Name: 2767-70-6|(4-Nitrobenzyl)triphenylphosphonium bromide|98%
Brand: Ambeed
SKU: A618978
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1
[ 14371-10-9 ]
[ 2767-70-6 ]
[ 27370-90-7 ]

Yield	Reaction Conditions	Operation in experiment
33%	With sodium hydroxide In dichloromethane at 20℃; for 1.5h;	General procedure for synthesis of compounds1a-c (Moran et al. 2009) General procedure: Salt 2 (3.90 g, 8.15 mmol) and aldehyde (10.35 mmol) were added to dichloromethane (150 mL) and stirred at room temperature. A sodium hydroxide solution (50% w/v) was added dropwise to the stirred solution (0.4 mL NaOH solution per 1 mmol of aldehyde). The solution was stirredat room temperature for 1.5 h and then washed with brine and water. The solvent was removed in vacuo to yield thecrude product. Finally, recrystallization from the appropriate solvent gave the pure compound 1.
	With ethanol; lithium ethoxide

Reference： [1]Rezaei-Seresht, Esmail; Mireskandari, Erfan; Kheirabadi, Mitra; Cheshomi, Hamid; Rezaei-Seresht, Hasan; Aldaghi, Leila Sadat [Chemical Papers, 2017, vol. 71, # 8, p. 1463 - 1469]
[2]McDonald; Campbell [Journal of Organic Chemistry, 1959, vol. 24, p. 1969,1973][Organic Syntheses, 1973, vol. Coll. Vol. V, p. 499]

2
[ 329-98-6 ]
[ 2767-70-6 ]
[ 51848-94-3 ]

Reference： [1]Canadian Journal of Chemistry,2005,vol. 83,p. 1543 - 1553
[2]Journal of Organic Chemistry,1974,vol. 39,p. 2728 - 2736

3
[ 2767-70-6 ]
[ 6933-17-1 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium amide
	With sodium amide In benzene
	With potassium carbonate In water for 1h;

	With sodium hydride In tetrahydrofuran for 3h; Heating;
	With n-butyllithium In tetrahydrofuran; cyclohexane at -60℃; for 1h;
	With sodium ethanolate In ethanol Inert atmosphere;
	With sodium methylate In 5,5-dimethyl-1,3-cyclohexadiene
	With potassium <i>tert</i>-butylate In 1,4-dioxane at 20 - 80℃; for 1h; Inert atmosphere;	6.1. General procedure Wittig reactions Table 1 General procedure: An adapted method published by Giannis et al.5e was used: KOt- Bu (2 equiv) was added to a solution of the phosphonium compound (2 equiv) in dry 1,4-dioxane (carbohydrate concentration 0.2 M) and stirred at room temperature for 30 min. and then at 80 C for 30 min. Next, the carbohydrate (1 equiv) was added and the mixture was heated to reflux until full or no further conversion of the reaction was confirmed by TLC. The specific isolation of the products is described for the individual carbohydrates.
	With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere;
	Stage #1: (p-nitrobenzyl)triphenylphosphonium bromide With potassium <i>tert</i>-butylate for 0.5h; Schlenk technique; Stage #2: In tetrahydrofuran for 1h; Schlenk technique;	4.1.5 General procedure for the preparation of conjugates 4.1-4.51 General procedure: 0.96mmol of the triphenylphosphonium salt was introduced in a dry Schlenk flask on the vacuum line, followed by 165mg (1.43mmol) of t-BuOK. After 30min of drying under vacuum, 2mL of dry THF was added, and the reaction was stirred for 1h to form the ylide. Then, the flask was cooled down in an ice bath, and after 10min, 150mg (0.32mmol) of the aldehyde (2) was added under an argon atmosphere. The reaction was stirred at 0°C until the ice bath melted and then at r. t. 2-18h. Completion of the reaction was monitored by TLC (toluene/diethyl ether 1 : 1) followed by extraction (1% HCl/DCM). Organic phases were combined, dried over MgSO4, and evaporated under reduced pressure. The residue was purified by flash column chromatography (toluene/diethyl ether 2 : 1), affording the final product in moderate to high yields. Modification of the conditions is described in the respective experiment if necessary.

Reference： [1]Grayson,M.; Keough,P.T. [Journal of the American Chemical Society, 1960, vol. 82, p. 3919 - 3924]
[2]Gupta, K. C.; Saxena, B. K.; Pathak, P. K. [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1986, vol. 25, p. 312 - 314]
[3]Phukan; Jagtap; Sudalai [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2000, vol. 39, # 12, p. 950 - 953]
[4]Sandulache, Angela; Silva, Artur M. S.; Pinto, Diana C. G. A.; Almeida, Lucia M. P. M.; Cavaleiro, Jose A. S. [New Journal of Chemistry, 2003, vol. 27, # 11, p. 1592 - 1598]
[5]Sandulache, Angela; Silva, Artur M. S.; Pinto, Diana C. G. A.; Almeida, Lucia M. P. M.; Cavaleiro, Jose A. S. [New Journal of Chemistry, 2003, vol. 27, # 11, p. 1592 - 1598]
[6]Location in patent: experimental part Mulzer, Johann; Huisgen, Rolf; Arion, Vladimir; Sustmann, Reiner [Helvetica Chimica Acta, 2011, vol. 94, # 8, p. 1359 - 1388]
[7]Location in patent: scheme or table Prajapati, Kiran; Varshney, Anuradha [Asian Journal of Chemistry, 2011, vol. 23, # 6, p. 2361 - 2368]
[8]Van Kalkeren, Henri A.; Van Rootselaar, Stefan; Haasjes, Frank S.; Rutjes, Floris P. J. T.; Van Delft, Floris L. [Carbohydrate Research, 2012, vol. 362, p. 30 - 37,8]
[9]Talpur, Mir Munsif Ali; Pirzada, Tajnees; Skabara, Peter; Westgate, Thomas; Shah, Mohammad Raza [Journal of the Chemical Society of Pakistan, 2013, vol. 35, # 4, p. 1219 - 1225]
[10]Frydrych, Ivo; Urban, Milan; Šarek, Jan; Benická, Sandra; Džubák, Petr; Gurská, Soňa; Hajdúch, Marián; Kotulová, Jana; Lišková, Barbora; Olejníková, Denisa; Pokorný, Jan [European Journal of Medicinal Chemistry, 2021, vol. 224]

4
[ 603-35-0 ]
[ 100-11-8 ]
[ 2767-70-6 ]

Yield	Reaction Conditions	Operation in experiment
100%	With sodium hydride; m-Chlorobenzaldehyde In toluene for 12h; Reflux;	5.2.8. General preparation of compounds 15a-c Compounds 15a-c were synthesized using the methods described by Cushman [22] and Fortin [17] . First, compound 14 was prepared according to the procedure of Fortin et al. [17] . Briefly, triphenyphosphine (1.0 Eq, 13.9 mmol) was added to a solution of 4-nitrobenzyl bromides (1.0 Eq, 13.9 mmol) in toluene (60 mL) and heated to reflux for 12 h. The mixture was then cooled at room temperature and the precipitate was filtrate and triturate with toluene to give a white solid in quantitative yield. Afterwards, sodium hydride (3 Eq, 12.5 mmol) was added portion-wise to a well-stirred suspension of 4-nitrobenzylphosphonium bromide 14 (2 Eq, 8.4 mmol) and a relevant benzaldehyde (2 Eq, 8.4 mmol) in methylene chloride (90 mL) under an argon atmosphere at 0 °C. Subsequently, the mixture was warmed to room temperature. After further stirring for 24 h, excess sodium hydride was quenched by the addition of water (20 mL) at 0 °C. The aqueous phase was extracted thrice by methylene chloride (20 mL). The combined organic phases were washed with brine (40 mL), dried over anhydrous sodium sulfate, filtered, and evaporated to dryness under vacuum. The residue was purified by flash chromatography on silica gel with a mixture of hexane/methylene chloride for 15a and hexane/ethyl acetate for 15b, c. The geometric isomers of compound 15b (yield, Z-isomer 33% and E-isomer 50%) were separated at this step whereas the geometric isomers of compounds 15a, c were used as a mixture for the next chemical reaction (yield, 83% for 15a and 98% for the 15c).
99%	In toluene Reflux;	4.2.4. General procedure C-2 (GP-C-2) General procedure: To a solution of substituted benzyl halide in toluene was added triphenylphosphine (1.5 equiv) and the mixture was refluxed. After cooling, the precipitate was collected by filtration to give the target compound.
98.6%	In toluene Heating;

97%	In benzene at 50℃; for 2h;
97%	In toluene at 50℃; for 8h;
96%	In toluene at 70℃;	4-Nitrobenzyltriphenylphosphonium Bromide Triphenylphosphonium salt was prepared from the corresponding4-nitrobenzyl bromide (Sigma-Aldrich N13054)and triphenylphosphine (Fluka 93090) in toluene by slightmodification of Wittig reaction [14]. In short, 2.16 g(10 mmol) of 4-nitrobenzyl bromide and 3.14 g (12 mmol)of triphenylphosphine were dissolved in 50 mL of toluene,and the reaction mixture was heated and stirred at 70 °Covernight. The precipitated salt was collected by vacuumfiltration on a Buchner funnel and washed twice with acetoneand petroleum ether and then dried in a vacuum oven at 80 °Cfor two hours. Yield of the crystalline white powder-4.58 g(96 %). It was used in the next step without furtherpurification.
95%	In toluene at 120℃;	3 Method C: Synthesis of 63 4-nitrobenzyltriphenylphosphonium bromide: 64 4-Nitrobenzyl bromide (3g, 13.89mmol) was dissolved in 65 toluene (50mL), then 66 triphenylphosphine (3.643g, 13.89mmol) was added and the mixture was heated at 120°C overnight. The product was filtered under vacuum, washed with hexane (50mL) to give a fine white powdered solid (6.333g, 13.18mmol, 95%).20 Mp 273-274°C; 1H NMR (400MHz, CDCl3) δ: 5.99 (2H, d, J=15.6Hz, Ar-H), 7.45 (2H, dd, J=7.2, 2.8Hz, Ar-H), 7.56-7.84 (17H, m, Ar-H); LRMS (ESI) m/z 398 (M+); HRMS (ESI) m/z found: M+, 398.1306; Calcd. for C25H21NO2P+, 398.1304. Synthesis of 12 (E)-7-diethylamino-3-(4′-nitrostyryl)coumarin 8. In a round bottom flask fitted with drying tube, 7-diethylaminocoumarin-3-aldehyde 7 (0.8g, 3.2mmol) and 4-nitrobenzyltriphenylphosphonium bromide (1.872g, 3.92mmol) were dissolved in dry methanol (80mL) and then CH3ONa (0.96g, 17.6mmol) was added. The mixture was stirred at room temperature overnight and was then poured into ice water (160mL), and stirred for 2h at room temperature. The solid was filtered under vacuum and triturated with ethanol (3×100mL) resulting in a mixture of the (E) and (Z) isomers of 8 (0.743g, 62%). This mixture of (E) and (Z)-8 (743mg, 2.036mmol) was dissolved in chloroform (60mL) in a round bottom flask fitted with drying tube then iodine (103.43mg, 0.204mmol) was added and the reaction mixture was stirred at room temperature overnight. The solution was washed thoroughly with saturated sodium metabisulfite solution (5×20mL). The organic layer was dried over sodium sulfate and evaporated under reduced pressure to give the product (E)-8 as a dark red solid (743mg, 100%).9,11 Mp 259-260°C (lit. 253-255°C); 1H NMR (400MHz, CDCl3) δ: 1.23 (6H, t, J=7.2Hz, 2×CH3), 3.44 (4H, q, J=7.2Hz, 2×CH2), 6.51 (1H, d, J=2.4Hz, Ar-H8), 6.62 (1H, dd, J=8.8, 2.4Hz, Ar-H6), 7.19 (1H, d, J=16Hz, CHA or CHB), 7.31 (1H, d, J=8.8Hz, Ar-H5), 7.59 (1H, d, J=16Hz, CHA or CHB), 7.61 (2H, d, J=8.8Hz, Ar-H2′,6′), 7.71 (1H, s, Ar-H4), 8.19 (2H, d, J=8.8Hz, Ar-H3′,5′); 13C NMR (100MHz, CDCl3) δ: 12.5 (2×CH3), 45.0 (2×CH2), 97.2 (CH), 108.9 (quat.), 109.4 (CH), 116.4 (quat.), 124.1 (CH-2′,6′ or CH-3′,5′), 126.8 (CH-2′,6′ or CH-3′,5′), 127.6 (CH), 128.0 (CH), 129.3 (CH), 140.5 (CH), 144.4 (CH), 146.5 (quat.), 151.0 (quat.), 156.0 (quat.), 161.0 (C=O); IR (υmax/cm-1): 1705 (C=O), 1616 (C=C), 1519 (NO2), 1331 (NO2); LRMS (ESI) m/z 365 (MH+); HRMS (ESI) m/z found: M+, 364.1421 and MH+, 365.1500; Calcd. for C21H20N2O4, 364.1418 and for C21H21N2O4+, 365.1451.
94%	In xylene for 0.05h; Heating; microwave;
92%	In toluene for 6h; Heating;
92%	In benzene at 60℃; for 20h;
92%	In chloroform for 1h; Inert atmosphere;	1.B Synthesis of p-nitrostyrene: Under inert conditions, Dissolve 5.0 g (23.1 mmol) nitrobenzyl bromide and 6.15 g (23.4 mmol) triphenylphosphine in 40 mL chloroform, After stirring for 1h, pour it into ether and filter to precipitate a solid. 10.3 g of white phosphine salt crystals were obtained by drying, with a yield of 92%, Melting point 274-275 . The above phosphine salt is directly used for witting reaction, Take 7.5 g phosphine salt (15.5 mmol) in a three-necked flask, Add 30 mL of 35-40% aqueous formaldehyde solution, Stir thoroughly to form a suspension, Use a dropping funnel to slowly and intermittently add a solution of 3g Na2CO3 dissolved in 10 mL of water, each time after the dark red phosphonium salt intermediate disappears, The suspension continues to stir for 4 h, After extraction with ether, Dry with anhydrous Na2SO4, filter, The crude product with the solvent removed is passed through the column with silica gel, The eluent is petroleum ether/ethyl acetate=10:1 (v/v), 1.8 g of light yellow solid was obtained, The yield was 78%,
92%	In diethyl ether; chloroform for 1h;	Synthesis of compound 4^[4]: Dissolved nitrobromide (5.0 g, 23.1 mmol) and triphenylphosphine(6.15 g, 23.4 mmol) in 40 mL chloroform, then poured it into diethyl ether, filtered and separated out after stirring for 1 h. White phosphine crystal (10.3 g) was gotten, yield: 92%, m.p: 274-275 °C. Stirred the mixture of phosphine (7.5 g, 15.5 mmol) and methanal (30 ml, 37%), then added Na2CO3 solution (10 mL, 2.83 mol/L) slowly and reacted for 4 h. After reaction, extracted the mixture with ether, dried it and filtered, then evaporated the solvent and purified by column chromatography using petroleum ether/ethyl acetate (10:1, v:v) as eluent. Light yellow solid (1.8 g) was acquired, yield: 78%
83%	In toluene at 20℃; for 16h;
81%	In benzene for 2h; Heating;
81.6%	at 50℃; for 3h;	2 2, Preparation of intermediate II In a 500 mL round bottom flask, 13.7 g (0.1 mol) of p-nitrotoluene and 21.4 g (0.12 mol) of N-bromosuccinimide (NBS) were dissolved in 150 mL of benzene, respectively, and 0.5 g benzoyl peroxide (BPO) catalyst was heated toreflux for 8h at 80 , TLC determined the completion of the reaction, cooled to room temperature, a white solid (succinimide) analysis ofthe, suction-filtered, filtered off white the solid filtrate was added 31.5g (0.12mol) of triphenylphosphine, the reaction was refluxed for 3 hours at 50 ; cooledto room temperature a large amount of solid was precipitated, filtered off with suction, the solid washed three times with benzene (5 mL), to give 39.0g of yellow solid.The yield was81.6%
80%	In acetonitrile at 25℃; for 24h;
79%	In 1,3-dimethylbenzene for 12h; Heating;
76%	In benzene for 1h; Heating;
60%	In tetrahydrofuran for 2h; Heating;
27%	In 5,5-dimethyl-1,3-cyclohexadiene for 26h; Reflux;
30 g	In benzene Heating;
	In benzene Heating;
	In tetrahydrofuran Ambient temperature; Yield given;
	In benzene for 8h; Heating;
	In xylene Heating;
	In toluene Heating;
	In toluene for 1h; Heating;
	In 1,3-dimethylbenzene for 16h; Heating;
	In benzene at 20℃;
	In benzene
	for 3h;
	In toluene
	In methanol at 70℃; for 3h;
	In chloroform for 0.5h; Inert atmosphere;
	In 5,5-dimethyl-1,3-cyclohexadiene for 3h;
	In benzene
	In N,N-dimethyl-formamide at 0 - 20℃; for 2.5h; Inert atmosphere;	5.1.5. N-{4-[(Z)-2-(4-Nitrophenyl)ethenyl]-1,3-thiazol-2-yl}acetamide (7) To a mixture of 4-nitrobenzyl bromide (6) (1.9 g) in DMF (20 mL) was added triphenylphosphine (2.3 g) at 0 °C under a nitrogen atmosphere, and the reaction mixture was stirred at room temperature for 2.5 h. Then potassium tert-butoxide (1.2 g) and 5 (1.5 g) were added at 0 °C, and the mixture was stirred at room temperature for 14 h. The reaction mixture was poured into ice-H2O and extracted with AcOEt. The organic layer was washed with 1 M HCl, H2O and brine, dried over anhydrous MgSO4, and concentrated in vacuo. The residue was purified by flash column chromatography over silica gel with hexane/AcOEt (1:1-1:2) as an eluent and triturated with Et2O to give 7 (1.6 g, 62%) as a yellow solid.
	In N,N-dimethyl-formamide at 0 - 20℃; Inert atmosphere;	5.1.34 A mixture of N-{5-[4-(methylthio)phenyl]-4-[(E)-2-(4-nitrophenyl)ethenyl]-1,3-thiazol-2-yl}acetamide and N-{5-[4-(methylthio)phenyl]-4-[(Z)-2-(4-nitrophenyl)ethenyl]-1,3-thiazol-2-yl}acetamide (32a) To a mixture of 4-nitrobenzyl bromide (31) (182 mg) in DMF (2 mL) was added triphenylphosphine (221 mg) at 0 °C under a nitrogen atmosphere, and the reaction mixture was stirred at room temperature for 3 h. Potassium tert-butoxide (111 mg) and 30a (145 mg) were then added to the mixture at 0 °C, which was stirred at room temperature for 15 h. The reaction mixture was poured into ice-H2O and extracted with AcOEt. The organic layer was washed with 1 M HCl, H2O and brine, dried over anhydrous MgSO4, and concentrated in vacuo. The residue was purified by flash column chromatography over silica gel with CHCl3/MeOH (40:1) as an eluent to give 32a (E:Z = 2:1) (177 mg, 87%) as a brown wax. FAB MS m/e (M+H)+ 412.
	In benzene
	In toluene
	In benzene
	With 1-n-butyl-3-methylimidazolium bistrifluoromethylsulfonylamide In acetonitrile at 24.4℃;
	In toluene at 90℃;
	Reflux;	4.1.3 General procedure for the preparation of triphenylphosphonium salts General procedure: 2.1mmol of triphenylphosphine was dissolved in 5mL of toluene or acetonitrile (for 4.2), and 2.0mmol of the corresponding bromide was added. The mixture was stirred overnight under reflux until white crystals of the salt precipitated. The precipitate was then filtered, washed with diethyl ether, and dried under a vacuum to provide white crystalline salt in quantitative yields. For 4.2: The mixture was cooled down after reflux, the solvent was almost evaporated, and the residue was precipitated by adding diethyl ether to obtain white crystals, which were filtered and dried under vacuum (56% yield). The salts were used without further purification.

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[2]Location in patent: experimental part Motoshima, Kazunori; Ishikawa, Minoru; Hashimoto, Yuichi; Sugita, Kazuyuki [Bioorganic and Medicinal Chemistry, 2011, vol. 19, # 10, p. 3156 - 3172]
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[39]Inoue, Takayuki; Morita, Masataka; Tojo, Takashi; Nagashima, Akira; Moritomo, Ayako; Imai, Keisuke; Miyake, Hiroshi [Bioorganic and Medicinal Chemistry, 2013, vol. 21, # 9, p. 2478 - 2494]
[40]Yang, Mingdi; Xu, Dongling; Xi, Wengang; Wang, Lianke; Zheng, Jun; Huang, Jing; Zhang, Jingyan; Zhou, Hongping; Wu, Jieying; Tian, Yupeng [Journal of Organic Chemistry, 2013, vol. 78, # 20, p. 10344 - 10359] Gan, Xiaoping; Liu, Guangjin; Chu, Mingjie; Xi, Wengang; Ren, Zili; Zhang, Xiuli; Tian, Yupeng; Zhou, Hongping [Organic and Biomolecular Chemistry, 2017, vol. 15, # 1, p. 256 - 264]
[41]Hamid; Hasanain, Mohammad; Singh, Arjun; Bhukya, Balakishan; Omprakash; Vasudev, Prema G.; Sarkar, Jayanta; Chanda, Debabrata; Khan, Feroz; Aiyelaagbe; Negi, Arvind S. [Steroids, 2014, vol. 87, p. 108 - 118]
[42]Yang, Mingdi; Zhang, Yan; Zhu, Weiju; Wang, Huizhen; Huang, Jing; Cheng, Longhuai; Zhou, Hongping; Wu, Jieying; Tian, Yupeng [Journal of Materials Chemistry C, 2015, vol. 3, # 9, p. 1994 - 2002] Xi, Wengang; Zhang, Yubin; Chen, Boyu; Gan, Xiaoping; Fang, Min; Zheng, Jun; Wu, Jieying; Tian, Yupeng; Hao, Fuying; Zhou, Hongping [Dyes and Pigments, 2015, vol. 122, p. 31 - 39] Rezaei-Seresht, Esmail; Mireskandari, Erfan; Kheirabadi, Mitra; Cheshomi, Hamid; Rezaei-Seresht, Hasan; Aldaghi, Leila Sadat [Chemical Papers, 2017, vol. 71, # 8, p. 1463 - 1469]
[43]Schaffarczyk McHale, Karin S.; Haines, Ronald S.; Harper, Jason B. [ChemPlusChem, 2018, vol. 83, # 12, p. 1162 - 1168]
[44]Zhao, Xiaolei; Zheng, Wei; Zhang, Yi; Huang, Wei [Chemical Communications, 2020, vol. 56, # 5, p. 814 - 817]
[45]Frydrych, Ivo; Urban, Milan; Šarek, Jan; Benická, Sandra; Džubák, Petr; Gurská, Soňa; Hajdúch, Marián; Kotulová, Jana; Lišková, Barbora; Olejníková, Denisa; Pokorný, Jan [European Journal of Medicinal Chemistry, 2021, vol. 224]

5
[ 50-00-0 ]
[ 2767-70-6 ]
[ 100-13-0 ]

Yield	Reaction Conditions	Operation in experiment
86%	With anhydrous sodium carbonate In ethanol for 3h;
78%	With anhydrous sodium carbonate In water monomer for 4h;	1.B Synthesis of p-nitrostyrene: Under inert conditions, Dissolve 5.0 g (23.1 mmol) nitrobenzyl bromide and 6.15 g (23.4 mmol) triphenylphosphine in 40 mL chloroform, After stirring for 1h, pour it into ether and filter to precipitate a solid. 10.3 g of white phosphine salt crystals were obtained by drying, with a yield of 92%, Melting point 274-275 . The above phosphine salt is directly used for witting reaction, Take 7.5 g phosphine salt (15.5 mmol) in a three-necked flask, Add 30 mL of 35-40% aqueous formaldehyde solution, Stir thoroughly to form a suspension, Use a dropping funnel to slowly and intermittently add a solution of 3g Na2CO3 dissolved in 10 mL of water, each time after the dark red phosphonium salt intermediate disappears, The suspension continues to stir for 4 h, After extraction with ether, Dry with anhydrous Na2SO4, filter, The crude product with the solvent removed is passed through the column with silica gel, The eluent is petroleum ether/ethyl acetate=10:1 (v/v), 1.8 g of light yellow solid was obtained, The yield was 78%,
78%	With anhydrous sodium carbonate In chloroform for 4h;	Synthesis of compound 4^[4]: Dissolved nitrobromide (5.0 g, 23.1 mmol) and triphenylphosphine(6.15 g, 23.4 mmol) in 40 mL chloroform, then poured it into diethyl ether, filtered and separated out after stirring for 1 h. White phosphine crystal (10.3 g) was gotten, yield: 92%, m.p: 274-275 °C. Stirred the mixture of phosphine (7.5 g, 15.5 mmol) and methanal (30 ml, 37%), then added Na2CO3 solution (10 mL, 2.83 mol/L) slowly and reacted for 4 h. After reaction, extracted the mixture with ether, dried it and filtered, then evaporated the solvent and purified by column chromatography using petroleum ether/ethyl acetate (10:1, v:v) as eluent. Light yellow solid (1.8 g) was acquired, yield: 78%, m.p: 27-28 °C. 1H-NMR (CDCl3, ppm): 8.15-8.17 (d, 2H), 7.51-7.53 (d, 2H), 6.73-6.81 (q, 1H), 5.90-5.95 (d, 1H), 5.48-5.51 (d, 1H). 13C-NMR (CDCl3, ppm): 147.14, 143.84, 136.97, 126.82, 123.94, 114.63.

10.5 g	With sodium hydroxide In water monomer at 0℃; for 4h;
	With anhydrous sodium carbonate In water monomer at 20℃; for 4h;

Reference： [1]Jacober, Stephen P.; Hanzlik, Robert P. [Journal of the American Chemical Society, 1986, vol. 108, # 7, p. 1594 - 1597]
[2]Current Patent Assignee: XIANGTAN UNIVERSITY - CN111943965, 2020, A Location in patent: Paragraph 0005
[3]Tian, Yong; Wang, Kaixuan; Zhang, Houpeng; Wu, Xianming; Zhong, Chaofan [Tetrahedron, 2022, vol. 113]
[4]Lin, Tzu-Chau; He, Guang S.; Prasad, Paras N.; Tan, Loon-Seng [Journal of Materials Chemistry, 2004, vol. 14, # 6, p. 982 - 991]
[5]Location in patent: experimental part Lin, Naibo; Liu, Xiang Yang; Diao, Ying Ying; Xu, Hongyao; Chen, Chunyan; Ouyang, Xinhua; Yang, Hongzhi; Ji, Wei [Advanced Functional Materials, 2012, vol. 22, # 2, p. 361 - 368]
[6]Location in patent: experimental part Lin, Zhao-Min; Zheng, Chao; Xiao, Jian-Jian; Chen, Run-Feng; Zhao, Ping; Song, Juan; An, Zhong-Fu; Tian, He; Huang, Wei [New Journal of Chemistry, 2012, vol. 36, # 7, p. 1512 - 1518]

6
[ 2767-70-6 ]
[ 100-52-7 ]
[ 1694-20-8 ]

Yield	Reaction Conditions	Operation in experiment
86%	With sodium hydroxide; lithium chloride In water for 6h; Heating;
73%	Stage #1: (p-nitrobenzyl)triphenylphosphonium bromide; benzaldehyde Stage #2: With iodine In ethyl acetate Heating;
51%	With sodium hydroxide In dichloromethane at 50℃; for 0.5h;

Reference： [1]Wu, Jinlong; Zhang, Da [Synthetic Communications, 2005, vol. 35, # 19, p. 2543 - 2551]
[2]Hooberman; Brezzell; Das; You; Sinsheimer [Mutation Research - Genetic Toxicology, 1994, vol. 341, # 1, p. 57 - 69]
[3]Nonoyama, Nobuaki; Oshima, Hiroshi; Shoda, Chizuru; Suzuki, Hitomi [Bulletin of the Chemical Society of Japan, 2001, vol. 74, # 12, p. 2385 - 2395]
[4]Ludolph, Björn; Klein, Markus; Erdinger, Lothar; Boche, Gernot [Mutation Research - Genetic Toxicology and Environmental Mutagenesis, 2001, vol. 491, # 1-2, p. 195 - 209]

7
[ 2767-70-6 ]
[ 123-11-5 ]
[ 4648-33-3 ]

Yield	Reaction Conditions	Operation in experiment
94%	In N,N-dimethyl-formamide at 20℃; for 16h;
72%	With lithium methanolate In methanol at 20℃;	Trans-4-Methoxy-4′-Nitrostilbene 4 . 5 8 g ( 9 . 6 mm o l ) o f t h e p r e p a r e d 4 -nitrobenzyltriphenylphosphonium salt and 1.50 g (11 mmol)of p-anisaldehyde (Sigma-Aldrich A88107) were dissolved in25 mL of absolute methanol. 25 mL of 0.4-M lithiummethoxide solution in absolute methanol was added, and thedark red reaction mixture was intensively stirred at roomtemperature for 20 min. The resulting solution was left tostand overnight at room temperature to provide the precipitation of the product. The precipitated orange crystalsof the trans-isomer were collected by vacuum filtration on aBuchner funnel and re-crystallised from ethanol. Yield of thebright orange crystals-1.77 g (72 %). 1H NMR (chemicalshifts are in ppm): δ 3.85 (singlet, 3H, MeO); CH=CH ABpattern: δ 6.98 (doublet, vinyl 1H), δ 7.23 (doublet, vinyl 1H);p-MeO-Ar AA‘XX’ pattern: δ 6.98 (doublet, 2H: H3, H5), δ7.49 (doublet, 2H: H2, H6); p-O2N-Ar AA‘XX’ pattern: δ7.59 (doublet, 2H: H2′, H6′), δ 8.20 (doublet, 2H: H3′, H5′).Melting point of 150-151 °C was found to be in a goodagreement with the literature value [14].
54%	With sodium hydroxide; lithium chloride In water for 9h; Heating;

40%	Stage #1: (p-nitrobenzyl)triphenylphosphonium bromide; 4-methoxy-benzaldehyde Stage #2: With iodine In ethyl acetate Heating;
25%	With sodium hydroxide In dichloromethane at 20℃; for 1.5h;	General procedure for synthesis of compounds1a-c (Moran et al. 2009) General procedure: Salt 2 (3.90 g, 8.15 mmol) and aldehyde (10.35 mmol) were added to dichloromethane (150 mL) and stirred at room temperature. A sodium hydroxide solution (50% w/v) was added dropwise to the stirred solution (0.4 mL NaOH solution per 1 mmol of aldehyde). The solution was stirredat room temperature for 1.5 h and then washed with brine and water. The solvent was removed in vacuo to yield thecrude product. Finally, recrystallization from the appropriate solvent gave the pure compound 1.

Reference： [1]Pati, Hari N.; Wicks, Martha; Holt Jr., Herman L.; LeBlanc, Regan; Weisbruch, Paul; Forrest, Lori; Lee, Moses [Heterocyclic Communications, 2005, vol. 11, # 2, p. 117 - 120]
[2]Papper, Vladislav; Pokholenko, Oleksandr; Wu, Yuanyuan; Zhou, Yubin; Jianfeng, Ping; Steele, Terry W. J.; Marks, Robert S. [Journal of Fluorescence, 2014, vol. 24, # 6, p. 1581 - 1591]
[3]Wu, Jinlong; Zhang, Da [Synthetic Communications, 2005, vol. 35, # 19, p. 2543 - 2551]
[4]Hooberman; Brezzell; Das; You; Sinsheimer [Mutation Research - Genetic Toxicology, 1994, vol. 341, # 1, p. 57 - 69]
[5]Rezaei-Seresht, Esmail; Mireskandari, Erfan; Kheirabadi, Mitra; Cheshomi, Hamid; Rezaei-Seresht, Hasan; Aldaghi, Leila Sadat [Chemical Papers, 2017, vol. 71, # 8, p. 1463 - 1469]

8
[ 2767-70-6 ]
[ 555-16-8 ]
[ 736-31-2 ]

Yield	Reaction Conditions	Operation in experiment
95%	With potassium <i>tert</i>-butylate In tetrahydrofuran; <i>tert</i>-butyl alcohol at 0 - 20℃; for 26h; Inert atmosphere;
	Stage #1: (p-nitrobenzyl)triphenylphosphonium bromide; 4-nitrobenzaldehdye Stage #2: With iodine In ethyl acetate Heating;
	With potassium <i>tert</i>-butylate In tetrahydrofuran; <i>tert</i>-butyl alcohol

Reference： [1]Kim, Sun Min; Kim, Dong Wan; Yang, Jung Woon [Organic Letters, 2014, vol. 16, # 11, p. 2876 - 2879]
[2]Hooberman; Brezzell; Das; You; Sinsheimer [Mutation Research - Genetic Toxicology, 1994, vol. 341, # 1, p. 57 - 69]
[3]Wu, Xin; Lin, Li-Rong; Huang, Yan-Jun; Li, Zhao; Jiang, Yun-Bao [Chemical Communications, 2012, vol. 48, # 36, p. 4362 - 4364]

9
[ 2767-70-6 ]
[ 81172-89-6 ]
[ 84645-79-4 ]

Yield	Reaction Conditions	Operation in experiment
93.7%	With lithium ethoxide In tetrahydrofuran; dichloromethane at 20℃; for 3h;

Reference： [1]Davis; Ratner; Wasielewski [Journal of the American Chemical Society, 2001, vol. 123, # 32, p. 7877 - 7886]

10
[ 2767-70-6 ]
[ 100-52-7 ]
4-nitrostilbene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	Stage #1: (p-nitrobenzyl)triphenylphosphonium bromide With sodium hydroxide In dichloromethane at 20℃; Stage #2: benzaldehyde In dichloromethane
79%	With dibenzo-18-crown-6; potassium carbonate In dichloromethane at 20℃; for 48h;

Reference： [1]Location in patent: scheme or table Rodrigues, Tiago; Guedes, Rita C.; dos Santos, Daniel J.V.A.; Carrasco, Marta; Gut, Jiri; Rosenthal, Philip J.; Moreira, Rui; Lopes, Francisca [Bioorganic and Medicinal Chemistry Letters, 2009, vol. 19, # 13, p. 3476 - 3480]
[2]Miljanic, Snezana; Frkanec, Leo; Meic, Zlatko; Zinic, Mladen [European Journal of Organic Chemistry, 2006, # 5, p. 1323 - 1334]

11
dimethyl (Z)-2-(bromomethyl)fumarate [ No CAS ]
[ 2767-70-6 ]
dimethyl 2-methylene-3-(4-nitrobenzyl)succinate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	Stage #1: (p-nitrobenzyl)triphenylphosphonium bromide With n-butyllithium In tetrahydrofuran at -100 - 0℃; Stage #2: dimethyl (Z)-2-(bromomethyl)fumarate In tetrahydrofuran at -100℃; for 3h; Further stages.;

Reference： [1]Patel, Ramesh M.; Argade, Narshinha P. [Journal of Organic Chemistry, 2007, vol. 72, # 13, p. 4900 - 4904]

12
[ 159709-36-1 ]
[ 2767-70-6 ]
C₁₆H₁₃NO₂S₂ [ No CAS ]
C₁₆H₁₃NO₂S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate In methanol for 24h; Heating;

Reference： [1]Mashraqui, Sabir H.; Ghadigaonkar, Shailesh; Ashraf, Mohamed; Sri Ranjini; Ghosh, Sampa; Das [Tetrahedron, 2007, vol. 63, # 40, p. 10011 - 10017]

13
[ 872-85-5 ]
[ 2767-70-6 ]
4-[(E)-2-(4-nitrophenyl)ethenyl]pyridine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
32%	With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 20℃; for 2.16667h;	B.1 Step 1. Preparation of 4-[(E)-2-(4-nitrophenyl)ethenyl]pyridine To an oven dried 500 mL 3-necked flask was added (4-nitrobenzyl)triphenylphosphonium bromide (15 g, 30.42 mmol) followed by the addition of THF (100 mL). The solution was cooled to 0° C. in an ice bath. Potassium t-butoxide (3.9 g, 33.02 mmol) was then added in one portion resulting in an orange suspension. The suspension was maintained at 0° C. while a solution of 4-pyridine-2-carboxaldehyde (2.7 g, 24.70 mmol) in THF (20 mL) was added in 10 minutes. The ice bath was removed and the reaction was stirred at room temperature for 2 h. At this time, the reaction was quenched with saturated ammonium chloride solution (50 mL) and stirred for 15 minutes. The mixture was then extracted with ethyl acetate (2*100 mL), the combined extracts was washed with saturated aqueous NaCl solution (100 mL) and dried (MgSO4). The solvent was removed at reduced pressure and the residue was chromatographed on silica with 0-50% ethyl acetate in hexanes to afford the desired product (1.8 g, 32%). TLC (50% ethyl acetate/50% hexane) Rf 0.28; 1H-NMR (DMSO-d6) δ 6.84 (d, J=12.4 Hz, 1H), 6.96 (d, J=12.4 Hz, 1H), 7.14 (d, J=6.2 Hz, 2H), 7.45 (d, J=8.7 Hz, 2H), 8.15 (d, J=8.7 Hz, 2H), 8.47 (d, J=6.2 Hz, 2H).
32%	With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 20℃; for 2.16667h;	B.B6.1 To an oven dried 500 mL 3-necked flask was added (4-nitrobenzyl)triphenylphosphonium bromide (15 g, 30.42 mmol) followed by the addition of THF (100 mL). The solution was cooled to 0° C. in an ice bath. Potassium t-butoxide (3.9 g, 33.02 mmol) was then added in one portion resulting in an orange suspension. The suspension was maintained at 0° C. while a solution of 4-pyridine-2-carboxaldehyde (2.7 g, 24.70 mmol) in THF (20 mL) was added in 10 minutes. The ice bath was removed and the reaction was stirred at room temperature for 2 h. At this time, the reaction was quenched with saturated ammonium chloride solution (50 mL) and stirred for 15 minutes. The mixture was then extracted with ethyl acetate (2*100 mL), the combined extracts was washed with saturated aqueous NaCl solution (100 mL) and dried (MgSO4). The solvent was removed at reduced pressure and the residue was chromatographed on silica with 0-50% ethyl acetate in hexanes to afford the desired product (1.8 g, 32%). TLC (50% ethyl acetate/50% hexane) Rf=0.28; 1H-NMR (DMSO-d6) δ6.84 (d, J=12.4 Hz, 1H), 6.96 (d, J=12.4 Hz, 1H), 7.14 (d, J=6.2 Hz, 2H), 7.45 (d, J=8.7 Hz, 2H), 8.15 (d, J=8.7 Hz, 2H), 8.47 (d, J=6.2 Hz, 2H).

Reference： [1]Current Patent Assignee: BAYER AG - US2004/2507, 2004, A1 Location in patent: Page/Page column 13
[2]Current Patent Assignee: BAYER AG - US2004/2508, 2004, A1 Location in patent: Page/Page column 16-17

14
[ 186193-08-8 ]
[ 2767-70-6 ]
[ 204440-45-9 ]
[ 204440-44-8 ]

Yield	Reaction Conditions	Operation in experiment
42%	Stage #1: (p-nitrobenzyl)triphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 1.5h; Stage #2: C₁₅H₂₈O₄Si In tetrahydrofuran at 0 - 20℃;	33; 7 To a 0° C. solution of potassium tert-butoxide (1.17 g, 10.5 mmol) in 120 mL of THF was added p-nitro-benzyl triphenylphosphonium bromide (5.0 g, 10.5 mmol), in small portions over a period of 30 min. The mixture was stirred at 0° C. for 1 h. Aldehyde 2 in 20 mL of THF, was added dropwise to the preformed ylide. The mixture was stirred at 0° C. for 15 min, then warmed up slowly to room temperature and stirred overnight. Saturated aqueous NH4Cl (50 mL) was added and the solution extracted with ethyl acetate. The organic layer was washed with brine, dried over MgSO4, filtered and concentrated in vacuo. The crude styrene as a mixture of E:Z isomers was purified on silica gel using 2% EtOAc/hexanes to yield 0.5 g of the Z isomer and 1.1 g of the E isomer (42%) as a yellow oil: [a] 20D +63.81° (c 1.05, MeOH); 1H NMR (300 MHz, CDCl3) d 8.18-8.15 (d, 2H, J=8.6 Hz), 7.47-7.44 (d, 2H, J=8.7 Hz), 7.0-6.85 (m, 1H), 6.5-6.3 (m, 2H), 5.87-5.82 (d, 1H, J=15.6 Hz), 3.8-3.73 (m, 1H), 3.73 (s, 3H), 2.55-2.35 (m, 3H), 1.13-1.11 (d, 3H, J=6.9 Hz), 0.90 (s, 9H), 0.059 (s, 3H), 0.047 (s, 3H); 13C NMR (75 MHz, CDCl3) 166.5, 145.5, 143.9, 137.3, 128.7, 126.4, 123.9, 123.1, 74.6, 51.3, 42.8, 37.8, 33.8, 25.7, 24.3, 21.9, 18.0, 16.3, -4.4, -4.7; IR (CHCl3) 2953, 2931, 2859, 1719, 1658, 1596, 1518, 1472, 1438, 1345, 1259, 1110 cm-1. The amide (3.06 g) was prepared from 2.55 g of acid in 65% yield using the procedure described above: [a]20D +70.67° (c 1.05, MeOH); 1H NMR (300 MHz, CDCl3) d 8.15-8.12 (d, 2H, J=8.7 Hz), 7.45-7.42 (d, 2H, J=8.7 Hz), 7.17-7.16 (d, 1H, J=2.0 Hz), 7.04-7.01 (dd, 1H, J=8.45, 1.9 Hz), 6.88-6.82 (m, 2H), 6.43-6.3 (m, 2H), 5.93-5.91 (d, 1H, J=7.5 Hz), 5.84-5.79 (d, 1H, J=15.3 Hz), 5.1-5.0 (m, 1H), 4.82-4.69 (q, 2H, J=11.9 Hz), 3.85 (s, 3H), 3.8-3.7 (m, 1H), 3.24-3.18 (dd, 1H, J=14.3, 5.7 Hz), 3.13-3.06 (dd, 1H, J=14.2, 6.05 Hz), 2.52-2.3 (m, 3H), 1.11-1.09 (d, 3H, J=6.8 Hz), 0.88 (s, 9H), 0.041 (s, 3H), 0.032 (s, 3H); 13C NMR (75 MHz, CDCl3) d 170.0, 165.0, 154.2, 146.5, 144.0, 142.2, 137.4, 136.0, 131.0, 128.7, 128.4, 126.4, 124.9, 123.9, 122.5, 112.1, 94.1, 74.72, 74.67. 56.0, 52.9, 42.7, 37.8, 36.4, 25.7, 18.0, 16.5, -4.7, -4.3; IR (CHCl3) 3429, 2957, 2931, 2858, 1757, 1677, 1645, 1597, 1517, 1503, 1345, 1259, 1180, 1110, 1067, 1026 cm-1. The substrate (3.3 g) was prepared from 2.54 g of the starting alcohol in 87% yield using the procedure described above: [a]20D +38.2° (c 1.07, MeOH); 1H NMR (300 MHz, CDCl3) d 8.23-8.2 (d, 2H, J=8.7 Hz), 7.52-7.49 (d, 2H, J=8.7 Hz), 7.21 (s, 1H), 7.12-7.08 (dd, 1H, J=8.2, 1.8 Hz), 6.89-6.86 (d, 1H, J=8.4 Hz), 6.86-6.75 (m, 1H), 6.6-6.58 (d, 1H, J=8.0 Hz), 6.55-6.5 (d, 1H, J=15.9 Hz), 6.31-6.23 (dd, 1H, J=15.8, 8.5 Hz), 5.97-5.92 (d, 1H, J=15.5 Hz), 5.4-5.3 (bt, 1H), 5.2-5.0 (m, 2H), 4.98-4.94 (dd, 1H, J=9.5, 3.6 Hz), 4.86-4.72 (q, 2H, J=12 Hz), 3.9 (s, 3H), 3.33-3.3 (d, 1H, J=6.6 Hz), 3.27-3.22 (dd, 1H, J=14.1, 5.7 Hz), 3.14-3.07 (dd, 2H, J=14.0, 6.7 Hz), 2.8-2.5 (m, 3H), 2.9-1.47 (m, 3H), 1.47 (s, 9H), 1.3-1.2 (m, 9H), 0.91-0.89 (d, 3H, J=6.4 Hz), 0.87-0.85 (d, 3H, J=6.4 Hz); 13C NMR (75 MHz, CDCl3) d 176.8, 170.6, 169.9, 165.1, 156.2, 154.0, 146.8, 143.2, 138.8, 135.8, 135.4, 131.1, 129.7, 128.7, 128.4, 126.7, 126.6, 125.5, 123.9, 122.2, 112.1, 94.2, 79.0, 76.2, 74.5, 71.2, 56.0, 53.1, 48.5, 43.9, 41.2, 39.4, 36.5, 33.3, 28.3, 24.7, 22.9, 22.7, 22.3, 21.4, 16.3; IR (CHCl3) 3426, 3385, 2967, 2936, 2874, 2841, 1712, 1681, 1646, 1597, 1519, 1500, 1345, 1280, 1259, 1170, 1150, 1067, 1024 cm-1. The styrene product (0.55 g) was prepared from 1.77 g of the starting carbamate in 42% yield using the procedure described above: 1H NMR (300 MHz, CDCl3) 8.23-8.21 (d, 2H, J=8.7 Hz), 7.52-7.49 (d, 2H, J=8.7 Hz), 7.24-7.2 (m, 2H), 7.11-7.08 (dd, 1H, J=8.5, 1.92 Hz), 6.89-6.87 (d, 1H, J=8.4 Hz), 6.86-6.72 (m, 1H), 6.56-6.51 (d, 1H, J=15.9 Hz), 6.33-6.25 (dd, 1H, J=15.9, 8.7 Hz), 5.94-5.91 (d, 1H, J=7.8 Hz), 5.83-5.78 (d, 1H, J=15.2 Hz), 5.17-5.12 (m, 1H), 4.92-4.88 (dd, 1H, J=9.7, 3.6 Hz), 4.8-4.75 (m, 1H), 3.92 (s, 3H), 3.5-3.43 (dd, 1H, J=13.5, 8.73 Hz), 3.2-3.1 (m, 3H), 2.7-2.35 (m, 3H), 1.8-1.6 (m, 2H), 1.4-1.19 (m, 1H), 1.2 (s, 3H), 1.16-1.14 (d, 6H), 0.82-0.81 (d, 3H, J=3.73 Hz), 0.80-79 (d, 3H, J=3.87 Hz).

Reference： [1]Current Patent Assignee: UNIVERSITY OF HAWAI'I - US6680311, 2004, B1 Location in patent: Page/Page column 77-78; 95-96

15
tert-butyl (4R,5R)-2,2-dimethyl-4-(3-oxopropyl)-5-phenyl-1,3-oxazolidine-3-carboxylate [ No CAS ]
[ 2767-70-6 ]
tert-butyl (4R,5R)-2,2-dimethyl-4-[(3E)-4-(4-nitrophenyl)but-3-en-1-yl]-5-phenyl-1,3-oxazolidine-3-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	With triethylamine In dichloromethane at 20℃; for 48h;	13.C To a solution of tert-butyl (4R, 5R)-2,2-dimethyl-4-(3-oxopropyl)-5-phenyl-1,3-oxazolidine-3-carboxylate (10.0 g, 30.0 mmol) from Step B in CH2Cl2 (200 mL) was added (4-nitrobenzyl)triphenyl-phosphonium bromide (21.5 g, 45,0 mmol) followed by Et3N (8.36 mL, 60.0 mmol). The red reaction mixture was stirred at ambient temperature for 48 h. Hexane (200 mL) was poured into the reaction mixture and the solid was filtered off. Flash chromatography on a Biotage Horizon system (silica gel, 0 to 10% ethyl acetate in hexanes gradient then 10% ethyl acetate in hexanes) afforded 10.7 g (79%) of the title compounds (cis trans mixture) as pale yellow foam. LC/MS 475.4 (M+23).

Reference： [1]Current Patent Assignee: MERCK & CO INC - US2009/253705, 2009, A1 Location in patent: Page/Page column 31

16
[ 497855-55-7 ]
[ 2767-70-6 ]
3-[(E)-2-(4-nitrophenyl)ether]-4-propyl-4H-1,2,4-triazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: (p-nitrobenzyl)triphenylphosphonium bromide With sodium methylate In methanol at 20℃; for 0.5h; Stage #2: 3-formyl-4-propyl-4H-1,2,4-triazole In tetrahydrofuran; methanol at 20℃; for 3h;	83 Reference Example 83 To a suspension of 4-nitrobenzyltriphenylphosphonium bromide (6.1 g) in THF (60 ml) was added a solution of sodium methoxide in methanol (28%, 2.46 g) was added at room temperature and the mixture was stirred for 0.5 hour at room temperature. To the reaction solution was added a solution of 3-formyl-4-propyl-4H,1,2,4-triazole (2.0 g) in THF (30 ml) and the mixture was stirred at room temperature for 3 hours. To the reaction solution was added water, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate and concentrated under reduced pressure, and the obtained residue was separated and purified by column chromatography (ethyl acetate → ethanol:ethyl acetate 1:9), to give 3-[(E)-2-(4-nitrophenyl)ether]-4-propyl-4H-1,2,4-triazole (1.6 g) as yellow crystals. m.p. 77 to 79°C 1H-NMR (200 MHz, CDCl3) δ 0.93 (3H, t, J = 7.3 Hz), 1.66 to 1.85 (2H, m), 3.82 (2H, t, J = 7.3 Hz), 6.50 (1H, d, J = 12.7 Hz), 7.03 (1H, d, J = 12.7 Hz), 7.80 (2H, d, J = 8.8 Hz), 8.15 to 8.19 (3H, m). IR (KBr) 1593, 1512, 1341, 1196, 1107, 883, 856 cm-1 Elemental Analysis for C13H14N4O2·0.1H2O Calcd. C, 60.04; H, 5.50; N, 21.54: Found. C, 50.76; H, 5.37; N, 21.71.

Reference： [1]Current Patent Assignee: TAKEDA PHARMACEUTICAL COMPANY LIMITED - EP1422228, 2004, A1 Location in patent: Page 193

17
[ 1206776-61-5 ]
[ 2767-70-6 ]
[ 1206774-17-5 ]

Yield	Reaction Conditions	Operation in experiment
106 mg (32%)	With hydrogenchloride; NaH In methanol; ethyl acetate; N,N-dimethyl-formamide	6 N-(4-{2-[3-tert-Butyl-2-methoxy-5-(2-oxo-1,2-dihydro-pyridin-3-yl)-phenyl]-ethyl}-phenyl)-methanesulfonamide-(2-oxo-1,2-dihydro-pyridin-3-yl)-phenyl]-ethyl}-3-fluoro-phenyl)-methanesulfonamide Example 6 N-(4-{2-[3-tert-Butyl-2-methoxy-5-(2-oxo-1,2-dihydro-pyridin-3-yl)-phenyl]-ethyl}-phenyl)-methanesulfonamide-(2-oxo-1,2-dihydro-pyridin-3-yl)-phenyl]-ethyl}-3-fluoro-phenyl)-methanesulfonamide (I-33 SCHEME D) step 1-To a solution of 4-nitro-benzyltriphenylphosphonium bromide (1.53 g, 3.20 mmol) in DMF (8 mL) at 0° C. was added NaH (60% in oil dispersion, 227 mg, 5.68 mmol). The reaction was stirred for 30 min at 0° C. and followed by addition of a solution of the B2a (R4=tert-Bu, R"=Me, 320 mg, 1.07 mmol) in DMF (7 mL). The resulting solution was gradually warmed to RT and stirred overnight. The reaction was quenched with 1N aqueous HCl solution and diluted with EtOAc. The organic layer was washed with brine, dried (Na2SO4), filtered and concentrated. The crude residue was purified by SiO2 chromatography eluding with an EtOAc/hexane gradient (0 to 8% EtOAc) to afford 351 mg (78%) 3-{3-tert-butyl-4-methoxy-5-[2-(4-nitro-phenyl)-vinyl]-phenyl}-2-methoxy-pyridine (44) of as an orange oil. step 2-To a solution of the above 44 (351 mg, 0.840 mmol) in EtOAc (15 mL) and MeOH (15 mL), was added Pd(OH)2 (20 wt % on carbon, 166 mg, 0.237 mmol). The reaction was stirred under an atmosphere of hydrogen for 45 min, the catalyst was filtered, and the filtrate concentrated. The residue was re-dissolved in a mixture of MeOH (15 mL) and EtOAc (15 mL) and a fresh batch of Pd(OH)2 (166 mg, 0.237 mmol) was added. The resulting reaction mixture was stirred under an atmosphere of hydrogen overnight, the catalyst was filtered and the filtrate concentrated. The crude residue was purified by SiO2 chromatography eluding with 20% EtOAc/hexanes to afford 106 mg (32%) of 4-{2-[3-tert-butyl-2-methoxy-5-(2-methoxy-pyridin-3-yl)-phenyl]-ethyl}-phenylamine (46) as a colorless oil.

Reference： [1]Current Patent Assignee: ROCHE HOLDING AG - US2010/21423, 2010, A1

18
[ 75-90-1 ]
[ 2767-70-6 ]
[ 78622-57-8 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at 100℃; Cooling with ice;	26 Reference Example 261-Nitro-4-[(1E)-3,3,3-trifluoroprop-1-en-1-yl]benzene; To a mixture of (4-nitrobenzyl)(triphenyl)phosphonium bromide (35.0 g), potassium tert-butoxide (8.38 g) and N,N-dimethylformamide (366 ml) in an ice water bath, trifluoroacetaldehyde produced at 80° C. from 1-ethoxy-2,2,2-trifluoroethanol (73.8 g), sulfuric acid (44.9 ml) and diphosphorus pentoxide (73.7 g), was added through a cannula. The resulting mixture was stirred for 24 hours at 100° C., and then was cooled to room temperature. Then, the mixture was poured into water, and the resultant was extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The residue was purified by chromatography, and thus 1-nitro-4-[(1E)-3,3,3-trifluoroprop-1-en-1-yl]benzene (9.40 g) was obtained as a yellow solid.1H NMR (400 MHz, CHLOROFORM-d) δ ppm 6.32-6.41 (1H, m), 7.23 (1H, d, J=16.0 Hz), 7.63 (2H, d, J=8.4 Hz), 8.27 (2H, d, J=8.4 Hz).

Reference： [1]Current Patent Assignee: TAKEDA PHARMACEUTICAL COMPANY LIMITED - US2010/190747, 2010, A1 Location in patent: Page/Page column 44

19
[ 464192-28-7 ]
[ 2767-70-6 ]
2-bromo-5-[2-(4-nitro-phenyl)-vinyl]-thiazole [ No CAS ]
2-bromo-5-[2-(4-nitro-phenyl)-vinyl]-thiazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		To a solution of (4-nitro-benzyl)-triphenyl-phosphonium bromide (1.6 g, 3.4 mmol) in anhydrous DMF (20 mL) was added 'BuOK (0.40 g, 3.6 mmol). The solution was stirred for 30 min before adding solution of <strong>[464192-28-7]2-bromo-thiazole-5-carbaldehyde</strong> (0.50 g, 2.6 mmol) in DMF (10 mL). The mixture was stirred overnight and poured into water. The mixture was extracted with EtOAc (2 x 40 mL) and the combined organic extracts washed with brine, dried over anhydrous Na2SO4 and filtered. The filtrate was concentrated and the residue purified by flash column on silica gel (hexanes to 15% EtOAc/hexanes) to afford title intermediate as a mixture of cis/trans isomers (0.25 g, 31%).

Reference： [1]Patent: WO2007/56023,2007,A2 .Location in patent: Page/Page column 64

20
[ 936845-87-3 ]
[ 2767-70-6 ]
[ 936845-88-4 ]

Yield	Reaction Conditions	Operation in experiment
100%	Stage #1: (p-nitrobenzyl)triphenylphosphonium bromide With sodium hydroxide In dichloromethane; water Stage #2: 4-[4-(5-formyl-thiazol-2-ylamino)-benzenesulfonyl]-piperidine-1-carboxylic acid tert-butyl ester With benzoic acid In dichloromethane; toluene at 90℃; for 16h;	40 (4-Nitro-benzyl)-triphenyl-phosphonium bromide (0.2 g, 0.42 mmol) was dissolved in 150 niL DCM and washed with IN NaOH. Resulting bright red solution was then dried over sodium sulfate, filtered and poured into 500 mL round bottom flask. Approximately 60 mL anhydrous toluene was added and solvents were reduced under rotary evaporation until only 40-50 mL of solvent remained. This was then added to a stirring premade solution of intermediate 26 (0.15 g, 0.33 mmol) and benzoic acid (0.01 g) in toluene (25 mL). Reaction immediately heated to 90 0C and stirred at that temperature overnight. After 16 h, reaction was cooled to room temperature, solvents were removed and residue used without further purification. (0.2 g, 100%).

Reference： [1]Current Patent Assignee: SANOFI - WO2007/56023, 2007, A2 Location in patent: Page/Page column 53

21
[ 4181-05-9 ]
[ 2767-70-6 ]
[ 142677-07-4 ]

Yield	Reaction Conditions	Operation in experiment
47%	With potassium <i>tert</i>-butylate
46.5%	With potassium <i>tert</i>-butylate for 0.0833333h;	3 3. Preparation of intermediate III 0.6 g (5.4 mmol) of t-BuOK (potassium t-butoxide) was ground in a mortar and then 1.0 g (2.2 mmol) ofbrominated (4-nitrobenzyl) triphenylphosphine (intermediate 2), 5 g (1.8 mmol) of 4- (N, N-diphenylamino) benzaldehyde (Intermediate I) was added to the mortar for5 minand ground, and the reaction was complete by thin layer chromatography.With CH2CI2todissolve, filtered and the filtrate washed with water, dried over anhydrous MgS04. 4G was dried, concentrated, and recrystallized from ethanol to give 0.33g of anhydrous dendritic red solid.Yield: 46.5%
	With potassium <i>tert</i>-butylate

Reference： [1]Location in patent: experimental part Zhou, Hongping; Zheng, Zheng; Xu, Guoyi; Yu, Zhipeng; Yang, Xiaofei; Cheng, Longhuai; Tian, Xiaohe; Kong, Lin; Wu, Jieying; Tian, Yupeng [Dyes and Pigments, 2012, vol. 94, # 3, p. 570 - 582]
[2]Current Patent Assignee: ANHUI UNIVERSITY - CN105670608, 2017, B Location in patent: Paragraph 0042-0043
[3]Liu, Yanqiu; Kong, Ming; Zhang, Qiong; Zhang, Zhiwen; Zhou, Hongping; Zhang, Shengyi; Li, Shengli; Wu, Jieying; Tian, Yupeng [Journal of Materials Chemistry B, 2014, vol. 2, # 33, p. 5430 - 5440]

22
[ 437-81-0 ]
[ 2767-70-6 ]
[ 1391935-03-7 ]

Yield	Reaction Conditions	Operation in experiment
69%	With sodium hydroxide In dichloromethane at 50℃;	3 Synthesis of (E)-1,3-Difluoro-2-(4-nitrostyryl)benzene (8). To a solution of 956 mg (2 mmol) of (4-nitrobenzyl)triphenylphosphonium bromide and 284 mg (2 mmol) of 2,6-difluorobenzaldehyde in 20 mL of CH2Cl2 was added 5 mL of 0.48 M NaOH solution (2.4 mmol, 1.2 equiv) dropwise over a 10 min period. The red solution was heated at 50° C. for 1 h. The organic layer was separated, washed with a saturated aqueous NaHSO3 solution and water, and dried over anhydrous MgSO4. The residue was recrystallized from ethanol to afford 360 mg (69%) of 8 as light yellow crystals: mp 136-137° C. 1H NMR (DMSO-d6): δ 8.23 (d, 2H, J=8.8 Hz), 7.93 (d, 2H, J=8.8 Hz), 7.50 (d, 1H, J=16.8 Hz), 7.46-7.40 (m, 1H), 7.37 (d, 1H, J=16.8 Hz), 7.23-7.17 (m, 2H). 13C NMR (DMSO-d6): δ 160.79 (dd, J1=249.4 Hz, J2=7.3 Hz, two C), 147.27, 143.81, 133.35 (t, J=7.9 Hz), 130.82 (t, J=10.7 Hz), 128.21 (two C), 124.46 (two C), 119.70 (t, J=1.6 Hz), 113.79 (t, J=15.1 Hz), 112.65 (dd, J1=19.5 Hz, J2=5.9 Hz, two C). MS: m/z (%) 261 (61), 231 (67), 214 (45), 194 (34), 183 (100). Anal. Calcd for C14H9F2NO: C, 64.37; H, 3.47. Found: C, 64.56; H, 3.42.

Reference： [1]Current Patent Assignee: UNIVERSITY OF KENTUCKY - US2012/196874, 2012, A1 Location in patent: Page/Page column 18

23
[ 619-22-7 ]
[ 2767-70-6 ]
(E)-3-dimethylamino-4’-nitrostilbene [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2012,vol. 134,p. 20440 - 20445

24
[ 1190391-88-8 ]
[ 2767-70-6 ]
[ 1190391-89-9 ]

Yield	Reaction Conditions	Operation in experiment
79%	With triethylamine In dichloromethane at 20℃; for 48h;	C To a solution of tert-butyl (4R, 5R)~2, 2-dimethyl-4-(3-oxopr.opyl)-5-phenyl-L 3- oxazolidme-3-carboxyIate (10.0 g, 30.0 mmol) from Step B in CH2C12 (200 mL) was added (4- nitrobenzyl)triphenyl-phosphonium bromide (21.5g, 45,0 mmol) followed by Et3N (8.36 mL, 60.0 mmol). The red reaction mixture was stirred at ambient temperature for 48 h. Hexane (200 mL) was poured into the reaction mixture and the solid was filtered off. Flash chromatography on a Biotage Horizon system (silica gel, 0 to 10% ethyl acetate in hexanes gradient then 10% ethyl acetate in hexanes) afforded 10.7 g (79%) of the title compounds cis tram mixture) as pale yellow foam. LC/MS 475.4 (M+23).

Reference： [1]Current Patent Assignee: MERCK & CO INC - WO2011/43942, 2011, A1 Location in patent: Page/Page column 31

25
N-(4-formyl-1,3-thiazol-2-yl)-2-methylpropanamide [ No CAS ]
[ 2767-70-6 ]
[ 1426055-80-2 ]
[ 737822-99-0 ]

Yield	Reaction Conditions	Operation in experiment
33.333 % de	With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at 0 - 20℃; for 14h; Inert atmosphere;	5.1.5. N-{4-[(Z)-2-(4-Nitrophenyl)ethenyl]-1,3-thiazol-2-yl}acetamide (7) General procedure: To a mixture of 4-nitrobenzyl bromide (6) (1.9 g) in DMF (20 mL) was added triphenylphosphine (2.3 g) at 0 °C under a nitrogen atmosphere, and the reaction mixture was stirred at room temperature for 2.5 h. Then potassium tert-butoxide (1.2 g) and 5 (1.5 g) were added at 0 °C, and the mixture was stirred at room temperature for 14 h. The reaction mixture was poured into ice-H2O and extracted with AcOEt. The organic layer was washed with 1 M HCl, H2O and brine, dried over anhydrous MgSO4, and concentrated in vacuo. The residue was purified by flash column chromatography over silica gel with hexane/AcOEt (1:1-1:2) as an eluent and triturated with Et2O to give 7 (1.6 g, 62%) as a yellow solid.

Reference： [1]Inoue, Takayuki; Morita, Masataka; Tojo, Takashi; Yoshihara, Kousei; Nagashima, Akira; Moritomo, Ayako; Ohkubo, Mitsuru; Miyake, Hiroshi [Bioorganic and Medicinal Chemistry, 2013, vol. 21, # 5, p. 1219 - 1233]

26
[ 737823-59-5 ]
[ 2767-70-6 ]
[ 737823-60-8 ]

Yield	Reaction Conditions	Operation in experiment
76%	With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at 0 - 20℃; for 14h; Inert atmosphere;	5.1.5. N-{4-[(Z)-2-(4-Nitrophenyl)ethenyl]-1,3-thiazol-2-yl}acetamide (7) General procedure: To a mixture of 4-nitrobenzyl bromide (6) (1.9 g) in DMF (20 mL) was added triphenylphosphine (2.3 g) at 0 °C under a nitrogen atmosphere, and the reaction mixture was stirred at room temperature for 2.5 h. Then potassium tert-butoxide (1.2 g) and 5 (1.5 g) were added at 0 °C, and the mixture was stirred at room temperature for 14 h. The reaction mixture was poured into ice-H2O and extracted with AcOEt. The organic layer was washed with 1 M HCl, H2O and brine, dried over anhydrous MgSO4, and concentrated in vacuo. The residue was purified by flash column chromatography over silica gel with hexane/AcOEt (1:1-1:2) as an eluent and triturated with Et2O to give 7 (1.6 g, 62%) as a yellow solid.

Reference： [1]Inoue, Takayuki; Morita, Masataka; Tojo, Takashi; Yoshihara, Kousei; Nagashima, Akira; Moritomo, Ayako; Ohkubo, Mitsuru; Miyake, Hiroshi [Bioorganic and Medicinal Chemistry, 2013, vol. 21, # 5, p. 1219 - 1233]

27
[ 16444-13-6 ]
[ 2767-70-6 ]
[ 737822-88-7 ]

Yield	Reaction Conditions	Operation in experiment
1.6 g	With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at 0 - 20℃; for 14h; Inert atmosphere;	5.1.5. N-{4-[(Z)-2-(4-Nitrophenyl)ethenyl]-1,3-thiazol-2-yl}acetamide (7) To a mixture of 4-nitrobenzyl bromide (6) (1.9 g) in DMF (20 mL) was added triphenylphosphine (2.3 g) at 0 °C under a nitrogen atmosphere, and the reaction mixture was stirred at room temperature for 2.5 h. Then potassium tert-butoxide (1.2 g) and 5 (1.5 g) were added at 0 °C, and the mixture was stirred at room temperature for 14 h. The reaction mixture was poured into ice-H2O and extracted with AcOEt. The organic layer was washed with 1 M HCl, H2O and brine, dried over anhydrous MgSO4, and concentrated in vacuo. The residue was purified by flash column chromatography over silica gel with hexane/AcOEt (1:1-1:2) as an eluent and triturated with Et2O to give 7 (1.6 g, 62%) as a yellow solid. Mp 155-157 °C; 1H NMR (DMSO-d6) δ 2.13 (3H, s), 6.64 (1H, d, J = 12.5 Hz), 6.71 (1H, d, J = 12.5 Hz), 7.18 (1H, s), 7.79 (2H, d, J = 9.0 Hz), 8.17 (2H, d, J = 9.0 Hz), 12.02 (1H, br s); FAB MS m/e (M+H)+ 290.

Reference： [1]Inoue, Takayuki; Morita, Masataka; Tojo, Takashi; Yoshihara, Kousei; Nagashima, Akira; Moritomo, Ayako; Ohkubo, Mitsuru; Miyake, Hiroshi [Bioorganic and Medicinal Chemistry, 2013, vol. 21, # 5, p. 1219 - 1233]

28
[ 2767-70-6 ]
[ 122-85-0 ]
[ 1426055-78-8 ]
[ 112098-17-6 ]

Yield	Reaction Conditions	Operation in experiment
42.857 % de	With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at 0 - 20℃; for 14h; Inert atmosphere;	5.1.5. N-{4-[(Z)-2-(4-Nitrophenyl)ethenyl]-1,3-thiazol-2-yl}acetamide (7) General procedure: To a mixture of 4-nitrobenzyl bromide (6) (1.9 g) in DMF (20 mL) was added triphenylphosphine (2.3 g) at 0 °C under a nitrogen atmosphere, and the reaction mixture was stirred at room temperature for 2.5 h. Then potassium tert-butoxide (1.2 g) and 5 (1.5 g) were added at 0 °C, and the mixture was stirred at room temperature for 14 h. The reaction mixture was poured into ice-H2O and extracted with AcOEt. The organic layer was washed with 1 M HCl, H2O and brine, dried over anhydrous MgSO4, and concentrated in vacuo. The residue was purified by flash column chromatography over silica gel with hexane/AcOEt (1:1-1:2) as an eluent and triturated with Et2O to give 7 (1.6 g, 62%) as a yellow solid.

Reference： [1]Inoue, Takayuki; Morita, Masataka; Tojo, Takashi; Yoshihara, Kousei; Nagashima, Akira; Moritomo, Ayako; Ohkubo, Mitsuru; Miyake, Hiroshi [Bioorganic and Medicinal Chemistry, 2013, vol. 21, # 5, p. 1219 - 1233]

29
[ 59755-25-8 ]
[ 2767-70-6 ]
[ 1426055-79-9 ]
N-{3-[(E)-2-(4-nitrophenyl)vinyl]phenyl}acetamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
20 % de	With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at 0 - 20℃; for 14h; Inert atmosphere;	5.1.5. N-{4-[(Z)-2-(4-Nitrophenyl)ethenyl]-1,3-thiazol-2-yl}acetamide (7) General procedure: To a mixture of 4-nitrobenzyl bromide (6) (1.9 g) in DMF (20 mL) was added triphenylphosphine (2.3 g) at 0 °C under a nitrogen atmosphere, and the reaction mixture was stirred at room temperature for 2.5 h. Then potassium tert-butoxide (1.2 g) and 5 (1.5 g) were added at 0 °C, and the mixture was stirred at room temperature for 14 h. The reaction mixture was poured into ice-H2O and extracted with AcOEt. The organic layer was washed with 1 M HCl, H2O and brine, dried over anhydrous MgSO4, and concentrated in vacuo. The residue was purified by flash column chromatography over silica gel with hexane/AcOEt (1:1-1:2) as an eluent and triturated with Et2O to give 7 (1.6 g, 62%) as a yellow solid.

Reference： [1]Inoue, Takayuki; Morita, Masataka; Tojo, Takashi; Yoshihara, Kousei; Nagashima, Akira; Moritomo, Ayako; Ohkubo, Mitsuru; Miyake, Hiroshi [Bioorganic and Medicinal Chemistry, 2013, vol. 21, # 5, p. 1219 - 1233]

30
[ 252662-37-6 ]
[ 2767-70-6 ]
[ 737823-44-8 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at 0 - 20℃; for 14h; Inert atmosphere;	5.1.5. N-{4-[(Z)-2-(4-Nitrophenyl)ethenyl]-1,3-thiazol-2-yl}acetamide (7) General procedure: To a mixture of 4-nitrobenzyl bromide (6) (1.9 g) in DMF (20 mL) was added triphenylphosphine (2.3 g) at 0 °C under a nitrogen atmosphere, and the reaction mixture was stirred at room temperature for 2.5 h. Then potassium tert-butoxide (1.2 g) and 5 (1.5 g) were added at 0 °C, and the mixture was stirred at room temperature for 14 h. The reaction mixture was poured into ice-H2O and extracted with AcOEt. The organic layer was washed with 1 M HCl, H2O and brine, dried over anhydrous MgSO4, and concentrated in vacuo. The residue was purified by flash column chromatography over silica gel with hexane/AcOEt (1:1-1:2) as an eluent and triturated with Et2O to give 7 (1.6 g, 62%) as a yellow solid

Reference： [1]Inoue, Takayuki; Morita, Masataka; Tojo, Takashi; Yoshihara, Kousei; Nagashima, Akira; Moritomo, Ayako; Ohkubo, Mitsuru; Miyake, Hiroshi [Bioorganic and Medicinal Chemistry, 2013, vol. 21, # 5, p. 1219 - 1233]

31
[ 2767-70-6 ]
[ 364631-73-2 ]
[ 1427308-40-4 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate In tetrahydrofuran; N,N-dimethyl-formamide for 6h; Reflux;	4.2.1. tert-Butyl 5-(4-aminophenethyl)-2,2-dimethyl-1,3-dioxan-5- ylcarbamate (10). A suspension of aldehyde 8 (5.50 g, 21.29 mmol), phosphonium salt 7 (12.24 g, 25.54 mmol), and K2CO3 (8.3 g, 59.61 mmol) in a mixture of THF (75 mL) and DMF (25 mL) was heated under reflux for 6 h. Aftercompletion of the reaction, THF was evaporated and the reaction mixture was quenched with water and then extracted with ethyl acetate (3 150 mL). The combined organic layers were washed with brine, dried over anhydrous Na2SO4, and concentrated to give a residue, which was purified by silica gel flash chromatography (ether:ethyl acetate¼7:1) to give a mixture of E/Z isomer alkene 9. Thereafter, to a mixture of 9 and methanol (150 mL) was added 10% Pd/C (0.8 g) and hydrogenated for 8 h at room temperature. The reaction mixture was filtered through Celite and the solvent was concentrated to give compound 10 (5.68 g, 76% yield from 8) as a white solid; mp 160e163 °C; 1HNMR (500 MHz, CDCl3): d 1.41 (s, 3H), 1.43 (s, 3H), 1.47 (s, 9H), 1.92 (t, J¼8 Hz, 2H), 2.44e2.48 (m, 2H), 3.55 (s, 2H), 3.66 (d, J¼12 Hz, 2H), 3.88 (d, J¼11 Hz, 2H), 4.98 (s,1H), 6.61 (d, J¼8 Hz, 2H), 6.96 (d, J¼8 Hz, 2H);HRMS (EI):m/z calcd for C19H30N2O4 [M]þ: 350.2206, found: 350.2203.

Reference： [1]Mei, Tie-Wen; Luo, Yu; Feng, Xiang-Jun; Lu, Wei; Yang, Bo [Tetrahedron, 2013, vol. 69, # 14, p. 2927 - 2932]

32
[ 2767-70-6 ]
[ 162359-55-9 ]