with formic acid, either as a hydrogen donor in a hydrogen-transfer reaction or as a solvent in a hydrogenation reaction, in the presence of a catalyst based on a transition metal, in order to obtain the corresponding compound of formula (n.
The formic acid used can be formic acid at 100% or a solution containing formic acid with a formic acid level that can range from 0.1 to 99% as long as said solution can dissolve the compound of formula (Il). Said solution can be an aqueous solution or an organic solution or a mixture of these two.
The transition-metal based catalyst employed either in the hydrogen-transfer reaction or in the hydrogenation reaction is advantageously selected from a homogeneous or heterogeneous catalyst.
The following can be cited as homogeneous catalysts based on a transition metal:
N ° * @.
CT oo 2003/7615,
Ir(COD)CI, Ru(p-cymene)Cl,, Ru(COD)Cl,, Ru(PPh3);Cl,, RuCls, Ru(PPH;),Cl, RuCl;-3H,0,
Ru(PPh;),H,, Rh(PPh;);Cl, RhCl3-3H,0, Ru(PPhs),H, Rh(COD)trifluoromethane sulfonate, (CeH12)sP(COD)pyridine-Ir(F)s, Ii(PPhs);H,Cl, Ir(PPh3);HCL,, If(PPhs)Hs, Ir(PPhs)sHs,
Ir(PPh;),(CO)X [X = CI, Br, I}, If(PPh;),(CO)H, Os(PPh;);HCI, Pd(OAc),, PdCl,, Pd(PPh;).Cl,,
Pd(NH,),Cls, Pt(PPh;),Cl,, PtClK,, Fe(PPh;),Cl,, Ni(PBu-n;),, ReCls.
The following can be cited as optionally supported heterogeneous catalysts based on a transition metal: Pt, Pt/C, Pt(O),, Pd, Pd/C, Pd/CaCO,, Pd/SiO,, Pd/BaCO,;, Pd(OH)./C, Ir, Ir/C,
Ru, Ru/C, Rh, Raney Ni, Fe.
The method according to the invention can optionally be implemented in the presence of a secondary solvent. Such a secondary solvent is advantageously selected from among water, a hydrocarbon such as hexane, heptane, octane, nonane, decane, benzene, toluene or xylene, an ether such as tetrahydrofuran, dioxane, dimethoxyethane, diisopropyl ether or diethylene glycol dimethyl ether, an ester such as ethyl acetate, butyl acetate or ethyl propionate, a ketone such as acetone, diisopropyl ketone, methyl isobutyl ketone, methylethyl ketone or acetylacetone, an alcohol such as methanol, ethanol, n-propanol, iso-propanol, butanol, isobutanol or methoxyethanol, an alkyl halide such as dichloromethane, chloroform or 1,2-dichloroethane, an acid such as acetic acid, propionic acid or butyric acid, an amide such as dimethylformamide or a sulfoxide such as dimethyl sulfoxide.
A preferred form of implementation of the method for the preparation of compounds of formula (1) by hydrogenation reaction according to the invention comprises the treatment of the compound of formula (Il) in the presence of formic acid and a catalyst under the following conditions: — the optional presence of a secondary solvent as previously defined; — a temperature comprised between 0 and +150°C; — a metal quantity/substrate quantity ratio comprised between 1/10,000 and 5%; — a hydrogen pressure between 0.1 and 50 bar; — a reaction duration comprised between 0.5 and 40 hours.
A preferred form of implementation of the method for the preparation of compounds of formula (1) by a hydrogen-transfer reaction according to the invention comprises the treatment of the compound of formula (ll) in the presence of formic acid and a catalyst under the following preferred operating conditions: — the optional presence of a secondary solvent as previously defined, — a temperature comprised between 0 and +150°C; — a metal quantity/substrate quantity ratio comprised between 1/10,000 and 5/100;
— a reaction duration comprised between 0.5 and 40 hours.
Other advantages and characteristics of the invention will become apparent from the examples below presented as an illustration of the method for the preparation of compounds of formula (I) from compounds of formula (Il). The compounds of formula (Il) constituting the substrates of the reaction can be prepared by any method of the prior art known from the literature.
Example 1: Preparation of the compound: {[(ethyl)-5-pyridyl-2-)ethoxy-4-]benzyl}-5-thiazolidine- 2,4-dione-2,4 by means of a hydrogenation reaction.
The following were introduced into a Buchi device: 20 g of {[(ethyl-5-pyridyl-2-)ethoxy-4- ]benzylylidene}-5-thiazolidine-2,4,-dione-2,4, 10 g of Pd/C at 10% and 200 ml of formic acid at 95-97%.
The nitrogen and then the hydrogen were purged.
The reaction medium was heated at 75-80°C for 6 hours under a hydrogen pressure of 8 bar.
The reaction medium was cooled to ambient temperature (20-25°C). The catalyst was filtered and rinsed with 60 ml of formic acid.
The filtrate was concentrated to 40 ml under vacuum at 40°C. We then added 80 ml of water and 60 ml of formic acid to the concentrate. The pH value of the solution was 0.93.
We then added to this medium 101 g of a solution of NaOH at 30% up to a pH value equal to 3.25. The medium was then agitated for 10 minutes at 20°C and the product was filtered.
The crude product was washed in ethanol as follows.
The product was put into solution in 172 ml of ethanol; this was heated at reflux for 30 minutes and then cooled to 10°C. The resultant product was filtered.
After drying under vacuum at 50°C we obtained 19.1 g of white powder.
Yield: 97.4%.
Example 2: Preparation of the compound: {[(ethyl-5-pyridyl-2-)ethoxy-4-]benzyl}-5-thiazolidine- 2,4-dione-2,4 by means of a hydrogen-transfer reaction by homogeneous catalysis.
The following were introduced under nitrogen into a 50-ml flask: 1 g of {[(ethyl-5-pyridyl-2-
Jethoxy-4-]benzylylidene}-5-thiazolidine-2,4-dione-2,4, 61 mg of chloro-1,5-COD iridium and 10 ml of formic acid at 97%.
The orangish solution was heated at reflux for 6 hours.
From the reaction medium, the HPLC profile indicated a transformation rate of 97%.
°» *=2003/6154
The medium was concentrated to 2 ml.
We then added 9 ml of water and filtered the product.
Example 3: Preparation of the compound: {[(ethyl-5-pyridyl-2-)ethoxy-4-]benzyl}-5-thiazolidine- 2,4-dione-2,4 by means of a hydrogen-transfer reaction by heterogeneous catalysis.
The following were introduced under nitrogen into a 50-ml flask: 2.5 g of {[(ethyl-5-pyridyl-2- )ethoxy-4-)benzylylidene}-5-thiazolidine-2,4-dione-2,4, 3 g of Rh/C at 5% with a moisture level of 57.8% (2.5% of metal rhodium/substrate) and 10 ml of formic acid at 99%.
The solution was heated at reflux for 5 hours.
The HPLC profile of the reaction medium indicated a transformation rate of 78%.
The medium was concentrated to 5 ml.
We then added 9 ml of water and filtered the product.
Example 4: Preparation of the compound: {[(ethyl-5-pyridyl-2-)ethoxy-4-]benzyl}-5-thiazolidine- 2,4-dione-2,4 by means of a hydrogen-transfer reaction by heterogeneous catalysis.
The following were introduced under nitrogen into a 50-ml flask: 2.5 g of {[(ethyl-5-pyridyl-2- )ethoxy-4-]benzylylidene}-5-thiazolidine-2,4-dione-2,4, 1.37 g of Pd/C at 10% with a moisture level of 53.2% (2.5% of metal palladium/substrate) and 10 ml of formic acid at 99%.
The solution was heated at reflux (105°C) for 21 hours.
The HPLC of the reaction medium indicated a transformation rate of 66%.
The medium was concentrated to 5 mi.
We then added 19 ml of water and filtered the product.
Example 5: Preparation of the compound: {[(ethyl-5-pyridyl-2-)ethoxy-4-]benzyl}-5-thiazolidine- 2,4-dione-2,4 by means of a hydrogen-transfer reaction by heterogeneous catalysis.
The following were introduced under nitrogen into a 0.5-| flask: 20 g of {[(ethyl-5-pyridyl-2-
Jethoxy-4-]benzylylidene}-5-thiazolidine-2,4-dione-2,4, 0.6 g of Pt0O), (25% of platinum/substrate) and 200 ml of formic acid at 99%.
The solution was heated at the temperature of 84°C for 19 hours 30 minutes.
The HPLC profile of the reaction medium indicated a transformation rate of 98.3% of product formed.
The reaction medium was filtered and the filtrate was concentrated to 40 ml.
We then added 140 ml of water and the pH was adjusted to 3.2 by addition of soda at 30%.
The product was filtered.
The product was purified by rethickening in ethanol.
After drying under vacuum at 50°C, we isolated 19.7 g of product.
Yield: 96.5%.
Example 6: Preparation of the compound: {[(ethyl-5-pyridyl-2-)ethoxy-4]benzyl}-5-thiazolidine- 2,4-dione-2,4 by means of a hydrogen-transfer reaction by heterogeneous catalysis.
The following were introduced under nitrogen into a 100-ml three-necked flask: 5 g of {l(ethyl-5-pyridyl-2-)ethoxy-4-]benzylylidene}-5-thiazolidine-2,4-dione-2,4, 0.148 g of PtO), (2.5% of platinum/substrate) and 35 mi of formic acid at 99%.
The solution was heated at the temperature of 80-85°C for 19 hours 30 minutes.
The HPLC profile of the reaction medium indicated a transformation rate of 98.4% of product formed.
The product was isolated as above with a yield of 96.5%.
Example 7: Preparation of the compound: {[(ethy!-5-pyridyl-2-)ethoxy-4-]benzyl}-5-thiazolidine- 2,4-dione-2,4 by means of a hydrogen-transfer reaction by heterogeneous catalysis.
The following were introduced under nitrogen into a 100-ml three-necked flask: 5 g of - {[(ethyl-5-pyridyl-2-)ethoxy-4-]benzylylidene}-5-thiazolidine-2,4-dione-2,4, 0.203 g of PO), (3.4% of platinum/substrate) and 50 ml of formic acid at 99%. }
The solution was heated at the temperature of 80-85°C for 16 hours.
The HPLC profile of the reaction mixture indicated a transformation rate of 98% of product formed. .
The product was isolated as above with a yield of 94.5%.
The unit “bar” which is used in the specification and which is not in accordance with the metric system may be converted with the aid of the following conversion factor: 1 bar = 1x10° Pa
Amended sheet 22/10/2004

Claims (1)

1. Method for the preparation of a thiazolidinedione, oxazolidinedione or hydantoin derivative compound of formula (I) from a compound of formula (lI) below: Q Ri ? Ri ; — wo (mn — SA (h) Q in which — Q represents an oxygen atom or a sulfur atom; — Q1 represents an oxygen atom or a sulfur atom; — R1 and R2, which can be identical or different, represent a hydrogen atom, a Cy. alkyl chain, a cycloalkyl, an alkylaryl, an arylalkyl; said alkyl, cycloalkyl, alkylaryl or arylalkyl groups being optionally substituted by an alkyl, an alkoxy or aryloxy, a halogen, a hydroxy, a suifino, a sulfonyl, an amino characterized in that a compound of formula (il) is brought to react with formic acid, either as a hydrogen donor in a hydrogen-transfer reaction or as a solvent in a hydrogenation reaction, in the presence of a catalyst based on a transition metal, in order to obtain the corresponding compound of formula (I). -
2. Method according to claim 1, characterized in that the amino is NH,, NHR; or N(Rs)z, with R3 representing an alkyl, an alkoxy or an alkylcarbonyl.
3. Method according to either claim 1 or 2, characterized in that the formic acid is formic acid at 100% or a solution containing formic acid with a formic acid level that can range from
0.1 to 99%, said solution being an aqueous solution or an organic solution or a mixture of these two.
4. Method according to any one of claims 1 to 3, characterized in that the transition-metal based catalyst is a homogenous or heterogeneous catalyst.
5. Method according to claim 4, characterized in that the homogeneous catalyst based on a transition metal is selected from among I(COD)Cl, Ru(p-cymene)Cl,, Ru(COD)Cl., Ru(PPh,);Cl>, RuCls, Ru(PPH,)4Cl, RuCl3-3H50, Ru(PPhs)aH,, Rh{(PPh3)5Cl, RhCl3-3H20, i : Amended sheet 22/10/2004
Ru(PPh;)sH, Rh(COD)trifluoromethane sulfonate, (CgHi2)sP(COD)pyridine-Ir(F)s, Ir(PPhs)sH,ClI, Ir(PPh3)sHCl,, Ir(PPhg)Hs, Ir(PPis)sHs, Ir(PPhy)(CO)X [X = CI, Br, 1], Ir(PPh3)(CO)H, Os(PPh;)sHCI, Pd(OAc),, PdCl,, Pd(PPh;),Cly, Pd(NH,),Cls, Pt(PPh;),Cl,, PtCl,K;, Fe(PPh;).Cly, Ni(PBu-n3),, ReCls.
6. Method according to claim 4, characterized in that the heterogeneous catalyst based on a transition metal is selected from among Pt, PVC, Pt(O),, Pd, Pd/C, Pd/CaCQO; Pd/SiO,, Pd/BaCO,, Pd(OH),/C, Ir, Ir/C, Ru, Ru/C, Rh, Raney Ni, Fe.
7. Method according to any one of the preceding claims, characterized in that a compound of formula (ll) is brought to react with formic acid in the presence of a transition-metal based catalyst and in the presence of a secondary solvent.
8. Method according to claim 7, characterized in that the secondary solvent is selected from among water, a hydrocarbon, an ether, an ester, a ketone, an alcohol, an alkyl halide, an acid, an amide or a sulfoxide.
9. Method according to claim 8, characterized in that the hydrocarbon is hexane, heptane, octane, nonane, decane, benzene, toluene or xylene.
10. Method according to claim 8, characterized in that the ether is tetrahydrofuran, dioxane, dimethoxyethane, diisopropyl ether or diethylene glycol dimethyl ether.
11. Method according to claim 8, characterized in that the ester is ethyl acetate, butyl acetate or ethyl propionate.
12. Method according to claim 8, characterized in that the ketone is acetone, diisopropyl! ketone, methyl isobutyl ketone, methyiethyl ketone or acetylacetone.
13. Method according to claim 8, characterized in that the alcohol is methanol, ethanol, n-propanol, iso-propanol, butanol, isobutanol or methoxyethanol.
14. Method according to claim 8, characterized in that the alkyl halide is dichloromethane, chloroform or 1,2-dichloroethane. Amended sheet 22/10/2004
15. Method according to claim 8, characterized in that the acid is acetic acid, propionic acid : or butyric acid.
18. Method according to claim 8, characterized in that the amide is dimethylformamide. 17 Method according to claim 8, characterized in that the sulfoxide is dimethyl sulfoxide.
18. Method according to any one of claims 1 to 17. characterized in that a compound of formula (II) is brought to react with formic acid as soivent in a hydrogenation reaction in the Co presence of hydrogen, and in the presence of a transition-metal based catalyst under the ’ following operating conditions: - the optional presence of a secondary sclvent; - a temperature comprised between 0 and +150°C; - a metal quantity/substrate quantity ratio comprised between 1/10,000 and 5%; - a hydrogen pressure between 0.1 and 50 bar (between 1x10* and 5x10° Pa); - a reaction duration comprised between 0.5 and 40 hours.
19. Method according to any one of claims 1 to 17. characterized in that a compound of formula (II) is brought to react with formic acid as hydrogen donor in a hydrogen-transfer reaction, in the presence of a transition-metal based catalyst under the following operating conditiens: - the optional presence of a secondary solvent as defined in any one of claims 8 to 17; - a temperature comprised between 0 and +150°C; - a metal quantity/substrate quantity ratio comprised between 1/10,000 and 5/100; - a reaction duration comorised between 0.5 and 40 hours.
20. Method according to claim 1, characterized in that compounds of formula (1) are active pharmaceutical agents selected in the group comprising pioglitazone, rosiglitazone, troglitazone and ciglitazone.
21. Mathod according $0 claim 1, characterized in that in formula | and Il, - Q represents a sulfur atom, - Q1 reprasants an oxygen 2tom, - R1 represents a hydrogen atom, znd - R2 reprasents an alkylaryl substituted by an alkoxy. Amended Sheet — 15-03-2005
[) , .~
22. tetrod zoocrding iC Claim 21 charzcierizec ret REZ 0s P 3 ; PN / Se A NT 0 a NZ 23 Method according fo claim 1, substantially es hersin described with reference to any one of the illustrative examples. : Amended Sheet — 15-03-2005
ZA200306164A 2001-02-14 2002-02-14 Method for preparing compounds derived from thiazolidinedione, oxazolidinedione or hydantoin. ZA200306164B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR0102010A FR2820741A1 (en) 2001-02-14 2001-02-14 Pure 5-alkyl-thiazolidinedione, oxazolidinedione or hydantoin derivative preparation, for use as drug or intermediate, by reduction of corresponding alkylidene compound using formic acid

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Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4812570A (en) * 1986-07-24 1989-03-14 Takeda Chemical Industries, Ltd. Method for producing thiazolidinedione derivatives
JP3163361B2 (en) * 1992-03-12 2001-05-08 味の素株式会社 Method for producing 5-alkylhydantoin derivative
US5399632A (en) * 1992-09-30 1995-03-21 Exxon Research & Engineering Co. Hydrogenation process for unsaturated homo and copolymers
JPH06199808A (en) * 1993-01-04 1994-07-19 Ajinomoto Co Inc Production of 5-cyclohexylmethylhydantoin derivative and intermediate for production thereof
JPH08277279A (en) * 1995-04-05 1996-10-22 Nitto Chem Ind Co Ltd Production of benzylthiazolidindione derivative
UY24886A1 (en) * 1997-02-18 2001-08-27 Smithkline Beecham Plc TIAZOLIDINDIONA
DE19711616A1 (en) * 1997-03-20 1998-09-24 Boehringer Mannheim Gmbh Improved process for the preparation of thiazolidinediones

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