Category: 31930-34-4

Application of 31930-34-4, As we all know, there are many different methods for the synthesis of a compound, and people can choose the synthesis method that suits their own laboratory according to the actual situation. 31930-34-4 name is Ethyl cis-3-Bromoacrylate, This compound is widely used in many fields, so it is necessary to find a new synthetic route. The downstream synthesis method of this compound is introduced below.

General procedure: A dry and argon-flushed 10 mL Schlenk-tube, equipped with a stirring bar and a septum, was charged with dryCoCl2 (6.5 mg, 0.05 mmol, 5 mol%) and dry THF (2.0 mL). The respective aryl halide (1.0 mmol, 1.0 equiv) wasadded at room temperature. Then, a solution of the appropriate (hetero)aryl zinc pivalate (1.5 mmol, 1.5 equiv)was added dropwise over 5 min via syringe. The reaction was stirred at 40 C and monitored by GC-analysis(C11H24 was used as an internal standard). Upon consumption of the starting material, saturated aqueous NH4Clsolution (5 mL) and ethyl acetate (5 mL) were added, the phases were separated and the aqueous phase was extracted with ethyl acetate (3 x 50 mL). The combined organic layers were washed with aqueous NaOHsolution (2 M, 50 mL) and dried over Na2SO4. The solvents were evaporated and the residue was subjected tocolumn chromatography purification on silica yielding the respective title compound.

At the same time, in my other blogs, there are other synthetic methods of this type of compound, Ethyl cis-3-Bromoacrylate, and friends who are interested can also refer to it.

Reference:
Article; Hofmayer, Maximilian S.; Hammann, Jeffrey M.; Lutter, Ferdinand H.; Knochel, Paul; Synthesis; vol. 49; 17; (2017); p. 3925 – 3930;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Application of 31930-34-4,Some common heterocyclic compound, 31930-34-4, name is Ethyl cis-3-Bromoacrylate, molecular formula is C5H7BrO2, traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route.

In a round-bottomed flask, at 0 C,were successively added Et3N (45 mL), F (5.25 g, 29 mmol), triisopropylsilylacetylene(6.5 mL, 29 mmol), PdCl2(PPh3)2 (330 mg, 0.5 mmol) and CuI (95 mg, 0.5 mmol). The mixture was stirred at 0 C for 4 h, then water (50 mL) was added. The crude was extracted with EtOAc(2 × 50 mL), washed with brine, dried over Na2SO4, filtered and concentrated in vacuum. After purification by chromatography on silica gel (cyclohexane/ethyl acetate 98:2), 6.6 g of an orange liquid were obtained (81% yield). 1H NMR (300 MHz, CDCl3) delta 6.14 (d, J = 11.7 Hz,1H), 6.05 (d, J = 11.7 Hz, 1H), 4.21 (q, J = 7.1 Hz, 2H), 1.27 (t, J = 7.1 Hz, 3H), 0.80-1.50 (m,21H). 13C NMR (126 MHz, CDCl3) delta 164.6, 129.4, 122.4, 105.1, 102.6, 60.5, 18.7, 14.4, 11.5. HRMS (ESI-TOF) m/z [M + Na]+ Calcd for C16H28NaO2Si 303.1751; Found 303.1764.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route Ethyl cis-3-Bromoacrylate, its application will become more common.

Reference:
Article; Fuentespina, Ruben Pomar; De La Cruz, Jose Angel Garcia; Durin, Gabriel; Mamane, Victor; Weibel, Jean-Marc; Pale, Patrick; Beilstein Journal of Organic Chemistry; vol. 15; (2019); p. 1416 – 1424;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Adding a certain compound to certain chemical reactions, such as: 31930-34-4, name is Ethyl cis-3-Bromoacrylate, belongs to esters-buliding-blocks compound, can increase the reaction rate and produce products with better performance than those obtained under traditional synthetic methods. Here is a downstream synthesis route of the compound 31930-34-4, 31930-34-4

General procedure: Pd(PPh3)4 (0.047g, 0.042 mmol) and CuI (0.016g, mmol) were dissolved in degassed NEt3 (11 mL). (Z)- Ethyl 3-bromopropenoate1 (0.75 g, 4.2mmol) was dissolved in degassed NEt3 (1.8 mL) and slowly added to the reaction mixture. After 5 minutes, propargyl alcohol (0.23 g, 4.1 mmol) in degassed NEt3 (1.8 mL) was added dropwise and the mixture was stirred for 24 h. The contents of the flask were filtered through Celite and washed with hexanes. Saturated NH4Cl solution was added to the filtrate, which was subjected to a conventional extractive workup (CH2Cl2)(3x). The residue (0.250 g, 1.62 mmol) was dissolved in 50 mL of CH2Cl2 (50 mL) and the solution was cooled to 0 C. Excess Co2(CO)8 was added to the flask and the mixture was stirred for 30 minutes. The solution was removed from the ice bath and allowed to come to room temperature while stirring for an additional 2 h. Following solvent removal under reduced pressure, the crude product was dissolved in petroleum ether and filtered through a silica plug. The silica gel was first washed with petroleum ether to flush out excess Co2(CO)8 and then washed with diethyl ether to collect hexacarbonyl [mu-eta4((Z)- ethyl 6-hydroxyhex-2-en-4-ynoate)]dicobalt (1.103 g, 60%). IR (neat): 3465, 2984, 2902, 2051, 2002, 1704; 1H NMR : 7.03 (d, J=11.4, 1H), 5.88 (d,J=11.4, 1H), 4.87 (d, J=6.9, 2H), 4.17 (q, J=7.2, 2H), 4.11 (t, J=6.9, 1H), 1.26 (t, J=7.2, 3H); 13C NMR :198.8, 166.4, 142.8, 117.2, 98.0, 79.8, 64.5, 60.64, 14.0; MS EI m/e: 384 (M+ -2CO), 356 (M+ – 3CO), 328(M+ – 4CO), 272 (M+ – 6CO); HRMS for C14H10Co2O9, calcd (M+-2CO) 383.9090, found 383.9091.To a solution of hexacarbonyl[mu-eta4((Z)- ethyl 6-hydroxyhex-2-en-4-ynoate)]dicobalt (0.363 g,0824 mmol) was stirred in acetic anhydride (1.5 mL) and pyridine (1.5 mL), starting at 0C and warming up to room temperature. After 2 hours, the reaction was placed under reduced pressure to obtain crude product and flash chromatography was performed (10:1 petroleum ether: diethyl ether) to yield (10) as a dark red oil (0.3599 g, 91%). IR (neat) 2960, 2094, 2054, 2019, 1744, 1719; 1H NMR : 7.07 (d, J = 11.4,1H), 5.93 (d, J = 11.4, 1H), 5.478 (s, 2H), 4.18 (q, J = 7.1, 2H), 2.14 (s, 3H), 1.29 (t, J = 7.1, 3H); 13C NMR :198.8, 170.8, 165.1, 141.6, 118.5, 109.6, 93.8, 79.7, 66.2, 60.3, 20.5, 14.2; MS EI m/e: 398 (M+ – 3CO),370 (M+ – 4CO), 342 (M+ – 5CO), 314 (M+ – 6CO); HRMS for C16H12Co2O10, calcd (M+-3CO) 397.9247,found 397.9262.

In the field of chemistry, the synthetic routes of compounds are constantly being developed and updated. I will also mention this compound in other articles, Ethyl cis-3-Bromoacrylate, other downstream synthetic routes, hurry up and to see.

Reference:
Article; Mahmood, Aqsa; Ngenzi, Rebecca; Penner, Page M.; Green, James R.; Synlett; vol. 27; 8; (2016); p. 1245 – 1250;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics