Home Cart 0 Sign in  

[ CAS No. 616-47-7 ]

{[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
Excepted Quantity Free
Inaccessible (Haz class 6.1), Domestic USD 41.00
Inaccessible (Haz class 6.1), International USD 64.00
Accessible (Haz class 3, 4, 5 or 8), Domestic USD 83.00
Accessible (Haz class 3, 4, 5 or 8), International USD 133.00
2D
Chemical Structure| 616-47-7
Chemical Structure| 616-47-7
Structure of 616-47-7 *Storage: {[proInfo.prStorage]}

Quality Control of [ 616-47-7 ]

Related Doc. of [ 616-47-7 ]

SDS
Alternatived Products of [ 616-47-7 ]
Alternatived Products of [ 616-47-7 ]

Product Details of [ 616-47-7 ]

CAS No. :616-47-7MDL No. :MFCD00005292
Formula : C4H6N2 Boiling Point : 198.6°C at 760 mmHg
Linear Structure Formula :-InChI Key :N/A
M.W :82.10Pubchem ID :1390
Synonyms :

Computed Properties of [ 616-47-7 ]

TPSA : 17.8 H-Bond Acceptor Count : 1
XLogP3 : - H-Bond Donor Count : 0
SP3 : 0.25 Rotatable Bond Count : 0

Safety of [ 616-47-7 ]

Signal Word:DangerClass:8,6.1
Precautionary Statements:P210-P264-P270-P280-P301+P312+P330-P301+P330+P331-P303+P361+P353-P304+P340+P310-P305+P351+P338+P310-P361+P364-P370+P378-P403+P235-P405-P501UN#:2922
Hazard Statements:H227-H302-H311-H314Packing Group:
GHS Pictogram:

Application In Synthesis of [ 616-47-7 ]

  • Upstream synthesis route of [ 616-47-7 ]
  • Downstream synthetic route of [ 616-47-7 ]

[ 616-47-7 ] Synthesis Path-Upstream   1~19

  • 1
  • [ 174899-82-2 ]
  • [ 616-47-7 ]
  • [ 1072-62-4 ]
  • [ 7098-07-9 ]
  • [ 693-98-1 ]
Reference: [1] Australian Journal of Chemistry, 2004, vol. 57, # 2, p. 145 - 147
  • 2
  • [ 110-85-0 ]
  • [ 288-32-4 ]
  • [ 290-37-9 ]
  • [ 616-47-7 ]
  • [ 109-08-0 ]
  • [ 13925-00-3 ]
  • [ 693-98-1 ]
Reference: [1] Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1990, vol. 39, # 7.1, p. 1340 - 1345[2] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1990, # 7, p. 1483 - 1488
  • 3
  • [ 616-47-7 ]
  • [ 1003-21-0 ]
  • [ 1003-50-5 ]
Reference: [1] Polish Journal of Chemistry, 1981, vol. 55, # 7/8, p. 1659 - 1665
[2] The Journal of organic chemistry, 2002, vol. 67, # 17, p. 5913 - 5918
  • 4
  • [ 616-47-7 ]
  • [ 1003-21-0 ]
Reference: [1] Tetrahedron Letters, 2015, vol. 56, # 25, p. 3855 - 3857
  • 5
  • [ 616-47-7 ]
  • [ 74-88-4 ]
  • [ 14486-52-3 ]
Reference: [1] Journal of the American Chemical Society, 2005, vol. 127, # 43, p. 15207 - 15217
  • 6
  • [ 616-47-7 ]
  • [ 624-92-0 ]
  • [ 14486-52-3 ]
Reference: [1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1994, # 3, p. 239 - 244
[2] Journal of Medicinal Chemistry, 2003, vol. 46, # 3, p. 427 - 440
  • 7
  • [ 616-47-7 ]
  • [ 624-92-0 ]
  • [ 14486-52-3 ]
  • [ 87946-06-3 ]
Reference: [1] Journal of Chemical Research, Miniprint, 1983, # 8, p. 1913 - 1941
  • 8
  • [ 616-47-7 ]
  • [ 1003-91-4 ]
YieldReaction ConditionsOperation in experiment
29% With bromine; sodium acetate In acetic acid at 20℃; for 2.5 h; To a solution of N-methylimidazole (1.64 g, 19.97 mmol) and sodium acetate (25 g, 300 mmol) in acetic acid (180 mL) at room temperature was added bromine (9.6 g, 60.07 mmol) dropwise as a solution in 20 mL acetic acid. The resulting mixture was stirred for 2.5 h at room temperature. Acetic acid was removed in vacuo, the residue was suspended in 500 mL water and stirred at room temperature for 10 minutes. The resultant precipitate was filtered, washed with water and dried under high vacuum to give 2,4,5-tribromo-l-methyl- lH-imidazole (1.82 g, 29percent - some product remained in the mother liquor) as a light yellow powder. Used without further characterization. To a suspension of the tribromide (1.82 g, 5.71 mmol) in 45 mL water was added sodium sulfite (13 g, 103 mmol) and the resulting mixture was stirred at rapid reflux for 24 h. After cooling to room temperature, organics were extracted with ether (3 χ 75 mL), dried over magnesium sulfate, filtered and concentrated to give 1.61 g of a mixture of tri-, di- and monobromoimidazoles. This mixture was re-subjected to the reduction conditions (same quantity of sodium sulfite) using 15 mL of 3: 1 water/acetic acid as solvent and heating in a sealed vessel at 130 °C for 60 h. After cooling to room temperature, the pH of the reaction mixture was adjusted to 9-10 by addition of 2 N sodium hydroxide. Organics were extracted with ether (3 χ 50 mL), dried over magnesium sulfate, filtered and concentrated to give crude 4-bromo-l -methyl- lH-imidazole (571 mg, ca. 62percent). Used without further characterization.. 4-Butyl-l -methyl- lH-imidazole (95 mg, 22 percent) was synthesized as in Example 3.1 using 4-bromo-l -methyl- lH-imidazole (571 mg, ca. 3.53 mmol) in place of 5-bromo-2- formylfuran and propylboronic acid (372 mg, 4.24 mmol) in place of hexylboronic acid. Used without further characterization. To a solution of diisopropylamine (0.13 mL, 0.918 mmol) in 2 mL anhydrous tetrahydrofuran at - 0°C was added -butyllithium (0.34 mL, 2.5 M in hexanes) dropwise. The solution was stirred while warming to -20 °C over 20 minutes. After cooling to -78 °C, 4-butyl-l -methyl- lH-imidazole (95 mg, 0.765 mmol) was added dropwise as a solution in 2 mL anhydrous tetrahydrofuran. The resulting solution was stirred for 40 minutes at -78 °C. Dimethylformamide (0.24 mL, 3.06 mmol) was added and the solution stirred while warming to room temperature. The reaction mixture was poured into 15 mL of 1 N hydrochloric acid and stirred for 5 minutes. The pH of the reaction mixture was adjusted to 7-8 by careful addition of saturated sodium bicarbonate solution. Organics were extracted with dichloromethane (3 χ 20 mL), dried over magnesium sulfate, filtered and concentrated. The crude residue was subjected to chromatography on silica gel with gradient elution (5-50percent ethyl acetate in hexanes) to give l -methyl-4-propyl-lH-imidazole-2-carbaldehyde (9 mg, 8percent) as an off-white solid. Used without further characterization
63.76 g With N-Bromosuccinimide In chloroform at 20℃; for 1.5 h; 2-(2-Ethynyl-1 -methyl-1 H-imidazol-4-yl)-thiazole    To a solution of compound N-methylimidazole (65.6 g, 0.8 mol) in CHCl3 (1 .5 L), N-bromosuccinimide (NBS; 476g,2.4 mol) was added in portion and then the mixture was stirred at roomtemperature for 1 .5 hour, filtered and concentrated, the residue was purifiedby column chromatography over silica gel (eluent: EA/PE 1/10) to afford 2,4,5-Tribromo-1 -methyl-1H-imidazole (63.76 g, 0.2 mol), which was dissolved in in dry THF (2L) andEtMgBr (220 ml_, 0.22 mol) was added slowly under N2 atmosphere at ambient temperature during 3 hourand stirred for another 2 hour. Then about 100ml_ water was added and filtered,concentrated and the residue was extracted with ethyl acetate, purified bycolumn chromatography over silica gel (eluent : EA/PE 1/10) to afford 2,4-dibromo-1 -methyl-1 H-imidazole (20 g, yield:41 .7percent). To a solution of 2,4-dibromo-1-methyl-1 H-imidazole (6 g, 25.6 mmol) in THF (26 ml_) was added Cul (0.2 g,1mmol), Et3N (12 ml_,86 mmol),Pd(dppf)CI2 (417 mg, 0.5 mmol),Ethynyl-trimethyl-silane (4.2 ml_,29.6 mmol), then the mixture was heated to40°C and stirred at this temperature for 40min. Then filtered, concentrated andpurified by column chromatography over silica gel (eluent: EA/PE 1/50), collectthe desire fraction and concentrated to give 4-Bromo-1-methyl-2-trimethylsilanylethynyl-1 H-imidazole (3.95 g, yield: 60percent). To a solution of 4-Bromo-1-methyl-2-trimethylsilanylethynyl-1 H-imidazole (5.14 g, 20 mmol) in toluene(100 ml_) , 2-Tributylstannanyl- thiazole (8.3 g, 22 mmol) was added followedwith Pd(PPh3) (1 .2 g, 1 mmol), then themixture was refluxed for 6 hour, when cooled, the mixture was filtered, thefiltrate was concentrated and purified by chromatography over silica gel (eluent :EA/PE 1/20 to 1/10) to afford 2-(1-Methyl-2-trimethylsilanylethynyl-1 H-imidazol-4-yl)-thiazole (2.5 g, yield:48percent). To the mixture of 2-(1 -Methyl -2-trimethylsilanylethynyl-1H-imidazol-4-yl)-thiazole in MeOH (50 ml_), Na2CO3 (1 .5 g, 18 mmol) was added quickly and stirred the mixture forabout one minutes, then filtered, concentrated and purified by column chromatographyover silica gel (eluent: EA PE 1/5) to afford 2-(2-Ethynyl-1 -methyl-1H-imidazol-4-yl)-thiazole (2 g, yield: 80percent). 1H NMR (CDCI3 400 MHz TMS):53.40 (s, 1 H), 3.80 (s, 3H), 7.27 (s, 1 H), 7.53 (s, 1 H), 7.26-7.27 (d, J=4.0Hz, 1 H).
95 g at 20℃; for 2.5 h; To a solution of Example 69a (82 g, 1.0 mol) and sodium acetate (125 g, 1.52 mol) in acetic acid (2.0 L) at room temperature was added bromine (480 g, 30 mmol) dropwise as a solution in 1.0L acetic acid. The resulting mixture was stirred for 2.5 h at room temperature. Acetic acid was removed in vacuo; the residue was suspended in 1.5L water and stirred at room temperature for 10 minutes. The resultant precipitate was filtered, washed with water and dried under high vacuum to give Example 69b (95.0 g, contained 30percent isomer) as light yellow powder. LCMS [M+H]+=319.1
Reference: [1] Synthesis, 1988, # 10, p. 767 - 771
[2] Tetrahedron Letters, 2006, vol. 47, # 12, p. 1949 - 1951
[3] Polish Journal of Chemistry, 1981, vol. 55, # 7/8, p. 1659 - 1665
[4] Chemische Berichte, 1991, vol. 124, p. 1639 - 1650
[5] Patent: WO2013/192352, 2013, A1, . Location in patent: Page/Page column 116; 117
[6] Chemische Berichte, 1883, vol. 16, p. 546 Anm. 1
[7] Patent: WO2013/50527, 2013, A1, . Location in patent: Page/Page column 38; 39; 40
[8] Patent: WO2017/218960, 2017, A1, . Location in patent: Paragraph 00638
  • 9
  • [ 616-47-7 ]
  • [ 1003-50-5 ]
  • [ 1003-91-4 ]
Reference: [1] Journal of the Chemical Society, 1924, vol. 125, p. 1569
  • 10
  • [ 616-47-7 ]
  • [ 67-66-3 ]
  • [ 7726-95-6 ]
  • [ 1003-50-5 ]
  • [ 1003-91-4 ]
Reference: [1] Journal of the Chemical Society, 1924, vol. 125, p. 1569
  • 11
  • [ 616-47-7 ]
  • [ 68-12-2 ]
  • [ 13750-81-7 ]
YieldReaction ConditionsOperation in experiment
68%
Stage #1: With n-butyllithium In tetrahydrofuran at -70℃; for 0.5 h;
Stage #2: at -70 - 0℃; for 2 h;
To a solution of 1- methylimidazole (8.2 g, 100 mmol) in dry THF (100 mL) cooled to -70 0C, was added dropwise a solution of nBuLi in THF. After stirring for 30 min at the same temperature, the solution was treated with freshly distilled DMF (7.3 g, 100 mmol). The resultant yellow suspension was stirred at 0 0C for 2 h, and quenched with ice- water. The mixture was extracted with EtOAc, and the organic extracts dried (Na2SO4) before evaporation to afford an oily residue, which was distilled under reduced pressure to afford the title product (68percent yield). 1H-NMR (CDCl3) 69.76 (s, EPO <DP n="82"/>IH, CHO), 7.22 (s, IH, Im-CH), 7.07 (s, IH, Im-CH), 3.96 (s, 3H, CH3). EI-HRMS: m/z calcd for C5H6N2O 110.0480, found 110.0481 (100percent), 82.0493 (60percent).
Reference: [1] Inorganica Chimica Acta, 2011, vol. 375, # 1, p. 213 - 219
[2] Dalton Transactions, 2015, vol. 44, # 17, p. 8013 - 8020
[3] Chemistry - A European Journal, 2015, vol. 21, # 36, p. 12735 - 12740
[4] Dalton Transactions, 2011, vol. 40, # 40, p. 10416 - 10433
[5] Tetrahedron, 2000, vol. 56, # 4, p. 645 - 657
[6] Bioorganic and Medicinal Chemistry, 2013, vol. 21, # 8, p. 2379 - 2386
[7] Monatshefte fur Chemie, 2016, vol. 147, # 12, p. 2209 - 2220
[8] New Journal of Chemistry, 2018, vol. 42, # 13, p. 10467 - 10471
[9] Patent: WO2007/45096, 2007, A1, . Location in patent: Page/Page column 41; 79-80
[10] Organic and Biomolecular Chemistry, 2009, vol. 7, # 8, p. 1633 - 1641
[11] European Journal of Organic Chemistry, 2011, # 30, p. 6092 - 6099
[12] Journal of Organometallic Chemistry, 1990, vol. 385, # 3, p. 417 - 427
[13] Journal of Medicinal Chemistry, 1991, vol. 34, # 4, p. 1363 - 1368
[14] Journal of Medicinal Chemistry, 1984, vol. 27, # 11, p. 1431 - 1438
[15] Tetrahedron, 1996, vol. 52, # 48, p. 15171 - 15188
[16] European Journal of Inorganic Chemistry, 2005, # 17, p. 3513 - 3523
[17] CrystEngComm, 2013, vol. 15, # 47, p. 10157 - 10160
[18] Croatica Chemica Acta, 2014, vol. 87, # 2, p. 153 - 160
  • 12
  • [ 616-47-7 ]
  • [ 67-56-1 ]
  • [ 68-12-2 ]
  • [ 62366-53-4 ]
  • [ 13750-81-7 ]
YieldReaction ConditionsOperation in experiment
79%
Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5 h;
Stage #2: at -78 - 20℃; for 2 h;
General procedure: n-BuLi (1.67 M solution in hexane, 1.3 mL, 2.2 mmol) was added dropwise into a solution of p-bromoanisole (383 mg, 2.0 mmol) in THF (3 mL) at -78 °C for 30 min. Then, DMF (0.22 mL, 2.2 mmol) was added to the mixture and the obtained mixture was stirred at rt. After 2 h at the same temperature, THF was removed. Then, MeOH (3 mL) was added to the residue and the mixture was stirred at room temperature. After 30 min, I2 (1523 mg, 6 mmol) and K2CO3 (829 mg, 6 mmol) were added at 0 °C and the obtained mixture was stirred for 22 h at rt. The reaction mixture was quenched with satd aq Na2SO3 (5 mL) and was extracted with CHCl3 (3.x.20 mL). The organic layer was washed with brine and dried over Na2SO4 to provide methyl 4-methoxy-1-benzoate in 82percent yield. If necessary, the product was purified by short column chromatography (SiO2:hexane:EtOAc=9:1) to give pure methyl 4-methoxybenzoate as a colorless oil.
Reference: [1] Tetrahedron, 2012, vol. 68, # 24, p. 4701 - 4709
  • 13
  • [ 616-47-7 ]
  • [ 13750-81-7 ]
YieldReaction ConditionsOperation in experiment
53% With sodium dihydrogenphosphate; diisopropylamine In tetrahydrofuran; water; ethyl acetate; N,N-dimethyl-formamide Synthesis of 1-Methyl-1H-imidazole-2-carbaldehyde (BB5)
To a solution of 1-methyl imidazole (57 g, 0.7 mmol) in THF (250 mL) was added LDA (2 M solution in THF, 348 mL) at -60° C. and the stirred for 3 h.
The reaction mixture was cooled -78° C., DMF (75 mL) was added rapidly, and the reaction mixture was slowly allowed to room temperature and stirred at ambient temperature overnight.
The reaction mixture was cooled to 0° C., a solution of NaH2PO4 (100 g in 350 mL H2O) was added and the resulting mixture was stirred for 30 min.
The mixture was filtered to remove insoluble material and the filtrate was extracted with DCM (4*400 mL).
The combined organic extracts were concentrated in vacuo and the crude residue was purified by column chromatography (silica gel, 100-200 mesh, 30percent EtOAc/pet. ether) to provide (BB5) (41 g, 53percent) as a yellow solid. Rf: 0.3 (15percent MeOH/CHCl3).
1H NMR (400 MHz, CDCl3): δ 9.82 (1H, s), 7.28 (1H, app d), 7.13 (1H, app d), 4.04 (3H, s); m/z 111 (MH)+.
Reference: [1] Patent: US2012/322722, 2012, A1,
[2] Liebigs Annalen der Chemie, 1980, # 4, p. 542 - 556
  • 14
  • [ 616-47-7 ]
  • [ 107-31-3 ]
  • [ 13750-81-7 ]
Reference: [1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1991, # 11, p. 2691 - 2698
  • 15
  • [ 616-47-7 ]
  • [ 109-94-4 ]
  • [ 13750-81-7 ]
Reference: [1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1991, # 11, p. 2691 - 2698
  • 16
  • [ 616-47-7 ]
  • [ 50-00-0 ]
  • [ 13750-81-7 ]
Reference: [1] Archives of Toxicology, 1998, vol. 72, # 5, p. 289 - 295
  • 17
  • [ 616-47-7 ]
  • [ 74-96-4 ]
  • [ 301-04-2 ]
  • [ 143314-17-4 ]
YieldReaction ConditionsOperation in experiment
92 %Spectr. at 50℃; for 0.5 h; Microwave irradiation Synthesis of 1-ethyl-3-methylimidazolium acetate ([Emim] Ac) in one step To a 500 ml round bottom flask was added 1.2 mol of bromoethane and 0.5 mol of lead acetate, To the constant-pressure dropping funnel was added 1 mol of N-methylimidazole, The reaction was carried out in an ultrasonic microwave combined reactor, The knob of the constant-pressure dropping funnel was controlled so that 1 mol of N-methylimidazole was dropped in one minute, The left through the cooling water, Set the ultrasonic power to 1000W, Microwave heating power of 900W, The reaction was carried out at 50 ° C for 30 minutes. The content of the target product [Emim] Ac in the reaction mixture was determined to be 92percent by nuclear magnetic resonance (NMR) and liquid chromatography-mass spectrometry.
Reference: [1] Journal of Molecular Liquids, 2012, vol. 165, p. 173 - 176
[2] Patent: CN105315215, 2016, A, . Location in patent: Paragraph 0013; 0014; 0015
  • 18
  • [ 616-47-7 ]
  • [ 64-17-5 ]
  • [ 64-19-7 ]
  • [ 143314-17-4 ]
YieldReaction ConditionsOperation in experiment
17% at 165℃; for 72 h; Autoclave Acetic acid 44 ml was added to a 250 ml Erlenmeyer flask containing 43 ml Ethanol. 6 ml 1-Methylimidazol was then added slowly to the stirred mixture. The mixture was then sealed inside a parr reactor whit continuous stirring for 72 hours at a temperature of 165 °C. The resulting dark liquid was placed in a rotary evaporator at 50 °C water bath. The mixture was then fed to a vacuum distillation equipment to remove the precursor and excess acetic acid. The still remaining liquid was then finally purified by Flash chromatography in a C18 pre-packet column with water as the eluent . The light yellow fractions were saved. This step was repeated 4 times. The final product was dissolved twice in 99,5percent ethyl alcohols and subjected to vacuum treatment. Yield 17percent. 13C-NMR (400HHz, DMSO) δ 175.0, 138.7, 124.6, 123.1, 44.9, 36.4, 26.4, 16.3.
Reference: [1] Journal of Molecular Structure, 2012, vol. 1028, p. 156 - 163
  • 19
  • [ 616-47-7 ]
  • [ 60634-74-4 ]
  • [ 137049-00-4 ]
Reference: [1] Patent: US5232922, 1993, A,
Historical Records

Related Parent Nucleus of
[ 616-47-7 ]

Imidazoles

Chemical Structure| 288-32-4

[ 288-32-4 ]

1H-Imidazole

Similarity: 0.87

Chemical Structure| 79917-88-7

[ 79917-88-7 ]

1,3-Dimethyl-1H-imidazol-3-ium chloride

Similarity: 0.85

Chemical Structure| 1467-16-9

[ 1467-16-9 ]

1H-Imidazole hydrochloride

Similarity: 0.83

Chemical Structure| 84661-56-3

[ 84661-56-3 ]

Di(1H-imidazol-1-yl)methane

Similarity: 0.82

Chemical Structure| 7098-07-9

[ 7098-07-9 ]

1-Ethyl-1H-imidazole

Similarity: 0.79