Structure of 3513-81-3
*Storage: {[sel_prStorage]}
*Shipping: {[sel_prShipping]}
The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
4.5
*For Research Use Only !
Change View
Size | Price | VIP Price | US Stock |
Global Stock |
In Stock | ||
{[ item.pr_size ]} |
Inquiry
{[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price, item.pr_usd) ]} {[ getRatePrice(item.pr_usd,item.pr_rate,1,item.pr_is_large_size_no_price, item.discount_usd) ]} {[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price, item.pr_usd) ]} |
Inquiry {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate,item.pr_is_large_size_no_price, item.vip_usd) ]} | Inquiry {[ item.pr_usastock ]} In Stock Inquiry - | {[ item.pr_chinastock ]} {[ item.pr_remark ]} In Stock 1-2 weeks - Inquiry - | Login | - + | Inquiry |
Please Login or Create an Account to: See VIP prices and availability
US Stock: ship in 0-1 business day
Global Stock: ship in 5-7 days
1-2weeks
Inquiry
{[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate,item.pr_is_large_size_no_price, item.vip_usd) ]}
{[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price, item.pr_usd) ]}
{[ getRatePrice(item.pr_usd,1,item.mem_rate,item.pr_is_large_size_no_price, item.pr_usd) ]}
Inquiry
{[ getRatePrice(item.pr_usd,item.pr_rate,1,item.pr_is_large_size_no_price, item.vip_usd) ]}
{[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price, item.pr_usd) ]}
{[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price, item.pr_usd) ]}
In Stock
- +
Please Login or Create an Account to: See VIP prices and availability
US Stock: ship in 0-1 business day
Global Stock: ship in 2 weeks
Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.
Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.
Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.
Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.
Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.
CAS No. : | 3513-81-3 |
Formula : | C4H8O2 |
M.W : | 88.11 |
SMILES Code : | C(C(CO)=C)O |
MDL No. : | MFCD00075162 |
InChI Key : | JFFYKITVXPZLQS-UHFFFAOYSA-N |
Pubchem ID : | 77048 |
GHS Pictogram: |
![]() |
Signal Word: | Warning |
Hazard Statements: | H227-H315-H319-H335 |
Precautionary Statements: | P305+P351+P338 |
Num. heavy atoms | 6 |
Num. arom. heavy atoms | 0 |
Fraction Csp3 | 0.5 |
Num. rotatable bonds | 2 |
Num. H-bond acceptors | 2.0 |
Num. H-bond donors | 2.0 |
Molar Refractivity | 23.19 |
TPSA ? Topological Polar Surface Area: Calculated from |
40.46 Ų |
Log Po/w (iLOGP)? iLOGP: in-house physics-based method implemented from |
1.52 |
Log Po/w (XLOGP3)? XLOGP3: Atomistic and knowledge-based method calculated by |
-0.44 |
Log Po/w (WLOGP)? WLOGP: Atomistic method implemented from |
-0.47 |
Log Po/w (MLOGP)? MLOGP: Topological method implemented from |
-0.33 |
Log Po/w (SILICOS-IT)? SILICOS-IT: Hybrid fragmental/topological method calculated by |
-0.18 |
Consensus Log Po/w? Consensus Log Po/w: Average of all five predictions |
0.02 |
Log S (ESOL):? ESOL: Topological method implemented from |
0.02 |
Solubility | 92.9 mg/ml ; 1.05 mol/l |
Class? Solubility class: Log S scale |
Highly soluble |
Log S (Ali)? Ali: Topological method implemented from |
0.06 |
Solubility | 100.0 mg/ml ; 1.14 mol/l |
Class? Solubility class: Log S scale |
Highly soluble |
Log S (SILICOS-IT)? SILICOS-IT: Fragmental method calculated by |
0.12 |
Solubility | 115.0 mg/ml ; 1.31 mol/l |
Class? Solubility class: Log S scale |
Soluble |
GI absorption? Gatrointestinal absorption: according to the white of the BOILED-Egg |
High |
BBB permeant? BBB permeation: according to the yolk of the BOILED-Egg |
No |
P-gp substrate? P-glycoprotein substrate: SVM model built on 1033 molecules (training set) |
No |
CYP1A2 inhibitor? Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set) |
No |
CYP2C19 inhibitor? Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set) |
No |
CYP2C9 inhibitor? Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set) |
No |
CYP2D6 inhibitor? Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set) |
No |
CYP3A4 inhibitor? Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set) |
No |
Log Kp (skin permeation)? Skin permeation: QSPR model implemented from |
-7.15 cm/s |
Lipinski? Lipinski (Pfizer) filter: implemented from |
0.0 |
Ghose? Ghose filter: implemented from |
None |
Veber? Veber (GSK) filter: implemented from |
0.0 |
Egan? Egan (Pharmacia) filter: implemented from |
0.0 |
Muegge? Muegge (Bayer) filter: implemented from |
2.0 |
Bioavailability Score? Abbott Bioavailability Score: Probability of F > 10% in rat |
0.55 |
PAINS? Pan Assay Interference Structures: implemented from |
0.0 alert |
Brenk? Structural Alert: implemented from |
1.0 alert: heavy_metal |
Leadlikeness? Leadlikeness: implemented from |
No; 1 violation:MW<1.0 |
Synthetic accessibility? Synthetic accessibility score: from 1 (very easy) to 10 (very difficult) |
1.34 |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate; In water; | A. Preparation of 2-methylene-1,3-propanediol A mixture of 100 g of 2-methylene-1,3-dichloropropane and 121.62 of potassium carbonate in 800 ml of water was stirred and refluxed for 40 hours. The reaction mixture was concentrated by evaporation under reduced pressure to give a thick slurry which was extracted with four 100-ml portions of ethyl acetate. The extracts were filtered, combined, dried over Na2 SO4 and concentrated under reduced pressure to an oil. Distillation of the oil gave 58.3 g of 2-methylene-1,3-propanediol, b.p. 68°-72°/0.24-0.25 mm Hg. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | With pyridine; thionyl chloride; In dichloromethane; for 3h;Reflux; | Example 7; 5-Cvclopropyl-2-(4-fluorophenyl)-6-rr(2-hvdroxy-1 ,2-oxaborolan-4- yl)methyll(methylsulfonyl)aminol-N-methyl-1 -benzofuran-3-carboxamide Step 1 : 3-chloro-2-(chloromethyl)prop-1 -eneA solution of thionyl chloride (290 g, 1 19 mmol) in DCM (200 mL) was added dropwise into a mixture of 2-methylenepropane-1 ,3-diol (88 g, 1 mol), dry pyridine (150 mL), and dry DCM (100 mL). The reaction mixture was heated to reflux with stirring for 3 hours and then allowed to stand overnight. The mixture was cooled to room temperature and poured into ice. The solution was neutralized with solid sodium bicarbonate and then extracted with diethyl ether(3 <0.6 L) followed by washing the ether extracts with dilute sulfuric acid. The combined organic layers were dried with anhydrous sodium sulfate, filtered, and concentrated in vacuo to give a residue which was fractionated to give 3-chloro-2- (chloromethyl)prop-l -ene (40.1 g, 32percent) as a colorless oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In pyridine; water; | Preparation 3 3-Octadecylaminocarbonyloxy-2-methylenepropan-1-ol Octadecyl isocyanate (59.1 g) and 2-methylene-propane-1,3-diol (17.7 g) were dissolved and stirred in pyridine (100 ml) for 24 hours at 22°C. Water (200 ml) was added, and the mixture was extracted with chloroform (3 * 200 ml). The chloroform extracts were washed with water, dried over anhydrous magnesium sulfate, filtered and evaporated to dryness in vacuo . The mixture was purified through a column of silica gel 60 (70-230 mesh, 100 g) eluding with chloroform/ether 1: 1. Further purification was achieved by chromatography on a Waters PrepLC.(R)./System 500A using a PrepPAK.(R).-500/SILICA cartridge with chloroform/ether/pentane 1: 1: 3 as eluent. The product was recrystallized from acetone. Mp. 71-73°C. Elemental analysis: calculated C 71.99percent, H 11.82percent, N 3.65percent, found C 71.93percent, H 11.93percent, N 3.64percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With pyridine; dmap; In dichloromethane; at 0 - 20℃; for 0.5h; | General procedure: Allyl alcohol (1 equiv.) and acetic anhydride (1.2 equiv.) were dissolved in DCM (-1M) at 0°C. Pyridine (1 equiv.) and DMAP (0.1 molpercent) were then added. The reaction mixture was stirred at 0 °C for 30 mm. and was then allowed to reach room temperature. After completion, the mixture was quenched with 2N HCI and the organic layer was washed with H20, brine and was dried over Na2SO4. Careful evaporation of the remaining solvents affords the pure compound without further purification.; 2-methylenepropane-1,3-diyl diacetate (2d). Prepared by general procedure B with the following notes:Column chromatography (hexanes ? ethyl acetate 20:1) affords the titled compound as a colorless oil (20g , 91 percent). Analytical data are identical to those in the reference.14 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30.3% | With 1H-imidazole; In dichloromethane; at 0 - 20℃; for 18h; | 2-Methylenepropane-l,3-diol (53, 5 g, 56.75 mmol) was dissolved in 100 mL of CH2C12and the resulting solution was cooled to 0 C. Imidazole (7.728 g, 1 13.5 mmol) was added followed by tert-butyl-chloro-diphenyl-silane (14.04 g, 13.07 mL, 51.08 mmol) and the resulting solution was stirred at room temperature for 18 hours. The reaction mixture was washed with water and the organic phase was dried with Na2S04, filtered and the filtrate concentrated under vacuum. The resulting material was purified by silica gel chromatography (hexane/EtOAc 0-100%). Appropriate fractions were combined and concentrated under vacuum to provide the desired compound (54, 5.62 g, 17.2 mmol, 30.3%). MS: 349.1 m/z (M+Na)+. |
With 1H-imidazole; In dichloromethane; at 20℃; | Step A Synthesis of Compound Int-19a TBDPSC1 (9.0 mL, 35.0 mmol) was added dropwise to a stirred hazy solution of 2- methylenepropane-l,3-diol (3 g, 34.1 mmol) and imidazole (4.70 g, 69.0 mmol) in DCM (340 mL). The reaction mixture was stirred at room temperature overnight. The following morning, the reaction mixture was concentrated under reduced pressure (~80 mL) before being filtered through a pad of celite, rinsing over with additional DCM / MeOH. The filtrate was evaporated under reduced pressure. The resulting oil was purified by silica gel column (220 g) (0452) chromatography eluting with 0-20% EtOAc / hexanes to afford compound Int-19a. NMR (500 MHz, CDCb): d 7.69 (d, J = 7.4 Hz, 4H); 7.49 - 7.37 (m, 6H); 5.16 (app. s, 1H); 5.13 (app. s, 1H); 4.27 (s, 2H); 4.19 (d, J = 6.2 Hz, 2H); 1.80 (t, J = 6.1 Hz, 1H); 1.08 (s, 9H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With sodium hydroxide;tetra(n-butyl)ammonium hydrogensulfate; In dichloromethane; water; at 15 - 30℃; for 7 - 8h; | To a solution of di-tert-butyl dicarbonate (6.6 kg) in methylene chloride (15.0 L, 15 volumes) was added <strong>[3513-81-3]2-methylene-1,3-propanediol</strong> (1.00 kg) and phase transfer catalyst tetrabutylammonium hydrogensulfate (0.641 kg). The resulting reaction mixture was then agitated vigorously at about 15° C. while adding over a 2 hr period, 6M aqueous sodium hydroxide solution (13.2 L) and controlling the temperature between 25 to 30° C. The resulting two-phase reaction mixture was subsequently agitated for a period of 2-3 hrs at 25° C.The aqueous layer was discarded and additional phase transfer catalyst tetrabutylammonium hydrogensulfate (0.064 kg, 10percent of the initial amount), di-tert-butyl dicarbonate (0.66 kg, 10percent of the initial amount), and methylene chloride (2.0 L, 2 volumes) was added to the remaining organic reaction mixture. To the reaction mixture was also added 6M aqueous sodium hydroxide solution (1.32 L, 10percent of the initial amount) over a period of about 0.5 to 1 hr, while controlling the temperature between 25 to 30° C. The resulting two-phase reaction mixture was then agitated at about 25° C. for additional 3 to 4 hr. Allowing more than 3 hrs of agitation time is often required to complete the hydrolysis of the excess di-tert-butyl dicarbonate. The aqueous layer was discarded. The resulting organic phase was washed with water (3.x.8.0 L), diluted with EtOAc (6 L, 6 volumes), and distilled to an oil foam with quantitative yield.1H (500 MHz, CDCl3) delta 5.15, 4.98, 4.79, 4.68, 4.68, 4.33, 4.31, 3.89, 3.77, 3.67, 3.45, 3.35, 3.19, 2.88, 2.78, 2.74, 2.42, 2.17, 2.11, 2.06, 1.95, 1.72, 1.66, 1.51, 1.48, 1.43, 1.34, 1.27, 1.19, 1.19, 1.18, 1.14, 1.13, 1.11, 0.95, 0.85. |
100% | tetra(n-butyl)ammonium hydrogensulfate; In dichloromethane; water; at 15 - 30℃; for 10.5 - 13h; | Example 1. Preparation of O-Bis (Boc)-2-Methylene-1, 3-Propanediol (Compound of formula II, wherein R11 is hdroen and Rl is tert-butyl).; To a solution of di-tert-butyl dicarbonate (6.6 kg) in methylene chloride (15.0 L, 15 volumes) was added 2-methylene-1, 3-propanediol (1.00 kg) and phase transfer catalyst tetrabutylammonium hydrogensulfate (0.641 kg). The resulting reaction mixture was then agitated vigorously at about 15°C while adding over a 2 hr period, 6M aqueous sodium hydroxide solution (13.2 L) and controlling the temperature between 25 to 30°C. The resulting two-phase reaction mixture was subsequently agitated for a period of 2-3 hrs at 25°C. The aqueous layer was discarded and additional phase transfer catalyst tetrabutylammonium hydrogensulfate (0.064 kg, 10percent of the initial amount), di-tert- butyl dicarbonate (0.66 kg, 10percent of the initial amount), and methylene chloride (2.0 L, 2 volumes) was added to the remaining organic reaction mixture. To the reaction mixture was also added 6M aqueous sodium hydroxide solution (1.32 L, 10percent of the initial amount) over a period of about 0.5 to 1 hr, while controlling the temperature between 25 to 30°C. The resulting two-phase reaction mixture was then agitated at about 25°C for additional 3 to 4 hr. Allowing more than 3 hrs of agitation time is often required to complete the hydrolysis of the excess di-tert-butyl dicarbonate. The aqueous layer was discarded. The resulting organic phase was washed with water (3X 8. 0L), diluted with EtOAc (6L, 6 volumes), and distilled to an oil foam with quantitative yield. IH (500MHz, CDC13) 8 5.15, 4.98, 4.79, 4.68, 4.68, 4.33, 4.31, 3.89, 3.77, 3.67, 3.45, 3. 35, 3.19, 2. 88, 2.78, 2. 74, 2.42, 2.17, 2.11, 2.06, 1.95, 1.72, 1.66, 1.51, 1.48, 1.43, 1.34, 1.27, 1.19, 1.19, 1.18, 1.14, 1.13, 1. 11, 0.95, 0.85 |
With sodium hydroxide; tetra(n-butyl)ammonium hydrogensulfate; In dichloromethane; water; at 20℃; | To a solution of 2-methylene-1, 3-propane diol (5.28g, 0.06 mmol) and di- tert-butyl dicarbonate (35 g, 0.16 mol) in 150 mi of dichloromethane is added 6N NAOH (70 ML) and TBAHS (3.4 g, 10 MMOL). The mixture is stirred at room temperature overnight. The organic layer is separated, washed with NAHCO3 (200 ml x 3) and brine (200 ML), dried over anhydrous MGS04, and concentrated in vacuo to give the title compound. H NMR (CDC13) : 8 5.20 (s, 2H); 4.44 (s, 4H); 1. 18 (s, 18H). 13C NMR (CDCI3) : 5 153.28, 138.50, 117.27, 82.27, 66.91, 27.83. |
With sodium hydroxide; tetra(n-butyl)ammonium hydrogensulfate; In dichloromethane; water; at 20℃; | Step lb : Compound of formula 1-3: R_ = H and Rl = t-Bu :; To a solution of 2-methylene-1, 3-propane diol (5. 28g, 0.06 mmol) and di-tert-butyl dicarbonate (35 g, 0.16 mol) in 150 ml of dichloromethane was added 6N NaOH (70 ml) and tetrabutylammoniahydrogensulfate (3.4 g, 10 mmol). The mixture was stirred at room temperature overnight. The organic layer was separated, washed with NaHC03 (200 ml x 3) and brine (200 ml), dried over anhydrous MgSO4, concentrated and dried over vacuum to give the title compound. 'H NMR (CDC13) : 5. 20 (s, 2H) ; 4.44 (s, 4H) ; 1.18 (s, 18H). 13C NMR (CDCl3) : 8 153. 3, 138. 5,117. 3,82. 3,66. 9,27. 8. | |
With sodium hydroxide; tetra(n-butyl)ammonium hydrogensulfate; In dichloromethane; water; at 20℃; | To a solution of 2-methylene-1, 3-propane diol (5.28g, 0.06 mmol) and di-tert-butyl dicarbonate (35 g, 0.16 mol) in 150 ml of dichloromethane was added 6N NaOH (70 ml) and tetrabutylammoniahydrogensulfate (3.4 g, 10 mmol). The mixture was stirred at room temperature overnight. The organic layer was separated, washed with NaHC03 (200 ml x 3) and brine (200 ml), dried over anhydrous MgS04, concentrated and dried over vacuum to give the title compound. 'H NMR (CDC13) : 6 5.20 (s, 2H) ; 4.44 (s, 4H); 1.18 (s, 18H). 13C NMR (CDCl3) : S 153.3, 138.5, 117.3, 82.3, 66.9, 27.8. | |
With sodium hydroxide; tetra(n-butyl)ammonium hydrogensulfate; In dichloromethane; water; at 20℃; | To a solution of 2-methylene-1, 3-propane diol (5.28g, 0.06 mmol) and di-tert-butyl dicarbonate (35 g, 0.16 mol) in 150 ml of dichloromethane was added 6N NaOH (70 ml) and tetrabutylammoniahydrogensulfate (3.4 g, 10 mmol). The mixture was stirred at room temperature overnight. The organic layer was separated, washed with NaHC03 (200 mi x 3) and brine (200 ml), dried over anhydrous MgS04, concentrated and dried over vacuum to give the title compound. 'H NMR (CDC13) : 5 5.20 (s, 2H); 4.44 (s, 4H); 1. 18 (s, 18H). 13c NMR (CDC13) : No. 153.3, 138.5, 117.3, 82.3, 66.9, 27.8. | |
With sodium hydroxide; tetra(n-butyl)ammonium hydrogensulfate; In dichloromethane; water; at 20℃; | Example 3.; Formation of 6-11 3-Carbon Bridged Erythromycin Derivatives.; Step 3a; To a solution of 2-methylene-1, 3-propane diol (5. 28g, 0.06 mmol) and di-tert-butyl dicarbonate (35 g, 0.16 mol) in 150 ml of dichloromethane was added 6N NaOH (70 ml) and TBAHS (3.4 g, 10 mmol). The mixture was stirred at room temperature overnight. The organic layer was separated, washed with NaHC03 (200 ml x 3) and brine (200 ml), dried over anhydrous MgS04, and concentrated in vacuo to give the desired product. 'H NMR (CDC13) : 8 5.20 (s, 2H); 4.44 (s, 4H); 1. 18 (s, 18H). I3C NMR (CDCl3) : 8 153.28, 138.50, 117.27, 82. 27,66. 91,27. 83. | |
With sodium hydroxide; tetra(n-butyl)ammonium hydrogensulfate; In dichloromethane; water; at 20℃; | To a solution of 2-methylene-1,3-propane diol (5.28 g, 0.06 mmol) and di-tert-butyl dicarbonate (35 g, 0.16 mol) in 150 ml of dichloromethane is added 6N NaOH (70 ml) and TBAHS (3.4 g, 10 mmol). The mixture is stirred at room temperature overnight. The organic layer is separated, wash with NaHCO3 (200 ml.x.3) and brine (200 ml), dry over anhydrous MgSO4, and concentrated in vacuo to give the title compound.1H NMR (CDCl3): delta 5.20(s, 2H); 4.44(s, 4H); 1.18(s, 18H).13CNMR(CDCl3): delta 153.28, 138.50, 117.27, 82.27, 66.91, 27.83. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With di-isopropyl azodicarboxylate; triphenylphosphine; In dichloromethane; for 5.5h; | Example IV; Scheme 6; 2- (4-TRIFLUOROMETHOXY-PHENOXYMETHYL)-PROP-2-EN-1-OL; To a mixture of 4-trifluoromethoxyphenol (2.37 g, 13.1 MMOL), 2- methylene-propane-1, 3-diol (1.73 g, 19.6 MMOL), and diisopropyl azodicarboxylate (3.96 g, 19.6 MMOL) in CH2C12 (50 mL) was added a solution of Ph3P (5.13 g, 19.6 MMOL) in 50 mL of CH2CI2 in 30 minutes. After stirring for 5 hours, the mixture was diluted with ET2O (100 mL), washed with 1 N NAOH, dried, concentrated, and column chromatographed to give 1.7 g (51percent) of 6-A; 1H NMR (300 MHz, CDC13) 5 7.13 (d, J = 9.1 Hz, 2 H), 6.91 (dd, J = 9.2, 2.3 Hz, 2 H), 5.31 (d, J = 0.9 Hz, 1 H), 5.28 (d, J = 0.9 Hz, 1 H), 4.59 (s, 2 H), 4.26 (d, J = 6.1 Hz, 2 H), 1.63 (t, J = 6. 1 Hz, 1 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With triethylamine; In dichloromethane; acetonitrile; at 0 - 20℃; | Example III; Scheme 5; Methanesulfonic acid 2-chloromethyl-allyl ester; To a solution of 2-METHYLENEPROPANE-1, 3-DIOL (257 mg, 2.92 MMOL) in CH2CI2 (4 mL) and CH3CN (4 mL) at 0°C were added Et3N (1.76 mL, 12.6 MMOL) and methanesulfonyl chloride (1.01 g, 8.79 MMOL). After the mixture was stirred at 0°C for 2 h and then allowed to warmed up to room temperature overnight, saturated NAHC03 was added. The organic layer was separated and the aqueous layer was extracted with CH2CI2. The combined organic phases were dried, concentrated, and column chromatographed (EtOAc/hexane: 1/3) to give 313 mg (58percent) of 5-A ; H NMR (300 MHz, CDCI3) 6 5.47 (s, 1 H), 5.42 (s, 1 H), 4.82 (s, 2 H), 4.16 (s, 2 H), 3.06 (s, 3 H); MS (ES) m/z: 207 (M+Na+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With di-isopropyl azodicarboxylate; triphenylphosphine; In dichloromethane; at 0 - 20℃; | 2- (4-TRIFLUOROMETHYI-PHENOXYMETHYL)-PROP-2-EN-1-OL; To a mixture of 4-TRIFLUOROMETHYLPHENOL (49.0 g, 302 mmol), 2-methylene- 1, 3-PROPANEDIOL (40.0 g, 454 MMOL), and diisopropyl azodicarboxylate (67.4 g, 333 MMOL) in CH2C12 (400 mL) at 0°C was charged with a solution of TRIPHENYLPHOSPHINE (87.2 g, 333 MMOL) in CH2Cl2 (400 mL) dropwise. After the mixture was stirred at 0°C and then allowed to warm up to room temperature overnight, CH2C12 was evaporated under reduced pressure. To the residue was added ET20 and hexane, and the mixture was cooled to 0°C. The precipitated solid was filtered, and the filtrate was concentrated and column chromatographed (EtOAc/hexane: 1/4) to give 35.2 g (50percent) of 2-A ;'H NMR (300 MHz, CDCl3) 8 7.55 (d, J = 8. 6 HZ, 2 H), 6.99 (d, J = 8. 6 HZ, 2 H), 5.33 (d, J = 0. 9 HZ, 1 H), 5.29 (d, J = 0. 9 Hz, 1 H), 4.65 (s, 2 H), 4.27 (d, J = 6. 0 Hz, 2 H). |
50% | With di-isopropyl azodicarboxylate; triphenylphosphine; In dichloromethane; at 0 - 20℃; | 2-(4-Trifluoromethyl-phenoxymethyl)-prop-2-en-1-ol To a mixture of 4-trifluoromethylphenol (49.0 g, 302 mmol), <strong>[3513-81-3]2-methylene-1,3-propanediol</strong> (40.0 g, 454 mmol), and diisopropyl azodicarboxylate (67.4 g, 333 mmol) in CH2Cl2 (400 mL) at 0° C. was charged with a solution of triphenylphosphine (87.2 g, 333 mmol) in CH2Cl2 (400 mL) dropwise. After the mixture was stirred at 0° C. and then allowed to warm up to room temperature overnight, CH2Cl2 was evaporated under reduced pressure. To the residue was added Et2O and hexane, and the mixture was cooled to 0° C. The precipitated solid was filtered, and the filtrate was concentrated and column chromatographed (EtOAc/hexane: 1/4) to give 35.2 g (50percent) of 2-A; 1H NMR (300 MHz, CDCl3) delta 7.55 (d, J=8.6 Hz, 2 H), 6.99 (d, J=8.6 Hz, 2 H), 5.33 (d, J=0.9 Hz, 1 H), 5.29 (d, J=0.9 Hz, 1 H), 4.65 (s, 2 H), 4.27 (d, J=6.0 Hz, 2 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With diethylzinc; In hexane; dichloromethane; at 0 - 20℃; for 5h; | A solution of 2-methylenel, 3-propanediol (2.00 g, 22.70 MM) in dichloromethane (20 mL) was treated at 0 °C with a solution of diethylzinc in hexane (1.0 M, 25.00 mL, 25.00 MM) and then slowly with a solution OF 4-BROMO-N-HYDROXYBENZENECARBOXIMIDOYL chloride in dichloromethane (20 mL). The reaction mixture was allowed to warm to room temperature and kept at room temperature for ca. 5 h The mixture was poured into an saturated aqueous solution of ammonium chloride and extracted (twice) with dichloromethane. The combined organic phase was dried (MgS04) and concentrated under vacuum to give the title compound (2.1 g) that was used without further purification. MS (APCI : 286, 288 (M, M+2) for CNHNBRNOS NMR (DMSO-D.sect.) 8: 3.28 (s, 2H); 3.49 (d, 4H) ; 5.02 (t, 2H); 7.59-7. 67 (M, 4H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With diethylzinc; In hexanes; dichloromethane; at 0 - 20℃; for 4h; | 2-METHYLENE-1, 3-propanediol (2.20 g, 25.0 MM) was stirred in dichloromethane (20 ML) and cooled to 0 °C. A 1 N solution of diethylzinc in hexanes (3.40 g, 27.5 MM) was added followed by a solution OF 4-BROMO-3-FLUORO-N-HYDROXYBENZENECARBOXIMIDOYL chloride (6.30 g, 25.0 MM) in dichloromethane (40 mL). The reaction was allowed to warm to room temperature and was complete after four hours. The solution was diluted with ammonium chloride and extracted using dichloromethane. The organic layer was dried (magnesium sulfate), filtered and concentrated to give the desired product as a yellow solid (4.72 g). MS (ESP : 305 (MH+) for CLLHLLBREINO3 300 MHz NMR (DMSO-D 6 : 3.29 (s, 2H); 3.55 (s, 2H); 3.57 (s, 2H) ; 5.10 (t, 2H); 7.52 (d, 1H); 7.68 (d, 1H); 7.86 (t, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In methanol; chloroform; for 24h;Heating / reflux; | 2-Methylene-propane-1,3-diol (2.2 g; 24.96 mmol) and dibutyltin oxide (6.85 g; 27.96 mmol) were refluxed in chloroform/methanol (100 ml 10: 1) for 24 h to obtain a clear solution. The solvent was removed under reduced pressure to give the stannoxane derivative as a white solid. Cesium fluoride (7.25 g; 47.7 mmol) was added and the mixture was dried under high vacuum. To this reaction mixture, DMF (20 ml) and benzyl bromide (3.27 ml ; 27.5 mmol) were added and the reaction mixture was stirred for 24 h at 25 °C. After that, the reaction mixture was heated at 50 °C for 1 h. The mixture is cooled to 25 °C and diluted with ethyl acetate (100 ml) and water (2 ml). The reaction mixture is stirred vigorously for 30 min and then filtered through a pad of celite to remove dibutyltin oxide. The filtrate was washed with water and then with brine, dried over Na2SO4 and the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography eluting with 20 percent ethyl acetate/hexane to yield 2.6 g (60percent) compound 71a) as oil. 1H-NMR (CDCl3) : delta 7.36-7.28 (m, 5H), 5.20 (s, 1H), 5.15 (s, 1H), 4.51 (s, 2H), 4.19 (s, 2H), 4.10 (s, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70.1% | With diisobutylaluminium hydride; In methanol; toluene; benzene; | (1)2-(4-Methylbenzyloxy)methyl-2-propenol A mixture of p-anisaldehyde (17.31 g, 0.127 mol), <strong>[3513-81-3]2-methylene-1,3-propanediol</strong> (14.00 g, 0.159 mol), and p-TsOH H2 O (121 mg, 0.64 mmol) in dry PhH (100 ml) was stirred and heated at reflux, and the water generated was azeotropically removed in a theoretical amount using a Dean-Stark apparatus. After 70 ml of PhH was distilled off, the resultant red PhH solution containing 2-(4-methoxyphenyl)-5-methylene-1,3-dioxane was cooled with salt-ice, and a solution of diisobutylaluminum hydride (DIBAL-H) in PhMe (1.02M, 100 ml and 1.50M, 67.0 ml; total 0.203 mol) was added dropwise under an atmosphere of N2; at the point when 20 ml of the PhMe solution of DIBAL-H was added, the reaction mixture changed from deep red to light yellow. After the addition was complete, the reaction mixture was allowed to stirr at room temperature overnight. The reaction mixture was ice-cooled, and MeOH (23 ml) was added carefully. H2 O (12 ml) was, then, added dropwise, wherein the mixture became thick and gelatinous, and finally granular. After the stirring was continued at room temperature for an hour, the mixture was filtered through a pad of Celite. The filter cake was washed with PhMe thoroughly. The combined filtrate and washings were dried (MgSO4), and concentrated in vacuo at a bath temperature of 65 C. to give a pale yellow oil (24.88 g). This was distilled in vacuo to give title compound (18.52 g, 70.1percent) as a colorless oil. bp 123-147 C./0.80-0.90 mm; IRmax (film): 3420(s), 1615(s), 1515(s), 1250(s), 1070(s), 1035(s), 918(m), 820(s) cm-1; 1 H-NMR delta: 7.26(d, J=8.8 Hz, 2H), 6.88(d, J=8.8 Hz, 2H), 5.19(br.s, 1H), 5.14(br.s, 1H), 4.45(s, 2H), 4.19(s, 2H), 4.07(s, 2H), 3.81(s, 3H), 1.98(br.s., 1H) ppm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine; In acetonitrile; | A. N-hydroxysuccinimidyl-1-methoxypropane-3-carbonate A solution of 355 mg of <strong>[3513-81-3]2-methylene-1,3-propanediol</strong> in acetonitrile (30 mL) was added sequentially, at ambient temperature, 65 mg of sodium hydride and 0.25 mL iodomethane. The mixture was stirred for 12 h and concentrated in vacuo. The residue was then taken up in 15 mL of acetonitrile and treated sequentially, at ambient temperature under an atmosphere of nitrogen, with 1.3 g of N,N-disuccinimidyl carbonate and 1.6 mL of triethylamine. After stirring for 14 h, the reaction mixture was concentrated in vacuo and the residue was diluted CH2 Cl2, washed with saturated sodium bicarbonate solution and saturated brine, dried over magnesium sulfate, filtered and concentrated in vacuo. The residue was purified by silica gel chromatography with EtOAc as eluant to give 95 mg of the title compound. (1 H)-NMR (CDCl3) consistent with structure. | |
With triethylamine; In acetonitrile; | A. N-hydroxysuccinimidyl-1-methoxypropane-3-carbonate A solution of 355 mg of <strong>[3513-81-3]2-methylene-1,3-propanediol</strong> in acetonitrile (30 mL) was added sequentially, at ambient temperature, 65 mg of sodium hydride and 0.25 mL iodomethane. The mixture was stirred for 12 h and concentrated in vacuo. The residue was then taken up in 15 mL of acetonitrile and treated sequentially, at ambient temperature under an atmosphere of nitrogen, with 1.3 g of N,N-disuccinimidyl carbonate and 1.6 mL of triethylamine. After stirring for 14 h, the reaction mixture was concentrated in vacuo and the residue was diluted CH2 Cl2, washed with saturated sodium bicarbonate solution and saturated brine, dried over magnesium sulfate, filtered and concentrated in vacuo. The residue was purified by silica gel chromatography with EtOAc as eluant to give 95 mg of the title compound. (1 H)-NMR (CDCl3) consistent with structure. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dmap; ammonium chloride; triethylamine; In dichloromethane; | Step A 2-t-Butyldiphenylsilyloxymethyl-2-propene-1-ol A solution of t-butyldiphenylsilylchloride (45 g, 165 mmol) in anhydrous dichloromethane (60 ml) is added dropwise to a stirred solution of 2-hydroxymethyl-2-propene-1-ol (12 g, 165 mmol) triethylamine (27.5 ml) and 4-dimethylaminopyridine (2 g) in anhydrous dichloromethane (300 ml) at 0° C. Then, the mixture is stirred at 20° C. overnight, washed with a saturated solution of ammonium chloride and brine. The title product is obtained by flash chromatography on silica gel (19.4 g, 40percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With toluene-4-sulfonic acid; In benzene; | A. Preparation of 2-chloromethyl-5-methylene-1,3-dioxane A mixture of 5.3 of <strong>[3513-81-3]2-methylene-1,3-propanediol</strong>, 6.7 g of chloroacetaldehyde dimethyl acetal and 0.05 g of p-toluenesulfonic acid was heated and stirred until distillation of by-product methanol ceased. The crude product was dissolved in 100 ml. of benzene and the benzene solution was washed with two 30-ml. portions of aqueous sodium carbonate and two 30-ml. portions of water. The washed solution was dried over MgSO4 and distilled under reduced pressure to obtain 4.8 g of colorless liquid, b.p. 81°-87°/14 mm Hg; nD24 1.4734. Redistillation gave 3.9 g of 2-chloromethyl-5-methylene-1,3-dioxane, b.p. 78°-79°/13 mm Hg; nD24 1.4746. The ir and nmr spectra were consistent with the assigned structure. Analysis: Calc'd for C6 H9 ClO2: C, 48.49; H, 6.11. Found: C, 48.68: H, 6.06. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium carbonate; toluene-4-sulfonic acid; In hexane; | A mixture of 16.3 g of propionaldehyde and 20.2 g of <strong>[3513-81-3]2-methylene-1,3-propanediol</strong> in 1200 ml of hexane containing 0.1 g p-toluenesulfonic acid was stirred thoroughly and the mixture was heated under reflux for two hours while 5.3 g of by-product water was collected in a Dean-Stark trap. The mixture was cooled, concentrated by evaporation under reduced pressure to 50 ml and then treated with 200 ml of ether. The ethereal solution was washed with 75 ml of ten percent sodium carbonate and two 75-ml portions of water, after which it was dried over MgSO4 and concentrated to an oil. Distillation of the oil gave 21.5 g of 2-ethyl-5-methylene-1,3-dioxane, b.p. 68° C/41 mm Hg. | |
With sodium carbonate; toluene-4-sulfonic acid; In hexane; water; | A. preparation of 2-ethyl-5-methylene-1,3-dioxane In a 2-liter flask equipped with a stirrer, Dean-Stark trap, and condenser with drying tube, a mixture of 16.3 g of propionaldehyde, 20.2 g of 1-hydroxy-2-hydroxymethyl-2-propene, 0.16 of p-toluenesulfonic acid, and 1200 ml of hexane was stirred and heated under reflux for 2 hours, during which time 5.3 ml of water was collected in the Dean-Stark trap. The reaction mixture was concentrated under reduced pressure to a volume of about 50 ml, then taken up in 200 ml of ether. The ether solution was washed with 75 ml of 10percent sodium carbonate and then twice with 75-ml portions of water. After drying over magnesium sulfate the ether solution was concentrated under reduced pressure to yield 26.5 g of yellow oil. The crude product was fractionated under reduced pressure to yield 21.5 g of 2-ethyl-5-methylene-1,3-dioxane, b.p. 68° C/41 mm Hg. The nmr spectrum was consistent with the assigned structure. The synthesis was later repeated, and the index of refraction of the product was found to be nD25 1.4432. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In pentane; | Preparation 1 3-Hexadecyloxy-2-methylenepropan-1-ol 1-Bromohexadecane (61.1 g), diethylformamide (200 ml) and 2-methylenepropane-1,3-diol (17.7 g) were mixed. Sodium hydride dispersion (55-60percent in oil, 21.8 g) was added over 10 minutes, and the mixture was then stirred at 55°C for 1 hour. The reaction mixture was cooled to room temperature and carefully quenched with water (400 ml), extracted with ether (2 * 200 ml), and the ether extracts were washed with water (200 ml), dried over anhydrous magnesium sulfate, filtered and evaporated to dryness in vacuo . The product was purified through a column of silica gel 60 (70-230 mesh, 30 g) eluding with ether/pentane 1: 3. Further purification was achieved by chromatography on Waters PrepLC.(R)./System 500A using a prepPAK.(R).-500/SILICA cartridge with ether/pentane 1: 4 followed by ether as eluent. Mp. 38-40°C. Elemental analysis: calculated C 76.86percent, H 12.90percent, found C 76.82percent, H 12.85percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With pyridine; dmap; | Preparation 5 3-Hexadecylaminothiocarbonyloxy-2-methylenepropan-1-ol Hexadecyl isothiocyanate (9.65 g) and 2-methylene-propane-1,3-diol) (3.0 g) were heated with pyridine (17 ml) and 4-dimethylaminopyridine (0.8 g) to 104°C for 6.5 hours. The mixture was evaporated to dryness in vacuo and chromatographed on a Waters PrepLC.(R)./System 500A using a PrepPAK.(R).-500/SILICA cartridge with ether/chloroform/hexane 2: 2: 9 as eluent. |
A113890 [54149-64-3]
O-(2-Methylallyl)hydroxylamine hydrochloride
Similarity: 0.58
A113890 [54149-64-3]
O-(2-Methylallyl)hydroxylamine hydrochloride
Similarity: 0.58
A354880 [4464-18-0]
Benzene-1,3,5-triyltrimethanol
Similarity: 0.50