EP0000042B1 - Procédé de préparation de 2,4,5-trichloropyrimidine - Google Patents

Procédé de préparation de 2,4,5-trichloropyrimidine Download PDF

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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
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EP
European Patent Office
Prior art keywords
chlorine
mol
trichloropyrimidine
cyanoethyl
reaction
Prior art date
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Expired
Application number
EP78100071A
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German (de)
English (en)
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EP0000042A1 (fr
Inventor
Gunther Dr. Beck
Helmut Dr. Heitzer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
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Bayer AG
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Publication date
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Publication of EP0000042A1 publication Critical patent/EP0000042A1/fr
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    • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Claims (3)

1. Procédé de production de 2,4,5-trichloropyrimidine, caractérisé en ce qu'on fait réagir des composé de formule:
Figure imgb0007
dans laquelle
R et R' représentent un groupe alkyle en C1 à C4, à des températures de 0 à 50°C avec moins de 7,5 moles de chlore, notamment 3,5 à 7,0 moles de chlore, par rapport à une mole de composé de départ, et on chauffe ensuite en l'absence de chlore à des températures de 100 à 150°C, notamment de 110 à 140°C.
2. Procédé suivant la revendication 1, caractérisé en ce qu'on effectue la chloration à des températures d'environ 30°C à environ 40°C jusqu'à ce que la réaction exothermique soit terminée, et on chauffe ensuite à des températures de 110 à 140°C en l'absence de chlore.
3. Procédé suivant la revendication 1, caractérisé en ce que, après le chauffage à 100-150°C en l'absence de chlore, on effectue une chloration subséquente à 150-200°C avec du chlore élémentaire.
EP78100071A 1977-06-08 1978-06-01 Procédé de préparation de 2,4,5-trichloropyrimidine Expired EP0000042B1 (fr)

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 (fr) 1978-12-20
EP0000042B1 true EP0000042B1 (fr) 1980-08-20

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100071A Expired EP0000042B1 (fr) 1977-06-08 1978-06-01 Procédé de préparation de 2,4,5-trichloropyrimidine

Country Status (4)

Country Link
US (1) US4171442A (fr)
EP (1) EP0000042B1 (fr)
JP (1) JPS543079A (fr)
DE (2) DE2725888A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Also Published As

Publication number Publication date
DE2860223D1 (en) 1980-12-04
EP0000042A1 (fr) 1978-12-20
DE2725888A1 (de) 1978-12-21
JPS543079A (en) 1979-01-11
US4171442A (en) 1979-10-16

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