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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
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Structure of 762-42-5 * Storage: {[proInfo.prStorage]}
Reference：
[1] Journal of Organic Chemistry, 1994, vol. 59, # 18, p. 5347 - 5357
4
[ 762-42-5 ]
[ 2450-71-7 ]
[ 605-38-9 ]
Yield
Reaction Conditions
Operation in experiment
93%
With dipotassium peroxodisulfate; silver trifluoromethanesulfonate In toluene at 80℃; for 6 h; Sealed tube
A mixture of propargylamine (1a, 1.0 mmol, 55.1 mg), dimethyl acetylenedicarboxylate (2a, 1.3 mmol, 185.0 mg), AgOTf (25.7 mg, 0.1 mmol) and K2S2O8 (270.0 mg, 1.0 mmol) in toluene (20 mL) in a thick-walled screw-capped Pyrex tube was stirred with a magnetic stirrer at 80 °C for 6 h. After removal of the solvent under reduced pressure, purification was performed by flash column chromatography on silica gel with petroleum ether/ethyl acetate (8:2) as eluent to afford 3aa in 93 percent yield (181.3 mg, 0.93 mmol).
Reference：
[1] Journal of Organic Chemistry, 2017, vol. 82, # 24, p. 13756 - 13767
7
[ 41609-04-5 ]
[ 762-42-5 ]
[ 108-44-1 ]
[ 5220-49-5 ]
Yield
Reaction Conditions
Operation in experiment
55%
With tert.-butylhydroperoxide; copper diacetate In water at 30℃; for 12 h;
General procedure: A mixture of N-benzyl enaminoketone (1.0 mmol), di-alkylacetylenedicarboxylate (1.0 mmol), aryl or alkyl amine (1.0 mmol), Cu(OAc)2 (8 molpercent) and TBHP (4.0 mmol, 0.56 mL of a 70percent aqueous solution) in water (0.5 mL) was stirred at 30 °C for 12 h under air. The reaction progress was monitored by TLC. After completion of the reaction, the solid was filtrated out and washed with hot ethyl acetate. Finally the solvent of the filtrate was removed under vacuum and the resulting crude product was purified by column chromatography over 60-120 mesh silica gel [ethyl acetate/ petroleum ether (60-80 °C)].
Reference：
[1] Synthesis, 1985, vol. NO. 12, p. 1100 - 1164
[2] Liebigs Annalen der Chemie, 1982, vol. No. 4, p. 817 - 820
[3] Journal of Medicinal Chemistry, 2012, vol. 55, # 2, p. 812 - 823
9
[ 762-42-5 ]
[ 10068-07-2 ]
Reference：
[1] Journal of Agricultural and Food Chemistry, 2015, vol. 63, # 28, p. 6304 - 6312
[2] RSC Advances, 2018, vol. 8, # 13, p. 7080 - 7088
[3] Journal of Medicinal Chemistry, 2016, vol. 59, # 13, p. 6329 - 6343
10
[ 127-07-1 ]
[ 762-42-5 ]
[ 10068-07-2 ]
Reference：
[1] Patent: US6200975, 2001, B1,
11
[ 127-07-1 ]
[ 762-42-5 ]
[ 77094-88-3 ]
[ 77094-89-4 ]
[ 10068-07-2 ]
Reference：
[1] Bulletin de la Societe Chimique de France, 1980, vol. 2, # 9-10, p. 478 - 480
[2] Bulletin de la Societe Chimique de France, 1980, vol. 2, # 9-10, p. 478 - 480
12
[ 613-92-3 ]
[ 762-42-5 ]
[ 62222-38-2 ]
Reference：
[1] Journal of Medicinal Chemistry, 2004, vol. 47, # 22, p. 5336 - 5339
13
[ 762-42-5 ]
[ 55781-86-7 ]
Reference：
[1] Patent: EP2530078, 2012, A1,
14
[ 762-42-5 ]
[ 60-34-4 ]
[ 51985-95-6 ]
Reference：
[1] Patent: US5405829, 1995, A,
[2] Patent: US5580986, 1996, A,
[3] Journal of Medicinal Chemistry, 2011, vol. 54, # 23, p. 8174 - 8187
[4] Patent: WO2012/122340, 2012, A1, . Location in patent: Page/Page column 69
15
[ 762-42-5 ]
[ 51985-95-6 ]
Reference：
[1] Patent: WO2010/127975, 2010, A1,
16
[ 302-15-8 ]
[ 762-42-5 ]
[ 52867-42-2 ]
Yield
Reaction Conditions
Operation in experiment
52%
Stage #1: With triethylamine In methanol; water at 20℃; for 0.5 h; Stage #2: at 70℃; for 18 h;
Step l:Methyl 3-hydroxy-l-methyl-lH-pyrazole-5-carboxylate (3_41_2) [00351] Triethylamine (66 mL, 474.4 mmol) was added to a solution of methylhydrazine sulfuric acid salt (30.4 g, 211 mmol) in water (150 mL) and methanol (300 mL) at room temperature. The mixture was stirred for 0.5 hour at room temperature, but-2-ynedioic acid dimethyl ester (30 g, 211 mmol) was added and the mixture was stirred for 18 hours at 70°C. The reaction mixture was kept at room temperature for two days and the solid was collected by filtration and dried to give 12 g of the desired compound. The filtrate was concentrated, treated with ice and the solid was collected by filtration, and dried to give an additional 5 g of the desired compound 3_41_2 (17 g, 52 percent yield) as a yellow solid. [00352] NMR (400 MHz, DMSO-c: δ = 3.79 (s, 3H), 3.88 (s, 3H), 6.01 (s, 1H), 10.05 (s, 1H).
16.6%
Stage #1: With triethylamine In methanol; water at 20℃; for 0.5 h; Stage #2: at 70℃; for 18 h;
TEA (44.2 mL, 316.7 mmol) was added to a solution of methylhydrazine sulfate (20.3 g, 140.7 mmol) in H2O (100 mL) and MeOH (200 mL) at room temperature, and the mixture was stirred for 0.5 h at rt. Dimethyl but-2-ynedioate (20 g, 140.7 mmol) was added to the mixture, the mixture was stirred for 18 h at 70° C., followed by stirring at rt for 36 h. The reaction mixture was filtered, and the filtrate concentrated under reduced pressure to give the product as a white solid (3.65 g, 16.6percent yield).
With methylhydrazine sulfuric acid; triethylamine In methanol for 15 h; Reflux
The lOOmmol methyl hydrazine sulfate was added to a three-necked round-bottomed flask, dissolved with 200mL of methanol, followed by addition of 200mmol triethylamine free, finally adding lOOmmol dimethyl butynoate, heated to 60 ° C, magnetic stirring, refluxed 15h ;After the reaction is complete, stop heating, cooled to 5 ° C, allowed to stand for 2 days, until the white crystals precipitated, filtered, washed with ethanol, and dried to obtain methyl 3-hydroxy-1-methylpyrazole-5-carboxylate Rate of 60percent, purity 95percent
Stage #1: With triethylamine In methanol; water at 20℃; for 0.5 h; Stage #2: at 70℃; for 22 h;
Et3N (17.3 mL, 0.12 mol) was added to a solution of dimethyl but-2-ynedioate (8 g, 0.05mmol) in MeOH (80 mL), H20 (40 mL) and stirred at RT for 30 min. Methyl hydrazinesulfate (8.92 g, 61.9 mol) was added and the reaction mixture was stirred at 70 °C for 22 h.The solution was allowed to stand at R T overnight and the solid formed was filtered, driedunder high vacuum to afford methyl5-hydroxy-2-methyl-pyrazole-3-carboxylate (3.5 g,40percent) as a pale brown solid.LCMS: m/z: 157.3 [M+Ht.
To a solution of dimethyl acetylenedicarboxylate (5 g, 35.18 mmol) in methanol (25 mL)-water (2.5mL) was added dropwise methylhydrazine (1.945 g, 42.22 mmol) at room temperature. The reaction mixture was stirred at 70°C overnight, cooled to room temperature, concentrated under reduced pressure, diluted with water, and extracted with ethyl acetate. The organic layer was washed with saturated brine, and dried over anhydrous sodium sulfate. The obtained residue was purified by silica gel column chromatography [eluent: hexane-ethyl acetate (90:10-3:4)] to give the title compound (1.26 g) as a colorless oil (yield 23percent). MS (ESI+): [M+H]+157. 1H NMR (300 MHz, DMSO-d6) δ 3.79 (3H, s), 3.88 (3H, s), 6.00 (1H, s), 10.06 (1H, s).
5 g
at 0 - 70℃; for 10 h;
The compound methyl hydrazine (10g) was dissolved in methanol (20mL) and water (10mL), cooled to 0 degree, stirred for 15min, then compound 21 (12g) was added dropwise to the reaction system, heated to 70 degrees for 10h, then the system temperature was returned to room temperature, the reaction 12h, filtered off with suction, the filter cake was washed with water (5mL), dried to give 22 as a pale yellow solid 5g
5 g
at 0 - 70℃; for 10.25 h;
The compound methyl hydrazine (10 g) was dissolved in methanol (20 mL) and water (10 mL).The temperature was lowered to 0 °, stirred for 15 min, and then Compound 21 (12 g) was added dropwise to the reaction system.Heat to 70 ° for 10 h, then return the system temperature to room temperature.After 12 h of reaction, suction filtration, and the filter cake was washed with water (5 mL).Get 22 pale yellow solids 5g
Reference：
[1] Patent: EP2530078, 2012, A1, . Location in patent: Page/Page column 208-209
[2] Chemische Berichte, 1988, vol. 121, p. 2007 - 2012
[3] Patent: CN108250122, 2018, A, . Location in patent: Paragraph 0312-0316
[4] Patent: CN108264520, 2018, A, . Location in patent: Paragraph 0193; 0194; 0195; 0196; 0197
20
[ 563-79-1 ]
[ 762-42-5 ]
[ 72163-16-7 ]
[ 72163-25-8 ]
[ 5331-33-9 ]
[ 28868-76-0 ]
Reference：
[1] Canadian Journal of Chemistry, 1981, vol. 59, p. 288 - 301
21
[ 563-79-1 ]
[ 762-42-5 ]
[ 72163-16-7 ]
[ 72163-26-9 ]
[ 72163-23-6 ]
[ 28868-76-0 ]
Reference：
[1] Canadian Journal of Chemistry, 1981, vol. 59, p. 288 - 301
Reference：
[1] Chemistry Letters, 1978, p. 649 - 652
27
[ 54125-02-9 ]
[ 762-42-5 ]
[ 22479-95-4 ]
Reference：
[1] Synthetic Communications, 1991, vol. 21, # 21, p. 2231 - 2256
[2] Journal of the American Chemical Society, 1974, vol. 96, p. 7807 - 7808
[3] Journal of the American Chemical Society, 1979, vol. 101, p. 6996 - 7000
[4] Synthetic Communications, 1991, vol. 21, # 8-9, p. 1055 - 1069
28
[ 762-42-5 ]
[ 22479-95-4 ]
Reference：
[1] Journal of Organic Chemistry, 1996, vol. 61, # 4, p. 1487 - 1489
29
[ 59414-23-2 ]
[ 762-42-5 ]
[ 22479-95-4 ]
Reference：
[1] Chemical and Pharmaceutical Bulletin, 1990, vol. 38, # 7, p. 1832 - 1835
[2] Chemical and Pharmaceutical Bulletin, 1990, vol. 38, # 7, p. 1832 - 1835
Reference：
[1] Journal of Medicinal Chemistry, 2006, vol. 49, # 23, p. 6646 - 6649
34
[ 518047-98-8 ]
[ 762-42-5 ]
[ 519032-08-7 ]
Yield
Reaction Conditions
Operation in experiment
58%
Stage #1: at 20℃; for 2 h; Stage #2: With xylene In methanol at 90 - 120℃; for 16 h; Inert atmosphere
Benzyl 2-amino-2-(hydroxyimino)-1,1-dimethylethylcarbamate (2.0 g, 8.0 mmol) was dissolved in 30 mL MeOH, dimethyl acetylenedicarboxylate (DMAD, 1.1 mL, 9.0 mmol) was added slowly. The mixture was stirred for 2 h at room temperature, and then concentrated under reduced pressure to give a white oil. The mixture of the oil and 80 mL xylene was stirred at 90 °C for 2 h and 120 °C for 2 h, then refluxed for 12 h under nitrogen, concentrated to yield the crude product. The crude product was recrystallized with 2 mL MeOH and 10 mL tert-butyl methyl ether to afford 5 as a yellow solid (1.7 g, 58 percent): 1H-NMR (DMSO-d6) δ: 7.35 (m, 5H), 5.00 (s, 2H), 3.83 (s, 3H), 1.48 (s, 6H); ESI-MS m/z 360 (M)－, 384 (M+Na) +.
Reference：
[1] Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 23, p. 7114 - 7118
35
[ 455-14-1 ]
[ 762-42-5 ]
[ 123158-31-6 ]
Reference：
[1] Journal of Heterocyclic Chemistry, 2012, vol. 49, # 6, p. 1323 - 1331
[2] Organic Letters, 2018, vol. 20, # 7, p. 1893 - 1897
[3] Patent: US5270309, 1993, A,
36
[ 762-42-5 ]
[ 1222174-92-6 ]
Reference：
[1] Patent: WO2012/122340, 2012, A1,
37
[ 762-42-5 ]
[ 1239726-11-4 ]
Reference：
[1] Journal of Medicinal Chemistry, 2012, vol. 55, # 17, p. 7636 - 7649
Alternatively, to a solution of 4-chloro-3-methyl aniline (20.0 g, 0.141 mol) in MEOH (400 mL) was added drop-wise dimethyl acetylenedicarboxylate (21.07 g, 0.148 mol). The reaction mixture was stirred at ambient temperature for 30 minutes. The solvent was removed by evaporation and the residue was added to stirred diphenyl ether (300 mL), which has been preheated to 250°C. After 30 minutes, the mixture was cooled to ambient temperature and the resulting precipitate was collected and washed with 1 L of hot petroleum ether to give a mixture (29.0 g) of 2-methoxycarbonyl-6-chloro-7-methyl-4-oxoquinoline and 2- methoxycarbonyl-6-chloro-5-methyl-4-oxoquinoline as a gray solid.The mixture was dissolved in boiling methanol (1 L) and filtered hot. The collected solids were boiled in 1.2 L of methanol and filtered hot to afford (6. 45 g, 16percent) of 2-METHOXYCARBONYL-6-CHLORO-7-METHYL-4-OXOQUINOLINE
i 3-Methoxycarbonyl-5-hydroxy-1-methylpyrazole 102.3 g (0.72 mol) dimethyl acetylenedicarboxylate was added to 1000 ml ether and cooled to -5 C. in an ice-methanol bath. 33 g (0.72 mol) Methylhydrazine in 100 ml ether was added dropwise so that the inner temperature did not rise above 0 C. The mixture was stirred for 1 hour at 0 C., the precipitate filtered off, washed with ether and dried in vacuo at 40 C. The intermediate was immersed for 10 minutes in an oil bath heated to 120 C. The reduction product was recrystallized from methanol. Yield: 67.6 g=60.1% of theory m.p. 197 C.
7. 5-Hydroxy-3-methoxycarbonyl-1-methylpyrazole 102.3 g (0.72 mol) Dimethyl acetylenedicarboxylate was added to 1000 ml ether and the mixture cooled to -5 C. in an ice-methanol bath. 33 g (0.72 mol) methylhydrazine in 100 ml ether was added dropwise at a rate that the inner temperature did not rise above 0 C. The mixture was stirred for one hour at 0 C., the precipitate suction filtered off, washed with ether and dried at 40 C. in vacuo. The intermediate was immersed in an oil-bath heated to 120 C. The reaction product was recrystallized from methanol. Yield: 67.6 g=60.1% of theory; mp: 197 C.
In diethyl ether; at -5 - 0℃; for 1h;
Methylhydrazine (37.4 mL, 704 mmol) is added to a solution of alkyne 17-64 (100 g, 704 mmol) in Et20 (450 mL) cooled to -5 C. The resulting mixture is allowed to stir at 0 C for 1 h, then is filtered to collect the solids. The solids are rinsed with additional Et20, then dried at 40 C. This material is heated in a 120 C oil bath for 10 min then cooled to room temperature and recrystallized from MeOH to afford intermediate 17-65 (80 g).
3.5 g
With trifluoroacetic acid; In methanol; at 60℃; for 15h;
To a mixture of compound B76 (8.00 g, 56.3 mmol) in MeOH (60 mL) was added TEA (11.4 g, 113 mmol) and methylhydrazine (8.11 g, 56.3 mmol) . The mixture was stirred at 60 C for 15 hours to form a brown mixture. Desired MS value was detected by LC-MS. The mixture was cooled to 5 C, allowed to stand for 2 hours, until the white crystals precipitated, filtered, washed with ethanol, and dried to obtain compound B77 (3.5 g) as a white solid.
General procedure: A flaskwas charged with 1 (0.32 mmol) andwater (30 mL). Then2 (0.38 mmol) was added to the reaction system. The reaction wasstirred at room temperature for 6 h in air. Then the reaction wasextracted with CH2Cl2 (20 mL) and dried over anhydrous Na2SO4.After the solvent was evaporated in vacuo, the residues were purifiedby column chromatography, eluting with petroleum ether(PE)eEtOAc to afford pure 3.
(E)-dimethyl 2,3-bis(4,4,6-trimethyl-1,3,2-dioxaborolan-2-yl)fumarate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
32%
With 4,4'-bipyridine; In tetrahydrofuran; at 60℃; for 14h;Inert atmosphere; Sealed tube;
Reaction of 7a: In a glove box, a glass tube having PTFE stopcock (J. Young),equipped with a magnetic stirring bar, was charged with 9e (1.5 mg, 0.010 mmol), 11 (58 mg,0.22 mmol), THF (0.4 mL), and 7a (29 mg, 0.20 mmol). The tube was sealed by the stopcockand was taken out from the glove box. The mixture was heated at 60 °C with stirring for 14 h.After cooling to room temperature, the volatiles were removed from the reaction mixture underreduced pressure. The residue was purified by column chromatography on silica gel(CHROMATOREX DIOL, eluent: hexane:CHCl3 = 7:1) to afford (E)-12a (27 mg, 32percent) as awhite solid. Geometry of the carbon?carbon double bond was assigned on the analogy of that of (E)-8a. Dimethyl 2,3-bis(4,4,6-trimethyl-1,3,2-dioxaborinan-2-yl)fumarate [(E)-12a] 1H NMR (400 MHz, CDCl3) delta 4.20-4.34 (m, 2H), 3.75 (s, 6H), 1.65-1.80 (m, 4H), 1.34 (s, 6H),1.27 (s, 6H), 1.23 (d, J = 6.0 Hz, 6H). 13C NMR (101 MHz, CDCl3) delta 169.4, 71.4, 65.4, 52.3,45.7, 31.2, 27.61 (either meso or racemate), 27.59 (either meso or racamate), 23.1. The boron-bound carbon was not detected due to quadrupolar relaxation. 11B NMR (128 MHz,CDCl3) delta 25.1. HRMS (APCI, positive) m/z calcd for C18H31B2O8+ [M + H]+: 397.2200, found:397.2190.
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