IL34419A - Methods and devices for the trituration of mixtures - Google Patents
Methods and devices for the trituration of mixturesInfo
- Publication number
- IL34419A IL34419A IL34419A IL3441970A IL34419A IL 34419 A IL34419 A IL 34419A IL 34419 A IL34419 A IL 34419A IL 3441970 A IL3441970 A IL 3441970A IL 34419 A IL34419 A IL 34419A
- Authority
- IL
- Israel
- Prior art keywords
- formula
- compound
- hydrogen
- stated
- propyl
- Prior art date
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C5/00—Filling or capping teeth
- A61C5/60—Devices specially adapted for pressing or mixing capping or filling materials, e.g. amalgam presses
- A61C5/66—Capsules for filling material
Landscapes
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Public Health (AREA)
- Dentistry (AREA)
- Dental Tools And Instruments Or Auxiliary Dental Instruments (AREA)
- Soil Working Implements (AREA)
- Packages (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Medical Preparation Storing Or Oral Administration Devices (AREA)
- Details Of Rigid Or Semi-Rigid Containers (AREA)
Description
i on asm ni»*jiBoiDiK'ni Phosphoric and thiophosphoric acid amidohalides and their preparation Case 1 0- 06 ■IMinOVE EiWPO IN 0Π RELATING TO ORGANIC COMPOUNDS The present invention relates to new phosphoric acid amidohalides of the formula I, wherein is hydrogen or lower alkyl of 1 to 3 carbon atoms, R_ and R, are lower alkyl of 1 to 5 carbon atoms, 2 5 X is hydrogen or chlorine, Y is oxygen or sulphur, and Z is chlorine OP bromino! The compounds of formula I are useful as intermediates in the production of biocidally active phosphoric acid esters.
Processes for the production of the compounds also form part of the present invention.
In accordance with the processes of the invention a . compound of the formula I may be obtained by: a) reacting a phosphoric acid halide of formula II, - .2 130-3063 wherein R X, Y and Z have the above significance, with an equivalent amount of an amine of formula III, wherein and have the above significance, in the presence of an acid acceptor, or b) reacting a compound of formula IV, Y tl IV -N— P-Z R1 Z wherein R , R , Y and Z have the above significance, with a compound of formula V, wherein R^ and X have the above significance, in the presence of an acid acceptor.
The production may be effected as follows: In accordance with process a) an equivalent amount of an amine of formula III in the presence of an acid acceptor, e.g. triethylamine, trimethylamine, dimethyl aniline, diethyl aniline or sodium carbonate, is added at a temperature of -20° to +50°C, preferably at -10° to room temperature, to a compound of 3 130-3063 formula II in a solvent which is inert under the reaction conditions, e.g. an aromatic hydrocarbon such as toluene or xylene, a halogenated hydrocarbon, e.g. chlorobenzene or chloroform, or dioxane, during the course of l/2 to 2 hours. The precipitate which generally results is filtered off and the filtrate is washed with water. The solvent is subsequently removed in a vacuum at a bath temperature of approximately 20° to 50°C. The residue is subsequently distilled in a high vacuum or, in the case of compounds which cannot be distilled, is crystallized.
In accordance with an embodiment of process a) it is possible to employ a second equivalent of an amine of formula III as acid acceptor. In this reactio an aqueous solution of the amine of formula III may be employed, and this is added to the compound of formula II.
Process a) may likewise be effected by reacting v-r-phosphorus oxychlorlde, .phnsphorue xybmmli e-, phosphorus thiochloride or phosphorus thiobromide with an acetoacetic ester of formula V, in which R and X have the above significance, in 3 the presence of an acid acceptor and, without isolating the resulting compound of general formula II, adding an equivalent amount of the compound of general formula III, in the presence of an acid acceptor, to the reaction mixture.
In accordance with process b) a compound of formula V is added, generally at -10 to +50°C, to a compound of formula IV, in an inert solvent, e.g. toluene or chlorobenzene, or optionally k - 130-5063 without solvent, and an acid acceptor, e.g. triethylamine, is added dropwise to the mixutre. After working up in the usual manner, the described compounds are obtained.
The compounds of formula I may be characterized in the usual manner by their physical constants.
Most of the compound of formula I obtained in accordance with the processes of the invention has a cis configuration in the crotonic acid radical, and only a small amount of the compound I has a trans configuration. The composition of the stereoisomeric forms of the compounds of formula I may be determined in known manner employing an NMR spectrum.
The production of compounds of formula II may be effected by reaction of a phosphorus, oxychloride ov oxybromlde, or phosphorus' thiochloride er- thiobromidc, with an acetoacetic ester of the above formula V, in which R, signifies a lower alkyl 3 radical containing 1 to 5 carbon atoms and X signifies a hydrogen or chlorine atom, in the presence of an acid acceptor.
The compounds of formula I obtained in accordance with the processes of the invention may be used as intermediates for the production of valuable biocides, e.g. insecticides. The processes of the invention open the possibility of producing the new compounds which may be used as intermediates in an economical and practical process.
The new compounds of formula I react, for example, with alcohols, thioalcohols, phenols, thiophenols or amines in * ■ the presence of an acid acceptor with the exchange of the chlorine - 5 - 130-5065 Thus, for example, compounds of formula I may be employed in the production of compounds of formula VI, wherein R. , R , R_, X and Y have the above significance, 1 2 3 and ^ is an alkyl group of 1 to k carbon atoms.
The compounds VI are thus prepared by reaction with equivalent amount of an alcohol of formula VII, wherein R^ has the above significance, in the presence of an acid acceptor, such as described above.
The compounds VI posses insecticidal,acaricidal and nematocidal properties, and may be used as such in conventional manner. Thus, for example, formulations containing between 2 and 90 by weight of active agent, preferably between 5 and 50 , may be employed in combatting insects and/or acarids and nematodes.
In the following non-limitative Examples all temperatures are indicated in degrees Centigrade.
Production of 0- (l-methoxycarbonyl-l-propen 2-yl) -N-methyl-phosphoramido-chlorldate (process a) 58.5 g (Ο.25 mols) of O-(l-methoxycarbonyl) -l-propen-2-yl) -phosphoro-dichloridate are dissolved in 300 cc of · chlorobenzene. A mixture of 7·8 g (0.25 mols) of methylamine in 30 g of chloroform and 25.5 g (0. 5 mols) of triethylamine as well as 100 cc of chlorobenzene are added dropwise to this solution at 20° during the course of Y2 hour.
After the addition is completed, the mixture is stirred for a further hour, the precipitated triethylamine hydrochloride is filtered off, the solvent is removed by evaporation and the resulting product is distilled at a pressure of 10 mm of Hg. Redistillation yields pure 0~(l-methoxycarbonyl-l~propen-2-yl) -N-methyl-phosphoramido-chloridate which has a boiling point of 95-97° at a pressure of 5.10 mm of Hg. It has a re- 20 fractive index of . n D = 1.482.
Analysis: C^H^CINO^P Molecular weight : 227.6 Found C 3I.9 H 5.2 % CI l6.0 % N 6.0 Calculated 31.7 .9 I5.6 6.2 % p 13.1 - 7 - 130-3063 Example 2 : Production of 0-(l-methoxycarbonyl-l^-propen-2- yl) -Ν,Ν-diethyl-phosphoramido -chloridate (process a) CI 0 76.7 g (0.5 mols) of POCl^ are dissolved in 200 cc of chlorobenzene. A mixture of 58 · 1 g (0.5 mols) of acstoacetlc acid methyl ester and 51 S (0.5 mols) of triethylamine is added dropwise at -10° during the course of 15 minutes. After the addition is completed, the reaction mixture is stirred at 0° for y2 hour and at 20° for one hour. The reaction solution is subsequently diluted with 300 cc of chlorobenzene, is cooled to -5° and 73.I g ( 1 mol) of diethylamine are added to the solution at -5° during the course of Y2 hour. The solution is subsequently stirred at 0° for !/2 hour and at 20° for 2 hours. The resulting precipitate is subsequently filtered off, the solvent is evaporated arid the resulting product is distilled. The resulting 0- imethoxycarbonyl-l-propen-2-yl) -N,N-diethyl-phosphoramido-chloridate has a boiling point of 69-71° at a pressure . of 5.IO mm of .Hg. It has a refractive index of Analysis : C^H^CIMO^P Molecular weight: 269.7 - 8 - I3O-3063 Found C 40.1 % H 6.7 CI 12.8 N 4.9 Calculated 40.1 6.4 # 13.1 5.2 £ P 11.1 # II.5 # Example 3 : Production of Q-(l-methoxycarbonyl-l-propen- 2-yl) -Ν,Ν-diethyl-phosphoramido -chloridate (process b) 51 g (0.5 mols) of triethylamine are added at +5° to a mixture of 95 g (0 .5 mols) of N,N-diethyl-phosphoramido- chloride and 58 g (0.5 mols) of acetoacetic acid methyl ester during the course of V2 hour. The reaction mixture is stirred at 5° for one hour and at 20° for 15 hours. 500 cc of toluene are subsequently added and the resulting precipitate is filtered off. The solvent is removed by evaporation and pure 0-(l-methoxycarbonyl-l-propen-2-yl) -N,N-.diethyl-phosphoramido-chloridate is obtained by distillation in a high vacuum.
The ratio cis : trans isomer the crotonic acid radical) amounts to 90 : 10 (determined by the NMR spectrum) .
Example : Production of Q-(l-methoxycarbonyl-l-propen- 2-yl) -N,N-diethyl-phosphoramido-chlorido thionate (process b) - 9 - 130-3063 i- A mixture of 51.5 g (0.25 mols) of N,N-diethyl-phosphoramldo-thioate-dichloride and 29 g (Ο.25 mols) of acetoacetic acid methyl ester is added at 20° during the course of 3 hours to 25.5 S (Ο.25 n101*3) of triethylamine. The reaction mixture is subsequently stirred at 20° for 10 hours and at 40° for 90 hours.
The resulting precipitate is subsequently filtered off, the filtrate is washed v/ith water and dried with magnesium sulphate. After distillation in a high vacuum pure 0-(l-methoxycarbonyl-l-propen-2-yl) -Ν,Ν-diethyl-phosphoramido-chlorido-thionate, having a boiling point of 78-8I0 (5.10"^ mm of Hg),is obtained. It has a re¬ fractive index of n = I.5II.
D Analysis : CQH1r-ClN0„ Molecular weight: 285.7 Found C 37.4 % H 5·9 CI 12,1 N 4.6 Calculated 37.8 % . 6.0 12.4 % 4.8 P 11.2 % S IO.7 .9 % 11.
Example 5: Production of 0- (l-methoxycarbonyl-l-chloro- l-p open-2-yl) -N-n-propyl-phosphoramido- chlorido-thionate (process b) CICOOCH, - 10 - 130-3063 A mixture of 48 g (Ο.25 mols) of N-n-propyl-phosphoramido-thioate-dichloride and 37 · 8 g (Ο.25 mols) of a-chloro-acetoacetic acid methyl ester in 150 cc of toluene is added to 25.5 S of triethylamine at -5° during the course of one hour. The reaction solution is subsequently stirred at 0° for one hour and at 20° for hours. The precipitated triethylamine hydrochloride is subsequently filtered off, the filtrate is washed with water, dried with sodium sulphate, the solvent is removed by evaporation and the residue is distilled. The resulting 0-(l-methoxycarbonyl-l-chloro-l-propen-2-yl) -N-n-propyl-phosphoramido-chlorido-thionate has a boiling point of 108 -110 ° at a pressure of 5.10""- mm of Hg.
It has a refractive index of n ^ = I.522.
Analysis: Molecular weight: 306.2 Found C 31.O $ H 4.7 CI 23.4 % N 4.5 Calculated 31.4 % 4.6 % 23.2 4.6 P 10.4 % 3 10.8 % .1 IO.5 Example 6: Production of 0- (l-ethoxycarbonyl-l-propen 2-yl) -N-n-propyl-phosphoramido-chlorido thionate (process a) CI S It P-0C=CHC00C^H, n-.C H NH _ 11 - 130-3063 A solution of I3I.5 g (0.5 mols) of 0-(l-ethoxycarbony 1-1-propen -2-yl) -phosphoro-dichlorido-thionate in 500 cc of toluene is added at 0° ■ during the course of one hour to a mixture of 29.6 g (0.5 mols) of n-propyl amine and 51 g (0.5 mols) of triethylamine.
The reaction mixture is subsequently stirred at 0° for Y2 hour and at 20° for one hour. The precipitated triethylamine hydrochloride is subsequently filtered off, the filtrate is washed with water, dried with Na2S0^ and distilled. The resulting 0-(l-ethoxycarbonyl-l-propen- 2-yl) ~N-n-propyl-phosphoramido-chlorido-thionate has a boiling point of 92° at a pressure of 5.10"^ mm of Hg.
It has a refractive index of n ^ = 1.51^ · Analysis: CQH,7C1N0_PS Molecular weight: 285.7 Pound C 37.9 % H 5.8 % CI 12.6 % N 5 * 2 Calculated 37 - 8 % 6.0 % 12.4 .9 % P 10.2 S 11.2 .8 % 11 , 2 % Production of 0- (l-iso-propoxycarbonyl- l-propen-2-yl) -N -ethyl-phosphoramido- chlorido-thionate (process a. in the presence of water) 12.8 g of a 70$ solution of ethylamine in water (0.2 mols) are added dropwise at -3° to 27.7 S (0.1 mol) of 0- (iso-propoxycarbonyl-l-propen-2-yl) -phosphoro-dichloridate during the course of 1 minutes while stirring. The mixture is stirred for a further 15 minutes, the oily product is separated, the residue is digested with water, dried and distilled in a high vacuum. 0- (l-lso-propoxycarbonyl-l-propen-2-yl) -N-eth l-phosphoramido - chlorido-thionate has a boiling point of 89°/5 · 10"- mm of Hg. It has a refractive index of n^° = l. lOO.
Analysis: C0H,„C1NQ,PS Molecular weight: 285.7 Found C 37.7 % H 5-9 CI 12.7 % Calculated 37.8 % 6.0 12Λ N 5.I P 10.8 % S 11.2 % .9 10.85 11.2 The compounds of general formula I indicated in the Table are obtained in a manner analogous to that described in Examples 1 to 6. In Examples 8 to 17 the symbol Z signifies a chlorine atom.
Claims (5)
1. What we claim is:- 1. A process for the production of a compound of the formula I, z Y p wherein is hydrogen or lower alkyl of 1 to 3 carbon atoms, and are lower alkyl of 1 to 5 carbon atoms, X is hydrogen or chlorine, Y is oxygen or sulphur, and Z is chlorine which comprises a) reacting a phosphoric acid halide of formula II, . - 15 - 150-3063 wherein R Xj Y and Z have the above signif cance, with an equivalent amount of an amine of formula III, R1R2NH III wherein R^ and R≥ have the above significance, in the presence of an acid acceptor, or b) reacting a compound of formula IV, Y II IV -N— P-Z I I R1 Z wherein R , R , Y and Z have the above significance, with a compound of formula V, wherein R^ and X have the above significance, in the presence of an acid acceptor.
2. A process according to Claim l,in which the acid acceptor is selected from triethylamine, trimethylamine, dimethyl aniline, diethyl aniline and sodium carbonate.
3. A process according to Claim l,in which the acid acceptor comprises a second equivalent of the amine of formula III. 16 130-3063 k. A process according to Claim 1, in which phosphorus oxychloride, phosphorus axybromlde,. phosphorus thiochloride o-r phocphorao thiobrom-ide- is reacted with a compound of formula V, stated in Claim 1, in the presence of an acid acceptor, and in which the resulting compound of formula II is reacted without isolation with the compound of formula III, in the presence of an acid acceptor. 5· A process according to Claim 3* i-n which the amine of formula III is in aqueous solution and in which this solution is added to a solution of the compound of formula II. 6. A process for the production of a compound of . formula I, stated in Claim 1, substantially as herein described, with reference to the Examples. 7. A compound of formula I, stated in Claim 1, whenever produced by the process of any one of the preceding Claims. 8. A compound of formula I, stated in Claim 1. 9. 0-(l-methoxycarbonyl-l-propen-2-yl)-N-methyl- phosphoramido-chloridate. 10. 0-(l-methoxycarbonyl-l-propen-2-yl)-N,N- diethyl-phosphoramido-chloridate. 11. 0-(l-methoxycarbonyl-l-propen-2-yl)-N,N- diethyl-phosphoramido-chlorido-thionate. 12. 0-(l-methoxycarbonyl-l-chloro-l-propen-2-yl)-N-n-propyl-phosphoramido-chlorido-thionate. .13. 0-(l-ethoxycarbonyl-l-propen-2-yl)-N-n-propyl-phosphoramido-chlorido-thionate. . l
4. 0-(l-isopropoxycarbonyl-l-propen-2-yl)-N-ethyl-phosphoramido-chlorido-thionate. 16. The compound of formula I, stated in Claim' 1, wherein R^ is hydrogen,R2 is i-propyl, R is methyl, X is hydrogen, and Y is oxygen. 17· The compound of formula I, stated in Claim 1, wherein R, is hydrogen, R. is n-propyl, R, is ethyl, X is hydrogen, 1 2
5 . and Y is oxygen. 18. The compound of formula I, stated in Claim 1, wherein R_^ is hydrogen, R2 is n-propyl, R^ is i-propyl, X is hydrogen, and Y is oxygen. 19. The compound of formula I, stated in Claim' 1, wherein R is methyl, R is methyl, is methyl, X is hydrogen, and Y is oxygen. 20. The compound of formula I, stated in Claim 1, wherein R. is ethyl, R. is ethyl, R_ is ethyl, X is hydrogen, 1 d 5 and Y is oxygen. 21. The compound of formula I, stated in Claim 1, wherein R, is hydrogen, R„ is ethyl, R_ is n-propyl, X is chlorine, 1 2 5 and Y is oxygen. 22. The compound of formula I, stated in Claim 1, wherein is hydrogen, Ji^ is ethyl, ^ is i-propyl, X is chlorine, and Y is oxygen. 25. The compound of formula I, stated in Claim 1, wherein ^ is hydrogen, Rg is n-propyl, ^ is n-propyl, X is chlorine, and Y is oxygen. 24. The compound of formula I, stated in Claim 1, wherein R is hydrogen, R is n-propyl, R, is ethyl, X is chlorine, 1 d 5 and Y is sulphur.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR6914008A FR2061819A5 (en) | 1969-05-02 | 1969-05-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL34419A0 IL34419A0 (en) | 1970-06-17 |
| IL34419A true IL34419A (en) | 1973-03-30 |
Family
ID=9033392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL34419A IL34419A (en) | 1969-05-02 | 1970-04-30 | Methods and devices for the trituration of mixtures |
Country Status (18)
| Country | Link |
|---|---|
| US (1) | US3809225A (en) |
| JP (1) | JPS5520954B1 (en) |
| BE (1) | BE749651R (en) |
| CA (1) | CA957983A (en) |
| DE (1) | DE2021356C3 (en) |
| DK (1) | DK125731B (en) |
| EG (1) | EG10541A (en) |
| FR (1) | FR2061819A5 (en) |
| GB (1) | GB1261675A (en) |
| IL (1) | IL34419A (en) |
| IT (1) | IT943118B (en) |
| LU (1) | LU60836A1 (en) |
| NL (1) | NL7005912A (en) |
| NO (1) | NO129786B (en) |
| OA (1) | OA03262A (en) |
| SE (1) | SE346908B (en) |
| TR (1) | TR18436A (en) |
| ZA (1) | ZA702957B (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3951387A (en) * | 1975-04-25 | 1976-04-20 | Grace Development Company | Cartridge for storing and mixing at least two independent ingredients |
| IT1085783B (en) * | 1976-05-05 | 1985-05-28 | Cheetham J J | CONTAINER |
| IL52695A (en) * | 1977-08-10 | 1979-11-30 | Silmet Ltd | Mixing capsule |
| SE444639B (en) * | 1978-08-02 | 1986-04-28 | Johnson & Johnson | SINGLE CAPS FOR DENTALAMALGAM |
| DE3025526A1 (en) * | 1980-07-05 | 1982-01-28 | Ernst Mühlbauer KG, 2000 Hamburg | MULTI-COMPONENT CAPSULE FOR STORING AND VIBRATING MIXING OF AT LEAST TWO COMPONENTS, IN PARTICULAR. FOR DENTAL PURPOSES |
| US4657534A (en) * | 1985-11-04 | 1987-04-14 | Alcon Laboratories, Inc. | Dual compartment, disposable, mixing and dispensing container |
| US5394980A (en) * | 1987-06-30 | 1995-03-07 | Tsai; Min H. | Multicompartment mixing capsule |
| GB8726062D0 (en) * | 1987-11-06 | 1987-12-09 | Plaspharm Uk Ltd | Fluid dispensing devices |
| US5114411A (en) * | 1990-11-19 | 1992-05-19 | Habley Medical Technology Corporation | Multi-chamber vial |
| JPH05212090A (en) * | 1992-02-04 | 1993-08-24 | Material Eng Tech Lab Inc | Transfusion container |
| US5330048A (en) * | 1993-07-09 | 1994-07-19 | Habley Medical Technology Corporation | Controlled access mixing vial |
| US6090092A (en) * | 1997-12-04 | 2000-07-18 | Baxter International Inc. | Sliding reconstitution device with seal |
| AR021220A1 (en) | 1998-09-15 | 2002-07-03 | Baxter Int | CONNECTION DEVICE FOR ESTABLISHING A FLUID COMMUNICATION BETWEEN A FIRST CONTAINER AND A SECOND CONTAINER. |
| US6022339A (en) | 1998-09-15 | 2000-02-08 | Baxter International Inc. | Sliding reconstitution device for a diluent container |
| US7074216B2 (en) | 1998-09-15 | 2006-07-11 | Baxter International Inc. | Sliding reconstitution device for a diluent container |
| US20050137566A1 (en) | 2003-12-23 | 2005-06-23 | Fowles Thomas A. | Sliding reconstitution device for a diluent container |
| US7358505B2 (en) | 1998-09-15 | 2008-04-15 | Baxter International Inc. | Apparatus for fabricating a reconstitution assembly |
| US6372816B1 (en) | 1999-06-25 | 2002-04-16 | Dentsply Detrey Gmbh | Dental materials packaging and method of use |
| US6360886B1 (en) | 2000-03-13 | 2002-03-26 | Kerr Corporation | Capsule for use in preparing a dental amalgam |
| US20050255425A1 (en) * | 2000-09-21 | 2005-11-17 | Pierson Paul R | Mixing tip for dental materials |
| US7641851B2 (en) | 2003-12-23 | 2010-01-05 | Baxter International Inc. | Method and apparatus for validation of sterilization process |
| US8104609B2 (en) * | 2007-03-08 | 2012-01-31 | Tokuyama Dental Corporation | Container |
| US20130015188A1 (en) * | 2011-07-13 | 2013-01-17 | Joshua James Cheetham | Liquid container |
| DE102013201297A1 (en) * | 2013-01-28 | 2014-07-31 | Robert Bosch Gmbh | A fluid storage unit and method of making a fluid storage unit |
| US11925748B1 (en) * | 2023-06-08 | 2024-03-12 | Microneb Tech Holdings, Inc. | Apparatus, methods, and systems for administering a medication to a patient from a capsule using an atomizer |
| US11944742B1 (en) * | 2023-06-08 | 2024-04-02 | Microneb Tech Holdings, Inc. | Apparatus, methods, and systems for administering a medication to an animal |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2717601A (en) * | 1949-08-10 | 1955-09-13 | Frederick M Turnbull | Syringe ampule |
| US2764983A (en) * | 1953-03-20 | 1956-10-02 | Barasch Hans Pius | Dual compartment mixing vial |
| US2869745A (en) * | 1954-02-05 | 1959-01-20 | Compule Corp | Plunger closures of containers |
| US3070094A (en) * | 1959-02-25 | 1962-12-25 | Stanley J Sarnoff | Medicament and diluent storing, mixing, and dispensing device |
| US3198194A (en) * | 1963-05-13 | 1965-08-03 | Upjohn Co | Admixing storage container with means preventing inadvertent removal of closure means |
| US3314563A (en) * | 1963-11-14 | 1967-04-18 | Owens Illinois Inc | Plural-compartment container |
| US3425598A (en) * | 1967-06-14 | 1969-02-04 | Gerald Kobernick | Dispensing container having a membrane puncturing means |
-
1969
- 1969-05-02 FR FR6914008A patent/FR2061819A5/fr not_active Expired
-
1970
- 1970-04-23 OA OA53911A patent/OA03262A/en unknown
- 1970-04-23 IT IT68399/70A patent/IT943118B/en active
- 1970-04-23 NL NL7005912A patent/NL7005912A/xx unknown
- 1970-04-28 BE BE749651D patent/BE749651R/en active
- 1970-04-28 GB GB20331/70A patent/GB1261675A/en not_active Expired
- 1970-04-28 SE SE05898/70A patent/SE346908B/xx unknown
- 1970-04-29 DK DK215670AA patent/DK125731B/en not_active IP Right Cessation
- 1970-04-29 NO NO01640/70A patent/NO129786B/no unknown
- 1970-04-30 IL IL34419A patent/IL34419A/en unknown
- 1970-04-30 LU LU60836D patent/LU60836A1/xx unknown
- 1970-04-30 DE DE2021356A patent/DE2021356C3/en not_active Expired
- 1970-05-01 US US00033780A patent/US3809225A/en not_active Expired - Lifetime
- 1970-05-01 CA CA081,690A patent/CA957983A/en not_active Expired
- 1970-05-01 ZA ZA702957A patent/ZA702957B/en unknown
- 1970-05-02 JP JP3722170A patent/JPS5520954B1/ja active Pending
- 1970-05-04 TR TR18436A patent/TR18436A/en unknown
-
1974
- 1974-09-15 EG EG394/74A patent/EG10541A/en active
Also Published As
| Publication number | Publication date |
|---|---|
| US3809225A (en) | 1974-05-07 |
| NL7005912A (en) | 1970-11-04 |
| IT943118B (en) | 1973-04-02 |
| EG10541A (en) | 1976-03-31 |
| OA03262A (en) | 1970-12-15 |
| JPS5520954B1 (en) | 1980-06-06 |
| FR2061819A5 (en) | 1971-06-25 |
| CA957983A (en) | 1974-11-19 |
| TR18436A (en) | 1977-02-16 |
| SE346908B (en) | 1972-07-24 |
| DK125731B (en) | 1973-04-30 |
| DE2021356A1 (en) | 1970-11-12 |
| GB1261675A (en) | 1972-01-26 |
| NO129786B (en) | 1974-05-27 |
| DE2021356B2 (en) | 1979-09-20 |
| IL34419A0 (en) | 1970-06-17 |
| ZA702957B (en) | 1971-04-28 |
| BE749651R (en) | 1970-10-28 |
| LU60836A1 (en) | 1970-07-01 |
| DE2021356C3 (en) | 1980-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| IL34419A (en) | Methods and devices for the trituration of mixtures | |
| US3825636A (en) | O-ethyl s-propyl-dithiophosphoric acid phenyl or naphthyl esters | |
| US2759937A (en) | Dialkyl pyridazinonyl phosphate esters and process of making same | |
| PL84208B1 (en) | ||
| US3652742A (en) | 2 2-dichloro-vinylphosphoric acid ester amides | |
| US2891984A (en) | New dithiophosphoric acid esters and their use for the control of mites | |
| US2552541A (en) | O-(halophenyl) o-alkyl amidothiophosphates | |
| US2552538A (en) | Diamidothiophosphates | |
| US2875233A (en) | Method for the preparation of o-aryl phosphoroamidothioates | |
| US2807637A (en) | Omicron-aryl omicron, omicron-dialkyl phosphorothioates | |
| CA1076585A (en) | Phosphoric acid derivatives | |
| US2867618A (en) | 3, 4-dihydro-2h-1, 3-benzoxazine | |
| CA1076576A (en) | 0-(1-fluoro-2-halo-ethyl) (thiono) phosphoric(phosphonic)acid ester-amides,processes for their preparation and their use as insecticides, acaricides and nematocides | |
| US3156718A (en) | Process for preparing thiophosphoric, thiophosphonic, and thiophosphinic acid esters | |
| US2954394A (en) | O-aryl o-alkyl o-hydrogen phosphorothioates and their salts | |
| CA1091686A (en) | Thiophosphorylguanidines for combating pests | |
| US3030404A (en) | Thiophosphoric acid esters and process for producing them | |
| US2852514A (en) | Thiophosphoric acid esters and their production | |
| US3763285A (en) | 1-phenyl-2-cyanovinyl(thio)-phosphoric or-phosphonic acid esters | |
| US2855426A (en) | O-(cyclohexylphenyl) phosphoroamidothioates | |
| US3365361A (en) | Plant root-knot gall nematode control with 5-carbamoyloxyimino-1, 3-dithianes | |
| US2891085A (en) | Process for production of | |
| US3649719A (en) | Phosphoric acid ester amidohalides | |
| US2870191A (en) | Thiophosphoric acid esters and process for their manufacture | |
| US3600444A (en) | Hydroxyarylthio compounds and process of preparation |