[ CAS No. 59159-39-6 ] {[proInfo.proName]}

Name: 59159-39-6|(2-(tert-Butoxy)-2-oxoethyl)triphenylphosphonium bromide|97%
Brand: Ambeed
SKU: A435674
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2D 3D

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Quality Control of [ 59159-39-6 ]

COA NMR CNMR HPLC LC-MS

Related Doc. of [ 59159-39-6 ]

SDS Specification

Alternatived Products of [ 59159-39-6 ]

Product Details of [ 59159-39-6 ]

CAS No. :	59159-39-6	MDL No. :	MFCD00075527
Formula :	C₂₄H₂₆BrO₂P	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	ZGLFRTJDWWKIAK-UHFFFAOYSA-M
M.W :	457.34	Pubchem ID :	2733853
Synonyms :

Calculated chemistry of [ 59159-39-6 ]

Physicochemical Properties

Num. heavy atoms :	28
Num. arom. heavy atoms :	18
Fraction Csp3 :	0.21
Num. rotatable bonds :	7
Num. H-bond acceptors :	2.0
Num. H-bond donors :	0.0
Molar Refractivity :	125.3
TPSA :	39.89 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	Yes
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	Yes
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-4.47 cm/s

Lipophilicity

Log Po/w (iLOGP) :	-0.71
Log Po/w (XLOGP3) :	6.5
Log Po/w (WLOGP) :	1.33
Log Po/w (MLOGP) :	5.54
Log Po/w (SILICOS-IT) :	5.38
Consensus Log Po/w :	3.61

Druglikeness

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

Water Solubility

Log S (ESOL) :	-6.78
Solubility :	0.0000752 mg/ml ; 0.000000164 mol/l
Class :	Poorly soluble
Log S (Ali) :	-7.13
Solubility :	0.0000336 mg/ml ; 0.0000000735 mol/l
Class :	Poorly soluble
Log S (SILICOS-IT) :	-8.79
Solubility :	0.000000743 mg/ml ; 0.0000000016 mol/l
Class :	Poorly soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	2.0
Synthetic accessibility :	4.89

Safety of [ 59159-39-6 ]

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

Application In Synthesis of [ 59159-39-6 ]

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

Upstream synthesis route of [ 59159-39-6 ]
Downstream synthetic route of [ 59159-39-6 ]

[ 59159-39-6 ] Synthesis Path-Upstream 1~2

1
[ 5292-43-3 ]
[ 603-35-0 ]
[ 59159-39-6 ]

Yield	Reaction Conditions	Operation in experiment
99%	at 20℃; for 12 h;	EXAMPLE 3; In yet another embodiment, the functionalized lactone comprises a carboxy protecting group, as shown in FIG. 10. Ylide synthesis is shown below using the reagents and conditions: (a) PPh₃, C₆H₆, 12 h, rt; (b) 20percent NaOH_(aq), 5 h, rt.
96%	at 60 - 62℃; for 4.41 h; Industry scale	30 liters of toluene was taken into a reactor and 3.2 kg of triphenyl phosphine was added to it under a nitrogen atmosphere. Another 2 liters of toluene was added to the reactor and stirred for about 25 minutes. The reaction mass was then heated to about 60° C. and 2.9 kg of tertiary-butyl bromo acetate was added to the reaction mass at 60° C. Temperature of the reaction mass was then raised to 62° C. and maintained for 4 hours. Reaction completion was checked using thin layer chromatography. After the reaction was completed, the reaction mass was cooled to about 35° C. and filtered. The filtered cake was washed with 9.5 liters of toluene. The wet solid was dried at 60° C. for 4 hours to yield 5.36 kg (96percent yield) of the title compound. Purity by HPLC: 99.1 area-percent.

Reference： [1] Patent: US2007/265243, 2007, A1, . Location in patent: Page/Page column 4
[2] Bioorganic and Medicinal Chemistry, 2001, vol. 9, # 1, p. 199 - 209
[3] Phosphorus, Sulfur and Silicon and the Related Elements, 2008, vol. 183, # 5, p. 1188 - 1208
[4] Patent: US2007/43088, 2007, A1, . Location in patent: Page/Page column 5
[5] Organic Process Research and Development, 2009, vol. 13, # 4, p. 710 - 715
[6] Heterocycles, 2007, vol. 73, # C, p. 751 - 768
[7] Bioscience, Biotechnology and Biochemistry, 2010, vol. 74, # 4, p. 741 - 745
[8] Journal of Organic Chemistry, 2008, vol. 73, # 23, p. 9465 - 9468
[9] Journal of the American Chemical Society, 1979, vol. 101, p. 6023 - 6027
[10] Journal of Organic Chemistry, 1988, vol. 53, # 23, p. 5558 - 5562
[11] Chemische Berichte, 1986, vol. 119, # 4, p. 1196 - 1207
[12] Advanced Synthesis and Catalysis, 2018, vol. 360, # 7, p. 1510 - 1516

2
[ 59159-39-6 ]
[ 626-34-6 ]
[ 643-79-8 ]
[ 103890-78-4 ]

Yield	Reaction Conditions	Operation in experiment
40.9%	Stage #1: With sodium hydroxide In dichloromethane; water at -5 - -3℃; for 2.75 h; Industry scale Stage #2: With trifluoroacetic acid In isopropyl alcohol at -7℃; for 2.75 h; Stage #3: With sodium hydrogencarbonate In water; ethyl acetate; isopropyl alcohol at 0 - 25℃; for 0.333333 h;	18 liters of dichloromethane was taken into a reactor and 5 kg of tertiary-butoxy carbonyl methyl triphenyl phosphonium bromide (obtained using a similar process as described in Example 1) was added to it. 2.05 kg of ortho-phtalaldehyde was added to the reaction mass and another 1 liter of dichloromethane was added to it. The reaction mass was stirred for about 15 minutes and then cooled to about -5° C. A solution of 2.65 kg of sodium hydroxide flakes in 5 liters of water at about 25° C. was added to the reaction mass at -3° C. and maintained at -3° C. for 2.5 hours. Reaction completion was checked using thin layer chromatography. After the reaction was completed, the temperature of the reaction mass was raised to 25° C. and stirred for 30 minutes. The organic layer was separated from the reaction mass and distilled without vacuum at a temperature of 52° C. The residue obtained was maintained at 52° C. for 15 minutes. 35 liters of n-heptane was added to the reaction mass at 52° C. 4 liters of the n-heptane was distilled off from the reaction mass under a vacuum of 500 mm Hg at 63° C. The reaction mass was then cooled to 35° C. and maintained for 1.5 hours. The reaction mass was then filtered under vacuum to remove the undissolved material. The filtered cake was washed with 7.5 liters of n-heptane. The filtrate was taken into another reactor and the solvent was distilled off completely under a vacuum of 610 mm Hg and at 68° C. The reaction mass was then cooled to 33° C. and 11.5 liters of isopropanol was charged into it. The reaction mass was then cooled to -7° C. A solution of 4.25 kg of ethyl-3-aminocrotonate in 12.5 liters of isopropanol was added to the reaction mass at -7° C. 2.8 liters of trifluoroacetic acid was added to the reaction mass at -7° C. followed by addition of 1 liter of isopropanol. The reaction mass was maintained at -7° C. for 2 hours 45 minutes. Reaction completion was checked using thin layer chromatography. A solution of 2.6 kg of sodium bicarbonate in 50 liters of water was added to the reaction mass 0° C. and 25 liters of ethyl acetate was added to it. The temperature of the reaction mass was heated to 25° C. and stirred for 20 minutes. The aqueous layer was separated and extracted with 12.5 liters of ethyl acetate. The combined organic layer was taken into a separate reactor and the solvent was distilled off atmospherically at 81° C. The residue was distilled off completely, and then 5 liters of isopropanol was added to it. The reaction mass was distilled off completely and again 5 liters of isopropanol was added to the residue obtained. The reaction mass was again distilled off completely and finally the residue was dissolved in 63 liters of isopropanol by heating to 85° C. to get clear dissolution. The reaction mass was then cooled to 2° C. and maintained for 1.5 hours. The isolated material was filtered and washed with 2.5 liters of isopropanol. The wet material was dried at 50° C. for 30 minutes. The dry material was taken into another reactor and 23 liters of isopropanol was added to it. The reaction mass was heated to 65° C. and maintained for 30 minutes. The reaction mass was then cooled to 2° C. and maintained for 1 hour. The reaction mass was filtered and washed with 1.5 liters of isopropanol. The wet solid was dried at a temperature of 60° C. and a vacuum of 630 mm Hg for 5 hours to yield 2.04 kg (yield: 40.9percent) of the title compound. Triphenyl phosphine oxide content: less than 0.0011 area-percent.

Reference： [1] Patent: US2007/43088, 2007, A1, . Location in patent: Page/Page column 6

[ 59159-39-6 ] Synthesis Path-Downstream 1~76

1
[ 3298-40-6 ]
[ 59159-39-6 ]
[ 41502-69-6 ]

Reference： [1]Journal of the American Chemical Society,1979,vol. 101,p. 6023 - 6027

2
[ 59159-39-6 ]
[ 91635-03-9 ]
[ 94029-65-9 ]
[ 94029-65-9 ]

Reference： [1]Chemische Berichte,1964,vol. 97,p. 1846 - 1856

3
[ 5292-43-3 ]
[ 603-35-0 ]
[ 59159-39-6 ]

Yield	Reaction Conditions	Operation in experiment
99%	In benzene; at 20℃; for 12h;	EXAMPLE 3; In yet another embodiment, the functionalized lactone comprises a carboxy protecting group, as shown in FIG. 10. Ylide synthesis is shown below using the reagents and conditions: (a) PPh3, C6H6, 12 h, rt; (b) 20% NaOH(aq), 5 h, rt.
96%	In toluene; at 60 - 62℃; for 4.41h;Industry scale;	30 liters of toluene was taken into a reactor and 3.2 kg of triphenyl phosphine was added to it under a nitrogen atmosphere. Another 2 liters of toluene was added to the reactor and stirred for about 25 minutes. The reaction mass was then heated to about 60 C. and 2.9 kg of tertiary-butyl bromo acetate was added to the reaction mass at 60 C. Temperature of the reaction mass was then raised to 62 C. and maintained for 4 hours. Reaction completion was checked using thin layer chromatography. After the reaction was completed, the reaction mass was cooled to about 35 C. and filtered. The filtered cake was washed with 9.5 liters of toluene. The wet solid was dried at 60 C. for 4 hours to yield 5.36 kg (96% yield) of the title compound. Purity by HPLC: 99.1 area-%.
	In toluene; for 12h;Inert atmosphere;	General procedure: The allenoates 2 were synthesized according to Kwon procedure.5 Under nitrogen atmosphere, to the solution of PPh3 (1.0 equiv) in toluene was added bromoacetic esters (1.0 equiv) over 15 minutes. The solution was stirred for 12 hours and the precipitate filtered, washed with ethyl acetate. The collected phosphonium salt was dissolved in dichloromethane and 2 M sodium hydroxide solution (1.0 equiv) was added. The mixture was stirred at room temperature for 20 minutes. The aqueous phase was extracted with dichloromethane. The combined organic extracts were washed with an aqueous saturated solution of sodium chloride, dried over sodium sulfate, filtered and concentrated under reduced pressure. The resulting crude material was the desired compound 6, which was directly used in the next step. A 250 mL flask was charged with stabilized ylide 11 (1.0 equiv), trimethylamine (2.2 equiv) and dichloromethane under nitrogen atmosphere, the mixture was stirred at 0 C. The acid chloride (2.2 equiv) was added slowly as a solution in dichloromethane over 30 minutes. After completion of the reaction (TLC), the solution was treated with pentane. The mixture was filtered and the filtrate evaporated and passed through a short pad of silica gel (pentane/dichloromethane) to afford the pure allenoates 2.

Reference： [1]Patent: US2007/265243,2007,A1 .Location in patent: Page/Page column 4
[2]Bioorganic and Medicinal Chemistry,2001,vol. 9,p. 199 - 209
[3]Phosphorus, Sulfur and Silicon and the Related Elements,2008,vol. 183,p. 1188 - 1208
[4]Patent: US2007/43088,2007,A1 .Location in patent: Page/Page column 5
[5]Organic Process Research and Development,2009,vol. 13,p. 710 - 715
[6]Heterocycles,2007,vol. 73,p. 751 - 768
[7]Bioscience, Biotechnology and Biochemistry,2010,vol. 74,p. 741 - 745
[8]Journal of Organic Chemistry,2008,vol. 73,p. 9465 - 9468
[9]Journal of the American Chemical Society,1979,vol. 101,p. 6023 - 6027
[10]Journal of Organic Chemistry,1988,vol. 53,p. 5558 - 5562
[11]Chemische Berichte,1986,vol. 119,p. 1196 - 1207
[12]Advanced Synthesis and Catalysis,2018,vol. 360,p. 1510 - 1516
[13]Tetrahedron Letters,2019,vol. 60,p. 1885 - 1890
[14]Organic Letters,2019,vol. 21,p. 7055 - 7059

4
[ 59159-39-6 ]
2-Azido-3-ethylbenzthiazolium-tetrafluoroborat [ No CAS ]
2-Amino-3-ethylbenzthiazoliumbromid [ No CAS ]
<Diazo(tert-butoxycarbonyl)-methyl>-triphenylphosphonium-tetrafluoroborat [ No CAS ]

Reference： [1]Liebigs Annalen der Chemie,1981,p. 1865 - 1873
[2]Liebigs Annalen der Chemie,1981,p. 1865 - 1873

5
[ 59159-39-6 ]
[ 86302-43-4 ]

Yield	Reaction Conditions	Operation in experiment
~ 100%	With sodium hydroxide; In water; at 20℃; for 5h;	EXAMPLE 3; In yet another embodiment, the functionalized lactone comprises a carboxy protecting group, as shown in FIG. 10. Ylide synthesis is shown below using the reagents and conditions: (a) PPh3, C6H6, 12 h, rt; (b) 20% NaOH(aq), 5 h, rt.
	With sodium hydroxide; In water;	(b) A suspension of the carbo-t-butoxymethyl triphenylphosphonium bromide (55.8 g, 122 mmol) in water (400 ml) was treated with sodium hydroxide (4.7 g, 117 mml) in water (100 ml). The mixture was stirred for 16 hours and the solid collected to give 43.7 g (95% of theory) of carbo-t-butoxymethylene triphenylphosphorane.
	With sodium hydroxide; In dichloromethane; water; at 20℃; for 0.333333h;	General procedure: The allenoates 2 were synthesized according to Kwon procedure.5 Under nitrogen atmosphere, to the solution of PPh3 (1.0 equiv) in toluene was added bromoacetic esters (1.0 equiv) over 15 minutes. The solution was stirred for 12 hours and the precipitate filtered, washed with ethyl acetate. The collected phosphonium salt was dissolved in dichloromethane and 2 M sodium hydroxide solution (1.0 equiv) was added. The mixture was stirred at room temperature for 20 minutes. The aqueous phase was extracted with dichloromethane. The combined organic extracts were washed with an aqueous saturated solution of sodium chloride, dried over sodium sulfate, filtered and concentrated under reduced pressure. The resulting crude material was the desired compound 6, which was directly used in the next step. A 250 mL flask was charged with stabilized ylide 11 (1.0 equiv), trimethylamine (2.2 equiv) and dichloromethane under nitrogen atmosphere, the mixture was stirred at 0 C. The acid chloride (2.2 equiv) was added slowly as a solution in dichloromethane over 30 minutes. After completion of the reaction (TLC), the solution was treated with pentane. The mixture was filtered and the filtrate evaporated and passed through a short pad of silica gel (pentane/dichloromethane) to afford the pure allenoates 2.

Reference： [1]Patent: US2007/265243,2007,A1 .Location in patent: Page/Page column 4
[2]Heterocycles,2007,vol. 73,p. 751 - 768
[3]Chemische Berichte,1986,vol. 119,p. 1196 - 1207
[4]Tetrahedron Letters,1984,vol. 25,p. 4959 - 4962
[5]Carbohydrate Research,1996,vol. 281,p. 69 - 77
[6]Tetrahedron Letters,2004,vol. 45,p. 1679 - 1681
[7]Journal of Organic Chemistry,2001,vol. 66,p. 4625 - 4629
[8]Patent: US4855086,1989,A
[9]Advanced Synthesis and Catalysis,2009,vol. 351,p. 1423 - 1430
[10]Bioorganic and Medicinal Chemistry,2010,vol. 18,p. 5224 - 5233
[11]Advanced Synthesis and Catalysis,2018,vol. 360,p. 1510 - 1516
[12]Tetrahedron Letters,2019,vol. 60,p. 1885 - 1890
[13]Organic Letters,2019,vol. 21,p. 7055 - 7059

6
[ 59159-39-6 ]
[ 407-25-0 ]
[ 106893-76-9 ]

Reference： [1]Journal of Organic Chemistry,1988,vol. 53,p. 5558 - 5562

7
[ 33317-04-3 ]
[ 59159-39-6 ]
[ 230645-71-3 ]

Reference： [1]Il Farmaco,1999,vol. 54,p. 101 - 111

8
[ 104-53-0 ]
[ 59159-39-6 ]
[ 131619-26-6 ]
[ 131619-25-5 ]

Reference： [1]Tetrahedron,2000,vol. 56,p. 7893 - 7902

9
[ 59159-39-6 ]
[ 139-85-5 ]
[ 845883-04-7 ]

Reference： [1]Bioorganic and Medicinal Chemistry,2001,vol. 9,p. 199 - 209

10
[ 26018-30-4 ]
[ 59159-39-6 ]
[ 346600-39-3 ]

Reference： [1]Bioorganic and medicinal chemistry letters,2002,vol. 12,p. 2153 - 2157

11
[ 2436-29-5 ]
[ 59159-39-6 ]
[ 600155-23-5 ]

Reference： [1]Organic Letters,2003,vol. 5,p. 3115 - 3118

12
[ 59159-39-6 ]
[ 114215-40-6 ]
C₁₈H₂₂O₃ [ No CAS ]

Reference： [1]Synthetic Communications,2007,vol. 37,p. 2989 - 2994

13
[ 59159-39-6 ]
3-(4-chloro-phenyl)-2-fluoro-acrylic acid <i>tert</i>-butyl ester [ No CAS ]

Reference： [1]Tetrahedron Letters,2004,vol. 45,p. 1679 - 1681

14
[ 59159-39-6 ]
[ 201221-73-0 ]

Reference： [1]Tetrahedron Letters,2004,vol. 45,p. 1679 - 1681

15
[ 59159-39-6 ]
[ 346600-40-6 ]

Reference： [1]Bioorganic and medicinal chemistry letters,2002,vol. 12,p. 2153 - 2157

16
[ 59159-39-6 ]
tert-butyl (Z)-2,3-dideoxy-D-lyxo-hept-2-enonate [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2001,vol. 66,p. 4625 - 4629

17
[ 59159-39-6 ]
[ 352462-28-3 ]

Reference： [1]Journal of Organic Chemistry,2001,vol. 66,p. 4625 - 4629

18
[ 59159-39-6 ]
tert-butyl (E)-2,3-dideoxy-D-lyxo-hept-2-enonate [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2001,vol. 66,p. 4625 - 4629

19
[ 59159-39-6 ]
tert-butyl D-glycero-L-galacto-heptonate [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2001,vol. 66,p. 4625 - 4629

20
[ 59159-39-6 ]
tert-butyl (E)-2,3-dideoxy-D-glycero-D-galacto-non-2-enonate [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2001,vol. 66,p. 4625 - 4629

21
[ 59159-39-6 ]
tert-butyl (Z)-2,3-dideoxy-D-glycero-D-gulo-non-2-enonate [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2001,vol. 66,p. 4625 - 4629

22
[ 59159-39-6 ]
tert-butyl (E)-2,3-dideoxy-D-glycero-D-gulo-non-2-enonate [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2001,vol. 66,p. 4625 - 4629

23
[ 59159-39-6 ]
3-(3,4-dihydroxy-phenyl)-propionic acid <i>tert</i>-butyl ester [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry,2001,vol. 9,p. 199 - 209

24
[ 59159-39-6 ]
tert-butyl 4-acetamido-2,3,4-trideoxy-D-gluco-oct-2-enonate [ No CAS ]

Reference： [1]Carbohydrate Research,1996,vol. 281,p. 69 - 77

25
[ 59159-39-6 ]
(E)-(4R,5S,6R)-4,5,6,7-Tetrahydroxy-hept-2-enoic acid tert-butyl ester [ No CAS ]

Reference： [1]Carbohydrate Research,1996,vol. 281,p. 69 - 77

26
[ 59159-39-6 ]
[ 175652-31-0 ]

Reference： [1]Carbohydrate Research,1996,vol. 281,p. 69 - 77

27
[ 59159-39-6 ]
[ 175652-33-2 ]

Reference： [1]Carbohydrate Research,1996,vol. 281,p. 69 - 77

28
[ 59159-39-6 ]
[ 35000-37-4 ]

Reference： [1]Tetrahedron Letters,1984,vol. 25,p. 4959 - 4962

29
[ 59159-39-6 ]
[ 95832-86-3 ]

Reference： [1]Tetrahedron Letters,1984,vol. 25,p. 4959 - 4962

30
[ 59159-39-6 ]
[ 95832-96-5 ]

Reference： [1]Tetrahedron Letters,1984,vol. 25,p. 4959 - 4962

31
[ 59159-39-6 ]
3-tert-Butoxycarbonyl-4-(6,6-dimethyl-bicyclo[3.1.1]hept-2-en-2-yl)-2-methoxycarbonyl-butyric acid methyl ester [ No CAS ]

Reference： [1]Journal of the American Chemical Society,1979,vol. 101,p. 6023 - 6027

32
[ 59159-39-6 ]
[ 96136-13-9 ]
5-methyl-3-(phenylmethoxycarbonyl)-(E)-hex-2-enoic 1,1-dimethylethyl ester acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
69%	With potassium tert-butylate; In DMF (N,N-dimethyl-formamide); at 20℃;	In a flask, introduce 46 g (0.10 mole) of tert-butoxycarbonyl methyl triphenyl phosphonium bromide. Add 12.8 g (0.1 05 mole) of tBuOK and stir for 30 minutes at room temperature. Add 20 g (0.091 mole) of compound a) diluted with 60 ml of DMF. Stir for one night at 20° C.Evaporate to dryness.Mix in isopropyl ether, filter, evaporate.Purify by flash chromatography on 600 g of silica (eluant heptane:AcOEt; 95:5).Recover 19.9 g (69percent) of product E.RMN (CDCl3): delta 7.4 (5H, s, HAr); 6.75 (1H, s, COCH=); 5.2 (2H, s, OCH2Ar); 2.75 (2H, d, CH2-C=); 1.9 (1H, m, CH-(CH3)2); 1.55 (9H, s, C(CH3)); 0.95 (6H, d, CH(CH3)2).

Reference： [1]Patent: US6344457,2002,B1 .Location in patent: Page column 38

33
(2R,4R)-1-benzyloxycarbonyl-2-(2-formylethyl)-4-t-butyldimethylsilyloxypyrrolidine [ No CAS ]
[ 59159-39-6 ]
(2R,4R)-1-benzyloxycarbonyl-2-(3-t-butoxycarbonylmethylidenepropyl)-4-t-butyldimethylsilyloxypyrrolidine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydrogencarbonate; In dichloromethane;	REFERENCE EXAMPLE 49 STR151 t-Butyloxycarbonylmethyltriphenylphosphonium bromide (2.15 g) was dissolved in 40 ml of dichloromethane, and 30 ml of a saturated sodium bicarbonate solution was added thereto, followed by stirring at room temperature for 5 minutes. The dichloromethane layer was separated and dried over anhydrous sodium sulfate. After filtration, a solution of 1.29 g of (2R,4R)-1-benzyloxycarbonyl-2-(2-formylethyl)-4-t-butyldimethylsilyloxypyrrolidine in 30 ml of dichloromethane was added to the filtrate, followed by refluxing for 30 minutes. After removal of the solvent, the residue was purified by silica gel column chromatography to obtain (2R,4R)-1-benzyloxycarbonyl-2-(3-t-butoxycarbonylmethylidenepropyl)-4-t-butyldimethylsilyloxypyrrolidine. IRmaxneat cm-1: 1702, 1649, 1408, 1363, 1148.

Reference： [1]Patent: US4962103,1990,A

Yield	Reaction Conditions	Operation in experiment
		(a) A solution of triphenylphosphine (33.8 g, 129 mmol) and t-butyl bromoacetate (25 g, 128.2 mmol) in dry benzene (150 ml) was stirred for 16 hours at room temperature. The precipitated product was collected by filtration, washed with dry ether and dried in vaco to give 56 g (96percent of theory) of carbo-t-butoxymethyl triphenylphosphonium bromide.

35
[ 623-27-8 ]
[ 59159-39-6 ]
[ 144374-53-8 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydroxide; In dichloromethane; water; at 0℃; for 0.25h;	100 ml of dichloromethane, 24 g of t-butoxy carbonyl methyl triphenyl phosphonium bromide and 10 g of terephalaldehyde were taken into a clean and dry round bottom flask and the resultant reaction mass was stirred for 15 minutes for attaining a homogenous solution. The reaction mass was then cooled to 0° C. followed by addition of a solution of 13.6 g of sodium hydroxide in 20.6 ml of water. The organic layer was separated and dried over 5 g of anhydrous sodium sulphate. The organic layer was then distilled completely at 40° C. The resultant residue was cooled to about 30° C. and then 50 ml of cyclohexane was added to the resultant residue followed by further cooling to about 0° C. The reaction mass was stirred at 0° C. for 1 hour followed by filtration of separated solid. The filtered solid was washed with 25 ml of cyclohexane. The filtrate was taken into a clean and dry round bottom and distilled off completely at about 65° C. to afford 11.6 grams of residue.

Reference： [1]Synthetic Communications,2009,vol. 39,p. 2137 - 2145
[2]Patent: US2007/43088,2007,A1 .Location in patent: Page/Page column 8

36
[ 59159-39-6 ]
[ 643-79-8 ]
[ 180515-27-9 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydroxide; In 1,4-dioxane; water; at 20 - 50℃; for 2h;	250 ml of 1,4-dioxane, 25 g of ortho-pthalaldehyde and 85.3 g of t-butoxy carbonyl methyl triphenyl phosphonium bromide were taken into a clean and dry round bottom flask and stirred for 30 minutes. Resultant reaction mixture was cooled to 20° C. followed by stirring for 15 minutes. 50 ml of 48percent aqueous sodium hydroxide solution was added to the reaction mass and stirred for 45 minutes. Reaction suspension was heated to 50° C. and stirred for 1 hour followed by cooling to 30° C. The organic layer was separated and distilled completely at about 50° C. under a vacuum of 300 mm Hg. The residue obtained was cooled to 30° C. 75 ml of cyclohexane was added to it and the reaction mass was further cooled to 0° C. The reaction mass was maintained at 0° C. for 30 minutes. Separated solid was filtered and the solid was washed with 25 ml of cyclohexane. The filtrate was taken into another round bottom flask and distilled at 50° C. under a vacuum of 300 mm Hg followed by cooling the residue to about 30° C. 50 ml of petroleum ether was added to the above resultant residue and was stirred for 45 minutes. Separated solid was filtered and washed with 25 ml of petroleum ether followed by drying the obtained solid at 50° C. for 2 hours to afford 9 g of the title compound.

Reference： [1]Organic Process Research and Development,2009,vol. 13,p. 710 - 715
[2]Patent: US2007/43088,2007,A1 .Location in patent: Page/Page column 9

37
[ 626-19-7 ]
[ 59159-39-6 ]
[ 170282-61-8 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydroxide; In dichloromethane; water; at 3℃; for 1h;	100 ml of dichloromethane, 25 g of t-butoxy carbonyl methyl triphenyl phosphonium bromide and 10.2 g of isophthalaldehyde were taken into a clean and dry round bottom flask and the resultant reaction mass was stirred for 20 minutes for homogenous solution. The reaction mass was then cooled to 3° C. followed by addition of a mixture of 13.2 g of sodium hydroxide and 20 ml of water in 40 minutes. The organic layer was separated and dried on 5 g of anhydrous sodium sulphate. The organic layer was then distilled off completely at about 40° C. 50 ml of n-heptane was added to the resultant residue and was stirred at 28° C. for 1 hour followed by filtration of separated solid and the solid was washed with 25 ml of n-heptane. The filtrate was taken into a clean and dry round bottom flask and the solvent was distilled off completely at about 62° C. to afford 12 g of intermediate residue.

Reference： [1]Patent: US2007/43088,2007,A1 .Location in patent: Page/Page column 8

38
[ 59159-39-6 ]
[ 1197-13-3 ]
[ 1041430-13-0 ]
[ 1041430-15-2 ]

Yield	Reaction Conditions	Operation in experiment
25.1%; 72.9%	With sodium hydride; In tetrahydrofuran; at 0 - 20℃;	2. Lb) Synthesis of (Z) -methyl 5-(3-tert-butoxy-3-oxoprop-l-enyl)-lH-pyrrole-2-carboxylate and (E)-methyl 5-(3-tert-butoxy-3-oxoprop-l-enyl)-lH-pyrrole-2-carboxylate[0303] To a suspension of NaH (5.74 g, 143.5 mmol; 60percent in oil) in THF (200 niL) at 0 0C was added (tert-butoxycarbonylmethyl)triphenylphosphonium bromide (66 g, 143.5 mmol) as a solid in three portions. Cooling was removed and the mixture was stirred at rt for 30 min. It was then cooled to 0 0C and methyl 5-formyl-l/-f-pyrrole-2-carboxylate (16.9 g, 110.4 mmol) in THF (60 mL) was added dropwise over 40 min. The reaction mixture was allowed to warm to rt and was stirred overnight. Silica was added and the solvent was removed. The crude product was purified by flash chromatography (0-20percent EtO Ac/Heptane) to afford two isomeric compounds:[0304] (Z)-methyl 5-(3-fert-butoxy-3-oxoprop-l-enyl)-l/-f-pyrrole-2-carboxylate (6.9 g, 25.1percent) as a white solid; 1H NMR (400 MHz, CHLOROFORM-^) delta ppm 1.55 (s, 9 H), 3.91 (s, 3 H), 5.67 (d, J= 12.64 Hz, 1 H), 6.43 (dd, J= 3.83, 2.32 Hz, 1 H), 6.67 (d, J= 12.64 Hz, 1 H), 6.88 (dd, J= 3.81, 2.44 Hz, 1 H), 12.80 (br s, 1 H); LCMS- MS (ESI+) 195.7 (M-56).[0305] (ii)-methyl 5-(3-tert-butoxy-3-oxoprop-l-enyl)-lH-pyrrole-2-carboxylate (20.3 g, 72.9percent) as a white solid; 1H NMR (400 MHz, CHLOROFORM-^) delta ppm 1.53 (s, 9 H), 3.90 (s, 3 H), 6.19 (d, J= 16.01 Hz, 1 H), 6.51 (dd, J= 3.86, 2.68 Hz, 1 H), 6.90 (dd, J= 3.88, 2.37 Hz, 1 H), 7.41 (d, J= 16.01 Hz, 1 H), 9.42 (br s, 1 H); LCMS- MS (ESI+) 195.8 (M-56).

Reference： [1]Patent: WO2008/89453,2008,A2 .Location in patent: Page/Page column 95

39
[ 59159-39-6 ]
[ 40611-79-8 ]
[ 1041430-85-6 ]
[ 1041430-87-8 ]

Yield	Reaction Conditions	Operation in experiment
26.2%; 57.8%		4.2.a) Synthesis of (Z) -methyl 4-(3-tert-butoxy-3-oxoprop-l-enyl)-lH-pyrrole-2-carboxylate and (E)-methyl 4-(3-tert-butoxy-3-oxoprop-l-enyl)-lH-pyrrole-2-carboxylate [0367] Methyl 5-formyl-lH-pyrrole-2-carboxylate (16.3 g) and its regioisomer methyl A- formyl-lH-pyrrole-2-carboxylate (6.94 g) were obtained (combined yield of 95percent) from a Vilsmeier formylation of lH-pyrrole-2-carboxylic acid methyl ester via exhaustive extraction of the neutralized aqueous layer with EtOAc to provide a better recovery of the more polar A- <n="115"/>formyl isomer [see, e.g., Charkraborty, T. K. et al., Tetrahedron Lett. 2006, 47: 4631 and Denmark, S. E.; Matsuhashi, H. J. Org. Chem. 2002, 67: 3479].[0368] To a suspension of NaH (0.54 g, 13.58 mmol; 60percent dispersed in oil) in THF (30 mL) at 0 0C was added <strong>[59159-39-6](tert-butoxycarbonylmethyl)triphenylphosphonium bromide</strong> (6.2 Ig, 13.585 mmol) as a solid in three portions. The cooling bath was removed and the mixture was stirred at rt for 30 min before cooling to 0 0C. Methyl 4-formyl-lH-pyrrole-2- carboxylate (1.6 g, 10.45 mmol) in THF (10 mL) was added dropwise over 10 min. The cooling bath was removed, and the reaction mixture was stirred at rt for about 12 h. The crude product was dried onto silica gel and was purified by flash chromatography (0-20percent EtO Ac/Heptane) to afford two isomeric compounds:[0369] (Z)-methyl 4-(3-tert-butoxy-3-oxoprop-l-enyl)-lH-pyrrole-2-carboxylate (0.81 g, 26.2 percent) as a white solid; 1H NMR (400 MHz, CDCl3) delta ppm 1.52 (s, 9 H), 3.87 (s, 3 H), 5.65 (d, J= 12.59 Hz, 1 H), 6.67 (d, J= 12.64 Hz, 1 H), 7.25 (dd, J= 2.54, 1.56 Hz, 1 H), 7.97 (dd, J= 3.10, 1.44 Hz, 1 H), 9.14 (br s, 1 H); LCMS- MS (ESI+) 195.7 (M-56). [0370] (^-methyl 4-(3-tert-butoxy-3-oxoprop-l-enyl)-lH-pyrrole-2-carboxylate (1.8 g, 57.8 percent) as a white solid; 1H NMR (400 MHz, CDCl3) delta ppm 1.52 (s, 9 H), 3.88 (s, 3 H), 6.12 (d, J= 15.86 Hz, 1 H), 7.08 (m, 1 H), 7.14 (dd, J= 3.03, 1.56 Hz, 1 H), 7.49 (d, J= 15.86 Hz, 1 H), 9.22 (br s, 1 H); LCMS- MS (ESI+) 195.8 (M-56).

Reference： [1]Patent: WO2008/89453,2008,A2 .Location in patent: Page/Page column 113-114

40
[ 49678-08-2 ]
[ 59159-39-6 ]
C₁₅H₁₇NO₄ [ No CAS ]