JP4119842B2 - 尿素を出発物質で使用するヒドラゾジカルボンアミドの製造方法及び装置 - Google Patents
尿素を出発物質で使用するヒドラゾジカルボンアミドの製造方法及び装置 Download PDFInfo
- Publication number
- JP4119842B2 JP4119842B2 JP2003538117A JP2003538117A JP4119842B2 JP 4119842 B2 JP4119842 B2 JP 4119842B2 JP 2003538117 A JP2003538117 A JP 2003538117A JP 2003538117 A JP2003538117 A JP 2003538117A JP 4119842 B2 JP4119842 B2 JP 4119842B2
- Authority
- JP
- Japan
- Prior art keywords
- ammonia
- reaction
- hydrazodicarbonamide
- biuret
- urea
- 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.)
- Expired - Fee Related
Links
- ULUZGMIUTMRARO-UHFFFAOYSA-N (carbamoylamino)urea Chemical compound NC(=O)NNC(N)=O ULUZGMIUTMRARO-UHFFFAOYSA-N 0.000 title claims description 87
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims description 42
- 239000004202 carbamide Substances 0.000 title claims description 42
- 238000000034 method Methods 0.000 title claims description 34
- 239000007858 starting material Substances 0.000 title description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 175
- 238000006243 chemical reaction Methods 0.000 claims description 139
- 229910021529 ammonia Inorganic materials 0.000 claims description 84
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 57
- 229910052751 metal Inorganic materials 0.000 claims description 51
- 239000002184 metal Substances 0.000 claims description 51
- 238000004519 manufacturing process Methods 0.000 claims description 42
- 150000003839 salts Chemical class 0.000 claims description 37
- 238000000197 pyrolysis Methods 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 21
- 229910052736 halogen Inorganic materials 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 150000002367 halogens Chemical class 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims description 7
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 239000000010 aprotic solvent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000000243 solution Substances 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 17
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 239000006227 byproduct Substances 0.000 description 9
- CPFKREDLOXJBPW-UHFFFAOYSA-N 1-carbamoyl-3-chlorourea;sodium Chemical compound [Na].NC(=O)NC(=O)NCl CPFKREDLOXJBPW-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 238000004811 liquid chromatography Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000005708 Sodium hypochlorite Substances 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910019093 NaOCl Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 3
- XKGPWQAPNIDUSV-UHFFFAOYSA-N chlorourea;sodium Chemical compound [Na].NC(=O)NCl XKGPWQAPNIDUSV-UHFFFAOYSA-N 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- XSBJHFRMBNLOGP-UHFFFAOYSA-N diaziridin-3-one Chemical class O=C1NN1 XSBJHFRMBNLOGP-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- WNVQBUHCOYRLPA-UHFFFAOYSA-N triuret Chemical compound NC(=O)NC(=O)NC(N)=O WNVQBUHCOYRLPA-UHFFFAOYSA-N 0.000 description 3
- 208000019901 Anxiety disease Diseases 0.000 description 2
- 239000004156 Azodicarbonamide Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000036506 anxiety Effects 0.000 description 2
- 235000019399 azodicarbonamide Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- RGENRDSNOFCRIP-UHFFFAOYSA-N CC(C)(C)CCNC(N(C(N)=O)N)=O Chemical compound CC(C)(C)CCNC(N(C(N)=O)N)=O RGENRDSNOFCRIP-UHFFFAOYSA-N 0.000 description 1
- 238000007167 Hofmann rearrangement reaction Methods 0.000 description 1
- 241000282849 Ruminantia Species 0.000 description 1
- PFLUPZGCTVGDLV-UHFFFAOYSA-N acetone azine Chemical compound CC(C)=NN=C(C)C PFLUPZGCTVGDLV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- -1 isocyanate compound Chemical class 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229940124597 therapeutic agent Drugs 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C281/06—Compounds containing any of the groups, e.g. semicarbazides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/KR2001/001796 WO2003035601A1 (en) | 2001-10-24 | 2001-10-24 | Method and apparatus for preparing hydrazo-dicarbonamide using urea as starting material |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2005506378A JP2005506378A (ja) | 2005-03-03 |
| JP2005506378A5 JP2005506378A5 (https=) | 2006-01-05 |
| JP4119842B2 true JP4119842B2 (ja) | 2008-07-16 |
Family
ID=19198462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003538117A Expired - Fee Related JP4119842B2 (ja) | 2001-10-24 | 2001-10-24 | 尿素を出発物質で使用するヒドラゾジカルボンアミドの製造方法及び装置 |
Country Status (9)
| Country | Link |
|---|---|
| US (2) | US20040199012A1 (https=) |
| EP (1) | EP1446378B1 (https=) |
| JP (1) | JP4119842B2 (https=) |
| CN (1) | CN1246293C (https=) |
| BR (1) | BR0117163B1 (https=) |
| DE (1) | DE60128012T2 (https=) |
| ES (1) | ES2284702T3 (https=) |
| MX (1) | MXPA04003884A (https=) |
| WO (1) | WO2003035601A1 (https=) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8260393B2 (en) | 2003-07-25 | 2012-09-04 | Dexcom, Inc. | Systems and methods for replacing signal data artifacts in a glucose sensor data stream |
| US8010174B2 (en) * | 2003-08-22 | 2011-08-30 | Dexcom, Inc. | Systems and methods for replacing signal artifacts in a glucose sensor data stream |
| US9282925B2 (en) | 2002-02-12 | 2016-03-15 | Dexcom, Inc. | Systems and methods for replacing signal artifacts in a glucose sensor data stream |
| KR100618947B1 (ko) | 2002-06-17 | 2006-09-01 | 주식회사 제이앤드제이 캐미칼 | 뷰렛을 이용한 하이드라조디카본아미드의 제조 방법 |
| US20190357827A1 (en) | 2003-08-01 | 2019-11-28 | Dexcom, Inc. | Analyte sensor |
| US20140121989A1 (en) | 2003-08-22 | 2014-05-01 | Dexcom, Inc. | Systems and methods for processing analyte sensor data |
| US8364231B2 (en) | 2006-10-04 | 2013-01-29 | Dexcom, Inc. | Analyte sensor |
| US8532730B2 (en) | 2006-10-04 | 2013-09-10 | Dexcom, Inc. | Analyte sensor |
| KR100826882B1 (ko) * | 2005-12-05 | 2008-05-06 | 한국전자통신연구원 | 버스트 모드 광 수신기에서 디지털 자동이득제어 방법 및장치 |
| JP2009288878A (ja) * | 2008-05-27 | 2009-12-10 | Hitachi Ltd | ストレージ装置、及びストレージ装置の冷却方法 |
| US9149220B2 (en) | 2011-04-15 | 2015-10-06 | Dexcom, Inc. | Advanced analyte sensor calibration and error detection |
| CN101462985B (zh) * | 2009-01-22 | 2013-07-24 | 杭州电化集团有限公司 | 一种偶氮二甲酰胺的清洁生产工艺 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2370065A (en) * | 1942-05-05 | 1945-02-20 | Sharples Chemicals Inc | Manufacture of biuret |
| US2524049A (en) * | 1947-03-25 | 1950-10-03 | Paul W Garbo | Production of biuret |
| US4654441A (en) * | 1980-08-15 | 1987-03-31 | Moorman Manufacturing Company | Biuret production by controlled pyrolysis of urea |
| AU4208185A (en) * | 1984-05-31 | 1985-12-05 | Olin Corporation | Preparing hydrazodicarbonamide |
| KR100345874B1 (ko) * | 2000-01-07 | 2002-07-27 | 주식회사 제이앤드제이 캐미칼 | 하이드라조디카본아미드의 합성 방법 |
-
2001
- 2001-10-24 BR BRPI0117163-1A patent/BR0117163B1/pt not_active IP Right Cessation
- 2001-10-24 WO PCT/KR2001/001796 patent/WO2003035601A1/en not_active Ceased
- 2001-10-24 CN CN01823726.6A patent/CN1246293C/zh not_active Expired - Fee Related
- 2001-10-24 JP JP2003538117A patent/JP4119842B2/ja not_active Expired - Fee Related
- 2001-10-24 ES ES01981121T patent/ES2284702T3/es not_active Expired - Lifetime
- 2001-10-24 MX MXPA04003884A patent/MXPA04003884A/es active IP Right Grant
- 2001-10-24 EP EP01981121A patent/EP1446378B1/en not_active Expired - Lifetime
- 2001-10-24 DE DE60128012T patent/DE60128012T2/de not_active Expired - Lifetime
-
2004
- 2004-04-21 US US10/829,418 patent/US20040199012A1/en not_active Abandoned
-
2007
- 2007-05-11 US US11/747,596 patent/US7422727B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US20040199012A1 (en) | 2004-10-07 |
| BR0117163A (pt) | 2004-10-26 |
| CN1246293C (zh) | 2006-03-22 |
| DE60128012T2 (de) | 2008-01-10 |
| CN1558896A (zh) | 2004-12-29 |
| DE60128012D1 (de) | 2007-05-31 |
| EP1446378A4 (en) | 2005-07-13 |
| EP1446378A1 (en) | 2004-08-18 |
| MXPA04003884A (es) | 2004-07-16 |
| BR0117163B1 (pt) | 2012-05-15 |
| US7422727B2 (en) | 2008-09-09 |
| US20070207072A1 (en) | 2007-09-06 |
| JP2005506378A (ja) | 2005-03-03 |
| EP1446378B1 (en) | 2007-04-18 |
| WO2003035601A1 (en) | 2003-05-01 |
| ES2284702T3 (es) | 2007-11-16 |
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