Home Cart 0 Sign in  
X

[ CAS No. 104366-23-6 ] {[proInfo.proName]}

,{[proInfo.pro_purity]}
Cat. No.: {[proInfo.prAm]}
HazMat Fee +

There will be a HazMat fee per item when shipping a dangerous goods. The HazMat fee will be charged to your UPS/DHL/FedEx collect account or added to the invoice unless the package is shipped via Ground service. Ship by air in Excepted Quantity (each bottle), which is up to 1g/1mL for class 6.1 packing group I or II, and up to 25g/25ml for all other HazMat items.

Type HazMat fee for 500 gram (Estimated)
Excepted Quantity USD 0.00
Limited Quantity USD 15-60
Inaccessible (Haz class 6.1), Domestic USD 80+
Inaccessible (Haz class 6.1), International USD 150+
Accessible (Haz class 3, 4, 5 or 8), Domestic USD 100+
Accessible (Haz class 3, 4, 5 or 8), International USD 200+
3d Animation Molecule Structure of 104366-23-6
Chemical Structure| 104366-23-6
Chemical Structure| 104366-23-6
Structure of 104366-23-6 * Storage: {[proInfo.prStorage]}
Cart0 Add to My Favorites Add to My Favorites Bulk Inquiry Inquiry Add To Cart

Search after Editing

* Storage: {[proInfo.prStorage]}

* Shipping: {[proInfo.prShipping]}

Quality Control of [ 104366-23-6 ]

Related Doc. of [ 104366-23-6 ]

Alternatived Products of [ 104366-23-6 ]
Product Citations

Product Details of [ 104366-23-6 ]

CAS No. :104366-23-6 MDL No. :MFCD03788265
Formula : C6H3ClN2OS Boiling Point : -
Linear Structure Formula :- InChI Key :XIZSUYSWKGAOCN-UHFFFAOYSA-N
M.W : 186.62 Pubchem ID :2737612
Synonyms :

Calculated chemistry of [ 104366-23-6 ]      Expand+

Physicochemical Properties

Num. heavy atoms : 11
Num. arom. heavy atoms : 5
Fraction Csp3 : 0.0
Num. rotatable bonds : 1
Num. H-bond acceptors : 2.0
Num. H-bond donors : 1.0
Molar Refractivity : 43.84
TPSA : 95.12 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : No
P-gp substrate : No
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -6.05 cm/s

Lipophilicity

Log Po/w (iLOGP) : 1.1
Log Po/w (XLOGP3) : 1.95
Log Po/w (WLOGP) : 1.68
Log Po/w (MLOGP) : -0.26
Log Po/w (SILICOS-IT) : 2.58
Consensus Log Po/w : 1.41

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 1.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -2.5
Solubility : 0.596 mg/ml ; 0.00319 mol/l
Class : Soluble
Log S (Ali) : -3.57
Solubility : 0.05 mg/ml ; 0.000268 mol/l
Class : Soluble
Log S (SILICOS-IT) : -1.96
Solubility : 2.05 mg/ml ; 0.011 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 1.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 2.67

Safety of [ 104366-23-6 ]

Signal Word:Danger Class:8,6.1
Precautionary Statements:P280-P301+P310-P305+P351+P338-P310 UN#:2923
Hazard Statements:H301-H314-H317 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 104366-23-6 ]

* 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.

  • Downstream synthetic route of [ 104366-23-6 ]

[ 104366-23-6 ] Synthesis Path-Downstream   1~48

  • 1
  • [ 104366-23-6 ]
  • [ 232281-19-5 ]
YieldReaction ConditionsOperation in experiment
68% With tert.-butylnitrite In DMF (N,N-dimethyl-formamide); acetonitrile at 20 - 37℃; a 5-Formyl-4-chlorothiophene-3-carbonitrile 35 g (325 mmol) of tert-butyl nitrite were added dropwise at room temperature to a solution of 53.0 g (250 mmol) of 2-amino-4-chloro-5-formylthiophene-3-carbonitrile (the synthesis of this compound is described in Patent DB 3738910) in 600 ml of a 1:1 mixture of acetonitrile and dimethylformamide, during which process the temperature of the reaction mixture rose from 20° C. to 37° C. and vigorous evolution of gas began. The mixture was cooled to 25° C. and stirred for 7 hours at room temperature, the black solution was concentrated on a rotary evaporator under a high vacuum, the residue was purified by column chromatography (eluant dichloromethane), and 29 g (68%) of the desired compound were obtained as yellow oil. 1H NMR (270 MHz, DMSO-d6): δ=9.1 (s, 1H), 10.0 (s, 1H)
  • 2
  • [ 104366-23-6 ]
  • [ 105559-07-7 ]
YieldReaction ConditionsOperation in experiment
With hydrogenchloride; sodium sulfite In water 43 Example 43 STR62 93.3 parts of 2-amino-4-chloro-3-cyano-5-formylthiophene, 126 parts of sodium sulfite and 300 parts of water are heated at the boil for 2 hours, after which 200 parts of concentrated hydrochloric acid are added to the ice-cooled mixture, and the mixture is left to stand overnight. Thereafter, the mixture is filtered under suction, and the residue is washed with a little ice water and dried. 85 parts (67% of theory) of sodium 2-amino-3-cyano-5-formylthien-4-ylsulfonate are obtained. Mp.:>300° C.; IR (KBr): 3385, 3303, 3191 (NH2), 2233 (C=N), 1608 cm-1 (C=0).
  • 3
  • [ 104366-23-6 ]
  • [ 108-98-5 ]
  • [ 105559-06-6 ]
YieldReaction ConditionsOperation in experiment
In methanol 42 Example 42 STR61 18.7 parts of 2-amino-4-chloro-3-cyano-5-formylthiophene are added to a solution of 11 parts of thiophenol, 5.4 parts of a 30% strength methanolic sodium methylate solution and 100 parts of methanol. The mixture is heated at the boil for 0.5 hour, after which it is allowed to cool and the precipitated product is filtered off under suction, washed with methanol, and then with water and dried. 21 parts (81% of theory) of 2-amino-3-cyano-5-formyl-4-phenylthiothiophene are obtained. Mp.: 230° C. (from glacial acetic acid); IR (KBr): 3360, 3292, 3142 (NH2), 2220 (C=N), 1643, 1621, 1588 cm-1 (C=0, C=C).
  • 4
  • [ 104366-23-6 ]
  • [ 109-86-4 ]
  • [ 873-55-2 ]
  • 2-amino-3-cyano-5-formyl-4-phenylsulfonylthiophene [ No CAS ]
YieldReaction ConditionsOperation in experiment
In water 45 Example 45 STR64 A solution of 82 parts of sodium phenylsulfinate in 500 parts of water is added to a mixture of 93.3 g of 2-amino-4-chloro-3-cyano-5-formylthiophene an 500 parts of methylglycol, and the reaction mixture is heated at the boil for 6 hours. Thereafter, the solution is filtered while hot and the filtrate is left to stand overnight. The precipitated product is then filtered off under suction, washed with water and dried. 121 parts (83% of theory) of 2-amino-3-cyano-5-formyl-4-phenylsulfonylthiophene are obtained. Decomposition temperature: 230° C. (from glacial acetic acid); IR (KBr): 3316, 3217 (NH2), 2220 (CN), 1648, 1626, 1609 cm-1.
  • 5
  • N,N-dimethyl-N'-(4-chloro-3-cyano-5-formylthien-2-yl)-formamidine [ No CAS ]
  • [ 104366-23-6 ]
YieldReaction ConditionsOperation in experiment
With formic acid In water 17 Example 17 STR29 48.3 parts of N,N-dimethyl-N'-(4-chloro-3-cyano-5-formylthien-2-yl)-formamidine in a mixture of 200 parts of formic acid and 200 parts of water are heated at the boil for 3 hours. After the mixture has cooled to room temperature, the product is filtered off under suction, washed with water and dried. 33.5 parts (90% of theory) of 2-amino-4-chloro-3-cyano-5-formylthiophene are obtained. Decomposition temperature: 270° C. (from glacial acetic acid), IR (KBr): 3377, 3298, 3156 (NH2), 2216 (C N), 1623 cm-1 (C=0).
YieldReaction ConditionsOperation in experiment
85% 7 EXAMPLE 8 STR9 To 280 g of 2-amino-3-cyano-4-hydroxythiophene dissolved in 1800 ml of N,N-dimethylformamide was added within a period of 30 min 612 g of phosphoryl chloride, the temperature being kept at from 70° C. to 80° C. by cooling with water. The mixture was stirred for a further 2 h at 80° C., then run into 1800 ml of water; the temperature of the resulting ebullient mixture rose to about 110° C. When the exothermic reaction ceased the mixture was boiled for a further 1 h, during which time the required product precipitated. After the mixture had cooled to room temperature the product was filtered off, washed with water, and dried; this gave 317 g (85% yield) of 2-amino-4-chloro-3-cyano-5-formylthiophene, m.p. 270° C.
  • 7
  • [ 104366-23-6 ]
  • [ 24653-75-6 ]
  • 5-acetyl-2-amino-3-cyanothieno[3,2-b]thiophene [ No CAS ]
YieldReaction ConditionsOperation in experiment
With potassium carbonate In N,N-dimethyl-formamide 1 EXAMPLE 1 STR13 EXAMPLE 1 STR13 A mixture of 18.7 parts of 2-amino-4-chloro-3-cyano-5-formylthiophene, 13.8 parts of potassium carbonate and 80 parts of N,N-dimethylformamide was introduced first, and 9 parts of acetonylmercaptan were then added. After the exothermic reaction had died down, the mixture was heated at 60° C. for 1 hour and then discharged onto water. The precipitate was filtered off with suction, washed with water and dried. This gave 17.9 parts (81% of theory) of 5-acetyl-2-amino-3-cyanothieno[3,2-b]thiophene. Melting point: 285° C. (decomposition, from methylglycol).
  • 8
  • [ 110-89-4 ]
  • [ 104366-23-6 ]
  • [ 105-56-6 ]
  • 2-amino-4-chloro-3-cyano-5-(β-cyano-β-carboethoxyvinyl)-thiophene [ No CAS ]
YieldReaction ConditionsOperation in experiment
In ethanol; acetic acid 290.a EXAMPLE 290 (a) 18.6 parts of 2-amino-4-chloro-3-cyano-5-formylthiophene were suspended in 140 parts by volume of ethanol, and 2 parts of glacial acetic acid and 2 parts of piperidine were added. Thereafter, 50 parts by volume of ethyl cyanoacetate were added dropwise at room temperature and the mixture was stirred for 7 hours at 60° C. It was then introduced into 500 parts of an ice/water mixture, and the precipitate was filtered off under suction, washed with water and dried at 60° C. under reduced pressure to give 20 parts of 2-amino-4-chloro-3-cyano-5-(β-cyano-β-carboethoxyvinyl)-thiophene of the formula STR326 which was reacted without further purification.
  • 9
  • [ 104366-23-6 ]
  • [ 742045-65-4 ]
YieldReaction ConditionsOperation in experiment
With tert.-butylnitrite In <i>N</i>-methyl-acetamide; acetonitrile a g a) 5-Aminomethyl-4-chlorothiophene-3-thiocarboxamide 5-Formyl-4-chlorothiophene-3-carbonitrile: 35 g (325 mmol) of tert-butyl nitrite were added dropwise at room temperature to a solution of 53.0 g (250 mmol) of 2-amino-4-chloro-5-formylthiophene-3-carbonitrile (the preparation of this compound is described in the patent DB 3738910) in 600 ml of a 1:1 mixture of acetonitrile and dimethylformamide, the reaction mixture warming up from 20° C. to 37° C. and vigorous gas evolution beginning. The mixture was cooled to 25° C. and stirred for seven hours at room temperature, the black solution was evaporated down in a rotary evaporator and under greatly reduced pressure, the residue was purified by column chromatography (mobile phase: dichloromethane) and 29 g (68%) of the desired compound were obtained as a yellow oil. 1H-NMR (270 MHz, DMSO-d6): δ=9.1 (s, 1H), 10.0 (s, 1H).
  • 10
  • [ 104366-23-6 ]
  • [ 855315-03-6 ]
  • C26H23ClN4O4S [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: 2-amino-4-chloro-5-formyl-3-cyanothiophene With nitrosylsulfuric acid; sulfuric acid at 0 - 5℃; for 3.5h; Stage #2: phenylcarbonylmethyl 3-[N-ethyl-N-(3'-methyl-phenyl)amino]-propionate With sulfuric acid; aminosulfonic acid In water 5 EXAMPLE 5; 18.6 parts of 2-amino-4-chloro-3-cyano-5-formylthiophene are dissolved in 200 parts of cold sulphuric acid 85%. 32 parts of nitrosylsulphuric acid 40% are added dropwise with stirring at 0 to 5°C in the course of 30 minutes. This is followed by 3 hours of stirring in an icebath, and the diazonium salt solution is poured continuously into a mixture of 32.5 parts of phenylcarbonylmethyl 3- [N-ethyl-N- (3'-methylphenylamino)]- propionate, 50 parts of 5% sulphuric acid, 2 parts of sulphamic acid and 300 parts of ice. The precipitated dye is filtered off, washed acid free with water and dried at 60°C under reduced pressure. The dye obtained having AmaX = 610 (DMF), conforms to the formula and dyes polyester materials in brillant reddish blue shades having good fastnesses
  • 11
  • [ 104366-23-6 ]
  • 5-((E)-((4-bromophenyl)imino)methyl)-4-chloro-2-(2-((Z)-3-methyl-5-oxo-1-phenyl-1,5-dihydro-4H-pyrazol-4-ylidene)hydrazinyl)thiophene-3-carbonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: sulfuric acid; phosphoric acid; sodium nitrite / water / 0.5 h / 0 - 5 °C 1.2: 1 h / 0 - 5 °C 2.1: acetic acid / acetonitrile / 12 h / Reflux
  • 12
  • [ 104366-23-6 ]
  • 4-chloro-5-((E)-((2,3-dimethylphenyl)imino)methyl)-2-(2-((Z)-3-methyl-5-oxo-1-phenyl-1,5-dihydro-4H-pyrazol-4-ylidene)hydrazinyl)thiophene-3-carbonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: sulfuric acid; phosphoric acid; sodium nitrite / water / 0.5 h / 0 - 5 °C 1.2: 1 h / 0 - 5 °C 2.1: acetic acid / acetonitrile / 12 h / Reflux
  • 13
  • [ 104366-23-6 ]
  • 4-chloro-2-(2-((Z)-3-methyl-5-oxo-1-phenyl-1,5-dihydro-4H-pyrazol-4-ylidene)hydrazinyl)-5-((E)-((4-nitrophenyl)imino)methyl)thiophene-3-carbonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: sulfuric acid; phosphoric acid; sodium nitrite / water / 0.5 h / 0 - 5 °C 1.2: 1 h / 0 - 5 °C 2.1: acetic acid / acetonitrile / 12 h / Reflux
  • 14
  • [ 104366-23-6 ]
  • 4-chloro-5-((E)-((3-chloro-4-fluorophenyl)imino)methyl)-2-(2-((Z)-3-methyl-5-oxo-1-phenyl-1,5-dihydro-4H-pyrazol-4-ylidene)hydrazinyl)thiophene-3-carbonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: sulfuric acid; phosphoric acid; sodium nitrite / water / 0.5 h / 0 - 5 °C 1.2: 1 h / 0 - 5 °C 2.1: acetic acid / acetonitrile / 12 h / Reflux
  • 15
  • [ 104366-23-6 ]
  • [ 942-32-5 ]
  • (Z)-4-chloro-5-formyl-2-(2-(3-methyl-5-oxo-1-phenyl-1,5-dihydro-4H-pyrazol-4-ylidene)hydrazinyl)thiophene-3-carbonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% Stage #1: 2-amino-4-chloro-5-formyl-3-cyanothiophene With phosphoric acid; sulfuric acid; sodium nitrite In water at 0 - 5℃; for 0.5h; Stage #2: 5-methyl-2-phenyl-2H-pyrazol-3-ol In methanol; water at 0 - 5℃; for 1h; 2.1.1 Preparation of compound 1 ((Z)-4-chloro-5-formyl-2-(2-(3-methyl-5-oxo-1-phenyl-1,5-dihydro-4H-pyrazol-4-ylidene)hydrazinyl)thiophene-3-carbonitrile) 2-Amino-4-chloro-5-formylthiophene-3-carbonitrile (1.87g, 10.0mmol) was dissolved in a mixture of concentrated sulfuric acid (6mL) and phosphoric acid (4.2mL) at 0-5°C in an ice bath. Sodium nitrite (0.76g, 11.0mmol) was dissolved in cold water (10mL) and added dropwise to the reaction mixture for 0.5h under stirring. The diazonium salt was obtained and used for the next coupling reaction. 1-Phenyl-3-methyl-5-pyrazolone (pyrazolone 1.92g, 11.0mmol) was added to a mixture of methanol/water (90mL, v/v=2:1) solution in a three-necked flask immersed in an ice bath. The freshly prepared diazonium salt was added dropwise to the reaction mixture for 1h under vigorous mechanical stirring (0-5°C). The precipitate was filtered and dried after thorough washing with distilled water. Deep red powder 1 was obtained by recrystallization from CH3CN in a yield of 2.89g (78%). Mp: 219-221°C. UV-Vis in methanol, λmax (nm)/ε (×104Lmol-1 cm-1)=529/3.1, 369/0.59, 305/1.41. Main FT-IR absorptions (KBr pellets, ν cm-1): 3445 (s), 3407 (s), 3133 (s), 2362 (w), 1686 (m), 1628 (m) and 1399 (vs). 1H NMR (300MHz, DMSO-d6, ppm): δ=9.69 (s, 1H), 7.92 (d, J=7.7Hz, 2H), 7.38 (t, J=7.9Hz, 2H), 7.10 (t, J=7.4Hz, 1H) and 2.41 (s, 3H). Anal. Calcd. for C16H10ClN5O2S: C, 51.69; H, 2.71; N, 18.84%. Found: C, 51.98; H, 2.85; N, 18.73%. ESI-MS in methanol (negative): found [M-H]-: 370.1, C16H9ClN5O2S; requires [M-H]-: 370.0.
  • 16
  • [ 104366-23-6 ]
  • [ 121-88-0 ]
  • (E)-4-chloro-5-formyl-2-(3-(2-hydroxy-4-nitrophenyl)triaz-1-en-1-yl)thiophene-3-carbonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% Stage #1: 2-amino-4-chloro-5-formyl-3-cyanothiophene With phosphoric acid; sulfuric acid; sodium nitrite In water at -5℃; for 0.5h; Stage #2: 5-Nitro-2-aminophenol In methanol; water at 0 - 5℃; for 1h; 2.1.1. Synthesis of H2L ((E)-4-chloro-5-formyl-2-(3-(2-hydroxy-4-nitrophenyl)triaz-1-en-1-yl)thiophene-3-carbonitrile) and itsisomeric compound D1 ((E)-2-((2-amino-3-hydroxy-5-nitrophenyl)diazenyl)-4-chloro-5-formylthiophene-3-carbonitrile) 2-Amino-3-cyano-4-chloro-5-formylthiophene (1.87 g,10.0 mmol) was dissolved in a mixture of concentrated sulfuric acid(6 mL) and phosphoric acid (4.2 mL) at 5 °C in an ice bath. Sodiumnitrite (0.76 g, 11.0 mmol) was dissolved in cold water (10 mL) andadded dropwise to the reaction mixture for 0.5 h under stirring. Thediazonium salt solution was obtained and used for the nextcoupling reaction. 2-Amino-5-nitrophenol (1.54 g, 10.0 mmol) wasadded to a mixture of methanol/water (90 mL, v/v 2:1) solution ina three-necked flask immersed in an ice bath. The abovementionedfreshly prepared diazonium salt was added dropwiseto the reaction mixture for 1 h under vigorous mechanical stirring(0-5 °C). The precipitate was filtered and dried after thoroughwashing with the distilled water. The crude product of H2L waspurified by column chromatography using acetonitrile as theeluent. Yield, 2.88 g (82%); M.P., 285-287 °C. 1H NMR (300 MHz,DMSO-d6) δ: 9.64 (s, 1H), 7.59-7.63 (dd, J1 2.4 Hz, J2 2.4 Hz, 1H),7.49 (d, J 2.4 Hz, 1H), 6.61 (d, J 9.0 Hz, 1H). Main FT-IR absorptions(KBr pellets, cm-1): 3335 (m), 3165 (w), 2219 (w), 1624(m), 1552 (vs), 1514 (vs), 1314 (s), 1271 (s), 1062 (m). NegativeESI-MS in methanol: m/z 349.75 (100%), [M-H]-. Anal. Calcd. forC12H6N5ClO4S: C, 40.98; H, 1.72; N, 19.91%. Found: C, 40.81; H, 1.84;N, 19.82%. UVeVis in methanol, lmax/ε (Lmol1cm1) 529 nm/37000.
  • 17
  • [ 104366-23-6 ]
  • [ 121-88-0 ]
  • (E)-2-((2-amino-3-hydroxy-5-nitrophenyl)diazenyl)-4-chloro-5-formylthiophene-3-carbonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
18% Stage #1: 2-amino-4-chloro-5-formyl-3-cyanothiophene With phosphoric acid; sulfuric acid; sodium nitrite In water at -5℃; for 0.5h; Stage #2: 5-Nitro-2-aminophenol In methanol; water at 0 - 5℃; for 1h; 2.1.1. Synthesis of H2L ((E)-4-chloro-5-formyl-2-(3-(2-hydroxy-4-nitrophenyl)triaz-1-en-1-yl)thiophene-3-carbonitrile) and itsisomeric compound D1 ((E)-2-((2-amino-3-hydroxy-5-nitrophenyl)diazenyl)-4-chloro-5-formylthiophene-3-carbonitrile) General procedure: 2-Amino-3-cyano-4-chloro-5-formylthiophene (1.87 g,10.0 mmol) was dissolved in a mixture of concentrated sulfuric acid(6 mL) and phosphoric acid (4.2 mL) at 5 °C in an ice bath. Sodiumnitrite (0.76 g, 11.0 mmol) was dissolved in cold water (10 mL) andadded dropwise to the reaction mixture for 0.5 h under stirring. Thediazonium salt solution was obtained and used for the nextcoupling reaction. 2-Amino-5-nitrophenol (1.54 g, 10.0 mmol) wasadded to a mixture of methanol/water (90 mL, v/v 2:1) solution ina three-necked flask immersed in an ice bath. The abovementionedfreshly prepared diazonium salt was added dropwiseto the reaction mixture for 1 h under vigorous mechanical stirring(0-5 °C). The precipitate was filtered and dried after thoroughwashing with the distilled water. The crude product of H2L waspurified by column chromatography using acetonitrile as theeluent.
  • 18
  • [ 104366-23-6 ]
  • [ 103629-45-4 ]
  • C14H8ClN5O3S [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% Stage #1: 2-amino-4-chloro-5-formyl-3-cyanothiophene With phosphoric acid; sulfuric acid; sodium nitrite at -5℃; for 0.5h; Stage #2: 1,4-dimethyl-2,6-dioxo-1,2,5,6-tetrahydro-pyridine-3-carbonitrile In methanol; water at 0 - 5℃; for 1h; 2.1.1. Synthesis of dye 2 Compound 1 (1.87g, 10.0mmol) was dissolved in a mixture of concentrated sulfuric acid (6mL) and phosphate (4.2mL) at-5°C in an ice bath. Sodium nitrite (0.76g, 7.0mmol) was dissolved in cold water and added dropwise to the reaction mixture for 0.5h under stirring. The diazonium salt was obtained and used for the next coupling reaction. 1,4-Dimethyl-3-cyano-6-hydroxy-2-pyridone (1.64g, 10.0mmol) was added to a mixture of methanol/water (90mL, v/v=2:1) solution in a three-necked flask immersed in an ice bath. Freshly prepared diazonium salt was added dropwise to the reaction mixture under vigorous mechanical stirring for 1h (0-5°C). The precipitate was filtered and dried after thorough washing with distilled water. The crude product was purified by recrystallization from acetonitrile, and compound 2 was finally obtained in a yield of 2.93g (81%). Mp: > 250°C. 1H NMR (500MHz, CD3CN) δ: 9.91 (s, 1H), 3.28 (s, 1H), 2.51 (s, 3H). Main FT-IR absorptions (KBr pellets, cm-1): 3427 (w), 2229 (m), 1641 (vs), 1496 (s), 793 (m), 1097 (m). Anal. Calcd. for C14H8ClN5O3S: C, 46.48; H, 2.23; N, 19.36%. Found: C, 46.66; H, 2.34; N, 19.47%. Negative ESI-MS in acetonitrile: m/z=360.25 (100%), [M-H]-.
  • 19
  • [ 104366-23-6 ]
  • 1-ethyl-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile [ No CAS ]
  • C15H10ClN5O3S [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% Stage #1: 2-amino-4-chloro-5-formyl-3-cyanothiophene With phosphoric acid; sulfuric acid; sodium nitrite at -5℃; for 0.5h; Stage #2: 1-ethyl-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile In methanol; water at 0 - 5℃; for 1h; 2.1.1. Synthesis of dye 2 General procedure: Compound 1 (1.87g, 10.0mmol) was dissolved in a mixture of concentrated sulfuric acid (6mL) and phosphate (4.2mL) at-5°C in an ice bath. Sodium nitrite (0.76g, 7.0mmol) was dissolved in cold water and added dropwise to the reaction mixture for 0.5h under stirring. The diazonium salt was obtained and used for the next coupling reaction. 1,4-Dimethyl-3-cyano-6-hydroxy-2-pyridone (1.64g, 10.0mmol) was added to a mixture of methanol/water (90mL, v/v=2:1) solution in a three-necked flask immersed in an ice bath. Freshly prepared diazonium salt was added dropwise to the reaction mixture under vigorous mechanical stirring for 1h (0-5°C). The precipitate was filtered and dried after thorough washing with distilled water. The crude product was purified by recrystallization from acetonitrile, and compound 2 was finally obtained in a yield of 2.93g (81%).
  • 20
  • [ 104366-23-6 ]
  • 1-Benzyl-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile [ No CAS ]
  • C20H12ClN5O3S [ No CAS ]
YieldReaction ConditionsOperation in experiment
86% Stage #1: 2-amino-4-chloro-5-formyl-3-cyanothiophene With phosphoric acid; sulfuric acid; sodium nitrite at -5℃; for 0.5h; Stage #2: 1-Benzyl-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile In methanol; water at 0 - 5℃; for 1h; 2.1.1. Synthesis of dye 2 General procedure: Compound 1 (1.87g, 10.0mmol) was dissolved in a mixture of concentrated sulfuric acid (6mL) and phosphate (4.2mL) at-5°C in an ice bath. Sodium nitrite (0.76g, 7.0mmol) was dissolved in cold water and added dropwise to the reaction mixture for 0.5h under stirring. The diazonium salt was obtained and used for the next coupling reaction. 1,4-Dimethyl-3-cyano-6-hydroxy-2-pyridone (1.64g, 10.0mmol) was added to a mixture of methanol/water (90mL, v/v=2:1) solution in a three-necked flask immersed in an ice bath. Freshly prepared diazonium salt was added dropwise to the reaction mixture under vigorous mechanical stirring for 1h (0-5°C). The precipitate was filtered and dried after thorough washing with distilled water. The crude product was purified by recrystallization from acetonitrile, and compound 2 was finally obtained in a yield of 2.93g (81%).
  • 21
  • [ 104366-23-6 ]
  • C9H10N2O3 [ No CAS ]
  • C15H10ClN5O4S [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% Stage #1: 2-amino-4-chloro-5-formyl-3-cyanothiophene With phosphoric acid; sulfuric acid; sodium nitrite at -5℃; for 0.5h; Stage #2: C9H10N2O3 In methanol; water at 0 - 5℃; for 1h; 2.1.1. Synthesis of dye 2 General procedure: Compound 1 (1.87g, 10.0mmol) was dissolved in a mixture of concentrated sulfuric acid (6mL) and phosphate (4.2mL) at-5°C in an ice bath. Sodium nitrite (0.76g, 7.0mmol) was dissolved in cold water and added dropwise to the reaction mixture for 0.5h under stirring. The diazonium salt was obtained and used for the next coupling reaction. 1,4-Dimethyl-3-cyano-6-hydroxy-2-pyridone (1.64g, 10.0mmol) was added to a mixture of methanol/water (90mL, v/v=2:1) solution in a three-necked flask immersed in an ice bath. Freshly prepared diazonium salt was added dropwise to the reaction mixture under vigorous mechanical stirring for 1h (0-5°C). The precipitate was filtered and dried after thorough washing with distilled water. The crude product was purified by recrystallization from acetonitrile, and compound 2 was finally obtained in a yield of 2.93g (81%).
  • 22
  • [ 104366-23-6 ]
  • C13H18N2O3 [ No CAS ]
  • C19H18ClN5O4S [ No CAS ]
YieldReaction ConditionsOperation in experiment
84% Stage #1: 2-amino-4-chloro-5-formyl-3-cyanothiophene With phosphoric acid; sulfuric acid; sodium nitrite at -5℃; for 0.5h; Stage #2: C13H18N2O3 In methanol; water at 0 - 5℃; for 1h; 2.1.1. Synthesis of dye 2 General procedure: Compound 1 (1.87g, 10.0mmol) was dissolved in a mixture of concentrated sulfuric acid (6mL) and phosphate (4.2mL) at-5°C in an ice bath. Sodium nitrite (0.76g, 7.0mmol) was dissolved in cold water and added dropwise to the reaction mixture for 0.5h under stirring. The diazonium salt was obtained and used for the next coupling reaction. 1,4-Dimethyl-3-cyano-6-hydroxy-2-pyridone (1.64g, 10.0mmol) was added to a mixture of methanol/water (90mL, v/v=2:1) solution in a three-necked flask immersed in an ice bath. Freshly prepared diazonium salt was added dropwise to the reaction mixture under vigorous mechanical stirring for 1h (0-5°C). The precipitate was filtered and dried after thorough washing with distilled water. The crude product was purified by recrystallization from acetonitrile, and compound 2 was finally obtained in a yield of 2.93g (81%).
  • 23
  • [ 104366-23-6 ]
  • 5-((E)-(4-chloro-3-cyano-5-((E)-((2,3-dimethylphenyl)imino)methyl)thiophen-2-yl)diazenyl)-2,6-bis((3-methoxypropyl)amino)-4-methylnicotinonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: sulfuric acid; phosphoric acid; nitrosylsulfuric acid / 0.5 h / -5 °C 1.2: 2 h / 0 - 5 °C 2.1: acetic acid / acetonitrile / 90 °C
  • 24
  • [ 104366-23-6 ]
  • methyl (E)-3-(3-chloro-4-cyano-5-((E)-(5-cyano-2,6-bis((3-methoxypropyl)amino)-4-methylpyridin-3-yl)diazenyl)thiophen-2-yl)-2-cyanoacrylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: sulfuric acid; phosphoric acid; nitrosylsulfuric acid / 0.5 h / -5 °C 1.2: 2 h / 0 - 5 °C 2.1: piperidine / chloroform / 4 h / 50 °C
  • 25
  • [ 104366-23-6 ]
  • 5-((E)-(4-chloro-3-cyano-5-((E)-((2,3-dimethylphenyl)imino)methyl)thiophen-2-yl)diazenyl)-1-ethyl-6-((3-methoxypropyl)amino)-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: sulfuric acid; phosphoric acid; nitrosylsulfuric acid / 0.5 h / -5 °C 1.2: 2 h / 0 - 5 °C 2.1: acetic acid / acetonitrile / 90 °C
  • 26
  • [ 104366-23-6 ]
  • methyl (E)-3-(3-chloro-4-cyano-5-((E)-(5-cyano-1-ethyl-2-((3-methoxypropyl)amino)-4-methyl-6-oxo-1,6-dihydropyridin-3-yl)diazenyl)thiophen-2-yl)-2-cyanoacrylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: sulfuric acid; phosphoric acid; nitrosylsulfuric acid / 0.5 h / -5 °C 1.2: 2 h / 0 - 5 °C 2.1: piperidine / chloroform / 4 h / 50 °C
  • 27
  • [ 104366-23-6 ]
  • 1-ethyl-6-((3-methoxypropyl)amino)-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile [ No CAS ]
  • (E)-5-((4-chloro-3-cyano-5-formylthiophen-2-yl)diazenyl)-1-ethyl-6-((3-methoxypropyl)amino)-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% Stage #1: 2-amino-4-chloro-5-formyl-3-cyanothiophene With nitrosylsulfuric acid; phosphoric acid; sulfuric acid at -5℃; for 0.5h; Stage #2: 1-ethyl-6-((3-methoxypropyl)amino)-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile In methanol; water at 0 - 5℃; for 2h; 2.1.1. Preparation of compound 5 ((E)-5-((4-chloro-3-cyano-5-formylthiophen-2-yl)diazenyl)-6-((3-methoxypropyl)amino)-1,4-dimethyl-2-oxo-1,2-dihydropyridine-3-carbonitrile) General procedure: 2-Amino-4-chloro-5-formylthiophene-3-carbonitrile (0.94 g, 5.00 mmol)was dissolved in a mixture of concentrated sulfuric acid (3 mL) and phosphoric acid (2.5 mL) at -5 °C in an ice-salt bath. Nitrosylsulphuric acid (5 mL) was added dropwise to the reaction mixture over 0.5 h under stirring. The diazonium salt was obtained and used for the next coupling reaction. 6-((3-Methoxypropyl) amino)-1,4-dimethyl-2-oxo-1,2-dihydropyridine-3-carbonitrile (1) (1.18 g, 5.00 mmol) was dissolved in a mixture of methanol and water (30 mL, v:v = 2:1) in a three necked flask immersed in an icesalt bath. The freshly prepared diazonium salt was added dropwise to the reaction mixture under vigorous mechanical stirring (0-5 °C). After additional stirring for 2 h, the precipitate was filtered and dried after thorough washing with distilled water. The crude product was obtained and the pure product was recrystallized from CHCl3/CH3OH in a yield of 1.88 g (87%).
  • 28
  • [ 104366-23-6 ]
  • 1-(3-isopropoxypropyl)-6-((3-methoxypropyl)amino)-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile [ No CAS ]
  • (E)-5-((4-chloro-3-cyano-5-formylthiophen-2-yl)diazenyl)-1-(3-isopropoxypropyl)-6-((3-methoxypropyl)amino)-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% Stage #1: 2-amino-4-chloro-5-formyl-3-cyanothiophene With nitrosylsulfuric acid; phosphoric acid; sulfuric acid at -5℃; for 0.5h; Stage #2: 1-(3-isopropoxypropyl)-6-((3-methoxypropyl)amino)-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile In methanol; water at 0 - 5℃; for 2h; 2.1.1. Preparation of compound 5 ((E)-5-((4-chloro-3-cyano-5-formylthiophen-2-yl)diazenyl)-6-((3-methoxypropyl)amino)-1,4-dimethyl-2-oxo-1,2-dihydropyridine-3-carbonitrile) General procedure: 2-Amino-4-chloro-5-formylthiophene-3-carbonitrile (0.94 g, 5.00 mmol)was dissolved in a mixture of concentrated sulfuric acid (3 mL) and phosphoric acid (2.5 mL) at -5 °C in an ice-salt bath. Nitrosylsulphuric acid (5 mL) was added dropwise to the reaction mixture over 0.5 h under stirring. The diazonium salt was obtained and used for the next coupling reaction. 6-((3-Methoxypropyl) amino)-1,4-dimethyl-2-oxo-1,2-dihydropyridine-3-carbonitrile (1) (1.18 g, 5.00 mmol) was dissolved in a mixture of methanol and water (30 mL, v:v = 2:1) in a three necked flask immersed in an icesalt bath. The freshly prepared diazonium salt was added dropwise to the reaction mixture under vigorous mechanical stirring (0-5 °C). After additional stirring for 2 h, the precipitate was filtered and dried after thorough washing with distilled water. The crude product was obtained and the pure product was recrystallized from CHCl3/CH3OH in a yield of 1.88 g (87%).
  • 29
  • [ 104366-23-6 ]
  • [ 51560-72-6 ]
  • (E)-5-((4-chloro-3-cyano-5-formylthiophen-2-yl)diazenyl)-2,6-bis((3-methoxypropyl)amino)-4-methylnicotinonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% Stage #1: 2-amino-4-chloro-5-formyl-3-cyanothiophene With nitrosylsulfuric acid; phosphoric acid; sulfuric acid at -5℃; for 0.5h; Stage #2: 2,6-bis-(3'-methoxy-n-propylamino)-3-cyano-4-methylpyridine In methanol; water at 0 - 5℃; for 2h; 2.1.1. Preparation of compound 5 ((E)-5-((4-chloro-3-cyano-5-formylthiophen-2-yl)diazenyl)-6-((3-methoxypropyl)amino)-1,4-dimethyl-2-oxo-1,2-dihydropyridine-3-carbonitrile) General procedure: 2-Amino-4-chloro-5-formylthiophene-3-carbonitrile (0.94 g, 5.00 mmol)was dissolved in a mixture of concentrated sulfuric acid (3 mL) and phosphoric acid (2.5 mL) at -5 °C in an ice-salt bath. Nitrosylsulphuric acid (5 mL) was added dropwise to the reaction mixture over 0.5 h under stirring. The diazonium salt was obtained and used for the next coupling reaction. 6-((3-Methoxypropyl) amino)-1,4-dimethyl-2-oxo-1,2-dihydropyridine-3-carbonitrile (1) (1.18 g, 5.00 mmol) was dissolved in a mixture of methanol and water (30 mL, v:v = 2:1) in a three necked flask immersed in an icesalt bath. The freshly prepared diazonium salt was added dropwise to the reaction mixture under vigorous mechanical stirring (0-5 °C). After additional stirring for 2 h, the precipitate was filtered and dried after thorough washing with distilled water. The crude product was obtained and the pure product was recrystallized from CHCl3/CH3OH in a yield of 1.88 g (87%).
  • 30
  • [ 104366-23-6 ]
  • 6-((3-methoxypropyl)amino)-1,4-dimethyl-2-oxo-1,2-dihydropyridine-3-carbonitrile [ No CAS ]
  • (E)-5-((4-chloro-3-cyano-5-formylthiophen-2-yl)diazenyl)-6-((3-methoxypropyl)amino)-1,4-dimethyl-2-oxo-1,2-dihydropyridine-3-carbonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% Stage #1: 2-amino-4-chloro-5-formyl-3-cyanothiophene With nitrosylsulfuric acid; phosphoric acid; sulfuric acid at -5℃; for 0.5h; Stage #2: 6-((3-methoxypropyl)amino)-1,4-dimethyl-2-oxo-1,2-dihydropyridine-3-carbonitrile In methanol; water at 0 - 5℃; for 2h; 2.1.1. Preparation of compound 5 ((E)-5-((4-chloro-3-cyano-5-formylthiophen-2-yl)diazenyl)-6-((3-methoxypropyl)amino)-1,4-dimethyl-2-oxo-1,2-dihydropyridine-3-carbonitrile) 2-Amino-4-chloro-5-formylthiophene-3-carbonitrile (0.94 g, 5.00 mmol)was dissolved in a mixture of concentrated sulfuric acid (3 mL) and phosphoric acid (2.5 mL) at -5 °C in an ice-salt bath. Nitrosylsulphuric acid (5 mL) was added dropwise to the reaction mixture over 0.5 h under stirring. The diazonium salt was obtained and used for the next coupling reaction. 6-((3-Methoxypropyl) amino)-1,4-dimethyl-2-oxo-1,2-dihydropyridine-3-carbonitrile (1) (1.18 g, 5.00 mmol) was dissolved in a mixture of methanol and water (30 mL, v:v = 2:1) in a three necked flask immersed in an icesalt bath. The freshly prepared diazonium salt was added dropwise to the reaction mixture under vigorous mechanical stirring (0-5 °C). After additional stirring for 2 h, the precipitate was filtered and dried after thorough washing with distilled water. The crude product was obtained and the pure product was recrystallized from CHCl3/CH3OH in a yield of 1.88 g (87%). Mp: 228-230 °C. UVeVis in MeOH, lmax (nm)/ε ( x 104 L mol-1 cm-1) = 510/1.12. Main FTeIR absorptions (KBr pellets, n cm-1): 2933 (w), 2869 (w), 2222 (m), 1677 (s), 1588 (s), 1258 (s) and 1189 (vs). 1H NMR (400 MHz, CDCl3, ppm): δ = 12.70 (s, 1H),10.00 (s, 1H), 3.93 (m, 2H), 3.68 (s, 3H), 3.49 (t, J = 5.4 Hz, 2H), 3.28 (s, 3H), 2.65 (s, 3H) and 2.20 (m, 2H). Anal. Calcd. For C18H17ClN6O3S: C, 49.94; H, 3.96; N, 19.41%. Found: C, 49.82; H, 3.92; N, 19.21%. Negative ESI-MS in CH3CN: m/z = 431.00 (100.0%), [M-H]-.
  • 31
  • [ 104366-23-6 ]
  • [ 28141-13-1 ]
  • (Z)-5-((5-amino-3-chloro-4-cyanothiophen-2-yl)methylene)-1-ethyl-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% With acetic anhydride at 90℃; for 2h; 2.1.1. Synthesis of dye 1 ((Z)-5-((5-amino-3-chloro-4-cyanothiophen-2-yl)methylene)-1-ethyl-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile) A mixture of 2-amino-4-chloro-5-formylthiophene-3-carbonitrile (0.93 g, 5.00 mmol) and 1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile (0.89 g, 5.00 mmol) was dissolved in(CH3CO)2O (5 mL) and stirred at 90 °C for 2 h. The precipitate was filteredand dried after thorough washing with isopropanol, and the pureproduct was obtained in a yield of 1.35 g (78%). Mp:>300 °C. UV-Visin CHCl3, λmax (nm)/ε (×104 L mol-1 cm-1)=510/4.56. Main FT-IRabsorptions (KBr pellets, ν cm-1): 3307 (w), 3155 (m), 2222 (m), 1620(s), 1550 (m), 1449 (vs), 1278 (s) and 1208 (s). 1H NMR (400 MHz,DMSO-d6, ppm): δ=9.42 (s, 2H), 7.91 (s, 1H), 3.84 (m, 2H), 2.54 (s,3H) and 1.09 (t, J=7.0 Hz, 3H). Anal. Calcd. For C15H11ClN4O2S: C,51.95; H, 3.20; N, 16.16%. Found: C, 51.82; H, 3.12; N, 16.31%.Negative ESI-MS in CH3CN: m/z=345.00 (100.0%), [M-H]-.
  • 32
  • [ 104366-23-6 ]
  • 2-(3-cyano-6-hydroxy-4-methyl-2-oxopyridin-1(2H)-yl)ethyl acetate [ No CAS ]
  • (Z)-2-(3-((5-amino-3-chloro-4-cyanothiophen-2-yl)methylene)-5-cyano-4-methyl-2,6-dioxo-3,6-dihydropyridin-1(2H)-yl)ethyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With acetic anhydride at 90℃; for 2h; 2.1.1. Synthesis of dye 1 ((Z)-5-((5-amino-3-chloro-4-cyanothiophen-2-yl)methylene)-1-ethyl-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile) General procedure: A mixture of 2-amino-4-chloro-5-formylthiophene-3-carbonitrile (0.93 g, 5.00 mmol) and 1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile (0.89 g, 5.00 mmol) was dissolved in(CH3CO)2O (5 mL) and stirred at 90 °C for 2 h. The precipitate was filteredand dried after thorough washing with isopropanol, and the pureproduct was obtained in a yield of 1.35 g (78%).
  • 33
  • [ 104366-23-6 ]
  • 6-hydroxy-1-(3-isopropoxypropyl)-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile [ No CAS ]
  • (Z)-5-((5-amino-3-chloro-4-cyanothiophen-2-yl)methylene)-1-(3-isopropoxypropyl)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% With acetic anhydride at 90℃; for 2h; 2.1.1. Synthesis of dye 1 ((Z)-5-((5-amino-3-chloro-4-cyanothiophen-2-yl)methylene)-1-ethyl-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile) General procedure: A mixture of 2-amino-4-chloro-5-formylthiophene-3-carbonitrile (0.93 g, 5.00 mmol) and 1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile (0.89 g, 5.00 mmol) was dissolved in(CH3CO)2O (5 mL) and stirred at 90 °C for 2 h. The precipitate was filteredand dried after thorough washing with isopropanol, and the pureproduct was obtained in a yield of 1.35 g (78%).
  • 34
  • [ 104366-23-6 ]
  • 5-hydroxy-1-phenyl-1H-pyrazole-3-carboxylic acid [ No CAS ]
  • ((E)-4-(2-(4-chloro-3-cyano-5-formylthiophen-2-yl)hydrazono)-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazole-3-carboxylic acid) [ No CAS ]
YieldReaction ConditionsOperation in experiment
77% Stage #1: 2-amino-4-chloro-5-formyl-3-cyanothiophene With phosphoric acid; sulfuric acid; sodium nitrite In water at -5℃; Stage #2: 5-hydroxy-1-phenyl-1H-pyrazole-3-carboxylic acid In ethanol; water at 0 - 5℃; for 3h; 2.2.1. Synthesis of 1 ((E)-4-(2-(4-chloro-3-cyano-5-formylthiophen-2-yl)hydrazono)-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazole-3-carboxylic acid) General procedure: Concentrated sulfuric acid (6.0 mL) and phosphoric acid (4.2 mL)were mixed together at -5 °C in an ice-salt bath and 2-amino-4-chloro-5-formylthiophene-3- carbonitrile (1.87 g, 10.0 mmol) was added. Andthen a water (5.0 mL) solution of sodium nitrite (0.76 g, 11.0 mmol)was added dropwise with stirring. The resultant diazonium salt wasused for the following coupling. 5-Hydroxy-1-phenyl-1H-pyrazole-3-carboxylic acid (2.04 g, 10.0 mmol) was added to an ethanol/watermixture (90.0 mL, v/v=2:1) in an ice bath. The aforementioned diazoniumsalt was added slowly under vigorous mechanical stirring(0-5 °C). After the addition of diazonium salt, the mixture was stirredfor additional 3.0 h, and the precipitate was filtered, washed with distilledwater and dried. The crude solid was subjected to the columnchromatography on silica gel (ethyl acetate/petroleum ether=1:1),and compound 2 was obtained as dark red powder in a yield of 3.09 g(77%). Mp: 250-252 °C. 1H NMR (400 MHz, DMSO-d6, ppm, TMS):δ=9.81 (s, 1H), 7.91 (d, J=7.9 Hz, 2H), 7.49 (t, J=7.9 Hz, 2H), 7.27(t, J=7.4 Hz, 1H). Main FT-IR absorptions (KBr pellets, ν, cm-1):2840 (w), 2531 (w), 2226 (w), 1669 (vs), 1564 (vs), 1495 (vs), 1222(s), 1124 (vs). Negative ESI-MS in methanol: (m/z)=400.92 (100%),[M-H]-. Anal. Calcd. for C16H8ClN5O4S: C, 47.83; H, 2.01; N, 17.43%.Found: C, 47.89; H, 2.12; N, 17.49%. UV-Vis in methanol, λmax/ε (dm3mol-1 cm-1)=489 nm/2.63×104.
Reference: [1][Dyes and Pigments]
  • 35
  • [ 104366-23-6 ]
  • C21H17ClN4S [ No CAS ]
  • C21H17ClN4S [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: sulfuric acid; phosphoric acid; sodium nitrite 2.1: sodium t-butanolate / tetrahydrofuran / 0.5 h / 0 °C / Inert atmosphere 2.2: 5 h / 70 °C / Inert atmosphere
  • 36
  • [ 104366-23-6 ]
  • C23H21ClN4S [ No CAS ]
  • C23H21ClN4S [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: sulfuric acid; phosphoric acid; nitrosylsulfuric acid / 0.75 h / -5 °C 1.2: 2 h / 0 - 5 °C 2.1: sodium t-butanolate / tetrahydrofuran / 0.5 h / 0 °C / Inert atmosphere 2.2: 5 h / 70 °C / Inert atmosphere
  • 37
  • [ 104366-23-6 ]
  • C24H23ClN4S [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: sulfuric acid; phosphoric acid; nitrosylsulfuric acid / 0.75 h / -5 °C 1.2: 2 h / 0 - 5 °C 2.1: sodium t-butanolate / tetrahydrofuran / 0.5 h / 0 °C / Inert atmosphere 2.2: 5 h / 70 °C / Inert atmosphere
  • 38
  • [ 104366-23-6 ]
  • C21H16ClN5O2S [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: sulfuric acid; phosphoric acid; sodium nitrite 2.1: sodium t-butanolate / tetrahydrofuran / 0.5 h / 0 °C / Inert atmosphere 2.2: 5 h / 70 °C / Inert atmosphere
  • 39
  • [ 104366-23-6 ]
  • [ 91-66-7 ]
  • C16H15ClN4OS [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% Stage #1: 2-amino-4-chloro-5-formyl-3-cyanothiophene With nitrosylsulfuric acid; phosphoric acid; sulfuric acid at -5℃; for 0.75h; Stage #2: N,N-diethylaniline In methanol; water at 0 - 5℃; for 2h;
  • 40
  • [ 104366-23-6 ]
  • [ 121-69-7 ]
  • C14H11ClN4OS [ No CAS ]
YieldReaction ConditionsOperation in experiment
With phosphoric acid; sulfuric acid; sodium nitrite
  • 41
  • [ 104366-23-6 ]
  • [ 2767-70-6 ]
  • C13H8ClN3O2S [ No CAS ]
YieldReaction ConditionsOperation in experiment
52% Stage #1: (p-nitrobenzyl)triphenylphosphonium bromide With sodium t-butanolate In tetrahydrofuran at 0℃; for 0.5h; Inert atmosphere; Stage #2: 2-amino-4-chloro-5-formyl-3-cyanothiophene In tetrahydrofuran at 70℃; for 5h; Inert atmosphere;
  • 42
  • [ 104366-23-6 ]
  • [ 769-42-6 ]
  • C12H8ClN5O4S [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: 2-amino-4-chloro-5-formyl-3-cyanothiophene With hydrogenchloride; sodium nitrite Stage #2: 1,3-dimethylbarbituric acid
  • 43
  • [ 104366-23-6 ]
  • C7H3ClN2O3S [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: pyridine / 3 h / 100 °C 2: formic acid; sodium acetate / Reflux 3: oxone / N,N-dimethyl-formamide / 18 h / 20 °C
Multi-step reaction with 3 steps 1: pyridine / 3 h / 100 °C 2: formic acid; sodium acetate / Reflux 3: Oxone / N,N-dimethyl-formamide / 18 h / 19 - 24 °C
  • 44
  • [ 104366-23-6 ]
  • C7H4ClN3O2S [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: pyridine / 3 h / 100 °C 2: formic acid; sodium acetate / Reflux 3: oxone / N,N-dimethyl-formamide / 18 h / 20 °C 4: N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate; N-ethyl-N,N-diisopropylamine; ammonia / tetrahydrofuran / 18 h / 20 °C
Multi-step reaction with 4 steps 1: pyridine / 3 h / 100 °C 2: formic acid; sodium acetate / Reflux 3: Oxone / N,N-dimethyl-formamide / 18 h / 19 - 24 °C 4: ammonia; HATU; N-ethyl-N,N-diisopropylamine / tetrahydrofuran; N,N-dimethyl-formamide / 18 h / 19 - 24 °C
  • 45
  • [ 104366-23-6 ]
  • C17H13Cl2N7O3S [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 5 steps 1: pyridine / 3 h / 100 °C 2: formic acid; sodium acetate / Reflux 3: oxone / N,N-dimethyl-formamide / 18 h / 20 °C 4: N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate; N-ethyl-N,N-diisopropylamine; ammonia / tetrahydrofuran / 18 h / 20 °C 5: potassium carbonate / N,N-dimethyl-formamide / 18 h / 20 °C
  • 46
  • [ 104366-23-6 ]
  • [ 4637-24-5 ]
  • C9H8ClN3OS [ No CAS ]
YieldReaction ConditionsOperation in experiment
With pyridine at 100℃; for 3h; Intermediate X.1 (General Route) To 5.00 g (26.8 mmol) 2-amino-4-chloro-3-cyano-5-formylthiophene (CAS: 104366-23-6) in 25 mL pyridine is added 5.70 mL (42.9 mmol) N,N-dimethylformamide dimethyl acetal. The mixture is stirred at 100° C. for 3 h. After cooling to ambient temperature, the mixture is concentrated under reduced pressure. The residue is resuspended in DCM and washed with water. The organic phase is dried over Na2SO4 and concentrated to yield the desired product.C9H8ClN3OS (M=241.7 g/mol)ESI-MS: 242 [M+H]+Rt (HPLC): 1.04 min (method B)
With pyridine at 100℃; for 3h; Intermediate VIII.1 (General Route) To 5.00 g (26.8 mmol) 2-amino-4-chloro-3-cyano-5-formylthiophene (CAS: 104366-23-6) in 25 mL pyridine is added 5.70 mL (42.9 mmol) N,N-dimethylformamide dimethyl acetal. The mixture is stirred at 100° C. for 3 h. After cooling to ambient temperature, the mixture is concentrated under reduced pressure. The residue is resuspended in DCM and washed with water. The organic phase is dried over Na2SO4 and concentrated to yield the desired product. (0157) C9H8ClN3OS (M=241.7 g/mol) (0158) ESI-MS: 242 [M+H]+ (0159) Rt (HPLC): 1.04 min (method B)
  • 47
  • [ 104366-23-6 ]
  • C7H3ClN2O2S [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: pyridine / 3 h / 100 °C 2: formic acid; sodium acetate / Reflux
  • 48
  • [ 104366-23-6 ]
  • C18H13Cl2N5O4S [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 5 steps 1: pyridine / 3 h / 100 °C 2: formic acid; sodium acetate / Reflux 3: Oxone / N,N-dimethyl-formamide / 18 h / 19 - 24 °C 4: ammonia; HATU; N-ethyl-N,N-diisopropylamine / tetrahydrofuran; N,N-dimethyl-formamide / 18 h / 19 - 24 °C 5: potassium carbonate / N,N-dimethyl-formamide / 18 h / 19 - 24 °C
Recommend Products
Same Skeleton Products
Historical Records