Patent GB-1421231-A (GB)
Title: Phosphorus derivatives of triazolin-5-ones and thiones
IPC: C07F9/6518
Filed: 1973-07-03
Abstract: 1421231 Phosphorus-containing triazolin derivatives ELI LILLY & CO 3 July 1973 [19 July 1972 (2)] 31746/73 Headings C2P and C2C [Also in Division C5] The invention comprises compounds having the general formula wherein R<SP>6</SP> is R<SP>4</SP> or -CH 2 XP(Y)(R<SP>1</SP>)R<SP>2</SP>, R<SP>8</SP> is R<SP>5</SP> or CH 2 XP(Y)(R<SP>1</SP>)R<SP>2</SP> with one and only one of R<SP>6</SP> and R<SP>8</SP> being CH 2 XP(Y)(R<SP>1</SP>)(R<SP>2</SP>), R<SP>7</SP> is R<SP>3</SP>, but additionally including the groups C 1 -C 6  fluoroalkyl and ClF 2 C when R<SP>8</SP> is R<SP>5</SP>, X, Y and Z are independently O or S and Z is O when R<SP>8</SP> is R<SP>5</SP>, R<SP>1</SP> is a C 1 -C 4 -alkyl, -alkylamino, or -alkoxy radical, R<SP>2</SP> is as defined for R<SP>1</SP> or is phenyl, R<SP>3</SP> and R<SP>4</SP> are C 1 -C 6  alkyl or C 3 -C 8  cycloalkyl and also include C 3  or C 4  alkenyl when R<SP>6</SP> is R<SP>4</SP>, and R<SP>5</SP> is C 1 -C 6  alkyl, C 3 -C 8  cycloalkyl or phenyl, either of which may be optionally mono-substituted by halo or methyl. They may be obtained by reacting a compound of the formula wherein R<SP>4</SP>' and R<SP>5</SP>' respectively are as defined above for R<SP>4</SP> and R<SP>5</SP> or are hydrogen and one and only one of R<SP>4</SP>' and R<SP>5</SP>' is hydrogen and R<SP>7</SP> and Z are as defined above, with formaldehyde to produce the corresponding 1- or 4-hydroxymethyl triazoline (III), and (a) when X in the product is oxygen, reacting III with an appropriately substituted halophosphorus derivative in the presence of a base, and when X in the product is sulphur, converting the 1- or 4- hydroxymethyl triazoline (III) to the 1- or 4- chloromethyl compound and then reacting with an alkali metal or ammonium salt of an appropriately substituted thiolo or thiolothiono phosphorus compound. The products have insecticidal, acaricidal and fungicidal properties and are also useful as anthelmintics, herbicides, viricides and plant bactericides. They may be used as active ingredients in conventional pesticidal compositions and can also be used in inks, adhesives, soaps, polymers, cutting oils and paints, applied to textiles or cellulose sheet materials, or used in the impregnation of wood, lumber or fibres. Compounds of Formula II except those in which the ring's 3-substituent is fluoroalkyl are obtained by ring closure of an appropriately substituted semicarbazide or thiosemicarbazide in basic aqueous solution and detailed examples are given for the production of 3,4-dimethyl-#<SP>2</SP>- 1,2,4 - triazolin - 5 - one 3 - cyclopropyl - 1- propyl - #<SP>2</SP> - 1,2,4 - triazolin - 5 - one and 3- butyl - 1 - ethyl - #<SP>2</SP> - 1,2,4 - triazolin - 5 - thione. Several other analogous compounds obtainable in a similar manner are also specified. 1-Acetyl- 4-methylsemicarbazide is obtained by reacting acetic anhydride with 4-methyl-semicarbazide in CH 2 Cl 2 , 4 - Hydroxymethyl - 1,3 - dimethyl - #<SP>2</SP>- 1,2,4-triazoline-5-thione is obtained by reacting the corresponding 1,3-disubstituted 5-thione with 37% formaldehyde in the presence of K 2 CO 3  and on treatment with SOCl 2  in CHCl 3  is converted to 4 - chloromethyl - 1,3 - dimethyl- #<SP>2</SP>-1,2,4-triazolin-5-thione.