Name: 5293-84-5|(chloromethyl)triphenylphosphoniumchloride|98%
Brand: Ambeed
SKU: A178128
Rating: 94 (25 reviews)

1
[ 5293-83-4 ]
[ 5293-84-5 ]

Reference： [1]Chemische Berichte,1961,vol. 94,p. 1373 - 1383
[2]Justus Liebigs Annalen der Chemie,1962,vol. 659,p. 49 - 63
[3]Journal of the Chemical Society. Perkin Transactions 1 (2001),2002,p. 2260 - 2267

2
[ 6640-25-1 ]
[ 5293-84-5 ]
1-Chloro-4-((Z)-2-chloro-1-cyclopropyl-vinyl)-benzene [ No CAS ]
1-Chloro-4-((E)-2-chloro-1-cyclopropyl-vinyl)-benzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1: 21 % Spectr. 2: 71 % Spectr.	With piperidine; n-butyllithium In diethyl ether; hexane 1.) room temp., 4 h, 2.) room temp., overnight; Title compound not separated from byproducts;
1: 71 % Spectr. 2: 29 % Spectr.	With piperidine; n-butyllithium In diethyl ether; hexane 1.) room temp., 4 h, 2.) room temp., overnight; Title compound not separated from byproducts;

Reference： [1]Takeuchi, Ken'ichi; Kitagawa, Toshikazu; Miyabo, Atsushi; Hori, Hideshi; Komatsu, Koichi [Journal of Organic Chemistry, 1993, vol. 58, # 21, p. 5802 - 5810]
[2]Takeuchi, Ken'ichi; Kitagawa, Toshikazu; Miyabo, Atsushi; Hori, Hideshi; Komatsu, Koichi [Journal of Organic Chemistry, 1993, vol. 58, # 21, p. 5802 - 5810]

3
[ 116194-47-9 ]
[ 5293-84-5 ]
2-[(3S,5R,9R,10R,13R,14S,17R)-14-((E)-3-Chloro-allyl)-17-((R)-1,5-dimethyl-hexyl)-4,4,10,13-tetramethyl-2,3,4,5,6,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxy]-tetrahydro-pyran [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With n-butyllithium In tetrahydrofuran for 2h; Heating;

Reference： [1]Frye, Leah L.; Robinson, Cecil H. [Journal of Organic Chemistry, 1990, vol. 55, # 5, p. 1579 - 1584]

4
[ 5293-84-5 ]
[ 75858-28-5 ]
[ 135346-65-5 ]

Yield	Reaction Conditions	Operation in experiment
87%	With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In tetrahydrofuran at 20℃;

Reference： [1]Rochigneux; Fontanel; Malanda; Doutheau [Tetrahedron Letters, 1991, vol. 32, # 18, p. 2017 - 2020]

5
[ 5293-84-5 ]
[ 105378-35-6 ]
[(Z)-1-((E)-2-Chloro-vinyl)-propenylselanyl]-benzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With n-butyllithium In tetrahydrofuran 1.) -30 deg C, 1 h, 2.) 20 deg C, 6 h;

Reference： [1]Lerouge, Patrice; Paulmier, Claude [Tetrahedron Letters, 1984, vol. 25, # 19, p. 1987 - 1990]

6
[ 5293-84-5 ]
[ 105378-35-6 ]
[ 105378-42-5 ]

Yield	Reaction Conditions	Operation in experiment
82%	With n-butyllithium In tetrahydrofuran at -30℃; for 1h;

Reference： [1]Lerouge, Patrice; Paulmier, Claude [Bulletin de la Societe Chimique de France, 1985, # 6, p. 1225 - 1229]

7
[ 5293-84-5 ]
[ 91890-50-5 ]
C₁₆H₁₃ClSe [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With n-butyllithium In tetrahydrofuran 1.) -30 deg C, 1 h, 2.) 20 deg C, 6 h;

Reference： [1]Lerouge, Patrice; Paulmier, Claude [Tetrahedron Letters, 1984, vol. 25, # 19, p. 1987 - 1990]

8
[ 5293-84-5 ]
[ 91890-50-5 ]
[ 105378-43-6 ]

Yield	Reaction Conditions	Operation in experiment
80%	With n-butyllithium In tetrahydrofuran at -30℃; for 1h;

Reference： [1]Lerouge, Patrice; Paulmier, Claude [Bulletin de la Societe Chimique de France, 1985, # 6, p. 1225 - 1229]

9
[ 5293-84-5 ]
(2S,3S)-3-[4-(tert-Butyl-dimethyl-silanyloxy)-butyl]-oxirane-2-carbaldehyde [ No CAS ]
tert-Butyl-{4-[(2S,3R)-3-((Z)-2-chloro-vinyl)-oxiranyl]-butoxy}-dimethyl-silane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
71%	With sodium hexamethyldisilazane In tetrahydrofuran at 0℃; for 2h;

Reference： [1]Nicolaou, K. C.; Prasad, C. V. C.; Somers, P. K.; Hwang, C.-K. [Journal of the American Chemical Society, 1989, vol. 111, p. 5335 - 5340]

10
[ 5293-84-5 ]
(2S,3S)-3-[4-(tert-Butyl-dimethyl-silanyloxy)-butyl]-oxirane-2-carbaldehyde [ No CAS ]
tert-Butyl-{4-[(2S,3R)-3-((E)-2-chloro-vinyl)-oxiranyl]-butoxy}-dimethyl-silane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
71%	With sodium hexamethyldisilazane In tetrahydrofuran at 0℃; for 2h;

Reference： [1]Nicolaou, K. C.; Prasad, C. V. C.; Somers, P. K.; Hwang, C.-K. [Journal of the American Chemical Society, 1989, vol. 111, p. 5335 - 5340]

11
[ 5293-84-5 ]
(2R,3S)-3-[4-(tert-Butyl-dimethyl-silanyloxy)-butyl]-oxirane-2-carbaldehyde [ No CAS ]
tert-Butyl-{4-[(2S,3S)-3-((Z)-2-chloro-vinyl)-oxiranyl]-butoxy}-dimethyl-silane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With sodium hexamethyldisilazane In tetrahydrofuran at 0℃; for 2h;

Reference： [1]Nicolaou, K. C.; Prasad, C. V. C.; Somers, P. K.; Hwang, C.-K. [Journal of the American Chemical Society, 1989, vol. 111, p. 5335 - 5340]

12
[ 5293-84-5 ]
(2R,3S)-3-[4-(tert-Butyl-dimethyl-silanyloxy)-butyl]-oxirane-2-carbaldehyde [ No CAS ]
tert-Butyl-{4-[(2S,3S)-3-((E)-2-chloro-vinyl)-oxiranyl]-butoxy}-dimethyl-silane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With sodium hexamethyldisilazane In tetrahydrofuran at 0℃; for 2h;

Reference： [1]Nicolaou, K. C.; Prasad, C. V. C.; Somers, P. K.; Hwang, C.-K. [Journal of the American Chemical Society, 1989, vol. 111, p. 5335 - 5340]

13
[ 5293-84-5 ]
[ 150668-37-4 ]
(Z)-β-Chloro-α-cyclopropyl-m-methylstyrene [ No CAS ]
(E)-β-Chloro-α-cyclopropyl-m-methylstyrene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1: 37 % Spectr. 2: 63 % Spectr.	With piperidine; n-butyllithium In diethyl ether; hexane 1.) room temp., 4 h, 2.) room temp., overnight; Title compound not separated from byproducts;

Reference： [1]Takeuchi, Ken'ichi; Kitagawa, Toshikazu; Miyabo, Atsushi; Hori, Hideshi; Komatsu, Koichi [Journal of Organic Chemistry, 1993, vol. 58, # 21, p. 5802 - 5810]

14
[ 5293-84-5 ]
[ 29949-92-6 ]

Yield	Reaction Conditions	Operation in experiment
	With piperidine; n-butyllithium In diethyl ether; pentane at 20℃; for 1.5h;
	deprotonation;
	With sodium hexamethyldisilazane In tetrahydrofuran

	With n-butyllithium In hexane
	With phenyllithium In diethyl ether; cyclohexane at 20℃; for 1h;

Reference： [1]Zefirov, N. S.; Averina, N. V.; Boganov, A. M.; Laryukova, M. V.; Rashchupkina, Z. A.; et al. [Journal of Organic Chemistry USSR (English Translation), 1981, p. 1291 - 1300][Zhurnal Organicheskoi Khimii, 1981, vol. 17, # 7, p. 1450 - 1462]
[2]Roth, Heinz D.; Abelt, Christopher J. [Journal of the American Chemical Society, 1986, vol. 108, # 8, p. 2013 - 2019]
[3]Taber, Douglass F.; Meagley, Robert P.; Doren, Douglas J. [Journal of Organic Chemistry, 1996, vol. 61, # 17, p. 5723 - 5728]
[4]Sheng, Shou-Ri; Wu, Lu-Ling; Huang, Xian [Journal of Chemical Research - Part S, 2003, # 5, p. 258 - 259]
[5]Ishibashi; Kobayashi; Nakashima; Tamura [Journal of Organic Chemistry, 2000, vol. 65, # 26, p. 9022 - 9027]

15
[ 5293-84-5 ]
[ 21204-67-1 ]
tert-Butyl-{3-[(2S,3R)-3-((Z)-2-chloro-vinyl)-oxiranyl]-propoxy}-dimethyl-silane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With sodium hexamethyldisilazane In tetrahydrofuran at 0℃; for 2h;

Reference： [1]Nicolaou, K. C.; Prasad, C. V. C.; Somers, P. K.; Hwang, C.-K. [Journal of the American Chemical Society, 1989, vol. 111, p. 5330 - 5334]

16
[ 5293-84-5 ]
[ 21204-67-1 ]
tert-Butyl-{3-[(2S,3R)-3-((E)-2-chloro-vinyl)-oxiranyl]-propoxy}-dimethyl-silane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With sodium hexamethyldisilazane In tetrahydrofuran at 0℃; for 2h;

Reference： [1]Nicolaou, K. C.; Prasad, C. V. C.; Somers, P. K.; Hwang, C.-K. [Journal of the American Chemical Society, 1989, vol. 111, p. 5330 - 5334]

17
[ 5293-84-5 ]
[ 171866-87-8 ]
(4S,5S)-4-Benzyloxymethyl-5-((E)-4-chloro-1,1,3-trimethyl-but-3-enyl)-2,2-dimethyl-[1,3]dioxolane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane 1.) 0 deg C, 45 min, 2.) -78 deg C, 10 min, 3.) -78 deg to room temperature, 18 h;

Reference： [1]Taber, Douglass F.; Sahli, Ayman; Yu, Han; Meagley, Robert P. [Journal of Organic Chemistry, 1995, vol. 60, # 20, p. 6571 - 6573]

19
[ 5293-84-5 ]
[ 369376-68-1 ]
[ 369376-66-9 ]

Yield	Reaction Conditions	Operation in experiment
76%	Stage #1: chloromethyltriphenylphosphonium chloride With potassium <i>tert</i>-butylate In tetrahydrofuran at -78℃; for 1h; Stage #2: benzo[b]oxepin-3(2H)-one In tetrahydrofuran at -78℃; for 0.666667h;

Reference： [1]Kahnberg, Pia; Sterner, Olov [Tetrahedron, 2001, vol. 57, # 33, p. 7181 - 7184]

20
[ 5293-84-5 ]
[ 381220-95-7 ]
7-Bromo-3-[1-chloro-meth-(Z)-ylidene]-2,3-dihydro-benzo[b]oxepine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%	With n-butyllithium In tetrahydrofuran at 20℃;

Reference： [1]Huang, Sheng-Tung; Kuo, Hsien-Shou; Chen, Chien-Tsu [Tetrahedron Letters, 2001, vol. 42, # 42, p. 7473 - 7475]

21
[ 5293-84-5 ]
[ 439859-70-8 ]
tert-Butyl-[(1R,3S,6S)-6-((E)-2-chloro-vinyl)-1,5,5-trimethyl-7-oxa-bicyclo[4.1.0]hept-3-yloxy]-dimethyl-silane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: chloromethyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran Stage #2: (-)-(1S,4S,6R)-4-(tert-butyldimethylsilyloxy)-2,2,6-trimethyl-7-oxabicyclo[4.1.0]heptane-1-carbaldehyde In tetrahydrofuran at -30℃; for 3h;
	With n-butyllithium In tetrahydrofuran at -30℃; for 3h;
	Stage #1: chloromethyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Stage #2: (-)-(1S,4S,6R)-4-(tert-butyldimethylsilyloxy)-2,2,6-trimethyl-7-oxabicyclo[4.1.0]heptane-1-carbaldehyde In tetrahydrofuran; hexane at -30℃; for 3h;

Reference： [1]Furuichi, Noriyuki; Hara, Hirokazu; Osaki, Takashi; Mori, Hajime; Katsumura, Shigeo [Angewandte Chemie - International Edition in English, 2002, vol. 41, # 6, p. 1023 - 1026]
[2]Kuba, Masako; Furuichi, Noriyuki; Katsumura, Shigeo [Chemistry Letters, 2002, # 12, p. 1248 - 1249]
[3]Furuichi, Noriyuki; Hara, Hirokazu; Osaki, Takashi; Nakano, Masayuki; Mori, Hajime; Katsumura, Shigeo [Journal of Organic Chemistry, 2004, vol. 69, # 23, p. 7949 - 7959]

22
[ 5293-84-5 ]
[ 530087-10-6 ]
[ 530087-11-7 ]

Yield	Reaction Conditions	Operation in experiment
86%	With n-butyllithium In tetrahydrofuran at 0℃; for 1h;

Reference： [1]Lin, Yuh-Lin; Kuo, Hsien-Shou; Wang, Yi-Wen; Huang, Sheng-Tung [Tetrahedron, 2003, vol. 59, # 8, p. 1277 - 1281]

23
[ 10521-91-2 ]
[ 5293-84-5 ]
((Z)-6-Chloro-hex-5-enyl)-benzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	Stage #1: 5-phenylpentan-1-ol With N-methyl-2-indolinone; tetrapropylammonium perruthennate; 4 Angstroem MS In dichloromethane Stage #2: chloromethyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran; hexane; dichloromethane at -78 - 20℃;

Reference： [1]MacCoss, Rachel N.; Balskus, Emily P.; Ley, Steven V. [Tetrahedron Letters, 2003, vol. 44, # 42, p. 7779 - 7781]

24
[ 4780-79-4 ]
[ 5293-84-5 ]
1-((Z)-2-Chloro-vinyl)-naphthalene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	Stage #1: 1-naphthalene methanol With N-methyl-2-indolinone; tetrapropylammonium perruthennate; 4 Angstroem MS In dichloromethane Stage #2: chloromethyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran; hexane; dichloromethane at -78 - 20℃;

Reference： [1]MacCoss, Rachel N.; Balskus, Emily P.; Ley, Steven V. [Tetrahedron Letters, 2003, vol. 44, # 42, p. 7779 - 7781]

25
[ 5293-84-5 ]
2,7,9,12,13,16-hexamethoxy-phenanthro[3,4-c]phenanthrene-11-carbaldehyde [ No CAS ]
11-ethynyl-2,7,9,12,13,16-hexamethoxy-phenanthro[3,4-c]phenanthrene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%	Stage #1: chloromethyltriphenylphosphonium chloride With lithium hexamethyldisilazane In tetrahydrofuran; hexane at -78 - 20℃; Stage #2: 2,7,9,12,13,16-hexamethoxy-phenanthro[3,4-<i>c</i>]phenanthrene-11-carbaldehyde In tetrahydrofuran; hexane for 1h; Heating; Stage #3: With methyllithium In tetrahydrofuran at 20℃; for 1h;

Reference： [1]Paruch, Kamil; Vyklicky, Libor; Wang, David Zhigang; Katz, Thomas J.; Incarvito, Christopher; Zakharov, Lev; Rheingold, Arnold L. [Journal of Organic Chemistry, 2003, vol. 68, # 22, p. 8539 - 8544]

26
[ 5293-84-5 ]
2,7,9,12,13,16-hexamethoxy-phenanthro[3,4-c]phenanthrene-11,14-dicarbaldehyde [ No CAS ]
11,14-diethynyl-2,7,9,12,13,16-hexamethoxy-phenanthro[3,4-c]phenanthrene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
56%	Stage #1: chloromethyltriphenylphosphonium chloride With lithium hexamethyldisilazane In tetrahydrofuran; hexane at -78 - 20℃; Stage #2: 2,7,9,12,13,16-hexamethoxy-phenanthro[3,4-<i>c</i>]phenanthrene-11,14-dicarbaldehyde In tetrahydrofuran; hexane for 1h; Heating; Stage #3: With methyllithium In tetrahydrofuran at 20℃; for 1h;

Reference： [1]Paruch, Kamil; Vyklicky, Libor; Wang, David Zhigang; Katz, Thomas J.; Incarvito, Christopher; Zakharov, Lev; Rheingold, Arnold L. [Journal of Organic Chemistry, 2003, vol. 68, # 22, p. 8539 - 8544]

27
[ 5293-84-5 ]
C₃₉H₃₄O₉ [ No CAS ]
C₄₀H₃₄O₈ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	Stage #1: chloromethyltriphenylphosphonium chloride With lithium hexamethyldisilazane In tetrahydrofuran; hexane at -78 - 20℃; Stage #2: C₃₉H₃₄O₉ In tetrahydrofuran; hexane Heating; Stage #3: With methyllithium In tetrahydrofuran at 20℃;

Reference： [1]Paruch, Kamil; Vyklicky, Libor; Wang, David Zhigang; Katz, Thomas J.; Incarvito, Christopher; Zakharov, Lev; Rheingold, Arnold L. [Journal of Organic Chemistry, 2003, vol. 68, # 22, p. 8539 - 8544]

28
[ 5293-84-5 ]
C₄₀H₃₄O₁₀ [ No CAS ]
C₄₂H₃₄O₈ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
53%	Stage #1: chloromethyltriphenylphosphonium chloride With lithium hexamethyldisilazane In tetrahydrofuran; hexane at -78 - 20℃; Stage #2: C₄₀H₃₄O₁₀ In tetrahydrofuran; hexane at 20℃; Stage #3: With methyllithium In tetrahydrofuran at 20℃; for 1h;

Reference： [1]Paruch, Kamil; Vyklicky, Libor; Wang, David Zhigang; Katz, Thomas J.; Incarvito, Christopher; Zakharov, Lev; Rheingold, Arnold L. [Journal of Organic Chemistry, 2003, vol. 68, # 22, p. 8539 - 8544]

29
[ 5293-84-5 ]
[ 411242-39-2 ]
methyl (3Z/E)-3-(chloromethylene)-2,3-dihydro-1-benzoxepine-7-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	Stage #1: chloromethyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran at 0℃; for 1h; Stage #2: 3-oxo-2,3-dihydro-benzo[b]oxepine-7-carboxylic acid methyl ester In tetrahydrofuran at 0℃;	32 EXAMPLE 32, Preparation of methyl 3-(chloromethylene)-2,3-dihydro-1-benzoxepin-7-carboxylate EXAMPLE 32 Preparation of methyl 3-(chloromethylene)-2,3-dihydro-1-benzoxepin-7-carboxylate 1.3 equivalents of n-butyllithium are added to a suspension of 122 mg (0.35 mmol) of chloromethyltriphenylphosphonium chloride in tetrahydrofuran cooled to 0° C. After stirring for one hour, the ylide is added at 0° C., via a hollow tube, to 55 mg (0.25 mmol) of methyl 3-oxo-2,3-dihydro-1-benzoxepin-7-carboxylate, prepared according to example 31. Immediately afterwards, water, 1N hydrochloric acid and dichloromethane are added. The phases are separated and then the aqueous phase is extracted three times with dichloromethane. The combined organic phases are washed with brine, are then dried and are finally concentrated under vacuum. The crude reaction product is then purified by chromatography on silica gel (ethyl acetate/heptane 5/95) to provide 61 mg (96%) of methyl 3-(chloromethylene)-2,3-dihydro-1-benzoxepin-7-carboxylate in the form of a yellow-white solid comprising two Z/E isomers as a mixture in an 85/15 ratio; M.p.=72-77° C.

Reference： [1]Current Patent Assignee: BAYER AG - US2004/249173, 2004, A1 Location in patent: Page 20-21

30
[ 5293-84-5 ]
[ 497960-30-2 ]
methyl 3-(chloromethylene)-2,3,4,5-tetrahydro-1-benzoxepin-7-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
24%	Stage #1: chloromethyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran; hexane at 0℃; for 1h; Stage #2: 3-oxo-2,3,4,5-tetrahydrobenzo[b]oxepine-7-carboxylic acid methyl ester In tetrahydrofuran; hexane at 0 - 20℃; for 1.5h;	5 EXAMPLE 5, Preparation of methyl 3-(chloromethylene)-2,3,4,5-tetrahydro-1-benzoxepin-7-carboxylate EXAMPLE 5 Preparation of methyl 3-(chloromethylene)-2,3,4,5-tetrahydro-1-benzoxepin-7-carboxylate 0.08 ml (0.2 mmol) of a 1.9M solution of n-butyllithium in hexane is added dropwise to a suspension of 76 mg (0.22 mmol) of chloromethyltriphenylphosphonium chloride in 1.7 ml of tetrahydrofuran cooled to 0° C. The solution is stirred for one hour and then 40 mg (0.18 mmol) of methyl 3-oxo-2,3,4,5-tetrahydro-1-benzoxepin-7-carboxylate, prepared according to example 4, in 2.5 ml of tetrahydrofuran are added at 0° C. via a hollow tube. The solution is stirred at ambient temperature for 1 h 30 and then water is added. After concentrating the solution, dichloromethane is added. The phases are separated and then the aqueous phase is extracted with dichloromethane. The combined organic phases are then washed using brine, are then dried and are finally concentrated under vacuum. The crude reaction product is then purified by chromatography on silica gel (ethyl acetate/heptane 10/90) to provide 11 mg (24%) of methyl 3-(chloromethylene)-2,3,4,5-tetrahydro-1-benzoxepin-7-carboxylate in the form of a mixture of two isomers in a Z/E ratio (70/30); 1H NMR (300 MHz, CDCl3): 2.6 (m, 2H), 2.99 (m, 2H), 3.9 (s, 3H), 4.79 (s, 2H), 6.07 (s, 1H), 7.04 (d, J=8.3 Hz, 1H), 7.84 (m, 2H).

Reference： [1]Current Patent Assignee: BAYER AG - US2004/249173, 2004, A1 Location in patent: Page 16

31
[ 5293-84-5 ]
[ 497960-35-7 ]
methyl 5-benzyl-3-(chloromethylene)-2,3,4,5-tetrahydro-1-benzoxepin-7-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
53%	Stage #1: chloromethyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran at 0℃; for 1h; Stage #2: 5-benzyl-3-oxo-2,3,4,5-tetrahydro-benzo[b]oxepine-7-carboxylic acid methyl ester In tetrahydrofuran at 0 - 20℃; for 0.5h;	10 EXAMPLE 10, Preparation of methyl 5-benzyl-3-(chloromethylene)-2,3,4,5-tetrahydro-1-benzoxepin-7-carboxylate EXAMPLE 10 Preparation of methyl 5-benzyl-3-(chloromethylene)-2,3,4,5-tetrahydro-1-benzoxepin-7-carboxylate 1.1 equivalents of n-butyllithium are added to a suspension of 40 mg (0.12 mmol) of chloromethyltriphenylphosphonium chloride in 3 ml of tetrahydrofuran cooled to 0° C. After stirring for one hour, the ylide is added at 0° C. via a hollow tube to 30 mg (0.1 mmol) of methyl 5-benzyl-3-oxo-2,3,4,5-tetrahydro-1-benzoxepin-7-carboxylate, prepared according to example 9. After stirring at ambient temperature for 30 minutes, water, 1N hydrochloric acid and dichloromethane are added. The phases are separated by settling and then the aqueous phase is extracted three times with dichloromethane. The combined organic phases are washed with brine, are then dried and are finally concentrated under vacuum. The crude reaction product is then purified by chromatography on silica gel (ethyl acetate/heptane 5/95) to provide 18 mg (53%) of methyl 5-benzyl-3-(chloromethylene)-2,3,4,5-tetrahydro-1-benzoxepin-7-carboxylate in the form of a mixture of two isomers in a Z/E ratio (60/40); exact mass (CI): calculated 343.11009; found 343.11027. ãã0-5ãã

Reference： [1]Current Patent Assignee: BAYER AG - US2004/249173, 2004, A1 Location in patent: Page 17

32
[ 5293-84-5 ]
1-[2,4-(endo,endo)-dimethyl-3-(endo)-(trimethyl-silanyloxy)-8-oxa-bicyclo[3.2.1]oct-6-en-3-yl]-propan-2-one [ No CAS ]
(+/-)-(Z)-[3-(exo)-(3-chloro-2-methyl-allyl)-2,4-(endo,endo)-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-3-yloxy]-trimethyl-silane [ No CAS ]
(+/-)-(E)-[3-(exo)-(3-chloro-2-methyl-allyl)-2,4-(endo,endo)-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-3-yloxy]-trimethyl-silane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1: 30% 2: 27%	Stage #1: chloromethyltriphenylphosphonium chloride With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at -78 - 20℃; Stage #2: 1-[2,4-(endo,endo)-dimethyl-3-(endo)-(trimethyl-silanyloxy)-8-oxa-bicyclo[3.2.1]oct-6-en-3-yl]-propan-2-one In tetrahydrofuran; hexane at -78 - 20℃; for 18h;

Reference： [1]Grainger, Richard S.; Owoare, Richard B. [Organic Letters, 2004, vol. 6, # 17, p. 2961 - 2964]

33
[ 5293-84-5 ]
(+/-)-1-[3-(endo)-(trimethyl-silanyloxy)-11-oxa-tricyclo[7.2.1.0^4,10]dodec-9⁽¹²⁾-en-3-yl]-propan-2-one [ No CAS ]
(+/-)-[3-(exo)-(3-chloro-2-methyl-allyl)-11-oxa-tricyclo[7.2.1.0^4,10]dodec-9⁽¹²⁾-en-3-yloxy]-trimethyl-silane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	Stage #1: chloromethyltriphenylphosphonium chloride With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at -78 - 20℃; Stage #2: (+/-)-1-[3-(endo)-(trimethyl-silanyloxy)-11-oxa-tricyclo[7.2.1.0^4,10]dodec-9⁽¹²⁾-en-3-yl]-propan-2-one In tetrahydrofuran; hexane at -78 - 20℃; for 18h;

Reference： [1]Grainger, Richard S.; Owoare, Richard B. [Organic Letters, 2004, vol. 6, # 17, p. 2961 - 2964]

34
[ 5293-84-5 ]
[ 96690-02-7 ]
(2R,3R,4S)-1-(tert-butyldiphenylsilyloxy)-3,4-(isopropylidenedioxy)hex-5-yne-1,2-diol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
62%	Stage #1: chloromethyltriphenylphosphonium chloride; 5-O-(tert-butyldiphenylsilyl)-2,3-O-isopropylidene-D-ribofuranose With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In tetrahydrofuran; hexane at 20℃; for 1.5h; Stage #2: With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h;

Reference： [1]Alcázar, Eva; Pletcher, Joseph M.; McDonald, Frank E. [Organic Letters, 2004, vol. 6, # 21, p. 3877 - 3880]

35
1-(2-pent-1-ynylcylopent-1-enyl)ethanone [ No CAS ]
[ 5293-84-5 ]
[ 861819-73-0 ]
[ 861819-65-0 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: chloromethyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran; hexane at 23℃; Stage #2: 1-(2-pent-1-ynylcylopent-1-enyl)ethanone In tetrahydrofuran; hexane for 6h;

Reference： [1]O'Connor, Joseph M.; Friese, Seth J.; Rodgers, Betsy L.; Rheingold, Arnold L.; Zakharov, Lev [Journal of the American Chemical Society, 2005, vol. 127, # 26, p. 9346 - 9347]

36
(+/-)-(2R,4R,5R,1'S)-5-(1'-acetylamino-3'-methylbutyl)-4-formylpyrrolidine-1,2-dicarboxylic acid di-tert-butyl ester [ No CAS ]
[ 5293-84-5 ]
(2S,4R,5S)-5-((R)-1-Acetylamino-3-methyl-butyl)-4-((Z)-2-chloro-vinyl)-pyrrolidine-1,2-dicarboxylic acid di-tert-butyl ester [ No CAS ]
(2S,4R,5S)-5-((R)-1-Acetylamino-3-methyl-butyl)-4-((E)-2-chloro-vinyl)-pyrrolidine-1,2-dicarboxylic acid di-tert-butyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1: 43% 2: 40%	Stage #1: chloromethyltriphenylphosphonium chloride With potassium <i>tert</i>-butylate In tetrahydrofuran; toluene at 20℃; for 2.5h; Stage #2: (+/-)-(2R,4R,5R,1'S)-5-(1'-acetylamino-3'-methylbutyl)-4-formylpyrrolidine-1,2-dicarboxylic acid di-tert-butyl ester In tetrahydrofuran; toluene for 1h;

Reference： [1]Maring, Clarence J.; Stoll, Vincent S.; Zhao, Chen; Sun, Minghua; Krueger, Allan C.; Stewart, Kent D.; Madigan, Darold L.; Kati, Warren M.; Xu, Yibo; Carrick, Robert J.; Montgomery, Debra A.; Kempf-Grote, Anita; Marsh, Kennan C.; Molla, Akhteruzzaman; Steffy, Kevin R.; Sham, Hing L.; Laver, W. Graeme; Gu, Yu-Gui; Kempf, Dale J.; Kohlbrenner, William E. [Journal of Medicinal Chemistry, 2005, vol. 48, # 12, p. 3980 - 3990]

37
[ 5293-84-5 ]
(1S,4S,4aR,7aS)-8,8-Dimethyl-4-phenyl-4,4a,5,6,7,7a-hexahydro-1,4-methano-cyclopenta[d]pyridazine-1-carbaldehyde [ No CAS ]
(1α,4α,4aα,7aα)-4,4a,5,6,7,7a-hexahydro-8,8-dimethyl-1-(E-2-chloro)ethenyl-1,4-methano-4-phenyl-1H-cyclopenta[d]pyridazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
53%	With potassium <i>tert</i>-butylate In toluene at 20℃; for 18h;

Reference： [1]Adam; Emmert [Journal of Organic Chemistry, 2000, vol. 65, # 13, p. 4127 - 4130]

38
[ 2142-68-9 ]
[ 5293-84-5 ]
[ 68913-15-5 ]
[ 68913-16-6 ]

Yield	Reaction Conditions	Operation in experiment
1: 25% 2: 15%	Stage #1: chloromethyltriphenylphosphonium chloride With sodium hydride In tetrahydrofuran at 0℃; for 1.5h; Stage #2: 1-(2-chlorophenyl)ethanone In tetrahydrofuran at 20℃; for 3h;

Reference： [1]Willis, Michael C.; Brace, Gareth N.; Findlay, Thomas J. K.; Holmes, Ian P. [Advanced Synthesis and Catalysis, 2006, vol. 348, # 7-8, p. 851 - 856]

39
[ 5162-03-8 ]
[ 5293-84-5 ]
(Z)-1-chloro-2-(2-chloro-1-phenylvinyl)benzene [ No CAS ]
(E)-1-chloro-2-(2-chloro-1-phenylvinyl)benzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
15%	Stage #1: chloromethyltriphenylphosphonium chloride With sodium hydride In tetrahydrofuran at 0℃; for 1.5h; Stage #2: (2-chlorophenyl)(phenyl)methanone In tetrahydrofuran at 20℃; for 3h; Title compound not separated from byproducts;

Reference： [1]Willis, Michael C.; Brace, Gareth N.; Findlay, Thomas J. K.; Holmes, Ian P. [Advanced Synthesis and Catalysis, 2006, vol. 348, # 7-8, p. 851 - 856]

40
[ 334994-06-8 ]
[ 5293-84-5 ]
[ 334994-02-4 ]

Yield	Reaction Conditions	Operation in experiment
68%	Stage #1: chloromethyltriphenylphosphonium chloride With potassium <i>tert</i>-butylate In tetrahydrofuran for 1h; Stage #2: 1,3-dimorpholin-4-yl-propan-2-one In acetonitrile for 12h; Heating; Further stages.;

Reference： [1]Dong; Macmillan [Journal of the American Chemical Society, 2001, vol. 123, # 10, p. 2448 - 2449]

41
[ 5293-84-5 ]
(1S,4S,4aR,7aS)-8,8-Dimethyl-4-phenyl-4,4a,5,6,7,7a-hexahydro-1,4-methano-cyclopenta[d]pyridazine-1-carbaldehyde [ No CAS ]
(1β,4β,4aα,7aα)-4,4a,5,6,7,7a-hexahydro-1-(Z-2-chloroethenyl)-8,8-dimethyl-4-phenyl-1,4-methano-1H-cyclopenta[d]pyridazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
45%	With potassium <i>tert</i>-butylate In toluene at 20℃; for 96h;

Reference： [1]Adam, Waldemar; Emmert, Oliver [Journal of Organic Chemistry, 2000, vol. 65, # 18, p. 5664 - 5667]

42
[ 1000-30-2 ]
[ 5293-84-5 ]
(Z)-1-Chloro-3,3,6-trimethyl-hepta-1,5-diene [ No CAS ]
[ 437610-59-8 ]

Yield	Reaction Conditions	Operation in experiment
	With piperidine; n-butyllithium In diethyl ether at 20℃; for 10h;

Reference： [1]Trost, Barry M.; Toste, F. Dean [Journal of the American Chemical Society, 2002, vol. 124, # 18, p. 5025 - 5036]

43
[ 52279-00-2 ]
[ 5293-84-5 ]
(Z)-1-Chloro-3,3,7-trimethyl-octa-1,6-diene [ No CAS ]
[ 437610-60-1 ]

Yield	Reaction Conditions	Operation in experiment
	With piperidine; n-butyllithium In diethyl ether at 20℃; for 10h;

Reference： [1]Trost, Barry M.; Toste, F. Dean [Journal of the American Chemical Society, 2002, vol. 124, # 18, p. 5025 - 5036]

44
4-(tert-butyl-dimethyl-silanyloxy)-2-(3-oxo-butyl)-pyrrolidine-1-carboxylic acid tert-butyl ester [ No CAS ]
[ 5293-84-5 ]
4-(tert-butyl-dimethyl-silanyloxy)-2-(4-chloro-3-methyl-but-3-enyl)-pyrrolidine-1-carboxylic acid tert-butyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With potassium hexamethylsilazane In tetrahydrofuran; toluene at 20℃; for 24h;

Reference： [1]Asari, Asnuzilawati; Angelov, Plamen; Auty, James M.; Hayes, Christopher J. [Tetrahedron Letters, 2007, vol. 48, # 14, p. 2631 - 2634]

45
[ 1028958-96-4 ]
[ 5293-84-5 ]
[ 1028958-88-4 ]

Yield	Reaction Conditions	Operation in experiment
80%	With N,N,N,N,N,N-hexamethylphosphoric triamide; n-butyllithium In tetrahydrofuran	i Compounds 1a-1c were obtained from cyclohexanone according to the method of Honda et al. 2005, which is incorporated herein by reference. Without separation, a mixture of 1a-1c was converted to a mixture of 1b and 1c with ethereal diazomethane. Compound 2 was obtained from the mixture of 1b and 1c by protection of their carbonyl groups with ethylene glycol (EG) in the presence of pyridinium p-toluenesulfonate (PPTS) in benzene (PhH) (Sterzycki, 1979), followed by LiAlH4 reduction (53% yield from the mixture of 1a-1c). Swern oxidation (DMSO and oxalyl chloride, Omura and Swem, 1978) of 2 gave 3 in quantitative yield. Compound 4 was prepared in 80% yield as a mixture of E/Z chlorovinyl isomers by Wittig reaction on 3 with (chloromethyl)triphenylphosphonium chloride (Mella et al., 1988). Dehydrochlorination of 4 with methyl lithium, followed by quenching the acetylide with aqueous NH4Cl solution afforded the common intermediate I in 95% yield (21% overall yield from cyclohexanone) (Mella et al., 1988). Noteworthy is that 100 g of I can be made from 160 g of cyclohexanone by this sequence.
	Stage #1: chloromethyltriphenylphosphonium chloride With N,N,N,N,N,N-hexamethylphosphoric triamide; n-butyllithium In tetrahydrofuran; hexane at 20℃; Stage #2: C₂₀H₃₀O₃ In tetrahydrofuran; hexane at 20℃; Further stages.;
	Stage #1: chloromethyltriphenylphosphonium chloride With N,N,N,N,N,N-hexamethylphosphoric triamide; n-butyllithium In tetrahydrofuran; hexane at 0 - 20℃; for 0.333333h; Stage #2: C₂₀H₃₀O₃ In tetrahydrofuran; hexane at 20℃; for 0.833333h;	B.3.c; 1 To the mixture was added HMPA (1.4 rnL). The mixture was stirred at room temperature for 20 min. To the mixture was added a solution of the aldehyde (630 mg, 2.3 mmol) in THF (9 mL) at room temperature. The mixture was stirred at room temperature for 50 min. To the mixture was added saturated aqueous NH4Cl solution (60 mL). The aqueous mixture was extracted with CH2Cl2-Et2O (1 :2, 40 mL x 4). The extract was washed with brine (x 2), then dried over MgSO4 and filtered. The filtrate was evaporated to give a brown residue. The residue was washed with a mixture of hexanes-ethyl acetate (10:1), and filtered through a glass filter. The solid residue in the filter was washed several times with hexanes-ethyl acetate (10:1 -110 mL, 7:1 - 80 mL, 5:1 - 60 mL, 4:1 - 50 mL). The filtrates were combined and evaporated to give a crude yellow solid (2.5 g). The crude product was purified by flash column chromatography [hexanes-ethyl acetate (10:1)] to give the product (+)-4 (556 mg, 65% from (+)-lc). [α]26D +5.9° (c 0.44, CHCl3).

With N,N,N,N,N,N-hexamethylphosphoric triamide; n-butyllithium In tetrahydrofuran

ii Enantiomer (+)-1c was treated with ethylene glycol and PPTS to give the protected ketone, which was subjected to Swern oxidation with oxalyl chloride and dimethyl sulfoxide. A Wittig reaction of the resulting aldehyde with (chloromethyl) triphenylphosphonium chloride afforded the alkenyl chloride (+)-4 in 65% yield.

Reference： [1]Current Patent Assignee: RUTGERS, THE STATE UNIVERSITY OF NEW JERSEY - US2008/233195, 2008, A1 Location in patent: Page/Page column 12
[2]Honda, Tadashi; Sundararajan, Chitra; Yoshizawa, Hidenori; Su, Xiaobo; Honda, Yukiko; Liby, Karen T.; Sporn, Michael B.; Gribble, Gordon W. [Journal of Medicinal Chemistry, 2007, vol. 50, # 8, p. 1731 - 1734]
[3]Current Patent Assignee: DARTMOUTH COLLEGE - WO2008/64133, 2008, A1 Location in patent: Page/Page column 55-56; 94-96
[4]Current Patent Assignee: RUTGERS, THE STATE UNIVERSITY OF NEW JERSEY - US2008/233195, 2008, A1 Location in patent: Page/Page column 14-15

46
(±)-(4a'S,8a'S,10a'R)-1',1',4a'-trimethyl-3',4',4a',6',7',8',8a',9',10',10a'-decahydro-1'H-spiro[[1,3]dioxolane-2,2'-phenanthrene]-8a'-carbaldehyde [ No CAS ]
[ 5293-84-5 ]
(±)-(4a'S,8a'R,10a'R)-8a'-(2-chlorovinyl)-1',1',4a'-trimethyl-3',4',4a',6',7',8',8a',9',10',10a'-decahydro-1'H-spiro[[1,3]dioxolane-2,2'-phenanthrene] [ No CAS ]
(±)-(4a'S,8a'R,10a'R)-8a'-(2-chlorovinyl)-1',1',4a'-trimethyl-3',4',4a',6',7',8',8a',9',10',10a'-decahydro-1'H-spiro[[1,3]dioxolane-2,2'-phenanthrene] [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	Stage #1: chloromethyltriphenylphosphonium chloride With N,N,N,N,N,N-hexamethylphosphoric triamide; n-butyllithium In tetrahydrofuran; hexane at 20℃; for 0.333333h; Stage #2: (±)-(4a'S,8a'S,10a'R)-1',1',4a'-trimethyl-3',4',4a',6',7',8',8a',9',10',10a'-decahydro-1'H-spiro[[1,3]dioxolane-2,2'-phenanthrene]-8a'-carbaldehyde In tetrahydrofuran; hexane at 20℃; for 0.833333h; Further stages. Title compound not separated from byproducts.;
60 % de	Stage #1: chloromethyltriphenylphosphonium chloride With N,N,N,N,N,N-hexamethylphosphoric triamide; n-butyllithium In tetrahydrofuran; hexane at 20℃; for 0.5h; Inert atmosphere; Cooling with ice; Stage #2: (±)-(4a'S,8a'S,10a'R)-1',1',4a'-trimethyl-3',4',4a',6',7',8',8a',9',10',10a'-decahydro-1'H-spiro[[1,3]dioxolane-2,2'-phenanthrene]-8a'-carbaldehyde In tetrahydrofuran; hexane at 0 - 20℃; for 1h; Inert atmosphere; Overall yield = 81 %; Overall yield = 11.3 g;	VIII VIII. (±)-(4a'S,8a'R,10a'R)-8a^,-(2-Chlorovinyl)-l^,,l',4a^,-trimethyI- S'^'^a'^'^ S Sa'^ lO lOa'-decahydro-l'H-s irotll^ldioxolane-l^'-phenanthrene] (8). [0065] To a suspension of (chloromethyl)triphenylphosphonium chloride (61.4 g, 168 mmol, 4.2 equiv) in anhydrous THF (182 mL) was added -BuLi (105 mL, 1.6 M in hexane, 168 mmol, 4.2 equiv) dropwise in an ice bath. To the mixture was added hexamethylphosphoramide (HMPA, 29.2 mL, 168 mmol, 4.2 equiv). The mixture was stirred at room temperature for 30 min and then a solution of 7 (12.7 g, 40.0 mmol) in anhydrous THF (180 mL) was added at 0 °C. The mixture was stirred at room temperature for 1 h. Saturated aqueous NH4C1 solution (300 mL) was added and the aqueous mixture was extracted with CH2Cl2-Et20 (1 :2, 200 mL χ 2). The extract was washed with brine (500 mL x 2), dried over MgSC filtered, and concentrated to give a brown residue. The residue was dissolved in CH2C12 (50 mL), and silica gel (100 g) was added to afford homogeneous powder. It was roughly purified with a short silica gel pad (Si02, 250 mL (8 cm diameter column, 5 cm height); hexanes/Et20 (10/1), 1.8 L) to give 8 (E-isomer: Z- isomer =1 :4, 11.3 g, 81%) as a colorless oil: FontWeight="Bold" FontSize="10" H NMR (300 MHz, CDC13) δ 6.32 (0.2H, d, J = 13.9 Hz), 5.89 (1.6H, s), 5.86 (0.2H, d, J= 13.9 Hz), 5.52 (0.2H, t, J= 4.0 Hz), 5.49 (0.8H, t, J= 4.0 Hz), 3.97 (4H, m), 2.85 (1H, dt, J= 13.6, 3.1 Hz), 1.13 (2.4H, s), 1.04 (0.6H, s), 0.96 (2.4H, s), 0.95 (0.6H, s), 0.85 (3H, s); MS (FAB) m/z 387 [M+Na]+ and 351 [M+H]+.

Reference： [1]Honda, Tadashi; Sundararajan, Chitra; Yoshizawa, Hidenori; Su, Xiaobo; Honda, Yukiko; Liby, Karen T.; Sporn, Michael B.; Gribble, Gordon W. [Journal of Medicinal Chemistry, 2007, vol. 50, # 8, p. 1731 - 1734]
[2]Current Patent Assignee: STATE UNIVERSITY OF NEW YORK - WO2014/151181, 2014, A1 Location in patent: Paragraph 0065

47
[ 5293-84-5 ]
[ 551-93-9 ]
[ 944546-68-3 ]
C₉H₁₀NCl [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1: 63% 2: 7%	Stage #1: chloromethyltriphenylphosphonium chloride With lithium diisopropyl amide In tetrahydrofuran; hexane at -78 - 20℃; for 0.5h; Stage #2: 2-aminoacetophenone In tetrahydrofuran; hexane at 20℃; for 24h; Further stages.;

Reference： [1]Miyauchi, Hironori; Chiba, Shunsuke; Fukamizu, Koji; Ando, Kaori; Narasaka, Koichi [Tetrahedron, 2007, vol. 63, # 26, p. 5940 - 5953]

48
[ 5293-84-5 ]
[ 357604-61-6 ]
1-chloro-3,4:5,7-di-O-isopropylidene-1,2-dideoxy-D-manno-hept-1-enitol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
61%	With N,N,N,N,N,N-hexamethylphosphoric triamide; n-butyllithium In tetrahydrofuran at 0 - 20℃;

Reference： [1]Castro, Steve; Cherney, Emily C.; Snyder, Nicole L.; Peczuh, Mark W. [Carbohydrate Research, 2007, vol. 342, # 10, p. 1366 - 1372]

49
[ 5293-84-5 ]
[ 497960-52-8 ]
(E/Z)-1-(3-chloromethylene-2,3-dihydrobenzo[b]oxepin-7-yl)ethanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
55%	With n-butyllithium In tetrahydrofuran at 0 - 20℃; for 2h;	80 EXAMPLE 80, Preparation of 1-[3-(chloromethylene)-2,3-dihydro-1-benzoxepin-7-yl]ethanone EXAMPLE 80 Preparation of 1-[3-(chloromethylene)-2,3-dihydro-1-benzoxepin-7-yl]ethanone 1.1 equivalents of n-butyllithium are added to 309 mg (0.89 mmol) of chloromethyltriphenylphosphonium chloride in 5 ml of tetrahydrofuran cooled to 0° C. After stirring for one hour, 150 mg (0.74 mmol) of 7-acetyl-1-benzoxepin-3(2H)-one, prepared according to example 79, are added at ambient temperature. The medium is stirred for a further 1 hour. After the usual treatments and evaporating the solvent under reduced pressure, the crude reaction product is taken up in pentane in order to precipitate triphenylphosphine oxide. Evaporation of the solvents provides 95.5 mg (55%) of 1-[3-(chloromethylene)-2,3-dihydro-1-benzoxepin-7-yl]ethanone in the form of a mixture of two Z/E isomers in a 90/10 ratio; 1H NMR (C6D6): 7.85 (d, 1H, J=2.2 Hz), 7.76 (dd, 2.2 Hz and 8.4 Hz), 7.04 (d, 8.4 Hz), 6.85 (d, J-=11.8 Hz, 1H), 6.57 (d, J=11.8 Hz, 1H), 6.16 (s, 1H), 4.57 (4.87) (s, 2H), 2.56 (s, 3H).

Reference： [1]Current Patent Assignee: BAYER AG - US2004/249173, 2004, A1 Location in patent: Page 26

50
[ 846060-69-3 ]
[ 5293-84-5 ]
[ 846060-74-0 ]

Yield	Reaction Conditions	Operation in experiment
57%	With potassium hexamethylsilazane In tetrahydrofuran at 20℃; for 2.5h;	16 Cloromethyltriphenylphosphonium chloride (2.74 g, 7.89 mmol) is suspended in dry THF (30 ml) under Argon and KHMDS (1.57 g, 7.89 mmol) is added portionwise at 0°C. The mixture is stirred at 0°C for 30 minutes, then allowed to warm to ambient temperature. (IS, 2R)-L- (3, 4-DICHLORO-PHENYL)-2-FONNYL-CYCLOPROPANECARBOXYLIC acid (4-fluoro-benzyl)- methyl-amide (1.0 g, 2.63 mmol) dissolved in dry THF (10 ml) is added dropwise and the mixture is stirred at ambient temperature for 2.5 hours. The reaction mixture is then poured onto ice cold water (30 ml) and the layers are separated. The aqueous phase is extracted with ethyl acetate (2 x 30 ml) and the combined organic fractions are washed with brine (sat. ), dried (MgS04), filtered and concentrated III vacuo. The crude product is purified by silica gel chromatography, eluting with a gradient of ethyl acetate: heptane (0: 100) - (50: 50). The product is isolated as a Z/E isomer mixture. Yield 630 mg (57%). LC/MS (m/z) 412.1 (M+H+).

Reference： [1]Current Patent Assignee: H. LUNDBECK A/S - WO2005/16884, 2005, A1 Location in patent: Page/Page column 66

51
[ 152953-33-8 ]
[ 5293-84-5 ]
[ 160242-79-5 ]

Yield	Reaction Conditions	Operation in experiment
	With n-butyllithium In tetrahydrofuran; hexane; water	4 EXAMPLE 4 A solution of 1.6M butyl lithium in hexane (44 ml) was added dropwise to a suspension of 24.4 g of chloromethyltriphenylphosphonium chloride in 500 ml of ether. After stirring for 15 min a solution of 5.4 g of (11β)-3,3,17,17-bis(ethylenedioxy)-estr-5-en-11-carboxaldehyde in 30 ml of tetrahydrofuran were added dropwise. After 12 h the mixture was poured into 0.5 l of water and the organic phase was separated, washed, dried and concentrated. The residue was chromatographed to provide 3.7 g of E/Z (11β)-3,3,17,17-bis(ethylenedioxy)-11-(2-chloroethenyl)-estr-5-en. Rf =0.4 (hexane-ethyl acetate 7/3).

Reference： [1]Current Patent Assignee: AKZO NOBEL NV - US5710144, 1998, A

52
[ 5293-84-5 ]
[ 90212-03-6 ]
3-chloromethylene-19-methylthio-4-androsten-17-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With n-butyllithium In tetrahydrofuran; water	1 3-Chloromethylene-19-methylthio-4-androsten-17-one EXAMPLE 1 3-Chloromethylene-19-methylthio-4-androsten-17-one 500 mg of 19-methylthio-4-androstene-3,17-dione (European patent 100,566) is added to a suspension of 5.21 g of chloromethyl triphenylphosphonium chloride in 50 ml of tetrahydrofuran, which was stirred with 9.5 ml of (1.6 m of butyllithium in ether) 0.5 hours at 20° C., and stirred for 30 minutes at 0° C. Then it is mixed with water, extracted three times with ethyl acetate, washed neutral, dried on sodium sulfate and concentrated to dryness. 995 mg of raw product is obtained, which after chromatographic purification yields 273 mg of pure 3-chloromethylene-19-methylthio-4-androsten-17-one with a melting point of 114°-115° C., [α]D +241.5° C. (CHCl3), as pure E form.

Reference： [1]Current Patent Assignee: BAYER AG - US4925834, 1990, A

53
[ 5293-84-5 ]
2-(tert-Butyldimethylsilyloxy)-5-(2'-chlorovinyl)-1,3-dimethoxy-benzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With n-butyllithium	18.b (b) (b) 2-(tert-Butyldimethylsilyloxy)-5-(2'-chlorovinyl)-1,3-dimethoxy-benzene The procedure was the same as described in Example 17a except there were used 2.90 g of the product of Example 18a, 4.08 g of (chloromethyl)-triphenylphosphonium chloride and 7.4 ml of n-butyllithium solution. After column chromatography with petroleum ether/ether (3:1) 2.74 g of the title compound were obtained. 1 H-NMR (CDCl3): 0.13 (s, 6 H); 1.03 (s, 9 H); 3.75 (s, 6 H); 5.97-6.83 (m, 4 H).
	With n-butyllithium	18.b (b) (b) 2-(tert-Butyldimethylsilyloxy)-5-(2'-chlorovinyl)-1,3-dimethoxy-benzene The procedure was the same as described in Example 17a except there were used 2.90 g of the product of Example 18a, 4.08 g of (chloromethyl)-triphenylphosphonium chloride and 7.4 ml of n-butyllithium solution. After column chromatography with petroleum ether/ether (3:1) 2.74 g of the title compound were obtained. 1 H-NMR (CDCl3): 0.13 (s, 6H); 1.03 (s, 9H); 3.75 (s, 6H); 5.97-6.83 (m, 4H).

Reference： [1]Current Patent Assignee: Gruenenthal Pharma GmbH & Co. Kommanditgesellschaft - US4959391, 1990, A
[2]Current Patent Assignee: Gruenenthal Pharma GmbH & Co. Kommanditgesellschaft - US4760087, 1988, A

54
[ 5293-84-5 ]
1,2-Bis-(tetrahydropyranyl-2'-oxy)-4-(2'-chlorovinyl)-benzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium <i>tert</i>-butylate	7.b (b) (b) 1,2-Bis-(tetrahydropyranyl-2'-oxy)-4-(2'-chlorovinyl)-benzene The procedure was the same as described in Example 5b, except there were used 20.0 g of (chloromethyl)-triphenylphosphonium chloride, 6.46 g of potassium tert-butylate and 11.8 g of the product of Example 7a to give after column chromatography with petroleum ether/ether (2:1) 10.56 g of the title compound. 1 H-NMR (CDCl3): 1.40-2.40 (m, 12H); 3.27-4.27 (m, 4H); 5.20-5.63 (m, 2H); 5.97-7.56 (m, 5H).

Reference： [1]Current Patent Assignee: Gruenenthal Pharma GmbH & Co. Kommanditgesellschaft - US4760087, 1988, A Current Patent Assignee: Gruenenthal Pharma GmbH & Co. Kommanditgesellschaft - US4959391, 1990, A

55
2R-benzoyloxy-4Z-decen-al [ No CAS ]
[ 5293-84-5 ]
3R-Benzoyloxy-1-chloro-undec-1,5Z-diene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With n-butyllithium In tetrahydrofuran	51 3R-Benzoyloxy-1-chloro-undec-1,5Z-diene EXAMPLE 51 3R-Benzoyloxy-1-chloro-undec-1,5Z-diene Chloromethyl triphenylphosphonium chloride (5.14 g, 14.8 mmole) is suspended in 40 ml dry tetrahydrofuran in an oven dried 100 ml 2-neck round bottom flask under nitrogen. The suspension is cooled to 0° C. and treated slowly dropwise with n-butyllithium (9.0 ml, 14.06 mmole). The red ylid is stirred 30 minutes at 0° C. and treated slowly dropwise with 2R-benzoyloxy-4Z-decen-al (2.03 g, 7.4 mmole) in 35 ml dry tetrahydrofuran. The reaction mixture is stirred one hour at 0° C., quenched with 40 ml saturated sodium chloride, and extracted with 450 ml ethyl acetate. The organics are combined, dried over magnesium sulfate, and concentrated to an orange solid residue. The residue is chromatographed over 90 g silica gel (230-400 mesh), eluding with 3% ethyl acetate/hexane and collecting 20 ml fractions. Fractions 6-13 are combined and concentrated to afford 1.4 g of the title compound. Mass spectrum: M/z (Relative Intensity); [M+H]+ =307(7) [M-PhCO2 ]+ =185(100).

Reference： [1]Current Patent Assignee: PFIZER INC - US5116981, 1992, A

56
[ 110-89-4 ]
3β,17β-dihydroxy-androst-5-en-18-al diacetate [ No CAS ]
[ 5293-84-5 ]
3β,17β-diacetoxy-13-(2-chlorovinyl)-10-methyl-gon-5-ene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With n-butyllithium In tetrahydrofuran; hexane	2.A EXAMPLE 2 A. A solution of 2.92 g of 3β,17β-diacetoxy-androst-5-en-18-al in 30 ml of tetrahydrofurane is added dropwise to a solution of a Wittig reagent prepared from 7.83 g of chloromethyl-triphenyl-phosphonium chloride, 144 ml of tetrahydrofurane, 2.23 ml of piperidine and 11.25 ml of a 1.56 molar solution of butyl-lithium in hexane and the mixture is allowed to react for 40 minutes at room temperature and is worked up as indicated in Example 1. On purification by chromatography, as also indicated in Example 1A, this gives the cis and trans isomers of 3β,17β-diacetoxy-13-(2-chlorovinyl)-10-methyl-gon-5-ene in a ratio of 1:3. The cis isomer crystallises from methylene chloride/hexane and then melts at 161°-162° C; [α]D25 = -70° (in chloroform); the trans isomer crystallises from methylene chloride/hexane, melting point 155°-156° C, [α]D25 = -42° (in chloroform).

Reference： [1]Current Patent Assignee: Novartis (w/o Sandoz); NOVARTIS AG - US4052421, 1977, A

57
[ 5293-84-5 ]
(3β,5α,20S)-23-chloro-4,4-dimethyl-24-norchola-8,14,22-trien-3-ol benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydrogencarbonate In tetrahydrofuran; ethyl acetate	12.A (3β,5α,20S)-4,4-Dimethyl-23-phenyl-24-norchola-8,14-dien-22-yn-3-ol ii)-A suspension of (chloromethyl)triphenylphosphonium chloride (17.5 g) in dry tetrahydrofuran (140 ml) was cooled to 0° C. Sodium t-butoxide (4.64 g) was added and the mixture was stirred for 20 min. A solution of the aldehyde obtained in the previous step (10.3 g) in dry tetrahydrofuran (80 ml) was added and the reaction mixture was stirred at 0° C. for 30 min. and at room temperature for another 2 h. Ethyl acetate was added and the mixture was concentrated to remove the tetrahydrofuran. Then it was washed with water and a mixture of a saturated aqueous solution of sodium hydrogencarbonate and brine. The organic phase was dried over magnesium sulfate and concentrated under reduced pressure. Column chromatography afforded (3β,5α,20S)-23-chloro-4,4-dimethyl-24-norchola-8,14,22-trien-3-ol benzoate (7.01 g). iii)-Following a procedure analogous to that described under iv of Example 1, the product obtained in the previous step (7.01 g) was converted to (3β,5α,20S)-23-chloro-4,4-dimethyl-24-norchola-8,14,22-trien-3-ol (6.28 g).

Reference： [1]Current Patent Assignee: ORGANON & CO - US6177420, 2001, B1

58
[ 5293-84-5 ]
[ 84459-32-5 ]
1-bromo-2-(2-chlorovinyl)-4-nitrobenzene [ No CAS ]
1-bromo-2-(2-chlorovinyl)-4-nitrobenzene [ No CAS ]

Reference： [1]Chemical Communications,2007,p. 4764 - 4766

59
[ 5293-84-5 ]
[ 6630-33-7 ]
1-bromo-2-(2-chlorovinyl)benzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	Stage #1: chloromethyltriphenylphosphonium chloride With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 1.5h; Stage #2: ortho-bromobenzaldehyde In tetrahydrofuran at 0℃; for 12h; Further stages.;

Reference： [1]Fletcher, Anthony J.; Bax, Matthew N.; Willis, Michael C. [Chemical Communications, 2007, # 45, p. 4764 - 4766]

60
[ 12093-10-6 ]
[ 5293-84-5 ]
2-chloro-1-ferrocenylethene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With t-BuOK In tetrahydrofuran Ar-atmosphere; addn. of t-BuOK to equimolar amt. of P-compd. at 0°C, stirring for 15 min, dropwise addn. of equimolar amt. of Fe-complex,warming to room temp.; solvent removal (after 15 h, vac.), extn., chromy. (SiO2, hexane/CH2Cl2=4:1);
67%	With n-BuLi In tetrahydrofuran; hexane Ar-atmosphere; addn. of BuLi (in hexane) to equimolar amt. of P-compd. (in THF) at 0°C, stirring for 15 min, dropwise addn. of equimolar amt. of Fe-complex (in THF), warming to room temp.; solvent removal (after 15 h, vac.), extn., chromy. (SiO2, hexane/CH2Cl2=4:1);

Reference： [1]Rodriguez, Jose-Gonzalo; Onate, Antonio; Martin-Villamil, Rosa M.; Fonseca, Isabel [Journal of Organometallic Chemistry, 1996, vol. 513, # 1-2, p. 71 - 76]
[2]Rodriguez, Jose-Gonzalo; Onate, Antonio; Martin-Villamil, Rosa M.; Fonseca, Isabel [Journal of Organometallic Chemistry, 1996, vol. 513, # 1-2, p. 71 - 76]

61
[ 172036-53-2 ]
[ 5293-84-5 ]
[Pd(C₆H(E-CHCHCl)-6-(OMe)3-2,3,4)Cl(N,N,N',N'-tetramethylethylenediamine)] [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81%	With t-BuOK In dichloromethane all manipulations under N2; t-BuOK, P compd. and Pd complex reacted in CH2Cl2 for 20 h; evapd. to dryness, residue stirred in Et2O for 1 h, filtered, washed with Et2O, C6H6/Et2O, Et2O and H2O, dissolved in CH2Cl2 and stirred with anhyd. MgSO4, filtered over anhyd. MgSO4, concd., pptd. with Et2O, elem. anal.;

Reference： [1]Vicente; Abad; Bergs; Ramirez de Arellano; Martinez-Viviente; Jones [Organometallics, 2000, vol. 19, # 26, p. 5597 - 5607]

62
[ 128925-12-2 ]
[ 5293-84-5 ]
[ 201472-67-5 ]

Yield	Reaction Conditions	Operation in experiment
68%	With n-butyllithium; potassium <i>tert</i>-butylate In tetrahydrofuran; hexane N2-atmosphere; slow addn. of equimolar amt. of BuLi (in hexane) to suspn. of phosphonium salt (in THF), stirring for 20 min, slow addn. of 0.9 equiv. of Fe-complex soln. (in THF), stirring for 3 h, addn. of 1.8 equiv. KO(t)Bu, refluxing for 10 d; addn. of H2O and hexane, washing of aq. layer (H2O), drying of org. layer (Na2SO4), solvent removal, flash chromy. (hexane), recrystn. (MeCN); elem. anal.;
56%	Stage #1: 1-formyl-2,2′,3,3′,4,4′5,5′-octamethylferrocene; chloromethyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran at 25℃; for 3h; Stage #2: With potassium <i>tert</i>-butylate for 24h; Reflux;

Reference： [1]Jutzi, Peter; Kleinebekel, Birgit [Journal of Organometallic Chemistry, 1997, vol. 545-546, p. 573 - 576]
[2]Fojta, Miroslav; Havran, Luděk; Hocek, Michal; Magriñá, Ivan; O'Sullivan, Ciara K.; Ortiz, Mayreli; Pohl, Radek; Sýkorová, Veronika; Simonova, Anna [Chemistry - A European Journal, 2020]

63
[ 1028958-96-4 ]
[ 5293-84-5 ]
(+/-)-(4a'S,8a'R,10a'R)-8a'-(2-chlorovinyl)-1',1',4a'-trimethyl-3',4',4a',6',7',8',8a',9',10',10a'-decahydro-1'H-spiro[[1,3]dioxolane-2,2'-phenanthrene] [ No CAS ]
(+/-)-(4a'S,8a'R,10a'R)-8a'-(2-chlorovinyl)-1',1',4a'-trimethyl-3',4',4a',6',7',8',8a',9',10',10a'-decahydro-1'H-spiro[[1,3]dioxolane-2,2'-phenanthrene] [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: chloromethyltriphenylphosphonium chloride With N,N,N,N,N,N-hexamethylphosphoric triamide; n-butyllithium In tetrahydrofuran at 0 - 20℃; for 0.333333h; Stage #2: C₂₀H₃₀O₃ In tetrahydrofuran at 20℃; for 0.833333h;	A.1.i; 1.i To a suspension of (chloromethyl)triphenylphosphonium chloride (17.6 g, 50.7 mmol) in THF (54 mL) was added /?-BuLi (30.2 mL, 1.6 M in hexane) dropwise in an ice bath under N2. To the mixture was added hexamethylphosphoramide (HMPA) (8.3 mL). The mixture was stirred at room temperature for 20 min. To the mixture was added a solution of 3 (3.85 g, 12.1 mmol) in THF (54 mL) at room temperature. The mixture was stirred at room temperature for 50 min. To the mixture was added saturated aqueous NH4OH solution (120 mL). The aqueous mixture was extracted with CH2Cl2-Et2O (1 :2, 75 mL x 4). The extract was washed with brine (100 mL x 2), then dried over MgSO4 and filtered. The filtrate was evaporated to give a brown residue (17.13 g). The residue was washed with hexanes/EtOAc (10:1) and filtered through a glass filter. The solid residue in the filter was washed several times with hexanes/EtOAc (7:1 -160 mL, 5:1 -120 mL, 4:1 -150 mL). The solid residue was checked by TLC and no product was present in it. The filtrates were combined and evaporated in vacuo to give a yellow residue (10 g). The residue was purified by flash column chromatography (hexanes/EtOAc 10:1) to give 4 (E -isomers- isomer =1 :4) as a colorless oil (3.38 g, 80%).

Reference： [1]Current Patent Assignee: DARTMOUTH COLLEGE - WO2008/64133, 2008, A1 Location in patent: Page/Page column 53; 86; 89

64
(+/-)-3-((4a'S,8a'R,10a'R)-1',1',4a'-trimethyl-3',4',4a',6',7',8',8a',9',10',10a'-decahydro-1'H-spiro[[1,3]dioxolane-2,2'-phenanthrene]-8a'-yl)prop-2-ynal [ No CAS ]
[ 5293-84-5 ]
C₂₃H₃₁ClO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	Stage #1: chloromethyltriphenylphosphonium chloride With N,N,N,N,N,N-hexamethylphosphoric triamide; n-butyllithium In tetrahydrofuran at 0 - 20℃; for 0.333333h; Stage #2: (+/-)-3-((4a'S,8a'R,10a'R)-1',1',4a'-trimethyl-3',4',4a',6',7',8',8a',9',10',10a'-decahydro-1'H-spiro[[1,3]dioxolane-2,2'-phenanthrene]-8a'-yl)prop-2-ynal In tetrahydrofuran at 20℃; for 0.833333h;	C.7.b; 1.b To a suspension of (chloromethyl)triphenylphosphonium chloride (4.76 g, 13.7 mmol) in THF (14 mL) was added n-BuLi (1.6 M in hexane, 8.2 mL, 13.1 mmol) dropwise in an ice bath under N2. To the mixture was added HMPA (2.4 mL). The mixture was stirred at room temperature for 20 min. To the mixture was added a solution of aldehyde 19 (798 mg, 2.3 mmol) in THF (14 mL) at room temperature. The mixture was stirred at room temperature for 50 min. To the mixture was added saturated NH4OH solution (100 mL). The aqueous mixture was extracted with CH2Cl2-Et2O (1 :2, 50 mL x 4). The extract was washed with brine (x 2), then dried over MgSO4 and filtered. The filtrate was evaporated to give a brown residue (4.56 g). The residue was washed with a mixture of hexanes-ethyl acetate (10:1), and filtered through a glass filter. The solid residue in the filter was washed several times with hexanes-ethyl acetate (10:1 -110 mL, 7:1 - 80 mL, 5:1 - 120 niL). The filtrates were combined and evaporated to give a crude yellow solid (3.4 g). The crude product was purified by flash column chromatography [hexanes-ethyl acetate (10:1)] to give the product 20 as a colorless oil (667 mg, 76%).
76%	Stage #1: chloromethyltriphenylphosphonium chloride With N,N,N,N,N,N-hexamethylphosphoric triamide; n-butyllithium In tetrahydrofuran; hexane at 20℃; for 0.333333h; Cooling with ice; Stage #2: (+/-)-3-((4a'S,8a'R,10a'R)-1',1',4a'-trimethyl-3',4',4a',6',7',8',8a',9',10',10a'-decahydro-1'H-spiro[[1,3]dioxolane-2,2'-phenanthrene]-8a'-yl)prop-2-ynal In tetrahydrofuran; hexane at 20℃; for 0.833333h;

Reference： [1]Current Patent Assignee: DARTMOUTH COLLEGE - WO2008/64133, 2008, A1 Location in patent: Page/Page column 59-60; 102-103
[2]Honda, Tadashi; Yoshizawa, Hidenori; Sundararajan, Chitra; David, Emilie; Lajoie, Marc J.; Favaloro Jr., Frank G.; Janosik, Tomasz; Su, Xiaobo; Honda, Yukiko; Roebuck, Bill D.; Gribble, Gordon W. [Journal of Medicinal Chemistry, 2011, vol. 54, # 6, p. 1762 - 1778]

65
C₂₂H₃₀O₃ [ No CAS ]
[ 5293-84-5 ]
C₂₃H₃₁ClO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With N,N,N,N,N,N-hexamethylphosphoric triamide; n-butyllithium In tetrahydrofuran	iii The aldehyde 19 was obtained by the formylation of alkyne I with dimethylformamide and boron triflouride etherate in 91% yield (Iguchi et al, 1993). The Wittig reaction of aldehyde 19 with (chloromethyl) triphenylphosphonium chloride gave the alkenyl chloride 20 in 76% yield. Treatment of 20 with methyl lithium and quenching of the resulting anion with TMSCl yielded the TMS protected alkyne. Treatment of this alkyne with aqueous HCl solution afforded the ketone 21 in 72% yield. Allylic oxidation of 21 gave the enone 22 in 50% yield. Double cyanation of 22 with p-TsCN gave the dinitrile intermediate, which was subsequently oxidized with DDQ to give the bis-enone 23 in 22% yield. Removal of the TMS group with TBAF gave the desired compound TBE-39 in 28% yield (2% overall yield from I).

Reference： [1]Current Patent Assignee: RUTGERS, THE STATE UNIVERSITY OF NEW JERSEY - US2008/233195, 2008, A1 Location in patent: Page/Page column 17-18

66
[ 1158728-95-0 ]
[ 5293-84-5 ]
[ 1158729-03-3 ]

Yield	Reaction Conditions	Operation in experiment
94%	Stage #1: chloromethyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran; hexanes at -78 - 0℃; for 1h; Stage #2: C₂₃H₄₂N₂O₆Si₂ In tetrahydrofuran; hexanes at 20℃; for 3h; Stage #3: With water; ammonium chloride In tetrahydrofuran; hexanes	Synthesis of compound 58; 50 58; To a suspension of chloromethyltriphenylphosphonium chloride (390 mg, 1.12 mmol) in THF (3 niL) was added n-BuLi (2.2 M in hexanes, 0.51 mL, 1.12 mmol) at -780C. The mixture was stirred at O0C for Ih and compound 50 (140 mg, 0.28 mmol) in anhydrous THF (3 mL) was added. The resulting mixture was stirred at rt for 3h, neutralized with saturated ammonium chloride, diluted with EtOAc, washed with brine, and dried over sodium sulfate. After filtration and concentration, the residue was purified by silica gel column chromatography (MeOH: CH2Cl2 = 1 :40) to give compound 58 as a white solid (140 mg, 94%).

Reference： [1]Current Patent Assignee: GILEAD SCIENCES INC - WO2009/67409, 2009, A1 Location in patent: Page/Page column 75

67
[ 5293-84-5 ]
[ 369376-68-1 ]
3-(chloromethylene)-2,3-dihydro-1-benzoxepin [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
52%	Stage #1: chloromethyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran at 0℃; for 1h; Stage #2: benzo[b]oxepin-3(2H)-one In tetrahydrofuran at 20℃; for 1h;	26 EXAMPLE 26, Preparation of 3-(chloromethylene)-2,3-dihydro-1-benzoxepin EXAMPLE 26 Preparation of 3-(chloromethylene)-2,3-dihydro-1-benzoxepin 1.1 eq. of n-butyllithium are added to 104 mg (0.3 mmol) of chloromethyltriphenylphosphonium chloride in solution in tetrahydrofuran cooled to 0° C. After stirring for one hour, 40 mg (0.25 mmol) of 1-benzoxepin-3(2H)-one, prepared according to example 25, are added at ambient temperature and the mixture is left for 1 hour. After the usual treatments and evaporating the solvent under reduced pressure, the crude reaction product is taken up in pentane in order to precipitate triphenylphosphine oxide, to give 25 mg (52%) of 3-(chloromethylene)-2,3-dihydro-1-benzoxepin in the form of two isomers as a Z/E mixture (90/10); 1H NMR (300 MHz, C6D6) 6.98-6.78 (m, 4H), 6.02 (d, J=11.8 Hz, 1H), 5.80 (d, J=11.8 Hz, 1H), 5.68 (s, 1H), 4.65 (4.06) (s, 2H).

Reference： [1]Current Patent Assignee: BAYER AG - US2004/249173, 2004, A1 Location in patent: Page 20

68
[ 5293-84-5 ]
[ 84199-61-1 ]
[ 1196079-67-0 ]
(E)-2-bromo-3-(1-chloroprop-1-en-2-yl)pyridine [ No CAS ]

Reference： [1]Tetrahedron,2009,vol. 65,p. 8940 - 8949

69
C₁₂H₁₈O₆ [ No CAS ]
[ 5293-84-5 ]
[ 1030595-47-1 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: chloromethyltriphenylphosphonium chloride With n-butyllithium In hexane at -78℃; for 1h; Stage #2: C₁₂H₁₈O₆ In tetrahydrofuran; hexane at -78 - 0℃;	2 The synthesis of compound i: DMSO (5.5ml, 77.5mmol) was added dropwise into the dichloromethane(80ml) solution of oxalyl chloride(3.4ml, 38.7mmol) at -60 °C. Then, the solution was stirred for 15 minutes and added dropwise with the dichloromethane (100ml) solution of compound h (25.7mmol). After the reaction was carried out for 30 minutes at -60 °C, triethylamine (10.9ml, 78.2mmol) was added in to continue the reaction at a room temperature for 30 minutes. Then, water was added to terminate the reaction, and the organic layer was separated and dried over anhydrous Na2SO4. The solvent was removed through evaporation and the residue was separated and purified by column chromatography to obtain a solid product. ClCH2P (C6H5)3Cl (2.15g, 6.19mmol) was added into anhydrous tetrahydrofuran (50ml). The solution was cooled to -78 °C, added with n-BuLi hexane solution(1.6M, 4.0ml), stirred for reaction for an hour, and added with the dry tetrahydrofuran solution(50ml) of the solid product (1.51mmol). The cooling temperature was gradually increased to 0 °C to continue the reaction for 3 hours. After completion of the reaction, a saturated NH4Cl solution (10ml) was carefully added dropwise, and the solution was subsequently extracted with ethyl acetate (2×100ml). The organic layer was washed with saline twice (2×75ml), finally dried over anhydrous MgSO4, and evaporated under a reduced pressure to remove the solvent. The residue produced was dissolved into anhydrous tetrahydrofuran (40ml), cooled to -78 °C, and slowly added dropwise with the hexane solution of n-BuLi (1.6M, 20ml). After the solution was stirred for reaction for 2 hours, the reaction was terminated by carefully adding a saturated NH4Cl solution (20ml). The organic layer was washed with saturated salt water, dried over anhydrous MgSO4, and evaporated under a reduced pressure to remove the solvent. Finally the residue was separated and purified by rapid silica gel column to obtain the compound i (yield=48.5%, ESI-MS: 255[M+H]).

Reference： [1]Current Patent Assignee: HENAN GENUINE BIOTECH - EP2177527, 2010, A1 Location in patent: Page/Page column 14

70
[ 952747-51-2 ]
[ 5293-84-5 ]
[ 952747-70-5 ]

Yield	Reaction Conditions	Operation in experiment
46%	Stage #1: chloromethyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere; Stage #2: 3,3:17,17-bis(ethylendioxy)-6α-formylandrostane In tetrahydrofuran at 70℃; for 1h; Inert atmosphere;

Reference： [1]Location in patent: experimental part Gobbini, Mauro; Armaroli, Silvia; Banfi, Leonardo; Benicchio, Alessandra; Carzana, Giulio; Ferrari, Patrizia; Giacalone, Giuseppe; Marazzi, Giuseppe; Moro, Barbara; Micheletti, Rosella; Sputore, Simona; Torri, Marco; Zappavigna, Maria Pia; Cerri, Alberto [Bioorganic and Medicinal Chemistry, 2010, vol. 18, # 12, p. 4275 - 4299]

71
[ 896472-24-5 ]
[ 5293-84-5 ]
[ 896472-36-9 ]

Yield	Reaction Conditions	Operation in experiment
95%	Stage #1: chloromethyltriphenylphosphonium chloride With sodium hexamethyldisilazane In tetrahydrofuran at 0℃; for 0.5h; Stage #2: 12-desethenyl-12-formyl-11-O-methoxymethylmutilin In tetrahydrofuran at 0 - 20℃; for 1h;	42.I (Example 42); Step I; 12-desethenyl-12-(1-chloroethene-2-yl)-11-O-methoxymethylmutil in; 2.84g (8-19 mmol) chloromethyl triphenylphosphonium chloride was suspended in tetrahydrofuran (30 mL). While this suspension was kept chilled on ice in an argon atmosphere, 8.19 mL (8.19 mmol) sodium bis (trimethylsilyl) amide (1mol/L tetrahydrofuran solution) was added dropwise. The mixture was stirred for 0.5 hours at the same temperature and a solution of 1.00 g (2.73 mmol) of the compound of Example 38 in tetrahydrofuran (10 mL) was subsequently added dropwise. The reaction mixture was then stirred for about 1 hour as it was allowed to warm to room temperature. The mixture was poured into diluted aqueous citric acid and was evaporated under reduced pressure. Water was then added to the residue and this mixture was extracted with ethyl acetate (20 mL x 3) . The organic layers were combined, washed with saturated brine (20mL) and dried over anhydrous magnesium sulfate. The dried product was filtered and the solvent was removed. The resulting residue was purified by silica gel column chromatography(hexane:ethylacetate=4:1, followed by hexane:ethyl acetate = 1:1) to afford 1.03 g of the title compound as a colorless powder (95% yield). MS (CI) (m/z) : 399 (MH+) . HRMS (CI) (m/z): Calcd. for C22H36ClO4(MH+) : 399.2302. Found, 399.2329.

Reference： [1]Current Patent Assignee: KYORIN HOLDINGS, INC. - EP1832591, 2007, A1 Location in patent: Page/Page column 107

72
[ 1207109-90-7 ]
[ 5293-84-5 ]
[ 1207110-49-3 ]

Yield	Reaction Conditions	Operation in experiment
76%	With N,N,N,N,N,N-hexamethylphosphoric triamide; n-butyllithium In tetrahydrofuran; hexane at 20℃; for 1.33333h; Cooling with ice;	2 Trimethyl((8-methyl-l,4-dioxaspiro[4.5]decan-8-yl)ethynyl)silane (6) To a suspension of chloromethylene triphenylphosphonyl chloride (95%, 24.2 g, 66 mmol) in THF (72 mL) was added n-BuLi (1.6 M in hexane, 41.5 mL, 66 mmol) dropwise in an ice-water bath. To the mixture was added HMPA (11.8 mL). The mixture was stirred at room temperature for 20 min. To the mixture was added a solution of 5 (3.06 g, 16.6 mmol) in THF (72 mL). The mixture was stirred at room temperature for 1 h. To the mixture was added saturated aqueous ammonium chloride solution (600 mL) The aqueous mixture was extracted with methylene chloride/ether (1 :2, 300 mL x3). The extract was washed with brine (x2), dried over MgSO4, and filtered. The filtrate was evaporated in vacuo to give a brown crystalline solid (21. 31 g). The solid was washed with ether several times. The ether solution was evaporated in vacuo to give a crystalline solid (9.78 g). The solid was purified by flash chromatography [petroleum ether-ether (5:1)] to give 8-(2-chlorovinyl)-8-methyl- l,4-dioxaspiro[4.5]decane (2.74 g, 76%). To a solution of the solid in THF (340 mL) was added MeLi (1.6 M in ether, 100 mL, 160 mmol) dropwise in an ice-water bath. The mixture was stirred at room temperature over night. To the reaction mixture was added water (500 mL). The aqueous mixture was extracted with methylene chloride/ether (1 :2, 300 mL x3). The extract was washed with saturated aqueous sodium bicarbonate solution (300 rnL xl) and brine (300 rnL x2), dried over MgSO4, and filtered. The filtrate was evaporated in vacuo to give an oil (3. 2 g). The oil was purified by flash chromatography to give 6 as a crystalline solid (2.86 g, 90%): 1H NMR (CDCl3) δ 3.94 (4H, m), 1.95, 1.73, 1.61, 1.50 (each 2H, m), 1.22 (3H, s), 0.14 (9H,s); 13C NMR (CDCl3) δ 112.8, 108.9, 85.1, 64.4, 36.9, 32.7, 32.2, 29.4, 0.5.
76%	Stage #1: chloromethyltriphenylphosphonium chloride With N,N,N,N,N,N-hexamethylphosphoric triamide; n-butyllithium In tetrahydrofuran; hexane at 20℃; for 0.333333h; Cooling with ice; Stage #2: 8-methyl-1,4-dioxa-spiro[4.5]decane-8-carbaldehyde In tetrahydrofuran; hexane at 20℃; for 1h;

Reference： [1]Current Patent Assignee: DARTMOUTH COLLEGE - WO2010/11782, 2010, A1 Location in patent: Page/Page column 103
[2]Zheng, Suqing; Santosh Laxmi; David, Emilie; Dinkova-Kostova, Albena T.; Shiavoni, Katherine H.; Ren, Yanqing; Zheng, Ying; Trevino, Isaac; Bumeister, Ronald; Ojima, Iwao; Wigley, W. Christian; Bliska, James B.; Mierke, Dale F.; Honda, Tadashi [Journal of Medicinal Chemistry, 2012, vol. 55, # 10, p. 4837 - 4846]

73
[ 1191255-88-5 ]
[ 5293-84-5 ]
[ 1191255-92-1 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: chloromethyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran; hexane at -30℃; Stage #2: 2',3'-O-cyclohexylidene-4'-C-formyl-5-methyl-5'-O-pivaloyluridine In tetrahydrofuran; hexane at -30℃; Stage #3: With ammonium chloride In tetrahydrofuran; hexane	1.1.6 Synthesis of (Z)-4'-C-(2-chloroethenyl)-2',3'-O-cyclohexylidene-5-methyl -5'-O-pivaloyluridine (Compound (10-1)) [Step 6] Synthesis of (Z)-4'-C-(2-chloroethenyl)-2',3'-O-cyclohexylidene-5-methyl -5'-O-pivaloyluridine (Compound (10-1)) To a suspension of chloromethyl triphenyl phosphonium chloride (8.53 g, 24.57 mmol) in THF (37 mL) cooled to -30°C, butyl lithium (1.6 M hexane solution, 15.4 mL, 24.57 mmol) was added dropwise. After the mixture was stirred at -30°C for 90 minutes, a solution of Compound (9-1) (3.69 g, 8.19 mmol) in THF (18mL) was added dropwise at -30°C. After the mixture was stirred at the same temperature for 2 hours, a saturated ammonium chloride solution (37 mL) was added dropwise. After THF and hexane were distilled off under reduced pressure, the residual solution was extracted with ethyl acetate (2 * 37 mL). From combined organic layers, the solvent was distilled off under reduced pressure to give a semisolid residual material (8.23 g). Silica gel column chromatography (silica gel: 90 g, heptane:ethyl acetate =2:1 (v/v) ->1:1 (v/v)) purified this, and the title compound (10-1) (3.65g, a yield: 92%) was obtained as white powdery material. (Properties) 1H-NMR (200 MHz, DMSO-d6): δ 1.135 (9H, s, 3 in vacuo Me of Pv), 1.26-1.80 (10H, m, 5 × CH2), 1.775 (3H, d, J=1.1 Hz, 5-Me), 4.29 and 4.37(1H each, ABq, J=11.4 Hz, 5'-H2), 4.88 (1H, d, J=6.6 Hz, 3'-H), 5.09 (1H, dd, J=6.6, 3.1 Hz, 2'-H), 5.88 (1H, d, J=3.1 Hz, 1'-H), 5.96 (1H, d, J=8.2 Hz, ClCH=CH-), 6.54 (1H, d, J=8.2 Hz, C1CH=CH-), 7.52 (1H, d, J=1.1 Hz, 6-H), and 11.46 (1H, br s, 3-H). 13C-NMR (50.3 MHz, DMSO-d6): δ 11.9 (5-Me), 23.2 (CH2) , 23.6 (CH2), 24.4 (CH2), 26.7(3 × Me of Pv), 34.0 (CH2), 35.4 (CH2), 65.7 (5'-C), 81.5 (3'-C), 82.8(2'-C), 86.8 (4'-C), 89.9 (1'-C), 109.8 (5-C), 114.8 (quaternary C of CyH), 120.2 (ClHC=CH-), 127.9 (ClHC=CH-), 137.4(6-C), 150.3 (2-C), 163.7 (4-C), and 177.0 (C=O of Pv).

Reference： [1]Current Patent Assignee: HAMARI CHEMICALS LTD - EP2277878, 2011, A1 Location in patent: Page/Page column 57

74
[ 27335-33-7 ]
[ 5293-84-5 ]
[ 1004989-26-7 ]

Yield	Reaction Conditions	Operation in experiment
58.3%	Stage #1: chloromethyltriphenylphosphonium chloride With potassium <i>tert</i>-butylate In tetrahydrofuran for 1.5h; Inert atmosphere; Cooling with liquid nitrogen; Stage #2: methyl (1R,3R)-3-formyl-2,2-dimethylcyclopropanecarboxylate In tetrahydrofuran at 20℃; for 6.33333h; Cooling with liquid nitrogen;	1.1.3 2.51 g of Ph3P+CH2Cl.Br- was added to a 100 mL round-bottomed flask, evacuated and filled with nitrogen, and then 20 mL of anhydrous THF was added and the mixture was cooled by liquid nitrogen. The mixture was added with 0.85 g of KOC(CH3)3 solution in THF (the reaction liquid turned red) and reacted at low temperature for 1.5 hours. 1 g (1R)-trans-methyl caronaldehydate solution in THF (8 ml) was added and the liquid nitrogen was removed after 20 minutes and the mixture was reacted at room temperature for 6 hours. The reaction liquid was poured into 40 mL of ice-water and extracted with ethyl ether. The organic phase was dried over anhydrous magnesium sulplate. The solvent was removed by rotary evaporation and the crude product was purified by column chromatography (elude: petroleum ether/ethyl acetate=200/1) to afford 0.7 g of colorless liquid, yield 58.3%. 1H NMR (CDCl3) δ: 1.18 (s, 3H,cyclic-CH3), 1.25 (s, 3H,cyclic-CH3), 1.56~1.58 (t, 1H, J=6 Hz,cyclic-H), 2.04~2.05 (m, 1H, cyclic-H), 3.68, 3.69 (2s, 3H,COOCH3), 5.47~5.51 (t,0.391H, J=8 Hz, Z-=CH),5.65~5.70 (dd,0.611H, J1=J2=14 Hz, E-=CH), 6.06 (d,0.611H, J=14 Hz, E-=CHCl),6.14 (d,0.391H, J=8 Hz, Z-=CHCl).

Reference： [1]Current Patent Assignee: EAST CHINA NORMAL UNIVERSITY - US2010/286265, 2010, A1 Location in patent: Page/Page column 3; 4

75
3,3:17,17-bis(ethylendioxy)-6α-formylandrostane [ No CAS ]
[ 5293-84-5 ]
3,3:17,17-bis(ethylendioxy)-6α-ethynylandrostane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
46%	Stage #1: chloromethyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; for 0.5h; Inert atmosphere; Stage #2: 3,3:17,17-bis(ethylendioxy)-6α-formylandrostane In tetrahydrofuran; hexane at 70℃; for 1h; Stage #3: With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; for 1h; Inert atmosphere;	27 Preparation 276α-Ethynylandrostane-3,17-dione (II-bb); To a stirred solution of (chloromethyl)triphenylphosphonium chloride (1.20 g) in dry THF (20 mL) at -78° C. under argon, 1.6 M n-butyllithium in n-hexane (1.5 mL) was added dropwise. After 30 min at room temperature, a solution of 3,3:17,17-bis(ethylendioxy)-6α-formylandrostane (Prepn. 11, 0.28 g) in dry THF (7 mL) was added dropwise. The mixture was heated at 70° C. for 1 h and then cooled to room temperature. The mixture was quenched by addition of brine and extracted with EtOAc (3×). The combined organic extracts were dried over Na2SO4, and evaporated to dryness. The crude product was dissolved in dry THF (20 mL) and stirred at -78° C. To the resulting solution 1.6 M n-butyllithium in n-hexane (2.24 mL) under argon was added dropwise. After 1 h at room temperature the mixture was quenched by addition of brine and extracted with Et2O (3×). The combined organic extracts were dried over Na2SO4, and evaporated to dryness to give 3,3:17,17-bis(ethylendioxy)-6α-ethynylandrostane (160 mg, 46%), sufficiently pure to be used in the next step without further purification. 1H-NMR (300 MHz, acetone-d6, ppm from TMS): δ 3.85 (m, 8H), 2.46 (d, 1H), 2.30-0.67 (m, 21H), 0.82 (s, 3H), 0.86 (s, 3H).The title compound II-bb was prepared in 46% yield from 3,3:17,17-bis(ethylendioxy)-6α-ethynylandrostane by the procedure described above for the preparation of 6α-cyanoandrostane-3,17-dione (II-ac, Prepn. 3). The combined organic extracts were washed with H2O, dried over Na2SO4 and evaporated to dryness. The residue was purified by flash chromatography (SiO2, cyclohexane/CH2Cl2/acetone 80/10/10). 1H-NMR (300 MHz, acetone-d6, ppm from TMS): δ 2.69-0.78 (m, 22H), 1.12 (s, 3H), 0.87 (s, 3H).

Reference： [1]Current Patent Assignee: ALFASIGMA GROUP - US2011/53902, 2011, A1 Location in patent: Page/Page column 37

76
[ 916991-43-0 ]
[ 5293-84-5 ]
[ 1286680-19-0 ]

Yield	Reaction Conditions	Operation in experiment
70%	Stage #1: chloromethyltriphenylphosphonium chloride With potassium <i>tert</i>-butylate In tetrahydrofuran at -40℃; for 0.166667h; Stage #2: (2R,3S,4R)-3-(benzyloxy)-4-hydroxytetrahydrofuran-2-carbaldehyde In tetrahydrofuran at -40 - 0℃; for 2h;

Reference： [1]Reddy, P. Venkat; Bajpai, Vikas; Kumar, Brijesh; Shaw, Arun K. [European Journal of Organic Chemistry, 2011, # 8, p. 1575 - 1586]

77
[ 33985-71-6 ]
[ 5293-84-5 ]
(1Z)-1-chloro-2-(9'-julolidinyl)-ethylene [ No CAS ]
[ 1285688-63-2 ]

Yield	Reaction Conditions	Operation in experiment
		To a solution of chloromethyltriphenylphosphonium chloride (3.98 mmol, 1.6 equiv) in THF (90 mL) at 0 C under an argon atmosphere, was slowly added n-BuLi (1.5 M in hexane, 3.74 mmol, 1.5 equiv). After 30 min stirring at -78 C, 9-formyljulolidine (2.49 mmol, 1.0 equiv) in THF (20 mL) was slowly added. The reaction mixture was stirred for 10 min at -78 C and then for 14 h at room temperature. The reaction mixture was quenched with a 10% aqueous solution of NaHCO3 (20 mL). The resulting solution was then extracted with dichloromethane (3×15 mL). The combined organic extracts were washed with saturated brine (10 mL) and dried over MgSO4. After evaporation the crude product was further purified by silica gel column chromatography (pentane/ether: 15/1) to give a mixture of two isomers 4a/4b (65/35). Yield: 0.574 g (99%) as a yellow oil. IR: 3073, 3005, 2937, 2885, 1604, 1505, 1464, 1282, 1073, 1053, 974, 737, 685, 620 cm-1. MS (EI) m/z: 233-235 (M+, 100%, 34%), 204 (17%), 196 (25%), 168 (24%), 154 (14%), 141 (11%), 115 (13%), 77 (4%). Anal. Calcd for C14H16ClN (233.45): C 71.96, H 6.85, N 6.00; found: C 71.81, H 6.91, N 5.98.

Reference： [1]Tetrahedron,2011,vol. 67,p. 2287 - 2298

78
C₂₅H₄₈O₃Si₂ [ No CAS ]
[ 5293-84-5 ]
C₂₆H₄₉ClO₂Si₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With n-butyllithium In tetrahydrofuran at 0 - 20℃;

Reference： [1]Location in patent: scheme or table Sugino, Kumi; Nakazaki, Atsuo; Isobe, Minoru; Nishikawa, Toshio [Synlett, 2011, # 5, p. 647 - 650]

79
[ 1391563-95-3 ]
[ 5293-84-5 ]
C₁₄H₂₃ClO₃Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%	With n-butyllithium In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide at 0 - 25℃; for 1.5h;

Reference： [1]Location in patent: scheme or table Mehta, Goverdhan; Roy, Subhrangsu; Pan, Subhas Chandra [Tetrahedron Letters, 2012, vol. 53, # 32, p. 4093 - 4095]

80
[ 1400008-54-9 ]
[ 5293-84-5 ]
[η⁵-1,2-(CH≡C)₂C₅H₃]Co(η⁴-C₄Ph₄) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: chloromethyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere; Stage #2: [η⁵-1,2-(CHO)₂C₅H₃]Co(η⁴-C₄Ph₄) In tetrahydrofuran; hexane at -78 - 20℃; for 15h; Inert atmosphere;	4.8 Preparation of [η⁵-1,2-(CH≡C)₂C₅H₃]Co(η⁴-C₄Ph₄) (6) General procedure: n-BuLi (2.40 mL, 1.6 M in hexanes, 3.84 mmol) was added to a solution of (chloromethyl) triphenylphosphonium chloride (0.82 g, 3.80 mmol) in 30 mL of THF at -78 °C. The solution was warmed to room temperature while stirring and then re-cooled to -78 °C. To the deep red-orange solution of the resulting ylide was added a solution of 3 (1.17 g, 2.05 mmol) in THF (20 mL) via cannula over a period of 5 min. The resulting reaction mixture was warmed to room temperature and stirred for 15 h. After evaporation of the solvent, the residue was extracted with 10% aqueous NH4Cl (50 mL) and Et2O (2 × 30 mL) The combined organic layers were dried (Na2SO4), filtered and evaporated to get a dark orange residue. This residue was washed with hexane, dried in vacuum and dissolved in 35 mL of THF. The solution was cooled to -40 °C and n-BuLi (4.00 mL, 1.6 M, 6.40 mmol) was added while stirring, The reaction mixture was found to darken slowly and after 15 min, the solution was cooled further to -80 °C. To the cooled solution, 20% H2SO4 (5 mL) was added upon which it turned yellow. The reaction mixture was warmed to room temperature and was extracted with diethyl ether (2 × 30 mL), washed with brine (30 mL) and dried over Na2SO4. The dried ether extract was filtered and the solvent was evaporated off to get a yellow residue which was chromatographed on alumina using ethyl acetate-hexane as eluent. The first band was collected at 2% ethyl acetate/hexane which upon evaporation of solvent gave a yellow crystalline powder characterized as 5

Reference： [1]Singh, Nem; Metla, Bhanu P.R.; Elias, Anil J. [Journal of Organometallic Chemistry, 2012, vol. 717, p. 99 - 107]

81
[ 1400008-53-8 ]
[ 5293-84-5 ]
[η⁵-1,3-(CH≡C)₂C₅H₃]Co(η⁴-C₄Ph₄) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: chloromethyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere; Stage #2: [η⁵-1,3-(CHO)₂C₅H₃]Co(η⁴-C₄Ph₄) In tetrahydrofuran; hexane at -78 - 20℃; for 15h; Inert atmosphere;	4.7 Preparation of [η⁵-1,3-(CH≡C)₂C₅H₃]Co(η⁴-C₄Ph₄) (5) General procedure: n-BuLi (2.40 mL, 1.6 M in hexanes, 3.84 mmol) was added to a solution of (chloromethyl) triphenylphosphonium chloride (0.82 g, 3.80 mmol) in 30 mL of THF at -78 °C. The solution was warmed to room temperature while stirring and then re-cooled to -78 °C. To the deep red-orange solution of the resulting ylide was added a solution of 3 (1.17 g, 2.05 mmol) in THF (20 mL) via cannula over a period of 5 min. The resulting reaction mixture was warmed to room temperature and stirred for 15 h. After evaporation of the solvent, the residue was extracted with 10% aqueous NH4Cl (50 mL) and Et2O (2 × 30 mL) The combined organic layers were dried (Na2SO4), filtered and evaporated to get a dark orange residue. This residue was washed with hexane, dried in vacuum and dissolved in 35 mL of THF. The solution was cooled to -40 °C and n-BuLi (4.00 mL, 1.6 M, 6.40 mmol) was added while stirring, The reaction mixture was found to darken slowly and after 15 min, the solution was cooled further to -80 °C. To the cooled solution, 20% H2SO4 (5 mL) was added upon which it turned yellow. The reaction mixture was warmed to room temperature and was extracted with diethyl ether (2 × 30 mL), washed with brine (30 mL) and dried over Na2SO4. The dried ether extract was filtered and the solvent was evaporated off to get a yellow residue which was chromatographed on alumina using ethyl acetate-hexane as eluent. The first band was collected at 2% ethyl acetate/hexane which upon evaporation of solvent gave a yellow crystalline powder characterized as 5

Reference： [1]Singh, Nem; Metla, Bhanu P.R.; Elias, Anil J. [Journal of Organometallic Chemistry, 2012, vol. 717, p. 99 - 107]

82
[ 135774-00-4 ]
[ 5293-84-5 ]
[ 193421-05-5 ]

Yield	Reaction Conditions	Operation in experiment
85.4%	Stage #1: chloromethyltriphenylphosphonium chloride With sodium amide In tetrahydrofuran at -0.16 - 24.84℃; for 1h; Inert atmosphere; Schlenk technique; Stage #2: 1',2',3',4',5'-pentamethylferrocenecarbaldehyde In tetrahydrofuran at 19.84 - 24.84℃; for 4.5h; Inert atmosphere; Schlenk technique; Stage #3: With potassium <i>tert</i>-butylate In tetrahydrofuran for 47h; Reflux; Inert atmosphere; Schlenk technique;

Reference： [1]Muratsugu, Satoshi; Kishida, Masa-Aki; Sakamoto, Ryota; Nishihara, Hiroshi [Chemistry - A European Journal, 2013, vol. 19, # 51, p. 17314 - 17327]

83
(4R)-4-methyl-4-((triethylsilyl)oxy)tetrahydro-2H-pyran-2-ol [ No CAS ]
[ 5293-84-5 ]
(S)-6-chloro-3-methyl-3-((triethylsilyl)oxy)hex-5-en-1-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
62%	Stage #1: chloromethyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Stage #2: (4R)-4-methyl-4-((triethylsilyl)oxy)tetrahydro-2H-pyran-2-ol In tetrahydrofuran; hexane at -78℃; for 39h;

Reference： [1]Kubota, Takaaki; Suzuki, Haruna; Takahashi-Nakaguchi, Azusa; Fromont, Jane; Gonoi, Tohru; Kobayashi, Jun'Ichi [RSC Advances, 2014, vol. 4, # 22, p. 11073 - 11079]

84
C₅₃H₆₀FN₅O₆Si₂ [ No CAS ]
[ 5293-84-5 ]
C₅₄H₆₁ClFN₅O₅Si₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	Stage #1: chloromethyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran at -78℃; for 2.16667h; Stage #2: C₅₃H₆₀FN₅O₆Si₂ In tetrahydrofuran at 25℃; for 15h;	27 EXAMPLE 27 j0320j To a stirred solution of chloromethyl-triphenyl-phosphonium chloride (1.9 g, 5.4 mmol) in anhydrous THF (30 mL) was added dropwise n-BuLi (2.16 mL, 5.4 mmol, 2.5 M in THF) at -78°C over 10 mins. Stirring was continued at -78°C for 2 hours. P25-6 (1.7 g, 1.8 mmol) was added, and the mixture and stirred at 25°C for 15 hours. The reaction was quenched with saturated NH4C1 (50 mL). The mixture was extracted with EtOAc. The combined organic phase was dried with Na2SO4, filtered and evaporated to dryness to give a light yellow oil. The oil was purified by column chromatography (DCM:MeOH = 200:1 to 50:1) to give P27-i as a white solid (1.2 g, 70%).

Reference： [1]Current Patent Assignee: JOHNSON & JOHNSON INC - WO2014/209979, 2014, A1 Location in patent: Paragraph 0320

85
[ 1445379-66-7 ]
[ 5293-84-5 ]
[ 1445380-54-0 ]

Yield	Reaction Conditions	Operation in experiment
91.2%	Stage #1: chloromethyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran at -70℃; for 0.833333h; Inert atmosphere; Stage #2: C₃₂H₄₃FN₂O₆Si₂ In tetrahydrofuran at -70 - 0℃; for 3h;	18 EXAMPLE 18 j0261j To a solution of (chloromethyl)triphenylphosphonium chloride (2.1 g, 6.0 mmol) in anhydrous THF (10 mL) was added dropwise n-BuLi (4.6 mL, 6.0 mmol) at -70°C under nitrogen. The reaction was stirred at -70°C for 50 mins. A solution of compound P3-5 (950 mg, 1.5 mmol) in anhydrous THF (5 mL) was added at -70°C, and the reaction was stirred at 0°C for 3 hours. The reaction was quenched by saturated aq. NH4C1 and extracted with EtOAc. The organic layer was separated, dried and concentrated to give a residue. The residue was purified by column chromatography on silica gel (eluting with PE:EtOAc = 6:1) to give P18-i as a yellow gum (900 mg, 91.2%).

Reference： [1]Current Patent Assignee: JOHNSON & JOHNSON INC - WO2014/209979, 2014, A1 Location in patent: Paragraph 0261

86
C₃₀H₃₆N₂O₇Si [ No CAS ]
[ 5293-84-5 ]
C₃₁H₃₇ClN₂O₆Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	Stage #1: chloromethyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran at -70 - 0℃; for 1h; Inert atmosphere; Stage #2: C₃₀H₃₆N₂O₇Si In tetrahydrofuran at 0℃; for 2h; Inert atmosphere;	28 Compound 38 To a solution of methyltriphenylphosphonium chloride (2.95 g, 8.51 mmol, 4 eq.) in anhydrous THF (20 mL) was added n-BuLi (3.2 mL, 8.1 mmol, 3.8 eq.) dropwise at -70° C. under nitrogen atmosphere. The mixture was stirred at 0° C. for 1 h. A solution of 38-8 (1.2 g, 2.13 mmol) in anhydrous THF (3 mL) was added dropwise at 0° C. under nitrogen atmosphere. The solution was stirred 0° C. for 2 h. The reaction was quenched with NH4Cl and extracted with EtOAc. The organic layer was washed with brine and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (20% EtOAc in hexane) to give 38-9 (0.9 g, 75%) as a white solid

Reference： [1]Current Patent Assignee: JOHNSON & JOHNSON INC - US2015/105341, 2015, A1 Location in patent: Paragraph 0534

87
4-[4-(4-formyl-2,6-dimethylphenoxy)pyrimidin-2-ylamino]benzonitrile [ No CAS ]
[ 5293-84-5 ]
[ 500288-18-6 ]
[ 500288-20-0 ]

Yield	Reaction Conditions	Operation in experiment
1: 14% 2: 15%	Stage #1: chloromethyltriphenylphosphonium chloride With n-butyllithium In tetrahydrofuran at -70℃; for 0.5h; Inert atmosphere; Stage #2: 4-[4-(4-formyl-2,6-dimethylphenoxy)pyrimidin-2-ylamino]benzonitrile In tetrahydrofuran at 20℃; Inert atmosphere;	B.B9A.b The Preparation of Compound 108 and 109 nBuLi[1.6] (0.00261 mol) was added dropwise at -70° C. to a mixture of (chloromethyl)triphenylphosphonium chloride (0.00261 mol) in THF (10 ml) under N2 flow. The mixture was stirred for 30 minutes. A solution of intermediate 31 (prepared according to A4.a) (0.00087 mol) in THF (5 ml) was added dropwise. The mixture was stirred at room temperature overnight, then poured out into H2O and extracted with EtOAc. The organic layer was separated, dried (MgSO4), filtered, and the solvent was evaporated. The residue (1.1 g) was purified by column chromatography over silica gel (eluent: CH2Cl2/CH3OH/NH4OH 98/2/0.1; 15-40 μm). The pure fractions were collected and the solvent was evaporated. The residue (0.3 g) was purified by column chromatography over hypersil C18 (eluent: CH3OH/NH4Ac 0.5% 70/30). Two fractions (F1, F2) were collected and the solvent was evaporated. Yield: 0.097 g F1 and 0.085 g F2. F1 was crystallized from DIPE. The precipitate was filtered off and dried. Yield: 0.045 g of compound 108 (14%) (mp. 165° C.). F2 was crystallized from DIPE. The precipitate was filtered off and dried. Yield: 0.049 g of compound 109 (15%) (mp. 200° C.).

Reference： [1]Current Patent Assignee: JOHNSON & JOHNSON INC - US9192577, 2015, B2 Location in patent: Page/Page column 80

88
[ 5293-84-5 ]
[ 500293-29-8 ]
[ 741256-93-9 ]

Yield	Reaction Conditions	Operation in experiment
9%	Stage #1: 4-[4-(4-formyl-2,6-dimethylphenylamino)pyrimidin-2-ylamino]benzonitrile With n-butyllithium In tetrahydrofuran at -70℃; for 0.5h; Inert atmosphere; Stage #2: chloromethyltriphenylphosphonium chloride In tetrahydrofuran at 20℃;	B.B9A.a The Preparation of Compound 107 nBuLi[1.6] (0.0026 mol) was added dropwise at -70° C. to a mixture of intermediate 13 (prepared according to A5.a) (0.0008 mol) in THF (10 ml) under N2 flow. The mixture was stirred at -70° C. for 30 minutes. A solution of (chloromethyl)triphenylphosphonium chloride (0.0026 mol) in THF (5 ml) was added dropwise. The mixture was stirred at room temperature overnight, poured out into H2O and extracted with EtOAc. The organic layer was separated, dried (MgSO4), filtered and the solvent was evaporated. The residue (0.7 g) was purified by column chromatography over kromasil (eluent: CH2Cl2/CH3OH 99/1; 10 μm). The pure fractions were collected and the solvent was evaporated. The residue (0.155 g) was purified by column chromatography over C18 (eluent: CH3CN/NH4Ac 0.5% 60/40). The pure fractions were collected and the solvent was evaporated. The residue (0.051 g) was crystallized from DIPE. The precipitate was filtered off and dried. Yield: 0.029 g of compound 107 (9%). (mp. 250° C.)

Reference： [1]Current Patent Assignee: JOHNSON & JOHNSON INC - US9192577, 2015, B2 Location in patent: Page/Page column 79

Purity	Size	Price	VIP Price	USA Stock *0-1 Day	Global Stock *5-7 Days	Quantity
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CAS No. :	5293-84-5	MDL No. :	MFCD00011867
Formula :	C₁₉H₁₇Cl₂P	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	SXYFAZGVNNYGJQ-UHFFFAOYSA-M
M.W :	347.22	Pubchem ID :	197823
Synonyms :

Num. heavy atoms :	22
Num. arom. heavy atoms :	18
Fraction Csp3 :	0.05
Num. rotatable bonds :	4
Num. H-bond acceptors :	0.0
Num. H-bond donors :	0.0
Molar Refractivity :	101.66
TPSA :	13.59 Å²

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	Yes
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	Yes
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-4.95 cm/s

Log Po/w (iLOGP) :	-1.91
Log Po/w (XLOGP3) :	4.89
Log Po/w (WLOGP) :	1.18
Log Po/w (MLOGP) :	5.85
Log Po/w (SILICOS-IT) :	5.22
Consensus Log Po/w :	3.05

[ CAS No. 5293-84-5 ] {[proInfo.proName]}

Quality Control of [ 5293-84-5 ]

Related Doc. of [ 5293-84-5 ]

Product Details of [ 5293-84-5 ]

Calculated chemistry of [ 5293-84-5 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 5293-84-5 ]

Application In Synthesis of [ 5293-84-5 ]

[ 5293-84-5 ] Synthesis Path-Downstream 1~88

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Lipinski :	1.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	1.0
Bioavailability Score :	0.55

Log S (ESOL) :	-5.41
Solubility :	0.00134 mg/ml ; 0.00000385 mol/l
Class :	Moderately soluble
Log S (Ali) :	-4.91
Solubility :	0.00426 mg/ml ; 0.0000123 mol/l
Class :	Moderately soluble
Log S (SILICOS-IT) :	-8.55
Solubility :	0.000000981 mg/ml ; 0.0000000028 mol/l
Class :	Poorly soluble

PAINS :	0.0 alert
Brenk :	2.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	4.37

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H302-H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

Precautionary Statements-General
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Response
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P301	IF SWALLOWED:
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P321
P322
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P342	If experiencing respiratory symptoms:
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P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
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P370	In case of fire:
P371	In case of major fire and large quantities:
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P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
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P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling