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Chemical Structure| 7400-05-7

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Product Details of [ 7400-05-7 ]

CAS No. :7400-05-7
Formula : C10H17N3O3S
M.W : 259.33
SMILES Code : OC1=NC(S)=NC(N)=C1CC(OCC)OCC
MDL No. :MFCD02094192
InChI Key :GKSGXTLNGDMLRR-UHFFFAOYSA-N
Pubchem ID :3003781

Safety of [ 7400-05-7 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H332-H335
Precautionary Statements:P280-P305+P351+P338-P310

Application In Synthesis of [ 7400-05-7 ]

* 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 [ 7400-05-7 ]

[ 7400-05-7 ] Synthesis Path-Downstream   1~2

  • 1
  • [ 52133-67-2 ]
  • [ 17356-08-0 ]
  • [ 7400-05-7 ]
YieldReaction ConditionsOperation in experiment
57% With sodium ethanolate; In ethanol; at 95℃; To the 250 mL round bottomed flask containing 14.2 g (61.8 mmol) of ethyl 2,2-diethoxy cyanoacetate was added 110 mL of absolute ethanol followed by 28 mL of sodium ethoxide (21percent, 75.0 mmol). Thiourea (5.7 g, 74.5 mmol) was added all at once and the mixture was heated to 95°C and refluxed overnight. The mixture was then cooled to room temperature and concentrated. Water (250 mL) was added and the aqueous layer was washed with diethyl ether (3 x 250 mL). The aqueous layer was then neutralized with acetic acid (1 eq.) and the precipitate was filtered. The yellow solid was dried under vacuum over P2O5 overnight to give 9.2 g (35.5 mmol, 57percent) of crude product. 1H-NMR (DMSO, 600 MHz): sigma 1.07 (t, 6H, J = 7.2 Hz), 2.43 (d, 2H, J = 5.4 Hz), 3.37 - 3.43 (m, 6H), 3.56 - 3.61 (m, 2H), 4.50 (t, 1H, J = 5.4 Hz), 6.07 (s, 2H), 11.5 (br s, 1H), 11.7 (br s, 1H). 13C-NMR (DMSO, 150 Mz): sigma 15.4, 27.9, 61.9, 85.7, 101.7, 151.9, 161.8, 172.9. HRMS (FAB): expected for C10H18N3O3S (M+H)+: 260.10634. Found: 260.10640. IR(neat): vmax 3342, 3219, 2973, 2879, 1563 cm-1.
With sodium ethanolate; In ethanol; at 95℃; Take a 250 mL single-necked flask and add compound 1 (34 g, 14.8 mmol)Treated with ethanol (100 mL)Add sodium ethoxide(12 g, 17.8 mmol, 1.2 eq.) Was added, thiourea (13.7 g, 17.8 mmol, 1.2 eq.) Was added, heated to 95 ° C and refluxed overnight. Cooled to room temperature, spin dry, add water dissolved, washed with ether, the water phase, add acetic acid to neutral, filtered and dried to obtain 20.3 g of crude product as a yellow solid in 55percent yield.
  • 2
  • [ 52133-67-2 ]
  • [ 17356-08-0 ]
  • [ 7400-05-7 ]
YieldReaction ConditionsOperation in experiment
62% With sodium ethanolate; In ethanol;Reflux; 2.15 g of <strong>[52133-67-2]ethyl 2-cyano-4,4-diethoxybutyrate</strong> was dissolved in 5.3 ml of 20% sodium ethoxide solution in ethanol, and then 1.2 g of thiourea was added and heated to reflux overnight. The reaction solution was concentrated to dryness on the next day, diluted with 38 ml of water and washed with ethyl ether. The pH of the aqueous phase was adjusted to be neutrality with acetic acid, and a large amount of solidswere precipitated, filtered, and the solids were collected and dried to give 1.5 g of pale yellow solids, yield 62%. 1H NMR (300 MHz, DMSO-d6) delta 11.75 (s, 1H), 11.44 (s, 1H), 6.07 (s, 2H), 4.50 (t, J = 5.6, 1H), 3.59 (dq, J = 7.0, 9.5, 2H), 3.40 (dq, J = 7.0, 9.6, 2H), 2.44 (d, J = 5.6, 2H), 1.07 (t, J = 7.0, 6H);
60.19% b. To a freshly prepared solution of sodium ethoxide [ethanol (250 mL) and sodium metal (9.02 g, 392.55 mmol)] was added <strong>[52133-67-2]ethyl 2-cyano-4,4-diethoxybutanoate</strong> (82) (45 g, 196.27 mmol) and thiourea (14.94 g, 196.27 mmol) in ethanol (200 mL). The reaction mixture was heated with stirring at reflux for 3.5 h. The reaction mixture was allowed to cool to room temperature and stirred overnight. The reaction was quenched with water (100 mL) and concentrated in vacuum to remove ethanol. The residue obtained was dissolved in water (100 mL) and neutralized to pH 7 using dilute aqueous hydrochloric acid (3N) by maintaining the temperature below 10 C. The solid obtained was collected by filtration to afford on drying in vacuum 6-amino-5-(2,2-diethoxyethyl)-2- mercaptopyrimidin-4-ol (83) (30.6 g, 60.19%) as a pale yellow solid. 1HNMR (300 MHz, DMSO) delta 11.75 (s, IH, D2O exchangeable), 11.44 (s, IH, D2O exchangeable), 6.07 (s, 2H, D2O exchangeable), 4.50 (t, J= 5.6, IH), 3.59 (dq, J= 7.0, 9.5, 2H), 3.40 (dq, J= 7.0, 9.6, 2H), 2.44 (d, J = 5.6, 2H), 1.07 (t, J= 7.0, 6H); IR (KBr): 3226, 2973, 2909, 1624, 1569, 1474, 1376, 1287, 1213, 1114, 1049, 993, 892, 822, 789 and 763 cm"1; MS (ES+1) 260.1 (M+l), 282.1 (M+23), (ES ): 258.3 (M -1); HPLC [(Column: Zorbax SBC3, 3.0 x 150 mm, 5 mum, with a ZGC SBC3, 2.1 x 12.5 mm guard cartridge. Mobile phase: 0.1 M Ammonium Acetate /Acetonitrile) Rt= 11.408 min (99.64%]); Analysis: Calculated for C10Hi7N3O3S: C, 46.45; H, 6.72; N, 16.06; Found: C, 46.31; H, 6.60; N, 16.20.
36% To ethanol (200 ml) was added sodium (2.05 g, 89 mmol) in small portions. The solution was stirred until complete dissolution of the sodium metal. 2-Cyano-4,4- diethoxy-butyric acid ethyl ester (J. Chem. Soc, I960, 131-138) (9.292 g, 40.5 mmol) was then added as a solution in ethanol (50 ml), followed by addition of thiourea (3.08 g, 40.4 mmol). The solution was heated at 85 C for 18 hours, and then cooled to room temperature. The solution was concentrated, and saturated aqueous ammonium chloride solution (150 ml) was added. The mixture was stirred EPO <DP n="125"/>at room temperature for 18 hours, after which time the solid was collected by filtration, and washed with water (20 ml) to yield the product (3.376 g, 36%).
36% PREPARATION 2; 4-Chloro-7H-pyrrolor2,3-<i1pyrimidine2A. 6-Amino-5-(2,2-diethoxy-ethyl)-2-mercapto-pyrimidin-4-olTo ethanol (200 ml) was added sodium (2.05 g, 89 mmol) in small portions. The solution was stirred until complete dissolution of the sodium metal. 2-Cyano-4,4-diethoxy-butyric acid ethyl ester (J Chem. Soc, 1960, 131-138) (9.292 g, 40.5 mmol) was then added as a solution in ethanol (50 ml), followed by addition of thiourea (3.08 g, 40.4 mmol). The solution was heated at 85 C for 18 hours, and then cooled to room temperature. The solution was concentrated, and saturated aqueous ammonium chloride solution (150 ml) was added. The mixture was stirred at room temperature for 18 hours, after which time the solid was collected by filtration, and washed with water (20 ml) to yield the product (3.376 g, 36%).
36% To ethanol (200 ml) was added sodium (2.05 g, 89 mmol) in small portions. The solution was stirred until complete dissolution of the sodium metal. 2-Cyano-4,4- diethoxy-butyric acid ethyl ester (J. Chem. Soc, 1960, 131-138) (9.292 g, 40.5 mmol) was then added as a solution in ethanol (50 ml), followed by addition of thiourea (3.08 g, 40.4 mmol). The solution was heated at 85 0C for 18 hours, and then cooled to room temperature. The solution was concentrated, and saturated aqueous ammonium chloride solution (150 ml) was added. The mixture was stirred at room temperature for 18 hours, after which time the solid was collected by filtration, and washed with water (20 ml) to yield the product (3.376 g, 36%).
36% EXAMPLE 12 1-(7/-/-Pyrrolor2,3-cf1pyrimidin-4-yl)-piperidin-4-ylamine12A. 6-Amino-5-(2,2-diethoxy-ethyl)-2-mercapto-pyrimidin-4-olTo ethanol (200 ml) was added sodium (2.05 g, 89 mmol) in small portions. The solution was stirred until complete dissolution of the sodium metal. 2-Cyano-4,4-diethoxy-butyric acid ethyl ester {J. Chem. Soc, 1960, 131-138) (9.292 g, 40.5 mmol) was then added as a solution in ethanol (50 ml), followed by addition of thiourea (3.08 g, 40.4 mmol). The solution was heated at 85 0C for 18 hours, and then cooled to room temperature. The solution was concentrated, and saturated aqueous ammonium chloride solution (150 ml) was added. The mixture was stirred at room temperature for 18 hours, after which time the solid was collected by filtration, and washed with water (20 ml) to yield the product (3.376 g, 36%).
36% EXAMPLE 18; C-f1-(7H-Pyrrolof2,3-o1Pyrimidin-4-yl)-piperidin-4-yl|-methylamine; 18A. 6-Amino-5-(2,2-diethoxy-ethyl)-2-mercapto-pyrimidin-4-olTo ethanol (200 ml) was added sodium (2.05 g, 89 mmol) in small portions. The solution was stirred until complete dissolution of the sodium metal. 2-Cyano-4,4-diethoxy-butyric acid ethyl ester (J. Chem. Soc, 1960, 131-138) (9.292 g, 40.5 mmol) was then added as a solution in ethanol (50 ml), followed by addition of thiourea (3.08 g, 40.4 mmol). The solution was heated at 85 0C for 18 hours, and then cooled to room temperature. The solution was concentrated, and saturated aqueous ammonium chloride solution (150 ml) was added. The mixture was stirred at room temperature for 18 hours, after which time the solid was collected by filtration, and washed with water (20 ml) to yield the product (3.376 g, 36%).
With sodium; In ethanol; at 0℃;Reflux; (b) 3.3 g (99 mmol) of sodium are added at 0 C. to 75 ml of ethanol, and 7.5 g (99 mmol) of thiourea and <strong>[52133-67-2]ethyl 2-cyano-4,4-diethoxybutyrate</strong> (20.6 g; 90 mmol) are added when the sodium has completely reacted. The mixture is then refluxed for 10 h, and, after cooling, the solvent is removed in vacuo. The residue is partitioned between water and ether, and, after phase separation, the aqueous phase is acidified using 5.7 ml (99 mmol) of acetic acid. The product precipitates out, is filtered off and dried in vacuo, giving 21.73 g (93%) of 6-amino-5-(2,2-diethoxyethyl)-2-mercapto-pyrimidin-4-ol in the form of a beige powder, which is employed in the subsequent reaction without further purification.

 

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