JPS5943479B2 - organic germanium compounds - Google Patents
organic germanium compoundsInfo
- Publication number
- JPS5943479B2 JPS5943479B2 JP57142148A JP14214882A JPS5943479B2 JP S5943479 B2 JPS5943479 B2 JP S5943479B2 JP 57142148 A JP57142148 A JP 57142148A JP 14214882 A JP14214882 A JP 14214882A JP S5943479 B2 JPS5943479 B2 JP S5943479B2
- Authority
- JP
- Japan
- Prior art keywords
- present
- compound
- group
- organic germanium
- methanol
- 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
Links
- 150000002291 germanium compounds Chemical class 0.000 title claims description 6
- 239000000126 substance Substances 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- 150000001875 compounds Chemical class 0.000 description 17
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 150000001408 amides Chemical group 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- CVMBLRBRUFIQFK-UHFFFAOYSA-N 2-trichlorogermylpropanamide Chemical compound NC(=O)C(C)[Ge](Cl)(Cl)Cl CVMBLRBRUFIQFK-UHFFFAOYSA-N 0.000 description 4
- 230000004071 biological effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical group O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241000699670 Mus sp. Species 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- -1 or a probyl group Chemical group 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- XEABSBMNTNXEJM-UHFFFAOYSA-N propagermanium Chemical compound OC(=O)CC[Ge](=O)O[Ge](=O)CCC(O)=O XEABSBMNTNXEJM-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 210000004881 tumor cell Anatomy 0.000 description 2
- ZWKNLRXFUTWSOY-QPJJXVBHSA-N (e)-3-phenylprop-2-enenitrile Chemical compound N#C\C=C\C1=CC=CC=C1 ZWKNLRXFUTWSOY-QPJJXVBHSA-N 0.000 description 1
- ZJUHNMADISSFJZ-UHFFFAOYSA-N 2-trichlorogermylpropanoic acid Chemical class OC(=O)C(C)[Ge](Cl)(Cl)Cl ZJUHNMADISSFJZ-UHFFFAOYSA-N 0.000 description 1
- YPAFZMPVLYOEAX-UHFFFAOYSA-N 2-trimethoxygermylpropanamide Chemical compound CO[Ge](OC)(OC)C(C)C(N)=O YPAFZMPVLYOEAX-UHFFFAOYSA-N 0.000 description 1
- XBRVPWBNRAPVCC-UHFFFAOYSA-N 4,6,11-trioxa-1-aza-5$l^{3}-silabicyclo[3.3.3]undecane Chemical compound C1CO[Si]2OCCN1CCO2 XBRVPWBNRAPVCC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000010171 animal model Methods 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- MUDDKLJPADVVKF-UHFFFAOYSA-N trichlorogermane Chemical compound Cl[GeH](Cl)Cl MUDDKLJPADVVKF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Description
【発明の詳細な説明】
本発明はアトラン骨格を有する有機ゲルマニウム化合物
に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an organic germanium compound having an atran skeleton.
１９６８年にＭ、Ｇ、Ｖｏｒｏｎｋｏｖらによりアトラ
ン骨格を有する最初の化合物であるシラトランが合成さ
れて以来、アトラン骨格を有するケイ素化合物やゲルマ
ニウム化合物の合成、物性に関して多くの報告がなされ
、それらのうちの数種は生物活性を有するとされている
。Since silatrane, the first compound with an atran skeleton, was synthesized in 1968 by M.G. Several species are said to have biological activity.
而して、有機ゲルマニウム化合物については、プロピオ
ン酸残基−ＣＨ２ＣＨ２Ｃ０ＯＨを有するゲルマニウム
原子同士が酸素原子により架橋された巨大分子構造を有
するカルボキシエチルゲルマニウムセスキオキサイド（
ＧｅＣＨ２ＣＨ２Ｃ００Ｈ）２０３が抗腫瘍性等極めて
優れた生物活性を有することが知られており、一方、生
物活性を有するアトラン構造の化合物はフェニル基を持
つものが多いので、前記アトラン骨格にプロピオン酸残
基や更にはフェニル基を導入した有機ゲルマニウム化合
物も優れた生物活性を発揮するものと期待される。As for organic germanium compounds, carboxyethyl germanium sesquioxide (
It is known that GeCH2CH2C00H)203 has extremely excellent biological activities such as antitumor properties.On the other hand, since many biologically active compounds with an atlan structure have a phenyl group, propionic acid residues are added to the atlan skeleton. Moreover, organic germanium compounds into which phenyl groups have been introduced are also expected to exhibit excellent biological activity.
本発明の発明者らは、上述した事情を背景として、アト
ラン骨格に新たな残基を導入した構造の有機ゲルマニウ
ム化合物に関して鋭意研究の結果、本発明を完成したも
ので、本発明の有機ゲルマニウム化合物は、式〔式中、
Ｒ、、Ｒ２は水素原子、低級アルキル基又はフェニル基
を、又、Ｒ３は水酸基、０−低級アルキル基又はアミノ
基をそれぞれ示す〕で表わされることを特徴とするもの
である。Against the background of the above-mentioned circumstances, the inventors of the present invention have completed the present invention as a result of intensive research into organic germanium compounds having a structure in which a new residue is introduced into the atlan skeleton. is the formula [in the formula,
R and R2 each represent a hydrogen atom, a lower alkyl group, or a phenyl group, and R3 represents a hydroxyl group, a 0-lower alkyl group, or an amino group, respectively.
以下、本発明化合物について詳細に説明する。本発明化
合物はアトラン骨格にプロピオン酸残基やその誘導体が
結合したものであり、アトラン骨格とは窒素原子とゲル
マニウム原子とが３本のオキシメチレン鎖で架橋された
略かご型で、その内部を通つて窒素の電子対がゲルマニ
ウム原子に配位した構造を特徴としている。又、本発明
化合物のプロピオン酸残基における置換基Ｒ１ 、Ｒ２
は水素原子、メチル革やエチル基、プロビル基等の低級
アルキル基、フェニル基のいずれかであり、同じく置換
基Ｒ３は水酸基、Ｒ１及びＲ２と同様の低級アルキル基
による０−低級アルキル基、アミノ基であり、従つて本
発明化合物は例えば次のようなものを包含する。The compounds of the present invention will be explained in detail below. The compound of the present invention has a propionic acid residue or a derivative thereof bonded to an atran skeleton, and the atran skeleton is a cage-shaped nitrogen atom and a germanium atom cross-linked with three oxymethylene chains. It is characterized by a structure in which a nitrogen electron pair is coordinated with a germanium atom. Furthermore, substituents R1 and R2 in the propionic acid residue of the compound of the present invention
is a hydrogen atom, a lower alkyl group such as a methyl group, an ethyl group, or a probyl group, or a phenyl group, and the substituent R3 is a hydroxyl group, a 0-lower alkyl group formed by a lower alkyl group similar to R1 and R2, or an amino The compounds of the present invention therefore include, for example, the following.
而して、本発明化合物中化合物（Ｉ）は次のようにして
合成される。Compound (I) among the compounds of the present invention is synthesized as follows.
即ち、トリクロルゲルミルプロピオン酸アミド（１）に
メタノール溶液中ナトリウムメトキサイドを作用させて
トリメトキシゲルミルプロピオン酸アミド（２）とし、
これに同じメタノール溶液中でトリエタノールアミンを
作用させるのである。That is, trichlorogermylpropionic acid amide (1) is reacted with sodium methoxide in a methanol solution to form trimethoxygermylpropionic acid amide (2),
This is then treated with triethanolamine in the same methanol solution.
１従つて、置換基Ｒ２及びＲ３は本発明物質であるト
リクロルゲルミルプロピオン酸誘導体にあらかじめ導入
しておくものとし、例えばＲ１＝Ｃ６Ｈ，，Ｒ２＝ Ｈ
，Ｒ３− ＮＨ２のものは、という方法で合成し、出発
原料とするが、最終的にＲ３＝０Ｈである本発明化合物
を得ようとする場合は、Ｒ３＝ＮＨ２の出発原料から対
応するアミド体を合成した後、加水分解するようにした
方が、副反応にわずられされずにすむので都合が良い。1 Therefore, the substituents R2 and R3 shall be introduced in advance into the trichlorogermylpropionic acid derivative which is the substance of the present invention, for example, R1=C6H,, R2=H
, R3-NH2 is synthesized by the following method and used as a starting material, but when it is desired to finally obtain the compound of the present invention in which R3=0H, the corresponding amide form is synthesized from the starting material in which R3=NH2. It is more convenient to hydrolyze the compound after it is synthesized, as this eliminates the need for side reactions.
以上のようにして得られた本発明化合物は、優れた生物
活性を発揮することが期待され、事実Ｒ１＝ Ｈ，Ｒ２
＝ Ｈ，Ｒ３＝ ＮＨ２の化合物（Ｉ）を腫瘍細胞を移
殖したマウスに投与してみると、従来公知の化合物であ
るカルボキシエチルゲルマニウムセスキオキサイド（Ｇ
ｅＣＨ２ＣＨ２ＣＯＯＨ）２０３より少量でほぼ同一の
抑制率を示した。次に本発明の実施例について述べる。The compound of the present invention obtained as described above is expected to exhibit excellent biological activity, and in fact R1=H,R2
When Compound (I) with = H, R3 = NH2 was administered to mice transplanted with tumor cells, carboxyethyl germanium sesquioxide (G
eCH2CH2COOH)203 showed almost the same inhibition rate at a lower amount. Next, examples of the present invention will be described.
１．２−カルバモイルエチルゲルマトラン（ｌ）の合成
トリクロルゲルミルプロピオン酸アミド
７．２８ｇ（０．０２９モル）を無水エタノール５０ｍ
１に溶解し、これに室温で、無水メタノール１００ｍ１
に金属ナトリウム２．０９（ ０．０８７モル）を溶解
して調製しておいたナトリウムメトキサイド溶液を攪拌
しながら徐々に加える。1. Synthesis of 2-carbamoylethylgermatoran (l) 7.28 g (0.029 mol) of trichlorogermylpropionic acid amide was dissolved in 50 ml of absolute ethanol.
1, and add 100 ml of anhydrous methanol to this at room temperature.
A sodium methoxide solution prepared by dissolving 2.09 (0.087 mol) of sodium metal in the solution was gradually added with stirring.
少々発熱し、塩が析出してくる。メタノールを減圧下留
去して約５０ゴとして塩をＰ過し、塩を２０ｍ１の無水
メタノールで洗つた溶液をｒ液と合わせ、更に無水メタ
ノールを加えて全量を約３００ｍ１とする。この無水メ
タノール溶液にトリエタノールアミン４．３９（ ０．
０２９モル）を加えて６時間加熱還流し、冷却後メタノ
ール等を留去すると白色の粗結晶を得るので、これをク
ロロホルムの１００ｗＬ１から再結晶すると２−カルバ
モイルエチルゲルマトラン（１）を５．２ｇ得られた。It will generate a little heat and salt will start to precipitate. The methanol is distilled off under reduced pressure to a concentration of about 50 methanol, the salt is filtered, the salt is washed with 20 ml of anhydrous methanol, the solution is combined with the r solution, and further anhydrous methanol is added to bring the total volume to about 300 ml. To this anhydrous methanol solution was added 4.39 (0.
029 mol) was added and heated under reflux for 6 hours, and after cooling, methanol etc. were distilled off to obtain white crude crystals. When this was recrystallized from 100 wL of chloroform, 5.2 g of 2-carbamoylethyl germatran (1) was obtained. Obtained.
収率は６２０１０であつた。２．１−フエニル一２−カ
ルバモイルエチルゲルマトラン（）（１） １−フエニ
ルトリクロルゲルミルプロピオン酸アミドの合成トリク
ロルゲルマン３５．３７９（０．１９６モル）を濃塩酸
２００ｍ１に溶解し、氷冷下はげしく攪拌し乍らシンナ
モニトリル２５．３０９（０．１９６モル）を徐々に滴
下すると発熱する。The yield was 62,010. 2.1-Phenyl-2-carbamoylethylgermatran () (1) Synthesis of 1-phenyltrichlorogermylpropionic acid amide 35.379 (0.196 mol) of trichlorogermane was dissolved in 200 ml of concentrated hydrochloric acid and cooled on ice. Cinnamonitrile 25.309 (0.196 mol) was gradually added dropwise while stirring vigorously, generating heat.
しばらくするとガム状となるが、一夜放置すると結晶化
するので、これをＰ取してｎ−ヘキサンで洗浄し、ベン
ゼンから再結晶すると、１−フエニルトリクロルゲルミ
ルプロピオン酸アミドの結晶３８．０９が得られた。収
率は５９．３％であつた。１−フエニルトリクロルゲル
ミルプロピオン酸アミド
）．） １−フエニル一２−カルバモイルエチルゲルマ
トラン（）の合成まず金属ナトリウム３．８８９（０．
１６８モル）を８０ｍ１の無水エタノールと反応させ、
ナトリウムメトキサイド溶液を調整しておく。After a while, it becomes gummy, but if left overnight, it crystallizes, so P is removed, washed with n-hexane, and recrystallized from benzene, resulting in crystals of 1-phenyltrichlorogermylpropionic acid amide (38.09) was gotten. The yield was 59.3%. 1-phenyltrichlorogermylpropionic acid amide). ) Synthesis of 1-phenyl-2-carbamoylethylgermatran () First, 3.889 (0.
168 mol) with 80 ml of absolute ethanol,
Prepare the sodium methoxide solution.
（１）で合成した１−フエニルトリクロルゲルミルプロ
ピオン酸アミド１８．４９（０．０５６モル）を１００
ＴＩＬＩのメタノールに溶解し、これに前記ナトリウム
メトキサイド溶液を攪拌し乍ら室温で徐々に滴下すると
、稍発熱して塩が析出するが、そのまま１時間半攪拌を
続ける。その後メタノールを減圧留去して１５０ｄまで
濃縮し、析出した塩をＰ過して除くと共に少量の無水メ
タノールで洗浄してＰ液と合わせ、更に無水メタノール
を加えて全量を２５０７ｎ１とし、トリエタノールアミ
ン８．３６９（０．０５６モル）を加えて１５時間還流
する。溶媒を除いて粗結晶を得、これをベンゼン、メタ
ノールの混液３００ｍ１から再結晶すると、１−フエニ
ル一２−カルバモイルエチルゲルマトラン（）の結晶１
４．３９が得られた。収率は７０％であつた。１−フエ
ニル一２−カルバモイルエチルゲ本発明化合物中の他の
ものについても概路上述した方法で合成することができ
る。18.49 (0.056 mol) of 1-phenyltrichlorogermylpropionic acid amide synthesized in (1) was added to 100
When TILI is dissolved in methanol and the sodium methoxide solution is gradually added dropwise thereto at room temperature while stirring, a slight heat is generated and salt precipitates, but stirring is continued for 1.5 hours. Thereafter, methanol was distilled off under reduced pressure and concentrated to 150d, precipitated salts were removed by P filtration, washed with a small amount of anhydrous methanol, combined with P solution, further anhydrous methanol was added to make a total volume of 2507n1, and triethanolamine was added. Add 8.369 (0.056 mol) and reflux for 15 hours. The solvent was removed to obtain crude crystals, which were recrystallized from 300 ml of a mixture of benzene and methanol to give crystals 1 of 1-phenyl-2-carbamoylethylgermatoran ().
4.39 was obtained. The yield was 70%. 1-phenyl-2-carbamoylethylge Other compounds of the present invention can also be synthesized by the method outlined above.
即ち、２−カルボキシエチルゲルマトラン（）のように
Ｒ３＝０Ｈの化合物は対応するアミノ体である２−カル
バモイルエチルゲルマトランを合成し、アミド基を酸化
的に処理するか、―あるいはＲ３にｔ−ブトキシ基等加
水分解の容易な基を導入しておき、事後的に加水分解す
ればよく、又、１−メチルエチルゲルマトラン（）のよ
うに１位に官能基を有するものは、出発原料に当該置換
基を導入したもの、例えばのように合成したトリクロル
ゲルミルプロピオン酸アミド誘導体を用いればよい。That is, for a compound in which R3=0H such as 2-carboxyethylgermatoran (), the corresponding amino form, 2-carbamoylethylgermatoran, is synthesized, and the amide group is oxidatively treated, or R3 is replaced with t. - It is sufficient to introduce an easily hydrolyzable group such as a butoxy group and then hydrolyze it.Also, those having a functional group at the 1-position such as 1-methylethylgermatran () are used as starting materials. For example, a trichlorogermylpropionic acid amide derivative synthesized as described above may be used.
３．本発明化合物の薬理試験
実験動物として９週◆のＣＤＩ，系マウスを用いこれに
腫瘍細胞であるＩＭＣｃａｒｃｉｎＯｍａを１×１０ｅ
個皮下に移殖し、本発明化合物（ｌ）を１５日間経口に
て連続投与し、抑制率を調べたところ、下表に示すよう
に抗腫瘍剤としての効果が認められるカルボキシエチル
ゲルマニウムセスキオサイド（表中ＣＥＧと略記した）
より．少ない投与量でほぼ同等の抑制率を示した。3. Pharmacological testing of the compounds of the present invention As experimental animals, 9-week ◆ CDI strain mice were used, and tumor cells, IMCcarcinOma, were injected at 1 x 10 e.
The compound (l) of the present invention was implanted subcutaneously, and the compound (l) of the present invention was orally administered continuously for 15 days, and the inhibition rate was examined. Side (abbreviated as CEG in the table)
Than. Almost the same inhibition rate was shown at a lower dose.
Claims (1)
はフェニル基を、又、Ｒ＿３は水酸基、Ｏ−低級アルキ
ル基又はアミノ基をそれぞれ示す。 〕で表わされることを特徴とする有機ゲルマニウム化合
物。[Claims] 1 Formula ▲ Numerical formulas, chemical formulas, tables, etc. The groups are shown respectively. ] An organic germanium compound characterized by being represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57142148A JPS5943479B2 (en) | 1982-08-18 | 1982-08-18 | organic germanium compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57142148A JPS5943479B2 (en) | 1982-08-18 | 1982-08-18 | organic germanium compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5931784A JPS5931784A (en) | 1984-02-20 |
| JPS5943479B2 true JPS5943479B2 (en) | 1984-10-22 |
Family
ID=15308475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57142148A Expired JPS5943479B2 (en) | 1982-08-18 | 1982-08-18 | organic germanium compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5943479B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019068589A1 (en) | 2017-10-02 | 2019-04-11 | Shell Internationale Research Maatschappij B.V. | Grease composition |
-
1982
- 1982-08-18 JP JP57142148A patent/JPS5943479B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019068589A1 (en) | 2017-10-02 | 2019-04-11 | Shell Internationale Research Maatschappij B.V. | Grease composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5931784A (en) | 1984-02-20 |
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