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WO1994015918A1 - Process for the preparation of substituted indolone derivatives - Google Patents

Process for the preparation of substituted indolone derivatives Download PDF

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Publication number
WO1994015918A1
WO1994015918A1 PCT/EP1993/003706 EP9303706W WO9415918A1 WO 1994015918 A1 WO1994015918 A1 WO 1994015918A1 EP 9303706 W EP9303706 W EP 9303706W WO 9415918 A1 WO9415918 A1 WO 9415918A1
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WIPO (PCT)
Prior art keywords
compound
compounds
formula
dihydro
indol
Prior art date
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.)
Ceased
Application number
PCT/EP1993/003706
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French (fr)
Inventor
Andrew S. Wells
Norman John Lewis
Timothy Charles Walsgrove
Paul Oxley
Joseph Marian Fortunak
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.)
SmithKline Beecham Ltd
SmithKline Beecham Corp
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SmithKline Beecham Ltd
SmithKline Beecham Corp
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Priority to PL93309645A priority Critical patent/PL176152B1/en
Publication of WO1994015918A1 publication Critical patent/WO1994015918A1/en
Priority to FI953361A priority patent/FI114094B/en
Priority to NO952713A priority patent/NO305363B1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D209/00Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04Indoles; Hydrogenated indoles
    • C07D209/30Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
    • C07D209/32Oxygen atoms
    • C07D209/34Oxygen atoms in position 2

Definitions

  • the present invention relates to an improved process for the preparation of substituted indolone derivatives.
  • substituted indolone derivatives are described in EP-113964-B as being useful in cardiovascular therapy, and in EP-299602-A as agents useful in the treatment of Parkinson's disease.
  • substituted indolone derivatives may be prepared in high yield and purity by reduction of the corresponding isatin precursor compounds.
  • High yields and purity in a process involving a number of reaction steps generally results in a much more efficient and cost-effective route to the end product.
  • the present invention therefore provides, in a first aspect, a process for the preparation of a compound of structure (I) or a pharmaceutically acceptable salt thereof:
  • each group R is independently hydrogen or Cj ⁇ alkyl; and RMs hydrogen, hydroxy or Cj ⁇ alkoxy which comprises reduction of a compound of structure (II):
  • the reduction is carried out using Raney nickel in a suitable solvent, for example a C]_4 alcohol such as isopropanol at a temperature of between ambient and the reflux temperature of the solvent used.
  • a suitable solvent for example a C]_4 alcohol such as isopropanol
  • Raney nickel is used in relation to the compound of formula (II) and the mixture heated under reflux in isopropanol as solvent.
  • one of the groups R is hydrogen and the other is hydrogen or C ⁇ _4alkyl; preferably, both groups R are C] _4alkyl, in particular n-propyl.
  • n is 1 to 3; preferably n is 2.
  • R is hydrogen, hydroxy or C]_4alkoxy such as methoxy; preferably R is hydrogen.
  • Preferred salts of compounds of formula (I) include those described in
  • EP-113694-B particularly preferred are acid addition salts such as the hydrochloride salt.
  • the above method is particularly useful for the preparation of the compound 4-[2-(di-n- propylamino)ethyl]-l,3-dihydro-2H-indol-2-one hydrochloride salt (INN:ropinirole), a compound useful for the treatment of Parkinson's disease (EP-299-602-A).
  • Certain compounds of structure (I) can be converted into further compounds of structure (I).
  • compounds of structure (I) in which both R groups are hydrogen, or one R group is hydrogen and the other is Cj ⁇ alkyl can be converted to compounds of structure (I) in which both R groups are C]_4alkyl by conventional techniques known in the art such as reductive alkylation with aldehydes, for example using sodium cyanoborohydride or hydrogen gas as reducing agents.
  • Such procedure are particularly useful for preparing the compound 4-[2-(di-n-propylamino)ethyl]- 1 ,3-dihydro-2H-indol-2- one hydrochloride salt, as described in the following examples.
  • Compounds of structure (II) can be prepared using standard techniques well known to those skilled in the art. For example, compounds of formula (II) can be prepared as shown in the following scheme:
  • R* and n are as described for compounds of formula (I) and X is a leaving group or a group N(R)2 in which the groups R are as defined for formula (I).
  • Preferred leaving groups X include halogen, particularly bromo, and oxygen leaving groups such as p-toluenesulphonyloxy. It will be appreciated that when X is N(R)2 the resulting compounds of formula (III) are themselves compounds of formula (II).
  • the mixture was stirred with cooling to 0°C for several hours before collection of the product by filtration.
  • the product was dried in vacuo at 40 °C. to a constant weight, giving 2.40 g of the title compound, m.p. 228-229.5 °C.
  • the aqueous phase was basified with sodium hydroxide (6.0g, 0.15mol) in water (40ml) and the product extracted into dichloromethane (100ml and 2 times 50ml). The organic extracts were dried (MgSO4) and concentrated to an oil in vacuo. The oil was taken up in isopropanol (315ml) at 80°C and hydrochloric acid (SG 1.18, 12ml, 0.14mol) was added. The mixture was allowed to cool to 40°C and was then chilled at 0°C for 15 minutes. The resulting solid was filtered, washed with a little isopropanol, and then dried at 80°C for 24 hours to give the title compound as a pale yellow solid (31.3g, 90%).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

A process for the preparation of indolone derivatives having general formula (I) in which n is 1 to 3; each group R is independently hydrogen or C1-4alkyl; and R1 is hydrogen, hydroxy or C¿1-4?alkoxy by reduction of the corresponding isatin precursor compounds.

Description

Process for the preparation of substituted I ndolone derivatives
The present invention relates to an improved process for the preparation of substituted indolone derivatives. Such compounds are described in EP-113964-B as being useful in cardiovascular therapy, and in EP-299602-A as agents useful in the treatment of Parkinson's disease.
Processes for the preparation of substituted indolone derivatives have been described in the art, for example in EP-113964-B, EP-300614-A1 and WO 91/16306.
It has now been found that substituted indolone derivatives may be prepared in high yield and purity by reduction of the corresponding isatin precursor compounds. High yields and purity in a process involving a number of reaction steps generally results in a much more efficient and cost-effective route to the end product.
The present invention therefore provides, in a first aspect, a process for the preparation of a compound of structure (I) or a pharmaceutically acceptable salt thereof:
Figure imgf000003_0001
(I) in which n is 1 to 3; each group R is independently hydrogen or Cj^alkyl; and RMs hydrogen, hydroxy or Cj^alkoxy which comprises reduction of a compound of structure (II):
Figure imgf000003_0002
(ID in which n, R and R* are as defined for structure (I) and optionally thereafter
• converting the compound of structure (I) into a further compound of structure (I) • forming a salt.
Suitably, the reduction is carried out using Raney nickel in a suitable solvent, for example a C]_4 alcohol such as isopropanol at a temperature of between ambient and the reflux temperature of the solvent used.
Preferably, an excess of Raney nickel is used in relation to the compound of formula (II) and the mixture heated under reflux in isopropanol as solvent.
Suitably, one of the groups R is hydrogen and the other is hydrogen or Cι_4alkyl; preferably, both groups R are C] _4alkyl, in particular n-propyl.
Suitably, n is 1 to 3; preferably n is 2.
Suitably R is hydrogen, hydroxy or C]_4alkoxy such as methoxy; preferably R is hydrogen.
Preferred salts of compounds of formula (I) include those described in
EP-113694-B, particularly preferred are acid addition salts such as the hydrochloride salt.
The above method is particularly useful for the preparation of the compound 4-[2-(di-n- propylamino)ethyl]-l,3-dihydro-2H-indol-2-one hydrochloride salt (INN:ropinirole), a compound useful for the treatment of Parkinson's disease (EP-299-602-A).
Certain compounds of structure (I) can be converted into further compounds of structure (I). In particular, compounds of structure (I) in which both R groups are hydrogen, or one R group is hydrogen and the other is Cj^alkyl, can be converted to compounds of structure (I) in which both R groups are C]_4alkyl by conventional techniques known in the art such as reductive alkylation with aldehydes, for example using sodium cyanoborohydride or hydrogen gas as reducing agents. Such procedure are particularly useful for preparing the compound 4-[2-(di-n-propylamino)ethyl]- 1 ,3-dihydro-2H-indol-2- one hydrochloride salt, as described in the following examples. Compounds of structure (II) can be prepared using standard techniques well known to those skilled in the art. For example, compounds of formula (II) can be prepared as shown in the following scheme:
Figure imgf000005_0001
(V)
1. NBS
2 H2O,M_OH
Figure imgf000005_0002
(ID (III)
In the above scheme R, R* and n are as described for compounds of formula (I) and X is a leaving group or a group N(R)2 in which the groups R are as defined for formula (I). Preferred leaving groups X include halogen, particularly bromo, and oxygen leaving groups such as p-toluenesulphonyloxy. It will be appreciated that when X is N(R)2 the resulting compounds of formula (III) are themselves compounds of formula (II).
Isatin compounds of formula (III) in which X is a leaving group can themselves, using the procedures hereinbefore described, be reduced to indolones of formula (VI):
Figure imgf000005_0003
(VI) in which n, and R are as described for compounds of formula (III) and X is a leaving group. The resulting compounds of formula (VI) can then be reacted with an amine (R)2NH to give compounds of formula (I). If a primary amine RNH2 is used, in which R is Cj.4alkyl, a compound of formula (I) is obtained in which one group R is hydrogen and the other is Cj^alkyl. If desired these compounds can then be subjected to reductive alkylation, as outlined above, to introduce a second Cι_4alkyl group. In particular such a procedure can be used to prepare compounds of formula (I) in which each of the groups R is a different C _4alkyl group.
Compounds of formulae (II), (III) and (IV) are themselves novel and form a further aspect of the invention.
Compounds of formula (VI) in which X is halo can also be treated with sodium azide, followed by reduction of the resulting azido-indolone, to give compounds of formula (I) in which both groups R are hydrogen.
Compounds of formula (V) can be prepared using standard procedures. For example compounds of formula (V) in which X is p-toluenesulphonyloxy can be prepared by treating the corresponding alcohol with p-toluenesulphonyl chloride and triethylamine.
The following examples serve to illustrate the invention. All temperatures are recorded in degrees centigrade.
Example I
4-(2-Dipropylaminoethyl)-1 -dihydro-2H-indol-2-one hydrochloride salt.
A suspension of 2.74 g (10.0 mmol) of 4-(2-di-n-propylamino)ethyl isatin in 70 ml of isopropanol was treated with 16.0 g (wet weight) of Raney nickel active catalyst (50% aqueous slurry, activity approximately W-2 grade). The resulting suspension was refluxed with stirring for 18 hours. After cooling to ambient temperature, the reaction mixture was washed through a pad of celite with suction, using an additional 100 ml of isopropanol to wash the filter cake. Evaporation of the isopropanol to a volume of about 30 ml followed by acidification by saturation with gaseous HC1 gave a turbid solution. The mixture was stirred with cooling to 0°C for several hours before collection of the product by filtration. The product was dried in vacuo at 40 °C. to a constant weight, giving 2.40 g of the title compound, m.p. 228-229.5 °C.
Example 2
4-(2-Dipropylaminoethyl)-13-dihydro-2H-indol-2-one hydrochloride salt.
A mixture of 4-(2-Propylaminoethyl)-l,3-dihydro-2H-indol-2-one (30.0g, 0.118mol) , 10% platinum on charcoal (3.0g), propionaldehyde (65.8g, 1.18mol), distilled water (300ml) and methanol was charged to a Buchi reactor and hydrogenated at 60 psi for 75 minutes. The liquors were filtered through celite and the methanol and excess propionaldehyde removed in vacuo. The residual aqueous phase was washed with dichloromethane (150ml and 75ml). The aqueous phase was basified with sodium hydroxide (6.0g, 0.15mol) in water (40ml) and the product extracted into dichloromethane (100ml and 2 times 50ml). The organic extracts were dried (MgSO4) and concentrated to an oil in vacuo. The oil was taken up in isopropanol (315ml) at 80°C and hydrochloric acid (SG 1.18, 12ml, 0.14mol) was added. The mixture was allowed to cool to 40°C and was then chilled at 0°C for 15 minutes. The resulting solid was filtered, washed with a little isopropanol, and then dried at 80°C for 24 hours to give the title compound as a pale yellow solid (31.3g, 90%). Example 3
4-(2-Dipropylaminoethyl)-l,3-dihydro-2H-ιndol-2-one.
4-(2-bromoethyl)-l,3-dihydro-2H-indol-2-one (0.12 moles) is added to propylamine (7 volumes) and the resulting mixture refluxed under nitrogen for 1 hour. The excess propylamine was then removed by distillation, isopropanol added, and the isopropanol then removed by distillation in vacuo. The resulting product was treated with propionaldehyde (2 equivalents) followed by sodium cyanoborohydride (1.3 equivalents) in methanol (15 volumes) . After 1 hour a further portion of propionaldehyde (1 equivalent) and sodium cyanoborohydride (0.3 equivalents) was added to complete the reaction. The mixture was then acidified with c. HC1, and the methanol and excess propionaldehyde removed in vacuo. The crude product was dissolved in water : methanol (4:1 15 volumes) and extracted with ethyl acetate. The aqueous layer was basified to pH 9 with potassium hydroxide, and the product extracted into ethyl acetate. The solvent was replaced with isopropanol, cooled to 0°C, and triturated with ethyl acetate to give 4-(2- aminoethyl)-l,3-dihydro-2H-indol-2-one hydrochloride salt.
Example 4
4-(2-DipropylaminoethyI)-1 -dihydro-2H-indol-2-one hydrochloride salt.
A. 4-(2-Azidoethyl)-l,3-dihydro-2H-indol-2-one
4-(2'-bromoethyl)-l,3-dihydro-2H-indol-2-one (12.02g, 50mmol), nitrogen degassed water (100ml), sodium azide (16.26g, 250mmol) and vacuum degassed ethylene glycol (50ml) were heated to 95 - 98°C under nitrogen with stirring. At 80°C, absolute ethanol (8 - 10ml) was added to effect dissolution of the starting material. The mixture was then heated for 4 hours and then cooled and stirred overnight. The resulting solid was filtered, washed with recycled mother liquor, and twice with water (40ml). The product was dried at 40°C to give the title compound as a tan solid (9.2g, 91%) m.p. 114 -116°C. B. 4-(2-Aminoethyl)-l,3-dihydro-2H-indol-2-one hydrochloride
A 500ml Parr pressure bottle was charged with 50% water wet 5% Pd/C (2.0g),
4-(2-azidoethyl)-l,3-dihydro-2H-indol-2-one (8.0g, 39.6mmol) and anhydrous methanol (300ml). The reaction mixture was then hydrogenated at 60 - 65 psi for 3 hours. After filtration of the catalyst the solution was acidified with excess gaseous HCl and about 2/3 of the solvent removed in vacuo. The resulting solid was filtered, washed with the recycled filtrate and then dried at 40°C to give a white solid. Recrystallisation from ethanol/water 2:1 gave the title compound as a tan solid (5.5g, 65%) m.p. 300°C dec.
C. 4-(2-Dipropylaminoethyl)- 1 ,3-dihydro-2H-indol-2-one hydrochloride salt.
A 250ml Parr pressure bottle was charged with 50% water wet 5% Pd/C (300 mg),
4-(2-aminoethyl)-l,3-dihydro-2H-indol-2-one hydrochloride (1.4g, 5mmol), glacial acetic acid (50ml) and propionaldehyde (1.5ml, 20mmol). The mixture was hydrogenated at 68°C and 70 psi for 5 hours. The catalyst was filtered and the filtrate removed in vacuo. The resulting orange oily concentrate was dissolved in refluxing ethanol and the solution saturated with HCl. On cooling a solid crystallised from solution which was filtered, washed with ether and then dried to give the title compound as a yellow solid (1.07g, 68%) m.p. 240 - 243°C

Claims

Claims
A process for the preparation of a compound of structure (I)
Figure imgf000010_0001
(I)
in which n is 1 to 3; each group R is independently hydrogen or Cj^alkyl; and R! is hydrogen, hydroxy or Cj^alkoxy which comprises reduction of a compound of structure (II):
Figure imgf000010_0002
(ID
in which n, R and R^ are as defined for structure (I) and optionally thereafter
• converting the compound of structure (I) into a further compound of structure (I)
• forming a salt.
2. A process according to claim 1 in which the reducing agent is Raney nickel.
3. A process according to claim 2 in which both groups R are Cι_4_ιlkyl and n is 2. 4. A process according to claim 1 in which the compound of structure (I) prepared is: 4-f2-(di-n-propylamino)ethyl]-l ,3-dihydro-2H-indol-2-one hydrochloride (INN: ropinirole).
5. A process according to claim 2 in which the compound of structure (I) prepared is: 4-[2-(di-n-propylamino)ethyl]-l ,3-dihydro-2H-indol-2-one hydrochloride (INN: ropinirole).
A compound of formula (III)
Figure imgf000011_0001
(HI)
in which n, and R are as defined for structure (I) in claim 1 and X is a leaving group or a group N(R)2 in which the groups R are as defined for structure (I) in claim 1.
7. A compound according to claim 6 which is 4-[2-(di-n-propylamino)ethyl] isatin.
8. A compound of formula (IV):
Figure imgf000011_0002
in which n, R and X are as defined for structure (III) in claim 6.
PCT/EP1993/003706 1993-01-08 1993-12-27 Process for the preparation of substituted indolone derivatives Ceased WO1994015918A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PL93309645A PL176152B1 (en) 1993-01-08 1993-12-27 Method of obtaining substituted indolone derivatives
FI953361A FI114094B (en) 1993-01-08 1995-07-07 Process for preparing substituted indolone derivatives
NO952713A NO305363B1 (en) 1993-01-08 1995-07-07 Process for the preparation of substituted indolone derivatives and their compounds

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB939300309A GB9300309D0 (en) 1993-01-08 1993-01-08 Process
GB9300309.3 1993-01-08

Publications (1)

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WO1994015918A1 true WO1994015918A1 (en) 1994-07-21

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FI (1) FI114094B (en)
GB (1) GB9300309D0 (en)
HU (1) HUT72075A (en)
MA (1) MA23081A1 (en)
NO (1) NO305363B1 (en)
PL (1) PL176152B1 (en)
WO (1) WO1994015918A1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005080333A1 (en) * 2004-02-19 2005-09-01 Torrent Pharmaceuticals Ltd Process for purification of ropinirole
WO2005074387A3 (en) * 2003-12-30 2005-10-06 Sun Pharmaceutical Ind Ltd Novel crystal forms of 4-[2-di-n-propylamino)ethyl]-2 (3h)- indolone hydrochloride
WO2005105741A1 (en) * 2004-02-11 2005-11-10 Sun Pharmaceutical Industries Limited Substantially pure 4-[2-(di-n-propylamino)ethyl]-2(3h)-indolone hydrochloride
US7230118B2 (en) * 2003-10-14 2007-06-12 Urquima S.A. Process for the preparation of ropinirole
WO2008075169A3 (en) * 2006-12-15 2011-04-28 Orchid Chemicals & Pharmaceuticals Limited A process for the purification of ropinirole hydrochloride
WO2011030330A3 (en) * 2009-09-09 2011-09-29 Taro Pharmaceutical Industries Ltd. Process for the purification of ropinirole hydrochloride
WO2018227553A1 (en) 2017-06-16 2018-12-20 浙江华海立诚药业有限公司 Method for purifying ropinirole hydrochloride

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3882236A (en) * 1973-12-26 1975-05-06 Lilly Co Eli Pharmaceutical compositions containing substituted 2-oxo-indolines and the use thereof to treat anxiety and tension
EP0046666A1 (en) * 1980-08-22 1982-03-03 Smithkline Beckman Corporation 2(3H)-indolones, process for their preparation and compositions containing them
EP0113964A1 (en) * 1982-12-07 1984-07-25 Smithkline Beckman Corporation 4-Aminoalkyl-2(3H)-indolones
EP0167288A2 (en) * 1984-06-04 1986-01-08 Smithkline Beecham Corporation 4-(2-(N,N-disubstituted-amino)ethyl]isatins
EP0299602A2 (en) * 1987-05-21 1989-01-18 Smith Kline & French Laboratories Limited Use of indolone derivatives for the preparation of medicaments for the treatment of Parkinsons disease
EP0300614A1 (en) * 1987-06-19 1989-01-25 Smith Kline & French Laboratories Limited Process for the preparation of substituted indolinone derivatives
WO1991016306A1 (en) * 1990-04-17 1991-10-31 Smith Kline & French Laboratories Limited An improved process for the preparation of substituted indolone derivatives

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3882236A (en) * 1973-12-26 1975-05-06 Lilly Co Eli Pharmaceutical compositions containing substituted 2-oxo-indolines and the use thereof to treat anxiety and tension
EP0046666A1 (en) * 1980-08-22 1982-03-03 Smithkline Beckman Corporation 2(3H)-indolones, process for their preparation and compositions containing them
EP0113964A1 (en) * 1982-12-07 1984-07-25 Smithkline Beckman Corporation 4-Aminoalkyl-2(3H)-indolones
EP0167288A2 (en) * 1984-06-04 1986-01-08 Smithkline Beecham Corporation 4-(2-(N,N-disubstituted-amino)ethyl]isatins
EP0299602A2 (en) * 1987-05-21 1989-01-18 Smith Kline & French Laboratories Limited Use of indolone derivatives for the preparation of medicaments for the treatment of Parkinsons disease
EP0300614A1 (en) * 1987-06-19 1989-01-25 Smith Kline & French Laboratories Limited Process for the preparation of substituted indolinone derivatives
WO1991016306A1 (en) * 1990-04-17 1991-10-31 Smith Kline & French Laboratories Limited An improved process for the preparation of substituted indolone derivatives

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
R.M. DEMARINIS ET AL.: "Synthesis and in vitro evaluation of 4-(2-aminoethyl)-2(3H)-indolones and related compounds as peripheral prejunctional dopamine receptor agonists.", JOURNAL OF MEDICINAL CHEMISTRY, vol. 29, no. 6, 1986, WASHINGTON US, pages 939 - 947 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7230118B2 (en) * 2003-10-14 2007-06-12 Urquima S.A. Process for the preparation of ropinirole
WO2005074387A3 (en) * 2003-12-30 2005-10-06 Sun Pharmaceutical Ind Ltd Novel crystal forms of 4-[2-di-n-propylamino)ethyl]-2 (3h)- indolone hydrochloride
WO2005105741A1 (en) * 2004-02-11 2005-11-10 Sun Pharmaceutical Industries Limited Substantially pure 4-[2-(di-n-propylamino)ethyl]-2(3h)-indolone hydrochloride
WO2005080333A1 (en) * 2004-02-19 2005-09-01 Torrent Pharmaceuticals Ltd Process for purification of ropinirole
WO2008075169A3 (en) * 2006-12-15 2011-04-28 Orchid Chemicals & Pharmaceuticals Limited A process for the purification of ropinirole hydrochloride
WO2011030330A3 (en) * 2009-09-09 2011-09-29 Taro Pharmaceutical Industries Ltd. Process for the purification of ropinirole hydrochloride
WO2018227553A1 (en) 2017-06-16 2018-12-20 浙江华海立诚药业有限公司 Method for purifying ropinirole hydrochloride
US10961194B2 (en) 2017-06-16 2021-03-30 Zhejiang Huahai Licheng Pharmaceutical Co., Ltd. Method for purifying ropinirole hydrochloride

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GB9300309D0 (en) 1993-03-03
NO305363B1 (en) 1999-05-18
FI953361L (en) 1995-07-07
HUT72075A (en) 1996-03-28
NO952713D0 (en) 1995-07-07
FI953361A0 (en) 1995-07-07
PL309645A1 (en) 1995-10-30
PL176152B1 (en) 1999-04-30
MA23081A1 (en) 1994-10-01
FI114094B (en) 2004-08-13
NO952713L (en) 1995-07-07

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