Claims
- 1. A process for the manufacture of compounds of the formula V ##STR11## wherein X.sub.1 is S or O, X.sub.2 is N or CH, Y is H, Cl, F or Br,
- R.sub.1 is H, F, Cl, Br or --COOR.sub.3,
- R.sub.2 is --COO(C.sub.1 -C.sub.4 -alkyl), --(CO)R.sub.3 or C.sub.1 -C.sub.2 -alkyl which is unsubstituted or substituted by halogen atoms, and
- R.sub.3 is H or C.sub.1 -C.sub.4 -alkyl,
- R.sub.8 is H, C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 alkoxy
- R.sub.9 is C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 haloalkyl, C.sub.1 -C.sub.3 alkoxy or C.sub.1 -C.sub.3 haloalkoxy, and
- R.sub.10 is H, halogen, NH.sub.2, NH(C.sub.1 -C.sub.3 alkyl), NH(C.sub.1 -C.sub.3 alkyl).sub.2, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 haloalkyl,
- C.sub.1 -C.sub.3 alkoxy or C.sub.1 -C.sub.3 haloalkoxy, by
- a) reacting in a first step 1 mole equivalent of a compound of the formula IIb ##STR12## wherein X.sub.3 represents hydroxyl, --OM or --O(M.sub.1).sub.1/2, where M is an alkali metal atom or a tertiary ammonium group, having from 3 to 18 carbon atoms, and M.sub.1 is an alkaline earth metal atom, with at least 1 mole equivalent of a compound of formula IIIb
- CHR.sub.1 .dbd.CHR.sub.2 (IIIb),
- optionally in the presence of an inert solvent, and in the presence of a catalytic amount of a homogeneous palladium catalyst and a base selected from alkali metal salts, alkaline earth metal salts and a tertiary ammonium salt of a carboxylic acid to give a compound of the formula IVb ##STR13## and b) hydrogenating in a second step the compound of the formula IVb optionally in the presence of an inert solvent and in the presence of catalytic amounts of a hydrogenation catalyst, to form a compound of the formula Ib ##STR14## c) reacting in a third step the compound of formula Ib with at least 1 mole of a halogenating agent to form the sulfochloride, which is then reacted with NH.sub.3 to give the sulfonamide of the formula Ic ##STR15## d) reacting the compound of the formula Ic with COCl.sub.2 or CSCl.sub.2 to obtain a compound of the formula VI ##STR16## e) reacting the compound of the formula VI with a compound of the formula VII ##STR17## to form the compound of the formula V, characterised in that the homogeneous palladium catalyst is reduced to insoluble palladium metal in the step a) reaction mixture, which is subsequently used as the heterogeneous hydrogenation catalyst.
- 2. A process according to claim 1, characterised in that the heterogeneous palladium hydrogenation catalyst in the step b) reaction is formed in situ from the homogeneous palladium catalyst in the obtained step a) reaction mixture in starting the hydrogenation by introducing hydrogen.
- 3. A process according to claim 1, wherein a solid palladium support material for the heterogeneous hydrogenation catalyst is added prior to the start of the hydrogenation.
- 4. A process according to claim 1, wherein X.sub.3 represents hydroxyl or a group --OM, wherein M is an alkali metal.
- 5. A process according to claim 1, wherein X.sub.3 represents the group --ONa.
- 6. A process according to claim 1, wherein X.sub.1 is O.
- 7. A process according to claim 1, wherein X.sub.2 is N.
- 8. A process according to claim 1, wherein R.sub.8 is H.
- 9. A process according to claim 1, wherein R.sub.9 is C.sub.1 -C.sub.3 alkyl.
- 10. A process according to claim 9, wherein R.sub.9 is methyl or ethyl.
- 11. A process according to claim 1, wherein R.sub.10 is C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 alkoxy.
- 12. A process according to claim 11, wherein R.sub.10 is methyl, ethyl, methoxy or ethoxy.
- 13. A process according to claim 1 for the production of N-(4-methoxy-6-methyl-1,3,5-triazine-2-yl)-N'-[2-(3,3,3-trifluoroprop-1-yl)-benzenesulfonyl]-urea.
- 14. A process according to claim 1, wherein in the step c) reaction the halogenating agent is COCl.sub.2.
- 15. A process according to claim 14, wherein the reaction is catalyzed by the addition of dimethylformamide.
- 16. A process according to claim 15, wherein 0.001 to 10 mole percent of dimethylformamide are used related to the amount of compound Ib.
- 17. A process according to claim 14, wherein the reaction temperature is from 20.degree. to 150.degree. C.
- 18. A process according to claim 14, wherein chlorobenzene is used as solvent.
- 19. A process according to claim 14, wherein the sulfochloride is treated without isolation in the obtained reaction mixture with aqueous NH.sub.3 to form the sulfonamide of formula Ic.
- 20. A process according to claim 19, wherein the reaction temperature is from 20.degree. to 100.degree. C.
- 21. A process according to claim 1, wherein the step d) reaction is carried out with an excess of phosgene or thiophosgene.
- 22. A process according to claim 21, wherein the reaction temperature is from 50.degree. to 180.degree. C.
- 23. A process according to claim 21, wherein the reaction is catalyzed by the addition of aliphatic or cycloaliphatic isocyanates having 1 to 10 carbon atoms.
- 24. A process according to claim 23, wherein cyclohexylisocyanate is used as catalyst.
- 25. A process according to claim 23, wherein 0.001 to 10 mole percent catalyst are used related to the amount of compound Ic.
- 26. A process according to claim 21, Wherein chlorobenzene is used as solvent.
- 27. A process according to claim 1, wherein the step e) reaction is carried out in the presence of chlorobenzene as solvent.
- 28. A process according to claim 1, wherein the step e) reaction is carded out at a temperature range from 20.degree. to 180.degree. C.
- 29. A process according to claim 1, wherein the step e) reaction is carded out under normal pressure or an elevated pressure of up to 1 bar.
- 30. A process according to claim 1, wherein the step e) reaction is carded out in adding the obtained reaction solution with the isocyanate of formula VI to the solution or suspension of the compound of the formula VII.
Parent Case Info
This is a divisional of Ser. No. 08/315,313, filed Sep. 29, 1994, now abandoned which is a continuation of Ser. No. 08/093,213, filed Jul. 19, 1993, now abandoned, which is a continuation-in-part of Ser. No. 07/932,135, filed Aug. 18, 1992, now abandoned.
US Referenced Citations (2)
Foreign Referenced Citations (2)
Number |
Date |
Country |
0044210 |
Jan 1982 |
EPX |
0187489 |
Jul 1986 |
EPX |
Non-Patent Literature Citations (10)
Entry |
Chem. Abst. 92:41471x (1980) (Corresponds to Kikukawa et al., Bull. Chem. Soc. JPN, 52:2609-10 (1979)) p. 741. |
Chem. Abst. 85:123545v (1976) (Corresponds to JP-A-51 014 495) Itaya et al, p. 609. |
Tetrahedron, vol. 37, pp. 31-36, Kikukawa et al (1981). |
Synthetic Commun 20 (22), pp. 3563-3574, Zhang et al (1990). |
4th JUPAC Symp. Summary. K. Oertle (Jul. 1987). |
J. Org. Chem., 56, pp. 1289-1293, (1991). |
Chem. Abst. 99:194410w (1983). |
Heterocycles 26:7, pp. 1783-1784 (1987). |
Synthetic Commun 15(13), pp. 1131-1136 (1985). |
J. Org. Chem. 46, pp. 4885-4888 (1981). |
Divisions (1)
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Number |
Date |
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Parent |
315313 |
Sep 1994 |
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Continuations (1)
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93213 |
Jul 1993 |
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Continuation in Parts (1)
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932135 |
Aug 1992 |
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