CH521999A - New halo-phosphoric acid derivs prepn - Google Patents
New halo-phosphoric acid derivs prepnInfo
- Publication number
- CH521999A CH521999A CH1564471A CH1564471A CH521999A CH 521999 A CH521999 A CH 521999A CH 1564471 A CH1564471 A CH 1564471A CH 1564471 A CH1564471 A CH 1564471A CH 521999 A CH521999 A CH 521999A
- Authority
- CH
- Switzerland
- Prior art keywords
- general formula
- phosphoric acid
- acid derivs
- prepn
- new halo
- Prior art date
Links
- 229910000147 aluminium phosphate Inorganic materials 0.000 title abstract 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title abstract 2
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 3
- 150000003015 phosphoric acid halides Chemical class 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 abstract description 4
- 230000000361 pesticidal effect Effects 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical group C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 2
- 230000000895 acaricidal effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- -1 dioxane Chemical compound 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 239000002026 chloroform extract Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CWJISFXBHNDSCO-UHFFFAOYSA-N ethoxy-dihydroxy-sulfanylidene-lambda5-phosphane dihydrochloride Chemical compound Cl.Cl.CCOP(O)(O)=S CWJISFXBHNDSCO-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008096 xylene 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
- 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
- C07F9/165—Esters of thiophosphoric acids
- C07F9/20—Esters of thiophosphoric acids containing P-halide groups
-
- 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
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/14—Esters of phosphoric acids containing P(=O)-halide groups
- C07F9/1403—Esters of phosphoric acids containing P(=O)-halide groups containing the structure Hal-P(=O)-O-unsaturated acyclic group
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
New halo-phosphoric acid derivs. prepn. Title cpds.: (where R1 and R2 are each 1 - 5C alkyl, X is H, Cl or Br, Y is O or S and Z is Cl or Br) are prepd. by reacting with R1OH. They are pesticidal intermediates.
Description
Verfahren zur Herstellung neuer Phosphorsäurehalogenide
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung neuer Phosphorsäurehalogenide der allgemeinen Formel I
EMI1.1
worin R1 und R2 je eine niedere Alkylgruppe mit 1-5 Kohlenstoffatomen, X ein Wasserstoff- oder Chloratom, Y ein Sauerstoff- oder Schwefelatom und Z Chlor oder Brom bedeuten, die als Zwischenprodukte zur Herstellung von insektizid, akarizid und nematozid wirksamen Phosphorsäureestern verwendet werden können und von denen einige selbst insektizide und akarizide Eigenschaften besitzen.
Die Verbindungen der allgemeinen Formel I können nach dem erfindungsgemässen Verfahren durch Umsetzung einer Verbindung der allgemeinen Formel II
EMI1.2
worin Rt, Y und Z die oben angeführten Bedeutungen besitzen, mit einer Verbindung der allgemeinen Formel III CHaCOCHXCOOR2 III worin R2 und X die oben bezeichneten Bedeutungen besitzen, in Gegenwart eines Säureakzeptors erhalten werden.
Die Herstellung kann wie folgt durchgeführt werden:
Nach dem erfindungsgemässen Verfahren wird zu einer Verbindung der allgemeinen Formel II, worin Rl, Y und Z die oben bezeichneten Bedeutungen besitzen, eine Verbindung der allgemeinen Formel III, worin R2 und X die oben bezeichneten Bedeutungen besitzen, und ein Säureakzeptor, wie z. B. Triäthylamin, Trimethylamin, innerhalb von einer Stunde bei -20" bis Raumtemperatur, vorzugsweise bei 100 bis 00, zugesetzt. Die Reaktion wird anfangs entweder ohne Lösungsmittel oder unter Zusatz eines unter den Reaktionsbedingungen inerten organischen Lösungsmittels, z. B. eines aromatischen Kohlenwasserstoffes, wie Toluol, Xylol usw., eines halogenierten Kohlenwasserstoffes, wie z. B. Chlorbenzol, Chloroform, eines Athers, wie Dioxan, u.a., durchgeführt.
Sofern beim Beginn der Reaktion ohne Lösungsmittel gearbeitet wird, ist es zweckmässig, im Verlaufe der Reaktion eine geringe Menge Lösungsmittel zuzusetzen. Die Reaktionsmischung wird anschliessend noch etwa 10-20 Stunden bei ungefähr -10" bis + 100. gerührt und danach auf übliche Weise aufgearbeitet.
Die Verbindungen der allgemeinen Formel I erhält man als farblose, im Hochvakuum unzersetzt destillierbare Öle.
Die Ausgangsstoffe der allgemeinen Formel II sind bereits in der Literatur beschrieben.
Die Herstellung der Verbindungen der allgemeinen Formel I nach dem erfindungsgemässen Verfahren ist als überraschend und nicht vorhersehbar anzusehen.
Die Zusammensetzung der erhaltenen Verbindungen der allgemeinen Formel I hinsichtlich der cis- und trans-Formen im Crotonsäurerest kann auf bekannte Weise durch das NMR-Spektrum bestimmt werden.
Die nach dem erfindungsgemässen Verfahren erhaltenen Verbindungen der allgemeinen Formel I kön nen als Zwischenprodukte für die Herstellung wertvoller Insektizide und Akarizide verwendet werden. Das erfindungsgemässe Verfahren bietet die Möglichkeit, die als Zwischenprodukte verwendbaren neuen Verbindungen in wirtschaftlich sehr interessanter Weise herzustellen, und stellt somit eine echte Bereicherung der Technik dar.
Die neuen Verbindungen der allgemeinen Formel I können beispielsweise mit einem Alkohol und einem Säureakzeptor unter Austausch des Halogenatoms Z durch einen Alkoxyrest zur Reaktion gebracht werden.
Anstatt durch einen Alkoxyrest kann das Halogenatom Z auch durch eine Aminogruppe ausgetauscht werden.
Auf diese Weise ist es möglich, zu interessanten Bioziden, z. B. Insektiziden, zu gelangen.
Die Verbindungen der allgemeinen Formel I, die hydrolytisch hinreichend beständig sind, besitzen selbst eine insektizide Wirkung.
Die folgenden Beispiele dienen zur Erläuterung des erfindungsgemässen Verfahrens, sollen die Erfindung jedoch in keiner Weise einschränken. Die Temperaturangaben erfolgen in Celsiusgraden.
Beispiel 1 O-Äthyl-O-(1-carbomethoxy- 1 -propen-2-yl)- phosphorothiochloridat
EMI2.1
Zu der Mischung von 53,7 g O-Athyl-phosphoro- thioat-dichlorid (Formel II; R, = C2Hs, Y = S, Z = C1) und 34,8 g Acetessigsäuremethylester werden unter Rühren bei 10-120 innerhalb 1 Stunde 301,5 g Triäthylamin und nach Zugabe der Hälfte Triäthylamin 50 ml Toluol zugesetzt. Danach wird die Reaktionsmischung weitere 2 Stunden bei 10 und 17 Stunden bei 200 gerührt. Anschliessend wird vom ausgefallenen Triäthylaminchlorhydrat abfiltriert. Das Filtrat wird mit Wasser gewaschen, getrocknet, filtriert und im Vakuum bei 400 eingedampft.
Durch Destillation im Hochvakuum erhält man das reine O-Sithyl-O-(1-carbomethoxy-1- propen-2-yl)-phosphorochloridat.
Kpo,03: 530.
Das Verhältnis der Isomeren cis : trans im Crotonsäurerest beträgt 9 : 1.
nD20: 1,496.
Analyse für C7Ht2ClO4PS Molgewicht: 258,7 berechnet: C 32,5 H 4,7 Cd 13,7 P 12,0 5 12,4 0/0 gefunden: C 32,1 H 5,0 Cd 14,2 P 12,0 5 13,2 O/o
Beispiel 2 O-n-Propyl-O-(1-carbomethoxy-1-propen-2-yl) phosphorochloridat
EMI2.2
Zu der Mischung von 53,1 g O-n-Propyl-phosphoro-dichlorid (Formel II:, R1=n-C3H7, Y=O, Z=C1) und 34,8 g Acetessigsäuremethylester werden unter Rühren bei -10 innerhalb einer Stunde 30,5 g Triäthylamin und beim Auftreten einer starken Menge eines Niederschlags 50 ml Toluol zugesetzt. Danach wird die Reaktionsmischung noch 15 Stunden bei 0 gerührt.
Anschliessend wird vom ausgefallenen Triäthylaminchlorhydrat abfiltriert. Das Filtrat wird mehrmals mit wenig Wasser gewaschen, danach getrocknet, filtriert und im Vakuum bei 400 eingeengt. Die wässrige Phase wird 2 mal mit 50 ml Chloroform extrahiert und der Chloroformextrakt nach dem Trocknen eingedampft. Durch Destillation im Hochvakuum erhält man das reine O-n-Propyl-O-(1-carbomethoxy-1-propen-2-yl)-phos phorochloridat.
Kp0,05: 670.
Das Verhältnis der Isomeren cis: trans im Crotonsäurerest beträgt 1 : 2.
nu20: 1,460.
Analyse für C8H14ClO4P Molgewicht: 256,6 berechnet: C 37,4 H 5,5 Cd 13,8 P 12,1 0/0 gefunden: C38,0 H5,7 Cl 13,0 P12,20/o
Process for the production of new phosphoric acid halides
The present invention relates to a process for the preparation of new phosphoric acid halides of the general formula I.
EMI1.1
where R1 and R2 are each a lower alkyl group with 1-5 carbon atoms, X is a hydrogen or chlorine atom, Y is an oxygen or sulfur atom and Z is chlorine or bromine, which can be used as intermediates for the preparation of insecticidally, acaricidally and nematocidally active phosphoric acid esters and some of which have insecticidal and acaricidal properties themselves.
The compounds of general formula I can be prepared by the inventive method by reacting a compound of general formula II
EMI1.2
in which Rt, Y and Z have the meanings given above, with a compound of the general formula III CHaCOCHXCOOR2 III in which R2 and X have the meanings given above, in the presence of an acid acceptor.
The production can be carried out as follows:
According to the inventive method, a compound of the general formula II in which Rl, Y and Z have the meanings indicated above, a compound of the general formula III in which R2 and X have the meanings indicated above, and an acid acceptor, such as. B. triethylamine, trimethylamine, added within one hour at -20 "to room temperature, preferably at 100 to 00. The reaction is initially either without a solvent or with the addition of an organic solvent which is inert under the reaction conditions, e.g. an aromatic hydrocarbon such as toluene, xylene, etc., a halogenated hydrocarbon such as chlorobenzene, chloroform, an ether such as dioxane, and others.
If the reaction is started without a solvent, it is advantageous to add a small amount of solvent during the course of the reaction. The reaction mixture is then stirred for about 10-20 hours at about -10 "to + 100 and then worked up in the usual way.
The compounds of general formula I are obtained as colorless oils which can be distilled without decomposition in a high vacuum.
The starting materials of the general formula II have already been described in the literature.
The preparation of the compounds of general formula I by the process according to the invention is to be regarded as surprising and not foreseeable.
The composition of the compounds of general formula I obtained with regard to the cis and trans forms in the crotonic acid residue can be determined in a known manner by the NMR spectrum.
The compounds of general formula I obtained by the process according to the invention can be used as intermediates for the preparation of valuable insecticides and acaricides. The process according to the invention offers the possibility of producing the new compounds which can be used as intermediates in an economically very interesting manner, and thus represents a real enrichment of technology.
The new compounds of the general formula I can, for example, be reacted with an alcohol and an acid acceptor, with the halogen atom Z being replaced by an alkoxy radical.
Instead of an alkoxy radical, the halogen atom Z can also be exchanged for an amino group.
In this way it is possible to obtain interesting biocides, e.g. B. insecticides to arrive.
The compounds of the general formula I, which are sufficiently hydrolytically stable, themselves have an insecticidal effect.
The following examples serve to illustrate the process according to the invention, but are not intended to restrict the invention in any way. The temperatures are given in degrees Celsius.
Example 1 O-ethyl-O- (1-carbomethoxy-1-propen-2-yl) phosphorothiochloridate
EMI2.1
To the mixture of 53.7 g of O-ethyl phosphorothioate dichloride (formula II; R, = C2Hs, Y = S, Z = C1) and 34.8 g of methyl acetoacetate are added within 1 hour with stirring at 10-120 301.5 g of triethylamine and, after adding half of the triethylamine, 50 ml of toluene were added. The reaction mixture is then stirred for a further 2 hours at 10 and 17 hours at 200. The precipitated triethylamine chlorohydrate is then filtered off. The filtrate is washed with water, dried, filtered and evaporated at 400 in a vacuum.
The pure O-sithyl-O- (1-carbomethoxy-1-propen-2-yl) -phosphorochloridate is obtained by distillation in a high vacuum.
Kpo, 03: 530.
The ratio of the isomers cis: trans in the crotonic acid residue is 9: 1.
nD20: 1.496.
Analysis for C7Ht2ClO4PS Molar weight: 258.7 calculated: C 32.5 H 4.7 Cd 13.7 P 12.0 5 12.4 0/0 found: C 32.1 H 5.0 Cd 14.2 P 12, 0.5 13.2 O / o
Example 2 O-n-Propyl O- (1-carbomethoxy-1-propen-2-yl) phosphorochloridate
EMI2.2
To the mixture of 53.1 g of on-propyl-phosphoro-dichloride (formula II :, R1 = n-C3H7, Y = O, Z = C1) and 34.8 g of methyl acetoacetate are added within one hour, with stirring at -10 , 5 g of triethylamine and, when a large amount of a precipitate occurs, 50 ml of toluene are added. The reaction mixture is then stirred at 0 for a further 15 hours.
The precipitated triethylamine chlorohydrate is then filtered off. The filtrate is washed several times with a little water, then dried, filtered and concentrated in vacuo at 400. The aqueous phase is extracted twice with 50 ml of chloroform and the chloroform extract is evaporated after drying. The pure O-n-propyl-O- (1-carbomethoxy-1-propen-2-yl) -phosphorochloridate is obtained by distillation in a high vacuum.
Bp 0.05: 670.
The ratio of the isomers cis: trans in the crotonic acid residue is 1: 2.
nu20: 1.460.
Analysis for C8H14ClO4P molecular weight: 256.6 calculated: C 37.4 H 5.5 Cd 13.8 P 12.1 0/0 found: C38.0 H5.7 Cl 13.0 P12.20 / o
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1564471A CH521999A (en) | 1969-07-18 | 1969-07-18 | New halo-phosphoric acid derivs prepn |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1564471A CH521999A (en) | 1969-07-18 | 1969-07-18 | New halo-phosphoric acid derivs prepn |
| CH1102969A CH521998A (en) | 1969-07-18 | 1969-07-18 | New halo-phosphoric acid derivs prepn |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH521999A true CH521999A (en) | 1972-04-30 |
Family
ID=4369321
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1102969A CH521998A (en) | 1969-07-18 | 1969-07-18 | New halo-phosphoric acid derivs prepn |
| CH1564471A CH521999A (en) | 1969-07-18 | 1969-07-18 | New halo-phosphoric acid derivs prepn |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1102969A CH521998A (en) | 1969-07-18 | 1969-07-18 | New halo-phosphoric acid derivs prepn |
Country Status (2)
| Country | Link |
|---|---|
| CH (2) | CH521998A (en) |
| SU (1) | SU372818A3 (en) |
-
1969
- 1969-07-18 CH CH1102969A patent/CH521998A/en not_active IP Right Cessation
- 1969-07-18 CH CH1564471A patent/CH521999A/en not_active IP Right Cessation
-
1970
- 1970-07-16 SU SU1462500A patent/SU372818A3/ru active
Also Published As
| Publication number | Publication date |
|---|---|
| SU372818A3 (en) | 1973-03-01 |
| CH521998A (en) | 1972-04-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased |