Structure of 2926-29-6
*Storage: {[sel_prStorage]}
*Shipping: {[sel_prShipping]}
The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
4.5
*For Research Use Only !
Change View
Size | Price | VIP Price | US Stock |
Global Stock |
In Stock | ||
{[ item.pr_size ]} |
Inquiry
{[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price, item.pr_usd) ]} {[ getRatePrice(item.pr_usd,item.pr_rate,1,item.pr_is_large_size_no_price, item.discount_usd) ]} {[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price, item.pr_usd) ]} |
Inquiry {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate,item.pr_is_large_size_no_price, item.vip_usd) ]} | Inquiry {[ item.pr_usastock ]} In Stock Inquiry - | {[ item.pr_chinastock ]} {[ item.pr_remark ]} In Stock 1-2 weeks - Inquiry - | Login | - + | Inquiry |
Please Login or Create an Account to: See VIP prices and availability
US Stock: ship in 0-1 business day
Global Stock: ship in 5-7 days
1-2weeks
Inquiry
{[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate,item.pr_is_large_size_no_price, item.vip_usd) ]}
{[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price, item.pr_usd) ]}
{[ getRatePrice(item.pr_usd,1,item.mem_rate,item.pr_is_large_size_no_price, item.pr_usd) ]}
Inquiry
{[ getRatePrice(item.pr_usd,item.pr_rate,1,item.pr_is_large_size_no_price, item.vip_usd) ]}
{[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price, item.pr_usd) ]}
{[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price, item.pr_usd) ]}
In Stock
- +
Please Login or Create an Account to: See VIP prices and availability
US Stock: ship in 0-1 business day
Global Stock: ship in 2 weeks
Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.
Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.
Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.
Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.
Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.
CAS No. : | 2926-29-6 |
Formula : | CF3NaO2S |
M.W : | 156.06 |
SMILES Code : | O=S(C(F)(F)F)[O-].[Na+] |
MDL No. : | MFCD03092989 |
InChI Key : | KAVUKAXLXGRUCD-UHFFFAOYSA-M |
Pubchem ID : | 23690734 |
GHS Pictogram: |
![]() |
Signal Word: | Warning |
Hazard Statements: | H315-H319 |
Precautionary Statements: | P264-P280-P337+P313-P305+P351+P338-P302+P352-P332+P313-P362 |
Num. heavy atoms | 8 |
Num. arom. heavy atoms | 0 |
Fraction Csp3 | 1.0 |
Num. rotatable bonds | 1 |
Num. H-bond acceptors | 5.0 |
Num. H-bond donors | 0.0 |
Molar Refractivity | 15.11 |
TPSA ? Topological Polar Surface Area: Calculated from |
59.34 Ų |
Log Po/w (iLOGP)? iLOGP: in-house physics-based method implemented from |
-8.6 |
Log Po/w (XLOGP3)? XLOGP3: Atomistic and knowledge-based method calculated by |
0.58 |
Log Po/w (WLOGP)? WLOGP: Atomistic method implemented from |
2.51 |
Log Po/w (MLOGP)? MLOGP: Topological method implemented from |
-0.22 |
Log Po/w (SILICOS-IT)? SILICOS-IT: Hybrid fragmental/topological method calculated by |
1.62 |
Consensus Log Po/w? Consensus Log Po/w: Average of all five predictions |
-0.82 |
Log S (ESOL):? ESOL: Topological method implemented from |
-1.11 |
Solubility | 12.2 mg/ml ; 0.0782 mol/l |
Class? Solubility class: Log S scale |
Very soluble |
Log S (Ali)? Ali: Topological method implemented from |
-1.4 |
Solubility | 6.22 mg/ml ; 0.0399 mol/l |
Class? Solubility class: Log S scale |
Very soluble |
Log S (SILICOS-IT)? SILICOS-IT: Fragmental method calculated by |
-0.18 |
Solubility | 104.0 mg/ml ; 0.667 mol/l |
Class? Solubility class: Log S scale |
Soluble |
GI absorption? Gatrointestinal absorption: according to the white of the BOILED-Egg |
High |
BBB permeant? BBB permeation: according to the yolk of the BOILED-Egg |
Yes |
P-gp substrate? P-glycoprotein substrate: SVM model built on 1033 molecules (training set) |
Yes |
CYP1A2 inhibitor? Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set) |
No |
CYP2C19 inhibitor? Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set) |
No |
CYP2C9 inhibitor? Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set) |
No |
CYP2D6 inhibitor? Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set) |
No |
CYP3A4 inhibitor? Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set) |
No |
Log Kp (skin permeation)? Skin permeation: QSPR model implemented from |
-6.84 cm/s |
Lipinski? Lipinski (Pfizer) filter: implemented from |
0.0 |
Ghose? Ghose filter: implemented from |
None |
Veber? Veber (GSK) filter: implemented from |
0.0 |
Egan? Egan (Pharmacia) filter: implemented from |
0.0 |
Muegge? Muegge (Bayer) filter: implemented from |
2.0 |
Bioavailability Score? Abbott Bioavailability Score: Probability of F > 10% in rat |
0.55 |
PAINS? Pan Assay Interference Structures: implemented from |
0.0 alert |
Brenk? Structural Alert: implemented from |
1.0 alert: heavy_metal |
Leadlikeness? Leadlikeness: implemented from |
No; 1 violation:MW<1.0 |
Synthetic accessibility? Synthetic accessibility score: from 1 (very easy) to 10 (very difficult) |
2.58 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80.20% | With trichlorophosphate;dimethylamine p-toluenesulfonate; at 40℃; for 14h;Product distribution / selectivity; | Comparative Example 13; [0123] Direct sulfinylation of N-phenyl pyrazole starting material (III) according to known methods was tested. As such, sulfinylation was attempted using CF3SO2Na in the presence of a halogenating agent such as POCl3, SOCl2 or PBr3. <n="35"/>(III) (II)The reaction reagents and conditions tested are provided in Table I below. <n="36"/>Table IUl <n="37"/>The results are provided in Table II below: Table II[0124] The reaction proceeded to the desired product, Fipronil, when SOCl2 or POCl3 were used as halogenating agents. However, PBr3 did not yield the desired product, or at least not in acceptable yield (about 6%~8% (II) in the reaction mixture, according to HPLC). |
74.80% | With thionyl chloride;dimethylamine p-toluenesulfonate; at 40℃; for 10h;Product distribution / selectivity; | Comparative Example 13; [0123] Direct sulfinylation of N-phenyl pyrazole starting material (III) according to known methods was tested. As such, sulfinylation was attempted using CF3SO2Na in the presence of a halogenating agent such as POCl3, SOCl2 or PBr3. <n="35"/>(III) (II)The reaction reagents and conditions tested are provided in Table I below. <n="36"/>Table IUl <n="37"/>The results are provided in Table II below: Table II[0124] The reaction proceeded to the desired product, Fipronil, when SOCl2 or POCl3 were used as halogenating agents. However, PBr3 did not yield the desired product, or at least not in acceptable yield (about 6%~8% (II) in the reaction mixture, according to HPLC). |
73% | Example 1; Sulfinylation of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile with triethylamine hydrochloride, sodium trifluoromethylsulfinate and thionylchloride, in 6.5 molar equivalents of tolueneWithin a 3-neck, 50 ml. round bottom flask equipped with a magnetic stirrer bar and a thermometer were placed vacuum dried sodium trifluoromethylsulfinate (4.29 g, 27.5 mmol), vacuum dried triethylamine hydrochloride (5.16 g, 37.5 mmol), and 13 ml. an- hydrous toluene (6.5 molar equivalents relative to 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H-pyrazole-3-carbonitrile) under an argon atmosphere. After cooling to 00C to 5 0C with an ice bath, thionylchloride (3.57 g, 30 mmol) was added slowly while keeping the reaction temperature below 5 0C. After stirring for another 30 min, vacuum dried 5-amino-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-1 H-pyrazole-3- carbonitrile (8.03 g, 25 mmol, 99 % purity) was added at 5 0C, and the reaction mixture was heated to 50 0C within 5 min by a preheated water bath. The temperature of 50 0C was kept for another 6 hours before quenching the reaction with 50 ml. of saturated NaHCO3 solution. The resulting suspension was diluted with 30 ml. of ethylacetate. After phase separa- tion the organic layer was washed once with saturated NaHCtheta3 solution and concentrated under reduced pressure until dryness. The crude product was crystallized from refluxing toluene (100 g) affording the title compound as a white crystalline powder (8.06 g, 70 % yield, 94 % purity by quantitative HPLC). 1H-NMR (Bruker DRX-500, d6- DMSO): delta [ppm]: 8.33 (s), 7.57 (s).; Comparative Examples; In order to demonstrate the advantages of the inventive process, the following examples are conducted employing the preparation procedure given above for example 1. |
73 - 76% | Example 1; Sulfinylation of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile with triethylamine hydrochloride, sodium trifluoromethylsulfinate and thionylchloride, in 6.5 molar equivalents of tolueneWithin a 3-neck, 50 ml. round bottom flask equipped with a magnetic stirrer bar and a thermometer were placed vacuum dried sodium trifluoromethylsulfinate (4.29 g, 27.5 mmol), vacuum dried triethylamine hydrochloride (5.16 g, 37.5 mmol), and 13 ml. an- hydrous toluene (6.5 molar equivalents relative to 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H-pyrazole-3-carbonitrile) under an argon atmosphere. After cooling to 00C to 5 0C with an ice bath, thionylchloride (3.57 g, 30 mmol) was added slowly while keeping the reaction temperature below 5 0C. After stirring for another 30 min, vacuum dried 5-amino-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-1 H-pyrazole-3- carbonitrile (8.03 g, 25 mmol, 99 % purity) was added at 5 0C, and the reaction mixture was heated to 50 0C within 5 min by a preheated water bath. The temperature of 50 0C was kept for another 6 hours before quenching the reaction with 50 ml. of saturated NaHCO3 solution. The resulting suspension was diluted with 30 ml. of ethylacetate. After phase separa- tion the organic layer was washed once with saturated NaHCtheta3 solution and concentrated under reduced pressure until dryness. The crude product was crystallized from refluxing toluene (100 g) affording the title compound as a white crystalline powder (8.06 g, 70 % yield, 94 % purity by quantitative HPLC). 1H-NMR (Bruker DRX-500, d6- DMSO): delta [ppm]: 8.33 (s), 7.57 (s).; Example 12; Sulfinylation of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H-pyrazole-3- carbonitrile with trimethylamine tosylate, sodium trifluoromethylsulfinate and thionyl- chloride, in 6.5 molar equivalents of tolueneThe preparation procedure was conducted as described above for example 1. The crude product was crystallized from refluxing toluene (100 g) affording the title compound as a white crystalline powder (76 % yield, 96 % purity by quantitative HPLC).; Example 14; Sulfinylation of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile with trimethylamine tosylate, sodium trifluoromethylsulfinate and thionylchloride, in 6.5 molar equivalents of tolueneThe preparation procedure was conducted as described above for example 11. The crude product was crystallized from refluxing toluene (100 g) affording the title com- pound as a white crystalline powder (73 % yield, 98 % purity by quantitative HPLC). | |
72 - 75% | Example 1; Sulfinylation of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile with triethylamine hydrochloride, sodium trifluoromethylsulfinate and thionylchloride, in 6.5 molar equivalents of tolueneWithin a 3-neck, 50 ml. round bottom flask equipped with a magnetic stirrer bar and a thermometer were placed vacuum dried sodium trifluoromethylsulfinate (4.29 g, 27.5 mmol), vacuum dried triethylamine hydrochloride (5.16 g, 37.5 mmol), and 13 ml. an- hydrous toluene (6.5 molar equivalents relative to 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H-pyrazole-3-carbonitrile) under an argon atmosphere. After cooling to 00C to 5 0C with an ice bath, thionylchloride (3.57 g, 30 mmol) was added slowly while keeping the reaction temperature below 5 0C. After stirring for another 30 min, vacuum dried 5-amino-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-1 H-pyrazole-3- carbonitrile (8.03 g, 25 mmol, 99 % purity) was added at 5 0C, and the reaction mixture was heated to 50 0C within 5 min by a preheated water bath. The temperature of 50 0C was kept for another 6 hours before quenching the reaction with 50 ml. of saturated NaHCO3 solution. The resulting suspension was diluted with 30 ml. of ethylacetate. After phase separa- tion the organic layer was washed once with saturated NaHCtheta3 solution and concentrated under reduced pressure until dryness. The crude product was crystallized from refluxing toluene (100 g) affording the title compound as a white crystalline powder (8.06 g, 70 % yield, 94 % purity by quantitative HPLC). 1H-NMR (Bruker DRX-500, d6- DMSO): delta [ppm]: 8.33 (s), 7.57 (s).; Example 7; Sulfinylation of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile with pyridine tosylate, sodium trifluoromethylsulfinate and thionylchloride, in 6.5 molar equivalents of tolueneThe preparation procedure was conducted as described above for example 1. The crude product was crystallized from refluxing toluene (100 g) affording the title compound as a white crystalline powder (75 % yield, 94 % purity by quantitative HPLC).; Example 11; Sulfinylation of 5-amino-1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile with thionylchloride, triethylamine hydrochloride and dosage of potassium trifluoromethylsulfinateWithin a 750 mL reactor with a mechanical stirrer and a thermometer were placed vac- uum dried triethylamine hydrochloride (51.1 g, 368 mmol), 147 g anhydrous toluene(6.5 molar equivalents relative to 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile), and thionylchloride (35.7 g, 294 mmol) under an argon atmosphere. After cooling to 00C to 5 0C with external cooling, vacuum dried potassium trifluoromethylsulfinate (50.4 g, 296 mmol) was added in three equal portions every 10 min while keeping the reaction temperature below 5 0C. After stirring for another 30 min, vacuum dried 5-amino-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-1 H-pyrazole-3- carbonitrile (79.5 g, 245 mmol, 99 % purity) was added at 5 0C, and the reaction mixture was kept at 5 0C for 60 min and then heated to 35 0C within 45 min. The temperature of 35 0C was kept for another 10 hours before quenching the reaction with 200 g of sodium hydroxide solution (10 wt.%).The resulting suspension was diluted with 176 mL of ethylacetate. After phase separation the organic layer was washed once with sodium hydroxide solution (10 wt.%). After phase separation, the organic layer was analyzed by quantitative HPLC (79 % yield). The content of compound F was below 2.9 weight percent in the crude mixture (without solvent). The product was crystallized from a mixture of ethylacetate and toluene affording the title compound as a white crystalline powder (77.1 g, 75 % yield, 98 % purity by quantitative HPLC).; Example 16; Sulfinylation of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H-pyrazole-3- carbonitrile with pyridine tosylate, sodium trifluoromethylsulfinate and thionylchloride, in 6.5 molar equivalents of toluene EPO <DP n="30"/>The preparation procedure was conducted as described above for example 11. The crude product was crystallized from refluxing toluene (100 g) affording the title compound as a white crystalline powder (72 % yield, 98 % purity by quantitative HPLC). | |
71% | Example 1; Sulfinylation of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile with triethylamine hydrochloride, sodium trifluoromethylsulfinate and thionylchloride, in 6.5 molar equivalents of tolueneWithin a 3-neck, 50 ml. round bottom flask equipped with a magnetic stirrer bar and a thermometer were placed vacuum dried sodium trifluoromethylsulfinate (4.29 g, 27.5 mmol), vacuum dried triethylamine hydrochloride (5.16 g, 37.5 mmol), and 13 ml. an- hydrous toluene (6.5 molar equivalents relative to 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H-pyrazole-3-carbonitrile) under an argon atmosphere. After cooling to 00C to 5 0C with an ice bath, thionylchloride (3.57 g, 30 mmol) was added slowly while keeping the reaction temperature below 5 0C. After stirring for another 30 min, vacuum dried 5-amino-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-1 H-pyrazole-3- carbonitrile (8.03 g, 25 mmol, 99 % purity) was added at 5 0C, and the reaction mixture was heated to 50 0C within 5 min by a preheated water bath. The temperature of 50 0C was kept for another 6 hours before quenching the reaction with 50 ml. of saturated NaHCO3 solution. The resulting suspension was diluted with 30 ml. of ethylacetate. After phase separa- tion the organic layer was washed once with saturated NaHCtheta3 solution and concentrated under reduced pressure until dryness. The crude product was crystallized from refluxing toluene (100 g) affording the title compound as a white crystalline powder (8.06 g, 70 % yield, 94 % purity by quantitative HPLC). 1H-NMR (Bruker DRX-500, d6- DMSO): delta [ppm]: 8.33 (s), 7.57 (s).; Example 8; Sulfinylation of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile with trimethylamine hydrochloride, sodium trifluoromethylsulfinate and thionylchloride, in 6.5 molar equivalents of tolueneThe preparation procedure was conducted as described above for example 1. The crude product was crystallized from refluxing toluene (100 g) affording the title compound as a white crystalline powder (71 % yield, 97 % purity by quantitative HPLC). | |
67% | With potassium fluoride; thionyl chloride;triethylamine hydrochloride; In toluene; at 0 - 50℃; for 5.08333h;Product distribution / selectivity; | Example 5; Sulfinylation of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile with triethylamine hydrochloride, sodium trifluoromethylsulfinate and thionylchloride under addition of potassium fluorideAn oven dried 100 mL 3 neck round bottom flask equipped with a magnetic stir bar, thermocouple, condenser, ISb inlet, and rubber septum, was charged with vacuum dried potassium fluoride (1.53 g, 26.1 mmol), anhydrous toluene (20.1 g), vacuum dried sodium trifluoromethylsulfinate (4.53 g, 29.0 mmol), and thionylchloride (3.76 g, 31.6 mmol) under nitrogen. The solution was cooled to 00C and triethylamine hydrochloride (5.44g, 39.5 mmol) was added slowly, controlling the temperature to less than 10 0C. Vacuum dried 5-amino-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-1 H-pyrazole-3- carbonitrile (8.48 g, 26.1 mmol, 99 % pure) was added at 00C. The solution was then quickly warmed to 50 0C, in less then 5 minutes, using a hot water bath. The reaction was allowed to stir for 5 hrs at 50 0C before quenching with 50 ml of saturated aqueous NaHCtheta3. The resulting suspension was diluted with 30 mL of ethylacetate and then allowed to phase separate. The aqueous phase was extracted with 30 mL ethyl acetate and the combined organic phases were washed with 30 ml of saturated aqueous NaCU3. The organic phase was concentrated under reduced pressure until dryness, affording the crude title compound (11.6 g, 67 % yield, 68.5 % purity). 1H-NMR (Bruker DRX-500, d6-DMSO): delta [ppm]: 8.33 (s), 7.57 (s). |
67% | Example 1; Sulfinylation of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile with triethylamine hydrochloride, sodium trifluoromethylsulfinate and thionylchloride, in 6.5 molar equivalents of tolueneWithin a 3-neck, 50 ml. round bottom flask equipped with a magnetic stirrer bar and a thermometer were placed vacuum dried sodium trifluoromethylsulfinate (4.29 g, 27.5 mmol), vacuum dried triethylamine hydrochloride (5.16 g, 37.5 mmol), and 13 ml. an- hydrous toluene (6.5 molar equivalents relative to 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H-pyrazole-3-carbonitrile) under an argon atmosphere. After cooling to 00C to 5 0C with an ice bath, thionylchloride (3.57 g, 30 mmol) was added slowly while keeping the reaction temperature below 5 0C. After stirring for another 30 min, vacuum dried 5-amino-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-1 H-pyrazole-3- carbonitrile (8.03 g, 25 mmol, 99 % purity) was added at 5 0C, and the reaction mixture was heated to 50 0C within 5 min by a preheated water bath. The temperature of 50 0C was kept for another 6 hours before quenching the reaction with 50 ml. of saturated NaHCO3 solution. The resulting suspension was diluted with 30 ml. of ethylacetate. After phase separa- tion the organic layer was washed once with saturated NaHCtheta3 solution and concentrated under reduced pressure until dryness. The crude product was crystallized from refluxing toluene (100 g) affording the title compound as a white crystalline powder (8.06 g, 70 % yield, 94 % purity by quantitative HPLC). 1H-NMR (Bruker DRX-500, d6- DMSO): delta [ppm]: 8.33 (s), 7.57 (s).; Example 9; Sulfinylation of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile with pyridine hydrochloride, sodium trifluoromethylsulfinate and thionylchloride, in 6.5 molar equivalents of tolueneThe preparation procedure was conducted as described above for example 1. The crude product was crystallized from refluxing toluene (100 g) affording the title com- pound as a white crystalline powder (67 % yield, 95 % purity by quantitative HPLC).; Example 13; Sulfinylation of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H-pyrazole-3- carbonitrile with pyridine hydrochloride, sodium trifluoromethylsulfinate and thionylchlo- ride, in 6.5 molar equivalents of tolueneThe preparation procedure was conducted as described above for example 1. The crude product was crystallized from refluxing toluene (100 g) affording the title compound as a white crystalline powder (67 % yield, 95 % purity by quantitative HPLC). | |
65% | Example 1; Sulfinylation of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile with triethylamine hydrochloride, sodium trifluoromethylsulfinate and thionylchloride, in 6.5 molar equivalents of tolueneWithin a 3-neck, 50 ml. round bottom flask equipped with a magnetic stirrer bar and a thermometer were placed vacuum dried sodium trifluoromethylsulfinate (4.29 g, 27.5 mmol), vacuum dried triethylamine hydrochloride (5.16 g, 37.5 mmol), and 13 ml. an- hydrous toluene (6.5 molar equivalents relative to 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H-pyrazole-3-carbonitrile) under an argon atmosphere. After cooling to 00C to 5 0C with an ice bath, thionylchloride (3.57 g, 30 mmol) was added slowly while keeping the reaction temperature below 5 0C. After stirring for another 30 min, vacuum dried 5-amino-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-1 H-pyrazole-3- carbonitrile (8.03 g, 25 mmol, 99 % purity) was added at 5 0C, and the reaction mixture was heated to 50 0C within 5 min by a preheated water bath. The temperature of 50 0C was kept for another 6 hours before quenching the reaction with 50 ml. of saturated NaHCO3 solution. The resulting suspension was diluted with 30 ml. of ethylacetate. After phase separa- tion the organic layer was washed once with saturated NaHCtheta3 solution and concentrated under reduced pressure until dryness. The crude product was crystallized from refluxing toluene (100 g) affording the title compound as a white crystalline powder (8.06 g, 70 % yield, 94 % purity by quantitative HPLC). 1H-NMR (Bruker DRX-500, d6- DMSO): delta [ppm]: 8.33 (s), 7.57 (s).; Comparative Examples; In order to demonstrate the advantages of the inventive process, the following examples are conducted employing the preparation procedure given above for example 1. | |
63 - 75% | Example 1; Sulfinylation of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile with triethylamine hydrochloride, sodium trifluoromethylsulfinate and thionylchloride, in 6.5 molar equivalents of tolueneWithin a 3-neck, 50 ml. round bottom flask equipped with a magnetic stirrer bar and a thermometer were placed vacuum dried sodium trifluoromethylsulfinate (4.29 g, 27.5 mmol), vacuum dried triethylamine hydrochloride (5.16 g, 37.5 mmol), and 13 ml. an- hydrous toluene (6.5 molar equivalents relative to 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H-pyrazole-3-carbonitrile) under an argon atmosphere. After cooling to 00C to 5 0C with an ice bath, thionylchloride (3.57 g, 30 mmol) was added slowly while keeping the reaction temperature below 5 0C. After stirring for another 30 min, vacuum dried 5-amino-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-1 H-pyrazole-3- carbonitrile (8.03 g, 25 mmol, 99 % purity) was added at 5 0C, and the reaction mixture was heated to 50 0C within 5 min by a preheated water bath. The temperature of 50 0C was kept for another 6 hours before quenching the reaction with 50 ml. of saturated NaHCO3 solution. The resulting suspension was diluted with 30 ml. of ethylacetate. After phase separa- tion the organic layer was washed once with saturated NaHCtheta3 solution and concentrated under reduced pressure until dryness. The crude product was crystallized from refluxing toluene (100 g) affording the title compound as a white crystalline powder (8.06 g, 70 % yield, 94 % purity by quantitative HPLC). 1H-NMR (Bruker DRX-500, d6- DMSO): delta [ppm]: 8.33 (s), 7.57 (s).; Example 3; Sulfinylation of 5-amino-1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile via addition of a mixture of sodium trifluoromethylsulfinate, triethylamine hydrochloride and thionylchloride to 5-amino-1-[2,6-dichloro-4- (trifluoromethyl)phenyl]-1 H-pyrazole-3-carbonitrileWithin a 3-neck, 50 ml. round bottom flask equipped with a magnetic stirrer bar and a thermometer were placed vacuum dried sodium trifluoromethylsulfinate (4.29 g, 27.5 mmol), vacuum dried triethylamine hydrochloride (5.16 g, 37.5 mmol), and 10 g anhydrous toluene under an argon atmosphere. After cooling to 0 - 5 0C with an ice bath thionylchloride (3.57 g, 30 mmol) was added while keeping the reaction temperature below 5 0C. After stirring for another 30 min the cooled sulfinic acid solution was added at once to a stirred suspension of vacuum dried 5-amino-1-(2,6-dichloro-4- trifluoromethyl-phenyl)-1 H-pyrazole-3-carbonitrile (8.03 g, 25 mmol, 99 % purity) in 5 g toluene with a temperature of 50 0C. The temperature of 50 0C was kept for another 5 hours before quenching the reaction with 50 ml. of saturated NaHCU3 solution. The resulting suspension was diluted with 30 ml. of ethylacetate. After phase separation the organic layer was washed once with saturated NaHCU3 solution and concentrated under reduced pressure until dryness. The crude product was crystallized from refluxing toluene (100 g) affording the title compound as a white crystalline powder (7.25 g, 63 % yield, 94 % purity by quantitative HPLC). 1H-NMR (Bruker DRX-500, d6- DMSO): delta [ppm]: 8.33 (s), 7.57 (s).; Example 11; Sulfinylation of 5-amino-1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile with thionylchloride, triethylamine hydrochloride and dosage of potassium trifluoromethylsulfinateWithin a 750 mL reactor with a mechanical stirrer and a thermometer were placed vac- uum dried triethylamine hydrochloride (51.1 g, 368 mmol), 147 g anhydrous toluene(6.5 molar equivalents relative to 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile), and thionylchloride (35.7 g, 294 mmol) under an argon atmosphere. After cooling to 00C to 5 0C with external cooling, vacuum dried potassium trifluoromethylsulfinate (50.4 g, 296 mmol) was added in three equal portions every 10 min while keeping the reaction temperature below 5 0C. After stirring for another 30 min, vacuum dried 5-amino-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-1 H-pyrazole-3- carbonitrile (79.5 g, 245 mmol, 99 % purity) was added at 5 0C, and the reaction mixture was kept at 5 0C for 60 min and then heated to 35 0C within 45 min. The temperature of 35 0C was kept for another 10 hours before quenching the reaction with 200 g of sodium hydroxide solution (10 wt.%).The resulting suspension was diluted with 176 mL of ethylacetate. After phase separation the organic layer was washed once with sodium hydroxide solution (10 wt.%). After phase separation, the organic layer was analyzed by quantitative HPLC (79 % yield). The content of compound F was below 2.9 weight percent in the crude mixture (without solvent). The product was crystallized from a mixture of ethylacetate and toluene affording the title compound as a white crystalline powder (77.1 g, 75 % yield, 98 % purity by quantitative HPLC).; Example 15; Sulfinylation of 5-amino-1-[2,6... | |
57% | Example 1; Sulfinylation of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile with triethylamine hydrochloride, sodium trifluoromethylsulfinate and thionylchloride, in 6.5 molar equivalents of tolueneWithin a 3-neck, 50 ml. round bottom flask equipped with a magnetic stirrer bar and a thermometer were placed vacuum dried sodium trifluoromethylsulfinate (4.29 g, 27.5 mmol), vacuum dried triethylamine hydrochloride (5.16 g, 37.5 mmol), and 13 ml. an- hydrous toluene (6.5 molar equivalents relative to 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H-pyrazole-3-carbonitrile) under an argon atmosphere. After cooling to 00C to 5 0C with an ice bath, thionylchloride (3.57 g, 30 mmol) was added slowly while keeping the reaction temperature below 5 0C. After stirring for another 30 min, vacuum dried 5-amino-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-1 H-pyrazole-3- carbonitrile (8.03 g, 25 mmol, 99 % purity) was added at 5 0C, and the reaction mixture was heated to 50 0C within 5 min by a preheated water bath. The temperature of 50 0C was kept for another 6 hours before quenching the reaction with 50 ml. of saturated NaHCO3 solution. The resulting suspension was diluted with 30 ml. of ethylacetate. After phase separa- tion the organic layer was washed once with saturated NaHCtheta3 solution and concentrated under reduced pressure until dryness. The crude product was crystallized from refluxing toluene (100 g) affording the title compound as a white crystalline powder (8.06 g, 70 % yield, 94 % purity by quantitative HPLC). 1H-NMR (Bruker DRX-500, d6- DMSO): delta [ppm]: 8.33 (s), 7.57 (s).; Comparative Examples; In order to demonstrate the advantages of the inventive process, the following examples are conducted employing the preparation procedure given above for example 1. | |
55% | Example 1; Sulfinylation of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile with triethylamine hydrochloride, sodium trifluoromethylsulfinate and thionylchloride, in 6.5 molar equivalents of tolueneWithin a 3-neck, 50 ml. round bottom flask equipped with a magnetic stirrer bar and a thermometer were placed vacuum dried sodium trifluoromethylsulfinate (4.29 g, 27.5 mmol), vacuum dried triethylamine hydrochloride (5.16 g, 37.5 mmol), and 13 ml. an- hydrous toluene (6.5 molar equivalents relative to 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H-pyrazole-3-carbonitrile) under an argon atmosphere. After cooling to 00C to 5 0C with an ice bath, thionylchloride (3.57 g, 30 mmol) was added slowly while keeping the reaction temperature below 5 0C. After stirring for another 30 min, vacuum dried 5-amino-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-1 H-pyrazole-3- carbonitrile (8.03 g, 25 mmol, 99 % purity) was added at 5 0C, and the reaction mixture was heated to 50 0C within 5 min by a preheated water bath. The temperature of 50 0C was kept for another 6 hours before quenching the reaction with 50 ml. of saturated NaHCO3 solution. The resulting suspension was diluted with 30 ml. of ethylacetate. After phase separa- tion the organic layer was washed once with saturated NaHCtheta3 solution and concentrated under reduced pressure until dryness. The crude product was crystallized from refluxing toluene (100 g) affording the title compound as a white crystalline powder (8.06 g, 70 % yield, 94 % purity by quantitative HPLC). 1H-NMR (Bruker DRX-500, d6- DMSO): delta [ppm]: 8.33 (s), 7.57 (s).; Comparative Examples; In order to demonstrate the advantages of the inventive process, the following examples are conducted employing the preparation procedure given above for example 1. | |
44% | Example 1; Sulfinylation of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile with triethylamine hydrochloride, sodium trifluoromethylsulfinate and thionylchloride, in 6.5 molar equivalents of tolueneWithin a 3-neck, 50 ml. round bottom flask equipped with a magnetic stirrer bar and a thermometer were placed vacuum dried sodium trifluoromethylsulfinate (4.29 g, 27.5 mmol), vacuum dried triethylamine hydrochloride (5.16 g, 37.5 mmol), and 13 ml. an- hydrous toluene (6.5 molar equivalents relative to 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H-pyrazole-3-carbonitrile) under an argon atmosphere. After cooling to 00C to 5 0C with an ice bath, thionylchloride (3.57 g, 30 mmol) was added slowly while keeping the reaction temperature below 5 0C. After stirring for another 30 min, vacuum dried 5-amino-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-1 H-pyrazole-3- carbonitrile (8.03 g, 25 mmol, 99 % purity) was added at 5 0C, and the reaction mixture was heated to 50 0C within 5 min by a preheated water bath. The temperature of 50 0C was kept for another 6 hours before quenching the reaction with 50 ml. of saturated NaHCO3 solution. The resulting suspension was diluted with 30 ml. of ethylacetate. After phase separa- tion the organic layer was washed once with saturated NaHCtheta3 solution and concentrated under reduced pressure until dryness. The crude product was crystallized from refluxing toluene (100 g) affording the title compound as a white crystalline powder (8.06 g, 70 % yield, 94 % purity by quantitative HPLC). 1H-NMR (Bruker DRX-500, d6- DMSO): delta [ppm]: 8.33 (s), 7.57 (s).; Example 17; Sulfinylation of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H-pyrazole-3- carbonitrile with triethylamine tosylate, sodium trifluoromethylsulfinate and thionylchlo- ride, in 6.5 molar equivalents of tolueneThe preparation procedure was conducted as described above for example 1. The crude product was crystallized from refluxing toluene (100 g) affording the title compound as a white crystalline powder (44 % yield, 76 % purity by quantitative HPLC). No formation of insoluble material (as with diethylamine tosylate as the amine acid complex, compare example C4 of Table 3) was observed. | |
6 - ~ 8% | With phosphorus tribromide;dimethylamine p-toluenesulfonate; at -15 - 57℃; for 2 - 14h;Product distribution / selectivity; | Comparative Example 13; [0123] Direct sulfinylation of N-phenyl pyrazole starting material (III) according to known methods was tested. As such, sulfinylation was attempted using CF3SO2Na in the presence of a halogenating agent such as POCl3, SOCl2 or PBr3. <n="35"/>(III) (II)The reaction reagents and conditions tested are provided in Table I below. <n="36"/>Table IUl <n="37"/>The results are provided in Table II below: Table II[0124] The reaction proceeded to the desired product, Fipronil, when SOCl2 or POCl3 were used as halogenating agents. However, PBr3 did not yield the desired product, or at least not in acceptable yield (about 6%~8% (II) in the reaction mixture, according to HPLC). |
57.3%Chromat. | Example 6; Sulfinylation of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile with triethylamine hydrochloride, sodium trifluoromethylsulfinate and phosporoxychlorideWithin a 3-neck, 50 mL round bottom flask equipped with a magnetic stirrer bar and a thermometer were placed sodium trifluoromethylsulfinate (8.84 g, 55.0 mmol) and 40 mL dried toluene (6.8 molar equivalents relative to 5-amino-1-[2,6-dichloro-4- (trifluoromethyl)phenyl]-1 H-pyrazole-3-carbonitrile) under a nitrogen atmosphere. After cooling to 00C to 5 0C with an ice bath, phosphoroxychloride (9.20 g, 60.0 mmol) was added slowly while keeping the reaction temperature below 5 0C. After complete addi- tion of phosphoroxychloride, triethylamine hydrochloride (10.32g, 75.0 mmol) was added at 5C. After stirring for another 30 min, vacuum dried 5-amino-1-(2,6-dichloro-4- EPO <DP n="27"/>trifluoromethyl-phenyl)-1 H-pyrazole-3-carbonitnle (16.06 g, 50 mmol, 99 % purity) was added at 5 0C, and the reaction mixture was heated to 50 0C within 5 min by a preheated water bath. The temperature of 50 0C was kept for another 6 hours before quenching the reaction with 100 g of 10% NaHCO3 solution. The resulting suspension was diluted with 100 ml. of ethylacetate. After phase separation, the organic layer was analyzed by quantitative HPLC (57.3% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | In N,N-dimethyl acetamide; at 70℃; for 72h;Inert atmosphere; | 2-bromo-1-morpholinoethanone (202 mg, 0.97 mmol, 1.0 equiv.) and sodium trifluoromethanesulfinate (311 mg, 1.94 mmol, 2.0 equiv.) were dissolved in DMA (2 mL), and the mixture was stirred for 3 days at 70 C under N2. The reaction was cooled to 60 C, concentrated to dryness, diluted with ether, filtered over Celite, and concentrated to dryness again. The resulting residue was purified by automated flash chromatography (10 g silica column, 50% EtOAc/hex) to afford 2-(trifluoromethanesulfonyl)-1-morpholinoethanone 11 (133 mg, 0.51 mmol, 52%) as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With dipotassium hydrogenphosphate; In acetone; at 20℃; for 12h;Inert atmosphere; Irradiation; Green chemistry; | General procedure: To a tube were added 1a (1.0 equiv), CF 3 SO 2 Na(4.0 equiv),K 2 HPO 4 , Acetone (2 mL). Then the tube was evacuated and backlledwith argon for three times. The tube around condensate water wasstirred at room temperature in argon with the irradiation of Xenon lampfor 12 h. After the reaction was nished, the mixture was washed withsaturated sodium chloride solution and then extracted with ethylacetate for three times. The combined organic layers were dried overNa 2 SO 4 and concentrated under reduced pressure, then puried bychromatography on silica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | In nitromethane; at 20℃; for 19.3333h;Inert atmosphere; Cooling with ice; | A reactor (a round-bottomed flask) was charged with 6.44g (41.3 mmol) of dried sodium trifluoromethanesulfinate, 5.0 g (18.8mmol) of 4,4?-di-tert-butylbiphenyl, and 25 mL of dry nitromethane. The reactor was purged with N2 gas and cooled on an ice bath. Into the stirred mixture, 12.7 g (45.0 mmol) of trifluoromethanesulfonic anhydridewas drop-wise addedfor 20 mm. The reaction mixture was gradually warmed to room temperature and stirred at room temperature for 19 hours. ?9FNMR analysis of the reaction solution using benzotrifluoride as a standard showed that the product, 3,7-di-tert-butyl-S- (trifluoromethyl)dibenzothiophenium trifluoromethanesulfonate, was produced in 87percent yield. After the reaction solution was evaporated to dryness, 25 mL of toluene was added and evaporated up. This evaporation process of toluene was repeated three times to completely remove the nitromethane solvent. Into the residue, 35m1 of water and 35m1 of diethyl ether were added and the mixture was stirred for about 1 hour. The resulting precipitates were collected by filtration, giving 8.3 g (86percent yield) of pure 3,7- di-tert-butyl-S-(trifluoromethyl)dibenzothiophenium trifluoromethanesulfonate as crystalline solid. The spectral analysis of this product proved the assigned chemical structure. The physical and spectral data are shown as follows: Decomposition-starting point 211 °C (by TGA/DSC);?H NMR (400.2 MHz, DMSO-d6) 8.75 (2H, d, 1=1.7 Hz, 4,6-H), 8.41 (2H, d, 1=8.3 Hz, 1,9-H), 8.09 (2H, dd, 1=1.7, 8.3 Hz, 2,8-H), 1.39 (18H, s, tert-Bu); ?9F NMR (376.5 MHz, DMSO-d6) -54.13 (3F, s, CF3), -77.75 (3F, s, SO2CF3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | A reactor (a round-bottomed flask) was charged with 3.8g (24.4mol) of dried sodium trifluoromethanesulfinate, 5.0 g (18.8mmol) of 4,4?-di-tert-butylbiphenyl, and 25 mL of dry nitromethane. The reactor was purged with N2 gas. Into the stirred mixture, 9.9 g (47.0 mmol) of trifluoroacetic anhydridewas drop-wise addedfor 10 mm, and the mixture was stirred for 1.5 hours. Trifluoromethanesulfonic acid (7.1 g, 47.0 mmol) was then added slowly in a period of about 15 mm so that the temperature of the reaction mixture did not exceed 25 °C under cooling with an ice bath.After the addition, the benzotrifluoride as a reaction mixture was stirred for 30 mm on an ice bath and then the bath was removed. The mixture was then stirred at room temperature for 22 hours. ?9FNMR analysis of the reaction solution using standard showed that the product, 3,7-di-tert-butyl-S- (trifluoromethyl)dibenzothiophenium trifluoromethanesulfonate, was produced in 51percent yield. After the reaction solution was evaporated to dryness, 25 mL of toluene was added and evaporated to dryness. The evaporation process of toluene was repeated three times. Into the residue, were added 35m1 of water and 35m1 of diethyl ether, and then the mixture was stirred for about 60 mm. The resulting precipitates were collecting by filtration, giving 4.8 g (50percent yield) of pure 3,7-di-tert-butyl-S- (trifluoromethyl)dibenzothiophenium trifluoromethanesulfonate as crystalline solid. The spectral data agreed with those of an authentic sample. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With tetrabutylammonium tetrafluoroborate; In acetonitrile; at 50℃; for 2h;Electrolysis; Schlenk technique; | General procedure: A mixture of 1 (0.3 mmol), 2a (1.5 eq.), n-Bu4NBF4 (0.3 eq.) in CH3CN (3 mL) was charged with a 10 mL three-necked round-bottomed flask which equipped with a magneton, a carbon anode (d = 6 mm, about 5 mm immersion depth in solution), and a platinum plate (5 mm × 5 mm × 0.3 mm) cathode. The reaction mixture was stirred and electrolyzed at a constant current of 15 mA at 50 C for 2 h. Then the mixture was cooled to room temperature, poured into H2O (10 mL) and extracted with ethyl acetate (10 × 3 mL). The combined organic solvent was dried over Na2SO4, filtered and concentrated under reduced pressure. The given residue was purified by column chromatography using PE:EtOAc (30:1) as an eluent to provide the desired product 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With N-chlorophthalimide; triphenylphosphine; eosin y; In acetonitrile; at 20℃; for 6h;Inert atmosphere; Schlenk technique; Irradiation; | 10 mL of Schlenk tube was added Eosin Y (0.01 mmol), sodium trifluoromethanesulfinate (0.3 mmol), triphenylphosphine(0.6 mmol), N-chlorophthalimide (0.3 mmol), evacuated and washed into dry nitrogen (this procedure was repeated three times)7-methylindole (0.2 mmol) was dissolved in the ultra-dry solvent acetonitrile and the resulting solution was passed through a syringe into a Schlenk tube. Room temperature, The reaction was allowed to stand under a white LED lamp and stirred for 6 hours. After completion of the reaction, the solvent was evaporated and the residue was passed through the residuePurification by silica gel column chromatography gave 33 mg of product, yield 60percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
25% | With 1,1,1,3',3',3'-hexafluoro-propanol; 2-tert-butylanthraquinine; ammonium carbonate; In acetonitrile; at 33℃; for 24h;Irradiation; Sealed tube; | General procedure: The desired indole (0.3 mmol, 1 eq) was mixed with sodium trifluoromethylsulfinate (0.6 mmol, 2 eq), 2-tert-butyl anthraquinone (0.06 mmol, 0.2 eq), ammonium carbonate (0.18 mmol, 0.6 eq), hexafluoroisopropyl alcohol (0.075 mmol, 0.25 eq), and acetonitrile (3 mL, 0.1 M) in a quartz tube and irradiated at 255 nm for 24 hours. The reaction was quenched with water and extracted with DCM or EtOAc (3 x 30 mL). The combined organic layers were dried over sodium sulfate, and the solvent removed in vacuo. The desired product was then isolated using preparative TLC with the appropriate solvent system. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
12%Spectr.; 26%Spectr. | With 1,1,1,3',3',3'-hexafluoro-propanol; 2-tert-butylanthraquinine; ammonium carbonate; In acetonitrile; at 33℃; for 24h;Irradiation; Sealed tube; | General procedure: The desired indole (0.3 mmol, 1 eq) was mixed with sodium trifluoromethylsulfinate (0.6 mmol, 2 eq), 2-tert-butyl anthraquinone (0.06 mmol, 0.2 eq), ammonium carbonate (0.18 mmol, 0.6 eq), hexafluoroisopropyl alcohol (0.075 mmol, 0.25 eq), and acetonitrile (3 mL, 0.1 M) in a quartz tube and irradiated at 255 nm for 24 hours. The reaction was quenched with water and extracted with DCM or EtOAc (3 x 30 mL). The combined organic layers were dried over sodium sulfate, and the solvent removed in vacuo. The desired product was then isolated using preparative TLC with the appropriate solvent system. |
Tags: 2926-29-6 synthesis path| 2926-29-6 SDS| 2926-29-6 COA| 2926-29-6 purity| 2926-29-6 application| 2926-29-6 NMR| 2926-29-6 COA| 2926-29-6 structure
Precautionary Statements-General | |
Code | Phrase |
P101 | If medical advice is needed,have product container or label at hand. |
P102 | Keep out of reach of children. |
P103 | Read label before use |
Prevention | |
Code | Phrase |
P201 | Obtain special instructions before use. |
P202 | Do not handle until all safety precautions have been read and understood. |
P210 | Keep away from heat/sparks/open flames/hot surfaces. - No smoking. |
P211 | Do not spray on an open flame or other ignition source. |
P220 | Keep/Store away from clothing/combustible materials. |
P221 | Take any precaution to avoid mixing with combustibles |
P222 | Do not allow contact with air. |
P223 | Keep away from any possible contact with water, because of violent reaction and possible flash fire. |
P230 | Keep wetted |
P231 | Handle under inert gas. |
P232 | Protect from moisture. |
P233 | Keep container tightly closed. |
P234 | Keep only in original container. |
P235 | Keep cool |
P240 | Ground/bond container and receiving equipment. |
P241 | Use explosion-proof electrical/ventilating/lighting/equipment. |
P242 | Use only non-sparking tools. |
P243 | Take precautionary measures against static discharge. |
P244 | Keep reduction valves free from grease and oil. |
P250 | Do not subject to grinding/shock/friction. |
P251 | Pressurized container: Do not pierce or burn, even after use. |
P260 | Do not breathe dust/fume/gas/mist/vapours/spray. |
P261 | Avoid breathing dust/fume/gas/mist/vapours/spray. |
P262 | Do not get in eyes, on skin, or on clothing. |
P263 | Avoid contact during pregnancy/while nursing. |
P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
Home
* Country/Region
* Quantity Required :
* Cat. No.:
* CAS No :
* Product Name :
* Additional Information :
Total Compounds: mg
The concentration of the dissolution solution you need to prepare is mg/mL