CN1210542A - N－(3,3－二甲基丁基)－L－天冬氨酰－D－α－氨基链烷酸N－(S－)－1－苯基－1－链烷酰胺 - Google Patents
N－(3,3－二甲基丁基)－L－天冬氨酰－D－α－氨基链烷酸N－(S－)－1－苯基－1－链烷酰胺 Download PDFInfo
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- CN1210542A CN1210542A CN97192136A CN97192136A CN1210542A CN 1210542 A CN1210542 A CN 1210542A CN 97192136 A CN97192136 A CN 97192136A CN 97192136 A CN97192136 A CN 97192136A CN 1210542 A CN1210542 A CN 1210542A
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- compound
- phenyl
- aspartyl
- dimethylbutyl
- solution
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Abstract
本发明公开了式(Ⅰ)化合物及其作为甜味剂的用途,其中,Y为C2H5、或CH(CH3)2或(R)CH(OH)CH3;和R”为(S)CH(C2H5)C6H5、(S)CH(CH3)C6H5、(R)CH(CH2OCH3)C6H5。
Description
本发明涉及新的用作甜味剂的由二肽衍生的化合物及其制备方法。
这些新化合物尤其适用于对多种产品，尤其是饮料、食品、糖食、面点、口香糖、保健产品和盥洗用品、以及化妆品、药物和兽医学制品产生增甜作用。
公认的是，为达到工业规模应用，甜味剂必须首先具有限制使用成本的高效甜化效能，其次是与应用条件相适应的良好稳定性。
市场上的常规甜味剂中，已知名为天冬甜精并具有下列结构式的二肽衍生物L-天冬氨酰基-L-苯基丙氨酸甲酯应用最广泛(美国专利3,475,403)：
以重量基准计，该化合物的相对较弱的增甜效能约是蔗糖的120-180倍。尽管具有优异的感官特性，但此化合物存在着因其相对较低的甜度造成其产品十分昂贵的主要缺陷，并且由于其在甜味剂的一般应用条件下呈现较低的稳定性而严重限制了它的工业应用范围。
在文献FR92 13615中，申请人披露了具有下面通式的甜味剂：其中：R代表饱和或不饱和的、无环、成环或混合的含有4-13个碳原子的烃基；n等于1或2；和R’代表下式：
其中，Y是选自COOCH3、COOC2H5、CH3、CH2OH、CON(CH3)2、C6H5、2-呋喃基、和H的基团；Z是选自CH2C6H5、C6H5、正C4H9、COOCH3、COOC2H5、COOC3H7、COO葑基、和CONHR”的基团，其中R”选自基团CH3、CH2CH3、CH2CH2CH3、CH2CH2CH(CH3)2、CH(CH3)COOCH3、CH(c-C3H5)2、CH(c-C3H5)C(CH3)3、葑基、2,6-二甲基环己基、2,2,5,5-四甲基环戊基、和2,2,4,4-四甲基-3-thietanyl。
文献FR92 13615的一个实施方案包括下式所示的L-天冬氨酸衍生物(n=1)：
其中R、Y和R”与上述定义相同。
上述发明该实施方案中的优选化合物是N-(3,3-二甲基丁基)-L-天冬氨酰基-N-(二环丙基carbinyl)-D-氨基丙酰胺：
其中，Y代表甲基并且R”代表二环丙基carbinyl，该化合物以2重量％蔗糖溶液为基准计的增甜效能是蔗糖的2,500倍。
已观察到的并成为该发明基础的是：通过适当选择上述通式的取代基Y和R”可以得到新的不同于该公开文献所提供化合物的甜味剂化合物。因此，当Y代表乙基、异丙基或(R)-α-羟乙基而且R”代表(S)-α-乙基苄基、(S)-α-甲基苄基、或(R)-α-甲氧基甲基苄基时，可以获得具有极佳感官特性同时具有以重量基准计的甜度为蔗糖8,000倍的高效增甜效能的新化合物。此外，这些新化合物在酸性或中性溶液中的稳定性明显高于天冬甜精，这就使它们在食品生产中的应用可能性要比天冬甜精大。
因此，本发明的目的是提供具有下式的新甜味剂：
其中：Y为C2H5、或CH(CH3)2或(R)CH(OH)CH3；和R”为(S)CH(C2H5)C6H5、(S)CH(CH3)C6H5、(R)CH(CH2OCH3)C6H5。
本发明特别优选实施方式中的化合物是下式所示的N-(3,3-二甲基丁基)-L-天冬氨酰-D-α-氨基丁酸N-(S)-1-苯基-1-丙酰胺：
该化合物以重量基准计相对于2％蔗糖溶液的增甜效能约是蔗糖的8,000倍；下式所示的N-(3,3-二甲基丁基)-L-天冬氨酰基-D-缬氨酸N-(S)-1-苯基-1-丙酰胺：
该化合物以重量基准计相对于2％蔗糖溶液的增甜效能约是蔗糖的3,000倍；如下式所示的N-(3,3-二甲基丁基)-L-天冬氨酰-D-α-氨基丁酸N-(S)-1-苯基-2-甲氧基-1-乙酰胺：该化合物以重量基准计相对于2％蔗糖溶液的增甜效能约是蔗糖的4,000倍；如下式所示的N-(3,3-二甲基丁基)-L-天冬氨酰基-缬氨酸N-(S)-1-苯基-2-甲氧基-1-乙酰胺：该化合物以重量基准计相对于2％蔗糖溶液的增甜效能约是蔗糖的4,000倍。
此外，业已证明本发明这些特有化合物的稳定性在食品制备应用的常规条件下明显优于天冬甜精。该优点由于在近中性即，pH约为7的介质中天冬甜精的稳定性太低致使其在某些食品制备中的应用受到限制而愈显重要，中性pH值常见于需高温蒸煮产品(例如奶制品、面点或其他制品)。
业已证明的还有，本发明化合物在pH值约为3的酸性介质中的稳定性也进一步得到改善，该pH值与甜味剂主要用途之一的充气饮料的pH值相对应。
因此，采用将水溶液在pH为3、温度为70℃条件下延长加热的方法完成的快速老化研究结果表明本发明特有化合物之一，即N-(3,3-二甲基丁基)-L天冬氨酰-D-α-氨基丁酸N-(S)-1-苯基-1-丙烷酰胺的半衰期约为72小时。经对比，天冬甜精在同样条件下的半衰期仅约是24小时，因此本发明化合物的稳定性约是后者的3倍高。
在pH7条件下进行的相同快速老化试验表明：同一化合物，即N-(3,3-二甲基丁基)-L天冬氨酰-D-α-氨基丁酸N-(S)-1-苯基-1-丙烷酰胺具有约12天的半衰期，而天冬甜精在此条件下的半衰期仅达10分钟，本发明化合物的稳定性约是后者的1,700倍高。还可以得到本发明其他特定化合物的对比结果。
由于高增甜效能，本发明化合物相对于天冬甜精的另一优越性使本发明化合物在食品制备应用中能够以极低的活性组分用量来使用。例如，在1L的充气饮料中，可以用约20mg本发明的N-(3,3-二甲基丁基)-L天冬氨酰-D-α-氨基丁酸N-(S)-1-苯基-1-丙烷酰胺代替550mg天冬甜精，即将甜味剂用量减少近27倍，而同时仍保持了相同的感官特性，
本发明所述甜味剂可以加至任何需有甜味的可食用产品中，条件是加入足够比例以得到所需甜度。甜味剂的最佳使用浓度取决于各种因素，例如甜味剂增甜效能、储存和产品使用条件、产品中的特殊组分和所需甜度。任何有资格人员都能够轻易地通过进行常规感觉分析试验来确定用于获得可食用产品所必需的最佳甜味剂比例。本发明甜味剂通常根据化合物的增甜效能并以每千克或每升可食用产品使用5-50mg甜味剂的添加用量加至可食用产品中。浓缩产品显然将含有大量的甜味剂并应根据使用的最终目的进行稀释。
本发明甜味剂也可以纯的形式加至待增甜的产品中，但由于具有高效增甜效能，它们通常与适当载体或填充剂混合使用。
适当的载体或填充剂有利地选自聚糊精、淀粉、麦芽糖糊精、纤维素、甲基纤维素、羧甲基纤维素或其他纤维素衍生物、藻酸钠、果胶、树胶、乳糖、麦芽糖、葡萄糖、亮氨酸、甘油、甘露醇、山梨糖醇、碳酸氢钠、磷酸、柠檬酸、酒石酸、富马酸、苯甲酸、山梨酸和丙酸及它们的钠、钾和钙盐、以及它们的等同物。
本发明甜味剂在可食用产品中可以单独或结合其他甜味剂使用，其他甜味剂例如是：蔗糖、玉米糖浆、果糖、甜味二肽类似物或衍生物(天冬甜精、天胺甜精)、新桔皮苷二氢查耳酮、氢化异麦芽寡糖、甜叶菊甙、左旋糖、甘草素、木糖醇、山梨糖醇、甘露醇、双氧噁噻嗪-K、糖精及其钠、钾、铵和钙盐、环己基氨基磺酸及其钠、钾和钙盐、氢化蔗糖衍生物、蒙那灵、非洲竹芋甜素和它们的等同物。
本发明化合物通过包括将下式二肽前体与3,3-二甲基丁醛在还原剂存在下缩合的还原性N-烷基化反应得到：其中，Y和R”与上述定义相同。还原剂即可以是在1-3巴的相对压力和在基于铂或钯的催化剂存在下并且按照WO95/30689记载方法采用的氢，也可以是按照FR 92 13615描述方法使用的氰基硼氢化钠。
上式所示的二肽前体可轻易根据肽合成基本原理制得：氨基酸前体的氨基和羧基的保护和脱保护、常规活化和肽偶联方法。
这些技术在许多文献中都有详细记载，其中以在此引用的M.Bodanszky和A.Bodanszky，《肽合成实践》Springer-Verlag出版，纽约，1984,284页记载的方法最为相关。
本发明化合物的纯化采用例如重结晶或色谱法的标准方法完成。它们的结构和纯度利用典型技术检测(薄层色谱、高效液体色谱法、红外光谱、核磁共振、元素分析)。
实施例中所述化合物的增甜效能是由8位有经验人员评估的。其中是将不同浓度的化合物水溶液与浓度分别为2％、5％或10％的蔗糖空白对照溶液进行甜味对比。受试化合物产生的甜度与蔗糖相同时，即多数评判人员认为受试化合物溶液的甜味与蔗糖空白对照溶液相同甜度时，相对于蔗糖测定的该化合物的增甜效能对应于该化合物与蔗糖之间重量比。
本发明化合物和天冬甜精的稳定性采用高效液体色谱(HPLC)法通过测定产品经过在酸性介质(pH3的磷酸缓冲液)或中性介质(pH7的磷酸缓冲液)中、70℃下进行的快速老化作用后的含量而测得。此方法测定的化合物稳定性根据其半衰期(降解50％的时间)来评定。
本发明实施方式及其优点通过下列具体实施例得到更好展现。实施例
下式所示N-(3,3-二甲基丁基)-L-天冬氨酰基-D-α-氨
基丁酸N-(S)-1-苯基-1-丙烷酰胺的制备方法
将15g(0.145mole)D-α-氨基丁酸(Aldrich产品，No.11,612-2)和5.82g(0.145mol)氢氧化钠在150cm3水中形成的混合液冷却至0℃。向该溶液内同时滴加24.38g(0.145mol)氯甲酸苄酯和5.82g(0.145mole)4N氢氧化钠水溶液。在0℃下搅拌3小时。反应混合物用乙醚(3×30cm3)洗涤，随后用盐酸溶液(6N)酸化至pH约为1。形成的白色沉淀经过滤分离，用水洗涤并干燥。得到26克熔点为80℃的N-苄氧基羰基-D-α-氨基丁酸(产率75％)。
向已冷却至-15℃的含3g(13mmol)所得化合物的50cm3四氢呋喃溶液中依次加入1.28g(13mmol)N-甲基吗啉和1.15g(13mmol)氯甲酸异丁酯。在此温度下搅拌2分钟后，加入1.71g(13mmol)(S)-1-苯基-1-丙胺(按照化学会志，1940，336-8页所述方法预先制得)。反应混合物缓慢升温并在室温下搅拌2小时。过滤除去N-甲基吗啉盐酸化物沉淀并用20cm3四氢呋喃洗涤。滤液在真空下浓缩至干并且用150cm3乙醚溶解所得残余物，依次用0.1N盐酸溶液、5％碳酸钠溶液、水(3×30cm3)洗涤所形成的溶液。该醚溶液用无水硫酸钠干燥后，溶液在真空下浓缩至干，得到3.8g白色固体残余物，即熔点为129℃的N-苄氧基羰基-D-α-氨基丁酸N-(S)-1-苯基-1-丙酰胺(产率82％)。其纯度采用硅胶G 60并以氯仿-丙酮(9∶1)为洗脱液的薄层色谱法检测(硅胶载体Merk No.1.05554)，并且用重铬酸钾-浓硫酸混合液显色，Rf=0.45。
将3.6g(10mmol)N-苄氧基羰基-D-α-氨基丁酸N-(S)-1-苯基-1-丙酰胺的100cm3甲醇溶液与氢气在350mg10％的活性炭载钯(Fluka产品No.74990)存在和常压下接触18小时。过滤除去催化剂后，将溶液在真空下浓缩至干。得到2.1g(产率91％)的油状残余物D-α-氨基丁酸N-(S)-1-苯基-1-丙酰胺。其纯度采用硅胶G 60并以丁醇-乙酸-水(8-2-2)为洗脱液的薄层色谱法检测(硅胶载体MerkNo.1.05554)，并且用茚三酮显色，Rf=0.57。
向冷却至-15℃的含3.58g(10mmol)N-苄氧羰基-L-天冬氨酸β-苄酯(Bachem产品No.C-1350)的50cm3四氢呋喃溶液中依次加入1g(10mmol)N-甲基吗啉和1.37g(10mmol)氯甲酸异丁酯。在此温度下搅拌2分钟后，加入预先制得的2.1g(10mmol)D-α-氨基丁酸N-(S)-1-苯基-1-丙酰胺。使反应混合物缓慢升温并在室温下搅拌2小时。过滤除去N-甲基吗啉盐酸化物沉淀并用20cm3四氢呋喃洗涤。滤液在真空下浓缩至干并且将所得残余物用50cm3乙醚研制。过滤分离出所得白色固体物，再用20cm3乙醚洗涤。得到5g熔点为130℃的N-苄氧基羰基-β-苄酯-L-天冬氨酰基-D-α-氨基丁酸N-(S)-1-苯基-1-丙酰胺(产率89％)。其纯度采用硅胶G 60并以氯仿-丙酮(8-2)为洗脱液的薄层色谱法检测(硅胶载体MerkNo.1.05554)，并且用洗液显色，Rf=0.64。
将5g(8.9mmol)N-苄氧基羰基-β-苄酯-L-天冬氨酰-D-α-氨基丁酸N-(S)-1-苯基-1-丙酰胺的100cm3甲醇溶液与氢气在500mg10％的活性炭载钯(Fluka产品No.74990)存在和常压下接触18小时。过滤除去催化剂后，将溶液在真空下浓缩至干。得到2.4g(产率80％)呈白色固体的L-天冬氨酰基-D-α-氨基丁酸N-(S)-1-苯基-1-丙酰胺。其纯度采用硅胶G 60并以丁醇-乙酸-水(8-2-2)为洗脱液的薄层色谱法检测(硅胶载体MerkNo.1.05554)，并且用茚三酮显色，Rf=0.50。其无定形的熔点为195℃。
向装有能将氢气很好地输送到液相内的搅拌器的反应器中、在搅拌的同时、依次引入下列物质：15cm3的0.1M乙酸溶液、26mg活性炭载钯(Fluka产品No.75990)、58mg(0.57mmol)市售3,3-二甲基丁醛(Aldrich No.35,990-4)、15cm3甲醇和130mg(0.38mmol)预制的L-天冬氨酰基-D-α-氨基丁酸N-(S)-1-苯基-1-丙酰胺。
用氮气流吹扫反应器后，在室温和1-2巴(0.1-0.2MP)的相对压力下将混合物暴露于氢气下18小时并在加入19mg(0.19mmol)3,3-二甲基丁醛后继续反应8小时。反应过程通过用铝板载硅胶60 F254(Merk No.1.05554)并以丁醇-乙酸-水(8∶2；2)为洗脱液的薄层色谱(TLC)监测，并用茚三酮显色：Rf=0.67。
最终用氮气流吹入反应器使反应终止，并且用细滤清器(0.5μm)滤除催化剂。真空蒸发浓缩溶液，所得白色固体，用约50cm3乙醚洗涤。得到150mg熔点为167℃的高纯(H.P.L.C.检测，高于98％)白色粉末状的N-(3,3-二甲基丁基)-L-天冬氨酰基-D-α-氨基丁酸N-(S)-1-苯基-1-丙烷酰胺(产率92％)。分子式：C23H37N3O4NMR(200 MHz,1H,ppm),DMSO D6：0.80(s,15H),1.33(t,2H),1.67(m,4H),2.4(m,4H),3.54(m,1H),4.30(q,1H),4.70(q,1H),7.22(m,1H),7.28(s,5H)，8.35(t，2H).
高效液体色谱采用了长为244mm、直径为4.6mm的Merk制“Lichrospher 100 RP-18端封”型色谱柱，洗脱液：65mM乙酸铵缓冲液-乙腈(70∶30)，流速：1ml/min，检测器：折射计，保留时间：16.1min。
以重量基准计，该化合物的增甜效能约是2％蔗糖溶液的8,000倍、5％蔗糖溶液的6,000倍、10％蔗糖溶液的5,000倍。
与天冬甜精相比，20mg/L该化合物水溶液与550mg/L天冬甜精溶液的增甜效能相同，即约比天冬甜精的增甜效能高27倍。
附图1是采用在pH为3的酸性介质中、在70℃下加热溶液的快速老化法得到的天冬甜精(曲线1)的和本发明N-(3,3-二甲基丁基)-L-天冬氨酰基-D-α-氨基丁酸N-(S)-1-苯基-1-丙烷酰胺(曲线2)的稳定性的对比图示。在上述条件下，天冬甜精的半衰期是24小时，而本发明化合物约是72小时，这表明本发明化合物的稳定性比天冬甜精高3倍。
附图2是采用在pH为7的中性介质中、在70℃下加热溶液的快速老化法得到的天冬甜精(曲线1)的和本发明N-(3,3-二甲基丁基)-L-天冬氨酰基-D-α-氨基丁酸N-(S)-1-苯基-1-丙烷酰胺(曲线2)的稳定性的对比图示。在上述条件下，天冬甜精不很稳定(10分钟的半衰期)，而本发明化合物约是12天，这表明本发明化合物的稳定性约是天冬甜精的1,700倍。
按照与上述方法相似及本领域技术人员容易想到的试验方案可以得到本发明其他化合物的增甜效能，结果如表1所示。
表1
| Y | R＂ | 增甜效能* |
| C2H5 | (S)CH(C2H5)C6H5 | 8,000 |
| (CH3)2CH | (S)CH(C2H5)C6H5 | 3,000 |
| C2H5 | (S)CH(CH3)C6H5 | 2,000 |
| C2H5 | (R)CH(CH2OCH3)C6H5 | 4,000 |
| (CH3)2CH | (R)CH(CH2OCH3)C6H5 | 4,000 |
*增甜效能是以重量基准计并与2％蔗糖溶液相比
Claims (9)
1．如下式所示的化合物：其中，
Y为C2H5、或CH(CH3)2或(R)CH(OH)CH3；和
R”为(S)CH(C2H5)C6H5、(S)CH(CH3)C6H5、或(R)CH(CH2OCH3)C6H5。
2．权利要求1的化合物，其特征在于：该化合物为下式的N-(3,3-二甲基丁基)-L-天冬氨酰基-D-α-氨基丁酸N-(S)-1-苯基-1-丙酰胺：
3．权利要求1的化合物，其特征在于：该化合物为下式所示的N-(3,3-二甲基丁基)-L-天冬氨酰基-D-缬氨酸N-(S)-1-苯基-1-丙酰胺：
4．权利要求1的化合物，其特征在于：该化合物为如下式所示的N-(3,3-二甲基丁基)-L-天冬氨酰基-D-α-氨基丁酸N-(S)-1-苯基-2-甲氧基-1-乙酰胺：
5．权利要求1的化合物，其特征在于：该化合物为如下式所示的N-(3,3-二甲基丁基)-L-天冬氨酰基-缬氨酸N-(S)-1-苯基-2-甲氧基-1-乙酰胺：
6．权利要求1-5中任一项的化合物作为甜味剂的应用。
7．制备权利要求1-5任一项的化合物的方法，其特征在于：该方法包括用还原剂处理3,3-二甲基丁醛和下式化合物的混合物：
其中，Y和R”如权利要求1所述。
8．权利要求7的方法，其特征在于：还原剂是在相对压力为1-3巴的基于铂或钯的催化剂存在下的氢。
9．权利要求7的方法，其特征在于：还原剂为氰基硼氢化钠。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9601491A FR2744454B1 (fr) | 1996-02-07 | 1996-02-07 | Acide n-(3,3-dimethylbutyl)-l-aspartyl-d-alpha- aminoalcanoique n-(s)-1-phenyl-1-alcanamide utile comme agent edulcorant |
| FR96/01491 | 1996-02-07 |
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| CN1210542A true CN1210542A (zh) | 1999-03-10 |
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| CN97192136A Pending CN1210542A (zh) | 1996-02-07 | 1997-02-07 | N－(3,3－二甲基丁基)－L－天冬氨酰－D－α－氨基链烷酸N－(S－)－1－苯基－1－链烷酰胺 |
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| Country | Link |
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| US (2) | US5777159A (zh) |
| EP (1) | EP0879243B1 (zh) |
| JP (1) | JP2000505799A (zh) |
| KR (1) | KR19990082328A (zh) |
| CN (1) | CN1210542A (zh) |
| AR (1) | AR005563A1 (zh) |
| AT (1) | ATE201695T1 (zh) |
| AU (1) | AU708899B2 (zh) |
| BR (1) | BR9707377A (zh) |
| DE (1) | DE69705024T2 (zh) |
| FR (1) | FR2744454B1 (zh) |
| IL (1) | IL125256A (zh) |
| NO (1) | NO983609L (zh) |
| RU (1) | RU2174983C2 (zh) |
| WO (1) | WO1997029122A1 (zh) |
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| CN1307405C (zh) * | 2003-01-11 | 2007-03-28 | 三星电子株式会社 | 使用寻呼信道的导航系统和用于提供交通信息的方法 |
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| US6692778B2 (en) | 1998-06-05 | 2004-02-17 | Wm. Wrigley Jr. Company | Method of controlling release of N-substituted derivatives of aspartame in chewing gum |
| JPWO2002062746A1 (ja) * | 2001-02-08 | 2004-06-03 | 味の素株式会社 | 新規ｎ−アルキルアスパルチルアミド誘導体及び甘味剤 |
| AR055329A1 (es) * | 2005-06-15 | 2007-08-15 | Senomyx Inc | Amidas bis-aromaticas y sus usos como modificadores de sabor dulce, saborizantes, y realzadores de sabor |
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| US5286509A (en) * | 1992-06-22 | 1994-02-15 | The Coca-Cola Company | L-aspartyl-D-α-aminoalkanoyl-(S)-N-alpha-alkylbenzyl amides useful as artificial sweeteners |
| FR2697844B1 (fr) * | 1992-11-12 | 1995-01-27 | Claude Nofre | Nouveaux composés dérivés de dipeptides ou d'analogues dipeptidiques utiles comme agents édulcorants, leur procédé de préparation. |
| FR2719590B1 (fr) * | 1994-05-09 | 1996-07-26 | Claude Nofre | Procédé perfectionné de préparation d'un composé dérivé de l'aspartame utile comme agent édulcorant. |
| FR2719592B1 (fr) * | 1994-05-09 | 1996-07-26 | Claude Nofre | Nouveaux dérivés dipeptidiques utiles comme agents édulcorants. |
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- 1997-02-07 DE DE69705024T patent/DE69705024T2/de not_active Expired - Fee Related
- 1997-02-07 AT AT97903422T patent/ATE201695T1/de not_active IP Right Cessation
- 1997-02-07 KR KR1019980706058A patent/KR19990082328A/ko not_active Application Discontinuation
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- 1997-02-07 RU RU98116597/04A patent/RU2174983C2/ru active
- 1997-02-07 AU AU18003/97A patent/AU708899B2/en not_active Ceased
- 1997-02-07 IL IL12525697A patent/IL125256A/en not_active IP Right Cessation
- 1997-02-07 BR BR9707377A patent/BR9707377A/pt unknown
- 1997-02-07 CN CN97192136A patent/CN1210542A/zh active Pending
- 1997-02-07 JP JP9528231A patent/JP2000505799A/ja active Pending
- 1997-02-07 EP EP97903422A patent/EP0879243B1/fr not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1307405C (zh) * | 2003-01-11 | 2007-03-28 | 三星电子株式会社 | 使用寻呼信道的导航系统和用于提供交通信息的方法 |
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| Publication number | Publication date |
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| ATE201695T1 (de) | 2001-06-15 |
| EP0879243A1 (fr) | 1998-11-25 |
| FR2744454A1 (fr) | 1997-08-08 |
| RU2174983C2 (ru) | 2001-10-20 |
| AU1800397A (en) | 1997-08-28 |
| FR2744454B1 (fr) | 1998-04-24 |
| IL125256A (en) | 2002-02-10 |
| EP0879243B1 (fr) | 2001-05-30 |
| JP2000505799A (ja) | 2000-05-16 |
| KR19990082328A (ko) | 1999-11-25 |
| NO983609D0 (no) | 1998-08-06 |
| IL125256A0 (en) | 1999-03-12 |
| US5777159A (en) | 1998-07-07 |
| ZA971022B (en) | 1997-08-25 |
| US5997933A (en) | 1999-12-07 |
| AR005563A1 (es) | 1999-06-23 |
| BR9707377A (pt) | 1999-04-13 |
| NO983609L (no) | 1998-10-06 |
| DE69705024D1 (de) | 2001-07-05 |
| WO1997029122A1 (fr) | 1997-08-14 |
| AU708899B2 (en) | 1999-08-12 |
| DE69705024T2 (de) | 2001-11-29 |
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