CA2545291A1 - Method for producing 4-pentafluoride-sulfanyl-benzoylguanidines - Google Patents
Method for producing 4-pentafluoride-sulfanyl-benzoylguanidines Download PDFInfo
- Publication number
- CA2545291A1 CA2545291A1 CA002545291A CA2545291A CA2545291A1 CA 2545291 A1 CA2545291 A1 CA 2545291A1 CA 002545291 A CA002545291 A CA 002545291A CA 2545291 A CA2545291 A CA 2545291A CA 2545291 A1 CA2545291 A1 CA 2545291A1
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- Prior art keywords
- zero
- carbon atoms
- formula
- alkyl
- hydrogen
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- 238000004519 manufacturing process Methods 0.000 title claims abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract 14
- 125000004432 carbon atom Chemical group C* 0.000 claims 22
- 125000000217 alkyl group Chemical group 0.000 claims 13
- 229910052739 hydrogen Inorganic materials 0.000 claims 12
- 239000001257 hydrogen Substances 0.000 claims 12
- 150000002431 hydrogen Chemical class 0.000 claims 8
- 125000003545 alkoxy group Chemical group 0.000 claims 7
- 150000003839 salts Chemical class 0.000 claims 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 4
- 125000005843 halogen group Chemical group 0.000 claims 3
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 229910052794 bromium Inorganic materials 0.000 claims 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 2
- 229910052801 chlorine Inorganic materials 0.000 claims 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims 2
- 229910052731 fluorine Inorganic materials 0.000 claims 2
- 125000001153 fluoro group Chemical group F* 0.000 claims 2
- 230000002140 halogenating effect Effects 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- 238000000034 method Methods 0.000 claims 2
- 150000002825 nitriles Chemical group 0.000 claims 2
- 238000003786 synthesis reaction Methods 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000012038 nucleophile Substances 0.000 claims 1
- -1 organoelement compound Chemical class 0.000 claims 1
- AGNCKMHGYZKMLN-UHFFFAOYSA-N pentafluoro-(4-nitrophenyl)-$l^{6}-sulfane Chemical class [O-][N+](=O)C1=CC=C(S(F)(F)(F)(F)F)C=C1 AGNCKMHGYZKMLN-UHFFFAOYSA-N 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 208000024172 Cardiovascular disease Diseases 0.000 abstract 1
- 108091006647 SLC9A1 Proteins 0.000 abstract 1
- 102100030980 Sodium/hydrogen exchanger 1 Human genes 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K51/00—Preparations containing radioactive substances for use in therapy or testing in vivo
- A61K51/02—Preparations containing radioactive substances for use in therapy or testing in vivo characterised by the carrier, i.e. characterised by the agent or material covalently linked or complexing the radioactive nucleus
- A61K51/04—Organic compounds
- A61K51/0404—Lipids, e.g. triglycerides; Polycationic carriers
- A61K51/0406—Amines, polyamines, e.g. spermine, spermidine, amino acids, (bis)guanidines
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P9/00—Drugs for disorders of the cardiovascular system
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- General Chemical & Material Sciences (AREA)
- Heart & Thoracic Surgery (AREA)
- Cardiology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Engineering & Computer Science (AREA)
- Biophysics (AREA)
- Molecular Biology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Epidemiology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention relates to a method for producing 4-pentafluoride-sulfanyl-benzoylguanidines of formula (I) wherein groups from R1 to R4 correspond to meanings given in claims. The compounds of the formula (I) constitute NHE1 inhibitors and can be used for curing cardiovascular diseases.
Claims (7)
1. A process for preparing compounds of the formula I
in which the meanings are:
R1 hydrogen, alkyl having 1, 2, 3 or4 carbon atoms, alkoxy having 1, 2, 3 or 4 carbon atoms, NR10R11, -O p-(CH2)n-CF2)o-CF3 or -(SO m)q-(CH2)r(CF2)s-CF3;
R10 and R11 independently of one another hydrogen, alkyl having 1, 2, 3 or 4 carbon atoms or -CH2-CF3;
m zero, 1 or 2 n, o, p, q, r and s independently of one another zero or 1;
R2 hydrogen, -(SO h)z-(CH2)k -(CF2)l -CF3, alkyl having 1, 2, 3, 4, or 6 carbon atoms, cycloalkyl having 3, 4, 5, 6, 7 or 8 carbon atoms, in which 1, 2, 3 or 4 hydrogen atoms may be replaced by fluorine atoms;
h zero, 1 or 2;
z zero or 1;
k zero, 1, 2, 3 or 4;
l zero or 1;
or R2 -(CH2)t phenyl or -O-phenyl, which are unsubstituted or substituted by 1, 2 or 3 radicals selected from the group consisting of -O u-(CH2)v-CF3, alkoxy having 1, 2, 3 or 4 carbon atoms, alkyl having 1, 2, 3 or 4 carbon atoms and -SO2CH3;
t zero, 1, 2, 3 or 4;
u zero or 1;
v zero, 1, 2 or 3;
or R2 -(CH2)w-heteroaryl which is unsubstituted or substituted by 1, 2 or 3 radicals selected from the group consisting of -O x-(CH2)y-CF3, alkoxy having 1, 2, 3 or 4 carbon atoms and alkyl having 1, 2, 3 or 4 carbon atoms, -SO2CH3;
w zero, 1, 2, 3 or 4;
x zero or 1;
y zero, 1, 2 or 3;
R3 and R4, independently of one another hydrogen or F;
and the salts thereof;
which comprises a) reducing a 4-nitrophenylsulfur pentafluoride derivative of the formula II to the amine of formula III, and b) halogenating the compound of the formula III in the ortho position to the amino group with a halogenating agent to give the compound of the formula IV, and c) replacing the halogen substituent in the compound of the formula IV with a suitable nucleophile or an organoelement compound, for example an alkylboron compound, where appropriate with catalysis, by a substituent R2, and d) replacing the amino function in the compound of the formula V by a halogen substituent, and e) replacing the halogen substituent in the compound of the formula VI by a nitrile function, and f) hydrolyzing the nitrile function of the compound of the formula VII
to the carboxylic acid, and g) converting the carboxylic acid of the formula VIII into the acylguanidine of the formula I, where in the compounds of the formulae II, III, IV, V, VI, VII and VIII
R1 to R4 are as defined in formula I and X and Y are independently of one another F, Cl, Br or I.
in which the meanings are:
R1 hydrogen, alkyl having 1, 2, 3 or4 carbon atoms, alkoxy having 1, 2, 3 or 4 carbon atoms, NR10R11, -O p-(CH2)n-CF2)o-CF3 or -(SO m)q-(CH2)r(CF2)s-CF3;
R10 and R11 independently of one another hydrogen, alkyl having 1, 2, 3 or 4 carbon atoms or -CH2-CF3;
m zero, 1 or 2 n, o, p, q, r and s independently of one another zero or 1;
R2 hydrogen, -(SO h)z-(CH2)k -(CF2)l -CF3, alkyl having 1, 2, 3, 4, or 6 carbon atoms, cycloalkyl having 3, 4, 5, 6, 7 or 8 carbon atoms, in which 1, 2, 3 or 4 hydrogen atoms may be replaced by fluorine atoms;
h zero, 1 or 2;
z zero or 1;
k zero, 1, 2, 3 or 4;
l zero or 1;
or R2 -(CH2)t phenyl or -O-phenyl, which are unsubstituted or substituted by 1, 2 or 3 radicals selected from the group consisting of -O u-(CH2)v-CF3, alkoxy having 1, 2, 3 or 4 carbon atoms, alkyl having 1, 2, 3 or 4 carbon atoms and -SO2CH3;
t zero, 1, 2, 3 or 4;
u zero or 1;
v zero, 1, 2 or 3;
or R2 -(CH2)w-heteroaryl which is unsubstituted or substituted by 1, 2 or 3 radicals selected from the group consisting of -O x-(CH2)y-CF3, alkoxy having 1, 2, 3 or 4 carbon atoms and alkyl having 1, 2, 3 or 4 carbon atoms, -SO2CH3;
w zero, 1, 2, 3 or 4;
x zero or 1;
y zero, 1, 2 or 3;
R3 and R4, independently of one another hydrogen or F;
and the salts thereof;
which comprises a) reducing a 4-nitrophenylsulfur pentafluoride derivative of the formula II to the amine of formula III, and b) halogenating the compound of the formula III in the ortho position to the amino group with a halogenating agent to give the compound of the formula IV, and c) replacing the halogen substituent in the compound of the formula IV with a suitable nucleophile or an organoelement compound, for example an alkylboron compound, where appropriate with catalysis, by a substituent R2, and d) replacing the amino function in the compound of the formula V by a halogen substituent, and e) replacing the halogen substituent in the compound of the formula VI by a nitrile function, and f) hydrolyzing the nitrile function of the compound of the formula VII
to the carboxylic acid, and g) converting the carboxylic acid of the formula VIII into the acylguanidine of the formula I, where in the compounds of the formulae II, III, IV, V, VI, VII and VIII
R1 to R4 are as defined in formula I and X and Y are independently of one another F, Cl, Br or I.
2. The process as claimed in claim 1, where steps a), b), c), d), e), f) and g) are managed independently of one another continuously or discontinuously.
3. The process as claimed in claim 1 and/or 2, in which R2 is hydrogen, and steps b) and c) are omitted.
4. A compound of the formula X
in which the meanings are:
R1 hydrogen, alkyl having 1, 2, 3 or 4 carbon atoms, alkoxy having 1, 2, 3 or 4 carbon atoms, NR10R11, -O p-(CH2)n-(CF2)o-CF3 or -(SO m)q-(CH2)r-(CF2)s-CF3;
R10 and R11 independently of one another hydrogen, alkyl having 1, 2, 3 or 4 carbon atoms or -CH2-CF3;
m zero, 1 or 2 n, o, p, q, r and s independently of one another zero or 1;
R6 -(SO h)z-(CH2)k -(CF2)l -CF3, alkyl having 1, 2, 3, 4, 5 or 6 carbon atoms, cycloalkyl having 3, 4, 5, 6, 7 or 8 carbon atoms, in which 1, 2, 3 or 4 hydrogen atoms may be replaced by fluorine atoms;
h zero, 1 or 2;
z zero or 1;
k zero, 1, 2, 3 or 4;
l zero or 1;
or R6 -(CH2)t-phenyl or -O-phenyl, which are unsubstituted or substituted by 1, 2 or 3 radicals selected from the group consisting of -O u-(CH2)v-CF3, alkoxy having 1, 2, 3 or 4 carbon atoms, alkyl having 1, 2, 3 or 4 carbon atoms and -SO2CH3;
t zero, 1, 2, 3 or 4;
u zero or 1;
v zero, 1, 2 or 3;
or R6 -(CH2)w-heteroaryl which is unsubstituted or substituted by 1, 2 or 3 radicals selected from the group consisting of -O x-(CH2)y-CF3, alkoxy having 1, 2, 3 or 4 carbon atoms and alkyl having 1, 2, 3 or 4 carbon atoms, -SO2CH3;
w zero, 1, 2, 3 or 4;
x zero or 1;
y zero, 1, 2 or 3;
R3 and R4, independently of one another hydrogen or F;
and the salts thereof;
in which the meanings are:
R1 hydrogen, alkyl having 1, 2, 3 or 4 carbon atoms, alkoxy having 1, 2, 3 or 4 carbon atoms, NR10R11, -O p-(CH2)n-(CF2)o-CF3 or -(SO m)q-(CH2)r-(CF2)s-CF3;
R10 and R11 independently of one another hydrogen, alkyl having 1, 2, 3 or 4 carbon atoms or -CH2-CF3;
m zero, 1 or 2 n, o, p, q, r and s independently of one another zero or 1;
R6 -(SO h)z-(CH2)k -(CF2)l -CF3, alkyl having 1, 2, 3, 4, 5 or 6 carbon atoms, cycloalkyl having 3, 4, 5, 6, 7 or 8 carbon atoms, in which 1, 2, 3 or 4 hydrogen atoms may be replaced by fluorine atoms;
h zero, 1 or 2;
z zero or 1;
k zero, 1, 2, 3 or 4;
l zero or 1;
or R6 -(CH2)t-phenyl or -O-phenyl, which are unsubstituted or substituted by 1, 2 or 3 radicals selected from the group consisting of -O u-(CH2)v-CF3, alkoxy having 1, 2, 3 or 4 carbon atoms, alkyl having 1, 2, 3 or 4 carbon atoms and -SO2CH3;
t zero, 1, 2, 3 or 4;
u zero or 1;
v zero, 1, 2 or 3;
or R6 -(CH2)w-heteroaryl which is unsubstituted or substituted by 1, 2 or 3 radicals selected from the group consisting of -O x-(CH2)y-CF3, alkoxy having 1, 2, 3 or 4 carbon atoms and alkyl having 1, 2, 3 or 4 carbon atoms, -SO2CH3;
w zero, 1, 2, 3 or 4;
x zero or 1;
y zero, 1, 2 or 3;
R3 and R4, independently of one another hydrogen or F;
and the salts thereof;
5. A compound of the formula X and/or the pharmaceutically suitable salts thereof as claimed in claim 4 for use as synthesis intermediate.
6. A compound of the formula XI
in which the meanings are:
R1 hydrogen, alkyl having 1, 2, 3 or 4 carbon atoms, alkoxy having 1, 2, 3 or 4 carbon atoms, NR10R11, -O p-(CH2)n-(CF2)o-CF3 or -(SO m)q-(CH2)r(CF2)s-CF3;
R10 and R11 independently of one another hydrogen, alkyl having 1, 2, 3 or 4 carbon atoms or -CH2-CF3;
m zero, 1 or 2 n, o, p, q, r and s independently of one another zero or 1;
R2 hydrogen, F, Cl, Br, l, -(SO h)z-(CH2)k -(CF2)l -CF3 or alkyl having 1, 2, 3, 4, 5 or 6 carbon atoms;
h zero, 1 or 2;
z zero or 1;
k zero, 1, 2, 3 or 4;
l zero or 1;
R3 and R4, independently of one another hydrogen or F;
R7 CN;
and the salts thereof.
in which the meanings are:
R1 hydrogen, alkyl having 1, 2, 3 or 4 carbon atoms, alkoxy having 1, 2, 3 or 4 carbon atoms, NR10R11, -O p-(CH2)n-(CF2)o-CF3 or -(SO m)q-(CH2)r(CF2)s-CF3;
R10 and R11 independently of one another hydrogen, alkyl having 1, 2, 3 or 4 carbon atoms or -CH2-CF3;
m zero, 1 or 2 n, o, p, q, r and s independently of one another zero or 1;
R2 hydrogen, F, Cl, Br, l, -(SO h)z-(CH2)k -(CF2)l -CF3 or alkyl having 1, 2, 3, 4, 5 or 6 carbon atoms;
h zero, 1 or 2;
z zero or 1;
k zero, 1, 2, 3 or 4;
l zero or 1;
R3 and R4, independently of one another hydrogen or F;
R7 CN;
and the salts thereof.
7. A compound of the formula XI and/or the pharmaceutically suitable salts thereof as claimed in claim 6 for use as synthesis intermediate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10353204.8 | 2003-11-13 | ||
| DE10353204A DE10353204A1 (en) | 2003-11-13 | 2003-11-13 | Process for the preparation of 4-pentafluorosulfanyl-benzoylguanidines |
| PCT/EP2004/012395 WO2005047241A1 (en) | 2003-11-13 | 2004-11-03 | Method for producing 4-pentafluoride-sulfanyl-benzoylguanidines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2545291A1 true CA2545291A1 (en) | 2005-05-26 |
| CA2545291C CA2545291C (en) | 2012-10-30 |
Family
ID=34585095
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2545291A Expired - Fee Related CA2545291C (en) | 2003-11-13 | 2004-11-03 | Method for producing 4-pentafluoride-sulfanyl-benzoylguanidines |
Country Status (23)
| Country | Link |
|---|---|
| EP (1) | EP1685097B1 (en) |
| JP (1) | JP4658955B2 (en) |
| KR (1) | KR101207223B1 (en) |
| CN (2) | CN100480237C (en) |
| AR (1) | AR046374A1 (en) |
| AT (1) | ATE386019T1 (en) |
| AU (1) | AU2004288760B2 (en) |
| BR (1) | BRPI0416570A (en) |
| CA (1) | CA2545291C (en) |
| CY (1) | CY1107922T1 (en) |
| DE (2) | DE10353204A1 (en) |
| DK (1) | DK1685097T3 (en) |
| ES (1) | ES2298838T3 (en) |
| HK (2) | HK1095582A1 (en) |
| IL (1) | IL175238A (en) |
| NO (1) | NO20062664L (en) |
| NZ (1) | NZ547170A (en) |
| PL (1) | PL1685097T3 (en) |
| PT (1) | PT1685097E (en) |
| RU (1) | RU2382030C2 (en) |
| TW (1) | TWI334859B (en) |
| WO (1) | WO2005047241A1 (en) |
| ZA (1) | ZA200602575B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7317124B2 (en) | 2003-11-13 | 2008-01-08 | Sanofi-Aventis Deutschland Gmbh | Ortho-substituted pentafluorosulfanylbenzenes, process for their preparation and their use as valuable synthetic intermediates |
| WO2010005783A1 (en) * | 2008-07-08 | 2010-01-14 | Boehringer Ingelheim International Gmbh | Pyrrolidinyl and piperidinyl compounds useful as nhe-1 inhibitors |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3721268A1 (en) * | 1987-06-27 | 1989-01-12 | Merck Patent Gmbh | ARYL SULFUR PENTAFLUORIDE |
| DK0589336T3 (en) * | 1992-09-22 | 1997-06-16 | Hoechst Ag | Benzylguanidines, methods for their preparation and their use as antiarrhythmics |
| GB9306183D0 (en) * | 1993-03-25 | 1993-05-19 | Zeneca Ltd | Novel compounds |
| DE4417004A1 (en) * | 1994-05-13 | 1995-11-16 | Hoechst Ag | Perfluoroalkyl-substituted benzoylguanidines, process for their preparation, their use as a medicament or diagnostic agent, and medicament containing them |
| DE19517848A1 (en) * | 1995-05-16 | 1996-11-21 | Merck Patent Gmbh | Fluorine-containing benzoylguanidines |
| GB9606015D0 (en) * | 1996-03-22 | 1996-05-22 | Rhone Poulenc Agriculture | New herbicides |
| DE10222192A1 (en) * | 2002-05-18 | 2003-11-27 | Aventis Pharma Gmbh | New pentafluorosulfanylbenzoylguanidine compound useful for treating e.g. infarction, angina pectoris and stroke |
-
2003
- 2003-11-13 DE DE10353204A patent/DE10353204A1/en not_active Withdrawn
-
2004
- 2004-11-03 RU RU2006120473/04A patent/RU2382030C2/en not_active IP Right Cessation
- 2004-11-03 EP EP04797536A patent/EP1685097B1/en active Active
- 2004-11-03 PT PT04797536T patent/PT1685097E/en unknown
- 2004-11-03 PL PL04797536T patent/PL1685097T3/en unknown
- 2004-11-03 JP JP2006538732A patent/JP4658955B2/en not_active Expired - Fee Related
- 2004-11-03 ES ES04797536T patent/ES2298838T3/en active Active
- 2004-11-03 AU AU2004288760A patent/AU2004288760B2/en not_active Ceased
- 2004-11-03 BR BRPI0416570-5A patent/BRPI0416570A/en not_active IP Right Cessation
- 2004-11-03 CN CNB2004800334806A patent/CN100480237C/en not_active Expired - Fee Related
- 2004-11-03 DE DE502004006216T patent/DE502004006216D1/en active Active
- 2004-11-03 CA CA2545291A patent/CA2545291C/en not_active Expired - Fee Related
- 2004-11-03 AT AT04797536T patent/ATE386019T1/en active
- 2004-11-03 WO PCT/EP2004/012395 patent/WO2005047241A1/en active IP Right Grant
- 2004-11-03 DK DK04797536T patent/DK1685097T3/en active
- 2004-11-03 CN CN2009100097561A patent/CN101475519B/en not_active Expired - Fee Related
- 2004-11-03 NZ NZ547170A patent/NZ547170A/en not_active IP Right Cessation
- 2004-11-11 TW TW093134389A patent/TWI334859B/en not_active IP Right Cessation
- 2004-11-11 AR ARP040104154A patent/AR046374A1/en not_active Application Discontinuation
-
2006
- 2006-03-29 ZA ZA200602575A patent/ZA200602575B/en unknown
- 2006-04-26 IL IL175238A patent/IL175238A/en not_active IP Right Cessation
- 2006-05-11 KR KR1020067009188A patent/KR101207223B1/en not_active IP Right Cessation
- 2006-06-09 NO NO20062664A patent/NO20062664L/en not_active Application Discontinuation
-
2007
- 2007-03-08 HK HK07102566.3A patent/HK1095582A1/en not_active IP Right Cessation
-
2008
- 2008-04-17 CY CY20081100431T patent/CY1107922T1/en unknown
-
2009
- 2009-12-29 HK HK09112272.5A patent/HK1133870A1/en not_active IP Right Cessation
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20161103 |