Patent EP-0195277-B1 (EP)
IPC: C07F11/00
Filed: 1986-02-22
Granted: 1989-06-21
Abstract: for the Contracting States : BE, CH, DE, FR, GB, IT, LI, LU, NL, SE 1. A process for the preparation of compounds of the formula I   see diagramm : EP0195277,P15,F1   in which Kat represents one molar equivalent of a cation, R is an organic radical which carrier no further phosphorylatable hydrogen atoms, X represents oxygen, sulfur or selenium, Z represents oxygen, sulfur or -NH- and n denotes at least 1, by phosphorylating a compound of the formula II R-(-Z-H)n with at least n moles of a phosphorylating reagent, oxidizing the resulting compound and liberating the compound of the formula I by means of bases, characterized by employing, in the presence of a weak acid, a phosphorylating reagent of the formula III   see diagramm : EP0195277,P15,F2   in which R**1 represents a group ofthe formula IIIa or IIIb   see diagramm : EP0195277,P15,F3   R**5, R**6 and R**7, which can be identical or different, denote hydrogen or methyl, R**8 denotes a group of the formula IIIc, IIId or IIIe or cyano or Ar   see diagramm : EP0195277,P15,F4   R**10 denotes lower alkyl or Ar, G, which can be identical or different, denotes C or N, but at least one G represents N, Ar denotes phenyl which can be substituted by 1 to 5 identical or different substituents belonging to the series chlorine, fluorine, nitro and cyano or, in addition to the electron-withdrawing substituents, can be substituted by one or two lipophilic radicals, y is 0,1 or 2, R**9 denotes a group of the formula IIIf or IIIg   see diagramm : EP0195277,P16,F5   Y denotes identical or different substituents belonging to the series chlorine, bromine or iodine, R**2 can have a meaning of R**1 and is then identical or different or denotes alkylhaving 1 to 4 carbon atoms, a group of the formula IIIh -CH2 -Ar or Ar, if the latter can be split off more readily than R**1 by alkalis, R**5 and R**8 together represent a group of the formula IIIi   see diagramm : EP0195277,P16,F6   and R**1 also represents methyl if R**2 is also methyl, and R**3 and R**4, which can be identical or different, denote alkyl having 1 to 8 carbon atoms, cycloakyl having 5 to 12 carbon atoms, benzyl or phenyl or, together with the nitrogen atom to which they are attached, denote a saturated or unsaturated heterocyclic ring which can, if appropriate, contain further heteroatoms and substituents, and oxidizing the resulting compound ofthe formula IV   see diagramm : EP0195277,P16,F7   in which R**1, R**2, R, Z and n have the meanings mentioned to give the compound of the formula V   see diagramm : EP0195277,P16,F8   in which n, R**1, R**2, X, Z and R have the meanings mentioned. for the Contracting State : Austria 1. A process for the preparation of compounds of the formula I   see diagramm : EP0195277,P17,F1   in which Kat represents one molar equivalent of a cation, R is an organic radical which carrier no further phosphorylatable hydrogen atoms, X represents oxygen, sulfur or selenium, Z represents oxygen, sulfur or -NH- and n denotes at least 1, by phosphorylating a compound of the formula II R-(-Z-H)n with at least n moles of a phosphorylating reagent, oxidizing the resulting compound and liberating the compound of the formula I by means of bases, characterized by employing, in the presence of a weak acid, a phosphorylating reagent of the formula III   see diagramm : EP0195277,P17,F2   in which R**1 represents a group of the formula IIIa or IIIb   see diagramm : EP0195277,P17,F3   R**5, R**6 and R**7, which can be identical or different, denote hydrogen or methyl, R**8 denotes a group of the formula IIIc, IIId or IIIe or cyano or Ar   see diagramm : EP0195277,P17,F4   R**10 denotes alkyl having 1 to 4 carbon atoms or Ar, G, which can be identical or different, denotes C or N, but at least one G represents N, AR denotes phenyl which can be substituted by 1 to 5 identical or different substituents belonging to the series chlorine, fluorine, nitro and cyano or, in addition to the electron-withdrawing substituents, can be substituted by one or two lipophilic radicals, y is 0, 1 or 2, R**9 denotes a group of the formula IIIf or IIIg   see diagramm : EP0195277,P18,F5   Y denotes identical or different substituents belonging to the series chlorine, bromine or iodine, R**2 can have a meaning of R**1 and is then identical or different, or denotes alkyl having 1 to 4 carbon atoms, a group of the formula IIIh -CH2 -Ar or Ar, if the latter can be split off more readily than R**1 by alkal is, R**5 and R**8 together represent a group of the formula IIIi   see diagramm : EP0195277,P18,F6   and R**1 also represents methyl if R**2 is also methyl, and R**3 and R**4, which can be identical or different, denote alkyl having 1 to 8 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, benzyl or phenyl or, together with the nitrogen atom to which they are attached, denote a saturated or unsaturated heterocyclic ring which can, if appropriate, contain further heteroatoms and substituents, and oxidizing the resulting compound of the formula IV   see diagramm : EP0195277,P18,F7   in which R**1, R**2, R, Z and n have the meanings mentioned to give the compound of the formula V   see diagramm : EP0195277,P18,F8   in which n, R**1, R**2, X, Z and R have the meanings mentioned.