the following definitions apply to the terms as used throughout this specification , unless otherwise limited in specific instances . as used herein , the term “ alkyl ” denotes branched or unbranched hydrocarbon chains . as used herein , the term “ alkoxide ” means an alkyl further consisting of a carbon - oxygen single bond , for example , methoxy , ethoxy , propoxy , isopropoxy , butoxy , isobutoxy , and tert - butoxy . the present disclosure provides an alternative process for preparing 3 -( 3 - chloro - 1h - pyrazol - 1 - yl ) pyridine ( 5b ) by cyclizing 3 - hydrazinopyridine . dihydrochloride with an alkyl methacrylate to provide 4 - methyl - 1 -( pyridin - 3 - yl ) pyrazolidin - 3 - one ( 1 ), by chlorinating ( 1 ) to provide 3 -( 3 - chloro - 4 - methyl - 4 , 5 - dihydro - 1h - pyrazol - 1 - yl ) pyridine ( 2 ), by oxidizing ( 2 ) to provide 3 -( 3 - chloro - 4 - methyl - 1h - pyrazol - 1 - yl ) pyridine ( 3 ), by further oxidizing ( 3 ) to provide 3 - chloro - 1 -( pyridin - 3 - yl )- 1h - pyrazole - 4 - carboxylic acid ( 4 ), and by decarboxylating ( 4 ) to provide 3 -( 3 - chloro - 1h - pyrazol - 1 - yl ) pyridine ( 5b ). thus , the present disclosure concerns a process for preparing 3 -( 3 - chloro - 1h - pyrazol - 1 - yl ) pyridine ( 5b ) in a ( c 1 - c 4 ) alkyl alcohol at a temperature of about 25 ° c . to about 80 ° c . in the presence of an alkali metal ( c 1 - c 4 ) alkoxide to provide 4 - methyl - 1 -( pyridin - 3 - yl ) pyrazolidin - 3 - one ( 1 ) b ) chlorinating 4 - methyl - 1 -( pyridin - 3 - yl ) pyrazolidin - 3 - one ( 1 ) with a chlorinating reagent in an organic solvent at a temperature of about 25 ° c . to about 100 ° c . to provide 3 -( 3 - chloro - 4 - methyl - 4 , 5 - dihydro - 1h - pyrazol - 1 - yl ) pyridine ( 2 ) c ) oxidizing 3 -( 3 - chloro - 4 - methyl - 4 , 5 - dihydro - 1h - pyrazol - 1 - yl ) pyridine ( 2 ) with an oxidant in a solvent at a temperature of about 25 ° c . to about 100 ° c . to provide 3 -( 3 - chloro - 4 - methyl - 1h - pyrazol - 1 - yl ) pyridine ( 3 ) d ) further oxidizing 3 -( 3 - chloro - 4 - methyl - 1h - pyrazol - 1 - yl ) pyridine ( 3 ) with an oxidant in a polar protic solvent at a temperature of about 50 ° c . to about 100 ° c . to provide 3 - chloro - 1 -( pyridin - 3 - yl )- 1h - pyrazole - 4 - carboxylic acid ( 4 ) e ) decarboxylating 3 - chloro - 1 -( pyridin - 3 - yl )- 1h - pyrazole - 4 - carboxylic acid ( 4 ) with copper oxide in a polar aprotic solvent at a temperature of about 80 ° c . to about 180 ° c . to provide 3 -( 3 - chloro - 1h - pyrazol - 1 - yl ) pyridine ( 5b ). in step 1a , 3 - hydrazinopyridine . dihydrochloride is cyclized with a ( c 1 - c 4 ) alkyl methacrylate , in a solution further comprising a ( c 1 - c 4 ) alkyl alcohol and an alkali metal ( c 1 - c 4 ) alkoxide , to provide 4 - methyl - 1 -( pyridin - 3 - yl ) pyrazolidin - 3 - one ( 1 ). step a is conducted at a temperature from about 25 ° c . to about 80 ° c . while stoichiometric amounts of 3 - hydrazinopyridine - dihydrochloride and ( c 1 - c 4 ) alkyl methacrylate may be used , it is often convenient to use about a 1 . 5 fold to about a 2 fold excess of ( c 1 - c 4 ) alkyl methacrylate compared to 3 - hydrazinopyridine . dihydrochloride . the ( c 1 - c 4 ) alkyl alcohol is preferably selected from methanol , ethanol , propanol , butanol , and mixtures thereof . the alkali metal ( c 1 - c 4 ) alkoxide is preferably selected from sodium methoxide , sodium ethoxide , and mixtures thereof . it is often convenient to use about a 2 fold to about a 3 fold excess of alkali metal ( c 1 - c 4 ) alkoxide compared to 3 - hydrazinopyridine - dihydrochloride . furthermore , it is most preferred if sodium ethoxide and ethanol is used . in another embodiment , 3 - hydrazinopyridine . dihydrochloride is cyclized with methyl methacrylate in the presence of sodium ethoxide and ethanol and this mixture is heated at about 50 ° c . the crude 4 - methyl - 1 -( pyridin - 3 - yl ) pyrazolidin - 3 - one ( 1 ) is used as is without further purification or isolation . in step 1b , 4 - methyl - 1 -( pyridin - 3 - yl ) pyrazolidin - 3 - one ( 1 ) is chlorinated with a chlorinating reagent in an organic solvent at a temperature from about 25 ° c . to about 100 ° c . to provide 3 -( 3 - chloro - 4 - methyl - 4 , 5 - dihydro - 1h - pyrazol - 1 - yl ) pyridine ( 2 ). suitable chlorinating reagents include phosphoryl chloride ( phosphorous oxychloride ), phosphorus pentachloride , and mixtures thereof . phosphoryl chloride is currently preferred . it is often convenient to use about a 1 . 1 fold to about a 10 fold excess of the chlorinating reagent compared to 4 - methyl - 1 -( pyridin - 3 - yl ) pyrazolidin - 3 - one ( 1 ). the chlorination is performed in an organic solvent that does not substantially react with the chlorinating reagent . suitable solvents include nitriles such as acetonitrile . it is currently preferred to use phosphoryl chloride as the chlorinating reagent and acetonitrile as the solvent . in another embodiment , 4 - methyl - 1 -( pyridin - 3 - yl ) pyrazolidin - 3 - one ( 1 ) in acetonitrile is chlorinated with phosphoryl chloride and the mixture is heated to about 75 ° c . the 3 -( 3 - chloro - 4 - methyl - 4 , 5 - dihydro - 1h - pyrazol - 1 - yl ) pyridine ( 2 ) can be isolated and purified by standard techniques . in step 1c , 3 -( 3 - chloro - 4 - methyl - 4 , 5 - dihydro - 1h - pyrazol - 1 - yl ) pyridine ( 2 ) is oxidized with an oxidant in an organic solvent at a temperature of about 25 ° c . to about 100 ° c . to provide 3 -( 3 - chloro - 4 - methyl - 1h - pyrazol - 1 - yl ) pyridine ( 3 ). suitable oxidants include copper ( i ) chloride in the presence of oxygen , potassium ferricyanide , and manganese ( iv ) oxide . it is often convenient to use about a 1 . 5 fold to about a 15 fold excess of oxidant compared to 3 -( 3 - chloro - 4 - methyl - 4 , 5 - dihydro - 1h - pyrazol - 1 - yl ) pyridine ( 2 ). the oxidation is performed in a solvent that does not substantially react with the oxidant . suitable solvents include water , n , n - dimethylformamide , n - methylpyrrolidinone , dichloromethane , tert - butanol , nitriles such as acetonitrile , aromatic hydrocarbons such as toluene , and mixtures thereof . it is currently preferred to use copper ( i ) chloride in the presence of oxygen as the oxidant , with n , n - dimethylformamide , n - methylpyrolidinone , and mixtures thereof as the solvent . it is also preferred to use potassium - ferricyanide as the oxidant , with water as the solvent . it is also preferred to use manganese ( iv ) oxide as the oxidant , with dichloromethane , tert - butanol , acetonitrile , toluene , and mixtures thereof as the solvent . it is also preferred to use manganese ( iv ) oxide as the oxidant , with acetonitrile as the solvent . in another embodiment , 3 -( 3 - chloro - 4 - methyl - 4 , 5 - dihydro - 1h - pyrazol - 1 - yl ) pyridine ( 2 ) in acetonitrile is oxidized with manganese ( iv ) oxide and the mixture is heated at about 40 ° c . the 3 -( 3 - chloro - 4 - methyl - 1h - pyrazol - 1 - yl ) pyridine ( 3 ) can be isolated and purified by standard techniques . in step 1d , 3 -( 3 - chloro - 4 - methyl - 1h - pyrazol - 1 - yl ) pyridine ( 3 ) is further oxidized with an oxidant in a protic solvent at a temperature of about 50 ° c . to about 100 ° c . to provide 3 - chloro - 1 -( pyridin - 3 - yl )- 1h - pyrazole - 4 - carboxylic acid ( 4 ). suitable oxidants include potassium permanganate and sodium permanganate . it is often convenient to use about a 2 . 5 fold to about a 4 . 5 fold , preferably about a 3 . 0 fold excess of oxidant compared to 3 -( 3 - chloro - 4 - methyl - 1h - pyrazol - 1 - yl ) pyridine ( 3 ). the oxidation is performed in a protic solvent that does not substantially react with the oxidant . suitable solvents include water , tert - butanol , tert - amyl alcohol , and mixtures thereof . in another embodiment , 3 -( 3 - chloro - 4 - methyl - 1h - pyrazol - 1 - yl ) pyridine ( 3 ) is further oxidized by sodium permanganate in water and tert - butanol and heated at about 80 ° c . the 3 - chloro - 1 -( pyridin - 3 - yl )- 1h - pyrazole - 4 - carboxylic acid ( 4 ) can be isolated and purified by standard techniques . in step 1e , 3 - chloro - 1 -( pyridin - 3 - yl )- 1h - pyrazole - 4 - carboxylic acid ( 4 ) is decarboxylated in the presence of copper oxide which may optionally be ligated with a bidentate ligand such as tetramethyl ethylenediamine in a polar aprotic solvent at a temperature from about 80 ° c . to about 180 ° c . to provide 3 -( 3 - chloro - 1h - pyrazol - 1 - yl ) pyridine ( 5b ). suitable copper oxide sources include copper ( i ) oxide and copper ( ii ) oxide as well as mixtures thereof . it is convenient to use about 5 wt % to about 20 wt % of copper oxide based on 3 - chloro - 1 -( pyridin - 3 - yl )- 1h - pyrazole - 4 - carboxylic acid ( 4 ). suitable solvents include n , n - dimethylformamide , n , n - dimethylacetamide , n - methylpyrrolidinone , and mixtures thereof . in another embodiment , 3 - chloro - 1 -( pyridin - 3 - yl )- 1h - pyrazole - 4 - carboxylic acid ( 4 ) and copper ( i ) oxide are mixed with n , n - dimethylacetamide and heated to about 125 ° c . the 3 -( 3 - chloro - 1h - pyrazol - 1 - yl ) pyridine ( 5b ) can be isolated and purified by standard techniques . an illustrative example of how 3 -( 3 - chloro - 1h - pyrazol - 1 - yl ) pyridine ( 5b ) may be used for preparing certain pesticidal ( 3 - halo - 1 -( pyridin - 3 - yl )- 1h - pyrazol - 4 - yl ) amides is outlined in scheme 2 . in step 2a , 3 -( 3 - chloro - 1h - pyrazol - 1 - yl ) pyridine ( 5b ) is nitrated with nitric acid ( hno 3 ), preferably in the presence of sulfuric acid ( h 2 so 4 ) to yield 3 -( 3 - chloro - 4 - nitro - 1h - pyrazol - 1 - yl ) pyridine ( 2 - 6 ). the nitration may be conducted at temperatures from about − 10 ° c . to about 30 ° c . in step 2b , 3 -( 3 - chloro - 4 - nitro - 1h - pyrazol - 1 - yl ) pyridine ( 2 - 6 ) is reduced to yield 3 - chloro - 1 -( pyridin - 3 - yl )- 1h - pyrazol - 4 - amine ( 2 - 7 ). for example , 3 -( 3 - chloro - 4 - nitro - 1h - pyrazol - 1 - yl ) pyridine ( 2 - 6 ) may be reduced with iron in acetic acid ( acoh ). 3 -( 3 - chloro - 4 - nitro - 1h - pyrazol - 1 - yl ) pyridine ( 2 - 6 ) may also be reduced with iron and ammonium chloride ( nh 4 cl ). alternatively , this reduction may be carried out using other techniques in the art , for example , 3 -( 3 - chloro - 4 - nitro - 1h - pyrazol - 1 - yl ) pyridine ( 2 - 6 ) may be reduced using palladium on carbon in the presence of hydrogen ( h 2 ). this reaction may be conducted at temperatures from about − 10 ° c . to about 30 ° c . in step 2c , 3 - chloro - 1 -( pyridin - 3 - yl )- 1h - pyrazol - 4 - amine ( 2 - 7 ) is acylated with acetylating agents such as acetyl chloride or acetic anhydride , preferably acetic anhydride ( ac 2 o ) to yield n -( 3 - chloro - 1 -( pyridin - 3 - yl )- 1h - pyrazol - 4 - yl ) acetamide ( 2 - 8 ). the acylation is conducted in the presence of a base , preferably an inorganic base , such as , sodium bicarbonate ( nahco 3 ), and preferably , a polar solvent , such as ethyl acetate and / or tetrahydrofuran . this reaction may be conducted at temperatures from about − 10 ° c . to about 30 ° c . in step 2d , n -( 3 - chloro - 1 -( pyridin - 3 - yl )- 1h - pyrazol - 4 - yl ) acetamide ( 2 - 8 ) is alkylated with ethyl bromide ( etbr ) in the presence of a base , such as sodium hydride ( nah ) or sodium tert - butoxide ( naot - bu ), in a polar aprotic solvent , such as tetrahydrofuran , at temperatures from about 20 ° c . to about 40 ° c ., over a period of time of about 60 hours to about 168 hours , to yield n -( 3 - chloro - 1 -( pyridin - 3 - yl )- 1h - pyrazol - 4 - yl )- n - ethylacetamide ( 2 - 9 ). it has been discovered that use of an iodide additive , such as potassium iodide ( ki ) or tetrabutylammonium iodide ( tbai ) can decrease the time necessary for the reaction to occur to about 24 hours . it has also been discovered that heating the reaction at about 50 ° c . to about 70 ° c . in a sealed reactor ( to prevent loss of ethyl bromide ) also decreases the reaction time to about 24 hours . in step 2e , n -( 3 - chloro - 1 -( pyridin - 3 - yl )- 1h - pyrazol - 4 - yl )- n - ethylacetamide ( 2 - 9 ) is treated with hydrochloric acid in water at temperatures from about 50 ° c . to about 90 ° c ., to yield 3 - chloro - n - ethyl - 1 -( pyridin - 3 - yl )- 1h - pyrazol - amine ( 2 - 10 ). steps d and e of scheme 2 may also be performed without the isolation of n -( 3 - chloro - 1 -( pyridin - 3 - yl )- 1h - pyrazol - 4 - yl )- n - ethylacetamide ( 2 - 8 ). in step 2f , 3 - chloro - n - ethyl - 1 -( pyridin - 3 - yl )- 1h - pyrazol - amine ( 2 - 10 ) is acylated with 3 -(( 3 , 3 , 3 - trifluoropropyl ) thio ) propanoyl chloride in the presence of a base preferably , sodium bicarbonate to yield pesticidal ( 3 - halo - 1 -( pyridin - 3 - yl )- 1h - pyrazol - 4 - yl ) amide ( 2 - 11 ). the reaction may also be conducted in the absence of a base to yield pesticidal ( 3 - halo - 1 -( pyridin - 3 - yl )- 1h - pyrazol - 4 - yl ) amide ( 2 - 11 ). in step 2g , pesticidal ( 3 - halo - 1 -( pyridin - 3 - yl )- 1h - pyrazol - 4 - yl ) amide ( 2 - 11 ) is oxidized with hydrogen peroxide ( h 2 o 2 ) in methanol to yield pesticidal ( 3 - halo - 1 -( pyridin - 3 - yl )- 1h - pyrazol - 4 - yl ) amide ( 2 - 12 ). these examples are for illustration purposes and are not to be construed as limiting the disclosure to only the embodiments disclosed in these examples . starting materials , reagents , and solvents that were obtained from commercial sources were used without further purification . anhydrous solvents were purchased as sure / seal ™ from aldrich and were used as received . melting points were obtained on a thomas hoover unimelt capillary melting point apparatus or an optimelt automated melting point system from stanford research systems and are uncorrected . examples using “ room temperature ” were conducted in climate controlled laboratories with temperatures ranging from about 20 ° c . to about 24 ° c . molecules are given their known names , named according to naming programs within isis draw , chemdraw or acd name pro . if such programs are unable to name a molecule , the molecule is named using conventional naming rules . 1 h nmr spectral data are in ppm ( δ ) and were recorded at 300 , 400 or 600 mhz ; 13 c nmr spectral data are in ppm ( δ ) and were recorded at 75 , 100 or 150 mhz , and 19 f nmr spectral data are in ppm ( δ ) and were recorded at 376 mhz , unless otherwise stated . to a 250 ml three - neck round bottom flask equipped with a reflux condenser was introduced 3 - hydrazinopyridine . dihydrochloride ( 15 . 0 g , 82 . 4 mmol ). sodium ethoxide ( 21 wt % in ethanol , 92 . 3 ml , 247 mmol ) was added over 5 minutes and the pot temperature increased from 23 ° c . to 38 ° c . the resultant light brown - slurry was stirred for 10 minutes . methyl methacrylate ( 17 . 7 ml , 165 mmol ) was added slowly over 15 minutes and the pot temperature remained at 38 ° c . the yellow mixture was stirred at 50 ° c . under nitrogen for 4 hours . the mixture was then cooled down to 10 ° c . and hydrochloric acid ( 4 m in 1 , 4 - dioxane , 20 . 6 ml ) was added slowly to quench excess base leading to a light brown suspension . the mixture was concentrated under reduced pressure to afford the title compound as a brown solid as a mixture with sodium chloride ( 35 . 2 g , 241 %): eims m / z 177 ([ m ] + ). the crude material was used directly in the next step . crude 4 - methyl - 1 -( pyridin - 3 - yl ) pyrazolidin - 3 - one ( 35 . 2 g , ˜ 82 . 4 mmol ) was introduced into a 250 ml three - neck round bottom flask equipped with a reflux condenser . acetonitrile ( 100 ml ) was then added . to this yellow mixture was added phosphoryl chloride ( 11 . 56 ml , 124 mmol ) slowly . the yellow slurry was stirred at 75 ° c . for 1 hour . the mixture was cooled down and concentrated to remove volatiles . the brown residue was carefully quenched with water ( 120 ml ), and basified with naoh ( 50 wt % in water ) to ph 10 while keeping the temperature below 60 ° c . the mixture was then extracted with ethyl acetate ( 3 × 150 ml ). the combined organic extracts were washed with water ( 80 ml ) and concentrated under reduced pressure to afford the crude product as dark purple oil . the crude product was purified by flash column chromatography using 0 - 70 % ethyl acetate / hexanes as eluent to provide the title compound as a brown oil ( 12 . 3 g , 76 % over two steps ): 1 h nmr ( 400 mhz , cdcl 3 ) δ 8 . 27 ( dd , j = 2 . 8 , 0 . 7 hz , 1h ), 8 . 15 ( dd , j = 4 . 6 , 1 . 4 hz , 1h ), 7 . 38 ( ddd , j = 8 . 4 , 2 . 9 , 1 . 4 hz , 1h ), 7 . 18 ( ddd , j = 8 . 4 , 4 . 7 , 0 . 7 hz , 1h ), 4 . 17 - 4 . 06 ( m , 1h ), 3 . 47 ( t , j = 8 . 9 hz , 1h ), 3 . 44 - 3 . 34 ( m , 1h ), 1 . 37 ( d , j = 6 . 8 hz , 3h ); 13 c nmr ( 101 mhz , cdcl 3 ) δ 148 . 17 , 142 . 07 , 141 . 10 , 134 . 74 , 123 . 39 , 119 . 92 , 56 . 62 , 43 . 62 , 16 . 16 ; eims m / z 195 ([ m ] + ). to a solution of 3 -( 3 - chloro - 4 - methyl - 4 , 5 - dihydro - 1h - pyrazol - 1 - yl ) pyridine ( 1 . 0 g , 5 . 0 mol ) in acetonitrile ( 10 . 0 ml ) at 0 ° c . was added manganese ( iv ) oxide ( 1 . 3 g , 15 mmol ) portionwise over 10 minutes . the mixture was slowly warmed to 22 ° c . over 40 minutes and then heated to 40 ° c . overnight . after 20 hours , additional manganese ( iv ) oxide ( 0 . 44 g , 5 . 0 mmol ) was added in one portion and the mixture was stirred for 1 hour . the mixture was cooled down and filtered . the filter cake was washed with acetonitrile ( 3 × 15 ml ). the organic filtrate was dried and concentrated to afford the title compound as a light yellow solid ( 0 . 92 g , 95 %): 1 h nmr ( 400 mhz , cdcl 3 ) δ 8 . 90 ( dd , j = 2 . 6 , 0 . 8 hz , 1h ), 8 . 52 ( dd , j = 4 . 8 , 1 . 5 hz , 1h ), 7 . 99 ( ddd , j = 8 . 3 , 2 . 7 , 1 . 4 hz , 1h ), 7 . 74 ( q , j = 0 . 9 hz , 1h ), 7 . 39 ( ddd , j = 8 . 3 , 4 . 8 , 0 . 8 hz , 1h ), 2 . 13 ( d , j = 0 . 9 hz , 3h ); 13 c nmr ( 101 mhz , cdcl 3 ) δ 147 . 26 , 142 . 87 , 139 . 53 , 135 . 90 , 126 . 53 , 125 . 69 , 123 . 84 , 116 . 86 , 22 . 47 ; eims m / z 193 ([ m ] + ). to a mixture of 3 -( 3 - chloro - 4 - methyl - 4 , 5 - dihydro - 1h - pyrazol - 1 - yl ) pyridine ( 2 . 0 g , 10 mmol ) in water ( 10 . 0 ml ) and tert - butanol ( 5 . 0 ml ) was added a solution of sodium permanganate ( namno4 ) ( 5 . 0 g , 35 mmol ) in water ( 15 ml ) over 20 minutes . the mixture was heated to 80 ° c . and stirred overnight . additional sodium permanganate ( 0 . 711 g , 5 . 0 mmol ) in water ( 2 . 0 ml ) was added after 16 hours and the mixture was stirred for another 4 hours . the dark mixture was filtered through celite ®, washed with water ( 5 . 0 ml ) and ethyl acetate ( 3 × 15 ml ). the aqueous layer was extracted with ethyl acetate ( 25 ml ) and acidified with concentrated hydrochloric acid to ph 5 leading to white precipitate which was collected by filtration . the filtrate was concentrated leading to white precipitate which was collected by filtration and washed with water ( 2 . 0 ml ). the solid products were combined and dried under high vacuum to afford the title compound as a white solid ( 1 . 0 g , 46 %): 1 h nmr ( 400 mhz , dmso - d 6 ) δ 9 . 11 ( s , 2h ), 8 . 59 ( d , j = 4 . 7 , 1h ), 8 . 28 ( ddd , j = 8 . 4 , 2 . 7 , 1 . 4 hz , 1h ), 7 . 58 ( dd , j = 8 . 0 , 4 . 4 hz , 1h ); 13 c nmr ( 101 mhz , dmso - d 6 ) δ 162 . 24 , 148 . 35 , 141 . 46 , 140 . 21 , 135 . 01 , 134 . 01 , 126 . 45 , 124 . 23 , 115 . 34 ; esims m / z 224 ([ m + h ] + ). to a mixture of 3 - chloro - 1 -( pyridin - 3 - yl )- 1h - pyrazole - 4 - carboxylic acid ( 0 . 223 g , 1 . 0 mmol ) in n , n - dimethylacetamide ( 3 . 0 ml ) was added copper ( i ) oxide ( 0 . 022 g , 10 wt %). the mixture was heated to 125 ° c . and stirred for 6 hours . the brown mixture was filtered and washed with n , n - dimethylacetamide ( 1 . 0 ml ) and acetonitrile ( 2 × 2 ml ). the light yellow filtrate was analyzed by lc using di - n - propyl phthalate as internal standard ( 0 . 124 g , 69 % in - pot yield ); mp 66 - 68 ° c . ; 1 h nmr ( 400 mhz , cdcl 3 ) δ 8 . 93 ( d , j = 27 hz , 1h ), 8 . 57 ( dd , j = 4 . 8 , 1 . 4 hz , 1h ), 8 . 02 ( ddd , j = 8 . 3 , 2 . 7 , 1 . 5 hz , 1h ), 7 . 91 ( d , j = 2 . 6 hz , 1h ), 7 . 47 - 7 . 34 ( m , 1h ), 6 . 45 ( d , j = 2 . 6 hz , 1h ); 13 c nmr ( 101 mhz , cdcl 3 ) δ 148 . 01 , 142 . 72 , 140 . 12 , 135 . 99 , 128 . 64 , 126 . 41 , 124 . 01 , 108 . 0 ; esims m / z 180 ([ m + h ] + ). to a 100 ml , round bottom flask was charged 3 -( 3 - chloro - 1h - pyrazol - 1 - yl ) pyridine ( 2 . 00 g , 11 . 1 mmol ) and concentrated sulfuric acid ( 4 ml ). this suspension was cooled to 5 ° c . and 2 : 1 concentrated nitric acid / sulfuric acid ( 3 ml , prepared by adding the concentrated sulfuric acid to a stirring and cooling solution of the nitric acid ) was added dropwise at a rate such that the internal temperature was maintained & lt ; 15 ° c . the reaction was allowed to warm to 20 ° c . and stirred for 18 hours . a sample of the reaction mixture was carefully diluted into water , basified with sodium hydroxide ( 50 wt % in water ) and extracted with ethyl acetate . analysis of the organic layer indicated that the reaction was essentially complete . the reaction mixture was carefully added to ice cold water ( 100 ml ) at & lt ; 20 ° c . it was basified with sodium hydroxide ( 50 wt % in water ) at & lt ; 20 ° c . the resulting light yellow suspension was stirred for 2 hours and filtered . the filter cake was rinsed with water ( 3 × 20 ml ) and dried to afford an off - white solid ( 2 . 5 g , quantitative ): mp 141 - 143 ° c . ; 1 h nmr ( 400 mhz , dmso - d 6 ) δ 9 . 86 ( s , 1h ), 9 . 23 - 9 . 06 ( m , 1h ), 8 . 75 - 8 . 60 ( m , 1h ), 8 . 33 ( ddd , j = 8 . 4 , 2 . 8 , 1 . 4 hz , 1h ), 7 . 64 ( ddd , j = 8 . 5 , 4 . 7 , 0 . 7 hz , 1h ); 13 c nmr ( 101 mhz , dmso - d 6 ) δ 149 . 49 , 140 . 75 , 136 . 02 , 134 . 43 , 132 . 14 , 131 . 76 , 127 . 22 , 124 . 31 ; eims m / z 224 ([ m ] + ). to a 100 ml , 3 - neck round bottom flask was charged 3 -( 3 - chloro - 4 - nitro - 1h - pyrazol - 1 - yl ) pyridine ( 2 . 40 g , 10 . 7 mmol ), acetic acid ( 4 ml ), ethanol ( 4 . 8 ml ) and water ( 4 . 8 ml ). the mixture was cooled to 5 ° c . and iron powder ( 2 . 98 g , 53 . 4 mmol ) was added portionwise over ˜ 15 minutes . the reaction was allowed to stir at 20 ° c . for 18 hours and diluted to 50 ml with water . it was filtered through celite ® and the filtrate was carefully basified with a sodium hydroxide solution ( 50 wt % in water ). the resulting suspension was filtered through celite ® and the filtrate was extracted with ethyl acetate ( 3 × 20 ml ). the organic layers were combined , dried over sodium sulfate and concentrated to dryness to afford a tan colored solid , which was further dried under vacuum for 18 hours ( 2 . 20 g , quantitative ): mp 145 - 147 ° c . ; 1 h nmr ( 400 mhz , dmso - d 6 ) δ 8 . 95 ( dd , j = 2 . 6 , 0 . 8 hz , 1h ), 8 . 45 ( dd , j = 4 . 7 , 1 . 4 hz , 1h ), 8 . 08 ( ddd , j = 8 . 4 , 2 . 7 , 1 . 4 hz , 1h ), 7 . 91 ( s , 1h ), 7 . 49 ( ddd , j = 8 . 3 , 4 . 7 , 0 . 8 hz , 1h ), 4 . 43 ( s , 2h ); 13 c nmr ( 101 mhz , dmso - d 6 ) δ 146 . 35 , 138 , 53 , 135 . 72 , 132 . 09 , 130 . 09 , 124 . 29 , 124 . 11 , 114 . 09 ; eims m / z 194 ([ m ] + ). alternate synthetic route to 3 -( 3 - chloro - 4 - amino - 1h - pyrazol - 1 - yl ) pyridine ( 2 - 7 ): in a 250 ml 3 - neck round bottom flask was added 3 -( 3 - chloro - 4 - nitro - 1h - pyrazol - 1 - yl ) pyridine ( 5 . 00 g , 21 . 8 mmol ), ethanol ( 80 ml ), water ( 40 ml ), and ammonium chloride ( 5 . 84 g , 109 mmol ). the suspension was stirred under nitrogen stream for 5 minutes then iron powder ( 4 . 87 g , 87 . 2 mmol ) was added . the reaction mixture was heated to reflux (˜ 80 ° c .) and held there for 4 hours . after 4 hours a reaction aliquot taken and the reaction had gone to full conversion as shown by hplc analysis . ethyl acetate ( 120 ml ) and celite ® ( 10 g ) were added to the reaction mixture and the mixture was let stir for 10 minutes . the black colored suspension was then filtered via a celite ® pad and rinsed with ethyl acetate ( 80 ml ). the filtrate was washed with saturated sodium bicarbonate solution in water ( 30 ml ) and the organic layer was assayed . the assay gave 4 . 19 g ( 99 % yield ) of product . the organic solvent was removed in vacuo to give a brown colored crude solid that was used without further purification . a 100 ml three - neck round bottom flask was charged with 3 - chloro - 1 ( pyridin - 3 - yl )- 1h - pyrazol - 4 - amine ( 1 . 00 g , 5 . 14 mmol ) and ethyl acetate ( 10 ml ). sodium bicarbonate ( 1 . 08 g , 12 . 9 mmol ) was added , followed by dropwise addition of acetic anhydride ( 0 . 629 g , 6 . 17 mmol ) at & lt ; 20 ° c . the reaction was stirred at 20 ° c . for 2 hours to afford a suspension , at which point thin layer chromatography analysis [ eluent : ethyl acetate ] indicated that the reaction was complete . the reaction was diluted with water ( 50 ml ) and the resulting suspension was filtered . the solid was rinsed with water ( 10 ml ) followed by methanol ( 5 ml ). the solid was further dried under vacuum at 20 ° c . to afford the desired product as a white solid ( 0 . 804 g , 66 %): mp 169 - 172 ° c . ; 1 h nmr ( 400 mhz , dmso - d 6 ) δ 9 . 84 ( s , 1h ), 9 . 05 ( dd , j = 2 . 8 , 0 . 8 hz , 1h ), 8 . 82 ( s , 1h ), 8 . 54 ( dd , j = 4 . 7 , 1 . 4 hz , 1h ), 8 . 20 ( ddd , j = 8 . 4 , 2 . 8 , 1 . 4 hz , 1h ), 7 . 54 , ( ddd , j = 8 . 3 , 4 . 7 , 0 . 8 hz , 1h ), 2 . 11 ( s , 3h ); 13 c nmr ( 101 mhz , dmso - d 6 ) δ 168 , 12 , 147 , 46 , 139 , 42 , 135 . 46 , 133 . 60 , 125 . 47 , 124 . 21 , 122 . 21 , 120 , 16 , 22 . 62 ; eims m / z 236 ([ m ] + ). in 125 ml 3 - neck round - bottomed flask was added n -( 3 - chloro - 1 -( pyridin - 3 - yl )- 1h - pyrazol - 4 - yl ) acetamide ( 2 . 57 g , 9 . 44 mmol ), tetrahydrofuran ( 55 ml ), and sodium tert - butoxide ( 1 . 81 g , 18 . 9 mmol ). the suspension was stirred for 5 minutes then ethyl bromide ( 1 . 41 ml , 18 . 9 mmol ), and tetrabutylammonium iodide ( 67 mg , 0 . 2 mmol ) were added . the resulting gray colored suspension was then heated to 38 ° c . the reaction was analyzed after 3 hours and found to have gone to 81 % completion , after 24 hours the reaction was found to have gone to completion . the reaction mixture was allowed to cool to ambient temperature and quenched with ammonium hydroxide / formic acid ( hco 2 h ) buffer ( 10 ml ). the mixture was then diluted with tetrahydrofuran ( 40 ml ), ethyl acetate ( 120 ml ), and saturated sodium bicarbonate solution in water ( 30 ml ). the layers were separated and the aqueous layer was extracted with ethyl acetate ( 2 × 30 ml ). the organic layers were combined and silica gel ( 37 g ) was added . the solvent was removed in vacuo to give a solid that was purified using semi - automated silica gel chromatography ( redisep silica 220 g column ; hexanes ( 0 . 2 % triethylamine )/ ethyl acetate , 40 / 60 to 0 / 100 gradient elution system , flow rate 150 ml / minute ) to give , after concentration , an orange solid ( 2 . 19 g , 88 %). a solution of n -( 3 - chloro - 1 -( pyridin - 3 - yl )- 1h - pyrazol - 4 - yl )- n - ethylacetamide ( 1 . 8 g , 6 . 80 mmol ) in 1 n hydrochloric acid ( 34 ml ) was heated at 80 ° c . for 18 hours , at which point hplc analysis indicated that only 1 . 1 % starting material remained . the reaction mixture was cooled to 20 ° c . and basified with sodium hydroxide ( 50 wt % in water ) to ph & gt ; 9 . the resulting suspension was stirred at 20 ° c . for 2 hours and filtered . the filter cake was rinsed with water ( 2 × 5 ml ), conditioned for 30 minutes , and air - dried to afford an off - white solid ( 1 . 48 g , 95 %): 1 h nmr ( 400 mhz , dmso - d 6 ) δ 9 . 00 ( dd , j = 2 . 8 , 0 . 8 hz , 1h ), 8 . 45 ( dd , j = 4 . 7 , 1 . 4 hz , 1h ), 8 . 11 ( ddd , j = 8 . 4 , 2 . 8 , 1 . 4 hz , 1h ), 8 . 06 ( d , j = 0 . 6 hz , 1h ), 7 . 49 ( ddd , j = 8 . 4 , 4 . 7 , 0 . 8 hz , 1h ), 4 . 63 ( t , j = 6 . 0 hz , 1h ), 3 . 00 ( qd , j = 7 . 1 , 5 . 8 hz , 2h ), 1 . 19 ( t , j = 7 . 1 hz , 3h ); 13 c nmr ( 101 mhz , dmso - d 6 ) δ 146 . 18 , 138 . 31 , 135 . 78 , 132 . 82 , 130 . 84 , 124 . 08 , 123 . 97 , 112 . 23 , 40 . 51 , 14 . 28 ; esims m / z 223 ([ m + h ] + ). alternate synthetic route to 3 - chloro - n - ethyl - 1 -( pyridin - 3 - yl )- 1h - pyrazol - amine ( 2 - 10 ): to a 3 - neck , 100 - ml round bottom flask was charged n -( 3 - chloro - 1 -( pyridin - 3 - yl )- 1h - pyrazol - 4 - yl ) acetamide ( 5 g , 21 . 13 mmol ) and tetrahydrofuran ( 50 ml ). sodium tert - butoxide ( 4 . 06 g , 42 . 3 mmol ) was added ( causing a temperature rise from 22 ° c . to 27 . 6 ° c . ), followed by ethyl bromide ( 6 . 26 ml , 85 mmol ). the reaction was stirred at 35 ° c . for 144 h at which point only 3 . 2 % ( auc ) starting material remained . the reaction mixture was concentrated to give a brown residue , which was dissolved in 1 n hydrochloric acid ( 106 ml , 106 mmol ) and heated at 80 ° c . for 24 hours , at which point hplc analysis indicated that the starting material had been consumed . the reaction was cooled to 20 ° c . and basified with sodium hydroxide ( 50 wt % in water ) to ph & gt ; 9 . the resulting suspension was stirred at 20 ° c . for 1 hour and filtered . the filter cake was rinsed with water ( 25 ml ) to afford a brown solid ( 5 . 18 g ). the resulting crude product was dissolved in ethyl acetate and passed through a silica gel plug ( 50 g ) using ethyl acetate ( 500 ml ) as eluent . the filtrate was concentrated to dryness to afford a white solid ( 3 . 8 g , 80 %). a 100 ml three neck round bottom flask was charged with 3 - chloro - n - ethyl - 1 -( pyridine - 3 - yl )- 1h - pyrazol - 4 - amine ( 5 . 00 g , 22 . 5 mmol ) and ethyl acetate ( 50 ml ). sodium bicarbonate ( 4 . 72 g , 56 . 1 mmol ) was added , followed by dropwise addition of 3 -(( 3 , 3 , 3 - trifluoropropyl ) thio ) propanoyl chloride ( 5 . 95 g , 26 . 9 mmol ) at & lt ; 20 ° c . for 2 hours , at which point hplc analysis indicated that the reaction was complete . the reaction was diluted with water ( 50 ml ) ( off - gassing ) and the layers were separated . the aqueous layer was extracted with ethyl acetate ( 20 ml ) and the combined organic layers were concentrated to dryness to afford a light brown solid ( 10 . 1 g , quantitative ). a small sample of crude product was purified by flash column chromatography using ethyl acetate as eluent to obtain an analytical sample : mp 79 - 81 ° c . ; 1 h nmr ( 400 mhz , dmso - d 6 ) δ 9 . 11 ( d , j = 2 . 7 hz , 1h ), 8 . 97 ( s , 1h ), 8 . 60 ( dd , j = 4 . 8 , 1 . 4 hz , 1h ), 8 . 24 ( ddd , j = 8 . 4 , 2 . 8 , 1 . 4 hz , 1h ), 7 . 60 ( ddd , j = 8 . 4 , 4 . 7 , 0 . 8 hz , 1h ), 3 . 62 ( q , j = 7 . 2 hz , 2h ), 2 . 75 ( t , j = 7 . 0 hz , 2h ), 2 . 66 - 2 . 57 ( m 2h ), 2 . 57 - 2 . 44 ( m , 2h ), 2 . 41 ( t , j = 7 . 0 hz , 2h ), 1 . 08 ( t , j = 7 . 1 hz , 3h ). eims m / z 406 ([ m ] + ). n -( 3 - chloro - 1 -( pyridin - 3 - yl )- 1h - pyrazol - 4 - yl )- n - ethyl - 3 -(( 3 , 3 , 3 - trifluoropropyl ) thio ) propanamide ( 57 . 4 g , 141 mmol ) was stirred in methanol ( 180 ml ). to the resulting solution was added hydrogen peroxide ( 43 . 2 ml , 423 mmol ) dropwise using a syringe . the solution was stirred at room temperature for 6 hours , at which point lcms analysis indicated that the starting material was consumed . the mixture was poured into dichloromethane ( 360 ml ) and washed with aqueous sodium carbonate ( na 2 co 3 ). the organic layer was dried over sodium sulfate and concentrated under reduced pressure to provide a thick yellow oil . the crude product was purified by flash column chromatography using 0 - 10 % methanol / ethyl acetate as eluent . the pure fractions were combined and concentrated to afford the desired product as an oil ( 42 . 6 g , 68 %): 1 h nmr ( 400 mhz , dmso - d 6 ) δ 9 . 09 ( dd , j = 2 . 8 , 0 . 7 hz , 1h ), 8 . 98 ( s , 1h ), 8 . 60 ( dd , j = 4 . 7 , 1 . 4 hz , 1h ), 8 . 24 ( ddd , j = 8 . 4 , 2 . 7 , 1 . 4 hz , 1h ), 7 . 60 ( ddd , j = 8 . 4 , 4 . 7 , 0 . 8 hz , 1h ), 3 . 61 ( q , j = 7 . 4 , 7 . 0 hz , 2h ), 3 . 20 - 2 . 97 ( m , 2h ), 2 . 95 - 2 . 78 ( m , 2h ), 2 . 76 - 2 . 57 ( m , 2h ), 2 . 58 - 2 . 45 ( m , 2h ), 1 . 09 ( t , j = 7 . 1 hz , 3h ); esims m / z 423 ([ m + h ] + ). example a bioassays on green peach aphid (“ gpa ”) ( myzus persicae ) ( myzupe .) gpa is the most significant aphid pest of peach trees , causing decreased growth , shriveling of leaves , and the death of various tissues . it is also hazardous because it acts as a vector for the transport of plant viruses , such as potato virus y and potato leafroll virus to members of the nightshade / potato family solanaceae , and various mosaic viruses to many other food crops . gpa attacks such plants as broccoli , burdock , cabbage , carrot , cauliflower , daikon , eggplant , green beans , lettuce , macadamia , papaya , peppers , sweet potatoes , tomatoes , watercress and zucchini among other plants . gpa also attacks many ornamental crops such as carnations , chrysanthemum , flowering white cabbage , poinsettia and roses . gpa has developed resistance to many pesticides . several molecules disclosed herein were tested against gpa using procedures described below . cabbage seedling grown in 3 - in pots , with 2 - 3 small ( 3 - 5 cm ) true leaves , were used as test substrate . the seedlings were infested with 20 - 5 - gpa ( wingless adult and nymph stages ) one day prior to chemical application . four posts with individual seedlings were used for each treatment . test compounds ( 2 mg ) were dissolved in 2 ml of acetone / methanol ( 1 : 1 ) solvent , forming stock solutions of 1000 ppm test compound . the stock solutions were diluted 5 × with 0 . 025 % tween 20 in water to obtain the solution at 200 ppm test compound . a hand - held aspirator - type sprayer was used for spraying a solution to both sides of the cabbage leaves until runoff . reference plants ( solvent check ) were sprayed with the diluent only containing 20 % by volume acetone / methanol ( 1 : 1 ) solvent . treated plants were held in a holding room for three days at approximately 25 ° c . and ambient relative humidity ( rh ) prior to grading . evaluation was conducted by counting the number of live aphids per plant under a microscope . percent control was measured by using abbott &# 39 ; s correction formula ( w . s . abbott , “ a method of computing the effectiveness of an insecticide ” j . econ . entomol 18 ( 1925 ), pp . 265 - 267 ) as follows . where x = no . of live aphids on solvent check plants and y = no . of live aphids on treated plants the results are indicated in the table entitled “ table 1 : gpa ( myzupe ) and sweetpotato whitefly - crawler ( bemita ) rating table ”. example b bioassays on sweetpotato whitefly crawler ( bemisia tabaci ) ( bemita .) the sweetpotato whitefly , bemisia tabaci ( gennadius ), has been recorded in the united states since the late 1800s . in 1986 in florida , bemisia tabaci became an extreme economic pest . whiteflies usually feed on the lower surface of their host plant leaves . from the egg hatches a minute crawler stage that moves about the leaf until it inserts its microscopic , threadlike mouthparts to feed by sucking sap from the phloem . adults and nymphs excrete honeydew ( largely plant sugars from feeding on phloem ), a sticky , viscous liquid in which dark sooty molds grow . heavy infestations of adults and their progeny can cause seedling death , or reduction in vigor and yield of older plants , due simply to sap removal . the honeydew can stick cotton lint together , making it more difficult to gin and therefore reducing its value . sooty mold grows on honeydew - covered substrates , obscuring the leaf and reducing photosynthesis , and reducing fruit quality grade . it transmitted plant - pathogenic viruses that had never affected cultivated crops and induced plant physiological disorders , such as tomato irregular ripening and squash silverleaf disorder . whiteflies are resistant to many formerly effective pesticides . cotton plants grown in 3 - inch pots , with 1 small ( 3 - 5 cm ) true leaf , were used at test substrate . the plants were placed in a room with whitefly adults . adults were allowed to deposit eggs for 2 - 3 days . after a 2 - 3 day egg - laying period , plants were taken from the adult whitefly room . adults were blown off leaves using a hand - held devilbliss sprayer ( 23 psi ). plants with egg infestation ( 100 - 300 eggs per plant ) were placed in a holding room for 5 - 6 days at 82 ° f . and 50 % rh for egg hatch and crawler stage to develop . four cotton plants were used for each treatment . compounds ( 2 mg ) were dissolved in 1 ml of acetone solvent , forming stock solutions of 2000 ppm . the stock solutions were diluted 10 × with 0 . 025 % tween 20 in water to obtain a test solution at 200 ppm . a hand - held devilbliss sprayer was used for spraying a solution to both sides of cotton leaf until runoff . reference plants ( solvent check ) were sprayed with the diluent only . treated plants were held in a holding room for 8 - 9 days at approximately 82 ° f . and 50 % rh prior to grading . evaluation was conducted by counting the number of live nymphs per plant under a microscope . pesticidal activity was measured by using abbott &# 39 ; s correction formula ( see above ) and presented in table 1 .