IL103532A - Preparation of derivatives of 6-trifluoromethyl-1,3, 5-triazine - Google Patents
Preparation of derivatives of 6-trifluoromethyl-1,3, 5-triazineInfo
- Publication number
- IL103532A IL103532A IL10353292A IL10353292A IL103532A IL 103532 A IL103532 A IL 103532A IL 10353292 A IL10353292 A IL 10353292A IL 10353292 A IL10353292 A IL 10353292A IL 103532 A IL103532 A IL 103532A
- Authority
- IL
- Israel
- Prior art keywords
- trifluoromethyl
- triazine
- organic radical
- formula
- vii
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Preparation of 6-trifluoromethyl-1,3,5-triazines I <IMAGE> (R<1> = H, R<1>, R<2> = C-organic radicals> by reacting salts of an N-amidino-S-alkylisothiourea II <IMAGE> (R<3> = C1-C10> with trifluoroacetic acid derivatives III and a strong base IV to give 6-trifluoromethyl-1,3,5-triazines V <IMAGE> and reacting the products V with alcohols VII R<2>-OH VII in the presence of a base. The triazines I are valuable intermediates for crop protection agents.
Description
Preparation od derivatives of 6-trifluoromethyl- 1 ,3,5-triazine BASF Aktiengeseilschaft C. 87767 O.Z. 0050/42858 Preparation of derivatives of 6-trifluoromethyl-1 , 3 , 5-triazine The present invention relates to a novel process for the preparation of derivatives of 6-trifluoromethyl-1,3, 5-triazine of the general formula I where R1 is hydrogen or a C-organic radical and R2 is a (inorganic radical .
The present invention furthermore relates to a novel process for the preparation of derivatives of 6-trifluoromethyl-1, 3, 5-triazine of the general formula V where R1 is hydrogen or a C-organic radical and R3 is a C-organic radical of 1 to 10 carbon atoms, which are used as intermediates for the preparation of I.
DE-A 16 70 147 relates to the reaction of N-amidino-S-alkylisothiuronium salts with carboxylic acid acyl equivalents to give 1,3,5-triazines. However, the high yields of 80-100% achieved thereby are obtained only in cyclization reactions with aromatic, nonpolar carbonyl chlorides. The synthesis of 2-amino-4-methylthio-6-trichloromethyl-1, 3, 5-triazine from the aliphatic, polar t r ichloroacety 1 chloride and N-amidino-S-methylisothiourea, on the other hand, takes place in the presence of triethylamine with a yield of only 60%. 6-Trichloromethyl-substituted 1,3, 5-triazines which carry amino in the 2-position and a thio - 2 - O.Z. 0050/42858 substxtuent in the 4-position are furthermore obtainable according to JP-A 48.038715 in a two-stage reaction. Here, 2-methylthio-4 , 6-bis- ( trichloromethyl ) -1 , 3 , 5-triazine is first prepared and is then reacted with a corresponding amine with liberation of chloroform to give the end product . 2-Alkoxy-4-amino-6-trif luoromethy 1- 1 ,3,5-triazines are obtainable by a process disclosed in Yakugaku Zasshi 95 (1975), 499. Here, N-cyanoguanidine is converted into a bis- (N-amidino-O-alkylisourea) -copper chelate complex, from which the ligand is liberated by treatment with hydrogen sulfide and is then cyclized with a trifluoroacetate to give the end product.
R, R' = Organic radicals Stoichiometric amounts of Cu salts are required for this process; in the absence of Cu salts, mainly guanylurea is formed instead of the N-amidino-O-alkylisourea (Kyushu Kogyo Daigaku Kenkyu Hokoku No. 12 (1962), 69-78).
A major disadvantage of this process is that large amounts of copper salts have to be separated off as byproducts and disposed of, making a procedure on an industrial scale appear unprofitable.
Zh. Obshch. Khim. 37 (1967), 2247-2251 describes nucleophilic substitution in 1,3,5-triazines, where an electronegative substxtuent can be substituted by a less - 3 - O.Z. 0050/42858 electronegative one. However, no information is given concerning the behavior of 6-trifluoromethyl-l , 3 , 5-triazines .
It is an object of the present invention to provide derivatives of 6-trifluoromethyl-l , 3 , 5-triazine in a more advantageous manner.
We have found that this object is achieved by a process for the preparation of derivatives of 6-tri-fluoromethyl-l, 3, 5-triazine of the general formula I where R1 is hydrogen or a C-organic radical and R2 is a C-organic radical, wherein a salt of an N-amidino-S-alkyl-isothiourea of the general formula II where R3 is a C-organic radical of 1 to 10 carbon atoms, is reacted with a halide, ester or anhydride of tri-fluoroacetic acid (compound III) and with a strong base (IV) to give a derivative of 6-trifluoromethyl-l , 3 , 5-triazine of the general formula V 3 ^ H ^^ N and the latter is converted in the presence of a base (VI) with an alcohol of the general formula VII R2-0H VII into the compound I . - 4 O.Z. 0050/42858 The salts of the N-amidino-S-alkylisothioureas II which are used as starting materials are known (Chem. Ber. 100 (1967), 1874) or can be prepared from known substances with the aid of the processes described there.
Salts of the N-amidino-S-alkylisothioureas are understood as meaning the reaction products of the compounds II with acids. The type of acid is unimportant for the novel process since the compounds II are liberated from their salts with the aid of a base in the course of the reaction. The compounds II or their salts are advantageously prepared or stored as adducts of N-methyl-2-pyrrolidone .
On the basis of observations to date, the success of the novel process is not evidently dependent on the nature of the substituents R1, R2 and R3.
In view of the use of the compounds I as intermediates for the synthesis of active ingredients, R1 preferably has the following meanings: hydrogen; aliphatic radicals of 1 to 6 carbon atoms, such as C^-Cg-alkyl, including in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, or cyclo-alkyl having up to 7 carbon atoms, such as cyclopropyl, cyclopentyl or cyclohexyl; aromatic radicals, such as phenyl.
R2 and R3 preferably have the following meanings: C^-C^-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl; C3- or C4-alkenyl, such as prop-2-en-l-yl, 1-methylprop- 2-en-l-yl, but-2-en-l-yl or but-3-en-l-yl; C3- or C-alkynyl, such as prop-2-yn-l-yl or but-2-yn-l-yi; C3-C6-cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, preferably cyclopentyl or cyclohexyl .
R3 is preferably one of the radicals stated for R2 or in particular benzyl which is unsubstituted or - 5 - O.Z. 0050/42858 substituted in the nucleus by methyl, chlorine, bromine or methoxy.
The stated radicals R1, R2 and R3 may also carry substituents which are inert under the reaction conditions .
Suitable compounds III are mainly trifluoroacetic anhydride, halides of trifluoroacetic acid and the esters of trifluoroacetic acid, the methyl and the ethyl esters being very particularly preferred.
For the preparation of the 4-thioalkyl-6-tri-fluoromethyl-1, 3 , 5-triazines V from II and III, it is advisable to use at least an equimolar amount of compound III; amounts of from 100 to 500, in particular from 100 to 250, mol %, based on II, of trifluoroacetic acid derivative III are preferred, unless III is also used as a solvent.
Suitable bases IV are inorganic and organic bases. The strength of the base used should be sufficiently great to enable it to liberate the N-amidino-S-alkylisothiourea II from its salt.
Preferred inorganic bases are alkali metal and alkaline earth metal hydroxides, and preferred organic bases are amines and alkali metal alcoholates.
The amount of base is usually from 110 to 300 mol % of the amount of the salt of N-amidino-S-alkylisothio-urea II used. Larger amounts are possible but as a rule have no further advantages. In carrying out the reaction with a trifluoroacetate, 2-3 equivalents, based on the salt of II, of base are particularly preferred.
Advantageously, the salt of II and the compound III are initially taken and the base is metered in.
An inert solvent or diluent is preferably used in the reaction of II with III.
Examples of suitable solvents are aliphatic or aromatic hydrocarbons, which may also be substituted by halogen or nitro, cyclic or open-chain ethers, aliphatic alcohols or lower aliphatic ketones. Acid derivatives of - 6 - O.Z. 0050/42858 lower carboxylic acids, such as acetates, formamides or nitriles, are also suitable solvents.
If the reaction of II is carried out with tri-fluoroacetic anhydride or trifluoroacetyl chloride, ethyl acetate, diethyl ether and tert-butyl methyl ether are particularly preferred solvents.
When the reaction is carried out with a tri-fluoroacetate, methanol, tetrahydrofuran, tert-butyl methyl ether or the trifluoroacetate itself is par-ticularly preferably used as the solvent.
The amount of solvent is not critical. Usually, the solvent is used in an amount which is from 1 to 5 times the amount of the N-amidino-S-alkylisothiourea II.
Particular conditions with regard to the pressure are not required and the reaction is generally carried out at atmospheric pressure.
The reaction is advantageously effected at from -40eC to the boiling point of the solvent, preferably from -20°C to 120eC, in particular from -10°C to 100°C.
It may be carried out either continuously or batchwise. In the continuous procedure, the reactants are preferably passed through a tube reactor.
The reaction mixture is generally worked up by removing the low boiling components under reduced pres-sure, neutralizing acid radicals and dissolving away the inorganic components while stirring the crude product with water.
The substitution of the thioalkyl group of the 6-trifluoromethyl-l,3,5-triazine V by an alkoxy group is advantageously carried out in an excess of the alcohol VII.
Suitable bases VI are inorganic and organic bases. Preferred inorganic bases are hydroxides and carbonates of alkali metal, alkaline earth metal or aluminum ions, and preferred organic bases are amines and alkali metal alcoholates.
The alkali metal alcoholates of the particular - 7 - O.Z. 0050/42858 alcohol VII are particularly preferably used.
The amount of base VI is in general from 1 to 200 mol %, based on the amount of 6-trifluoromethyl-1, 3, 5-triazine V. From 50 to 150 mol % of base are preferably used in the case of C:- and C2-alcohols VII, and over 50 mol % in the case of compounds VII having 3 or more carbon atoms .
The amount of solvent is not critical. Usually, the solvent is used in an amount which is from 5 to 10 times that of 6-trifluoromethyl-1 , 3 , 5-triazine V, an excess of alcohol VII preferably being used as a solvent.
For complete conversion, the amount of alcohol of the formula VII must be at least equimolar relative to the amount of 6-trifluoromethyl-1, 3, 5-triazine V used. If no additional solvents are used, from 4 to 5 mol of the alcohol V per mol of 6-trifluoromethyl-1 , 3 , 5-triazine V are preferably employed.
The reaction of V with VII is carried out, as a rule, at from -40°C to the boiling point of the particular solvent, preferably from -30°C to 150°C, in particular from -10 to 80°C, particularly preferably from 0 to 50°C.
The reaction mixture is worked up in a conventional manner, as a rule by removing the low boiling components under reduced pressure after neutralization.
The reaction of V with VII can be carried out both continuously and batchwise. In the continuous procedure, the reactants are passed, for example, over a fixed bed of an insoluble base, or the reaction is carried out in a solution saturated with the product I, with continuous removal of freshly formed product.
In a variant of the novel process, the product V in the reaction of II with III is reacted, without isolation from the reaction mixture, simultaneously with VI and VII, and acidic byproducts from the first reaction can be neutralized by a relatively high concentration of base VI. The procedure can be modified so that, after - 8 - O.Z. 0050/42858 carrying out the reaction of II with III, the low boiling components are removed and the resulting crude product is reacted with VI and VII, if desired in another solvent.
The novel process (reaction of V with VII) can be successfully used for the synthesis of all 6-trifluoro-methyl-l,3,5-triazines I according to the definition, especially the compounds contained in Table 1. The 6-trifluoromethyl-1 , 3 , 5-triazines I are useful intermediates for crop protection agents, as disclosed in, for example, EP-A 111 442 or DE-A 39 09 146. - 9 - O.Z. 0050/42858 TABLE 1 NH-R1 R1 R2 H CH3 H C2H5 H n-C3H7 H i-C3H7 H n—C4H9 H i-C4H9 H s—C4H9 H t~C4H9 H CH2CH=CH2 H E-CH2CH=CHCH3 H CH2CeCH H CH2CaCCH3 H Cyclopropyl H Cyclobutyl H Cyclopentyl H Cyclohexyl CH3 CH3 CH3 C2Hs CH3 n-C3H CH3 i-C3H7 CH3 n—C4H9 CH3 i-C4H9 CH3 S—C4H9 CH3 t—C4H9 CH3 CH2CH=CH2 CH3 E-CH2CH=CHCH3 CH3 CH2CaCH CH3 CH2CaCCH3 CH3 Cyclopropyl - 10 - O.Z. 0050/42858 - 11 - O.Z. 0050/42858 The novel process (reaction of II with III) can be successfully used for the synthesis of all 6-tri- fluoromethyl-1 , 3 , 5-triazines V according to the definition, especially the compounds stated in Table 2.
TABLE 2 CF, N ^J^ N R°-S N NH-R R1 R3 H CH3 H C2H5 H n-C3H7 H i-C3H7 H n—C H9 H i-C4H9 H S-C4H9 H t—C4H9 H CH2CH=CH2 H E-CH2CH=CHCH3 H CH2CeCH H CH2C"CCH3 H Cyclopropyl H Cyclobutyl H Cyclopentyl H Cyclohexyl CH3 CH3 CH3 C2H5 CH3 n-C3H7 CH3 i-C3H7 CH3 n-C4H9 CH3 i—C4H9 CH3 S-C4H9 CH3 t—C4H9 CH3 CH2CH=»CH2 - 12 - O.Z. 0050/42858 - 13 - O.Z. 0050/42858 Preparation of 2-amino-4-methylthio-6-trifluoromethyl- 1, 3,5-triazine (V: R1 « H, R3 - CH3) 90.0 g (0.5 mol) of a 30% strength by weight solution of sodium methylate in methanol were added dropwise at 0°C to a suspension of 90.0 g (0.25 mol) of N-amidino-S-methylisothiuronium iodide (adduct of N- methyl-2-pyrrolidone) in 128.0 g (1.0 mol) of methyl trifluoroacetate, after which a homogeneous, slightly yellow solution was formed. The reaction mixture was then stirred for 5 hours at 25 °C.
The volatile components were removed under reduced pressure at 40°C, the residue was stirred vigorously with 200 ml of water and the solid formed was filtered off under suction and dried under reduced pressure at 50°C.
The title compound was obtained as colorless crystals (mp. 181-183eC) in a yield of 94%.
EXAMPLE 2 Preparation of 2-amino-4-methylthio-6-trifluoromethyl- 1, 3,5-triazine (V: R1 - H, R3 - CH3) 104.4 g (0.58 mol) of a 30% strength by weight solution of sodium methylate in methanol were added dropwise at 0eC to a suspension of 90.0 g (0.29 mol) of N-amidino-S-methylisothiuronium iodide (adduct of N- methyl-2-pyrrolidone) in 128.0 g (1.0 mol) of methyl trifluoroacetate, after which a homogeneous, slightly - 14 - O.Z. 0050/42858 yellow solution was formed. The reaction mixture was then stirred for 5 hours at 25 °C. The volatile components were removed under reduced pressure at 40°C, the residue was stirred vigorously with 200 ml of water and the solid formed was filtered off under suction and dried under reduced pressure at 50°C.
The title compound, which still contained about 5% by weight of N-methyl-2-pyrrolidone, was obtained in a yield of 90%.
EXAMPLE 3 Preparation of 2-amino-4-methylthio-6-trifluoromethyl-1,3,5-triazine (V: R1 - H, R3 = CH3) 23.4 g (112.2 mmol) of trifluoroacetic anhydride were added dropwise at 5-15°C to a suspension of 20.0 g (55.6 mmol) of N-amidino-S-methylisothiuronium iodide (adduct of N-methyl-2-pyrrolidone) in 100 ml of ethyl acetate and 6.2 g (61.4 mmol) of triethylamine . Stirring was carried out for 15 hours at 25 °C, the mixture was diluted with 300 ml of methylene chloride and washed with 2 x 100 ml of water, the phases were separated and the organic phase was dried over Na2S04. The volatile components were removed under reduced pressure at 40°C, and the oily, pale orange residue was stirred vigorously with 200 ml of water, after which crystallization occurred. The solid formed was filtered off under suction and dried under reduced pressure at 50 °C.
The title compound was obtained in a yield of 80%.
EXAMPLE 4 Preparation of 2-amino-4-methylthio-6-trifluoromethyl-1,3,5-triazine (V: R1 ■ H, R3 « CH3) 31.5 g (0.25 mol) of dimethyl sulfate were added dropwise at 30°C to a suspension of 54.0 g (0.25 mol) of N-amidinothiourea (adduct of N-methyl-2-pyrrolidqne) in 250 ml of methanol. The rapidly forming homogeneous solution was stirred for 3 hours at 30 eC. After the addition of 32.0 g (0.25 mol) of methyl trifluoroacetate - 15 - O.Z. 0050/42858 at 25 °C, 54.0 g (0.30 mol) of a 30% strength by weight solution of sodium methylate in methanol were added dropwise at 0"C and stirring was carried out for 18 hours at 20-25 °C. Neutralization was effected by adding 4 N HC1, the volatile components were removed under reduced pressure at 40eC and the residue was stirred vigorously with 200 ml of water. The product was filtered off under suction, washed with 200 ml of water and dried under reduced pressure at 40°C.
The title compound was obtained in a yield of 75%, contaminated with about 5% of the secondary product 2-amino-4-methoxy-6-trifluoromethyl-l , 3 , 5-triazine .
EXAMPLE 5 Preparation of 2-amino-4-methoxy-6-trifluoromethyl-l , 3 , 5-triazine (I: R1 - H, R2 = CH3) 40.2 g (0.22 mol) of a 30% strength by weight solution of sodium methylate in methanol were added dropwise at 0°C to a solution of 46.9 g (0.22 mol) of 2-amino-4-methylthio-6-trifluoromethyl-l , 3 , 5-triazine and 400 ml of methanol. Stirring was carried out for 2 hours at 0°C and for 65 hours at 25 °C. Neutralization was effected by adding 4 N HC1, the volatile components were removed under reduced pressure at 30°C and the residue was stirred vigorously with 100 ml of water. The product was filtered off under suction and dried under reduced pressure at 40°C.
The title compound was obtained as colorless crystals (mp. 163°C) in a yield of 85%.
Claims (3)
1. 03532/2 - 16 - O.Z. 0050/42858 We claim: - 1. A process for the preparation of derivatives of 6-trifluoromethyl-1 , 3 , 5-triazine of the formula I where R1 is hydrogen or a C-organic radical and R2 is a C- organic radical, wherein a salt of an N-amidino-S-alkyl- isothiourea of the formula II where R3 is a C-organic radical of 1 to 10 carbon atoms, is reacted with a halide, ester or anhydride of tri- fluoroacetic acid (compound III) and with a strong base (IV) to give a derivative of 6-trifluoromethyl-1 , 3 , 5-triazine of the formula V 3 ^ HN N and the latter is converted in the presence of a base (VI) with an alcohol of the formula VII R2-OH VII into the compound I .
2. A process accordi ng to cl aim 1 for the preparati on of deri vati ves of 6-tri fl uoromethyl -1 , 3 , 5-triazi ne of the formul a V CF3 N N R1^ HN *N I s" 103532/2 - 17 - O.Z. 0050/42858 where R1 is hydrogen or a C-organic radical and R3 is a C- organic radical of 1 to 10 carbon atoms, wherein a salt of an N-amidino-S-alkylisothiourea of the formula II is reacted with a halide,. ester or anhydride of tri- fluoroacetic acid (compound III) and with a strong base (IV) .
3. A process according to claim 1 for the preparation of derivatives of 6-trif1uoromethyl-l,3,5-triazine of the formula I 'where R1 is hydrogen or a C-organic radical and R2 is a C-organic radical, wherein a compound of the formula V CF3 N -j^- N where R3 is a C-organic radical of 1 to 10 carbon atoms, is converted in the presence of a base (VI) with an alcohol of the formula VII R2-0H VII into the compound I. For thft iiijjii ants REINHQQ) COHNVAND PARTNERS
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4139624A DE4139624A1 (en) | 1991-11-30 | 1991-11-30 | PROCESS FOR THE PREPARATION OF DERIVATIVES OF 6-TRIFLUOROMETHYL-1,3,5-TRIAZINE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL103532A0 IL103532A0 (en) | 1993-03-15 |
| IL103532A true IL103532A (en) | 1996-10-31 |
Family
ID=6446037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL10353292A IL103532A (en) | 1991-11-30 | 1992-10-23 | Preparation of derivatives of 6-trifluoromethyl-1,3, 5-triazine |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0545149B1 (en) |
| JP (1) | JP3192783B2 (en) |
| KR (1) | KR100255570B1 (en) |
| AT (1) | ATE111088T1 (en) |
| CA (1) | CA2081413C (en) |
| DE (2) | DE4139624A1 (en) |
| ES (1) | ES2060443T3 (en) |
| HU (1) | HU212346B (en) |
| IL (1) | IL103532A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19830902A1 (en) | 1998-07-10 | 2000-01-13 | Hoechst Schering Agrevo Gmbh | Process for the preparation of 2-amino-4-chloro-1,3,5-triazines |
| US8846704B2 (en) | 2007-01-31 | 2014-09-30 | YM Biosciences Austraila Pty Ltd | Thiopyrimidine-based compounds and uses thereof |
| JP6441334B2 (en) | 2013-07-16 | 2018-12-19 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Herbicidal azine |
| EP3126348B1 (en) | 2014-04-03 | 2017-11-29 | Basf Se | Diaminotriazine compound useful as herbicide |
| EP2930174A1 (en) | 2014-04-07 | 2015-10-14 | Basf Se | Diaminotriazine derivatives as herbicides |
| WO2015155272A1 (en) | 2014-04-11 | 2015-10-15 | Basf Se | Diaminotriazine derivatives as herbicides |
| BR112016023556B1 (en) | 2014-04-11 | 2021-05-25 | Basf Se | diaminotriazine compound, agrochemical composition, method to control unwanted vegetation and use of a compound |
| WO2015162169A1 (en) | 2014-04-23 | 2015-10-29 | Basf Se | Diaminotriazine compounds as herbicides |
| EP3134391A1 (en) | 2014-04-23 | 2017-03-01 | Basf Se | Diaminotriazine compounds and their use as herbicides |
| KR102022323B1 (en) * | 2018-03-30 | 2019-09-18 | 정하윤 | Triazine Compound And Use Thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1670147A1 (en) * | 1966-09-10 | 1970-10-29 | Basf Ag | Process for the preparation of amino-alkyl mercapto-s-triazines |
| DE4034078A1 (en) * | 1990-10-26 | 1992-04-30 | Basf Ag | METHOD FOR PRODUCING 6-TRIFLUORMETHYL-1,3,5-TRIAZINES |
-
1991
- 1991-11-30 DE DE4139624A patent/DE4139624A1/en not_active Withdrawn
-
1992
- 1992-10-23 IL IL10353292A patent/IL103532A/en not_active IP Right Cessation
- 1992-10-26 CA CA002081413A patent/CA2081413C/en not_active Expired - Fee Related
- 1992-11-19 DE DE59200474T patent/DE59200474D1/en not_active Expired - Lifetime
- 1992-11-19 AT AT92119689T patent/ATE111088T1/en not_active IP Right Cessation
- 1992-11-19 EP EP92119689A patent/EP0545149B1/en not_active Expired - Lifetime
- 1992-11-19 ES ES92119689T patent/ES2060443T3/en not_active Expired - Lifetime
- 1992-11-27 HU HU9203764A patent/HU212346B/en not_active IP Right Cessation
- 1992-11-28 KR KR1019920022749A patent/KR100255570B1/en not_active IP Right Cessation
- 1992-11-30 JP JP31988792A patent/JP3192783B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| IL103532A0 (en) | 1993-03-15 |
| DE4139624A1 (en) | 1993-06-03 |
| JPH05262749A (en) | 1993-10-12 |
| HU212346B (en) | 1996-05-28 |
| JP3192783B2 (en) | 2001-07-30 |
| CA2081413C (en) | 2003-02-25 |
| ES2060443T3 (en) | 1994-11-16 |
| HUT62568A (en) | 1993-05-28 |
| ATE111088T1 (en) | 1994-09-15 |
| EP0545149A1 (en) | 1993-06-09 |
| HU9203764D0 (en) | 1993-03-29 |
| CA2081413A1 (en) | 1993-05-31 |
| EP0545149B1 (en) | 1994-09-07 |
| DE59200474D1 (en) | 1994-10-13 |
| KR100255570B1 (en) | 2000-05-01 |
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