[ CAS No. 21204-67-1 ] {[proInfo.proName]}

,{[proInfo.pro_purity]}

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Quality Control of [ 21204-67-1 ]

COA NMR CNMR HPLC LC-MS

Related Doc. of [ 21204-67-1 ]

SDS Specification

Alternatived Products of [ 21204-67-1 ]

Product Details of [ 21204-67-1 ]

CAS No. :	21204-67-1	MDL No. :	N/A
Formula :	C₂₁H₁₉O₂P	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	-
M.W :	334.35	Pubchem ID :	-
Synonyms :

Safety of [ 21204-67-1 ]

Signal Word:	Danger	Class:	6.1
Precautionary Statements:	P261-P264-P270-P271-P280-P301+P310-P302+P352-P304+P340-P305+P351+P338-P312-P330-P362+P364-P403+P233-P405-P501	UN#:	2811
Hazard Statements:	H301-H315-H319-H335	Packing Group:	Ⅲ
GHS Pictogram:

Application In Synthesis of [ 21204-67-1 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

Upstream synthesis route of [ 21204-67-1 ]
Downstream synthetic route of [ 21204-67-1 ]

[ 21204-67-1 ] Synthesis Path-Upstream 1~14

1
[ 55164-16-4 ]
[ 21204-67-1 ]
[ 854280-54-9 ]
[ 22913-24-2 ]

Reference： [1] Tetrahedron Letters, 2005, vol. 46, # 21, p. 3719 - 3723

2
[ 21204-67-1 ]
[ 2605-68-7 ]

Reference： [1] European Journal of Organic Chemistry, 1999, # 11, p. 2909 - 2914
[2] Chemische Berichte, 1962, vol. 95, p. 2921 - 2927

3
[ 21204-67-1 ]
[ 74-88-4 ]
[ 2605-68-7 ]

Reference： [1] Journal of Medicinal Chemistry, 1999, vol. 42, # 14, p. 2662 - 2672

4
[ 123-72-8 ]
[ 21204-67-1 ]
[ 2396-77-2 ]

Reference： [1] Bulletin of the Chemical Society of Japan, 1979, vol. 52, # 1, p. 184 - 185

5
[ 111-71-7 ]
[ 21204-67-1 ]
[ 111-79-5 ]

Reference： [1] Bulletin of the Chemical Society of Japan, 1979, vol. 52, # 1, p. 184 - 185

6
[ 21204-67-1 ]
[ 135034-79-6 ]
[ 851762-70-4 ]
[ 51544-64-0 ]
[ 200125-18-4 ]

Reference： [1] Tetrahedron, 2005, vol. 61, # 15, p. 3651 - 3657

7
[ 100-07-2 ]
[ 21204-67-1 ]
[ 7515-17-5 ]

Reference： [1] Bioorganic and Medicinal Chemistry Letters, 2003, vol. 13, # 18, p. 3083 - 3086

8
[ 1685-97-8 ]
[ 21204-67-1 ]
[ 1779-58-4 ]
[ 134898-37-6 ]

Reference： [1] Phosphorus, Sulfur and Silicon and the Related Elements, 1991, vol. 60, # 1.2, p. 49 - 55

9
[ 134898-34-3 ]
[ 21204-67-1 ]
[ 1779-58-4 ]
[ 134898-37-6 ]

Reference： [1] Phosphorus, Sulfur and Silicon and the Related Elements, 1991, vol. 60, # 1.2, p. 49 - 55

10
[ 16619-55-9 ]
[ 21204-67-1 ]
[ 1779-58-4 ]
[ 134898-28-5 ]

Reference： [1] Phosphorus, Sulfur and Silicon and the Related Elements, 1991, vol. 60, # 1.2, p. 49 - 55

11
[ 134898-25-2 ]
[ 21204-67-1 ]
[ 1779-58-4 ]
[ 134898-28-5 ]

Reference： [1] Phosphorus, Sulfur and Silicon and the Related Elements, 1991, vol. 60, # 1.2, p. 49 - 55

12
[ 96-32-2 ]
[ 21204-67-1 ]
[ 1779-58-4 ]

Reference： [1] Chemische Berichte, 1962, vol. 95, p. 2921 - 2927

13
[ 75567-85-0 ]
[ 105-07-7 ]
[ 21204-67-1 ]
[ 83101-12-6 ]

Reference： [1] Patent: US4987132, 1991, A,

14
[ 872-85-5 ]
[ 21204-67-1 ]
[ 24489-96-1 ]

Reference： [1] European Journal of Organic Chemistry, 2014, vol. 2014, # 33, p. 7347 - 7352

[ 21204-67-1 ] Synthesis Path-Downstream 1~88

1
[ 1779-58-4 ]
[ 21204-67-1 ]

Yield	Reaction Conditions	Operation in experiment
96%	With sodium hydroxide; In dichloromethane; water;Inert atmosphere;	(Methoxycarbonylmethyl)triphenylphosphoniumbromide (25 g,60.2 mmol, 1.0 eq) and sodium hydroxide (4.82 g, 120.4 mmol, 2.0 eq) weredissolved in a mixture of dichloromethane (150 mL) and H2O (100 mL)and shaken vigorously in a separatory funnel. The layers were separated and theaqueous layer extracted with dichloromethane (2x75 mL). The combined organicswere washed with water and brine, dried over Na2SO4 andconcentrated to give methyl (triphenylphosphoranylidene)acetate (19.3 g, 96%)as a white solid. To this solid was added a solution of S4 (3.93g, 38.5 mmol) in THF (100 mL) dropwise. The mixture was then heated to refluxovernight, then cooled down and concentrated. The solid residue was stirred ina 7:3 mixture of ether:petroleum ether (50 mL) for 1h, then filtered to removethe triphenylphosphine oxide byproduct. The solid was washed with ether and thefiltrate was concentrated. The residue was purified by flash column chromatograph(2:1 ? 1:1 Hexanes:Ethyl Acetate) to yield the title compound as an oil in aninconsequential 10:1 ratio of E:Z olefin isomers (5.14 g, 84% total yield).
90%	With sodium hydroxide; In dichloromethane; water; at 20℃; for 2h;	An aqueous solution of 1.15 N NaOH (60 ml) was added at room temperature to a solution of <strong>[1779-58-4][(methoxycarbonyl)methyl]triphenylphosphonium bromide</strong> (14.3 g, 34.6 mmoles, 1 eq.), obtained previously, in CH2Cl2 (90 ml). The resulting mixture was stirred vigorously at room temperature for 2 hours. After that time, the phases were separated. The aqueous phase was extracted with CH2Cl2 (3 x 10 ml). The organic phase was dried with anhydrous MgSO4, filtered and the solvent was removed under reduced pressure, obtaining (10.5 g, yield 90%) [(methoxycarbonyl)methylene]-triphenylphosphorane as a white solid. 1H-NMR (200MHz, CDCl3). delta 7.61 (15H, m, Ar-H), 5.62 (1H, m, H-1), 3.50 (3H, s, - OCH3).
	With sodium hydroxide; tetrabutylammomium bromide; In methanol; dichloromethane; water; at 0 - 20℃; for 1h;	In a 500 mL round bottom flask fitted with a stirring bar, an addition funnel and a calcium chloride guard tube, methyl bromoacetate (18.6 mL, 0.196 mol) was taken in dry benzene (300 mL). The mixture was cooled to 0 C. and added with triphenylphosphine (51.4 g, 0.096 mol) in portions over a period of half an hour. The reaction mixture was warmed to room temperature and stirred for 24 hrs. The white solid obtained was filtered, washed with benzene and dried over vacuum to yield 75.5 g of Wittig salt. This salt was suspended in a mixture of dichloromethane/MeOH (125 mL/300 mL), cooled to 0 C., added with NaOH (8 g, 0.2 mol) in 30 mL of water and tetrabutylammonium bromide (0.58 g, 1 mol %), slowly warmed to RT, and stirred for 1 hr. The layers were separated. The aqueous layer was extracted with dichloromethane (3×50 mL). The combined organic layer was dried over sodium sulfate and concentrated to afford Ph3PCHCOOMe as a white solid (58 g, 88%). To a cooled solution (0 C.) of Ph3PCHCOOMe (50 g, 0.15 mol) in dry dichloromethane (150 mL), isobutraldehyde (15 mL, 0.165 mol) was added dropwise at 0 C. over a period of 10 minutes. The reaction mixture was slowly warmed to RT and stirred for 24 hrs. The excess solvent was removed under reduced pressure and the residue was treated with petroleum ether (250 mL). The triphenylphosphine oxide precipitate was filtered off. This process was repeated two to three times to remove the maximum triphenylphonsphine oxide. The filtrate was concentrated and purified by silica gel column chromatography using EtOAc/petroleum ether to yield 17 (7.22 g, 34%): Rf 0.5, EtOAc/petroleum ether (3:7, v/v).

57.4 g	With sodium hydroxide; In water; for 1h;	General procedure: To a stirred solution of triphenylphosphine (52.4 g, 0.2 mol) in benzene (300 mL) was added dropwise a solution of methyl bromoacetate (30.4 g, 0.2 mol) in benzene (100 mL) over 1 h. The reaction was allowed to stir for 4 h. The solid phosphonium bromide product was filtered and washed with hexane to provide a white solid. The crude solid was dissolved in water (600 mL) and sodium hydroxide (20.2 g, 0.2 mol) was added. After 1 h, the precipitate was filtered and washed with water to provide a white solid. The crude product was recrystallized from benzene/petroleum ether to provide methyl 2-(triphenylphosphoranylidene) acetate (57.4 g, 86% for two steps).CommentA solution containing the appropriate 5 (3 mmol) and methyl (triphenylphosphoranylidene) acetate (4.5 mmol) in toluene (30 mL) was heated at 100 C for 2 h. After evaporation of the solvent, the residue was purified by column chromatography (ethyl acetate-hexane; 1:3) to give the product.
	With sodium hydroxide; In dichloromethane; water; at 20℃; for 0.333333h;	General procedure: The allenoates 2 were synthesized according to Kwon procedure.5 Under nitrogen atmosphere, to the solution of PPh3 (1.0 equiv) in toluene was added bromoacetic esters (1.0 equiv) over 15 minutes. The solution was stirred for 12 hours and the precipitate filtered, washed with ethyl acetate. The collected phosphonium salt was dissolved in dichloromethane and 2 M sodium hydroxide solution (1.0 equiv) was added. The mixture was stirred at room temperature for 20 minutes. The aqueous phase was extracted with dichloromethane. The combined organic extracts were washed with an aqueous saturated solution of sodium chloride, dried over sodium sulfate, filtered and concentrated under reduced pressure. The resulting crude material was the desired compound 6, which was directly used in the next step. A 250 mL flask was charged with stabilized ylide 11 (1.0 equiv), trimethylamine (2.2 equiv) and dichloromethane under nitrogen atmosphere, the mixture was stirred at 0 C. The acid chloride (2.2 equiv) was added slowly as a solution in dichloromethane over 30 minutes. After completion of the reaction (TLC), the solution was treated with pentane. The mixture was filtered and the filtrate evaporated and passed through a short pad of silica gel (pentane/dichloromethane) to afford the pure allenoates 2.

Reference： [1]Journal of the American Chemical Society,1992,vol. 114,p. 6044 - 6050
[2]European Journal of Organic Chemistry,1999,p. 2909 - 2914
[3]European Journal of Organic Chemistry,2002,p. 2094 - 2108
[4]Tetrahedron Letters,2015,vol. 56,p. 3160 - 3164
[5]Journal of the Chemical Society. Perkin transactions I,1994,p. 1569 - 1572
[6]Heterocycles,2007,vol. 73,p. 751 - 768
[7]Patent: EP2287157,2011,A1 .Location in patent: Page/Page column 15-16
[8]European Journal of Organic Chemistry,2012,p. 2323 - 2330
[9]Journal of Organic Chemistry,2014,vol. 79,p. 1386 - 1398
[10]Helvetica Chimica Acta,1957,vol. 40,p. 1242,1246
[11]Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical and Analytical,1985,vol. 24,p. 398 - 402
[12]Phosphorus, Sulfur and Silicon and the Related Elements,1999,vol. 144-146,p. 577 - 580
[13]Chemistry - A European Journal,2006,vol. 12,p. 2994 - 3005
[14]Advanced Synthesis and Catalysis,2009,vol. 351,p. 1423 - 1430
[15]Patent: US2005/203162,2005,A1 .Location in patent: Page/Page column 19
[16]Bioorganic and Medicinal Chemistry,2011,vol. 19,p. 7262 - 7269
[17]Chemical Communications,2013,vol. 49,p. 3470 - 3472
[18]Tetrahedron,2013,vol. 69,p. 7395 - 7402
[19]European Journal of Organic Chemistry,2013,p. 8214 - 8244
[20]Organic Letters,2014,vol. 16,p. 2990 - 2992
[21]RSC Advances,2014,vol. 4,p. 21134 - 21140
[22]Organic Letters,2014,vol. 16,p. 3440 - 3443
[23]Organic Letters,2015,vol. 17,p. 1573 - 1576
[24]Green Chemistry,2017,vol. 19,p. 511 - 518
[25]Chemistry - An Asian Journal,2018,vol. 13,p. 3885 - 3894
[26]Angewandte Chemie - International Edition,2018,vol. 57,p. 17125 - 17129
Angew. Chem.,2018,vol. 130,p. 17371 - 17375,5
[27]Tetrahedron Letters,2019,vol. 60,p. 1885 - 1890
[28]Journal of the American Chemical Society,2019,vol. 141,p. 16991 - 16996

2
[ 96-32-2 ]
[ 21204-67-1 ]
[ 1779-58-4 ]

Reference： [1]Chemische Berichte,1962,vol. 95,p. 2921 - 2927

3
[ 1864-94-4 ]
[ 21204-67-1 ]
[ 90843-43-9 ]

Reference： [1]Comptes Rendus des Seances de l'Academie des Sciences, Serie C: Sciences Chimiques,1973,vol. 276,p. 963 - 966

4
[ 1864-94-4 ]
[ 21204-67-1 ]
[ 41343-65-1 ]

Reference： [1]Comptes Rendus des Seances de l'Academie des Sciences, Serie C: Sciences Chimiques,1973,vol. 276,p. 963 - 966

5
[ 111-71-7 ]
[ 21204-67-1 ]
[ 111-79-5 ]

Reference： [1]Bulletin of the Chemical Society of Japan,1979,vol. 52,p. 184 - 185

6
[ 16339-93-8 ]
[ 21204-67-1 ]
[ 18812-31-2 ]

Reference： [1]Chemische Berichte,1963,vol. 96,p. 465 - 469
[2]Chemische Berichte,1963,vol. 96,p. 465 - 469

7
[ 7512-17-6 ]
[ 21204-67-1 ]
[ 20757-41-9 ]

Reference： [1]Bulletin of the Academy of Sciences of the USSR Division of Chemical Science,1967,p. 2365 - 2370
Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya,1967,p. 2483 - 2490

8
[ 31984-10-8 ]
[ 21204-67-1 ]
[ 17615-08-6 ]

Reference： [1]Chemische Berichte,1963,vol. 96,p. 465 - 469
[2]Chemische Berichte,1963,vol. 96,p. 465 - 469

9
[ 186581-53-3 ]
[ 36122-35-7 ]
[ 21204-67-1 ]
[ 120626-55-3 ]
(Z)-4-Oxo-2-phenyl-5-(triphenyl-λ⁵-phosphanylidene)-hex-2-enedioic acid dimethyl ester [ No CAS ]

Reference： [1]Canadian Journal of Chemistry,1992,vol. 70,p. 1985 - 1996

10
[ 60032-57-7 ]
[ 21204-67-1 ]
[ 137146-28-2 ]

Reference： [1]Journal of Heterocyclic Chemistry,1991,vol. 28,p. 1315 - 1324

11
[ 5926-51-2 ]
[ 21204-67-1 ]
[ 120626-57-5 ]
[ 120626-56-4 ]

Reference： [1]Tetrahedron Letters,1988,vol. 29,p. 6203 - 6206

12
[ 13031-04-4 ]
[ 21204-67-1 ]
[ 86453-60-3 ]
[ 86453-59-0 ]

Reference： [1]Journal of Organic Chemistry,1988,vol. 53,p. 5704 - 5709
[2]Archiv der Pharmazie,1983,vol. 316,p. 530 - 536
[3]Australian Journal of Chemistry,1991,vol. 44,p. 87 - 101

13
[ 36122-35-7 ]
[ 21204-67-1 ]
[ 120626-55-3 ]

Reference： [1]Tetrahedron Letters,1988,vol. 29,p. 6203 - 6206

14
[ 623-27-8 ]
[ 21204-67-1 ]
[ 7560-50-1 ]

Yield	Reaction Conditions	Operation in experiment
89%	In tetrahydrofuran; at 20℃; for 4h;	To a solution of terephthalaldehyde (5 g, 36.54 mmol) in tetrahydrofuran (THF) methyl (triphenylphosphoranylidene)acetate (13.09 g, 38.37 mmol) was added at room temperature. The solution was stirred at room temperature for 4 hours. The resulting solution was washed with water three times and the organic layer was collected. The residue was purified via chromatography eluted with ethyl acetare and hexane to provide a solid (6.17 g, 89 %). H NMR (300 MHz, DMSO-rfe): delta 3.74 (s, 3H, OCH3), 6.81 (d, 1H, / = 16.2 Hz, CH=CH), 7.73 (d, 1Eta, J = 16.2 Hz, CH=CH), 7.90-7.97 (m, 4Eta, ArH), 10.02 (brs, 1Eta, CHO).

Reference： [1]Patent: WO2017/200966,2017,A1 .Location in patent: Page/Page column 12-13
[2]Russian Chemical Bulletin,1993,vol. 42,p. 866 - 869
Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya,1993,p. 910 - 913
[3]Journal of the Chemical Society. Perkin transactions I,1979,p. 1 - 6

15
[ 453-17-8 ]
[ 21204-67-1 ]
[ 81703-94-8 ]
[ 81703-93-7 ]

Reference： [1]Journal of the Chemical Society. Perkin transactions I,1989,p. 1363 - 1364

16
[ 16619-55-9 ]
[ 21204-67-1 ]
[ 1779-58-4 ]
[ 134898-28-5 ]

Reference： [1]Phosphorus, Sulfur and Silicon and the Related Elements,1991,vol. 60,p. 49 - 55

17
[ 1685-97-8 ]
[ 21204-67-1 ]
[ 1779-58-4 ]
[ 134898-37-6 ]

Reference： [1]Phosphorus, Sulfur and Silicon and the Related Elements,1991,vol. 60,p. 49 - 55

18
[ 65874-27-3 ]
[ 21204-67-1 ]
[ 146943-27-3 ]

Reference： [1]Journal of Organic Chemistry,1993,vol. 58,p. 1696 - 1701
[2]Chemical and Pharmaceutical Bulletin,2001,vol. 49,p. 1280 - 1287

19
[ 134898-34-3 ]
[ 21204-67-1 ]
[ 1779-58-4 ]
[ 134898-37-6 ]

Reference： [1]Phosphorus, Sulfur and Silicon and the Related Elements,1991,vol. 60,p. 49 - 55

20
[ 134898-25-2 ]
[ 21204-67-1 ]
[ 1779-58-4 ]
[ 134898-28-5 ]

Reference： [1]Phosphorus, Sulfur and Silicon and the Related Elements,1991,vol. 60,p. 49 - 55

21
[ 67-56-1 ]
[ 60031-08-5 ]
[ 21204-67-1 ]
(E)-3-{3-[1-Phenyl-meth-(E)-ylidene]-indan-5-yl}-acrylic acid methyl ester [ No CAS ]
(E)-3-(3-Benzyl-1H-inden-5-yl)-acrylic acid methyl ester [ No CAS ]

Reference： [1]Tetrahedron,1995,vol. 51,p. 203 - 216

22
[ 67-56-1 ]
[ 60031-08-5 ]
[ 21204-67-1 ]
3-(3-Benzyl-indan-5-yl)-propionic acid methyl ester [ No CAS ]

Reference： [1]Tetrahedron,1995,vol. 51,p. 203 - 216

23
[ 21204-67-1 ]
[ 10111-08-7 ]
(Z)-3-(1H-Imidazol-2-yl)-acrylic acid methyl ester [ No CAS ]
Methyl 3-(imidazolyl)acrylate [ No CAS ]

Reference： [1]Journal of the Chemical Society. Perkin transactions I,1997,p. 2203 - 2209

24
[ 109-89-7 ]
[ 21204-67-1 ]
[ 163164-47-4 ]
(E)-3-[4-(2-Diethylamino-ethyl)-phenyl]-acrylic acid methyl ester [ No CAS ]

Reference： [1]Tetrahedron Letters,1998,vol. 39,p. 979 - 982

25
[ 113732-84-6 ]
[ 21204-67-1 ]
[ 216318-32-0 ]

Reference： [1]Journal of the American Chemical Society,1998,vol. 120,p. 10814 - 10826

26
[ 53581-86-5 ]
[ 21204-67-1 ]
methyl 3-(4-chloro-2-methoxyphenyl)acrylate [ No CAS ]

Reference： [1]Synthetic Communications,1999,vol. 29,p. 929 - 936

27
[ 223778-54-9 ]
[ 21204-67-1 ]
(E)-3-(3-Chloro-2-methoxy-phenyl)-acrylic acid methyl ester [ No CAS ]

Reference： [1]Synthetic Communications,1999,vol. 29,p. 929 - 936

28
[ 108149-63-9 ]
[ 21204-67-1 ]
[ 123751-09-7 ]

Reference： [1]Chemical Communications,1999,p. 1337 - 1338

29
[ 105228-46-4 ]
[ 21204-67-1 ]
5R,6S-2-methoxycarbonylmethyl-5,6-diphenyl-5,6-dihydro-[1,4]oxazine-4-carboxylic acid benzyl ester [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2002,vol. 67,p. 6361 - 6365

30
[ 6361-22-4 ]
[ 21204-67-1 ]
(E)-3-(2-Chloro-6-nitro-phenyl)-acrylic acid methyl ester [ No CAS ]

Reference： [1]Tetrahedron Letters,2003,vol. 44,p. 7269 - 7271

31
[ 21204-67-1 ]
[ 100-49-2 ]
[ 26429-98-1 ]
[ 26429-99-2 ]

Reference： [1]Synlett,2004,p. 738 - 740
[2]Synlett,2004,p. 738 - 740

32
[ 21204-67-1 ]
[ 380151-85-9 ]
[ 372193-92-5 ]
methyl (2Z)-3-[2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]acrylate [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2004,vol. 69,p. 3478 - 3487

33
[ 21204-67-1 ]
[ 135034-79-6 ]
[ 851762-70-4 ]
[ 51544-64-0 ]
[ 200125-18-4 ]

Reference： [1]Tetrahedron,2005,vol. 61,p. 3651 - 3657

34
[ 21204-67-1 ]
[ 52606-02-7 ]
[ 869006-36-0 ]
[ 107166-88-1 ]

Reference： [1]Journal of Heterocyclic Chemistry,2005,vol. 42,p. 1135 - 1142

35
[ 13031-04-4 ]
[ 21204-67-1 ]
[ 86453-59-0 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2006,vol. 16,p. 872 - 875

36
[ 138971-65-0 ]
[ 21204-67-1 ]
[ 68282-53-1 ]
(S)-1-((R)-2-Amino-3,3-diphenyl-propionyl)-pyrrolidine-2-carboxylic acid [(E)-3-(5-methyl-3H-imidazol-4-yl)-allyl]-amide [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2006,vol. 16,p. 338 - 342

37
[ 5381-20-4 ]
[ 21204-67-1 ]
[ 546114-94-7 ]

Reference： [1]Organic Letters,2006,vol. 8,p. 4827 - 4829

38
[ 3453-33-6 ]
[ 21204-67-1 ]
[ 744241-46-1 ]

Yield	Reaction Conditions	Operation in experiment
92%	In tetrahydrofuran;Heating / reflux;	A solution of 6-methoxy naphthaldehyde (0.5 g, 2.6 mmol) and methyl (triphenylphosphoranylidene) acetate (0.97 g, 2.9 mmol) in THF (1OmL) was refluxed overnight under an argon atmosphere. Once the solution cooled, the solvent was evaporated and the remaining solids were treated with 20 mL diethyl ether. After stirring for 2 hours, the undissolved solids were removed. The filtrate was concentrated and purified by column chromatography using silica gel and hexanes-EtOAc 9:1 to obtain 0.58 g (92%) of methyl 3- (6-methoxy-2-naphthyl) -acrylate (7A). NMR 1H (300 MHz, CDCIs) delta ppm: EPO <DP n="50"/>7.94-7.80 (m, 4H) 7.65 (dd, .5 Hz, IH), 7.2-7.14 (m, 2H), 6.52 (d, J=15.9 Hz, IH), 3.96 (s, 3H), 3.85 (s, 3H)NMR 13C ((300 MHz, CDCl3) delta ppm: 168.12, 159.22, 145.54, 136.10, 130.54, 130.22, 130.15, 129.05, 127.90, 124.56, 119.90, 117.13, 106.34, 55.79, 52.10 LRMS (FAB) : 243 (Ci5Hi4O3, M+H) .
92%	In dichloromethane; at 20℃; for 16h;Inert atmosphere;	The stable Wittig ylide carbomthoxymethylenetriphenylphosphorane (Ph3PCHCO2Me, 43.0 g, 129 mmol) was added to a solution of the aldehyde 59 (20.0 g, 107 mmol) in CH2Cl2 (200 mL) under nitrogen atmosphere and the reaction mixture was stirred 16 h at ambient temperature. TLC monitored the completion of the reaction (16 h). CH2Cl2 was removed under reduced pressure and FCC using 10% ethyl acetate-hexanes gave the corresponding trans-alpha,beta-unsaturated ester 62 (24.0 g, 92%) as a white solid: 1H NMR (400 MHz, CDCl3) delta 7.88-7.82 (m, 1H), 8.81 (d, J=15.8 Hz, 1H), 7.73 (d, J=9.0 Hz, 1H), 7.70 (d, J=8.8 Hz, 1H), 7.61 (dd, J=8.8, 2.2 Hz, 1H), 7.15 (dd, J=9.2, 2.2 Hz, 1H), 7.11 (d, J=2.2 Hz, 1H), 6.49 (d, J=15.8 Hz, 1H), 3.82 (s, 3H), 3.82 (s, 3H).
	In toluene; at 120℃; for 18h;	To a solution of 6-methoxy-2-naphthaldehyde (3.72 g, 20.0 mmol) in toluene (40 mL) placed in a pressure vessel, was added methyl(triphenylphosphoranylidene)acetate (6.7 g, 20 mmol). The resulting mixture was refluxed at 120 C. for 18 h. The reaction mixture was concentrated and purified using a Biotage flash 40M column with 15% ethyl acetate-hexanes as the eluant, to provide the enoate.

Reference： [1]Angewandte Chemie - International Edition,2006,vol. 45,p. 637 - 642
[2]Patent: WO2007/22263,2007,A1 .Location in patent: Page/Page column 48; 49
[3]Patent: US2014/171447,2014,A1 .Location in patent: Paragraph 0321; 0322
[4]Patent: US2006/293364,2006,A1 .Location in patent: Page/Page column 33; 54

39
[ 21204-67-1 ]
[ 188815-30-7 ]
[ 695187-03-2 ]

Yield	Reaction Conditions	Operation in experiment
84%	In dichloromethane; at 18 - 25℃; for 4h;	Methyl (E)-3-[3-fluoro-5-(trifluoromethyl)phenyl]prop-2-enoate was prepared as follows:; <strong>[188815-30-7]3-fluoro-5-trifluromethylbenzaldehyde</strong> (0.999 g, 5.2 mmol) and methyl(triphenyl-phosphoranylidene)acetate (2.62 g, 7.8 mmol) in dichloromethane (25 ml) were stirred at ambient temperature for 4 h. After evaporating under reduced pressure the crude product was purified by column chromatography on silica using a gradient 2-10% of ethyl acetate in hexanes. The desired fractions were taken and evaporated to afford methyl (E)-3-[3-fluoro-5-(trifluoromethyl)phenyl]prop-2-enoate as an oil (1.08 g 84%). 1H NMR (399.9 MHz, DMSO-d6) delta3.76 (3H, s), 6.92 (1H, d), 7.68-7.74 (3H, m), 8.01-8.02 (2H, m).

Reference： [1]Patent: US2008/4302,2008,A1 .Location in patent: Page/Page column 68-69

40
[ 57476-50-3 ]
[ 21204-67-1 ]
C₁₇H₁₈BrNO₄ [ No CAS ]
[ 952148-20-8 ]

Reference： [1]Tetrahedron,2007,vol. 63,p. 9465 - 9475

41
[ 2133-40-6 ]
[ 21204-67-1 ]
[ 50596-66-2 ]

Reference： [1]Organic Letters,2007,vol. 9,p. 4939 - 4942

42
[ 32559-18-5 ]
[ 21204-67-1 ]
[ 186135-52-4 ]

Reference： [1]Organic Letters,2007,vol. 9,p. 4939 - 4942

43
[ 67515-60-0 ]
[ 21204-67-1 ]
[ 695186-99-3 ]

Yield	Reaction Conditions	Operation in experiment
83%	In dichloromethane; at 20℃; for 0.0833333h;	Example 53: trans 2- [4- [3- (3-TRIFLUOROMETHYL-4-FLUOROPHENYL)-2-PROPENAMIDO]-3- FLUOROPHENYL] BENZOXAZOL-5-YLACETIC ACID a) trans 3- (3-TRIFLUOROMETHYL-4-FLUOROPHENYL)-2-PROPENOIC acid methyl ester 3-TRIFLUOROMETHYL-4-FLUOROBENZALDEHYDE (250mg, 1. 30mmol) and methyl (triphenylphosphineanylidene)- acetate (520MG, 1. 56MMOL) in dichloromethane (5ml) were stirred at room temperature for 5 min. The solvent was removed under reduced pressure and the residue was purified using column chromatography the subtitle compound was obtained (267mg, 83%).

Reference： [1]Patent: WO2004/46122,2004,A2 .Location in patent: Page 35

44
[ 15832-09-4 ]
[ 21204-67-1 ]
[ 796851-73-5 ]

Yield	Reaction Conditions	Operation in experiment
76%	In toluene; for 48h;Heating / reflux;	Step 4: A mixture of 6-METHOXY-BENZOFURAN-3 (2H) -one (1.64 g, 10 mmol) and (carboxymethylene) triphenylphosphorane (5.22 g, 15 mmol) was refluxed in toluene (100 ml) for 48 hrs. Afterwards, reaction mixture was concentrated and loaded over a silica-gel column. The column was eluted with hexane (500 ml) and then with 25% ethyl acetate. The product, ethyl (6-METHOXY-1-BENZOFURAN-3-YL) acetate, was obtained as a white oil. Yield: 1.8 g (76%); (M+H) : 235.

Reference： [1]Patent: WO2004/99191,2004,A2 .Location in patent: Page 52-53

45
[ 3260-78-4 ]
[ 21204-67-1 ]
[ 82156-62-5 ]

Yield	Reaction Conditions	Operation in experiment
87%	for 48h;Heating / reflux;	Step 4: A mixture of 6-chloro-benzofuran-3 (2H)-ONE (1.68 g, 10 mmol) and (carboxymethylene) triphenylphosphorane (5.22 g, 15 mmol) was refluxed in toluene (100 ml) for 48 hrs. Afterwards, the reaction mixture was concentrated and loaded over a silica-gel column. The column was eluted with hexane (500 ml) and then with 25% ethyl acetate. The product, ethyl (6-chloro-1-benzofuran-3-yl) acetate, was obtained as a white oil. Yield: 2.1 g (87%) ; (M+H): 239.

Reference： [1]Patent: WO2004/99191,2004,A2 .Location in patent: Page 49-50

46
[ 401564-36-1 ]
[ 21204-67-1 ]
(2S)-4-Methoxycarbonylmethylene-2-(thiazolidine-3-carbonyl)-pyrrolidine-1-carboxylic Acid Tert-butyl Ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In dichloromethane; at 40℃; for 48h;	To a solution of Example 1A (5.77 g, 0.0192 mol) in anhydrous dichloromethane (30 mL) was added methyl (triphenylphosphoranylidene)-acetate (8.22 g, 0.0246 mol) and the resulting solution heated to 40 C. for two days. The mixture was cooled, concentrated and purified by column chromatography (ethyl acetate/hexane, 4/6) to provide the titled compound (3.42 g). MS (ESI APCI) m/e 355 (M-H)+; 1H NMR (400 MHz, DMSO-d6): delta ppm 5.87 (m, 1H), 4.41-4.78 (m, 4H), 4.31 (d, 1H), 3.74-3.78 (m, 2 H), 3.17 (t, 2H), 3.04 (t, 1H), 2.74-2.80 (d, 1 H), 1.40 (s, 9H).

Reference： [1]Patent: US2005/209249,2005,A1 .Location in patent: Page/Page column 26

47
[ 21204-67-1 ]
[ 386704-12-7 ]
[ 731810-44-9 ]

Yield	Reaction Conditions	Operation in experiment
	In dichloromethane; for 20h;Heating / reflux;	A. Synthesis of propionic acid derivatives:; 1. Synthesis of 3- (6-trifluoromethyl-pyridin-3-yl)-propionic acid:; 1.1 Synthesis of 3-(6-trifluoromethyl-pyridin-3-yl)-acrylic acid methyl ester:; A solution of 6-trifluoromethyl-pyridine-3-carbaldehyde (570 mg) in DCM (1.0 mL) is added to a solution of (triphenyl-No.5-phosphanylidene) -acetic acid methyl ester (990 mg) in DCM (2.5 ml). The mixture is stirred under nitrogen at reflux for 20h and concentrated in vacuo. The residue is purified by flash chromatography (EA/heptane 3/7) to give the desired unsaturated ester as a white solid. ¹H-NMR (300MHz, CDCl3) : No. = 3.85 (s, 3H), 6.59 (d, J = 16.2 Hz, 1H), 7.70 (d, J = 16.2 Hz, 1H), 7.71 (d, J = 8.1 Hz, 1H), 7.98 (dd, J = 8.1 Hz, J = 2.1 Hz, 1H), 8.84 (bs, 1H).

Reference： [1]Patent: WO2005/118548,2005,A1 .Location in patent: Page/Page column 14

48
[ 16801-63-1 ]
[ 21204-67-1 ]
[ 880271-23-8 ]

Yield	Reaction Conditions	Operation in experiment
	In toluene; for 18h;Heating / reflux;	Part 1: Methyl (4-benzyloxycarbonylaminocyclohexylidene)acetate (9): A solution of <strong>[16801-63-1]benzyl 4-oxocyclohexylcarbamate</strong> (1.24 g, 5.1 mmol) and methyl (triphenylphosphoranylidene)acetate (2.09 g, 6.3 mmol) in toluene (10 mL) was refluxed for 18 h. The solvent was removed in vacuo and the residue was purified by silica gel chromatography (1-5% MeOH in CH2Cl2) to afford methyl (4-benzyloxycarbonylaminocyclohexylidene)acetate. 1H NMR (CDCl3, 400 MHz): delta 1.28-1.41 (m, 2H), 2.05-2.30 (m, 5H), 3.60-3.64 (m, 1H), 3.09 (s, 3H), 3.76-3.82 (m, 1H), 4.62-4.68 (m, 1H), 5.10 (s, 2H), 5.65 (s, 1H), 7.31-7.37 (m, 5H). MS (ES+): m/z 304 [M+1].

Reference： [1]Patent: US2006/63791,2006,A1 .Location in patent: Page/Page column 14

49
[ 78775-11-8 ]
[ 21204-67-1 ]
[ 877064-90-9 ]

Yield	Reaction Conditions	Operation in experiment
	In toluene; at 90℃; for 1h;	2.1 g (6.45 mmol, 1.5 eq) of methyl triphenylphosphoranylideneacetate are added to a solution of 900 mg of <strong>[78775-11-8]4-bromo-3-methylbenzaldehyde</strong> in 5 ml of toluene. The reaction mixture is heated at 90°C for 1 hour. The solvent is evaporated off and the residual oil is chromatographed on silica gel (8/2 heptane/ethyl acetate). 610 mg of methyl (E)-3-(4-bromo-3-methylphenyl)acrylate are obtained in oil form. Yield = 55percent over steps a, b and c

Reference： [1]Patent: WO2006/18326,2006,A1 .Location in patent: Page/Page column 44

50
[ 21204-67-1 ]
[ 170384-29-9 ]
[ 911634-60-1 ]

Yield	Reaction Conditions	Operation in experiment
45%	With benzoic acid; In benzene; at 80℃; for 3h;	500 mg (2.88 mmol) of (2-oxo-propyl)-carbamic acid t-butyl ester obtained in the above step (2) was dissolved in 8 mL of benzene, and then 1.45 g (4.33 mmol) of methyl (triphenyl phosphoranilidene) acetate and 35 mg (0.28 mmol) of benzoic acid was added thereto. The reaction solution was heated to 80C for 3 hours. The solvent was distilled off under reduced pressure, then the residue was purified by column chromatography to give 54 mg (6.64 mmol) of the title compound in a yield of 23% and 301 mg (1.31 mmol) of the trans compound in a yield of 45%.[381] NMR: 1H-NMR(CDCl3) delta 5.77(1H, s), 5.17(1H, brs), 4.16(2H, d, J=6.4Hz),3.69(3H, s), 2.05(3H, s), 1.44(9H, s)[382] Mass(EI) 230(M++.)

Reference： [1]Patent: WO2006/104356,2006,A1 .Location in patent: Page/Page column 27-28

51
[ 75567-85-0 ]
[ 105-07-7 ]
[ 21204-67-1 ]
[ 83101-12-6 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; sodium chloride; In tetrahydrofuran; water;	REFERENCE EXAMPLE 79 STR116 A solution of 1M superhydride/tetrahydrofuran (3.3 ml) in anhydrous tetrahydrofuran (5 ml) was cooled to -50° to -60° C. under an argon gas stream. Thereto was added dropwise a solution of 210 mg of methyl 3-(4-cyanophenyl)propionate synthesised from 4-cyanobenzaldehyde and methyl (triphenylphosphoranylidene)acetate by the procedure of Reference Examples 69 and 76) in 2 ml of tetrahydrofuran. The resultant mixture was stirred at that temperature for 10 minutes, then made acidic by addition of water and 1N hydrochloric acid in that order at the same temperature, and extracted with ethyl acetate. The organic layer was washed with saturated aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 120 mg of 3-(4-cyanophenyl)propanol. NMR (CDCl3) delta: 1.61~2.20 (3H), 2.60~3.06 (2H), 3.68 (2H, t, J=6 Hz), 7.10~7.75 (4H)

Reference： [1]Patent: US4987132,1991,A

52
[ 24973-22-6 ]
[ 21204-67-1 ]
[ 940890-71-1 ]

Yield	Reaction Conditions	Operation in experiment
	In toluene; for 24h;Heating / reflux;Product distribution / selectivity;	A mixture of <strong>[24973-22-6]3-methoxy-4-methylbenzaldehyde</strong> (19.3 g, 0.129 mol), carbomethoxy methylene triphenylphosphorane (51 g) in toluene (250 ml) was refluxed for 24 h. The mixture was quenched with aqueous ammonium chloride and extracted with ethyl acetate and concentrated in vacuo to give a residue. The residue was purified by flash chromatography using ethyl acetate-heptane (1:1) to give 3-(3-methoxy-4-methylphenyl)acrylic acid methyl ester (27 g, 0.126 mol). A mixture of 3-(3-methoxy4-methylphenyl)acrylic acid methyl ester (27 g), sodium hydroxide (14 g), water (70 ml), methanol (140 ml) and tetrahydrofuran (70 ml) was refluxed at 50 C. for 1 h. The mixture was concentrated in vacuo and then water added. The mixture was filtered and 5 M HCl was added until precipitation occurred. The mixture was filtered and the solid precipitate washed with water and dried in-vacuo to give 3-(3-methoxy-4-methylphenyl)acrylic acid (23.5 g, 0.122 mol). Toluene (750 ml) and thionyl chloride (11 ml) were subsequently added to 3-(3-methoxy-4-methylphenyl)acrylic acid (20 g, 0.104 mol) at room temperature. The suspension was refluxed for 2 h while vigorously stirring to give a clear slightly yellow solution. The reaction mixture was concentrated in vacuo, then toluene added and the mixture re-concentrated in vacuo to give 3-(3-methoxy4-methylphenyl)acryloyl chloride for use in the next step. The 3-(3-methoxy4-methylphenyl)acryloyl chloride was dissolved in acetone (800 ml). The resulting solution was added slowly (15 min) at 0 C. to a mixture of sodium azide (13 g) in water (100 ml) and acetone (100 ml) while vigorously stirring and cooling with an ice-bath. After addition was complete the reaction mixture was stirred at 0 C. for 90 minutes while vigorously stirring. The reaction mixture was then poured out on ice-water (300 ml). After stirring for 15 minutes the mixture was filtered and the solid residue washed with excess water. The remaining solid residue was dissolved in dichloromethane (45 ml). The liberated water was removed with a separatory funnel. The dichloromethane layer was dried with Na2SO4 and filtered to give a dichloromethane solution of 3-(3-methoxy4-methylphenyl)acryloyl azide for immediate use in the next step. The dichloromethane azide solution was added in portions (Carefully .) using a dropping funnel to preheated diphenyl ether (50 ml) at 150 C., while gently stirring, in a three-necked roundbottomed flask, equiped with a Dean-Stark trap. During the addition nitrogen gas evolution takes place under formation of the isocyanate. The added dichloromethane is evaporated and collected with the Dean-Stark trap. After the addition was complete (30 min) and no gas evolution observed, the mixture was heated to reflux (250 C.) while stirring (at 200 C. no more dichloromethane is evaporated and the Dean-Stark trap is removed quickly). The reaction mixture is kept at 250 C. for 1 h then cooled to 125 C. and poured out in a mixture of acetone and heptane (1:10) . A solid precipitated and this was filtered and dried in vacuo to give 6-methoxy-7-methyl-2H-isoquinolin-1-one (12 g, 63.49 mmol). A suspension of 6-methoxy-7-methyl-2H-isoquinolin-1-one (5 g, 26.45 mmol) was treated at room temperature with phosphorus oxychloride (22 ml). The mixture was heated at 100 C. for 1 h with stirring then concentrated in vacuo to give a residue. Toluene was added to the residue which was further concentrated in-vacuo to give a residue which was taken up in toluene and slowly added to saturated aqueous sodium carbonate. The toluene layer was then separated. The aqueous layer was further mixed and extracted with toluene. The combined toluene layers were dried (MgSO4) and concentrated in vacuo to give a residue. The residue was triturated with diethyl ether then filtered and dried in vacuo to give 1-chloro-6-methoxy-7-methyl-isoquinoline (4 g, 19.32 mmol). A mixture of 1-chloro-6-methoxy-7-methyl-isoquinoline (9 g, 43.48 mol), phenol (16.3 g), potassium hydroxide (9.45 g) and xylene (100 ml) was refluxed for 4 days. The reaction mixture was poured out into aqueous sodium hydroxide (4 M) and the xylene layer separated. The aqueous layer was extracted twice with toluene. The combined organic layers were dried (Na2SO4) and concentrated in vacuo to give a residue. The residue was purified by flash chromatography using dichloromethane gave 6-methoxy-7-methyl-1-phenoxy-isoquinoline (9 g, 33.96 mmol). A mixture of the crude 6-methoxy-7-methyl-1-phenoxy-isoquinoline (9 g, 33.96 mmol) and ammonium acetate (26 g) was melted with stirring at 170 C. for 5 h. The mixture was partitioned between aqueous sodium hydroxide (2 M) and ethyl acetate. The phases were separated and the organic phase extracted with dilute aqueous hydrochloric acid. The acidic aqueous phase was neutralized to pH 12 using sodium hydroxide (2M), extracted with ethyl acetate, dried (MgSO4) then dried in vacuo to give 6-methoxy-7-methyl-isoquinolin-1-ylamine (5.11 g, 27.18 mmol). A mixtu...
	In toluene; for 24h;Heating / reflux;	Example 15 7-Methyl-6-(piperidin-3-yloxy)-isoquinolin-1-ylamine A[ 1-Amino-7-methyl-isoquinolin-6-ol hvdrobromideA mixture of <strong>[24973-22-6]3-methoxy-4-methylbenzaldehyde</strong> (19.3 g, 0.129 mol), carbometh- oxy methylene triphenylphosphorane (51 g) in toluene (250 ml) was refluxed for 24 h. The mixture was quenched with aqueous ammonium chloride and extracted with ethyl acetate and concentrated in vacuo to give a residue. The residue was purified by flash chromatography using ethyl acetate-heptane (1 :1 ) to give 3-(3-methoxy-4-methyl- phenyl)acrylic acid methyl ester (27 g, 0.126 mol). A mixture of 3-(3-methoxy-4- methylphenyl)acrylic acid methyl ester (27 g), sodium hydroxide (14 g), water (70 ml), methanol (140 ml) and tetrahydrofuran (70 ml) was refluxed at 50 C for 1 h. The mixture was concentrated in vacuo and then water added. The mixture was filtered and 5 M HCI was added until precipitation occurred. The mixture was filtered and the solid precipitate washed with water and dried in-vacuo to give 3-(3-methoxy-4-methylphenyl)acrylic acid (23.5g, 0.122 mol). Toluene (750 ml) and thionyl chloride (11 ml) were subsequently added to 3-(3-methoxy-4-methylphenyl)acrylic acid (20 g, 0.104 mol) at room temperature. The suspension was refluxed for 2 h while vigorously stirring to give a clear slightly yellow solution. The reaction mixture was concentrated in vacuo, then toluene added and the mixture re-concentrated in vacuo to give 3-(3-methoxy-4- methylphenyl)acryloyl chloride for use in the next step. The 3-(3-methoxy-4- methylphenyl)acryloyl chloride was dissolved in acetone (800 ml). The resulting solution was added slowly (15 min) at 0 C to a mixture of sodium azide (13 g) in water (100 ml) and acetone (100 ml) while vigorously stirring and cooling with an ice-bath. After addition was complete the reaction mixture was stirred at 0 C for 90 minutes while vigorously stirring. The reaction mixture was then poured out on ice-water (300ml). After stirring for 15 minutes the mixture was filtered and the solid residue washed with excess water. The remaining solid residue was dissolved in dichloromethane (45 ml). The liberated water was removed with a separatory funnel. The dichloromethane layer was dried with Na2SO4 and filtered to give a dichloromethane solution of 3-(3-methoxy-4-methyl- phenyl)acryloyl azide for immediate use in the next step. The dichloromethane azide solution was added in portions (Carefully !) using a dropping funnel to preheated diphenyl ether (50 ml) at 150 C, while gently stirring, in a three-necked roundbottomed flask, equiped with a Dean-Stark trap. During the addition nitrogen gas evolution takes place under formation of the isocyanate. The added dichloromethane is evaporated and collected with the Dean-Stark trap. After the addition was complete (~ 30 min) and no gas evolution observed, the mixture was heated to reflux (-250 C) while stirring (at -200 C no more dichloromethane is evaporated and the Dean-Stark trap is removed quickly). The reaction mixture is kept at -250 C for 1 h then cooled to 125 C and poured out in a mixture of acetone and heptane (1 :10) . A solid precipitated and this was filtered and dried in vacuo to give 6-methoxy-7-methyl-2/-/-isoquinolin-1-one (12 g, 63.49 mmol). A suspension of 6-methoxy-7-methyl-2/-/-isoquinolin-1-one (5 g, 26.45 mmol) was treated at room temperature with phosphorus oxychloride (22 ml). The mixture was heated at 100 C for 1 h with stirring then concentrated in vacuo to give a residue. Toluene was added to the residue which was further concentrated in-vacuo to give a residue which was taken up in toluene and slowly added to saturated aqueous sodium carbonate. The toluene layer was then separated. The aqueous layer was further mixed and extracted with toluene. The combined toluene layers were dried (MgSO4) and concentrated in vacuo to give a residue. The residue was triturated with diethyl ether then filtered and dried in vacuo to give 1-chloro-6-methoxy-7-methyl-isoquinoline (4 g, 19.32 mmol). A mixture of 1-chloro-6-methoxy-7-methyl-isoquinoline (9 g, 43.48 mol), phenol (16.3 g), potassium hydroxide (9.45 g) and xylene (100 ml) was refluxed for 4 days. The reaction mixture was poured out into aqueous sodium hydroxide (4 M) and the xylene layer separated. The aqueous layer was extracted twice with toluene. The combined organic layers were dried (Na2SO4) and concenntrated in vacuo to give a residue. The residue was purified by flash chromatography using dichloromethane gave 6-methoxy-7-methyl-1-phenoxy-isoquinoline (9 g, 33.96 mmol). A mixture of the crude 6- methoxy-7-methyl-1-phenoxy-isoquinoline (9 g, 33.96 mmol) and ammonium acetate (26 g) was melted with stirring at 170 C for 5 h. The mixture was partitioned between aqueous sodium hydroxide (2 M) and ethyl acetate. The phases were separated and the organic phase extracted with dilute aqueous hydrochloric acid. The acidic aqueous phase was neutralized to pH 12 using sodium hydroxide (2M), extracted with...
	In toluene; for 24h;Heating / reflux;	Example 26 (S)-7-Methyl-6-(piperidin-3-yloxy)-2/-/-isoquinolin-1-one 26A: 6-Hvdroxy-7-methyl-2/-/-isoquinolin-1-oneA mixture of <strong>[24973-22-6]3-methoxy-4-methylbenzaldehyde</strong> (19.3 g, 0.129 mol), carbo- methoxy methylene triphenylphosphorane (51 g) in toluene (250 ml) was refluxed for 24 h. The mixture was quenched with aqueous ammonium chloride and extracted with ethyl acetate and concentrated in vacuo to give a residue. The residue was purified by flash chromatography using ethyl acetate-heptane (1 :1 ) to give 3-(3-methoxy-4-methyl- phenyl)acrylic acid methyl ester (27 g, 0.126 mol). A mixture of 3-(3-methoxy-4-methyl- phenyl)acrylic acid methyl ester (27 g), sodium hydroxide (14 g), water (70 ml), methanol (140 ml) and tetrahydrofuran (70 ml) was refluxed at 50 C for 1 h. The mixture was concentrated in vacuo and then water added. The mixture was filtered and 5 M HCI was added until precipitation occurred. The mixture was filtered and the solid precipitate washed with water and dried in-vacuo to give 3-(3-methoxy-4-methylphenyl)acrylic acid (23.5g, 0.122 mol).Toluene (750 ml) and thionyl chloride (11 ml) were subsequently added to 3-(3- methoxy-4-methylphenyl)acrylic acid (20 g, 0.104 mol) at room temperature. The suspension was refluxed for 2 h while vigorously stirring to give a clear slightly yellow solution. The reaction mixture was concentrated in vacuo, then toluene added and the mixture re-concentrated in vacuo to give 3-(3-methoxy-4-methylphenyl)acryloyl chloride for use in the next step. The 3-(3-methoxy-4-methylphenyl)acryloyl chloride was dissolved in acetone(800 ml). The resulting solution was added slowly (15 min) at 0 C to a mixture of sodium azide (13 g) in water (100 ml) and acetone (100 ml) while vigorously stirring and cooling with an ice-bath. After addition was complete the reaction mixture was stirred at 0 C for 90 minutes while vigorously stirring. The reaction mixture was then poured out on ice- water (300ml). After stirring for 15 minutes the mixture was filtered and the solid residue washed with excess water. The remaining solid residue was dissolved in dichloro- methane (45 ml). The liberated water was removed with a separatory funnel. The di- chloromethane layer was dried with Na2SO4 and filtered to give a dichloromethane solution of 3-(3-methoxy-4-methylphenyl)acryloyl azide for immediate use in the next step.The dichloromethane azide solution was added in portions (Carefully !) using a dropping funnel to preheated diphenyl ether (50 ml) at 150 C, while gently stirring, in a three-necked roundbottomed flask, equiped with a Dean-Stark trap. During the addition nitrogen gas evolution takes place under formation of the isocyanate. The added dichloromethane is evaporated and collected with the Dean-Stark trap. After the addition was complete (~ 30 min) and no gas evolution observed, the mixture was heated to reflux (-250 C) while stirring (At -200 C no more dichloromethane is evaporated and the Dean-Stark trap is removed quickly). The reaction mixture is kept at -250 C for 1 h then cooled to 125 C and poured out in a mixture of acetone and heptane (1 :10) . A solid precipitated and this was filtered and dried in vacuo to give 6-methoxy-7-methyl- 2H-isoquinolin-1-one (12 g, 63.49 mmol).A 1 M solution of boron tribromide (2.9 ml, 2.91 mmol) was added dropwise to a stirred suspension of 6-methoxy-7-methyl-2/-/-isoquinolin-1-one (100 mg, 0.53 mmol) in 1 ml of dichloromethane at 0 - 4 C (ice bath). After stirring for 1 day at ambient temperature the reaction mixture was poured into ice and the pH was adjusted to 9 by adding concentrated aqueous ammonia. The precipitated material was collected by filtration, washed with water, and dried in vacuo to give 6-Hydroxy-7-methyl-2H- isoquinolin-1-one (51 mg, 55%), EI-MS: 176.6 [M+H]+

In toluene; for 24h;Heating / reflux;

A mixture of <strong>[24973-22-6]3-methoxy-4-methylbenzaldehyde</strong> (19.3 g, 0.129 mol), carbomethoxy methylene triphenylphosphorane (51 g) in toluene (250 ml) was refluxed for 24 h. The mixture was quenched with aqueous ammonium chloride and extracted with ethyl acetate and concentrated in vacuo to give a residue. The residue was purified by flash chromatography using ethyl acetate-heptane (1:1) to give 3-(3-methoxy-4-methyl-phenyl)acrylic acid methyl ester (27 g, 0.126 mol). A mixture of 3-(3-methoxy-4-methylphenyl)acrylic acid methyl ester (27 g), sodium hydroxide (14 g), water (70 ml), methanol (140 ml) and tetrahydrofuran (70 ml) was refluxed at 50 C. for 1 h. The mixture was concentrated in vacuo and then water added. The mixture was filtered and 5 M HCl was added until precipitation occurred. The mixture was filtered and the solid precipitate washed with water and dried in-vacuo to give 3-(3-methoxy-4-methylphenyl)acrylic acid (23.5 g, 0.122 mol).

Reference： [1]Patent: US2007/135479,2007,A1 .Location in patent: Page/Page column 10; 14
[2]Patent: WO2007/65916,2007,A1 .Location in patent: Page/Page column 22-24
[3]Patent: WO2007/65916,2007,A1 .Location in patent: Page/Page column 32-33
[4]Patent: US2008/45566,2008,A1 .Location in patent: Page/Page column 7

53
[ 5381-20-4 ]
[ 21204-67-1 ]
[ 477250-16-1 ]

Reference： [1]Journal of Organic Chemistry,2008,vol. 73,p. 8705 - 8710

54
[ 3453-33-6 ]
[ 21204-67-1 ]
[ 60533-02-0 ]

Yield	Reaction Conditions	Operation in experiment
	In toluene; at 120℃; for 18h;Heating / reflux;	To a solution of 6-methoxy-2-naphthaldehyde (3.72 g, 20.0 mmol) in toluene (40 mL) placed in a pressure vessel was added methyl(triphenylphosphoranylidene)acetate (6.7 g, 20 mmol). The resulting mixture was refluxed at 120 C. for 18 hours. The reaction mixture was concentrated in vacuo and purified using Biotage flash 40M column with 15% ethyl acetate-hexanes as the eluant.

Reference： [1]Patent: US2009/62269,2009,A1 .Location in patent: Page/Page column 37

55
[ 25016-02-8 ]
[ 21204-67-1 ]
[ 94006-37-8 ]

Yield	Reaction Conditions	Operation in experiment
	In dichloromethane; at 20℃;	Example A24; a) Preparation of intermediate 68; A mixture of <strong>[25016-02-8]2-methoxy-5-nitrobenzaldehyde</strong> (0.058 mol) in DCM (200 ml) was stirred at r.t.. 2-(triphenylphosphoranylidene)acetic acid, methyl ester (0.058 mol) was added <n="76"/>portionwise. The reaction mixture was stirred at r.L. More 2-(triphenylphosrhohoranylidene)acetic acid, methyl ester (6 g) was added and the reaction mixture was stirred overnight at r.t.. The solvent was evaporated. The residue was purified by column chromatography over silica gel (eluent: DCM/MeOH 99/1). The product fractions were collected and the solvent was evaporated. Yield: 9.7 g of intermediate 68.

Reference： [1]Patent: WO2009/16132,2009,A1 .Location in patent: Page/Page column 74-75

56
[ 504414-32-8 ]
[ 21204-67-1 ]
[ 1131871-60-7 ]

Yield	Reaction Conditions	Operation in experiment
	In tetrahydrofuran; for 16h;Heating / reflux;	Preparation 74: (_E)-3-(4-Benzyloxy-2-fTuorophenyl)acrylic acid methyl ester; <n="47"/>(Triphenyl-lambda5-phosphanylidene)acetic acid methyl ester (25.0 g, 74.8 mmol) was added to a solution of <strong>[504414-32-8]4-benzyloxy-2-fluorobenzaldehyde</strong> (9.10 g, 39.5 mmol) in THF (400 inL) and the resulting solution was stirred under reflux conditions for 16 h, before being absorbed onto silica and purified by column chromotogarphy (EtOAc-IH, 1:3) to afford the title compound: RT = 4.15 min; mlz (ES+) = 287.17 [M + H]+.
	In tetrahydrofuran; for 16h;Reflux;	Methyl (triphenylphosphoranylidene)acetate (25.Og, 74.8mmol) was added to a solution of <strong>[504414-32-8]4-benzyloxy-2-fluorobenzaldehyde</strong> (9.1Og, 39.5mmol) in THF (40OmL) and the resulting solution was stirred under reflux conditions for 16h, before being absorbed onto silica and purified by column chromotogarphy (IH: EtOAc, 3:1) to afford the title compound: RT = 4.15 min; m/z (ES+) = 287.2 [M + H]+.

Reference： [1]Patent: WO2009/34388,2009,A1 .Location in patent: Page/Page column 45-46
[2]Patent: WO2010/103333,2010,A1 .Location in patent: Page/Page column 52

57
[ 16744-81-3 ]
[ 21204-67-1 ]
[ 608881-04-5 ]

Yield	Reaction Conditions	Operation in experiment
71.6%	In dichloromethane; at 20℃; for 18.083h;	Methyl 3-(4-methoxypyridin-2-yl)prop-2-enoate, used as starting material was prepared as follows :- Methyl 2-triphenylphosphoranylideneacetate (11.34 g, 33.91 mmol, 1.5eq) was added portionwise to <strong>[16744-81-3]4-methoxypyridine-2-carbaldehyde</strong> (3.1g, 22.61 mmol, leq) in DCM (10OmL) at 2O0C over a period of 5 mins. The resulting solution was stirred at 20 0C for 18 h. The resulting mixture was evaporated to dryness and the crude product was purified by flash silica chromatography, elution gradient 20 to 50percent EtOAc in isohexane. Pure fractions were evaporated to dryness to afford methyl 3-(4-methoxypyridin-2-yl)prop-2- enoate (3.13 g, 16.18 mmol, 71.6 percent) as a white solid. <n="55"/>IH NMR (400.132 MHz, DMSO) delta 3.76 (3H, s), 3.88 (3H, s), 6.91 (IH, d), 7.00 (IH, m), 7.38 (IH, d), 7.63 (IH, d), 8.45 (IH, d). MS m/z 194 (MH+).

Reference： [1]Patent: WO2009/56886,2009,A1 .Location in patent: Page/Page column 53-54

58
[ 21204-67-1 ]
[ 147118-37-4 ]
[ 1024024-26-7 ]

Yield	Reaction Conditions	Operation in experiment
96.0%	In acetonitrile; at 20 - 81℃;	EXAMPLE 1; Preparation of 3-[4-(4-Fluorophenyl)-6-Isopropyl-2-(N-Methyl-N-Methylsulfonylamino)Pyrimidin-5-yl]-(2E)-PropenalStep I:Preparation of Methyl (2E)-3-[4-(4-Fluorophenyl)-6-Isopropyl-2-(N-Methyl-N-Methylsulfonylamino)Pyrimidin-5-yl] Propenoate4-(4-Fluorophenyl)-6-isopropyl-2-(N-methyl-N-methylsulfonylamino)pyrimidine-5-ylcarboxaldehyde (5 g) was dissolved in acetonitrile (25 ml) and to the resulting solution Methyl (triphenylphosphoranylidene)acetate (5.23 g) was added at room temperature. The reaction mixture was stirred at 80-81 C. for 8 h for completion. Thereafter, acetonitrile was distilled off under reduced pressure to give crude mass, which was crystallized from isopropyl alcohol to yield pure methyl (2E)-3-[4-(4-fluorophenyl)-6-isopropyl-2-(N-methyl-N-methylsulfonylamino)pyrimidin-5-yl]propenoate.Yield: 5.4 g (96.0%)1H NMR (300 MHz) in CDCl3; delta(ppm): 1.32 (d, J=6 Hz, 6H), 3.34-3.43 (m, 1H), 3.52 (s, 3H), 3.59 (s, 3H), 3.77 (s, 3H), 5.86 (d, J=15 Hz, 1H), 7.10-7.27 (n, 2H), 7.58-7.63 (m, 2H), 7.74 (d, J=15 Hz, 1H)

Reference： [1]Patent: US2010/48899,2010,A1 .Location in patent: Page/Page column 11

59
[ 816-39-7 ]
[ 21204-67-1 ]
[ 50428-87-0 ]

Yield	Reaction Conditions	Operation in experiment
	In tetrahydrofuran; for 4.5h;Reflux;	Compound 252a:[307] The mixture of 1,3-dibromoaceton (0.863 g, purity 75%, 3.0 mmol) and methyl (triphenylphosphoranylidene)acetate (1.505 g, 4.5 mmol) in anhydrous THF (15 mL) was heated to reflux for 4.5 hours. The solution was cooled to room temperature and evaporated. The residue was purified by silica gel chromatography (hexanes/ethyl acetate) to give compound 252a as colorless liquid (485 mg, yield = 60%). 1H NMR (400 MHz, CDCl3): delta 6.06 (s, IH), 4.76 (s, 2H), 4.19 (s, 2H), 3.79 (s, 3H); 13C NMR (400 MHz, CDCl3): delta 165.1, 150.4, 121.3, 51.8, 33.6, 25.5

Reference： [1]Patent: WO2010/91150,2010,A1 .Location in patent: Page/Page column 181

60
[ 54221-96-4 ]
[ 21204-67-1 ]
(E)-methyl 3-(6-methoxypyridin-2-yl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	In toluene; at 60℃;	EXAMPLE 26; S-C-Methoxypyridin^-yO-N'-CCS-methylquinolin-- yl)methylene)propanehydrazide; [0547] (a) (E)-Methyl 3-(6-methoxypyridin-2-yl)acrylate: To a stirred solution of <strong>[54221-96-4]6-methoxypyridine-2-carboxaldehyde</strong> (0.35 mL, 2.9 mmol) in toluene was added methyl (triphenylphosphoranylidene) acetate (1.95 g, 5.8 mmol) and the reaction was heated at 60 0C overnight. The reaction was diluted with EtOAc and washed with water, brine and dried (Na2SO4). Purification on silica gel using EtOAc-hexane (0 to 30percent) provided 530 mg (94percent) of the desired product.

Reference： [1]Patent: WO2010/132615,2010,A1 .Location in patent: Page/Page column 121

61
[ 4771-50-0 ]
[ 21204-67-1 ]
[ 156355-80-5 ]

Yield	Reaction Conditions	Operation in experiment
94%	In 1,4-dioxane; toluene; at 85℃;	EXAMPLE 48; N'-(3,4-Dimethoxybenzylidene)-3-(l,7-dimethyl-lH-indol-3- yl)propanehydrazide; [0593] (a) (E)-Methyl 3-(7-methyl-lH-indol-3-yl)acrylate: To a stirred suspension of <strong>[4771-50-0]7-methylindole-3-carboxaldehyde</strong> (796 mg, 5 mmol) in toluene (15 mL) and 1,4-dioxane (15 mL) was added methyl (triphenylphosphoranylidene)acetate (1.84 g, 5.5 mmol). The reaction mixture was heated to 85 0C and became homogeneous after 30 min. After 6.5 hours, LCMS indicated that some starting material was still present. An additional 900 mg of the ylide was added and the reaction mixture was maintained at 85 0C overnight. The reaction mixture was cooled and the solvent was evaporated. Purification on silica gel using EtOAc -hexane (0 to 40%) provided a pale yellow solid (1.02 g, 94%).

Reference： [1]Patent: WO2010/132615,2010,A1 .Location in patent: Page/Page column 135

62
[ 7035-09-8 ]
[ 21204-67-1 ]
[ 223778-67-4 ]

Reference： [1]Chemical Communications,2011,vol. 47,p. 2679 - 2681

63
[ 1196155-68-6 ]
[ 21204-67-1 ]
[ 1309365-79-4 ]

Yield	Reaction Conditions	Operation in experiment
	In tetrahydrofuran; at 50℃; for 0.666667h;	Step 2; 6-Bromoquinoline-3-carbaldehyde 2 (2.8 g, 12.0 mmol) and methyl(triphenylphosphoranylidene) acetate (4.0 g, 12.0 mmol) were dissolved in dry THF (50 mL) and heated to 50 C. After 40 min the solution was evaporated to dryness under reduced pressure. Purification using silica chromatography (hexane to 60% ethyl acetate in hexane gradient) gave methyl 3-(6-bromoquinolin-3-yl)acrylate 3 as a mixture of E and Z isomers.

Reference： [1]Patent: WO2011/63233,2011,A1 .Location in patent: Page/Page column 32

64
[ 21204-67-1 ]
[ 121660-37-5 ]
[ 1403338-19-1 ]

Yield	Reaction Conditions	Operation in experiment
97%	In isopropyl alcohol; at 25 - 82℃;	EXAMPLE 1PREPARATION OF METHYL (2£ 3-[2-CYCLOPROPYL-4-(4- FLUOROPHENYL)QUINOLIN-3YLJACRYLATEMixture of 2-Cyclopropyl-4-(4-fluorophenyl)quinoline-3-carboxaldehyde (50 g, 0.171 mole) and methyl(triphenylphosphoranylidene)acetate (68.86 g, 0.205 mole) was suspended in isopropyl alcohol (250 ml) at 25-30C. The contents were heated to 78- 82C during which a clear solution was obtained. The completion of the reaction was confirmed by TLC. After completion of the reaction, the temperature was subsequently lowered to 25-30C during which product was precipitated out. The product was cooled to 0-5C, filtered, washed with precooled isopropyl alcohol and dried at 40-45C under reduced pressure (-20 mm Hg) till water content is < 0.3%. Yield: 58.0 g (97%).1H NMR (CDCb, 300 MHz): delta 1.06-1.09 (m, 2H), 1.38-1.40 (m, 2H), 2.37-2.39 (m, 1H), 3.73 (s, 3H), 6.04 (d, J = 16.2 Hz, 1H), 7.19-7.25 (m, 4H), 7.33-7.36 (m,2H), 7.63-7.66 (m, lH), 7.78 (d, J = 16.2 Hz, 1H), 7.96 (d, J = 8.7 Hz, 1H).

Reference： [1]Patent: WO2012/140490,2012,A2 .Location in patent: Page/Page column 18

65
[ 24019-66-7 ]
[ 21204-67-1 ]
[ 1416708-66-1 ]

Reference： [1]Beilstein Journal of Organic Chemistry,2012,vol. 8,p. 1630 - 1636,7

66
[ 57476-50-3 ]
[ 21204-67-1 ]
[ 1414703-94-8 ]

Reference： [1]European Journal of Medicinal Chemistry,2012,vol. 56,p. 225 - 236

67
[ 265108-36-9 ]
[ 21204-67-1 ]
[ 1430091-59-0 ]

Yield	Reaction Conditions	Operation in experiment
83%	In tetrahydrofuran; at 20℃; for 6h;	Methyl(triphenylphosphoranylidene)acetate (8.827 g, 26 mmol, 1.1 eq) is added at room temperature to a solution of <strong>[265108-36-9]4,4-difluorocyclohexanecarbaldehyde</strong> (3.55 g, 24 mmol, 1 eq) in dry THF (60 ml). The mixture is stirred for 6 h and the solvent is evaporated. Hexane (50 ml) is added to the crude, the mixture is put a few minutes in an ultrasonic bath, stirred for 1 h and filtered. The filtrate is concentrated under reduced pressure to afford 4.05 g of methyl 3-(4,4-difluorocyclohexyl)prop-2-enoate a1 -16.Yield: 83 %.H NMR (400 MHz, CDCI3) delta 6.91 (m, 1 H), 5.85 (m, 1 H), 3.75 (m, 3 H), 2.29 (m, 1 H), 2.12 (m, 3 H), 1 .80 (m, 5 H), 1 .56 (t, 2 H, J = 12.5 Hz).

Reference： [1]Patent: WO2013/53725,2013,A1 .Location in patent: Page/Page column 37-38

68
[ 138229-59-1 ]
[ 21204-67-1 ]
[ 1586740-45-5 ]

Yield	Reaction Conditions	Operation in experiment
90%		General procedure: A mixture of dimethylbromosulfoniumbromide (50 mmol) and methyl(triphenylphosphoranylidene) acetate (30 mmol) in CH2Cl2(30 mL) was stirred at r.t. under N2 atmosphere for 1 h. Then, itwas cooled to -78 C.Aldehyde (20 mmol) and NEt3 (160 mmol) were added dropwise. Thereaction mixture was slowly warmed to r.t. over 2 h and continued to stir at r.t.overnight. The resulting mixture was diluted with CH2Cl2 (50mL), and washed with saturatedaqueous Na2SO3. The organic layer was separated, dried over Na2SO4and then concentrated under vacuum. The residue was purified by flashchromatography on silica gel eluted with petroleum/CH2Cl2 to provide 2-bromoacrylates

Reference： [1]Tetrahedron Letters,2014,vol. 55,p. 2056 - 2060

69
[ 90178-78-2 ]
[ 21204-67-1 ]
[ 1586740-50-2 ]

Yield	Reaction Conditions	Operation in experiment
42%		General procedure: A mixture of dimethylbromosulfoniumbromide (50 mmol) and methyl(triphenylphosphoranylidene) acetate (30 mmol) in CH2Cl2(30 mL) was stirred at r.t. under N2 atmosphere for 1 h. Then, itwas cooled to -78 °C.Aldehyde (20 mmol) and NEt3 (160 mmol) were added dropwise. Thereaction mixture was slowly warmed to r.t. over 2 h and continued to stir at r.t.overnight. The resulting mixture was diluted with CH2Cl2 (50mL), and washed with saturatedaqueous Na2SO3. The organic layer was separated, dried over Na2SO4and then concentrated under vacuum. The residue was purified by flashchromatography on silica gel eluted with petroleum/CH2Cl2 to provide 2-bromoacrylates

Reference： [1]Tetrahedron Letters,2014,vol. 55,p. 2056 - 2060

70
[ 33538-83-9 ]
[ 21204-67-1 ]
[ 1616795-49-3 ]

Reference： [1]Bioorganic and Medicinal Chemistry,2014,vol. 22,p. 2771 - 2782

71
[ 21204-67-1 ]
[ 99970-84-0 ]
[ 845307-47-3 ]

Reference： [1]Monatshefte fur Chemie,2014,vol. 145,p. 1101 - 1108

72
[ 21204-67-1 ]
[ 262450-65-7 ]
C₁₁H₁₁BrO₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	In toluene;Reflux;	Example 1 5B: 3 -(E)-methyl 3 -(bromo-5-methoxyphenyl)acrylate j00296j Example 15A (0.48 g, 2.232 mmol) was dissolved in toluene (26.6 mL). Methyl (triphenylphosphoranylidine)acetate (0.746 g, 2.232 mmol) was added, and the reaction heated to reflux overnight. The reaction was cooled to ambient temperature andconcentrated in vacuo. The crude material was purified by silica gel column chromatography (gradient from 0 to 100% EtOAc in hexanes) to yield Example 15B (0.580 g, 2.14 mmol, 96% yield). MS (ESI) m/z: 271/273 (M+H). ?HNMR(400 MHz, CHLOROFORM-cl) oe ppm 7.56 (1 H, d, J=16.06 Hz), 7.26 (1 H, s), 7.07 (1 H, s), 6.95 (1 H, s), 6.41 (1 H, d, J=16.06 Hz), 3.82 (3 H, s), 3.81 (3 H, s).

Reference： [1]Patent: WO2014/201073,2014,A1 .Location in patent: Paragraph 00296

73
[ 201230-82-2 ]
[ 21204-67-1 ]
[ 175278-00-9 ]
methyl-3-oxo-3-(2-(trifluoromethoxy)phenyl)-2-(triphenylphosphoranylidene)propanoate [ No CAS ]

Reference： [1]Organic Letters,2016,vol. 18,p. 4824 - 4827

74
[ 201230-82-2 ]
[ 64248-58-4 ]
[ 21204-67-1 ]
methyl 3-(3,4-difluorophenyl)-3-oxo-2-(triphenylphosphoranylidene)propanoate [ No CAS ]

Reference： [1]Organic Letters,2016,vol. 18,p. 4824 - 4827

75
[ 3453-33-6 ]
[ 21204-67-1 ]
3-(6-methoxynaphthalen-2-yl)propan-1-ol [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2017,vol. 139,p. 1191 - 1197

76
[ 22929-52-8 ]
[ 21204-67-1 ]
methyl (2E)-2-tetrahydrofuran-3-ylideneacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In toluene; at 100 - 110℃; for 16h;Inert atmosphere;	A solution of methyl 2-(triphenyl-lambda5-phosphanylidene)acetate (3.89 g, 11.62 mmol) and <strong>[22929-52-8]tetrahydrofuran-3-one</strong> (1.00 g, 11.62 mmol) in toluene (10.0 mL) was stirred at 100-110 °C for 16 hrs under nitrogen. On completion, the mixture was concentrated to remove the solvent, the residue was diluted with ethyl acetate (30 mL) and filtered, and the filtrate was concentrated to get the crude product. The crude product was purified by column chromatography (petroleum ether:ethyl acetate = 30:1 to 10:1) to yield the title compound. 1H NMR (400MHz, CDCl3) delta = 5.98 - 5.84 (m, 1 H), 4.72 (s, 2 H), 3.88 (t, J = 6.90 Hz, 2 H), 3.70 (s, 3 H), 2.76 - 2.67 (m, 2 H).

Reference： [1]Patent: WO2017/156177,2017,A1 .Location in patent: Paragraph 00327

77
[ 57476-50-3 ]
[ 21204-67-1 ]
(E)-tert-butyl 3-(3-methoxy-3-oxoprop-1-en-1-yl)-1H-indole-1-carboxylate [ No CAS ]

Reference： [1]Organic Letters,2017,vol. 19,p. 6236 - 6239

78
[ 21204-67-1 ]
[ 262450-65-7 ]
methyl (E)-3-(3-bromo-5-methoxyphenyl)acrylate [ No CAS ]

Reference： [1]ACS Medicinal Chemistry Letters,2017,vol. 8,p. 67 - 72

79
[ 111851-98-0 ]
[ 21204-67-1 ]
(E)-methyl 3-(1-ethyl-1H-imidazol-2-yl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
39%	In dichloromethane; at 20℃; for 16h;	(Reference Example 23) Synthesis of (E)-methyl 3-(1-ethyl-1H-imidazol-2-yl)acrylate: Methyl (triphenylphosphoranylidene)acetate (3.15 g, 9.42 mmol) was added to a solution of <strong>[111851-98-0]1-ethyl-1H-imidazole-2-carbaldehyde</strong> (1.17 g, 9.42 mmol) in dichloromethane (28.3 mL) at room temperature. The reaction liquid was stirred for 16 hours and concentrated under reduced pressure. The residue was washed with a mixed solvent of hexane/dichloromethane = 20/1 and the washing solution was concentrated. The residue was purified by flash column chromatography (silica gel, hexane/ethyl acetate) to obtain (E)-methyl 3-(1-ethyl-1H-imidazol-2-yl)acrylate (0.670 g, 3.72 mmol, 39percent) as a white solid. 1H-NMR (400 MHz, CDCl3) delta: 1.45 (3H, t, J=7.6 Hz), 3.81(3H, s), 4.10 (2H, dd, J=7.6, 14.8 Hz), 6.85 (1H, d, J=15.2 Hz), 7.03 (1H, brs), 7.17 (1H, brs), 7.52 (1H, d, J=15.2 Hz). ESI-MS: m/z= 181 (M+H)+.

Reference： [1]Patent: EP3263565,2018,A1 .Location in patent: Paragraph 0443; 0444

80
[ 1181816-12-5 ]
[ 21204-67-1 ]
tert-butyl 6-(2-methoxy-2-oxoethylidene)-2-azaspiro[3.3]heptane-2-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1.9 g	In toluene; at 20℃; for 19h;Inert atmosphere; Reflux;	To a stirred of 6-Oxo-2-aza-spiro[3.3]heptane-2-carboxylic acid tert-butyl ester (2.00 g; 9.47 mmol; 1.0 eq.) in toluene (30 mL), were added methyl (triphenylphosphoranylidene)acetate (3.48 g; 10.41 mmol; 1.1 eq). The resulting suspension was stirred for 3 hours at reflux and left to stir over 16 hours at room temperature. The suspension was filtered and the solid washed with MTBE (2 X 10 mL). The filtrate was concentratted to dryness and purified by flash chromatography (silica gel, EtOAc-heptane 10/90) to afford (1.9 g) tert-butyl 6-(2-methoxy-2-oxoethylidene)-2-azaspiro[3.3]heptane-2-carboxylateas a colourless oil.MS(ES+) m/z 168(M-Boc+H+).

Reference： [1]Bioorganic and Medicinal Chemistry,2018,vol. 26,p. 945 - 956

81
[ 6429-44-3 ]
[ 21204-67-1 ]
methyl (E,4S)-4-(((benzyloxy)carbonyl)amino)pent-2-enoate [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2017,vol. 82,p. 1046 - 1052

82
[ 2058-72-2 ]
[ 21204-67-1 ]
C₁₂H₁₀BrNO₃ [ No CAS ]