0-1-phenyl-2 halovinyl-dithio phosphates
United States Patent [1 1 Beriger et al.  
 [ 51 Apr. 22, 1975 0-l-PHENYL-2 HALOVINYLDITHIO PHOSPHATES [75] Inventors: Ernst Beriger; Jozef Drabek, both of Allschwil, Switzerland [73] Assignee: Ciba-Geigy Corporation, Ardsley,  
  22 Filed: June 26, 1973 211 App]. No.: 373,825  
 [30] Foreign Application Priority Data June 27, 1972 Switzerland 9609/72 May I6, 1973 Switzerland 7060/73 [52] U.S. Cl. 260/957; 260/950; 260/960;  
  260/972; 260/986 [5l] Int. Cl C07f 9/16; AOln 9/36 [58] Field of Search 260/957 [56] References Cited UNITED STATES PATENTS 3/1965 Ward et al. 260/957 l/l968 Haering 260/957 X Primary Examiner-Anton H. Sutto Attorney, Agent, or Firm-Frederick H. Rabin [57] ABSTRACT Compounds of the formula Hal Y isobutyl or 6 Claims, No Drawings 0-l-PHENYL-2 HALOVINYL-DITHIO PHOSPHATES The present invention relates to O-l-phenyl-Z- halovinylthioand dithio-phosphoric acid esters, pro- 5 cesses for their manufacture, and to their use in pest control.  
 The compounds have the formula wherein R represents methyl or ethyl, R represents n-propyl, n-butyl, isobutyl or sec.butyl,  
 (R represents one or more hydrogen atoms, or represents similar or different chlorine, bromine, methyl or methoxy, n is 1,2, or 3, Y represents hydrogen or chlorine and Hal represents chlorine or bromine.  
  Preferred compounds on account of their action are those of the formula I, wherein R, represents methyl or ethyl, R represents n-propyl, sec.butyl or isobutyl, R represents hydrogen, chlorine, bromine, methyl or 10 methoxy, n is l, 2 or 3, Y represents hydrogen or chlorine and Hal represents chlorine or bromine.  
  Particularly preferred compounds are those of the formula I, wherein R, represents ethyl, R represents n-propyl, sec.butyl or isobutyl, R represents hydrogen 15 or chlorine, n is l,2. or 3, Y represents hydrogen or chlorine and Hal represents chlorine.  
  The compounds of the formula I are manufactured by the following known methods:  
  X Hal R10 ll (R3)n acid acceptor R P-Hal acc (II) Y (111) R OPHal H-CII-CWQ acid acceptormm (Iv) Y (III) /Y acid acceptor I X c t R SH l 1e-mr- (v1) or x (VII) Ha1 Y 5) Hal Y X 0 am x c (R R10 ll ll 3 n Hal (R 0) Poc SO01 or (VIII) 5 /Y I acid acceptor X c R s11 1 R10 n 11 5 2 P-WC (v1) MeSR I 4) VIII S061 or Hal Y Pol  X C (R )n Pt:1onally 1n succession ll ll 01 1mm: E1011 and R sH acid acceptor X a O ll i1 (R3)n acid acceptor. c P -43;  
 &#39; Y (XII) Hal Y ll ll (R3)n optionally in succession e g R &#39;OH and a sn X XI acid acceptor In the formulae II to XII, R R R; X, Y, n, and Hal have the meanings given for the formula I and Me represents an alkali metal, in particular sodium or potassium, ammonium or (C -C -alkyl) ammonium.  
  Suitable acid acceptors are: tertiary amines, e.g. trialkylamines, pyridine, dialkyl anilines; inorganic bases, e.g. hydroxides; carbonates and bicarbonates of alkali metals and alkaline earth metals.  
  Processes l to 5 are carried out at a reaction temperature between l0 to 100 C, in particular between 80 C, at normal or elevated pressure, and in solvents or diluents.  
  Examples of suitable solvents or diluents are: ether and ethereal compounds, e.g. diethyl ether, dipropyl ether dioxan, dimethoxy ethane, tetrahydrofuran; amides, e.g. N,N-dialkylated carboxylic acid amides; aliphatic, aromatic and halogenated hydrocarbons, in particular benzene, toluene, xylene, chloroform, chlorobenzene; nitriles, e.g. acetonitriles; sulphoxides, e.g. dimethyl-suphoxide, ketones, e.g. acetone, methyl ethyl ketone.  
  some of the starting materials of the formulae II, III, IV, VIII, IX, and XII are known or can be manufactured by methods analogous to known ones.  
  The compounds of the formula I have a broad biocidal activity spectrum and can therefore be used for combating various plant and animal pests. In particular they are suitable for combating insects of the families: Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Phyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Chrysomelidae, Coccinellidae, Bruchidae, Scarabaeidae, Dermestidae, Tenebrionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleriidae, Culicidae,  
 Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae, Pulicidae, as well as Acaridae of the families: Ixodidae, Argasidae, Tetranychidae, Dermanyssidae.  
  By addition of other insecticidesand/or acaricides, e.g. those listed in German Offenlegungschrift 2,248,307, pages 6 to 10, it is possible to improve substantially the insecticidal or acaricidal action and to adapt it to given circumstances.  
  Furthermore, the new compounds of the formula I act against plant parasitic nematodes.  
  The compounds of the formula I may be used as pure active substance or together with suitable carriers and- /or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances conventially used in formulation technique such, for example, as solvents, dispersants, wetting agents, adhesives,  
 The agents according to the invention are manufactured in known manner by intimately mixing and/or grinding active substances of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active substances. The active substances may take, and be used in, the application forms described in German Offen- Iegungsschrift 2,248,307 on pages 12 to 18.  
 EXAMPLE 1 the benzene solution washed with water. The benzene while Stirred, 300 g o ethyl s propylchlorodithio is distilled off after the drying with Na SO to yield the phosphate are added dropwise to a suspension of 6.25 compound of the formula g. of NaOH (50 7r oil suspension) in 150 ml of tetrahydrofuran. Then, while stirring, 30.7 g of 2-chl0ro-2&#39;, 5 S CHCl cl 4&#39;-dichloro-acetophenone are added dropwise over the C 1L0 ll ll course of l/. hours at -30 C. The reaction mixture PO&#39;-C-Cl is stirred for 3 hours at room temperature and for l n j 7 hour at C. After carefully destroying the excess sodium hydride with 20 ml of absolute ethyl alcoa hol, the reaction mixture is diluted with 400 ml of wawith bollmg P&#34; of 152 C/0-06 the form of ter, the active substance extracted&#39;with benzene, and P yellow P The following Compounds are also manufactured m analagous manner:  
 s GCl c1 2 c H o u u 2 5 l b. .:140c/o,o01 Torr (n)C H 5 cHc1 01&#39; n c H o n n 2 5 n (n)c 1 -0c 1 D 1,57 7  
 - S e01 c gt crs u Pr PO-C v (nte u s I n 1,5130  
 - 0 HI) ll ll 25 V 2 Qii CH n 1 553 (nXHS 0 3 D s cc1 c1 02H o n u P-O-C OCH. 2 (n)c n s 5 4 n 1,5102  
  s 001 Br C2H5O n u 24 H D ocu - s CHCl 01 c H.O n n ocH s CHCl 0 H 0 II II 25 2 5 n 1 5588 3 7 POC 0011 D S CHCl Br C H O ll ll P- (n)C H S OCH  S CHCl C H 0 II II 2 5 9 OCH (n)c n s 3 S CHCl Cl C H O ll u n P l H S 4 9 We claim: 5 1. A compound of the formula Hal Y S \C/ (R 0 u 3 n 2 PO-C wherein R represents methyl or ethyl, R represents n-propyl, n-butyl. isobutyl or sec.butyl, (125),, represents one or more hydrogen atoms, or represents chlorine bromine or methyl, which can be the same or different, n is l 2, or 3, Y represents hydrogen or chlo- 4. O-ethyl-S-n-propyl-O-[ l-( 2,4-dichlorophenyl 2,2-dichlorovinyl]-dithio-phosphate, according to claim 3.  
  5. O-ethyl-S-n-propyl-O-[ l-(2-4,5-trichlorophenyl)- 2chloroviny]l-dithio-phosphate, according to claim 3.  
  6. O-ethyl-S-n-propyl-O-[l-(2,4-dichlorophenyl)-2- chlorovinyl]-dithio-phosphate, according to claim 3.  
  UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,879,499 DATED April 22, 1975 INVENTOR(S) Ernst Beriger, Jozef Drabek it is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:  
 Column 8, Claim 3, line 35 delete &#34;or isobutyl&#34;.  
 Signed and Sealed this third Day of February 1976 [SEAL] Attest:  
 RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner ofParents and Trademarks