DE1246732B - Process for the production of organic tin-boron compounds - Google Patents
Process for the production of organic tin-boron compoundsInfo
- Publication number
- DE1246732B DE1246732B DEA49969A DEA0049969A DE1246732B DE 1246732 B DE1246732 B DE 1246732B DE A49969 A DEA49969 A DE A49969A DE A0049969 A DEA0049969 A DE A0049969A DE 1246732 B DE1246732 B DE 1246732B
- Authority
- DE
- Germany
- Prior art keywords
- organic tin
- boron compounds
- general formula
- production
- boric acid
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 7
- GSPPDMIMNFYKRI-UHFFFAOYSA-N boron tin Chemical class [B].[Sn] GSPPDMIMNFYKRI-UHFFFAOYSA-N 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000003606 tin compounds Chemical class 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims 1
- 239000004480 active ingredient Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- WINSNBNKIWUWNF-UHFFFAOYSA-N tripropylstannanylium borate Chemical compound B([O-])([O-])[O-].C(CC)[Sn+](CCC)CCC.C(CC)[Sn+](CCC)CCC.C(CC)[Sn+](CCC)CCC WINSNBNKIWUWNF-UHFFFAOYSA-N 0.000 description 3
- MIBOUHLEDOATFN-UHFFFAOYSA-N tris(tributylstannyl) borate Chemical compound CCCC[Sn](CCCC)(CCCC)OB(O[Sn](CCCC)(CCCC)CCCC)O[Sn](CCCC)(CCCC)CCCC MIBOUHLEDOATFN-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000256111 Aedes <genus> Species 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910020923 Sn-O Inorganic materials 0.000 description 1
- 229910020997 Sn-Y Inorganic materials 0.000 description 1
- 229910008859 Sn—Y Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- -1 bis (trin-butyl-stannyl) borate Chemical compound 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- LVXJQUIBFFIBAE-UHFFFAOYSA-N hydrogen borate tripropylstannanylium Chemical compound B([O-])([O-])O.C(CC)[Sn+](CCC)CCC.C(CC)[Sn+](CCC)CCC LVXJQUIBFFIBAE-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000926 not very toxic Toxicity 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- DZWGKMVDRPKMPD-UHFFFAOYSA-N tripropyl(tripropylstannyloxy)stannane Chemical compound CCC[Sn](CCC)(CCC)O[Sn](CCC)(CCC)CCC DZWGKMVDRPKMPD-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2224—Compounds having one or more tin-oxygen linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Paints Or Removers (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Int ClInt Cl
Nummer
Aktenzeichen
Anmeldetag
Auslegetag.number
File number
Filing date
Display day.
C07fC07f
C07F 7 / 2 2C07F 7/2 2
Deutsche Kl- 12 ο - 26/03 German class 12 ο - 26/03
I 246 732I 246 732
A 49969 IVb/12oA 49969 IVb / 12o
II August 1965
10 August 1967II August 1965
10 August 1967
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung neuer organischer Zinn-Bor-Verbindungen, die im Molekül mindestens einen Organozinnrest aufweisenThe present invention relates to a method for the production of new organic tin-boron compounds that contain at least one organotin residue in the molecule exhibit
Das erfindungsgemaße Verfahren zur Herstellung organischer Zinn-Bor-Verbindungen der allgemeinen Formel IThe inventive method for the preparation of organic tin-boron compounds of the general Formula I.
R,R,
R3 R 3
Sn-OSn-O
B — (OH)x B - (OH) x
(I)(I)
3 χ 3 χ
in der Ri, R2 und Rj je einen Alkylrest mit 1 bis 4 Kohlenstoffatomen und χ die Zahl O oder 1 bedeuten, ist dadurch gekennzeichnet, daß man in an sich bekannter Weise eine organische Zinnverbmdung der allgemeinen Formel IIin which Ri, R 2 and Rj each denote an alkyl radical having 1 to 4 carbon atoms and χ denotes the number O or 1, is characterized in that an organic tin compound of the general formula II is obtained in a manner known per se
R>- Sn-Y
R3 R> - Sn-Y
R 3
Verfahren zur Herstellung von organischen Zinn-Bor-Verbindungen Process for the production of organic tin-boron compounds
AnmelderApplicant
AGRIPAT S A , Basel (Schweiz)AGRIPAT S A, Basel (Switzerland)
Vertreterrepresentative
Dr -Ing F Zumstein,Dr -Ing F Zumstein,
Dipl -Chem Dr ier nat E Assmann,Dipl-Chem Dr ier nat E Assmann,
Dipl -Chem Dr R KoenigsbergerDipl -Chem Dr R Koenigsberger
und Dipl -Phys R Holzbauer, Patentanwälte,and Dipl -Phys R Holzbauer, patent attorneys,
München 2 Brauhausstr 4Munich 2 Brauhausstr 4
Als Erfinder benanntNamed as the inventor
Dr Denis Varsanyi, Basel (Schweiz)Dr Denis Varsanyi, Basel (Switzerland)
Beanspruchte PrioritätClaimed priority
Schweiz vom 12 August 1964(10 505)Switzerland of 12 August 1964 (10 505)
(II)(II)
in der Ri, R> und R3 die unter der allgemeinen Formel I angegebenen Bedeutungen haben und Y einen als Anion abspaltbaren Rest bedeutet, mit Borsaure oder einem reaktionsfähigen Derivat der Borsaure umsetzt Als reaktionsfähige Derivate der Borsaure kommen ihre partiellen Anhydride, d h die Metabor- und Polyborsauren, als auch das Anhydrid B2O3 in Frage Die Umsetzung wird gewunschtenfalls in Gegenwart gegenüber den Reaktionsteilnehmern inerter Losungsmittel durchgeführtin the Ri, R> and R3 those under the general Formula I have given meanings and Y denotes a radical which can be split off as an anion, with Boric acid or a reactive derivative of boric acid converts as reactive derivatives of Boric acid comes with its partial anhydrides, i.e. the metaboric and polyboric acids, as well as that Anhydride B2O3 in question Implementation is possible if desired carried out in the presence of solvents inert to the reactants
Unter dem in der allgemeinen Formel II mit Y bezeichneten, als Anion abspaltbaren Rest ist Halogen, insbesondere Chlor, eine Alkoxygruppe oder die Hydroxylgruppe zu verstehenUnder the in the general formula II designated with Y, The radical which can be split off as an anion is halogen, in particular chlorine, an alkoxy group or the To understand hydroxyl group
Die nach dem erfindungsgemaßen Verfahren erhaltenen Verbindungen der allgemeinen Formel I sind stabile, geruchlose, farblose ölige Verbindungen Sie besitzen ausgezeichnete biozide Eigenschaften und sind fur Warmbluter wenig toxisch Die Verbindüngen sind in Wasser unlöslich, dagegen in den üblichen organischen Losungsmitteln loslich Gegenüber ζ B dem in der deutschen Patentschrift 950 970 beschriebenen Bis-(tn-n-butylstdnnyl)-oxid sind die neuen Verbindungen weniger fluchtig Die neuen Verbindungen können zur Bekämpfung von Mikroorganismen ζ Β zum Schützen organischer und anorganischer Substraten vor dem Befall durch Schädlinge und Mikroorganismen, als herbizide Wirkstoffe sowie als Stabilisatoren fur Kunststoffe verwendet werdenThe compounds of the general formula I obtained by the process according to the invention are stable, odorless, colorless oily compounds They have excellent biocidal properties and are not very toxic to warm blooded animals. The compounds are insoluble in water, but in the Soluble to common organic solvents ζ B the bis (tn-n-butylstdnnyl) oxide described in German patent specification 950 970 The new connections are less volatile New compounds can help fight microorganisms ζ Β to protect organic and inorganic substrates from attack by pests and microorganisms, as herbicidal Active ingredients as well as stabilizers for plastics can be used
Fur den Schutz organischer und anorganischer Substrate werden die neuen Wirkstoffe der allgemeinen Formel I entweder in das Substrat eingearbeitet, oder dieses wird mit den Wirkstofflosungen die gewunschtenfalls oberflächenaktive Substanzen enthalten, imprägniert Auf diese Weise lassen sich keratinische Materialien sowie Materialien auf Cellulosebasis, ferner Zubereitungen wie Anstrichfarben und Lacke, Schleime, Druckverdicker aus Starkeoder Cellulosederivaten, öle aller Art, ferner Papierbehandlungsflotten, Kunststoffe und synthetisches Fasermatenal aller Art, Weichmacher und Seifen vor dem Befall durch Schädlinge, Bakterien und Pilze schützenFor the protection of organic and inorganic substrates, the new active ingredients are the general Formula I either incorporated into the substrate, or this is mixed with the active ingredient solutions which, if desired, contain surface-active substances, can be impregnated in this way keratinic materials as well as cellulose-based materials, also preparations such as paints and varnishes, slimes, printing thickeners made from starch or Cellulose derivatives, oils of all kinds, and paper treatment liquors, Plastics and synthetic fiber materials of all kinds, plasticizers and soaps protect against attack by pests, bacteria and fungi
Die folgenden Beispiele dienen zur Erläuterung der Erfindung Soweit nichts anderes ausdrucklich vermerkt ist, bedeuten »Teile« Gewichtstelle und die Temperaturen sind in Celsiusgraden angegebenThe following examples serve to illustrate of the invention Unless otherwise expressly stated, "parts" mean weight and the temperatures are given in degrees Celsius
60 Teile Bis-(tn-n-butyl-zinn)-oxid und 6 5 Tgue Borsaure werden unter Stickstoffatmosphare 10 Stunden bei 150 bis 170° erwärmt Dabei scheidet sich Wasser ab Nach dem Erkalten wird das Reaktions-60 parts of bis (tn-n-butyltin) oxide and 6 5 Tgue boric acid are heated under a nitrogen atmosphere for 10 hours at 150 to 170 °.
709 620 3"i<709 620 3 "i <
gemisch in 50 Volumteilen Petroläther gelöst und der in Petroläther unlösliche Teil abfiltriert. Das Lösungsmittel wird dann abdestilliert. Der Rückstand wird im Vakuum fraktioniert. Man erhält 28 Teile Tris-(tri-n-butyl-stannyl)-borat, Kp.o ooi = 192 bis 196°.mixture dissolved in 50 parts by volume of petroleum ether and the part which is insoluble in petroleum ether is filtered off. That Solvent is then distilled off. The residue is fractionated in vacuo. You get 28 parts of tris (tri-n-butyl-stannyl) borate, b.p. o ooi = 192 up to 196 °.
Als zweite Fraktion erhält man 28 Teile Bis-(trin-butyl-stannyl)-borat, Κρ.ο,οοι = 230 bis 235°.The second fraction obtained is 28 parts of bis (trin-butyl-stannyl) borate, Κρ.ο, οοι = 230 to 235 °.
78,3 Teile Bis-(tri-n-propyl-zinn)-oxid und 6 Teile Bortrioxid werden in 150 Volumteilen Toluol 10 Stunden unter Rückfluß erhitzt. Das Reaktionsgemisch wird nach dem Erkalten zur Entfernung der überschüssigen Borsäure filtriert. Das Lösungsmittel wird abdestilliert und der Rückstand fraktioniert. Man erhält als erste Fraktion 56 Teile Tris-(trin-propyl-stannyl)-borat, Κρ.ο,οοι = 174 bis 178°.78.3 parts of bis (tri-n-propyl-tin) oxide and 6 parts of boron trioxide are in 150 parts by volume of toluene for 10 hours heated to reflux. After cooling, the reaction mixture is used to remove the excess Boric acid filtered. The solvent is distilled off and the residue is fractionated. The first fraction obtained is 56 parts of tris (trin-propyl-stannyl) borate, Κρ.ο, οοι = 174 to 178 °.
Als zweite Fraktion erhält man 5 Teile Bis-(trin-propyl-stannyl)-borat, Κρ.ο,οοι = 184 bis 192°.The second fraction obtained is 5 parts of bis (trin-propyl-stannyl) borate, Κρ.ο, οοι = 184 to 192 °.
Zur Feststellung der Insektiziden Kontaktgiftwirkung wurden die Wirkstoffe in Aceton gelöst, in Petrischalen gegeben und das Lösungsmittel abgedampft. Nach etwa einer Stunde wurden die Petrischalen mit Aedes-Mücken besetzt. In der Tabelle ist die Zeit in Minuten (') angegeben, in der alle Testinsekten (lOO«/o) Rückenlage einnehmen.To determine the insecticidal contact poison effect, the active ingredients were dissolved in acetone, in Given Petri dishes and evaporated the solvent. After about an hour the petri dishes were occupied with Aedes mosquitoes. The table shows the time in minutes (') in which all Test insects (100%) supine.
diese Lösung in einen lO"/oigen Stärkekleister, bestehend aus 10 g Kartoffelstärke, welche in 90 g destilliertem Wasser von 60 bis 65'C gequollen wurde, so eingearbeitet, daß im Substrat 12,5 ppm Wirksubstanz enthalten waren. Diese Mischung wurde bei einer Temperatur von 23 bis 28'C in einem geschlossenen Glasgefäß stehengelassen. Die Anzahl Tage, während der die Mischung unverändert bleibt, dient als Maß für die Wirksamkeit für die Wirksubstanz. Die Veränderungen sind sehr ausgesprochen und leicht erkennbar.this solution in a 10% starch paste from 10 g of potato starch, which swelled in 90 g of distilled water from 60 to 65 ° C was incorporated so that the substrate contained 12.5 ppm of active ingredient. This mixture was left to stand in a closed glass vessel at a temperature of 23 to 28 ° C. the The number of days during which the mixture remains unchanged serves as a measure of the effectiveness for the Active ingredient. The changes are very pronounced and easy to see.
ResultateResults
(Konzentration: 12,5 ppm)Duration of the protective effect in days
(Concentration: 12.5 ppm)
II
IIII.
II
III
15
179
15th
17th
3535
Zur Bestimmung der bioziden Wirksamkeit wurden die folgenden Verbindungen geprüft und miteinander verglichen:To determine biocidal effectiveness, the following compounds were tested and used together compared:
I. Bis-(tri-n-butyl-stannyl)-oxid (gemäß deutscher Patentschrift 950 970),I. bis (tri-n-butyl-stannyl) oxide (according to German patent specification 950 970),
II. Tris-(tri-n-butyl-stannyl)-borat (gemäß der vorliegenden Erfindung),II. Tris (tri-n-butyl-stannyl) borate (according to the present invention),
III. Tris-(tri-n-propyl-stannyl)-borat (gemäß der vorliegenden Erfindung).III. Tris (tri-n-propyl-stannyl) borate (according to the present invention).
4545
Methodemethod
Die zu prüfenden Wirksubstanzen wurden in Wasser oder in einem Lösungsmittel, z. B. in Äthylenglykoläthyläther, im Verhältnis 1 : 200 gelöst undThe active substances to be tested were in water or in a solvent, e.g. B. in ethylene glycol ethyl ether, solved in a ratio of 1: 200 and
Claims (1)
Deutsche Auslegeschrift Nr. 1 171 920;
D u b , »Organometallic Compounds«, Bd.
(1961), S. 205.Considered publications:
German Auslegeschrift No. 1 171 920;
D ub, "Organometallic Compounds", Vol.
(1961), p. 205.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1050564 | 1964-08-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1246732B true DE1246732B (en) | 1967-08-10 |
Family
ID=4363940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEA49969A Pending DE1246732B (en) | 1964-08-12 | 1965-08-11 | Process for the production of organic tin-boron compounds |
Country Status (9)
| Country | Link |
|---|---|
| AT (2) | AT255435B (en) |
| BE (1) | BE668247A (en) |
| BR (1) | BR6572039D0 (en) |
| DE (1) | DE1246732B (en) |
| ES (2) | ES316379A1 (en) |
| GB (1) | GB1115047A (en) |
| IL (1) | IL24133A (en) |
| NL (1) | NL6510469A (en) |
| SE (2) | SE314676B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3404253A1 (en) * | 1984-02-07 | 1985-08-08 | Lentia GmbH Chem. u. pharm. Erzeugnisse - Industriebedarf, 8000 München | 1,3,2-DIOXABORINANE |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1171920B (en) * | 1961-06-27 | 1964-06-11 | Stauffer Chemical Co | Process for the production of organotin sulfonates and thiosulfonates |
-
1965
- 1965-08-11 NL NL6510469A patent/NL6510469A/xx unknown
- 1965-08-11 BR BR172039/65A patent/BR6572039D0/en unknown
- 1965-08-11 AT AT741965A patent/AT255435B/en active
- 1965-08-11 AT AT03118/66A patent/AT284779B/en active
- 1965-08-11 ES ES0316379A patent/ES316379A1/en not_active Expired
- 1965-08-11 GB GB34293/65A patent/GB1115047A/en not_active Expired
- 1965-08-11 ES ES0316378A patent/ES316378A1/en not_active Expired
- 1965-08-11 SE SE10491/65A patent/SE314676B/xx unknown
- 1965-08-11 SE SE08450/67A patent/SE347513B/xx unknown
- 1965-08-11 DE DEA49969A patent/DE1246732B/en active Pending
- 1965-08-11 IL IL24133A patent/IL24133A/en unknown
- 1965-08-12 BE BE668247D patent/BE668247A/xx unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1171920B (en) * | 1961-06-27 | 1964-06-11 | Stauffer Chemical Co | Process for the production of organotin sulfonates and thiosulfonates |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1115047A (en) | 1968-05-22 |
| SE347513B (en) | 1972-08-07 |
| BE668247A (en) | 1966-02-14 |
| AT284779B (en) | 1970-09-25 |
| BR6572039D0 (en) | 1973-11-29 |
| ES316379A1 (en) | 1966-03-16 |
| SE314676B (en) | 1969-09-15 |
| AT255435B (en) | 1967-07-10 |
| NL6510469A (en) | 1966-02-14 |
| ES316378A1 (en) | 1966-03-16 |
| IL24133A (en) | 1969-03-27 |
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