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[ CAS No. 1779-49-3 ] {[proInfo.proName]}

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Chemical Structure| 1779-49-3
Chemical Structure| 1779-49-3
Structure of 1779-49-3 * Storage: {[proInfo.prStorage]}
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Product Details of [ 1779-49-3 ]

CAS No. :1779-49-3 MDL No. :MFCD00011804
Formula : C19H18BrP Boiling Point : -
Linear Structure Formula :- InChI Key :LSEFCHWGJNHZNT-UHFFFAOYSA-M
M.W : 357.22 Pubchem ID :74505
Synonyms :

Calculated chemistry of [ 1779-49-3 ]      Expand+

Physicochemical Properties

Num. heavy atoms : 21
Num. arom. heavy atoms : 18
Fraction Csp3 : 0.05
Num. rotatable bonds : 3
Num. H-bond acceptors : 0.0
Num. H-bond donors : 0.0
Molar Refractivity : 99.94
TPSA : 13.59 Ų

Pharmacokinetics

GI absorption : Low
BBB permeant : No
P-gp substrate : Yes
CYP1A2 inhibitor : No
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : Yes
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -5.38 cm/s

Lipophilicity

Log Po/w (iLOGP) : -1.74
Log Po/w (XLOGP3) : 4.37
Log Po/w (WLOGP) : 0.61
Log Po/w (MLOGP) : 5.74
Log Po/w (SILICOS-IT) : 4.74
Consensus Log Po/w : 2.74

Druglikeness

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

Water Solubility

Log S (ESOL) : -5.24
Solubility : 0.00204 mg/ml ; 0.0000057 mol/l
Class : Moderately soluble
Log S (Ali) : -4.37
Solubility : 0.0152 mg/ml ; 0.0000425 mol/l
Class : Moderately soluble
Log S (SILICOS-IT) : -7.93
Solubility : 0.0000042 mg/ml ; 0.0000000117 mol/l
Class : Poorly soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 1.0 alert
Leadlikeness : 2.0
Synthetic accessibility : 4.5

Safety of [ 1779-49-3 ]

Signal Word:Danger Class:6.1
Precautionary Statements:P261-P264-P270-P271-P301+P310-P304+P340-P312-P330-P403+P233-P405-P501 UN#:2811
Hazard Statements:H301-H411 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 1779-49-3 ]

* 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.

  • Downstream synthetic route of [ 1779-49-3 ]

[ 1779-49-3 ] Synthesis Path-Downstream   1~96

  • 2
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  • [ 56133-38-1 ]
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  • [ 55453-87-7 ]
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  • [ 113836-35-4 ]
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  • [ 61995-20-8 ]
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  • [ 138163-15-2 ]
YieldReaction ConditionsOperation in experiment
45% To a solution of PPh3CH3Br (230 g, 0.64 mol) in THF (0.8 L) is added a solution of n- BuLi (240 mL, 0.6 mol) at 0C under N2. The mixture is stirred at 0C for 1 h then R-7 (100 g, 0.43 mol) in THF (0.8 L) is added to the reaction mixture at 0C. The mixture is allowed to warm to ambient temperature, stirred for 1 h, then poured into H20 and extracted with EtOAc. The organic layers are washed with brine, dried with Na2S04, concentrated and purified by flash chromatography (Si02, Hep to 25%EtOAc in Hep) to give compound R-8 (45 g, 45%). To a solution of R-8 (20.0 g, 86 mmol) in 1,4-dioxane (200 mL) is added Zn-Cu (33.2 g, 259 mmol) at rt under N2. Trichloroacetyl chloride (31.4 g, 173 mmol) in 1,4-dioxane (200 mL) is added. The mixture is allowed to warm to rt and stirred for 2 days. The mixture is treated with aqueous NaHCC>3 and extracted with EtOAc. The organic layers are washed with brine, dried with Na2S04, concentrated and purified by flash chromatography (Si02, Hep to 25 EtOAc in Hep) to give R-9 (11 g, 34%).
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  • [ 87567-27-9 ]
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  • [ 121-33-5 ]
  • [ 7786-61-0 ]
YieldReaction ConditionsOperation in experiment
83% With Amberlite IR-400; In N,N-dimethyl-formamide; at 95℃; for 10h;Inert atmosphere; General procedure: A round-bottom flask was charged with the suspension of ylide (1.5 mmol) in DMF (4 mL) and then Amberlite IR-400 (OH-) (1.2 g) was added to it. The content was stirred for the next 20 min at 95 C under inert atmosphere, then appropriate aldehyde (1 mmol) was added to the reaction mixture and heating was continued for next 10 h. On completion of the reaction (TLC [thin layer chromatography]), the resin was filtered off and the crude reaction mixture was evaporated to dryness. Isolation of the product was performed by flash chromatography (CombiFlash Rf 200i with UV/VIS and ELSD, Isco Teledyne Inc., USA) using RediSep column (SiO2). All the products were identified on the basis of their spectral data.
82% General procedure: 4.1.1. General procedure for the preparation of p-vinylphenols (1a, 1c,1d, and 1e). A mixture of alkyl triphenylphosphonium bromide(15 mmol) in THF (20 mL)was treated with potassium tert-butoxide(2.81 g, 25 mmol). After stirring for 10 min at room temperature,a solution of p-hydroxybenzaldehydes (10 mmol) in THF (10 mL)was added in drops to the above suspension, and the resultingmixture was stirred at room temperature for 4 h, which wasmonitored by TLC. The resulting solution was quenched with saturatedNH4Cl solution (50 mL), and concentrated in vacuo toremove THF. The concentrated mixture was extracted with CH2Cl2(520 mL). The organic layers werewashed with brine (20 mL) anddried over MgSO4 were filtered, evaporated, and the residue waspurified by column chromatography (ethyl acetate/n-hexane1:15)to give pure 1a, 1c, 1d, and 1e
  • 10
  • [ 3883-58-7 ]
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  • 2,2-Dimethyl-3-methylencyclopentanon [ No CAS ]
  • 11
  • [ 20098-17-3 ]
  • [ 1779-49-3 ]
  • [ 155396-26-2 ]
  • 12
  • [ 1003-29-8 ]
  • [ 7089-68-1 ]
  • [ 1779-49-3 ]
  • [ 207505-40-6 ]
  • 18
  • [ 711-33-1 ]
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  • [ 326879-13-4 ]
  • 20
  • [ 703-67-3 ]
  • [ 1779-49-3 ]
  • 6-fluoro-1-methylene-1,2,3,4-tetrahydro-naphthalene [ No CAS ]
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  • [ 1779-49-3 ]
  • [ 2840-44-0 ]
  • 7-fluoro-1-methylene-1,2,3,4-tetrahydro-naphthalene [ No CAS ]
  • 22
  • [ 62909-66-4 ]
  • [ 1779-49-3 ]
  • [ 101183-39-5 ]
YieldReaction ConditionsOperation in experiment
With potassium carbonate; In 1,4-dioxane; water; Preparation of the new alkenes of the formula VII 4-Amino-3,5-dichloro-styrene 4.75 g (0.025 mol) of <strong>[62909-66-4]4-amino-3,5-dichloro-benzaldehyde</strong> are heated at the reflux temperature in 50 ml of dioxane with 13.4 g (0.0375 mol) of methyl-triphenylphosphonium bromide and 5.2 g of potassium carbonate, with the addition of 0.75 ml of water, for 3 hours. After cooling, the precipitate is filtered off with suction, the filtrate is concentrated in vacuo and the residue is triturated with a large quantity of cyclohexane. The cyclohexane phase is concentrated and the residue is chromatographed over silica gel on a short column. 4.5 g (95%) of 4-amino-3,5-dichlorostyrene of melting point 63 C. are obtained.
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  • [ 398489-26-4 ]
  • [ 1779-49-3 ]
  • [ 934664-41-2 ]
YieldReaction ConditionsOperation in experiment
100% A mixture of potassium /e/t-butoxide (15.5 g, 137 mmol) and methyltriphenylphosphine bromide (49 g, 137 mmol) in diethyl ether (300 mL) was stirred at room temperature for 1 hour, followed by the addition of 1,1-dimethylethyl 3-oxoazetidine- 1 -carboxylate (10 g, 58 mmol in 100 mL diethyl ether). The mixture was stirred at 35 C for 2 hours and then allowed to cool to room temperature. The mixture was filtered through a pad of celite, washing with diethyl ether. The filtrate was partitioned with water and washed twice with water, brine, dried over sodium sulfate, filtered and concentrated in vacuo to give an orange oil which was purified by column chromatography. Eluting with 10% ethyl acetate in hexanes, isolated product was concentrated in vacuo to afford 9.80 g, 58 mmol (100%) of 1,1-dimethylethyl 3 -methylideneazetidine- 1-carboxylate as a colorless oil. 1H NMR (400 MHz, DMSO): 5.05-4.85 (m, 2H)3 4.95-4.63 (m, 4H), 1.45 (s, 9H). GC-MS for C9H15NO2: 169.
100% A mixture of potassium ter/-butoxide (15.5 g, 137 mmol) and methyltriphenylphosphine bromide (49 g, 137 mmol) in diethyl ether (300 mL) was stirred at room temperature for 1 hour, followed by the addition of 1,1-dimethylethyl 3-oxoazetidine-l-carboxylate (10 g, 58 mmol in 100 mL diethyl ether). The mixture was stirred at 35 0C for 2 hours and then allowed to cool to room temperature. The mixture was filtered through a pad of celite, washing with diethyl ether. The filtrate was partitioned with water and washed twice with water, brine, dried over sodium sulfate, filtered and concentrated in vacuo to give an orange oil which was purified by column chromatography. Eluting with 10% ethyl acetate in hexanes, isolated product was concentrated in vacuo to afford 9.80 g, 58 mmol (100%) of 1,1-dimethylethyl <n="341"/>3-methylideneazetidine-l-carboxylate as a colorless oil. 1H NMR (400 MHz, DMSO): 5.05-4.85 (m, 2H), 4.95-4.63 (m, 4H), 1.45 (s, 9H). GC-MS for C9H15NO2: 169.
100% A mixture of potassium tert-butoxide (15.5 g, 137 mmol) and methyltriphenylphosphine bromide (49 g, 137 mmol) in diethyl ether (300 mL) was stirred at room temperature for 1 hour, followed by the addition of 1,1 -dimethyl ethyl 3-oxoazetidine- 1-carboxylate (10 g, 58 mmol in 100 mL diethyl ether). The mixture was stirred at 35 C for 2 hours and then allowed to cool to room temperature. The mixture was filtered through a pad of celite, washing with diethyl ether. The filtrate was partitioned with water and washed twice with water, brine, dried over sodium sulfate, filtered and concentrated in vacuo to give an orange oil which was purified by column chromatography. Eluting with 10% ethyl acetate in hexanes, isolated product was concentrated in vacuo to afford 9.80 g, 58 mmol (100%) of 1,1-dimethylethyl 3-methylideneazetidine-l-carboxylate as a colorless oil. 1H NMR (400 MHz, DMSO): 5.05-4.85 (m, 2H), 4.95-4.63 (m, 4H), 1.45 (s, 9H). GC-MS for C9H15NO2: 169.
82.6% 3-(3-Chlorophenyl-ethynyl)-7-(6-methyl-3-nitro-2-pyridyl)-l-oxa-2.7-diazaspiro[4.31oct-2-ene l-(t.butoxycarbonyl)-3-methylene-azetidine (Compund 28a)To a suspension of methyltriphenylphosponium bromide (1.56 g, 4.37 mmol) in 30 ml of Et20 stirred at 0C was added potassium tert-butylate (0.459 g, 4.09 mmol). After 0.5h the cold bath was removed and the mixture was stirred for lh at r.t. Afterrwards, it was cooled off in water- ice bath, and l-(t.butoxycarbonyl)-3-azetidinone (500 mg, 2.92 mmol) was added. The cold bath was removed. After overnight resting, the reaction mixture was quenched with a saturated solution of NH4C1 in water, extracted with Et20, dried on a2S04, evaporated to dryness in vacuo, dissolvent. The residual crude was purified by automated flash chromatography (SP1TM - Biotage; gradient Petroleum Ether - Acetone from 10 : 0 to 7 : 3) to give the title compound ( 426 mg) as a dense colourless oil. Yield: 86.2%. MS: [M+H]+ = 170.45
81% A mixture of methyltriphenylphosphonium bromide (49 g, 137 mmol), potassium 2-methylpropan- 2-olate (15.5 g, 138 mmol) in tetrahydrofuran (400 mL) was stirred for 1 h at room temperature. This was followed by the addition of a solution of fert-butyl 3-oxoazetidine-l-carboxylate (10 g, 58.4 mmol) in tetrahydrofuran (100 mL) drop wise with stirring. Then the reaction system was stirred for additional 2 h while the temperature was maintained at 35 C. The solution was diluted with water, extracted with ethyl acetate, washed with brine and concentrated in vacuo. The resulting residue was purified by silica gel chromatography (solvent gradient: 0-10% ethyl acetate in petroleum ether) to afford the title compound (8.0 g, 81%) as a yellow oil. LCMS (ESI): [M+H]+ = 170.
80% Step 1: Preparation of tert-butyl 3-methyleneazetidine-l-carboxylate [0217] Potassium tert-butoxide (4.27 g, 37.96 mmol) was added to a suspension of methyltriphenylphosphonium bromide (13.56 g, 37.96 mmol) in tetrahydrofuran (80 mL) and the reaction mixture was heated at 70 C for 4 h. Then the reaction mixture was cooled to 50 C and added a solution of tert-butyl 3-oxoazetidine-l-carboxylate (5 g, 29.2 mmol) in tetrahydrofuran (20 mL) and heated at 70 C for 15 h. The reaction mixture was cooled to room temperature and evaporated to dryness. The crude material was purified by combiflash purifier using 4% ethyl acetate in hexane to afford the title compound tert-butyl 3- methyleneazetidine-l-carboxylate (4 g, 80% yield) as a colorless liquid. 1H NMR (400 MHz, CDC13) delta 4.98 (s, 2H), 4.47 (s, 4H), 1.45 (s, 9H).
78.7% To a 00C mixture of KOtBu (5.90 g, 52.6 mmol) in 95 mL ether was added methyltriphenylphosphonium bromide (18.8 g, 52.6 mmol). The reaction mixture was warmed to ambient temperature and stirred 1.5 hours. A solution of tert-bvXyl 3- oxoazetidine-1-carboxylate (4.50 g, 26.3 mmol) in 10 mL ether was added. The reaction mixture was heated to reflux for 2 hours, then cooled to ambient temperature. Solids were removed by vacuum filtration through compressed Celite and rinsed with ether, and the filtrate was concentrated. The resulting residue was suspended in 1 :1 hexanes: ethyl acetate, and the solids were removed by vacuum filtration through GF/F paper and rinsed with 1 : 1 hexanes: ethyl acetate. The filtrate was concentrated, and the resulting oil was purified on silica gel (5-20% ethyl acetate in hexanes gradient) to give the desired product (3.50 g, 78.7 % yield) as a clear colorless oil.
Step 1 : A solution of sodium bis(trimethylsilyl)amide in THF (2M; 137 ml_, 274 mmol, 2.36 eq) is added over 30 min to methyltriphenylphosphonium bromide (98.0 g, 274 mmol, 2.36 eq) in anhydrous THF (825 ml_). The reaction mixture is stirred at RT for 1 h. A solution of te/t-butyl 3-oxoazetidine-1 -carboxylate (CNH-Tech) (20.0 g, 1 16 mmol) in anhydrous THF (115 ml_) is added over 10 min, and the stirring is continued at RT for 1 h. The solution is diluted with hexanes (1 .0 L) and filtered through Celite. The filtrate is concentrated under reduced pressure at 10C. The crude material is purified by silica gel flash chromatography (20 % diethyl ether in hexanes) to afford intermediate 8007A.
Step 1 : A solution of sodium bis(trimethylsilyl)amide in THF (2M; 137 mL, 274 mmol, 2.36 eq) is added over 30 min to methyltriphenylphosphonium bromide (98.0 g, 274 mmol, 2.36 eq) in anhydrous THF (825 mL). The reaction mixture is stirred at RT for 1 h. A solution of te/t-butyl 3- oxoazetidine-1 -carboxylate (CNH-Tech) (20.0 g, 1 16 mmol) in anhydrous THF (1 15 mL) is added over 10 min, and the stirring is continued at RT for 1 h. The solution is diluted with hexanes (1 .0 L), filtered through Celite, and the filtrate is concentrated under reduced pressure at 10C. The crude material is purified by silica gel flash chromatography (20 % diethyl ether in hexanes) to afford intermediate 1006A.
10.9 g [0379] After potassium tert-butoxide (13.3 g) was added to a mixture of methyl(triphenyl)phosphonium bromide (38.7 g) and THF (150 mL) at 0C, the resultant was stirred for 1 hour. A solution of tert-butyl 3-oxoazetidine-l-carboxylate (16.9 g) in THF (50 mL) was added to the reaction mixture, and the resultant was stirred for 2 hours at 50C. After water was added to the reaction rnixture, extraction thereof was performed using ethyl acetate. The obtained organic layer was sequentially washed with water and a saturated saline solution, dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was dissolved into a solution in which ethyl acetate and hexane is mixed at a ratio of 1:3, the resultant was filtered using celite, and then the filtrate was concentrated under reduced pressure. The obtained residue was purified by a silica gel column chromatography (hexane/ethyl acetate), thereby obtaining the title compound (10.9g). NMR (300 MHz, DMSO-ds) delta 1.45 (9H, s), 4.46-4.51 (4H, m), 4.96-5.02 (2H, m).

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  • [ 78775-11-8 ]
  • [ 1779-49-3 ]
  • [ 90560-53-5 ]
  • 25
  • [ 1779-49-3 ]
  • [ 105258-93-3 ]
  • [ 934664-23-0 ]
YieldReaction ConditionsOperation in experiment
75% A suspension of methyltriphenylphosphonium bromide (23.0 g, 0.0649 mol) and potassium tert-butoxide (7.3 g, 0.0649 mol) in diethyl ether (140 mL) was stirred at room temperature for 20 min, and then heated to 35 0C for 1 h. To this bright yellow reaction mixture was slowly added a dilute solution of phenylmethyl 3- oxoazetidine-1-carboxylate (3.33 g, 0.0162 mol) in diethyl ether (50 mL). The reaction mixture was stirred at 35 0C for 12 hours then filtered through a bed of celite and rinsed with ethyl ether. The filtrate was washed with water and brine, dried over anhydrous magnesium sulfate and concentrated. The residue was purified by flash chromatography (SiO2, 5-10% ethyl acetate in hexanes) to afford phenylmethyl 3-methylideneazetidine-l-carboxylate (2.46 g, 75% yield) as a clear and colorless oil). 1H NMR (400 MHz, CDCl3): 7.27-7.22 (m, 5H), 5.02 (s, 2H), 4.93-4.90 (m, 2H), 4.48-4.47 (m, 4H). MS (EI) for Ci2H)3NO2: 203 (M+).
75% A suspension of methyltriphenylphosphonium bromide (23.0 g, 0.0649 mol) and potassium tert-butoxide (7.3 g, 0.0649 mol) in diethyl ether (140 mL) was stirred at room temperature for 20 min, and then heated to 35 0C for 1 h. To this bright yellow reaction mixture was slowly added a dilute solution of phenylmethyl 3-oxoazetidine-l-carboxylate <n="181"/>(3.33 g, 0.0162 mol) in diethyl ether (50 mL). The reaction mixture was stirred at 35 0C for 12 hours then filtered through a bed of celite and rinsed with ethyl ether. The filtrate was washed with water and brine, dried over anhydrous magnesium sulfate and concentrated. The residue was purified by flash chromatography (SiO2, 5-10% ethyl acetate in hexanes) to afford phenylmethyl 3-methylideneazetidine-l-carboxylate (2.46 g, 75% yield) as a clear and colorless oil). 1H NMR (400 MHz, CDCl3): 7.27-7.22 (m, 5H), 5.02 (s, 2H), 4.93-4.90 (m, 2H), 4.48-4.47 (m, 4H). MS (EI) for C12H13NO2: 203 (M+).
14.1 g A suspension of methyltriphenylphosphonium bromide (93 g) and potassium tert- butoxide (29.3 g) in diethyl ether (700 mL) was stirred at RT for 20 minutes and heated at 35 C for 1 hour under nitrogen. The bright yellow mixture was treated with the sub-title product of step (ii) (17.9 g) in diethyl ether (200 mL) dropwise over 1 hour at 35 C (orange suspension formed). The resulting mixture was stirred at 35 C for 12 hours. The mixture was cooled and filtered through a pad of celite and washed with diethyl ether. The filtrate was washed with water (300 mL), dried over magnesium sulfate, filtered and evaporated to afford crude product. The crude product was purified by flash silica chromatography, elution 10%> ethyl acetate in isohexane to 50% ethyl acetate in isohexane (stained with KMn04). Pure fractions were evaporated to dryness to afford the sub -title product (14.1) as a colorless oil.1H NMR (400 MHz, CDCL3) delta 7.39 - 7.28 (m, 5H), 5.12 (s, 2H), 5.01 (m, 2H), 4.57(t, 4H).
14.1 g A suspension of methyltriphenylphosphonium bromide (93 g) and potassium tert-butoxide (29.3 g) in diethyl ether (700 mL) was stirred at RT for 20 minutes and heated at 35 C for 1 hour under nitrogen. The bright yellow mixture was treated with the sub-title product of step (ii) (17.9 g) in diethyl ether (200 mL) dropwise over 1 hour at 35 C (orange suspension formed). The resulting mixture was stirred at 35 C for 12 hours. The mixture was cooled and filtered through a pad of celite and washed with diethyl ether. The filtrate was washed with water (300 mL), dried over magnesium sulfate, filtered and evaporated to afford crude product. The crude product was purified by flash silica chromatography, elution 10% ethyl acetate in isohexane to 50% ethyl acetate in isohexane (stained with KMn04). Pure fractions were evaporated to dryness to afford the sub -title product (14.1) as a colorless oil. 1H NMR (400 MHz, CDCL3) delta 7.39 - 7.28 (m, 5H), 5.12 (s, 2H), 5.01 (m, 2H), 4.57 (t, 4H).

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  • [ 71690-05-6 ]
  • [ 1779-49-3 ]
  • [ 1001193-62-9 ]
YieldReaction ConditionsOperation in experiment
70% To a stirred slurry of methyltriphenylphosphonium bromide (10.0 g) in toluene (200 mL) at 0 C. was added potassium t-butoxide (3.07 g) portionwise to produce a yellow slurry. After 1 hr, the reaction mixture was cooled to -20 C. and 4 (4.0 grams, 22.72 mmol) dissolved in tetrahydrofuran (6 mL) was added dropwise to produce a purple colored slurry. The reaction mixture was heated to 0 C. and stirred for an additional 1 hr. Then the reaction mixture was treated with saturated aqueous brine (150 mL) and diluted with ethyl acetate (200 mL). The resulting organic portion was washed with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting product was chromatographed by silica gel chromatography column eluting with a gradient of ethyl acetate (0%-10%)/hexanes to provide 2.77 g of 1 (70% yield). 1H NMR (400 MHz, CDCl3) delta 8:30 (1H, d, J=2.19 Hz), 7.80 (1H, d, J=2.19 Hz), 6.63 (1H, dd, J=10.96, 17.80 Hz), 5.86 (1H, d, J=17.80 Hz), 5.45 (1H, d, J=10.96 Hz). LC/MS (M+1): 174.
70% To a stirred slurry of methyltriphenylphosphonium bromide (10.0 g) in toluene (200 mL) at 0 C. was added potassium t-butoxide (3.07 g) portionwise to produce a yellow slurry. After 1 hr, the reaction mixture was cooled to -20 C. and 4 (4.0 grams, 22.72 mmol) dissolved in tetrahydrofuran (6 mL) was added dropwise to produce a purple colored slurry. The reaction mixture was heated to 0 C. and stirred for an additional 1 hr. Then the reaction mixture was treated with saturated aqueous brine (150 mL) and diluted with ethyl acetate (200 mL). The resulting organic portion was washed with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting product was chromatographed by silica gel chromatography column eluting with a gradient of ethyl acetate (0%-10%)/hexanes to provide 2.77 g of 1 (70% yield). 1H NMR (400 MHz, CDCl3) delta 8.30 (1H, d, J=2.19 Hz), 7.80 (1H, d, J=2.19 Hz), 6.63 (1H, dd, J=10.96, 17.80 Hz), 5.86 (1H, d, J=17.80 Hz), 5.45 (1H, d, J=10.96 Hz). LC/MS (M+1): 174.
70% To a stirred slurry of methyltriphenylphosphonium bromide (10.0 g) in toluene (200 mL) at 0 C. was added potassium t-butoxide (3.07 g) portionwise to produce a yellow slurry. After 1 hr, the reaction mixture was cooled to -20 C. and 4 (4.0 grams, 22.72 mmol) dissolved in tetrahydrofuran (6 mL) was added dropwise to produce a purple colored slurry. The reaction mixture was heated to 0 C. and stirred for an additional 1 hr. Then the reaction mixture was treated with saturated aqueous brine (150 mL) and diluted with ethyl acetate (200 mL). The resulting organic portion was washed with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting product was chromatographed by silica gel chromatography column eluting with a gradient of ethyl acetate (0%-10%)/hexanes to provide 2.77 g of 1 (70% yield). 1H NMR (400 MHz, CDCl3) delta 8.30 (1H, d, J=2.19 Hz), 7.80 (1H, d, J=2.19 Hz), 6.63 (1H, dd, J=10.96, 17.80 Hz), 5.86 (1H, d, J=17.80 Hz), 5.45 (1H, d, J=10.96 Hz). LC/MS (M+1): 174.
70% 2,3-Dichloro-5-vinylpyridine. To a stirred slurry of methyltriphenylphosphonium bromide (10.0 g) in toluene (200 mL) at O0C was added potassium /-butoxide (3.07 g) portionwise to produce a yellow slurry. After 1 hr, the reaction mixture was cooled to -2O0C and 65 (4.0 grams, 22.72 mmol) dissolved in tetrahydrofuran (6 mL) was added dropwise to produce a purple colored slurry. The reaction mixture was heated to O0C and stirred for additional 1 hr. Then the reaction mixture was treated with saturated aqueous brine ( 150 mL) and diluted with ethyl acetate (200 mL). The resulting organic layer was washed with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting product was chromatographed by silica gel chromatography column eluting with a gradient of ethyl acetate (0%-10%)/hexanes to provide 2.77 g of 66 (70% yield). 1H NMR (400 MHz, CDCl3) delta 8.30 (IH, d, J=2.19Hz), 7.80 (IH, d, J=2.19Hz), 6.63 (IH, dd, J=10.96, 17.80Hz), 5.86 (IH, d, J=17.80Hz), 5.45 (IH, d, J=10.96Hz). LC/MS (M+l ): 174.
70% To a cooled 0C, stirred slurry of methyltriphenylphosphonium bromide (10.0 g) in toluene (200 mL) was added potassium t-butoxide (3.07 g) portionwise to produce a yellow slurry. After 1 hr, the reaction mixture was cooled to -20C and 2,3-dichloro-5- formylpyridine (2, 4.0 grams, 22.72 mMol) which dissolved in tetrahydrofuran (6 mL) was added dropwise to produce a purple colored slurry. The reaction mixture was warmed to 0C and stirred for additional 1 hr. Then the reaction mixture was treated with saturated aqueous brine (150 mL) and diluted with ethyl acetate (200 mL). The resulting organic layer was washed with brine, dried over anhydrous sodium sulfate and concentrated in vacuo. The crude product was purified by silica gel chromatography column eluting with a gradient of ethyl acetate (0-10%)/hexanes to afford 2.77 g of the desired product 3 (70%). 1H NMR (400 MHz, CDCl3) delta 8.30 (1 H, d, J = 2.19 Hz), 7.80 (1 H, d, J = 2.19 Hz), 6.63 (1 H, dd, J = 10.96, 17.80 Hz), 5.86 (1 H, d, J = 17.80 Hz), 5.45 (1 H, d, J = 10.96 Hz). LC/MS (M+l): 174.
64% 2,3-dichloro-5-vinylpyridine. To a suspension of methyltriphenylphosphonium bromide (PPh3CH3Br, 7.08 g, 19.8 mmol, Sigma-Aldrich) in THF (40 mL) at O0C was added dropwise a 0.5N solution of potassium bis(trimethylsilyl)amide [K(N(TMS)2)]in toluene (39.6 mL, 19.8 mmol, Sigma-Aldrich). Then the resultant mixture was stirred at 00C for lhour. To the mixture was added a solution of 65 (3.17g, 18.0 mmol) in THF (20 mL) at 00C. The reaction mixture was stirred for 2 h at O0C. The reaction was quenched with water, and the mixture was extracted three times with EtOAc (150 mL for each extraction). The organic portions were combined, washed with brine, and concentrated to dryness. Compound 66 was obtained as a slight yellowish oil via flash chromatography using ethyl acetate/hexane gradient as an eluent (64% yield). 1H NMR: (CDCl3) delta 8.28 (d, J=2.1 Hz, I H), 7.82 (d, J=2.2 Hz, I H), 6.65 (dd, J=I 1.0, 17.5 Hz, I H), 5.85 (d, J=17.5 Hz, I H), 5.48 (d, J=I LO Hz, l H) ppm.

  • 27
  • [ 2460-58-4 ]
  • [ 1779-49-3 ]
  • [ 70-11-1 ]
  • [ 1191064-96-6 ]
  • 28
  • [ 1779-49-3 ]
  • [ 73365-02-3 ]
  • [ 340129-94-4 ]
YieldReaction ConditionsOperation in experiment
Reference Example 71 To a mixture of Boc D-prolinol (5.10 g) and dimethylsulfoxide (35 mL) was added at 10C triethylamine (12.1 mL) and pyridine-sulfur trioxide (13.8 g). After stirring for 2.5 hours, the mixture was poured into iced water and extracted with dichloromethane. The extracts were washed with a 50% citric acid solution, a sodium hydrogen carbonate solution and water, dried and concentrated to obtain a pale yellow oily matter (2.30 g). A mixture of sodium hydride (60% in oil, 402 mg) and dimethylsulfoxide (10 mL) was stirred at 55C for 1 hour. A mixture of methyltriphenylphosphonium bromide (3.59 g) and dimethylsulfoxide (15 mL) was added, and the mixture was stirred for 45 minutes. After cooling to room temperature, the mixture was added to a mixture of the obtained oily matter (2.00 g) and dimethylsulfoxide (30 mL). The resulting mixture was stirred for 15 hours. The reactant was poured into water and extracted with dichloromethane. The extracts were water-washed, dried and concentrated. The obtained residue was purified by silica gel column chromatography to obtain tert-butyl (2R)-2-vinyl-1-pyrrolidine carboxylate (191 mg). 1H-NMR (300 MHz, CDCl3) delta: 1.44 (9H, s), 1.64-2.10 (4H, m), 3.34-3.45 (2H, m), 4.20-4.38 (1H, m), 5.03-5.06 (2H, m), 5.66-5.80 (1H, m).
  • 29
  • [ 30361-28-5 ]
  • [ 1779-49-3 ]
  • 1,3,5-nonatriene [ No CAS ]
  • 30
  • [ 54287-99-9 ]
  • [ 1779-49-3 ]
  • [ 1252582-83-4 ]
  • 31
  • [ 53590-49-1 ]
  • [ 1779-49-3 ]
  • [ 1253060-22-8 ]
  • 33
  • [ 31170-78-2 ]
  • [ 1779-49-3 ]
  • [ 92800-05-0 ]
  • 34
  • [ 1779-49-3 ]
  • [ 65181-78-4 ]
  • [ 68-12-2 ]
  • [ 227176-02-5 ]
  • [ 847690-46-4 ]
  • 35
  • [ 190271-78-4 ]
  • [ 1779-49-3 ]
  • [ 918870-83-4 ]
  • 36
  • [ 1779-49-3 ]
  • [ 98977-36-7 ]
  • [ 276872-89-0 ]
  • 39
  • [ 54221-96-4 ]
  • [ 1779-49-3 ]
  • [ 204569-88-0 ]
YieldReaction ConditionsOperation in experiment
16% To a suspension of methyl(triphenyl)phosphonium bromide (7.07 g, 19.8 mmol, 1 .1 eq) in dry THF (50 ml) at 0°C is added n-butyl lithium (1.6M in cyclohexane, 12.5 ml, 19.8 mmol, 1 .1 eq). After stirring at 0°C for 20 minutes, a solution of 6-methoxypyridine- 2-carbaldehyde a1 -50 (2.5 g, 18 mmol, 1 eq) in dry THF (10 ml) is added dropwise to the mixture. The reaction mixture is warmed to room temperature for 30 minutes. The reaction mixture is quenched with 3 drops of water, and Rochelle salt is added (10 g). The mixture is filtered on Celite and MgSC>4. The crude residue is distilled to afford 400 mg of pure 2-ethenyl-6-methoxypyridine a1 -51.Yield: 16 percent.H NMR ? 7.51 (t, J = 7.6 Hz, 1 H), 6.82 (d, J = 7.2 Hz, 1 H), 6.72 (dd, J = 17.0, 10.6 Hz, 1 H), 6.62 (d, J = 8.2 Hz, 1 H), 6.29 (dd, J = 17.2, 1.4 Hz, 1 H), 5.41 (dd, J = 10.6, 1.4 Hz, 1 H), 3.96 (s, 3 H).
  • 40
  • [ 1779-49-3 ]
  • [ 90-94-8 ]
  • [ 7478-69-5 ]
YieldReaction ConditionsOperation in experiment
92% The synthesis of BDADPE was conducted by the classic Wittig reaction using 4,4?-bis(dimethylamino)benzophenone as substrate under an argon atmosphere (described in detail by Hirao [29]). Typically, methyltriphenylphosphonium bromide (45.58g, 127.6mmol) and freshly distilled THF (500mL) were added into a round bottom flask equipped with a reflux condenser and a magnetic bar. Potassium tert-butoxide (138.4mL of a 1.0M solution in THF, 138.4mmol) was then added dropwise to the reaction flask via constant pressure funnel. The reaction mixture was stirred for 2h at 0C. Then the solution of 4,4?-bis(dimethylamino)benzophenone (21.4g, 79.75mmol) in dry THF (690mL) was dropped to the reaction mixture via constant pressure funnel at 0C. The orange-brown reaction mixture was heated to reflux for 7h with stirring and then quenched with distilled water. The resultant mixture was extracted with ether three times. Such ethereal layer was washed with aqueous NaHCO3 solution and saturated aqueous NaCl solution and then dried over MgSO4. After filtration, the ethereal layer was poured into hexane to precipitate triphenylphosphine oxide. Flash column chromatography (petroleum ether/ethyl acetate 2:1 v/v) gave BDADPE in 92% yield (19.52g, 73.37mmol) and Rf=0.76. 1H NMR (CDCl3, 400MHz): delta 2.96 (s, 12H, 2×N(CH3)2), 5.19 (s, 2H, CH2=C), 6.68-6.70 (d, 4H, aromatic proton ortho to N(CH3)2), 7.25-7.28 (d, 4H, aromatic proton meta to N(CH3)2).
  • 42
  • [ 40624-07-5 ]
  • [ 1779-49-3 ]
  • [ 1454661-82-5 ]
  • 43
  • [ 82104-74-3 ]
  • [ 1779-49-3 ]
  • [ 352-13-6 ]
  • 4-(1-(4-fluorophenyl)vinyl)-3-(hydroxymethyl)benzonitrile [ No CAS ]
  • 44
  • [ 58012-34-3 ]
  • [ 1779-49-3 ]
  • ethyl 2-(4-methylenecyclohexyl)-acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
73.7% Step 2: Synthesis of ethyl 2-(4-methylenecyclohexyl)acetate. [00419] To a cooled (0°C) suspension of methyl triphenylphosphonium bromide (8.58 g, 23.5 mmol) in THF (60 mL) was added KOtBu (3.17 g, 28.3 mmol) in portions under N2. The reaction was slowly warmed to rt and stirred for 1 h. The resulting mixture was cooled to 0°C and added a solution of <strong>[58012-34-3]ethyl 2-(4-oxocyclohexyl)acetate</strong> (2.9 g, 15.7 mmol) in THF (15 mL). The resulting mixture was stirred at RT for 2 h and at 50°C overnight. After cooling to RT, the reaction was quenched by addition of saturated NH4C1, extracted with EtOAc, washed with brine, dried over Na2S04. Purification by flash column chromatography (eluent: 20percent EtOAc in hexanes) gave the product as colorless oil (2.11 g, 73.7percent).
60% To a solution of methyl triphenyl phosphonium bromide (2.74 g, 8.2 mmol) inTHE was added n-BuLi (3.4 mL, 2.5 M, 8.2 mmol) at -70°C. The mixture solution was stirred at 0 °C for 2 hrs. Then a solution of reagent KR-48 (1 g, 30 mmol) in THE was added to the solution at -70°C. The mixture solution was stirred at r.t overnight. The mixture was quenched with aqueous NH4CI and extracted with EtOAc, the organic layer was washed with brine, driedover anhydrous Na2504, concentrated to give the crude product which was purified by the column to give the reagent R-23c (0.5 g, 60 percent yield) as a white solid. calc. for C11H1802: 182.1.
  • 45
  • [ 348-27-6 ]
  • [ 1779-49-3 ]
  • 3-fluoro-4-vinyl phenol [ No CAS ]
YieldReaction ConditionsOperation in experiment
With potassium tert-butylate; In tetrahydrofuran; Step 6: KOtBu, THF, MePPh3Br.
  • 46
  • [ 32811-75-9 ]
  • [ 1779-49-3 ]
  • [ 37575-80-7 ]
YieldReaction ConditionsOperation in experiment
24% To a solution of methyl triphenyl phosphonium bromide (14 g, 30 mmol) in THE was added n-BuLi (12 mL, 2.5 M, 30 mmol) at -70C. The mixture solution was stirred at 0C for 2 hrs. After to a solution of commercially available methyl 3-oxocyclopentanecarboxylate (3 g, 21 mmol) in THE was added to the solution at -70C. The mixture solution was stirred at r.tovernight. The mixture was quenched with aqueous NH4CI and extracted with EtOAc, the organic layer was washed with brine, dried over anhydrous Na2504, concentrated to give the crude product which was purified by the column to give reagent R-23d (0.7 g, 24 % yield) as a white solid. calc. forC8H1202: 140.0.
  • 47
  • [ 55479-94-2 ]
  • [ 1779-49-3 ]
  • [ 35106-82-2 ]
  • 48
  • [ 13949-93-4 ]
  • [ 1779-49-3 ]
  • [ 2183-89-3 ]
  • 50
  • [ 54884-55-8 ]
  • [ 1779-49-3 ]
  • [ 72473-09-7 ]
  • 52
  • [ 1006-33-3 ]
  • [ 1779-49-3 ]
  • 1-bromo-4-fluoro-2-(prop-1-en-2-yl)benzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
General procedure: To the mixture of methyltriphenylphosphonium bromide (21.6 g, 60.0 mmol) and t-BuOK (9.0 g, 80.0 mmol) was added anhydrous THF (80.0 mL) and stirred at r.t. for 1 hour under argon, then a solution of 1-(2-bromophenyl)ethan-1-one (8.0 g, 40.0 mmol) in THF (40.0 mL) was added dropwise. The resulting reaction mixture was stirred overnight at room temperature and quenched with saturated NH4Cl solution. The organic layer was separated and the aqueous layer was extracted with EtOAc (3 × 30 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated in vacuo. The residue was purified by flash chromatography on silica gel using petroleum/EtOAc as eluent to yield 1-bromo-2-(prop-1-en-2-yl)benzene (6.9 g, 88%)
  • 53
  • [ 935-99-9 ]
  • [ 1779-49-3 ]
  • 1-bromo-4-chloro-2-(prop-1-en-2-yl)benzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
General procedure: To the mixture of methyltriphenylphosphonium bromide (21.6 g, 60.0 mmol) and t-BuOK (9.0 g, 80.0 mmol) was added anhydrous THF (80.0 mL) and stirred at r.t. for 1 hour under argon, then a solution of 1-(2-bromophenyl)ethan-1-one (8.0 g, 40.0 mmol) in THF (40.0 mL) was added dropwise. The resulting reaction mixture was stirred overnight at room temperature and quenched with saturated NH4Cl solution. The organic layer was separated and the aqueous layer was extracted with EtOAc (3 × 30 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated in vacuo. The residue was purified by flash chromatography on silica gel using petroleum/EtOAc as eluent to yield 1-bromo-2-(prop-1-en-2-yl)benzene (6.9 g, 88%)
  • 55
  • [ 450-83-9 ]
  • [ 1779-49-3 ]
  • 4-fluoro-2-methoxy-1-vinylbenzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
321 mg Synthesis of 4-fluoro-2-methoxy-1-vinylbenzene. A suspension of 12.73 g of methyl triphenylphosphonium bromide in 100 mL of dry THF was treated at room temperature with 15.6 mL of n-BuLl (2.5 M solution in n-hexane). The resulting orange solution was stirred for 4 hours. Then, a solution of 5.00 g of <strong>[450-83-9]4-fluoro-o-anisaldehyde</strong> in 25 mL of dry THF was added dropwise. Upon addition a white precipitate formed. The suspension was stirred for 1 hour and concentrated in vacuo to give aviscous orange oil that was purified by passing through a short column of Si02 (heptane) then vacuum distillation to yield 321 mg of 4-fluoro-2-methoxy-1-vinylbenzene as a colorless liquid. 1H-NMR (300MHz, CDCI3): 63.76 (s, 3H), 5.15 (dd, Ji=11.1 Hz, J2=1.4 Hz, IH), 5.69 (dd, J1=17.6 Hz, J2=1.4 Hz,1H), 6.48-6.60 (m, 2H), 6.81-6.94 (m, IH), 7.29-7.37 (m, 1H). GC-MS: 97.5% MS (El): 152.
  • 56
  • [ 57415-35-7 ]
  • [ 1779-49-3 ]
  • 2-methoxy-4-methyl-1-vinylbenzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
99% Example 5A: To a solution of methyl -(triphenyl)phosphonium bromide (4.745g, 13.32 mmol, 1 eq) in THF (20 mL) was added t-BuONa (1.28 g, 13.32 mmol, 4 eq) at 0 °C under N2 atmosphere. The mixture was stirred at 0 °C for 0.5 hr. To the mixture was added 2-methoxy-4- methyl-benzaldehyde (500 mg, 3.33 mmol, 1 eq) dropwise over 15 min, then the mixture was stirred at 0 °C for 0.5 hr. To this reaction was added H20 (20 mL) and the mixture was extracted with ethyl acetate (20 mL*2). The combined organic phase was washed with brine (20 mL), dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was purified by flash silica gel chromatography to give the target compound (490 mg, 3.31 mmol, 99percent yield) as a white oil. NMR (400 MHz, CHLOROFORM-d) delta 2.36 (3 H, s) 3.85 (3 H, s) 5.19 - 5.23 (1 H, m) 5.70 (1 H, dd, J=17.82, 1.51 Hz) 6.70 (1 H, s) 6.74 - 6.79 (1 H, m) 6.97 - 7.06 (1 H, m) 7.37 (1 H, d, J=7.53 Hz).
93% Under argon atmosphere, MePPh3Br (2.02 g, 5.65 mmol, 1.2 equiv) was suspended in THF (40 mL) and cooled to 0 °C. Then, a n-BuLi solution (2.5 M in hexanes, 2.3 mL, 5.76 mmol, 1.2 equiv) was added and the mixture was stirred for 2 h at 0 °C. Afterwards, the aldehyde 14(0.730 g, 4.89 mmol, 1.0 equiv) dissolved in THF (4 mL) was added dropwise and stirring was continued for 14 h at r.t. The solvent was removed under reduced pressure and the residue was purified by column chromatography (Rf = 0.72, cHex/EtOAc 10:1) to yield 0.647 g of vinylarene 11 as a yellow oil (4.55 mmol, 93percent).IR (ATR): 3005 (w), 2936 (w), 2253 (w), 1609 (w), 1502 (w), 1465 (w),1412 (w), 1285 (w), 1266 (w), 1193 (w), 1161 (w), 1121 (w), 1042(w), 998 (w), 904 (vs), 817 (w), 724 (vs), 650 cm?1 (m).1H NMR (300 MHz, CDCl3): delta = 7.38 (d, J = 7.8 Hz, 1 H, H6), 7.04 (dd, J =17.8, 11.2 Hz, 1 H, =CH), 6.78 (d, J = 7.8 Hz, 1 H, H5), 6.72 (s, 1 H, H3),5.72 (dd, J = 17.8, 1.6 Hz, 1 H, =CH2), 5.24 (dd, J = 11.1, 1.6 Hz, 1 H,=CH2), 3.86 (s, 3 H, OCH3), 2.38 (s, 3 H, CH3).13C NMR (75 MHz, CDCl3): delta = 156.8 (C2), 139.2 (C4), 131.7 (CH=),126.5 (C6), 124.1 (C1), 121.5 (C5), 113.6 (C3), 111.9 (CH2), 55.6(OCH3), 21.4 (CH3).GC-MS (70 eV): m/z (percent) = 148 (63, [M]+), 133 (67, [M ? CH3]+), 105(100).
1.46 g Synthesis of 2-methoxy-4-methyl-1-vinylbenzene. A suspension of 13.08 g of methyl triphenyiphosphonium bromide in 75 mL of dry THF was treated at room temperature with 16.0 mL of n-BuLi (2.5 M solution in n-hexane). The resulting orange solution was stirred for 4 hour. Then, a solution of 5.00 g of <strong>[57415-35-7]2-methoxy-4-methyl-benzaldehyde</strong> in 25 mL of dry THE was added dropwise. Upon addition, a white precipitate formed. The suspension was stirred for 1 hour and concentrated invacuo to give a viscous yellow oil that was purified by passing through a short column of Si02 (heptane) then vacuum distillation to yield 1.46 g of 2-methoxy-4-methyl-1-vinylbenzene as a colorless liquid. 1H-NMR (300 MHz, CDCI3): O 2.27 (s, 3H), 3.76 (s, 3H), 5.13 (dd, J1=11.2 Hz, J2=1.5 Hz, 1H), 5.61 (dd, J1=17.7 Hz, J2=1.5 Hz, 1H), 6.61 (s, 1H), 6.67 (m, 1H), 6.93 (m, IH), 7.28 (d, J=7.7 Hz, 1H). GC-MS: 97.8percent MS (El): 148.
  • 57
  • [ 1181816-12-5 ]
  • [ 1779-49-3 ]
  • tert-butyl 6-methylidene-2-azaspiro[3.3]heptane-2-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
50% tert-Butyl N-(2-[3-[([2-fluoro-4-[2-(1-methyl-1H-pyrazol-4-yl)-3H-imidazo[4,5-b]pyridin-7-yl]phenyl]methyl)carbamoyl]-1,2,4-oxadiazol-5-yl]propan-2-yl)carbamate In a 25-mL round bottom flask purged and maintained with an inert atmosphere of nitrogen, sodium hydride (60percent in oil, 12.50 mg, 0.52 mmol, 1.10 equiv) was suspended in tetrahydrofuran (5 ml), to which was added a solution of methyltriphenylphosphanium bromide (507.3 mg, 1.42 mmol, 3.0 equiv) in DMSO (2 ml) dropwise at 0° C. The mixture was warmed up to room temperature and stirred for 2 h. Then a solution of <strong>[1181816-12-5]tert-butyl 6-oxo-2-azaspiro[3.3]heptane-2-carboxylate</strong> (100 mg, 0.47 mmol, 1.00 equiv) in tetrahydrofuran (2 ml) was added at room temperature. The resulting mixture was stirred for another 16 h at room temperature. When the reaction was done, it was quenched by the addition of 10 mL water and the mixture was extracted with ethyl acetate (3*10 ml). The organic layers were combined, dried over sodium sulfate and concentrated under reduce pressure. The residue was purified in a silica gel column eluting with ethyl acetate in petroleum ether (5percent to 20percent gradient) to afford tert-butyl 6-methylidene-2-azaspiro[3.3]heptane-2-carboxylate (50 mg, 50percent) as yellow solid.
  • 58
  • [ 1779-49-3 ]
  • [ 1022-13-5 ]
  • C15H14ClN [ No CAS ]
  • 59
  • [ 1779-49-3 ]
  • [ 190011-87-1 ]
  • 1-chloro-3-ethenyl-2,4-difluorobenzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
13% To a cooled (-20 C) suspension of methyltriphenylphosphonium bromide (6.68 g, 18.69 mmol) in diethyl ether (48.6ml) was added dropwise nBuLi (6.80 ml, 16.99 mmol). The resulting yellow suspension was allowed to warm to 0 C and stir for 2 h. In a separate flask, a solution of 1-chloro-2,6-difluorobenzaldehyde (3.0 g, 16.99 mmol) in diethyl ether(20 mL) was prepared and cooled to 0 C. Next, the solution of theylide was added via cannula to give a thick suspension. The suspension wasstirred at 0 C for 30 min and then the reaction was allowed to warmed to rt. After 22 h, the reaction was cooled to 0 C and then water was added. The reactionwas warmed to rt and the layers were separated. The aqueous layer was extracted with diethyl ether. Theorganic layers were combined and washed with brine, dried over sodium sulfate,filtered and concentrated to give an orange-brown solid weighing 3.20 g. Purification by normal phase chromatography provided the desired product (0.510g, 13%) as a clear, colorless liquid.
13% To a cooled (-20 oC) suspension of methyltriphenylphosphonium bromide (6.68 g, 18.7 mmol) in Et2O (48.6 ml) was added dropwise 2.5 M nBuLi in Hex (6.80 mL, 17.0 mmol). The resulting yellow suspension was allowed to warm to 0 oC and stir for 2 h. In a separate flask, a solution of <strong>[190011-87-1]3-chloro-2,6-difluorobenzaldehyde</strong> (3.0 g, 17.0 mmol) in Et2O (20 ml) was prepared and cooled to 0 oC. Next, the solution of the ylide was added via cannula to give a thick suspension. The suspension was stirred at 0 oC for 30 min and then the reaction was allowed to warm to rt. After 22 h, the reaction was cooled to 0 oC and then water was added. The reaction was warmed to rt and the layers were separated. The aqueous layer was extracted with Et2O. The organic layers were combined and washed with brine, dried over Na2SO4, filtered and concentrated to give an orange-brown solid weighing 3.20 g. Purification by normal phase chromatography provided 1-chloro-3-ethenyl-2,4- difluorobenzene (0.510 g, 13% yield) as a clear, colorless liquid. 1H NMR (500 MHz, CHCl3) delta 7.22 (td, J=8.5, 5.5 Hz, 1H), 6.84 (td, J=9.4, 1.8 Hz, 1H), 6.69 (dd, J=18.0, 12.0 Hz, 1H), 6.07 (d, J=17.9 Hz, 1H), 5.65 (dd, J=12.1, 1.1 Hz, 1H).
  • 60
  • [ 30314-45-5 ]
  • [ 1779-49-3 ]
  • [ 31006-99-2 ]
YieldReaction ConditionsOperation in experiment
3.7 g Step 3 : To a solution of methyl triphenylphosphonium bromide (8.8 g) in THF (100 mL) at -78 C was added n-BuLi (2.5 M in hexane, 10.4 mL) slowly. The mixture was stirred at 0 C for 30 min. To the reaction mixture was added a solution of <strong>[30314-45-5](4-bromophenyl)(t-butyl)methanone</strong> (21) (5.3 g) in THF (10 mL). The mixture was allowed to warm to room temperature, stirred 24 h, and partitioned between TBME and saturated NH4CI solution. The combined organics were dried, filtered and concentrated in vacuo. The residue was purified by flash chromatography with 50: 1 hexane/EA to provide 3, 3 -dimethyl -2-(4-bromophenyl)-l-butene (3.7 g).
  • 62
  • [ 1676-90-0 ]
  • [ 1779-49-3 ]
  • [ 725255-57-2 ]
  • 63
  • [ 2977-45-9 ]
  • [ 1779-49-3 ]
  • [ 2977-47-1 ]
YieldReaction ConditionsOperation in experiment
85% Step B: Preparation of 2,2-dimethyl-l-methylene-l,2,3,4-tetrahydronaphthalene To a suspension of methyltriphenylphosphonium bromide (5.1 g, 14.28 mmol) in 20 mL toluene, 1 M potassium 2-mefhylpropan-2-olate in THF (17.2 mL, 17.20 mmol) was added. After stirring at 120C (oil bath) for 40 min, a solution of 2,2-dimethyl-3,4-dihydronaphthalen-l(2 )-one (1.1 g, 6.313 mmol) in 3 mL toluene was added. The mixture was stirred at 120C for 10 min, allowed to cool to room temperature, and extracted with water and AcOEt. Organic phase was dried over MgS04, filtered, and concentrated. The residue was purified by biotage column chromatography (Si02, hexane/AcOEt gradient) to give 2,2-dimethyl-l-methylene- l,2,3,4-tetrahydronaphthalene (927 mg, 85%) as a colorless liquid. NMR (400 MHz, CDC13) delta 1.22 (s, 6H), 1.68 (t, / = 6.6 Hz, 2H), 2.86 (t, J = 6.6 Hz, 2H), 5.07 (s, 1H), 5.44 (s, 1H), 7.08-7.19 (m, 3H), 7.58-7.60 (m, 1H).
  • 64
  • [ 954236-44-3 ]
  • [ 1779-49-3 ]
  • [ 1415813-01-2 ]
YieldReaction ConditionsOperation in experiment
90% Methyltriphenylphosphonium bromide (8.4 g, 24 mmol) was added portion-wise to a mixture of sodium hydride (60% dispersion in mineral oil; 940 mg, 23.5 mmol) in dimethyl sulfoxide (40 mL), and the reaction mixture was stirred for 30 minutes at room temperature. A solution of te/ -butyl 3-oxo-1-oxa-8-azaspiro[4.5]decane-8-carboxylate (2.0 g, 7.8 mmol) in dimethyl sulfoxide (18 mL) was then added drop-wise, and the reaction mixture was allowed to continue stirring at room temperature for 72 hours. The reaction was then carefully quenched with water (250 mL), and extracted with diethyl ether (5 x 50 mL). The combined organic layers were washed with water (2 x 25 mL), dried over magnesium sulfate, filtered, and concentrated in vacuo. The residue was triturated three times with heptane to afford an off-white solid, which proved to be largely triphenylphosphine oxide on analysis. The combined heptane portions from the triturations were concentrated in vacuo and subjected to silica gel chromatography (Eluents: 0%, followed by 10% and 20% ethyl acetate in heptane), which afforded the product as a colorless oil. Yield: 1.77 g, 6.99 mmol, 90%. GCMS nVz 253.1 [M+]. 1H NMR (400 MHz, CDCI3) 8 5.02-4.98 (m, 1 H), 4.95-4.91 (m, 1 H), 4.37-4.33 (m, 2H), 3.60 (ddd, J=13, 5, 5 Hz, 2H), 3.34 (ddd, J=13.3, 9.9, 3.3 Hz, 2H), 2.42-2.38 (m, 2H), 1.70-1.63 (m, 2H), 1.55 (ddd, J=13.3, 10.0, 4.5 Hz, 2H), 1.46 (s, 9H).
90% Methyltriphenylphosphonium bromide (8.4 g, 24 mmol) was added portion-wise to a mixture of sodium hydride (60% dispersion in mineral oil; 940 mg, 23.5 mmol) in dimethyl sulfoxide (40 mL), and the reaction mixture was stirred for 30 minutes at room temperature. A solution of <strong>[954236-44-3]tert-butyl 3-oxo-1-oxa-8-azaspiro[4.5]decane-8-carboxylate</strong> (2.0 g, 7.8 mmol) in dimethyl sulfoxide (18 mL) was then added drop-wise, and the reaction mixture was allowed to continue stirring at room temperature for 72 hours. The reaction was then carefully quenched with water (250 mL), and extracted with diethyl ether (5*50 mL). The combined organic layers were washed with water (2*25 mL), dried over magnesium sulfate, filtered, and concentrated in vacuo. The residue was triturated three times with heptane to afford an off-white solid, which proved to be largely triphenylphosphine oxide on analysis. The combined heptane portions from the triturations were concentrated in vacuo and subjected to silica gel chromatography (Eluents: 0% followed by 10% and 20% ethyl acetate in heptane), which afforded the product as a colorless oil. Yield: 1.77 g, 6.99 mmol, 90%. GCMS m/z 253.1 [M+]. 1H NMR (400 MHz, CDCl3) delta 5.02-4.98 (m, 1H), 4.95-4.91 (m, 1H), 4.37-4.33 (m, 2H), 3.60 (ddd, J=13, 5, 5 Hz, 2H), 3.34 (ddd, J=13.3, 9.9, 3.3 Hz, 2H), 2.42-2.38 (m, 2H), 1.70-1.63 (m, 2H), 1.55 (ddd, J=13.3, 10.0, 4.5 Hz, 2H), 1.46 (s, 9H).
  • 65
  • [ 15115-59-0 ]
  • [ 1779-49-3 ]
  • 4-chloro-1-methylene-2,3-dihydro-1H-indene [ No CAS ]
  • 66
  • [ 10035-16-2 ]
  • [ 1779-49-3 ]
  • 5-vinyl-1-benzofuran [ No CAS ]
  • 68
  • [ 4903-09-7 ]
  • [ 1779-49-3 ]
  • 2-chloro-1-methoxy-4-vinylbenzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
94% General procedure: n-Butyl lithium (1 equiv., 2.5 M in THF) was added dropwise to a 0.12 M solution of methyltriphenylphosphonium bromide (1 equiv.) in THF. The yellow solution was allowed to stir for 15 minutes before addition of aldehyde (1 equiv.), upon which, the mixture turned white or pale yellow. After 2 hours (or observed completion of the reaction by TLC), saturated ammonium chloride was added and the mixture extracted with CH2Cl2. The organic layer was dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. Purification of the crude residue with column chromatography (ethyl acetate/petroleum ether or petroleum ether only was used as the eluent) afforded the substituted styrene.
  • 70
  • [ 1779-49-3 ]
  • [ 107834-03-7 ]
  • [ 168269-58-7 ]
  • 71
  • [ 1779-49-3 ]
  • [ 612-14-6 ]
  • [ 35106-82-2 ]
  • 72
  • [ 89891-69-0 ]
  • [ 1779-49-3 ]
  • C9H6BrN [ No CAS ]
  • 73
  • [ 80278-67-7 ]
  • [ 1779-49-3 ]
  • 5-vinylisoquinoline [ No CAS ]
  • 74
  • uranyl nirate hexahydrate [ No CAS ]
  • [ 46022-05-3 ]
  • [ 1779-49-3 ]
  • [ 68-12-2 ]
  • [PPh3Me][H2NMe2]3[(UO2)4(R-t-1,2-chdc)6]·H2O [ No CAS ]
  • 75
  • [ 85366-66-1 ]
  • [ 1779-49-3 ]
  • 2-bromo-1-(trifluoromethoxy)-4-vinylbenzene [ No CAS ]
  • 78
  • [ 2795-41-7 ]
  • [ 1779-49-3 ]
  • [ 1608150-16-8 ]
  • 79
  • [ 1779-49-3 ]
  • [ 4771-49-7 ]
  • 6-methyl-3-vinyl-1H-indole [ No CAS ]
  • 80
  • [ 3562-99-0 ]
  • [ 1779-49-3 ]
  • C16H16O3 [ No CAS ]
  • 81
  • [ 1779-49-3 ]
  • [ 122433-29-8 ]
  • [ 61841-34-7 ]
  • 82
  • [ 1016-78-0 ]
  • [ 1779-49-3 ]
  • [ 29265-81-4 ]
YieldReaction ConditionsOperation in experiment
82% General procedure: Ph3PCH3Br (1.20 equiv) was added to a flame-dried round-bottom flask, evacuated, backfilled with N2 three times, and suspended in THF (0.25 M) at 0C. To this vigorously stirring heterogeneous solution was added nBuLi (1.20 equiv) dropwise, and the reaction was allowed to stirred at room temperature for 30 min until a bright yellow heterogeneous mixture was achieved. Then commercially available 1,1-diarylmethanone (1.00 equiv) was added slowly. Upon complete addition, the cooling bath was removed and the reaction was allowed to stir overnight. Then, the solution was washed by brine and extracted with EtOAc (3×10 mL). The combined organic layers were dried over MgSO4, and concentrated under vacuum. The residue was purified by silica gel flash chromatography (PE:EA = 100:1) to afford the corresponding 1,1-diarylethene 5 and NMR spectra was compared to known literatures values.
  • 83
  • [ 1779-49-3 ]
  • [ 101682-68-2 ]
  • 2-bromo-4-ethenyl-nitrobenzene [ No CAS ]
  • 84
  • [ 161798-03-4 ]
  • [ 1779-49-3 ]
  • ethyl 2-(4-isobutoxy-3-vinylphenyl)-4-methylthiazole-5-carboxylate [ No CAS ]
  • 85
  • [ 1779-49-3 ]
  • [ 146137-79-3 ]
  • [ 1260539-05-6 ]
YieldReaction ConditionsOperation in experiment
14 g In 1,4-dioxane; at 110℃; for 6h;Inert atmosphere; The 1L four-necked flask was fitted with a reflux condenser and mechanically agitated for N2 flow protection.15 g of the compound of formula III (0.1 mol) was added to the reaction flask.43 g of methyltriphenylphosphonium bromide (0.12 mol),21g potassium carbonate and 300g 1,4-dioxane,Turn on mechanical agitation. The temperature was raised to 110 ° C and refluxed for 6 h until the compound of formula III was completely reacted. After the reaction was completed, the temperature was lowered to room temperature, and quenched by the addition of 150 g of water.150 mL of n-ethane was extracted three times, layered, and the organic phase was combined, concentrated under reduced pressure to a fraction without distillation, and purified by column chromatography to obtain 14 g of the compound of formula II.White solid.
  • 86
  • [ 93118-03-7 ]
  • [ 1779-49-3 ]
  • 2-chloro-1-(trifluoromethyl)-3-vinylbenzene [ No CAS ]
  • 87
  • [ 1779-49-3 ]
  • [ 213193-32-9 ]
  • 2-methoxy-5-(prop-1-en-2-yl)pyridine [ No CAS ]
  • 88
  • [ 128071-75-0 ]
  • [ 1779-49-3 ]
  • [ 243145-83-7 ]
  • 2-(4-fluorobenzyl)-3-vinylpyridine [ No CAS ]
YieldReaction ConditionsOperation in experiment
26% General procedure: A microwave vial was charged with 14d (250 mg, 1.3 mmol, 1 eq.), 4-fluorobenzylboronicacid pinacol ester (317 mg, 1.3 mmol, 1 eq.), [1,1 ?-Bis(diphenylphosphino)ferrocene] dichloropalladium(II) (49 mg, 0.07 mmol, 0.05 eq.), and K3P04 (560 mg, 4 mmol, 3 eq.) and capped with a Teflon lined lid. The vial was evacuated and purged with argon (3x) and then dioxane (15 mL) was added. The reaction mixture was heated to 90 C for 14 h, cooled to rt, and diluted with EtOAc (40 mL) and water (15 mL). The aqueous layer was extracted with EtOAc (2 x 20 mL). The combined organic layers were dried, concentrated and purified via through a filter column (Si02, 1:2 EtOAc:Hexanes) and used as obtained. The residue was added to a stirred solution of n-butyl lithium (1.5 eq.) and methyltriphenylphosphonium bromide (1.3 eq.) at 0 C. The reaction was stirred for 8 h at rt and quenched with water (10 mL). The aqueous phase was extracted with EtOAc (2 x 15 mL). The combined organic layers were dried, concentrated, and purified via flash chromatography (Si02, 1:3 EtOAc:Hexanes) to provide 9r as a clear oil (73 mg, 26%). ?HNMR (400 IVIHz, Chloroform-d) 8.51 -8.46 (m, 1H), 7.82-7.72 (m, 1H),7.16 (ddd, J = 15.5, 8.1, 5.1 Hz, 3H), 6.92 (dt, J = 18.4, 9.7 Hz, 3H), 5.65 (d, J = 17.3 Hz,1H), 5.36 (d, J = 11.0 Hz, 1H), 4.22 (s, 2H). ?3C NIVIR (126 IVIHz, CDC13) 162.8, 160.8,157.5, 149.0, 135.3, 134.1, 133.4, 130.4, 130.3, 122.5, 118.3, 115.7, 115.5, 41.3. HRIVIS(ESI) [M+H] for C,4H,3FN 214.1032, found 214.1036.
  • 89
  • [ 16957-70-3 ]
  • [ 1779-49-3 ]
  • C25H25OP [ No CAS ]
  • 90
  • [ 355134-13-3 ]
  • [ 1779-49-3 ]
  • 3-bromo-5-ethenyl-nitrobenzene [ No CAS ]
  • 91
  • [ 31680-07-6 ]
  • [ 1779-49-3 ]
  • [ 35921-01-8 ]
  • 93
  • [ 137052-08-5 ]
  • [ 1779-49-3 ]
  • [ 26170-25-2 ]
  • 94
  • [ 1836-05-1 ]
  • [ 1779-49-3 ]
  • C9H9BrO [ No CAS ]
  • 95
  • [ 64622-16-8 ]
  • [ 1779-49-3 ]
  • C8H6BrCl [ No CAS ]
  • 96
  • [ 5731-01-1 ]
  • [ 1779-49-3 ]
  • [ 1071629-00-9 ]
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