CN1035293A - 制备n-膦酰基甲基亚氨基双乙酸的方法 - Google Patents
制备n-膦酰基甲基亚氨基双乙酸的方法 Download PDFInfo
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- AZIHIQIVLANVKD-UHFFFAOYSA-N N-(phosphonomethyl)iminodiacetic acid Chemical compound OC(=O)CN(CC(O)=O)CP(O)(O)=O AZIHIQIVLANVKD-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 13
- KKHJQZVEUKJURX-UHFFFAOYSA-N 2-(carboxymethylamino)acetic acid;hydrochloride Chemical compound Cl.OC(=O)CNCC(O)=O KKHJQZVEUKJURX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- HQNNCDJMFMJHDH-UHFFFAOYSA-L calcium;2-(carboxylatomethylamino)acetate Chemical compound [Ca+2].[O-]C(=O)CNCC([O-])=O HQNNCDJMFMJHDH-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000013019 agitation Methods 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 238000009835 boiling Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- -1 compound calcium salt Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 159000000007 calcium salts Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- YBPUBXQZBUQACE-UHFFFAOYSA-N 2-aminoacetic acid;phosphoric acid Chemical compound NCC(O)=O.OP(O)(O)=O YBPUBXQZBUQACE-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- UTPOUAZEFGTYAY-UHFFFAOYSA-N azanium;2-chloroacetate Chemical compound [NH4+].[O-]C(=O)CCl UTPOUAZEFGTYAY-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- HAXVIVNBOQIMTE-UHFFFAOYSA-L disodium;2-(carboxylatomethylamino)acetate Chemical compound [Na+].[Na+].[O-]C(=O)CNCC([O-])=O HAXVIVNBOQIMTE-UHFFFAOYSA-L 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
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- Life Sciences & Earth Sciences (AREA)
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明涉及用简易的合成法，从亚氨基双乙酸钙盐起始来制备N-膦酰基甲基亚氨基双乙酸，该方法包括在50-100℃时，加热摩尔比为2-3∶1的亚氨基双乙酸钙盐和浓盐酸，分离所得到的亚氨基双乙酸盐酸盐，随后将其溶解于水，并使其与磷酸以摩尔比为1.0-1.2∶1(按亚氨基双乙酸盐酸盐计算)及与甲醛以摩尔比为1.0-1.4∶1，在水溶液中，在搅拌下进行反应，分离所得产物。
Description
本发明涉及自亚氨基乙酸的酸性钙盐起始制备N-膦酰基甲基亚氨基双乙酸。
N-膦酰基甲基亚氨基双乙酸是制备具有广谱活性的N-膦酰基甲基甘氨酸（甘氨酸磷酸盐）的重要的中间体。HU-PS 177，155号涉及N-膦酰基甲基亚氨基双乙酸的制备，其中介绍了亚氨基双乙酸的酸性钙盐。按照该专利说明书，式A复盐的制备是以一给定的摩尔比，通过将氢氧化钙加入在水性介质中的一氯代乙酸铵盐中，除去该可溶性亚氨基双乙酸钙盐附近的氨，并用盐酸将溶液的pH值调至2-6之间。制备上述复盐的目的是要制备N-膦酰基甲基亚氨基双乙酸，在此制备过程中，用30%摩尔过量的硫酸钠溶液，使该复盐的水悬浮液进行复分解，而后离心除去所形成的石膏，将亚氨基双乙酸-钠盐的水溶液与50%摩尔过量的仲甲醛和5%摩尔过量的三氯化磷反应。反应后加入氢氧化钠水溶液，冷却分离产物，按一氯乙酸计算，收率约为60%。上述方法的缺点是由于进行复分解，要加入钠盐，使本方法中形成一定量的无机盐，并会对环境造成严重的污染。为进行复式钙盐的反应，要使用大量的三氯化磷，会形成盐酸，就应当用氢氧化钠加以中和，以便以适宜的收率沉淀出N-膦酰基甲基亚氨基双乙酸。而在该方法中由于加入氢氧化钠，又会形成一定量的氯化钠，它会污染终产物。还由于使用三氯化磷，中和大量的盐酸需要相当高的成本费用。式A的复盐为：
本发明的主题一方面是提供制备N-膦酰基甲基亚氨基双乙酸的简易合成法，另一方面是提供除去所形成的会污染环境的副产物。
按照本发明的方法是采用自一氯乙酸、氨气和氢氧化钙反应所形成的亚氨基双乙酸钙盐为起始，来制备N-膦酰基甲基亚氨基双乙酸，该方法特征在于：在50-100℃时，加热摩尔比为2-3∶1的亚氨基双乙酸钙盐和浓盐酸，分离所得到的亚氨基双乙酸盐酸盐，然后将其溶解于水，并还可在纯化反应后，在亚氨基双乙酸盐酸盐与磷酸以摩尔比为1.0-1.2∶1及与甲醛以摩尔比为1.0-1.4∶1，在水溶液中，于沸腾下进行反应，还可在蒸发该混合物分离所得的产物。
按如下所述实施本发明方法。
在20-30℃时，将氨气通入60%-氯乙酸的水溶液中，两者的摩尔比为0.6∶1。通完后，在35-40℃时，将氢氧化钙慢慢加入受冷却的反应混合物中，两者的摩尔比为1.05∶1，在60-80℃时，经煮沸该混合物，用浓盐酸使反应所形成的亚氨基双乙酸钙盐转变为亚氨基双乙酸氢氯化物，两者的摩尔比为2.5∶1。反应后，混合物冷却至10-20℃，滤出沉淀的亚氨基双乙酸盐酸盐，然后，在转变为亚氨基双乙酸后，将其溶解于水，除去机械杂质，加入磷酸，两者的摩尔比为1.05∶1。加热所得到的混合物至其沸点，加入甲醛的水溶液，两者的摩尔比为1.2∶1。过滤所得到的N-膦酰基甲基亚氨基双乙酸。
本发明方法的优越性可概括如下：
1.可用简易的合成方法制得收率高的终产物。
2.无需分离亚氨基双乙酸。
3.可用较少的步骤实施本发明，且所形成的副产物要少得多，因为既无需从亚氨基双乙酸的盐酸盐制备亚氨基双乙酸，也无需将亚氨基双乙酸的钙盐转变为其钠盐。
4.亚氨基双乙酸盐酸盐中间体无需纯化和干燥即可直接用作本发明方法的原料。
5.采用磷酸，即可排除制备时所形成的大量盐酸的中和等技术难题。
6.可用简单的装置和/或设备实施本发明。
现用下列非限制性实施例详细地说明本发明。
实施例1
将190kg 50%一氯代乙酸水溶液（1000摩尔）导入一个容积为500升，装配有一搅拌器、温度计和回流冷凝器的可冷却、可加热、涂有瓷釉的压热器中。冷却后，将12.75kg（750摩尔）氨气在搅拌下通入该溶液中。当保持该混合物温度于35-40℃时，在1.5-2.5小时内加入等剂量的77.7kg（1050摩尔）氢氧化钙。之后于40-50℃时搅拌所得到的反应混合物6小时。于约80℃真空蒸除该50升混合物中的过量氨气。接着将200升37%盐酸加入反应器中，于60-80℃搅拌1小时。将所得到的反应混合物冷却至10-20℃，搅拌2-3小时后，滤出该亚氨基双乙酸盐酸盐。
取101kg湿度为30%所得到的亚氨基双乙酸盐酸盐，随后将其溶解在100升水中，滤除机械杂质，接着进行分析。此水溶液中含有约68kg的亚氨基双乙酸盐酸盐，其为理论量的80%。
在该混合物沸点温度时，在一装配有可加热、可冷却的冷却器和回流冷凝器和搅拌器装置的压热器内，将上述水溶液连同34.1kg（400摩尔）的96%磷酸一起加热。在1小时内加入39.7kg（450摩尔）的34%甲醛水溶液，接着在沸腾下再搅拌2小时。随后使其冷却至10-15℃，滤出沉淀的N-膦酰基甲基亚氨基双乙酸，用水洗涤随后干燥之。得到78.6kg产物，其为理论量的98.2%。该膦酰基甲基化步骤的收率为85.1%，以一氯乙酸计算的收率为67.9%。
实施例2
将154.5kg（1000摩尔）60%-氯乙酸水溶液导入一容积为500升装配有可冷却、可加热搅拌器、冷却器和回流冷却器的涂有瓷釉的装置中。在冷却和搅拌下，把11.1kg（650摩尔）氨气导入上述装置中。保持该反应混合物的温度在35-40℃，并在2小时内加入等份的77.7kg（50摩尔）氢氧化钙。于45-50℃搅拌所得到的反应混合物7小时，加入200升37%盐酸水溶液，接着在60-80℃搅拌一小时。使所得到的反应混合物冷却至10-20℃，结晶3-4小时，随后过滤，得到湿度为30%的105kg固体产物。
将该产物溶于100升水中，滤除机械杂质后将其导入一装配有可冷却、可加热的冷却器、回流冷凝器和搅拌器的压热器中。根据分析结果，所得到的溶液中亚氨基双乙酸盐酸盐含量为69.7kg（410摩尔）。将19.7kg（200摩尔）37%盐酸和40.3kg（490摩尔）磷酸加入上述溶液中。将所得反应混合物加热至其沸点，并在沸点时，在一小时内加入43.4kg（490摩尔）34%甲醛水溶液，随后使反应混合物再沸腾2小时。随后将反应混合物蒸发至其原体积的2/3，冷却至10-15℃，滤出沉淀的结晶，水洗涤并干燥之。所得到的79.4kg N-膦酰基甲基亚氨基双乙酸的纯度为98%，其分解点为208-209℃。膦酰基甲基化步骤的收率为83.6%，按一氯乙酸计算的收率为68.0%。
Claims (1)
- 一种由一氯乙酸、氨气和氢氧化钙反应所形成的亚氨基双乙酸钙盐为起始，制备N-膦酰基甲基亚氨基双乙酸的方法，其中包括在50-100℃时，加热摩尔比为2-3∶1的亚氨基双乙酸钙盐和浓盐酸、分离所得的亚氨基双乙酸盐酸盐，随后将其溶解于水，如有需要，可在纯化后，使其与磷酸以摩尔比为1.0-1.2∶1(按亚氨基双乙酸盐酸盐计算)和与甲醛以摩尔比为1.0-1.4∶1，在水溶液中，在搅拌下进行反应，如有需要，可在蒸发该混合物后，分离所得的产物。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HU88562A HU200780B (en) | 1988-02-08 | 1988-02-08 | Process for producing n-phosphonomethyl iminodiacetic acid from double salt of iminodiacetic acid |
| HU2251-562/88 | 1988-02-08 |
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| Publication Number | Publication Date |
|---|---|
| CN1035293A true CN1035293A (zh) | 1989-09-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN89100720.2A Pending CN1035293A (zh) | 1988-02-08 | 1989-02-03 | 制备n-膦酰基甲基亚氨基双乙酸的方法 |
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| Country | Link |
|---|---|
| US (1) | US4931585A (zh) |
| JP (1) | JPH01228996A (zh) |
| CN (1) | CN1035293A (zh) |
| AU (1) | AU607040B2 (zh) |
| BE (1) | BE1002095A5 (zh) |
| BR (1) | BR8900621A (zh) |
| DE (1) | DE3903715A1 (zh) |
| DK (1) | DK39789A (zh) |
| ES (1) | ES2010396A6 (zh) |
| FR (1) | FR2626883B1 (zh) |
| GB (1) | GB2215720B (zh) |
| GR (1) | GR890100070A (zh) |
| HU (1) | HU200780B (zh) |
| IT (1) | IT1229522B (zh) |
| NL (1) | NL8900280A (zh) |
| NZ (1) | NZ227703A (zh) |
| PL (1) | PL277488A1 (zh) |
| PT (1) | PT89578B (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5312972A (en) * | 1992-10-29 | 1994-05-17 | Hampshire Chemical Corp. | Conversion of hydroxymethyl-iminodiacetic acid to phosphonomethyl-iminodiacetic acid |
| US5312973A (en) * | 1993-03-25 | 1994-05-17 | Finchimica S.P.A. | Process for producing n-phosphono-methyl-imino-diacetic acid |
| PT833831E (pt) * | 1995-06-07 | 2002-07-31 | Monsanto Technology Llc | Processo para a preparacao de acido n-fosfonometiliminodiacetico |
| IES980552A2 (en) * | 1998-07-09 | 1999-08-11 | Agritech Chemical Ltd | Improved process for preparing N-phosphonomethyl iminodiacetic acid |
| AU6024599A (en) * | 1998-09-08 | 2000-03-27 | Hampshire Chemical Corp. | Synthesis of phosphonomethyliminodiacetic acid with reduced effluent |
| RU2015103314A (ru) | 2012-07-17 | 2016-09-10 | Страйтмарк Холдинг Аг | Способ синтеза N-фосфонометилиминодиуксусной кислоты |
| CN104812766B (zh) | 2012-07-17 | 2017-06-06 | 斯特雷特马克控股股份公司 | 用于合成氨基亚烷基膦酸的方法 |
| WO2014012991A1 (en) | 2012-07-17 | 2014-01-23 | Straitmark Holding Ag | Method for the synthesis of n-(phosphonomethyl)glycine |
| RU2674022C9 (ru) | 2012-07-17 | 2019-01-24 | МОНСАНТО ТЕКНОЛОДЖИ ЭлЭлСи | Способ синтеза альфа-аминоалкиленфосфоновой кислоты |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2895989A (en) * | 1956-06-22 | 1959-07-21 | Dow Chemical Co | Method for the preparation of iminodiacetic acid |
| US3455675A (en) * | 1968-06-25 | 1969-07-15 | Monsanto Co | Aminophosphonate herbicides |
| HU184168B (en) * | 1979-05-11 | 1984-07-30 | Mta Koezponti Kemiai Kutato In | Process for producing n-bracket-phosphono-methyl-bracket closed-glycine |
| US4724103A (en) * | 1984-02-27 | 1988-02-09 | Monsanto Company | Process for preparing N,N-diacetic acid aminomethylenephosphonic acid |
| US4657705A (en) * | 1985-09-23 | 1987-04-14 | Monsanto Company | Process for the preparation of N-substituted aminomethylphosphonic acids |
-
1988
- 1988-02-08 HU HU88562A patent/HU200780B/hu not_active IP Right Cessation
-
1989
- 1989-01-24 NZ NZ227703A patent/NZ227703A/en unknown
- 1989-01-25 AU AU28798/89A patent/AU607040B2/en not_active Expired - Fee Related
- 1989-01-27 DK DK039789A patent/DK39789A/da not_active Application Discontinuation
- 1989-01-27 GB GB8901806A patent/GB2215720B/en not_active Expired - Fee Related
- 1989-01-31 PL PL27748889A patent/PL277488A1/xx unknown
- 1989-01-31 PT PT89578A patent/PT89578B/pt active IP Right Grant
- 1989-02-01 FR FR898901265A patent/FR2626883B1/fr not_active Expired - Fee Related
- 1989-02-02 US US07/306,032 patent/US4931585A/en not_active Expired - Fee Related
- 1989-02-03 BR BR898900621A patent/BR8900621A/pt unknown
- 1989-02-03 BE BE8900121A patent/BE1002095A5/fr not_active IP Right Cessation
- 1989-02-03 CN CN89100720.2A patent/CN1035293A/zh active Pending
- 1989-02-03 IT IT8919299A patent/IT1229522B/it active
- 1989-02-06 NL NL8900280A patent/NL8900280A/nl not_active Application Discontinuation
- 1989-02-06 GR GR890100070A patent/GR890100070A/el unknown
- 1989-02-07 ES ES8900421A patent/ES2010396A6/es not_active Expired
- 1989-02-07 JP JP1028531A patent/JPH01228996A/ja active Pending
- 1989-02-08 DE DE3903715A patent/DE3903715A1/de not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| FR2626883B1 (fr) | 1991-02-22 |
| AU2879889A (en) | 1989-08-10 |
| IT1229522B (it) | 1991-09-03 |
| PT89578A (pt) | 1989-10-04 |
| DK39789A (da) | 1989-08-09 |
| NZ227703A (en) | 1990-11-27 |
| PL277488A1 (en) | 1989-10-16 |
| BE1002095A5 (fr) | 1990-06-26 |
| GR890100070A (el) | 1994-03-31 |
| DE3903715A1 (de) | 1989-08-17 |
| BR8900621A (pt) | 1989-10-10 |
| IT8919299A0 (it) | 1989-02-03 |
| FR2626883A1 (fr) | 1989-08-11 |
| GB8901806D0 (en) | 1989-03-15 |
| NL8900280A (nl) | 1989-09-01 |
| US4931585A (en) | 1990-06-05 |
| GB2215720A (en) | 1989-09-27 |
| JPH01228996A (ja) | 1989-09-12 |
| DK39789D0 (da) | 1989-01-27 |
| AU607040B2 (en) | 1991-02-21 |
| PT89578B (pt) | 1994-01-31 |
| HUT49360A (en) | 1989-09-28 |
| GB2215720B (en) | 1991-07-10 |
| HU200780B (en) | 1990-08-28 |
| ES2010396A6 (es) | 1989-11-01 |
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