a cotton flower is depicted in fig1 . a collection of petals 10 is surrounded by a trio of bracts 12 having a plurality of fingers 14 thereupon . the petals serve to contain and protect the male and female sexual organs of the cotton flower and to attract insect pollination media thereto . thus , the male sexual organs are represented by pollen - producing stamens 16 each comprising an anther 18 located on a filament 20 . each of the 90 to 100 stamens of the cotton flower is attached to a staminal column 22 . the female portion of a cotton flower comprises the pistil composed of the stigma 24 , style 26 , and ovary 28 . the ovary contains a plurality of ovules 30 . the cotton flower also comprises a calyx 32 located between the bracts and the petals . the foregoing description has been adapted from &# 34 ; growth and development of the cotton plant in arizona ,&# 34 ; dennis et . al ., u . of ariz . pamphlet 8168 , which is incorporated by reference herein . cotton plants may be rendered male sterile while retaining substantial female fertility in accordance with the present invention by contacting the plants with an effective amount of the gametocidal compound , followed by monitoring the degree of burning of the developing bracts of the plant and by adjusting the amount of compound applied to the plants in response to the degree of burning to maintain an effective amount of compound for the appropriate time duration . fig2 a shows a bract in greater detail . thus , the bract 12 and its fingers 14 are more clearly presented . the inter - finger gaps , 38 are shown . the bract has been removed from the base of the cotton flower at the position indicated by reference number 34 . no burning is evidenced in this figure . fig2 b portrays a bract exhibiting some finger burning . thus , crosshatching , 36 indicates areas of browning , wilting or other evidence of phytotoxicity localized on the fingers . fig2 c discloses a bract which has undergone extensive finger burning in accordance with the practice of the processes of this invention . thus , the fingers 14 have been somewhat eroded in size . an area of browning , wrinkling , or other evidence of local phytotoxicity is indicated by crosshatching 36 . in this figure , the burning involves most or all of the fingers 14 of the bract and has extended somewhat into the main body portion of the bract beyond the inter - finger gaps , 38 of the bract . fig2 d shows an extensively burned bract such as would be the result of an application of an excessive amount of gametocide to a cotton plant . thus , the fingers have been largely eroded or burned away and an extensive portion of the main bract body beyond the inter - finger gap region has been involved with browning or other evidence of local phytotoxicity , 36 . excessive burning such as depicted in fig2 d would be evidence of the application of an excessive amount of gametocide and would imply either loss of reproductive vigor , excessive decline in female fertility , or excessive phytotoxicity generally to the plant . when sufficient gametocide is applied to cotton plants such that the bracts which subsequently develop on the plant exhibit a sensible degree of &# 34 ; burning &# 34 ; of the finger region -- finger burning -- then that amount of regulator is sufficient to render the plant male sterile for a period of time . when , however , an amount of gametocide is administered to a cotton plant such the bracts are burned extensively in areas beyond the inter - finger gaps -- denominated excessive burning -- then such an amount will result in objectionable degrees of female infertility , loss of reproductive vigor , or overall plant phytotoxicity , in addition to rendering the plant male sterile . when an amount of gametocide is administered to cotton plants which is insufficient to result in effective male sterility of the plants , then the bracts will exhibit substantially no burning . it will be appreciated that a continuum exists between states of relative non - burning , states of finger burning according to this invention , and states of excessive burning of the bracts of cotton plants treated with gametocide . it is believed that those skilled in the art will have no difficulty , after routine experimentation , in acquainting themselves with that degree of burning which is optimum to provide male sterility without incurring female sterility or other detrimental effects . it will similarly to appreciated that as increasing amount of burning is evidenced on the bracts of cotton plants , that increasing tendencies towards female sterility , loss of reproductive vigor and general phytotoxicity will occur . in general , therefore , finger burning as used in this specification will mean any sensible degree of burning of the fingers of the bracts of a cotton flower which is less than that degree of burning which progresses substantially inwardly of the inter - finger gaps of the bract . that degree of burning depicted in fig2 c is intended to represent an approximation of the maximum amount of burning inwardly of the inter - finger gaps , which burning falls within the definition of &# 34 ; finger burning &# 34 ; for most cotton varieties in accordance with this invention . in this regard , however , it will be noted that some burning inwardly of the inter - finger gaps may be exhibited . this burning is far less than the burning exhibited by fig2 d wherein substantial involvement inwardly of the inter - finger gaps occurs . it must further be emphasized that finger burning is intended as a qualitative rather than a quantitative term . it is believed that those skilled in the art will have no difficulty in rendering the requirements of finger burning into ordinary practice . it should also be noted that the burning of the bracts need not be symmetric and that an average degree of burning may be employed to determine compliance with the spirit of this invention as described herein . the active compounds for practicing the invention are as defined in the summary of the invention . as these compounds are also novel , the methods of preparation are described in examples 1 through 23 . the most preferred compounds , because of the ability to provide longer periods of male sterility prior to subsequent application , are cyclohexyl 3 , 4 - dichloro - 5 - isothiazolecarboxylate ; phenyl 3 , 4 - dichloro - 5 - isothiazolecarboxylate ; p - chlorophenyl 3 , 4 - dichloro - 5 - isothiazolecarboxylate ; p - tolyl 3 , 4 - dichloro - 5 - isothiazolecarboxylate ; p - anisyl 3 , 4 - dichloro - 5 - isothiazolecarboxylate ; p - bromphenyl 3 , 4 - dichloro - 5 - isothiazolecarboxylate ; 3 - trifluoromethylphenyl 3 , 4 - dichloro - 5 - isothiazolecarboxylate ; 2 - naphthyl 3 , 4 - dichloro - 5 - isothiazolecarboxylate ; 4 - methylcyclohexyl 3 , 4 - dichloro - 5 - isothiazolecarboxylate ; s -( 3 - propylthio ) propyl 3 , 4 - dichloro - 5 - isothiazolecarboxylate ; 2 -( p - methoxyphenoxy ) ethyl 3 , 4 - dichloro - 5 - isothiazolecarboxylate ; 2 -( p - chlorophenylthio ) ethyl 3 , 4 - dichloro - 5 - isothiazolecarboxylate ; 3 , 4 - dichloro - 5 - isothiazolecarboxylate ; and n -( 2 - pyridyl )- 3 , 4 - dichloro - 5 - isothiazolecarboxylate . these 3 , 4 - dichloro - 5 isothiazole carboxylic esters , amides and thioesters are normally either solid or water insoluble liquids which must be formulated into a gametocidal composition for use in the process of this invention . to accomplish this , the gametocidally active ingredient described above is combined with an agriculturally acceptable carrier as exemplified hereinafter . the amount of gametocidally active compound in the composition will range from as little as 1 % to as high as 90 % active material , prior to any dilution which may be necessary for application to the plants . preferably , the composition will contain from about 5 % to about 20 % active ingredient , and most preferably about 10 %, although these concentrations are merely for the sake of convenience in applying the gametocidally active constituent in the most efficient and economical manner . the carrier , which is preferably an aqueous system , will normally include a solvent for the active ingredient and an emulsifier suitable for forming an emulsion of said compound in water . although the active ingredient may be either solid or liquid , solvents are employed to facilitate dilution of the active ingredient in water for spray application to large areas of land in the aforementioned dosage of about 0 . 1 to about 2 . 0 pounds of active ingredient per acre of cotton plants . in a preferred embodiment , the solvent comprises a mixture of a polar solvent and an aromatic solvent . in the experiments described hereinafter , a mixture of equal parts diacetone alcohol and xylene was used as the solvent . to properly accomplish the formation of an aqueous emulsion of the composition , various emulsifiers are employed which may be used in agricultural applications without adverse effect . emulsifiers used in the examples described hereinafter are tween ® 20 and tween ® 80 , which are well - known commercially available emulsifiers . as stated above , the amount of active ingredient which is applied to the cotton plants is sufficient such that the bracts which subsequently develop on the plant exhibit a degree of &# 34 ; burning &# 34 ; of the finger region , and at that point , the amount of gametocide is sufficient to render the plant male sterile for a period of time . it should also be noted that the burning of the bracts need not be symmetric and that an average degree of burning may be employed to comply with the spirit of this invention . when , however , an amount of gametocide is administered to a cotton plant such that the bracts are burned extensively in areas beyond the interfinger gaps , then such an amount will result in objectionable degrees of female infertility , loss of reproduction vigor , or overall plant phytotoxicity . in general , therefore , finger burning as used in this specification will mean any sensible degree of burning of the fingers of the bracts of a cotton flower which is less than that degree of burning which progresses substantially inward of the interfinger gaps of the bract . it must further be emphasized that finger burning is intended as a qualitative rather than a quantitative term in the alternativbe , when the amount of gametocide which is administered to the cotton plants is insufficient to result in effective male sterility in the plants , then the bracts will exhibit substantially no burning . according to the practice of this invention , the amount of gametocidally active material applied to the cotton plants will be monitored in terms of subsequent bract burning and the amount will be altered if necessary , in response to the degree of burning . preferably , the gametocidally active material may be topically applied such as by a ground level foliar spray or , alternatively it may be applied through irrigation water . obviously , substantially more material will be required when the compounds are applied through irrigation as opposed to topical sprays . also , the amount of active material to be applied will vary depending upon the mass of the plants to be treated and , accordingly , with the particular time in the growing season at the time of treatment . the bracts of the cotton plants should be monitored from three to five days after application of the treatement . in three days , indication of the degree of developing burning of the bracts will be exhibited . in five days , the extent of burning will have been indicated clearly . this process of application followed by monitoring and modification of the amount of application can be practiced throughout the period of time that it is desired that the cotton plants remain male sterile . it has been found that if monitoring of the bracts subsequent to application indicates that an excessive amount has been applied , as evidenced by excessive bract burning , then moderation of the effects of the successive applications may be had such as by application of irrigation water to the plants . it is believed that the usual growth spurt found in cotton which has been irrigated will effectively dilute the concentration of the additive in the plant and cause ti to return to more desirable level as reflected by bract burning monitoring . in general , it will be appreciated , that through a monitoring of a degree of burning of the bracts of cotton flowers , a feedback loop may be obtained whereby the proper amount of gametocidally active material may be established and maintained . table i illustrates the effect of application of various compounds of the present invention which were found to provide complete male sterility in cotton plants while producing moderate to slight plant injury and inducing little if any female plant sterility . the various compounds , in an amount ranging from about 5 % to about 20 %, based on the weight of the solution , were first dissolved in a solvent containing a suitable emulsifier as previously described . the solubilized composition was then formed into an aqueous emulsion and applied to cotton plants in the southwestern united states on jul . 1 of the test year by topical spray . one hundred square foot areas of the cotton plants were sprayed in each of the tests listed in table i . the condition of the plants after spraying was then monitored to determine the number of days after application that bract burning was present in the plants . to effectively maintain male sterility of the plants while retaining the substantial female fertility , additional applications were necessary at the end of the number of days noted for each compound . for example , if plants treated with a given gametocide compound exhibited only thirteen days of 100 % male sterility , as evidenced by monitoring the degree of burning of the bracts of the plants , an additional quantity of compound will be required to maintain the male sterility after that thirteen day period of time . conversely , if the observed sterility was shorter or longer , reapplication of the compound would be necessarily adjusted to comply with the amount of burning of the bracts . table i__________________________________________________________________________compounds active gametocide pounds active duration of maleof examples comound per acre sterility , days__________________________________________________________________________ control 0 . 0 0 2 phenyl 3 , 4 - dichloro - 5 - 0 . 72 11 isothiazolecarboxylate ; 3 p - chlorophenyl 3 , 4 - dichloro - 0 . 64 11 5 - isothiazolecarboxylate ; 23 p - bromophenyl 3 , 4 - dichloro - 5 - 0 . 56 14 isothiazolecarboxylate 4 p - tolyl 3 , 4 - dichloro - 5 - 0 . 68 16 isothiazolecarboxylate ; 5 p - anisyl 3 , 4 - dichloro - 5 - 0 . 65 17 isothiazolecarboxylate ; 9 2 , 4 - dintrophenyl 3 , 4 - dichloro - 0 . 65 4 5 - isothiazolecarboxylate13 2 - sec - butyl - 4 , 6 - dinitrophenyl 0 . 65 8 3 , 4 - dichloro - 5 - isothiazolecarboxylate14 3 ,- trifluoromethylphenyl 0 . 58 11 3 , 4 - dichloro - 5 - isothiazolecarboxylate15 2 , 6 - dichloro - 4 -( fluorosulfonyl ) 0 . 65 3 phenyl 3 , 4 - dichloro - 5 - isothiazolecarboxylate19 4 - chloro - 2 - fluorosulfonylphenyl 0 . 65 8 3 , 4 - dichloro - 5 - isothiazolecarboxylate20 allyl 3 , 4 - dichloro - 5 - 0 . 65 3 isothiazolecarboxylate21 2 -( p - methoxyphenoxy ) ethyl 3 , 4 - 0 . 57 14 dichloro - 5 - isothiazolecarboxylate22 2 -( p - chlorophenylthio ) ethyl 0 . 54 13 3 , 4 - dichloro - 5 - isothiazolecarboxylate10 3 , 4 - dichloro - 5 - 0 . 72 14 isothiazolecarboxanilide17 3 , 4 - dichloro - 2 &# 39 ;, 4 &# 39 ;- dinitro - 5 - 0 . 65 7 isothiazolecarboxanilide18 n -( 2 - pyridyl )- 3 , 4 - dichloro - 5 - 0 . 72 15 isothiazolecarboxamide 1 cyclohexyl 3 , 4 - dichloro - 5 - 0 . 73 13 isothiazolecarboxylate11 4 - methylcyclohexyl 3 , 4 - dichloro - 0 . 67 11 5 - isothiazolecarboxylate12 3 , 3 , 5 - trimethylcyclohexyl 3 , 4 - 0 . 65 4 dichloro - 5 - isothiazolecarboxylate 6 2 - napthyl 3 , 4 - dichloro - 5 - 0 . 70 17 isothiazolecarboxylate 7 poly ( ethylene glycol ) 200 bis - 0 . 72 17 ( 3 , 4 - dichloro - 5 - isothiazolecarboxylate ) 16 s -( 3 - propylthio ) propyl 3 , 4 - 0 . 60 11 dichloro - 5 - isothiazolecarbothioate__________________________________________________________________________ the following examples describe the preparation of the novel isothiazole compounds useful in the practice of this invention . empirical formula : c 10 h 11 cl 2 no 2 s ; equation for preparation : ## str6 ## color and phys . state : yellow oil odor : indistinct miscellaneous analyses : calcd . : c , 43 . 0 %: h , 3 . 93 %; cl , 25 . 40 %; n , 5 . 00 %. found : c , 41 . 83 %; h , 3 . 75 %; cl , 25 . 50 %; n , 5 . 89 %. solubility : water &# 34 ; i &# 34 ; ( insoluble ); diacetone alcohol : s ; acetone : &# 34 ; s &# 34 ; ( soluble ); xylene : s . procedure : to a solution of 21 . 6 g . ( 0 . 1 m ) of 3 , 4 - dichloro - 5 - isothiazolecarboxylate acid chloride in 200 ml . of benzene was added 10 . 0 g . ( 0 . 1 m ) of cyclhexanol and the solution was stirred at room temperature for 30 minutes , followed by heating at 50 ° 0 c . for 1 hour . the solution was allowed to stand at room temperature overnight and then concentrated in vacuum . the oil obtained was vacuum distilled to give 8 . 2 g . ( 28 . 5 %) of yellow oil , b . p . 80 ° c . ( 0 . 3 mm . ), n d 25 1 . 5443 . alternate procedure : to 43 . 3 g . ( 0 . 2 m .) of 3 , 4 - dichloro - 5 - isothiazolecarboxylate acid chloride and 22 . 2 g . ( 0 . 22 m .) of triethylamine in 250 ml . of toluene was added 20 g . ( 0 . 2 m .) of cyclohexanol in 25 ml . of toluene . the resulting slurry was heated to 80 ° c . for 3 hours , cooled and filtered to remove 28 g . of triethylamine hydrochloride . the filtrate was contrated at 40 ° c . under reduced pressure and the residue distilled to give 41 . 7 g . ( 74 . 3 % conversion ) of product , b . p . 139 °- 140 ° c . ( 0 . 7 mm . ); n d 25 1 . 5444 . empirical formula : c 10 h 5 cl 2 no 2 s ; equation for preparation : ## str7 ## color and phys . state : white solid odor : none miscellaneous analyses : calcd . c , 44 . 0 %; h , 2 . 01 %; cl , 25 . 80 %; n , 5 . 12 %. found : c , 43 . 81 %; h , 1 . 92 %; cl , 26 . 11 %; n , 5 . 05 %. procedure : to a solution of 21 . 6 g . ( 0 . 1 m ) of 3 , 4 - dichloro - 5 - isothiazolecarboxylate acid chloride and 10 . 0 g . ( 0 . 1 m ) of triethylamine in 200 ml . of benzene was added 9 . 4 g . ( 0 . 1 m ) of warm phenol drops with stirring at room temperature . the mixture was filtered and the filtrate was concentrated in vacuum and refrigerated 65 hours . the dark solid obtained was recrystallized from ethanol to give 7 . 1 g . ( 38 . 5 % conversion ) of product , m . p . 61 °- 63 ° c . empirical formula : c 10 h 4 cl 3 no 2 s ; equation for preparation : ## str8 ## color and phys . state : off - white solid m . p . 79 °- 81 ° c . miscellaneous analyses : calcd : c , 38 . 9 %; h , 1 . 30 %; cl , 34 . 5 %; s , 10 . 37 %. found : c , 38 , 99 %; h , 1 . 23 %; cl , 34 . 19 %; s , 10 . 32 %. procedure : to a solution of 11 g . ( 0 . 05 m .) of 3 , 4 - dichloro - 5 - isothiazolecarboxylate acid chloride in 200 ml . of benzene and 5 . 6 g . ( 0 . 055 m .) of triethylamine was added 6 . 5 g . ( 0 . 05 m .) of p - chlorophenol at room temperature . the resulting mixture as stirred at room temperature for 2 hours , and filtered to remove the triethylamine hydrochloride . the solvent was removed from the filtrate in vacuum leaving a tan solid ; recrystallization from ethanol ( 90 ml .) gave 11 . 8 g . ( 76 % conversion ) of product , m . p . 79 °- 81 ° c . empirical formula : c 11 h 7 cl 2 no 2 s ; equation for preparation : ## str9 ## color and phys . state : white crystalline solid m . p . 73 °- 75 ° c . miscellaneous analyses : calcd : c , 45 . 80 %; h , 2 . 43 %; cl , 24 . 38 %; s , 11 . 11 %. found : c , 45 . 80 %; h , 2 . 61 %; cl , 24 . 79 %; s , 11 . 24 %. procedure : to a solution of 11 g . ( 0 . 05 m .) of 3 , 4 - dichloro - 5 - isothiazolecarboxylate acid chloride in 200 ml . of benzene and 5 . 6 g . ( 0 . 055 m .) of triethylamine was added 5 . 4 g . ( 0 . 05 m .) of p - cresol . the resulting slurry was stirred at ambient temperature for 2 hours , filtered to remove triethylamine hydrochloride and the filtrate evaporated in vacuum to leave a tan solid . recrystallization from ethanol gave 11 . 9 g . ( 82 . 2 %) conversion of white solid product , m . p . 73 °- 75 ° c . empirical formula : c 11 h 7 cl 2 no 3 s ; equation for preparation : ## str10 ## color and phys . state : yellow needles m . p . 104 °- 106 ° c . miscellaneous analyses : calcd : c , 43 . 40 %; h , 2 . 30 %; cl , 23 . 39 ; s , 10 . 53 %: found : c , 43 . 86 %; h , 2 . 77 %; cl , 22 . 52 %; s , 11 . 01 %. procedure : to a solution of 11 . 0 g . ( 0 . 05 m .) of 3 , 4 - dichloro - 5 - isothiazolecarboxylate acid chloride in 200 ml . of benzene and 5 . 6 g . ( 0 . 055 m .) of triethylamine was added 6 . 2 g . of p - methoxyphenol . the resulting slurry was stirred for 2 hours at ambient temperature , filtered to remove triethylamine hydrochloride and the filtrate evaporated in vacuum to leave a brown solid . recrystallization from ethanol gave 13 . 7 g . ( 90 . 0 % conversion ) of yellow product , m . p . 104 °- 106 ° c . empirical formula : c 14 h 7 cl 2 no 2 s ; equation for preparation : ## str11 ## color and phys . state : white solid m . p . 127 °- 128 ° c . miscellaneous analyses : calcd : c , 51 . 80 %; h , 2 . 16 %; cl , 21 . 82 %; s 9 . 88 %. found : c , 52 . 08 %; h , 2 . 57 %; cl , 22 . 13 %; s , 9 . 71 %. procedure : to a solution of 11 g . ( 0 . 05 m .) of 3 , 4 - dichloro - 5 - isothiazolecarboxylate acid chloride in 200 ml . of benzene and 5 . 6 g . ( 0 . 055 m .) of triethylamine was added 7 . 2 g . ( 0 . 05 m .) of β - naphthol . the resulting slurry was stirred for 2 hours , filtered to remove the amine hydrochloride and the filtrate evaporated in vacuum to leave a brown solid . recrystallization from ethanol gave 13 . 7 g . ( 84 . 5 % conversion ) of product , m . p . 127 °- 128 ° c . empirical formula : c 16 . 2 h 16 . 5 cl 4 n 2 o 7 . 1 s 2 ; equation for preparation : ## str12 ## color and phys . state : brown oil ref . ind . : 1 . 552 2 d 5 miscellaneous analyses : calcd : c , 34 . 9 %; h , 2 . 94 %; cl , 25 . 38 %; s , 11 . 42 %. found : c , 35 . 03 %; h , 2 . 99 %; cl , 24 . 99 %; s , 11 . 52 %. procedure : to a solution of 11 g . ( 0 . 05 m .) of 3 , 4 - dichloro - 5 - isothiazolecarboxylate acid chloride and 5 . 6 g . ( 0 . 55 m .) of triethylamine in 200 ml . of benzene was added a solution of 5 g . ( 0 . 025 m .) of poly ( ethylene glycol ) m . w . 200 . the resulting mixture was stirred for 2 hours at ambient temperature and the amine hydrochloride filtered off . the filtrate was washed four times with 25 ml . portions of 10 % na 2 co 3 and four times with 50 ml . portions of water , dried over anhyd . mgso 4 and filtered . the filtrate was evaporated in vacuum at 50 ° c . to give 11 . 6 g . ( 82 . 7 % conversion ) of a dark brown oil , n d 25 1 . 5520 . empirical formula : c 52 . 6 h 89 . 2 cl 4 n 2 o 25 . 3 s 2 ; equation for preparation : ## str13 ## color and phys . state : brown oil ref . ind . : 1 . 5004 d 25 miscellaneous analyses : calcd : c , 46 . 4 %; h , 6 . 57 %; cl , 10 . 43 %; s , 4 . 71 %. found : c , 45 . 59 %, h , 6 . 47 %; cl , 11 . 18 %; s , 6 . 00 %. procedure : to a solution of 11 g . ( 0 . 05 m .) of 3 , 4 - dichloro - 5 - isothiazolecarboxylate acid chloride and 5 . 6 g . ( 0 . 055 m .) of triethylamine in 200 ml . of benzene was added a solution of 25 g . ( 0 . 025 m .) of poly ( ethylene glycol ) m . w . 1000 in 25 ml . of benzene . the resulting slurry was stirred at ambient temperature for 2 hours and the amine hydrochloride filtered off . the filtrate was washed three times with 25 ml . portions of 10 % hcl , three times with 25 ml . portions of 10 % na 2 co 3 , and three times with 50 ml . portions of h 2 o , dried over anhyd . mgso 4 and filtered . the filtrate was evaporated in vacuum at 50 ° c . to give 23 . 7 g . ( 69 . 7 % conversion ) of a brown oil , n d 25 1 . 5004 . empirical formula : c 10 h 3 cl 2 n 3 o 6 s ; equation for preparation : ## str14 ## color and phys . state : off - white solid m . p . 109 °- 110 ° c . miscellaneous analyses : calcd : c , 33 . 00 %; h , 0 . 83 %; s , 8 . 80 %. found : c , 33 . 52 %; h , 1 . 39 %; s , 8 . 83 %. procedure : to 10 g . ( 0 . 05 m .) of the sodium salt of 2 , 4 - dinitrophenol in 125 ml . of toluene was added 11 g . ( 0 . 05 m ) of 3 , 4 - dichloro - 5 - isothiazolecarboxylate acid chloride . the resulting slurry was heated at 80 ° c . for 24 hours , cooled and filtered . the filtrate was concentrated in vacuum and the brown oil treated with ether to give 6 . 6 g . of product , m . p . 104 °- 107 ° c . recrystallization from acetone - petroleum ether gave 6 . 2 g . ( 34 . 1 % conversion ), m . p . 109 °- 110 ° c . empirical formula : c 10 h 6 cl 2 n 2 os ; equation for preparation : ## str15 ## color and phys . state : white solid odor : none miscellaneous analyses : calcd : c , 44 . 0 %; h , 2 . 2 %; cl , 26 . 04 %. found : c , 43 . 96 %; h , 2 . 33 %; cl , 25 . 85 %. procedure : to a solution of 6 . 5 g . ( 0 . 03 m ) of 3 , 4 - dichloro - 5 - isothiazolecarboxylate acid chloride in 150 ml . of benzene was added 5 . 6 g . ( 0 . 06 m ) of aniline in 30 ml . of benzene in 5 min . the reaction mixture was stirred for 7 hours and left standing overnight . the solvent was evaporated under reduced pressure and 50 ml . of water was added to residue . the reaction mixture was extracted with 250 ml . of chloroform an the chloroform extract was washed ( h 2 o ) and dried ( mgso 4 ). evaporation of the solvent gave 7 . 5 g . ( 91 %) of white solid , m . p . 122 °- 124 ° c . a 0 . 6 g . portion was recrystallized from 30 ml . of chloroform and 10 ml . of hexane to give product of m . p . 123 °- 124 ° c . empirical formula : c 11 h 13 cl 2 no 2 s ; equation for preparation : ## str16 ## color and phys . state : yellow oil odor : none miscellaneous analyses : calcd : c , 45 . 0 %; h , 4 . 45 %; s , 10 . 90 %. found : c , 44 . 89 %; h , 4 . 63 %; s , 10 . 63 %. procedure : a mixture of 5 . 5 g . ( 0 . 02 m .) of 3 , 4 - dichloro - 5 - isothiazolecarboxylate acid chloride , 2 . 8 g . ( 0 . 025 m .) of 4 - methylcyclohexanol and 2 . 5 g . of triethylamine in 100 ml . of benzene was stirred at room temperature for 2 hours and then heated on the steam bath for 2 hours . the mixture was allowed to remain at room temperature overnight , filtered and the filtrate concentrated in vacuum to obtain 6 . 6 g . ( 89 . 0 % conversion ) of yellow oil , n d 25 1 . 5330 . the product could not be distilled at 180 ° ( 1 . 0 m . m ) head temperature . empirical formula : c 13 h 17 cl 2 no 2 s ; equation for preparation : ## str17 ## color and phys . state : brown oil ref . ind . : 1 . 5255 d 25 miscellaneous analyses : calcd : c , 48 . 5 %; h , 5 . 3 %; cl , 22 . 1 %. found : c , 48 . 88 %; h , 5 . 58 %; cl , 22 . 19 %. procedure : to 11 . 0 g . ( 0 . 05 m ) of 3 , 4 - dichloro - 5 - isothiazolecarboxylate acid chloride , 5 . 0 g . ( 0 . 05 m .) of triethylamine in 100 ml . of benzene was added 7 . 1 g . ( 0 . 05 m .) of 3 , 3 , 5 - trimethyl - cyclohexanol . the mixture was stirred at room temperature for 2 and on a steam bath for 2 hours , then filtered . the filtrate was concentrated in vacuum to obtain 11 . 2 g . ( 70 % conversion ) brown oil which could not be distilled , at head temperature of 172 ° c . ( 0 . 8 mm . ); n d 25 1 . 5255 . empirical formula : c 14 h 11 cl 2 n 3 o 6 s ; equation for preparation : ## str18 ## color and phys . state : white solid odor : none miscellaneous analyses : calcd : c , 40 . 0 %; h , 2 . 62 %; s , 7 . 60 %. found : c , 39 . 81 %; h , 3 . 02 %; s , 7 . 74 %. procedure : to 11 . 0 g . ( 0 . 05 m .) of 3 , 4 - dichloro - 5 - isothiazolecarboxylate acid chloride , and 5 . 0 g . ( 0 . 05 m .) of triethylamine in 100 ml . of toluene was added 12 . 0 g . ( 0 . 05 m .) of 2 - sec - butyl - 4 , 6 - dinitrophenol ( distilled ). the reaction mixture was heated on a steam bath for 4 hours and filtered . the filtrate was concentrated in vacuum to obtain a brown oil which , on standing overnight , showed the presence of solid . the reaction product was then treated with 95 % ethanol and filtered to give 17 . 4 g . ( 83 % conversion ) of solid which was recrystallized from hexane to give product , m . p . 85 °- 86 ° c . empirical formula : c 11 h 4 cl 2 f 3 no 2 s ; equation for preparation : ## str19 ## color and phys . state : yellow solid distn . range : 180 ° ( 1 . 5 mm .) miscellaneous analyses : calcd : c , 38 . 7 %; h , 1 . 17 %; s , 9 . 35 %. found : c , 39 . 21 %; h , 1 . 46 %; s , 9 . 51 %. procedure : a mixture of 11 . 0 g . ( 0 . 05 m .) of 3 , 4 - dichloro - 5 - isothiazolecarboxylate acid chloride , 5 . 0 g . of triethylamine , and 8 . 1 g . ( 0 . 05 m .) of m - trifluoromethylphenol in 100 ml . of benzene was stirred at room temperature for 2 hours , and then heated on a steam bath for 2 hours . the mixture was filtered and the filtrate concentrated in vacuum to obtain a dark brown oil which was vacuum distilled to give 9 . 8 g . ( 57 % conversion ) of product , b . p . 180 ° c . ( 1 . 5 mm .) the product solidified on cooling , m . p . 53 °- 56 ° c . empirical formula : c 10 h 2 cl 4 fno 4 s 2 ; mol . wt . : 425 equation for preparation : ## str20 ## color and phys . state : pale yellow solid odor : none miscellaneous analyses : calcd : c , 28 . 3 %; h , 0 . 47 %; cl , 33 . 5 %. found : c , 28 . 66 %; h , 0 . 87 %; cl , 33 . 85 %. procedure : to a mixture of 8 . 7 g . ( 0 . 05 m .) of 3 , 4 - dichloro - 5 - isothiazolecarboxylate acid chloride and 4 . 0 g . of triethylamine in 100 ml . of benzene was added 9 . 8 g . ( 0 . 04 m .) of 2 , 6 - dichloro - 4 -( fluorosulfonyl ) phenol and the mixture stirred at room temperature for 2 hours and on the steam bath for 2 hours . the mixture was filtered and the filtrate concentrated in vacuum to obtain a solid which was recrystallized from ether - petroleum ether to give 11 . 9 g . ( 70 % conversion ) of product , m . p . 130 °- 131 ° c . empirical formula : c 10 h 13 cl 2 nos 3 ; equation for preparation : ## str21 ## color and phys . state : dark brown oil odor : stench miscellaneous analyses : calcd : c , 36 . 50 %; h , 3 . 95 %; cl , 21 . 5 %; s , 29 . 0 %. found : c , 37 . 67 %; h , 4 . 53 %; cl , 19 . 86 %; s , 28 . 52 %. procedure : to 11 . 0 g . ( 0 . 05 mole ) of 3 , 4 - dichloro - 5 - isothiazolecarboxylate acid chloride and 5 . 0 g . ( 0 . 05 m ) of triethylamine in 150 ml . of benzene was added 7 . 5 g . ( 0 . 05 m ) of ( 3 - propylthio ) propanethiol . the mixture was refluxed for 6 hours , and allowed to stand at room temperature over the weekend . the mixture was filterd and the filtrate concentrated in vacuum to obtain 16 . 0 g . ( 97 % conversion ) of dark brown oil , n d 25 1 . 5805 . the product decomposed on attempted distillation and analysis was obtained on the undistilled material . empirical formula : c 10 h 4 cl 2 n 4 o 5 s ; equation for preparation : ## str22 ## color and phys . state : tan solid odor : none miscellaneous analyses : calcd : c , 33 . 05 % h , 1 . 18 %; cl , 19 . 58 %. found : c , 32 . 68 %; h , 1 . 27 %; cl , 19 . 62 %. procedure : a solution of 3 . 9 g . ( 10 m mole ) of 3 , 4 - dichloro - 5 - isothiazolecarboxylate acid chloride and 2 . 75 g . ( 15 m mole ) of 2 , 4 - dinitroaniline in 50 ml . of dmf was stirred at room temperature overnight . a solid appeared which was collected and air - dried to give 0 . 55 g . of a yellow powder , m . p . 231 °- 233 ° c . which was not characterized . the filtrate was returned to the reaction pot and stirred for several days with no visible change occurring ; 1 . 8 g . of triethylamine was then added and a solid immediately formed . after stirring at room temperature for 6 hours , the triethylamine hydrochloride was filtered off and the filtrate was poured into 400 ml . of water . the resulting solid was collected ; washed with water and air - dried to give 3 . 8 g . of pale yellow solid , m . p . 122 °- 132 ° c . the solid was immediately dissolved in ca 75 ml of acetone and precipitated with water . there resulted 3 . 0 g . ( 50 % conversion ) of tan solid , m . p . 154 °- 155 ° c . an analytical sample was prepared by recrystallization from acetone , m . p . 154 °- 155 ° c . empirical formula : c 9 h 5 cl 2 n 3 os ; mol . wt . : 274 equation for preparation : ## str23 ## color and phys . state : light violet solid odor : none m . p . 109 °- 111 ° c . miscellaneous analyses : calcd : c , 39 . 43 %; h , 1 . 84 %; s , 11 . 69 %. found : c , 38 . 64 %; h , 2 . 06 %; s , 12 . 10 %. procedure : to a solution of 64 . 8 g . ( 0 . 3 m ) of 3 , 4 - dichloro - 5 - isothiazolecarboxylate acid chloride in 250 ml . of benzene was added simultaneously ( using two additional funnels ) 30 grams ( 0 . 3 m ) of triethylamine and a solution of 28 g . ( 0 . 3 m ) of 2 - aminopyridine in 100 ml . of benzene . the solution was stirred vigorously during the addition and the temperature was maintained between 25 °- 30 ° c . after the addition , the mixture was set aside at room temperature for 6 hours . the amine hydrochloride was filtered off and the residue washed with 100 ml . of hot benzene . the filtrate was then washed thoroughly with water , dried over mg 2 so 4 , and concentrated in vacuo to give the solid which was recrystallized from benzene to get 70 g . ( 87 % conversion ) of product , m . p . 109 °- 111 ° c . empirical formula : c 10 h 3 cl 3 fno 4 s 2 ; equation for preparation : ## str24 ## color and phys . state : off - white solid odor : none miscellaneous analyses : found : c , 31 . 23 %; h , 1 . 07 %; n , 4 . 58 %. calcd : c , 30 . 74 %; h , 0 . 76 %; n , 4 . 85 %. procedure : to a stirring solution of 8 . 4 g . ( 0 . 04 m ) of 3 - chloro - 5 - hydroxybenzene sulfonyl fluoride , 4 . 2 g . ( 0 . 04 m ) of triethylamine , and 100 ml . of toluene , was added 8 . 7 g . ( 0 . 04 mole ) of 3 , 4 - dichloro - 5 - isothiazolecarboxylate acid chloride in 10 ml . of toluene . after the slight exotherm had abated , the reaction was stirred 11 / 2 hours , at reflux , cooled and filtered . the triethylamine hydrochloride cake was washed with a little toluene , and the filtrate was evaporated in vacuum to give a residue of 16 g . of light tan solid , m . p . 106 °- 109 ° c . this residue was treated with a boiling mixture of petroleum ether and toluene , filtered hot to remove a small amount of insoluble material , and the filtrate chilled to obtain 10 . 5 g . ( 67 . 5 % conversion ) of off - white solid , m . p . 109 °- 111 ° c . an analytical sample was recrystallized twice more , m . p . 110 °- 111 ° c . empirical formula : c 7 h 5 cl 2 no 2 s ; equation for preparation : ## str25 ## color and phys . state : brown liquid and solid ref . ind . : 1 . 5510 d 25 miscellaneous analyses : calcd : c , 35 . 4 %; h , 2 . 1 %; s , 13 . 4 %. found : c , 35 . 93 %; h , 2 . 58 %; s , procedure : to a mixture of 10 . 8 g . ( 0 . 05 m ) of 3 , 4 - dichloro - 5 - isothiazolecarboxylic acid chloride and 5 . 0 g ( 0 . 05 m ) of triethylamine in 150 ml of benzene at room temperature was added 3 . 0 g . ( 0 . 5 m ) of allyl alcohol . the mixture was stirred at room temperature for 3 hours , on a steam bath for 1 hour , cooled and filtered . the filtrate was concentrated in vacuum to give 9 . 6 g ( 81 % conversion ) of brown oil . empirical formula : c 13 h 11 cl 2 no 4 s ; equation for preparation : ## str26 ## color and phys . state : yellow solid m . p . 62 °- 64 ° c . miscellaneous analyses : calcd : c , 44 . 8 %; h , 3 . 16 %; s , 9 . 2 %. found : c , 44 . 95 %; h , 3 . 28 %; s , 9 . 36 %. procedure : a mixture of 5 . 5 g . ( 0 . 025 m ) of 3 , 4 - dichloro - 5 - isothiazolecarboxylic acid chloride , 4 . 2 g . ( 0 . 025 m ) of 2 -( 4 - methoxyphenoxy ) ethanol and 2 . 5 g . ( 0 . 025 m ) of triethylamine in 150 ml . of benzene was heated on a steam bath for 6 hours , and filtered hot . the filtrate was concentrated in vacuum to give an oil which crystallized within 24 hours at room temperature . the solid was recrystallized from ethanol to give 5 . 8 g . ( 67 % conversion ) of product , m . p . 62 °- 64 ° c . empirical formula : c 12 h 8 cl 3 no 2 s 2 ; equation for preparation : ## str27 ## color and phys . state : white solid odor : none miscellaneous analyses : calcd : c , 39 . 0 %; h , 2 . 17 %; s , 17 . 4 %. found : c , 39 . 15 %; h , 2 . 45 %; s , 17 . 21 %. procedure : a mixture of 11 . 0 g . ( 0 . 05 m ) of 3 , 4 - dichloro - 5 - isothiazolecarboxylic acid chloride , 9 . 5 g . ( 0 . 05 m ) of 2 -( 4 - chlorophenyl ) thioethanol and 5 . 0 g ( 0 . 05 m ) of triethylamine in 150 ml . of benzene was heated on a steam bath for 4 hours and filtered hot . the filtrate was concentrated in vacuum to give an oil which solidified on standing at room temperature for 24 hours . the solid was recrystallized from ethanol to give 8 . 9 g . ( 47 . 5 % conversion ) of product , m . p . 58 °- 60 ° c . empirical formula : c 10 h 4 brcl 2 no 2 s ; equation for preparation : ## str28 ## color and phys . state : white solid m . p . 94 °- 96 ° c . miscellaneous analyses : calcd : c , 34 . 05 % h , 1 . 13 %; br , 22 . 68 %; s , 9 . 06 % found : c , 34 . 09 %; h , 1 . 40 %; br , 23 . 06 %; s , 9 . 00 %. procedure : to a solution of 11 g . ( 0 . 05 m .) of 3 , 4 - dichloro - 5 - isothiazolecarboxylic acid chloride in 200 ml . of benzene and 5 . 6 g . ( 0 . 055 m .) of triethylamine was added 8 . 7 g . ( 0 . 05 m .) of p - bromophenol in 25 ml . of benzene . the resulting slurry was stirred at ambient temperature for 2 hours , filtered to remove amine hydrochloride ; and the filtrate evaporated in vacuum . the solid residue was recrystallized from ethanol to give 16 . 1 g . ( 91 % conversion ) of a white product , m . p . 94 °- 96 ° c .
cotton plants may be rendered male sterile while retaining substantial female fertility by contracting the plants with a gametocidally effective amount of a novel compound which has the formula : ## str1 ## where x is oxygen , sulfur , or ## str2 ## and where r is a substituted and unsubstituted aryl , alkyl , cycloalkyl , alkoxy and alkene group , and maintaining the effective amount for a sufficient time to form sterile plant flowers that can then be pollinated by a second variety cotton plant to provide cotton having hybrid cotton seeds .