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United States Patent Office Patented Aug 3,050,526 United States Patent Office Patented Aug. 2, 1962 2 carbon disulfide or a xanthate, reactions which are known 3,050,526 to give compounds of the structure 3.THOCYANOMETHYL-2-BENZOTHAZOL. NONES AND BENZOXAZOLNONES -NH Chien-Pen Lo, Philadelphia, Pa., asisgn.or to Rohm & 5 R Haas Company, Philadelphia, Pa., a corporation of CY eaware NX/ No Drawing. Fied Alig. 8, 1960, Ser. No. 47,949 which are then reacted with formaldehyde and then a 8 Caims. (C. 260-304) halogenating agent, such as thionyl chloride, phosphorus This invention concerns N-thiocyanomethyl compounds 0 trichloride or tribromide or phosphorus and iodine to of the structure give the halomethyl derivative. When it is desired to have sulfur as X, there may be used an ortho-nitro-chlorobenzene, which is reacted step NCESCN wise with an alkali metal disulfide and monosulfide, fol lowed by ring formation with phosgene or urea. a. Typical methods for preparation of intermediates for forning the necessary halomethyl starting materials may wherein R represents hydrogen, chlorine, bromine, alkyl be summarized as follows: groups, especially lower alkyl groups of one to 8 carbon atoms, alkoxy groups of one to 4 carbon atoms, phenyl, (A) cycloalkyl groups, and Saturated aliphatic monocarboxylic NH --NH acyl groups of 2 to 4 carbon atoms, and X and Y repre R - COCl2 or (NH2)30O - R sent oxygen or sulfur with the proviso that only one of OH Cas O these in a given compound represents sulfur. These No/ compounds are active fungicidal agents for the control of fungus diseases of plants. (B) Although some organic thiocyanates have been used NH NH as insecticides and other thiocyanates have been suggested R -- CS, or R O CSSK - R. as possible fungicides, practical application of thiocyanates OH / at S as fungicides has not yet occurred. Furthermore, it is O not possible to predict whether an organic thiocyanate (C) will have fungicidal value. It has now been found that thiocyanates of the above structure can control the -NH NE growth of various fungi which cause diseases of growing R -- COC or (NH2)9CO - R plants without deleterious action on the host plants. -SE C-O These compounds are prepared by reacting a halo s/ methyl compound of the formula (D) NCHahalogen NH NH 40 -- Br or Cls --> CY Y Br- C=Y X/ NX/ (Cl) NX/ (R, X, and Y being as above), with a salt of thiocyanic (E) acid, such as ammonium, sodium, potassium, calcium, NH t magnesium, or similar thiocyanate. in the above for R HO - R. mula, the halogen has an atomic weight of at least 35. –s - HO Cat-O The methyl halide may be one such as a 3-chloromethyl NX/ X/ 2-benzoxazolinone, 3-bromomethyl-2-benzoxazolinone, or a 3-iodomethyl-2-benzoxazolinone. Starting compounds i (F) include 3-halomethyl-2-benzoxazolinone with chlorine or NE bromine in the 5 or 6 position or with a lower alkyl -- K. Fe(CN)6 -) group, including cycloalkyl groups, such as cyclohexyl, R- C-O C2H5 or phenyl, or alkoxy, or acyl, on the benzene ring, the s^ methyl group being the most important of the alkyl 5 5 -N groups, but the ethyl, tert-butyl, sec-butyl, tert-octyl, or -NE Sec-octyl groups being typical of other useful alkyl groups. Of importance also are the 3-chloromethyl-2-benzthia R- N 9–0 C25- O Zolinone, 3-bromomethyl-2-benzthiazolinone, 3-chloro S R- s/ methyl-2-benzoxazolinethione, 3-bromomethyl-2-benzoxa 60 The reaction with the starting halomethyl compounds Zolinethione, and chloro, bromo, alkyl, including cyclo and thiocyanates is carried out preferably in an inert, alkyl, alkoxy, phenyl, and carboxylic aliphatic acyl volatile, solvent, i.e., one which is inert to the reactants derivatives of these ring compounds. There may be and which can be volatilized from the reaction product two or more such substituents on the benzene ring as in without causing decomposition thereof. Useful solvents the case of 3-chloromethyl-5-methyl-7-chloro-2-benzoxa 65 include acetone, methyl ethyl ketone, benzene, toluene, Zolinone, lower alkanols, dimethylformamide, acetonitrile, ethylene These halomethyl compounds can be prepared by dichloride, and perchloroethylene. A water-miscible sol known methods, starting, for instance, with a phenol (to vent is preferred. provide oxygen as X) without or with suitable substitu Reaction can be effected between about room tempera ents on the ring thereof, going through nitration followed to ture and about 125° C., preferably between 25° and 65 by reduction of the ortho-nitro group to the amino group C., started at low temperature and hastened and/or com with Subsequent ring formation with phosgene, urea, or pleted as temperature is elevated. Product may be iso 3,050,526 3 4. lated by removing solvent from the reaction mixture with is cooled in an ice bath. The solid which forms is filtered extraction with water of the halide salt formed or by off and dried to give 6.5 parts of 3-thiocyanomethyl-2- precipitating the thiocyanomethyl compound by dilution benzoxazolinethione. After recrystallization from ethanol of the reaction mixture with water. Solid products may it melts at 1419-143° C. It contains by analysis 12.0% be purified by recrystallization. 3 of nitrogen and 28.3% of sulfur (theory 12.6% and The following illustrative examples provide additional 28.8% respectively). details of preparation. Parts are by weight unless other Again it has been demonstrated that the substituted wise designated. analogs of the above 3-chloromethyl-2-benzoxazolinethi Example 1 one form 3-thiocyanomethyl derivatives by the above (a) There are mixed 75.5 parts of 2-benzothiazolinone, 10 procedure. 5 parts of anhydrous potassium carbonate, 45 parts of There was also prepared 3-thiocyanomethyl-2-benzo aqueous 37% formaldehyde solution, and 350 parts of thiazolinethione, but this compound failed to exhibit the ethanol. The mixture is stirred and heated under reflux particularly favorable fungistatic and fungitoxic action for three hours. A clear solution results. It is concen of the compounds wherein only one of the entities X and trated by heating under reduced pressure to about one Y was sulfur. third of the original volume. The concentrated Solution Example 4 is cooled in an ice bath. Solid forms and is filtered off A mixture of 5-chloro-3-chloromethyl-2-benzoxazoli and dried in the air to give 64 parts of product identified none (5 parts), (melting point 113-117 C.), ammoni as 3-hydroxymethyl-2-benzothiazolinone. It is recrystal um thiocyanate (2 parts) and acetone (25 parts) is stirred lized from ethylene dichloride and then melts at 93-97 and heated under reflux. A solution is first obtained and C. It contains by analysis 7.4% of nitrogen (7.73% then a fine precipitate of ammonium chloride forms. The theory) and 17.5% of sulfur (17.68% theory). mixture is refluxed for 15 minutes. The reaction mixture (b) There are mixed 51.5 parts of 3-hydroxymethyl is poured into water (200 parts). A light brown solid 2-benzothiazoline, 51 parts of thionyl chloride, and consisting of 5-chloro-3 - thiocyanomethyl-2-benzoxazo 300 parts of ethylene dichloride. The mixture is heated linone separates. It is collected and air dried to afford under reflux for two hours. Excess thionyl chloride and 3 parts of a solid melting at 127-129° C. After re solvent are removed by warming under reduced pres crystallization from ethanol the 5-chloro-3-thiocyano sure. There results a solid, which is identified as 3 methyl-2-benzoxazolinone has a melting point of 130'- chloromethyl- 2 - benzothiazolinone. It is recrystallized 132° C. and the following analysis. from carbon tetrachloride and then melts at 97-99 C. 30 It contains by analysis 17.6% of chlorine and 6.8% of Calcd. for CHCINOS: C, 44.9; H, 2.09; N, 11.6. nitrogen (17.8% and 7.0% theory, respectively). Found: C, 44.7; H, 2.37; N, 11.6. In place of thionyl chloride there may be used phos Example 5 phorus trichloride or if the bromomethyl compound is desired, phosphorus tribromide, while phosphorus and 3-chloromethyl-5-methyl-2-benzoxazolinone (11.7 parts, iodine may be used to give the 3-iodomethyl compound. melting point 106-108 C.) is dissolved in acetone (32 (c) There are mixed 5 parts of 3-chloromethyl-2- parts). To this is added a solution of ammonium thio benzothiazolinone, 2 parts of ammonium thiocyanate, and cyanate (7.6 parts) in acetone (20 parts). A white pre 60 parts of acetone. The mixture is stirred for 15 min cipitate of ammonium chloride forms immediately. The utes at 25°-30° C. and then heated under reflux on a 40 mixture is stirred at room temperature for 30 minutes, steam bath for 30 minutes. The reaction mixture is refluxed for 15 minutes, and poured into water (250 poured into 400 parts of water. An oil separates which parts). A yellow oil separates which solidifies after being solidifies when cooled in an ice bath. The solid is filtered cooled. The solid is collected and air dried to give 13 off, washed with water, and dried in air. It is identified parts of 5-methyl-3-thiocyanomethyl-2-benzoxazolinone. as 3-thiocyanomethyl-2-benzothiazolinone. It contains by 45 After recrystallization from carbon tetrachloride, it has a analysis 12.3% of nitrogen and 28.0% of sulfur (12.6% melting point of i00-101° C. and the following analysis. and 28.8% theory, respectively). The product is re Calcd. for CohaNOS: C, 54.5; H, 3.66; N, 12.7. crystallized from ethanol and then melts at 95-98 C.
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