EP0000042B1 - Verfahren zur Herstellung von 2,4,5-Trichlorpyrimidin - Google Patents
Verfahren zur Herstellung von 2,4,5-Trichlorpyrimidin Download PDFInfo
- Publication number
- EP0000042B1 EP0000042B1 EP78100071A EP78100071A EP0000042B1 EP 0000042 B1 EP0000042 B1 EP 0000042B1 EP 78100071 A EP78100071 A EP 78100071A EP 78100071 A EP78100071 A EP 78100071A EP 0000042 B1 EP0000042 B1 EP 0000042B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- chlorine
- mol
- trichloropyrimidine
- cyanoethyl
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/30—Halogen atoms or nitro radicals
Definitions
- the present invention relates to a new process for the preparation of 2,4,5-trichloropyrimidine.
- chlorination is carried out at temperatures of from about 20 ° C. to about 40 ° C. until the exothermic reaction has ended and then subsequently reheated to temperatures of 110 to 140 ° C. in the absence of chlorine.
- Sulfur-containing by-products are converted into 2,4,5-trichloropyrimidine, so that the yield can be increased in some cases.
- the chlorine can be used in the chlorination reaction both in the form of elemental chlorine and in the form of customary chlorinating agents, for example sulfur dichloride, sulfuryl chloride, phosphorus pentachloride. Appropriate amounts of chlorinating agent must of course be used, for example instead of 1 mol of CI 2 2 mol of SCI 2 .
- the starting compounds of the formula (I) are not known, they can easily be prepared according to the literature for the preparation of alkyl dialkyldithiocarbamic acid esters (for example J. Chem. Soc. 1944, p. 151) by using the following formula initially reacting cyanoethylated amines (11), in which R has the abovementioned meaning, with carbon disulfide in aqueous sodium hydroxide solution to give the dithiocarbamates of the formula (III), which are subsequently converted into the esters of the formula (I) by alkylation, for example with (substituted) ) Alkyl halides, sulfonic acid alkyl esters or dialkyl sulfates, for example with dimethyl sulfate according to the following formula:
- Diluents which are inert under the reaction conditions are all chlorine resistant solvents e.g. chlorinated aliphatic and aromatic hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, 1,1,2,2-tetrachloroethane, tetrachlorethylene, 1,1,2,3,3-pentachloropropane, hexachlorocyclopentadiene, octachlorocyclopentene, 1,2,4-trichlorobenzene, chlorinated Pyrimidines and phosphorus oxychloride.
- chlorinated aliphatic and aromatic hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1,1,2,2-tetrachloroethane, tetrachlorethylene, 1,1,2,3,3-pentachloropropane, hexachlorocyclopentadiene, octachlorocyclopentene, 1,2,4-trichlor
- the chlorinating agent is a liquid under the reaction conditions, such as sulfur dichloride or sulfuryl chloride, the additional use of an inert diluent can be omitted.
- disulfur dichloride can be used particularly advantageously as a diluent.
- the reaction is initially very exothermic. It is therefore expedient to work with an excess of chlorine, especially in the case of larger batches, until the exothermic reaction has subsided. After the strongly exothermic first chlorination phase has subsided, in order to end the reaction as quickly as possible, advantageously with an excess of chlorine (recognizable by the greenish color of the chlorination offgas).
- the process is carried out in detail in such a way that first a (2-cyanoethyl dithiocarbamic acid ester of the formula (1), in particular the (2-cyanoethyl) methyl dithiocarbamide acid methyl ester, with one of the diluents mentioned, for example chloroform, is added Mixing the room temperature and then adding the chlorinating agent, the external cooling and metering of the chlorinating agent are coordinated so that the initially strongly exothermic reaction does not become too violent and does not exceed 40 ° C.
- Chlorination is preferably carried out at 30-4.0 ° C. until the exothermic reaction has completely subsided.
- 2,4,5-Trichloropyrimidine is suitable as a starting component for the production of reactive dyes (reaction with dyes containing amino groups).
- 2,4,5-trichloropyrimidine can be converted into tetrachloropyrimidine by gas phase chlorination (GB-PS 1 201 228).
- Tetrachloropyrimidine is suitable as a reactive component for the production of reactive dyes (see e.g. Belgian Patent No. 578 933).
- 2,4,5-trichloropyrimidine has fungicidal and sporicidal properties (see US Pat. No. 3,227,612).
- the reaction mixture is then heated with stirring to reflux (137 ° C.) in about 2 hours, a thick precipitate being formed in the range at about 60 ° C., which dissolves again at about 120 ° C.
- the formation of 2,4,5-trichloropyrimidine is complete when a clear solution is present and no more gas evolution is observed. All parts of the reaction mixture which can be distilled up to a bath temperature of 150 ° C./14 torr are then distilled off. According to gas chromatographic analysis, the distillate contains 78 g (corresponding to 85% of theory) of 2,4,5-trichloropyrimidine.
- Example 2 The procedure is analogous to Example 1, including post-chlorination at 150-180 ° C, with the difference that instead of 670 g (6.5 mol) of sulfur dichloride, only 360.5 g (3.5 mol) of sulfur dichloride are introduced. According to gas chromatographic analysis, the distillates contain 51.6 g (corresponding to 56.3% of theory) of 2,4,5-trichloropyrimidine.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19772725888 DE2725888A1 (de) | 1977-06-08 | 1977-06-08 | Verfahren zur herstellung von 2,4,5-trichlorpyrimidin |
DE2725888 | 1977-06-08 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0000042A1 EP0000042A1 (de) | 1978-12-20 |
EP0000042B1 true EP0000042B1 (de) | 1980-08-20 |
Family
ID=6011059
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78100071A Expired EP0000042B1 (de) | 1977-06-08 | 1978-06-01 | Verfahren zur Herstellung von 2,4,5-Trichlorpyrimidin |
Country Status (4)
Country | Link |
---|---|
US (1) | US4171442A (ja) |
EP (1) | EP0000042B1 (ja) |
JP (1) | JPS543079A (ja) |
DE (2) | DE2725888A1 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4299961A (en) * | 1980-01-07 | 1981-11-10 | Pcr, Incorporated | 2,4,5 Trifluoro pyrimidine and process for preparing |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1545314A (fr) * | 1967-06-08 | 1968-11-08 | Bayer Ag | Procédé de préparation de trichloro- et tétrachloropyrimidines |
CH505114A (de) * | 1967-06-08 | 1971-03-31 | Bayer Ag | Verfahren zur Herstellung von 2,4,5-Trichlorpyrimidin und 2,4,5,6-Tetrachlorpyrimidin |
DE2307863A1 (de) * | 1973-02-17 | 1974-08-22 | Bayer Ag | Verfahren zur herstellung von chlorpyrimidinen |
DE2451630A1 (de) * | 1974-10-30 | 1976-05-06 | Bayer Ag | Verfahren zur herstellung von tetrachlorpyrimidin |
-
1977
- 1977-06-08 DE DE19772725888 patent/DE2725888A1/de not_active Withdrawn
-
1978
- 1978-06-01 EP EP78100071A patent/EP0000042B1/de not_active Expired
- 1978-06-01 DE DE7878100071T patent/DE2860223D1/de not_active Expired
- 1978-06-06 US US05/913,119 patent/US4171442A/en not_active Expired - Lifetime
- 1978-06-06 JP JP6734978A patent/JPS543079A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
DE2725888A1 (de) | 1978-12-21 |
US4171442A (en) | 1979-10-16 |
EP0000042A1 (de) | 1978-12-20 |
JPS543079A (en) | 1979-01-11 |
DE2860223D1 (en) | 1980-12-04 |
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