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Chemical Structure| 78583-84-3 Chemical Structure| 78583-84-3

Structure of 78583-84-3

Chemical Structure| 78583-84-3

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Product Details of [ 78583-84-3 ]

CAS No. :78583-84-3
Formula : C9H6ClN
M.W : 163.60
SMILES Code : N#C/C=C(Cl)/C1=CC=CC=C1
MDL No. :MFCD00277431
InChI Key :GVKYEBRJHLHHOE-TWGQIWQCSA-N
Pubchem ID :736604

Safety of [ 78583-84-3 ]

GHS Pictogram:
Signal Word:Danger
Hazard Statements:H315-H318-H335
Precautionary Statements:P261-P264-P271-P280-P302+P352-P304+P340+P312-P305+P351+P338+P310-P332+P313-P362-P403+P233-P405-P501
Class:8
UN#:1759
Packing Group:

Application In Synthesis of [ 78583-84-3 ]

* 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 [ 78583-84-3 ]

[ 78583-84-3 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 78583-84-3 ]
  • [ 2365-48-2 ]
  • [ 100063-22-7 ]
YieldReaction ConditionsOperation in experiment
69% With sodium methylate; In methanol; for 3h;Reflux; General procedure: An apropriate substrate S2a-n, from the previous step, in dry MeOH (15 ml) [THF (15 ml) was used in the case of 3,4-dirnethoxyphenyl substrate S2m] was added dropwise to a stirred mixture of methyl thioglycolate (3.5 ml, 38 mmol) and NaOMe, prepared by dissolving Na (1.15 g, 50 mmol) in dry MeOH (20 ml), at 0 C during 30 min. The formed suspension was intensely stirred and heated at reflux for 3 h. Then, the reaction mixture was poured in ice cold water (100 ml) and neutralized with AcOH (1.10 ml). The precipitate was filtered, washed with water (5x10 ml), MeOH (10 ml) and dried under air. Esters 1 were purified by crystallization from EtOH, except for compoimd 1l, which was crystallized from Et2O. Yields of esters 1a-n are based on methyl ketones S1a-n. 5-Styryl-substituted derivative 1o was prepared in the same manner by the reaction of substrate S2o (4.55 g, 24 mmol) with methyl thioglycolate (2.75 ml, 30 mmol) in the presence of NaOMe, from Na (0.92 g, 40 mmol), dry MeOH (30 ml). Compound 1o was purified by crystallization from EtOH.
50% Step b:Methyl S-amino-S-phenylthiophene^-carboxylate: To a solution of methyl thioglycolate (1 g, 9.43 mmol) in methanol (5 mL) was added a solution of sodium methoxide (0.5 g, 9.43 mmol) in methanol (5 mL) and stirred for 0.5 h. To the above mixture, a solution of 3-chloro-3-phenylprop-2-enenitrile (1.22 g, 7.5 mmol) in DMF (3.5 mL) was added dropwise for 10 min at rt and stirred the mixture at 6O0C for 2 h. Then, a solution of sodium methoxide (1 g, 18.6 mmol) in methanol (10 mL) was added dropwise at rt and stirring was continued for 2 h at 6O0C. The mixture was allowed to rt and poured into cold water and stirred for 15 min. The solution was extracted with chloroform (3 x 100 mL) and the combined chloroform layer was washed with water, brine and dried over sodium sulfate. The solution was filtered and evaporated the solvent. The residue was chromatographed over silica gel using hexane-ethyl acetate (92:8) as eluent to give the product as a pale yellow color solid (1.1 g, 50%), mp 130-1320C. 1H NMR (400 MHz, DMSO-de): δ 7.62-7.65 (2H, m), 7.38-7.48 (3H, m), 7.00 (IH, s), 4.29 (2H, br s), 3.74 (3H, s); LC-MS (positive ion mode): m/z 234 (M+H)+.
50% Step b:Methyl 3-amino-5-phenylthiophene-2-carboxylate:; To a solution of methyl thioglycolate (1 g, 9.43 mmol) in methanol (5 mL) was added a solution of sodium methoxide (0.5 g, 9.43 mmol) in methanol (5 mL) and stirred for 0.5 h. To the above mixture, a solution of 3-chloro-3-phenylprop-2-enenitrile (1.22 g, 7.5 mmol) in DMF (3.5 mL) was added dropwise for 10 min at rt and stirred the mixture at 60 C. for 2 h. Then, a solution of sodium methoxide (1 g, 18.6 mmol) in methanol (10 mL) was added dropwise at rt and stirring was continued for 2 h at 60 C. The mixture was allowed to rt and poured into cold water and stirred for 15 min. The solution was extracted with chloroform (3×100 mL) and the combined chloroform layer was washed with water, brine and dried over sodium sulfate. The solution was filtered and evaporated the solvent. The residue was chromatographed over silica gel using hexane-ethyl acetate (92:8) as eluent to give the product as a pale yellow color solid (1.1 g, 50%), mp 130-132 C. 1H NMR (400 MHz, DMSO-d6): δ 7.62-7.65 (2H, m), 7.38-7.48 (3H, m), 7.00 (1H, s), 4.29 (2H, br s), 3.74 (3H, s); LC-MS (positive ion mode): m/z 234 (M+H)+.
With methanol; sodium; for 0.5h;Reflux; General procedure: POCl3 (26.1 g, 0.17 mol) was added dropwise to DMF (24.9 g, 0.34 mol) maintaining the temperature beyond 25 C (cooling in ice bath) and stirred for additional 15 min. The acetophenone I (85.0 mmol) was added slowly and the temperature was kept between 40 and 60 C. After complete addition, the mixture was stirred for 30 min at room temperature. Hydroxylamine hydrochloride (23.6 g,0.34 mol) was carefully added portionwise (exothermic reaction) and the reaction was stirred for additional 30 min without heating. After cooling to room temperature, the mixture was poured into ice water (300 mL). The precipitated b-chloro-cinnamonitrile was collected by filtration, washed with H2O(2 50 mL) and dried under reduced pressure over CaCl2. In the next step sodium (1.93 g, 84.0 mmol) was dissolved in MeOH(85 mL) and methylthioglycolate (6.97 g, 65.6 mmol) was added to the stirred solution. The b-chloro-cinnamonitrile (61.1 mmol) was added and the mixture was heated to reflux for 30 min. After cooling to room temperature, the mixture was poured into icewater (300 mL). The precipitated solid was collected by filtration, washed with H2O (2 50 mL) and dried under reduced pressure over CaCl2. If necessary, recrystallisation from EtOH was performed.
With sodium; In methanol; for 0.5h;Reflux; General procedure: POCl3 (26.1 g, 0.17 mol) was added dropwise to DMF (24.9 g, 0.34 mol) maintaining the temperature beyond 25 C (cooling in ice bath) and stirred for additional 15 min. The acteophenon I (85.0 mmol) was added slowly and the temperature was kept between 40 and 60 C. After complete addition, the mixture was stirred for 30 minutes at room temperature. Hydroxylamine hydrochloride (23.6 g, 0.34 mol) was carefully added portionwise (exothermic reaction) and the reaction was stirred for additional 30 min without heating. After cooling to room temperature, the mixture was poured into ice water (300 mL). The precipitated β-chloro-cinnamonitrile was collected by filtration, washed with H2O (2 x 50 mL) and dried under reduced pressure over CaCl2. In the next step sodium (1.93 g, 84.0 mmol.) was dissolved in MeOH (85 mL) and methyl thioglycolate (6.97 g, 65.6 mmol) was added to the stirred solution. The β-chloro-cinnamonitrile (61.1 mmol) was added and the mixture was heated to reflux for 30 min. After cooling to room temperature, the mixture was poured in ice water (300 mL). The precipitated solid was collected by filtration, washed with H2O (2 x 50 mL) and dried under reduced pressure over CaCl2. If necessary, recrystallisation was performed from EtOH.

 

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