JPS6410516B2 - - Google Patents
Info
- Publication number
- JPS6410516B2 JPS6410516B2 JP60115179A JP11517985A JPS6410516B2 JP S6410516 B2 JPS6410516 B2 JP S6410516B2 JP 60115179 A JP60115179 A JP 60115179A JP 11517985 A JP11517985 A JP 11517985A JP S6410516 B2 JPS6410516 B2 JP S6410516B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- ammonium
- metal cation
- substituted
- alkaline earth
- 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
- 150000001875 compounds Chemical class 0.000 claims description 15
- -1 alkali metal cation Chemical class 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 2
- 125000000623 heterocyclic group Chemical group 0.000 claims 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims 1
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical compound [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 150000003839 salts Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- RFYBNOZYOOWYBK-UHFFFAOYSA-N P(SCCCO)([O-])[O-].[Mg+2] Chemical compound P(SCCCO)([O-])[O-].[Mg+2] RFYBNOZYOOWYBK-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- MNVKBJFKKJDBGR-UHFFFAOYSA-N butylsulfanylphosphonous acid Chemical compound CCCCSP(O)O MNVKBJFKKJDBGR-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- PAFZNILMFXTMIY-UHFFFAOYSA-O cyclohexylammonium Chemical group [NH3+]C1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-O 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- HWSUUGHIDOOOOJ-UHFFFAOYSA-N dioxaphosphinane Chemical class C1COOPC1 HWSUUGHIDOOOOJ-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- HNSYHCVBZGSRGQ-UHFFFAOYSA-N tripotassium dioxido(sulfido)phosphane Chemical compound P([S-])([O-])[O-].[K+].[K+].[K+] HNSYHCVBZGSRGQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
-
- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/201—Esters of thiophosphorus acids
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Dentistry (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、新規化合物であるある種のチオ亜燐
酸モノエステル及びそれらの塩並びにそれらの製
法に係る。これらのエステルをチオホスホン酸モ
ノエステルＯアルキルと称してもよいが、本明細
書中では以後チオ亜燐酸モノアルキルと称する。
本発明は更に、文献に記載されていないこれらの
化合物のいくつかの製法に係る。
特に本発明の化合物は、植物の寄生菌類を抑制
すべく使用されるのに適しており、下記の一般式
（）で示されるチオ亜燐酸モノエステル及びそ
れらの塩である：
［式中、Ｒは炭素原子１〜８個のヒドロキシアル
キル基であり、Ｍは水素原子、アンモニウム、炭
素原子１〜４個のアルキル基もしくはヒドロキシ
アルキル基１〜４個により置換されたアンモニウ
ム、シクロヘキシル基もしくはフエニル基により
置換されたアンモニウム、任意に原子数５〜６個
の複数環に属する窒素、あるいはアルカリ金属、
アルカリ土類金属の陽イオンであり、ｎはＭの原
子価に等しい整数である］。
特に有利な化合物は、式中、Ｒがβヒドロキシ
エチル基又はαもしくはγヒドロキシプロピル基
である炭素原子２又は５個のヒドロキシアルキル
基であり、Ｍが水素原子、アルカリ金属もしくは
アルカリ土類金属の金属陽イオン、メチル基もし
くはエチル基１〜４側により置換もしくは非置換
のアンモニウム基又はピリジニウム基であり、好
ましくは、Ｍがアルカリ金属又はアルカリ土類金
属の陽イオンである。
因みに、例えばチオ亜燐酸アンモニウム、ナト
リウム及びカリウム、チオ亜燐酸エチル及びブチ
ル並びにそれらのナトリウム塩（Chemical
Abstracts、48巻、3243e）は公知である。
しかし乍ら、本発明の化合物は新規である。更
に、公知化合物を殺菌剤として使用することを示
す文献はなく、まして本発明の化合物については
そうである。
塩の形状の本発明化合物は３個の互変異性式で
表現し得る。
従来の習慣に従つて、以後は式(B)、即ち一般式
（）を使用する。
しかし乍ら式(A)及び(C)で示される化合物はいず
れも本発明の範囲に含まれる。
通常、第二チオ亜燐酸モノエステル塩の加水分
解又は鹸化によつて本発明の化合物を製造し得
る。
第二チオ亜燐酸モノエステル塩が環状ジエステ
ルの場合、第一段階で式（）の範囲に含まれる
チオ亜燐酸ヒドロキシアルキルが生成し、次に下
記反応式に従つてさらに加水分解を継続するとチ
オ亜燐酸塩が生成する。
次に、本発明の化合物の製法を製造実施例を以
つて説明する。
製造実施例 １
下記の反応式に従つて２−チオ−2H−１，３，
２−ジオキサホスホラン又はジオキサホスホリナ
ン誘導体を、部分的に加水分解又は鹸化すると
夫々、チオ亜燐酸２−ヒドロキシエチル及び３−
ヒドロキシプロピルが生成する。
収率は良好であり、しばしば定量可能である。
この方法により３−ヒドロキシプロピルチオ亜
燐酸マグネシウムを製造した。
水100ml中、２−チオ−2H−１，３，２−ジオ
キサホスホリナン6.9ｇと焼成マグネシア１ｇと
の懸濁液を２時間撹拌する。反応体を完全に溶解
させる。蒸発させて乾燥すると白色吸湿性粉末
8.5ｇを得る。
収率：100％
C3H8MgO3PSの分析百分率：
％ Ｃ Ｈ Mg Ｐ Ｓ
計算値 21.54 4.79 7.27 18.55 19.14
測定値 21.60 5.09 7.18 18.29 18.99
核磁気共鳴（NMR）分光光度計により構造を
確認する。NV14変形装置を使用し、磁界を60ｍ
ｃ／ｓに等しくして、溶媒として重水素含有メタ
ノールを用い、リフアレンスとしてヘキサメチレ
ンジシロキサン（HMDS）を用いる。文字Ｊは
カツプリング定数を１秒当りのサイクルで示して
おり、δはシフトをppmで示している。
JP-H：590c／ｓ
δ：7.90ppm
種々の環状誘導体及び／又は鹸化塩基を使用
し、同様の方法で他の合属化合物を製造した。こ
れらの化合物の式、収率、特性及び分析白分率を
次表に示す。
The present invention relates to certain novel thiophosphite monoesters and salts thereof, and processes for their production. These esters may be referred to as O-alkyl thiophosphonate monoesters, but hereinafter referred to as monoalkyl thiophosphites.
The present invention further relates to methods for preparing some of these compounds that have not been described in the literature. In particular, the compounds of the invention are thiophosphite monoesters and salts thereof, which are suitable for use in controlling parasitic fungi on plants, and are represented by the following general formula (): [Wherein, R is a hydroxyalkyl group having 1 to 8 carbon atoms, and M is a hydrogen atom, ammonium, ammonium substituted with an alkyl group having 1 to 4 carbon atoms or 1 to 4 hydroxyalkyl groups, cyclohexyl ammonium substituted with a group or a phenyl group, optionally nitrogen belonging to a plurality of rings having 5 to 6 atoms, or an alkali metal,
is an alkaline earth metal cation, n is an integer equal to the valence of M]. Particularly preferred compounds are hydroxyalkyl groups of 2 or 5 carbon atoms in which R is a β-hydroxyethyl group or an α- or γ-hydroxypropyl group, and M is a hydrogen atom, an alkali metal or an alkaline earth metal. It is an ammonium group or a pyridinium group substituted or unsubstituted by a metal cation, methyl group or ethyl group 1 to 4, and preferably M is an alkali metal or alkaline earth metal cation. Incidentally, for example, ammonium, sodium and potassium thiophosphite, ethyl and butyl thiophosphite and their sodium salts (Chemical
Abstracts, Vol. 48, 3243e) is publicly known. However, the compounds of the present invention are new. Furthermore, there is no literature indicating the use of known compounds as fungicides, much less the compounds of the present invention. The compounds of the present invention in salt form can be expressed in three tautomeric forms. In accordance with conventional practice, formula (B), the general formula (), will be used hereafter. However, both compounds represented by formulas (A) and (C) are included within the scope of the present invention. Generally, compounds of the invention may be prepared by hydrolysis or saponification of secondary thiophosphite monoester salts. When the secondary thiophosphite monoester salt is a cyclic diester, a hydroxyalkyl thiophosphite within the range of formula () is produced in the first step, and then further hydrolysis is continued according to the reaction formula below to form a thiophosphite. Phosphite is formed. Next, the method for producing the compound of the present invention will be explained using production examples. Production Example 1 2-thio-2H-1,3,
Partial hydrolysis or saponification of 2-dioxaphosphorane or dioxaphosphorinane derivatives results in 2-hydroxyethyl thiophosphite and 3-hydroxyethyl thiophosphite, respectively.
Hydroxypropyl is produced. Yields are good and often quantifiable. Magnesium 3-hydroxypropylthiophosphite was produced by this method. A suspension of 6.9 g of 2-thio-2H-1,3,2-dioxaphosphorinane and 1 g of calcined magnesia in 100 ml of water is stirred for 2 hours. Allow the reactants to completely dissolve. White hygroscopic powder when evaporated and dried
Obtain 8.5g. Yield: 100% Analysis percentage of C 3 H 8 MgO 3 PS: % C H Mg PS Calculated value 21.54 4.79 7.27 18.55 19.14 Measured value 21.60 5.09 7.18 18.29 18.99 Confirm structure with nuclear magnetic resonance (NMR) spectrophotometer . Using NV14 deformation device, magnetic field is 60m
c/s, using deuterium-containing methanol as the solvent and hexamethylene disiloxane (HMDS) as the reference. The letter J indicates the coupling constant in cycles per second and δ indicates the shift in ppm. J PH : 590c/s δ: 7.90ppm Other hybrid compounds were prepared in a similar manner using various cyclic derivatives and/or saponification bases. The formulas, yields, properties and analytical white fractions of these compounds are shown in the following table.
【表】【table】
Claims (1)
キル基であり、Ｍは水素原子、アンモニウム、炭
素原子１〜４個のアルキル基もしくはヒドロキシ
アルキル基１〜４個により置換されたアンモニウ
ム、シクロヘキシル基もしくはフエニル基により
置換されたアンモニウム、任意に原子数５〜６個
の複素環に属する窒素あるいはアルカリ金属陽イ
オン、アルカリ土類金属陽イオンであり、ｎはＭ
の原子価に等しい整数である］ で示されるチオ亜燐酸モノエステル。 ２ Ｒが置換又は非置換の２−ヒドロキシエチル
基又は１−もしくは３−ヒドロキシプロピル基で
あることを特徴とする特許請求の範囲第１項に記
載の化合物。 ３ Ｍが水素原子、アルカリ金属もしくはアルカ
リ土類金属の金属陽イオン、メチル基もしくはエ
チル基１〜４個により置換もしくは非置換のアン
モニウム基又はピリジニウム基である特許請求の
範囲第１項または第２項に記載の化合物。 ４ Ｍがアルカリ金属又はアルカリ土類金属の陽
イオンであることを特徴とする特許請求の範囲第
１項又は第２項に記載の化合物。 ５ 置換又は非置換の２−チオ−１，３，２−ジ
オキサホスホラン又はホスホリナンを加水分解又
は鹸化することから成る一般式（）： ［式中、Ｒは炭素原子１〜８個のヒドロキシアル
キル基であり、Ｍは水素原子、アンモニウム、炭
素原子１〜４個のアルキル基もしくはヒドロキシ
アルキル基１〜４個により置換されたアンモニウ
ム、シクロヘキシル基もしくはフエニル基により
置換されたアンモニウム、任意に原子数５〜６個
の複素環に属する窒素あるいはアルカリ金属陽イ
オン、アルカリ土類金属陽イオンであり、ｎはＭ
の原子価に等しい整数である］で示されるチオ亜
燐酸モノエステルの製造方法。[Claims] 1 General formula (): [Wherein, R is a hydroxyalkyl group having 1 to 8 carbon atoms, and M is a hydrogen atom, ammonium, ammonium substituted with an alkyl group having 1 to 4 carbon atoms or 1 to 4 hydroxyalkyl groups, cyclohexyl or phenyl group, optionally nitrogen or alkali metal cation or alkaline earth metal cation belonging to a heterocycle having 5 to 6 atoms, n is M
is an integer equal to the valence of the thiophosphite monoester. 2. The compound according to claim 1, wherein 2R is a substituted or unsubstituted 2-hydroxyethyl group or 1- or 3-hydroxypropyl group. Claim 1 or 2, wherein 3M is a hydrogen atom, a metal cation of an alkali metal or alkaline earth metal, an ammonium group or a pyridinium group substituted or unsubstituted with 1 to 4 methyl groups or ethyl groups. Compounds described in Section. 4. The compound according to claim 1 or 2, wherein M is an alkali metal or alkaline earth metal cation. 5 General formula () consisting of hydrolyzing or saponifying substituted or unsubstituted 2-thio-1,3,2-dioxaphosphorane or phospholinane: [Wherein, R is a hydroxyalkyl group having 1 to 8 carbon atoms, and M is a hydrogen atom, ammonium, ammonium substituted with an alkyl group having 1 to 4 carbon atoms or 1 to 4 hydroxyalkyl groups, cyclohexyl or phenyl group, optionally nitrogen or alkali metal cation or alkaline earth metal cation belonging to a heterocycle having 5 to 6 atoms, n is M
is an integer equal to the valence of the thiophosphite monoester.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7508642 | 1975-03-14 | ||
| FR7508642A FR2303476A1 (en) | 1975-03-14 | 1975-03-14 | FUNGICIDE COMPOSITION BASED ON THIOPHOSPHITES |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6133191A JPS6133191A (en) | 1986-02-17 |
| JPS6410516B2 true JPS6410516B2 (en) | 1989-02-22 |
Family
ID=9152798
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP51027599A Granted JPS51128435A (en) | 1975-03-14 | 1976-03-13 | Germicide |
| JP59140407A Granted JPS6069086A (en) | 1975-03-14 | 1984-07-05 | Fungicide |
| JP11517985A Granted JPS6133191A (en) | 1975-03-14 | 1985-05-28 | Fungicide |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP51027599A Granted JPS51128435A (en) | 1975-03-14 | 1976-03-13 | Germicide |
| JP59140407A Granted JPS6069086A (en) | 1975-03-14 | 1984-07-05 | Fungicide |
Country Status (25)
| Country | Link |
|---|---|
| JP (3) | JPS51128435A (en) |
| AR (1) | AR228418A1 (en) |
| AU (1) | AU507474B2 (en) |
| BE (1) | BE839514A (en) |
| BG (2) | BG24938A3 (en) |
| BR (1) | BR7601525A (en) |
| CA (1) | CA1086644A (en) |
| CH (1) | CH610185A5 (en) |
| CS (2) | CS193082B2 (en) |
| DD (1) | DD125771A5 (en) |
| DE (1) | DE2606761C2 (en) |
| ES (1) | ES446025A1 (en) |
| FR (1) | FR2303476A1 (en) |
| GB (1) | GB1525339A (en) |
| GR (1) | GR60033B (en) |
| HU (1) | HU177025B (en) |
| IL (1) | IL49203A (en) |
| IT (1) | IT1058002B (en) |
| NL (1) | NL183889C (en) |
| OA (1) | OA05271A (en) |
| PH (1) | PH14304A (en) |
| PL (2) | PL99758B1 (en) |
| PT (1) | PT64902B (en) |
| SU (1) | SU651649A3 (en) |
| ZA (1) | ZA761522B (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6021553B2 (en) * | 1979-09-14 | 1985-05-28 | 三菱マテリアル株式会社 | White conductive coated powder and its manufacturing method |
-
1975
- 1975-03-14 FR FR7508642A patent/FR2303476A1/en active Granted
-
1976
- 1976-02-19 DE DE2606761A patent/DE2606761C2/en not_active Expired
- 1976-03-05 NL NLAANVRAGE7602309,A patent/NL183889C/en not_active IP Right Cessation
- 1976-03-11 CS CS77458A patent/CS193082B2/en unknown
- 1976-03-11 CS CS761595A patent/CS193066B2/en unknown
- 1976-03-12 DD DD191815A patent/DD125771A5/xx unknown
- 1976-03-12 HU HU76PI509A patent/HU177025B/en unknown
- 1976-03-12 ES ES446025A patent/ES446025A1/en not_active Expired
- 1976-03-12 IL IL49203A patent/IL49203A/en unknown
- 1976-03-12 CA CA247,826A patent/CA1086644A/en not_active Expired
- 1976-03-12 BG BG032598A patent/BG24938A3/en unknown
- 1976-03-12 PT PT64902A patent/PT64902B/en unknown
- 1976-03-12 BE BE165119A patent/BE839514A/en not_active IP Right Cessation
- 1976-03-12 ZA ZA761522A patent/ZA761522B/en unknown
- 1976-03-12 AR AR262536A patent/AR228418A1/en active
- 1976-03-12 CH CH312476A patent/CH610185A5/en not_active IP Right Cessation
- 1976-03-12 SU SU762333104A patent/SU651649A3/en active
- 1976-03-12 AU AU11919/76A patent/AU507474B2/en not_active Expired
- 1976-03-12 BR BR7601525A patent/BR7601525A/en unknown
- 1976-03-12 PH PH18206A patent/PH14304A/en unknown
- 1976-03-12 GB GB9986/76A patent/GB1525339A/en not_active Expired
- 1976-03-12 BG BG033550A patent/BG24944A3/en not_active Expired
- 1976-03-13 GR GR50298A patent/GR60033B/en unknown
- 1976-03-13 OA OA55765A patent/OA05271A/en unknown
- 1976-03-13 PL PL1976187915A patent/PL99758B1/en unknown
- 1976-03-13 JP JP51027599A patent/JPS51128435A/en active Granted
- 1976-03-13 PL PL1976200283A patent/PL101317B1/en unknown
- 1976-03-15 IT IT48579/76A patent/IT1058002B/en active
-
1984
- 1984-07-05 JP JP59140407A patent/JPS6069086A/en active Granted
-
1985
- 1985-05-28 JP JP11517985A patent/JPS6133191A/en active Granted
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