CN1018179B - 活性烯酮及烯醛之水解作用 - Google Patents
活性烯酮及烯醛之水解作用Info
- Publication number
- CN1018179B CN1018179B CN88100615A CN88100615A CN1018179B CN 1018179 B CN1018179 B CN 1018179B CN 88100615 A CN88100615 A CN 88100615A CN 88100615 A CN88100615 A CN 88100615A CN 1018179 B CN1018179 B CN 1018179B
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- hydrolysis
- water
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- 238000006460 hydrolysis reaction Methods 0.000 title claims description 26
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- 238000009833 condensation Methods 0.000 description 1
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
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- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- KNVAYBMMCPLDOZ-UHFFFAOYSA-N propan-2-yl 12-hydroxyoctadecanoate Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)OC(C)C KNVAYBMMCPLDOZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/42—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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Abstract
将含有一或多个碳—碳双键及一个与至少一个双键共轭之羰基所组成之酮类或醛类,经由批式或连续式方法于水存在下藉热与压力之作用而水解。该酮或醛系于与羰基共轭之双键位置分裂而制成另一种含羰基之化合物。
Description
在有机化学领域中,由不同形式起始物质制成之反应产物可经由极多种反应顺序而得,特别易于反应之起始物质为烯类化合物,另称为烯烃类。烯烃之特征为存在一或多个碳-碳双键。涉及烯烃之反应通常发生于其碳-碳双键上。该双键可经由原子之加入烯烃分子中而消除。此双键亦可经由一个碳-碳配对而转移至分子内之另一处。此双键亦可由一个具有一或多个双键之烯烃分子,经分裂而形成两个或多个更小分子。分裂作用系藉少数反应顺序完成,例如臭氧分解作用、氧化作用等。一般而言,分裂作用系藉氧之加入双键碳上而发生,然后破坏碳间键结。
一取代基存在于烯烃化合物上,有时可允许该双键以较不激烈之条件断裂。此种取代基之一为羰基,它由一个以双键与氧结合之碳所组成。一个具有以其双键与烯烃双键共轭之羰基,可活化该烯烃双键并在碱性催化剂、热及水存在下造成其断裂。已知此反应为一种逆或反-醇醛缩合反应,它易发生副反应与反应产物缩合。在仅有热与水存在下,一般地无反应发生。
有一项已发表之参考文献描述一种经取代之共轭环己酮分子之分裂系发生在热、压力与水存在下而无任何添加之碱性催化剂。此反应系引述自Annalen、第289卷,第337页(1986),其涉及由胡薄荷酮与水在压热器中于250℃下生成丙酮与3-甲基-环己酮。未有其他有关裂解之已知参考文献仅使用热、压力与水,再者,一般认为胡薄荷酮在上述条件下进行反应是因其环己基环上取代基之位置造成其烯烃之不稳定化,故允许反应发生。
目前已发现某些具有至少一个碳-碳双键及一个共轭羰基碳-氧键之非环状化合物可于碱性催化剂不存在下进行分裂反应。详言之,我们已发现具有一碳-碳双键与羰基双键共轭之非环状未饱和酮与醛可在热、压力及水存在下进行水解,其使得该共轭碳-碳双键断裂并形成新的含羰基反应产物。而且,此水解反应以实用产率造成起始物质相当部份之分裂。当以本发明实际操作α,β-不饱和化合物之水解时,其实际上与寻常的酸或碱催化醇醛反应进行结果相反。此有利的结果系由该含羰基化合物与水之形成而制得一种α,β-不饱和化合物。本发明之一项优点为由天然物制造天然香料仅须在温度、压力、及水之反应条件下进行,而无须催化剂。
在上述申请案序列第10,902号中,已报告该反应系在水存在下,以约200℃至约300℃范围内之温度及约1551-8618千帕范围内之压力下进行。吾人亦已发现该水解反应可有效地于甚至更高温度与压力下在约325℃与13789.5千帕下进行,于至少约200℃之温度与至少约1551千帕之压力下进行该反应较佳。于反应期间在温度或压力上之微小变异,对于产物之生成无显著影响。因此可以忍受。因此,以较广方面而言,本发明系针对上述化合物类之水解方法,于几乎中性pH值下在水存在中并于足以完成该水解作用之超大气压力下加热。本文所用之「超大气压」系意谓高于正常大气压之状况,通常在约1551-13789.5千帕范围。起始物质与水在上文所示范围内以令人满意之超大气温度与压力,同时受到压力与温度之作用是极重要的。仅受热或仅受压力作用之起始物质与水不会产生水解产物。该水可为经蒸馏或去离子者,但自来水亦足够。
欲于包含在本发明内之起始物质为具有一或多个碳-碳双键之非环状不饱和酮类与醛类,而其中至少一个碳-碳双键系与羰基碳-氧双键共轭。「非环状」一词系意谓将此类化合物限制于其中羰基碳或共轭碳-碳双键上之碳均非一个环结构(无论是环族或芳族)之构成成份。然
而,环族或芳族取代基可存在于同一分子中。
本文所请求专利之水解反应,典型地系以批式方法在压热器中进行。但是,该反应可成功地在一种连续流动反应器(譬如管式反应器)中完成。
因为此水解反应之本性,故在其起始物质中存在之非反应性物料,对于共轭碳-碳双键之分裂,无甚影响。因此,可使用非环状不饱和酮类与醛类之天然物以获得大量产率之产物。
本方法在其较广方面而言,系藉水解经活化之非环状烯烃而运作,如以下列化学反应式所表示者:
取代基R、R′及R″为氢、烷基、环烷基或芳烃基或经取代之烷基、环烷基或芳烃基。取代基A为选自与烯烃共轭之醛或酮类之基团;R″可能亦为A。此反应系于水存在下在几乎中性之pH值下,于超大气压力与温度下,例如在约1551-13789.5千帕范围内之压力与在约200℃至约325℃范围内之温度下,较佳是在至少约1551千帕与约200℃下进行。
大量的经活化烯烃化合物可根据本发明之陈述水解。在下列未完全涵盖之列示化合物系包括在可水解之经活化烯烃化合物之描述下:桂皮醛产生苯甲醛、柠檬醛产生6-甲基-5-庚烯-2-酮、2,4-癸二烯醛产生己醛、3-癸烯-2-酮产生庚醛与丙酮、2-十二烯醛产生癸醛、1,2-二苯甲醯乙烯产生苯乙酮、1,7-双(4-羟基-3-甲氧苯基)-1,6-庚二烯-3,5-二酮产生4-羟基-3-甲氧基苯甲醛、2-庚烯醛产生戊醛、2-己烯醛产生丁醛、紫萝兰酮产生3,3-二甲基辛-7-酮醛与丙酮、鸢尾根酮产生3,
3,4-三甲基辛-7-酮醛与丙酮、1-(4-甲氧苯基)-1-戊烯-3-酮产生对甲氧基苯甲醛与甲乙酮、5-甲基-3-己烯-2-酮产生异丁醛与丙酮、α-甲基-异-紫萝兰酮产生柠檬醛与甲乙酮、5-甲基-2-苯基-2-己烯醛产生苯乙醛与3-甲基丁醛、4-苯基-3-丁烯-2-酮产生苯甲醛与丙酮、及邻-甲氧基桂皮醛产生邻-甲氧基苯甲醛。任何可水解之经活化烯烃化合物之来源均可令人满意地用以进行本发明之陈述,其范围包括未经加工之天然或合成原料至其经纯化之萃取物。
下文详述操作实例,以其最佳形式说明本发明之实际作业,藉以使在此项技艺中之普通技术人员能够实际运作本发明。本发明之原理、其操作参数及其他显而易见的修正均可经由下文详述之作业程序而明了。
实例Ⅰ
在一升帕尔(Parr)压热器中置入80克桂皮油(72%桂皮醛)与720克HO。然后将装有桂皮油与水之压热器加热至250℃,保持此温度历约八小时。反应期间之压热器压力系维持在4688-4826千帕。
在反应终了时,移除热与压力并冷却压热器。藉二氯甲烷萃取,将水相与有机相分离。
藉回转式蒸发除去大部分二氯甲烷后,再分级蒸馏其有机相。第一部份馏出物系为苯甲醛,其量为18克。回收之第二馏份为14克桂皮醛。
实例Ⅱ
于一升帕尔压热器中置入80克桂皮醛与720克水。然后将含有起始物质之压热器在4688千帕压力下加热至250℃经历大约八小时。
冷却后,藉二氯甲烷萃取,将水相与有机相分离。藉回转式蒸发除去大部分二氯甲烷后,再分级蒸馏其有机相而得23克苯甲醛与13.8克桂皮醛。
实例Ⅲ
于一升帕尔压热器中置入80克桂皮醛与720克水。然后将压热器在
4826千帕压力下加热至250℃历两小时。
冷却后,以二氯甲烷自含水相中萃取出有机相,再按实例Ⅰ与Ⅱ分级蒸馏。回收之产物为22克苯甲醛与36.5克桂皮醛。
实例Ⅳ
于一升帕尔压热器中置入720克水与80克不含萜之柠檬草油,其内含约95%柠檬醛。然后于4964千帕压力下将含有油与水之压热器加热至250℃历两小时。
然后冷却压热器之内容物并以二氯甲烷萃取。藉回转式蒸发除去大部份二氯甲烷。再分级蒸馏经分离之有机相,产生14.16克6-甲基-5-庚烯-2-酮与9.0克柠檬醛。
实例Ⅴ
于600毫升帕尔压热器中置入10克1,2-二苯甲酰基乙烯与390克水。然后以6136千帕之合成压力将压热器加热至275℃历两小时。
冷却后,以二氯甲烷(100毫升)自含水相中萃取有机相。在真空中除去溶剂而得8.4克油。气相色层分析显示此油系由苯乙酮(1.43克)与1,2-二苯甲酰基乙烯(1.86克)所组成。
实例Ⅵ
于600毫升帕尔压热器中置入40克4-苯基-3-丁烯-2-酮与360克水。然后以6343千帕之合成压力将压热器加热至275℃历两小时。
冷却后,以二氯甲烷(60毫升)自含水相中萃取有机相。在真空中除去溶剂,则得20.7克油。此油之气相色层分析显示其系由9.46克苯甲醛与10.87克4-苯基-3-丁烯-2-酮所组成。
实例Ⅶ
于600毫升帕尔压热器中置入10克3-癸烯-2-酮与390克水。然后以6343千帕合成压力将压热器加热至275℃历两小时。
冷却后,以醋酸乙酯(60毫升)自含水相中萃取有机相。在真空中
除去溶剂而得4.8克液体。此油之气相色层分析显示其系由3.01克庚醛与1.49克3-癸烯-2-酮所组成。
实例Ⅷ
于600毫升帕尔压热器中置入10克姜黄素〔1,7-双(4-羟基-3-甲氧苯基)-1,6-庚二烯-3,5-二酮〕与水(390克)。然后以3999千帕合成压力将压热器加热至250℃历两小时。
冷却后,以醋酸乙酯(60毫升)自含水相中萃取有机相。在真空中除去溶剂而得7.7克油。此油之气相色层分析显示其系由1.07克香荚兰醛〔4-羟基-3-甲氧基苯甲醛〕所组成。
实例Ⅸ
于600毫升帕尔压热器中置入330克水。然后将其加热至325℃并保持历经下文指定之时间。调整压力使其不超过13789.5千帕。一旦温度达325℃,即将水以15毫升/分钟之流速泵进压热器中历一分钟,再将进料管线转至桂皮醛,将含有0.40克(0.45毫升)十氢萘(内标准)之桂皮醛40克泵入压热器中,接着泵入15毫升水(全部添加时间为5分钟)。于12928千帕之合成反应器压力下保持325℃温度5分钟。然后迅速冷却压热器(约3分钟冷却至200℃)。于冷却至室温后,以400毫升醋酸乙酯萃取内容物。此萃液之气相色层分析显示回收苯甲醛(10.40克)与桂皮醛(25.20克)。
实例Ⅹ
于600毫升帕尔压热器中置入50毫克癸烷(内标准)、5.0克反,反-2,4-癸二烯醛与395克水。然后以3999千帕之合成压力将压热器加热至250℃历两小时。
冷却后,以醋酸乙酯(400毫升)自含水相中萃取有机相。此油之气相色层分析显示其有机相系由0.62克己醛与0.49克癸二烯醛加上一些癸二烯醛重排产物所组成。
以连续式基础进行此水解反应亦可行。可将该经活化之烯烃与水泵经一种具有背压调节器之受热不锈钢管,该调节器可保持管中压力稍高于水蒸汽压力。会影响该经活化烯烃转化速率之参数为该烯烃在水中之浓度、管线之温度、及烯烃-水混合物在管中之滞留时间。
因此,可明了遵照本发明之指示,可藉批式或连续式方法水解非环状不饱和共轭酮类与醛类,以优良产率制成期望之分裂产物。所得产物之量系令人惊讶的,因迄今仍完全未知不须碱性催化剂之存在可进行此等非环状酮类与醛类之水解作用。目前已可能仅使用水、热及压力以水解经由酮或醛取代基羰基所活化之烯烃化合物。
Claims (14)
2、根据权利要求1的方法,其中的温度至少约为200℃且压力至少约为1551千帕。
3、根据权利要求1的方法,其中温度约为200℃至325℃且压力约为1551-13789.5千帕。
4、根据权利要求1的方法,其中反应是在压热器或其他压力反应器中进行。
5、根据权利要求1的方法,其中水解反应是连续地在管状反应器中完成。
6、根据权利要求1的方法,其中水之体积超过活化烯醛之体积。
7、根据权利要求1的方法,其中活化烯烃桂皮醛经水解而制得含羰基化合物苯甲醛。
8、根据权利要求1的方法,其中活化烯烃柠檬醛经水解而制得含羰基化合物6-甲基-5-庚烯-2-酮。
9、根据权利要求1的方法,其中活化烯烃2,4-癸二烯醛经水解而制得含羰基化合物己醛。
10、一种水解姜黄素以制取调味成份的方法,所述方法是在有水存在下,以及在足以完成所述反应的热和超大气压力的作用下,进行反应,藉此制取调味成分。
11、水解经活化烯烃1,2-二苯甲酰基乙烯以生产苯乙酮的方法,所述方法是在有水存在及在几乎中性pH值的条件下进行反应,并且在足以完成该水解反应的超大气压力下加热,藉此制得苯乙酮。
12、水解经活化烯烃4-苯基-3-丁烯-2-酮以生产苯甲醛的方法,所述方法是在有水存在及在几乎中性pH值的条件下进行反应,并且在足以完成该水解反应的超大气压力下加热,藉此制得苯甲醛。
13、水解经活化烯烃3-癸烯-2-酮以生产庚醛的方法,所述方法是在有水存在及在几乎中性pH值的条件下进行反应,并且在足以完成该水解反应的超大气压力下加热,藉此制得庚醛。
14、水解经活化烯烃姜黄素以生产香草醛(香英兰醛)的方法,所述方法是在有水存在及在几乎中性pH值的条件下进行反应,并且在足以完成该水解反应的超大气压力下加热,藉此制得香草醛。
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Application Number | Priority Date | Filing Date | Title |
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US010,902 | 1987-02-04 | ||
US07/010,902 US4709098A (en) | 1987-02-04 | 1987-02-04 | Hydrolysis of activated olefinic ketones and aldehydes |
US07/123,137 US4810824A (en) | 1987-02-04 | 1987-11-20 | Hydrolysis of activated olefinic ketones and aldehydes |
US123,137 | 1987-11-20 |
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CN88100615A CN88100615A (zh) | 1988-08-17 |
CN1018179B true CN1018179B (zh) | 1992-09-09 |
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CN88100615A Expired CN1018179B (zh) | 1987-02-04 | 1988-02-03 | 活性烯酮及烯醛之水解作用 |
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US (1) | US4810824A (zh) |
EP (2) | EP0346383B1 (zh) |
JP (2) | JP2630334B2 (zh) |
KR (1) | KR960001702B1 (zh) |
CN (1) | CN1018179B (zh) |
AT (2) | ATE111433T1 (zh) |
AU (1) | AU1363588A (zh) |
CA (1) | CA1333489C (zh) |
DE (2) | DE3851528T2 (zh) |
ES (1) | ES2006072A6 (zh) |
GR (1) | GR880100035A (zh) |
MY (1) | MY103053A (zh) |
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US4871881A (en) * | 1987-02-04 | 1989-10-03 | Mallinckrodt, Inc. | Hydrolysis of activated olefinic ketones and aldehydes |
US5426118A (en) * | 1993-12-30 | 1995-06-20 | Allergan, Inc. | [4-(1,2-epoxycyclohexanyl)but-3-en-1-ynyl]aromatic and heteroaromatic acids and derivatives having retinoid-like biological activity |
US6048560A (en) * | 1995-01-25 | 2000-04-11 | Quest International B.V. | Process for the preparation of a flavoring component |
WO2010023211A2 (de) * | 2008-08-29 | 2010-03-04 | Basf Se | Verfahren zur herstellung von zyklischen ketonen |
NZ758408A (en) | 2013-10-23 | 2021-08-27 | Arla Foods Amba | High protein, fruit flavoured beverage; high protein, fruit and vegetable preparation; and related methods and food products |
JP6612745B2 (ja) | 2013-10-23 | 2019-11-27 | アーラ フーズ エエムビエ | 高タンパクの変性ホエータンパク質組成物、関連製品、製造方法、およびその使用 |
EP3071047B2 (en) | 2013-10-23 | 2023-02-15 | Arla Foods amba | Caseinomacropeptide-containing, high protein denatured whey protein compositions, products containing them, and uses thereof |
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US1999620A (en) * | 1929-05-23 | 1935-04-30 | Shell Dev | Process for the manufacture of alcohols |
US2623905A (en) * | 1950-08-23 | 1952-12-30 | Universal Oil Prod Co | Production of aliphatic aldehydes |
DE875512C (de) * | 1951-04-01 | 1953-05-04 | Bayer Ag | Verfahren zur Spaltung von ungesaettigten Ketonen |
DE927688C (de) * | 1953-01-23 | 1955-05-16 | Basf Ag | Verfahren zur Herstellung von Cyclohexanon |
DE946443C (de) * | 1953-02-24 | 1956-08-02 | Bayer Ag | Verfahren zur Spaltung von ungesaettigten Ketonen |
US3833659A (en) * | 1969-12-08 | 1974-09-03 | Universal Oil Prod Co | Preparation of oxygen-containing compounds |
GB1519093A (en) * | 1976-03-04 | 1978-07-26 | Rhone Poulenc Ind | Process for preparing methyl heptenone |
US4617419A (en) * | 1985-09-26 | 1986-10-14 | International Flavors & Fragrances Inc. | Process for preparing natural benzaldehyde and acetaldehyde, natural benzaldehyde and acetaldehyde compositions, products produced thereby and organoleptic utilities therefor |
US4709098A (en) * | 1987-02-04 | 1987-11-24 | Mallinckrodt, Inc. | Hydrolysis of activated olefinic ketones and aldehydes |
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1987
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1988
- 1988-01-26 CA CA000557360A patent/CA1333489C/en not_active Expired - Fee Related
- 1988-01-27 GR GR880100035A patent/GR880100035A/el unknown
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- 1988-02-01 KR KR1019880701226A patent/KR960001702B1/ko not_active IP Right Cessation
- 1988-02-01 EP EP94200013A patent/EP0606934B1/en not_active Expired - Lifetime
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Publication number | Publication date |
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EP0606934A1 (en) | 1994-07-20 |
JP2667141B2 (ja) | 1997-10-27 |
ES2006072A6 (es) | 1989-04-01 |
DE3856006D1 (de) | 1997-09-25 |
MY103053A (en) | 1993-04-30 |
KR890700562A (ko) | 1989-04-25 |
CA1333489C (en) | 1994-12-13 |
JPS63301841A (ja) | 1988-12-08 |
KR960001702B1 (ko) | 1996-02-03 |
EP0606934B1 (en) | 1997-08-20 |
ATE111433T1 (de) | 1994-09-15 |
ATE157076T1 (de) | 1997-09-15 |
CN88100615A (zh) | 1988-08-17 |
DE3856006T2 (de) | 1997-12-11 |
JPH0912503A (ja) | 1997-01-14 |
EP0346383B1 (en) | 1994-09-14 |
WO1988005771A1 (en) | 1988-08-11 |
US4810824A (en) | 1989-03-07 |
AU1363588A (en) | 1988-08-24 |
NZ223388A (en) | 1991-01-29 |
JP2630334B2 (ja) | 1997-07-16 |
DE3851528D1 (de) | 1994-10-20 |
GR880100035A (el) | 1988-12-16 |
DE3851528T2 (de) | 1995-02-16 |
EP0346383A1 (en) | 1989-12-20 |
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