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CAS No. : | 28170-07-2 | MDL No. : | MFCD07784341 |
Formula : | C14H12O3 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | SNGLYCMNDNOLOF-UHFFFAOYSA-N |
M.W : | 228.24 | Pubchem ID : | 11183772 |
Synonyms : |
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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: |
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* 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 |
---|---|---|
94% | With pyridine; In dichloromethane; for 4h; | This compound is a known compound, but it is not commercially available. It was prepared by following a published procedure. (Rich et al., J. Org. Chem., 1978, 43, 3624). To a mixture of benzyl alcohol (freshly distilled, 69.2 g, 0.64 mol), pyridine (64 mL) and CH2Cl2 (115 mL) in a 500 mL 3 -necked flask equipped with a condenser, mechanical stirring and an addition funnel was added phenyl chloroformate (100 g, 0.64 mol) over a period of 1 h. The reaction mixture was stirred for an additional 3 h, and H2O (160 mL) was added. The organic phase was washed with aqueous H2SO4 (2 M; 150 mL), dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The crude product was distilled in vacuum 127-131 C/0.1 mm Hg to give the desired compound as colorless oil, Yield: 108 g (94%) (literature yield: 79%).[0215] 1H NMR (500 MHz, CDCl3, 25 0C): delta 5.37 (s, 2H, CH2), 7.18-7.48 (m, 10 H, ArH). MS (FAB): m/z = 372.1 (MH+). |
91% | With pyridine; In dichloromethane; for 1h; | According to: Pittelkow, M.; Lewinsky, R.; and Christensen, J. B. Synthesis 2002, 15, 2195- 2202.Phenyl chloroformate (54.1 g, 500 mmol) was added dropwise to a mixture of benzyl alcohol (78.3 g, 500 mmol), dichloromethane (90 ml) and pyridine (50 ml) in a 1 l-f lask with condenser and addition funnel. The mixture was stirred for 1 h. Water (125 ml) was added. The phases were separated. The organic phase was washed with dilute sulfuric acid (2 M, 2x125 ml). Brine had to be added in the final wash in order to obtain good separation. The organic phase was dried over sodium sulfate, filtered, and concentrated in vacuo. The crude compound was vacuum destilled to yield a colourless liquid. Yield:104.3 g, 91 % EPO <DP n="71"/>1H-NMR (CDCI3) delta: 7.46-7.17 (2 multiplthetats, 10H), 5.27 (s, 2H)13C- NMR (CDCI3) delta: 152.5, 149.9, 133.5, 128.3, 127.6, 127.5, 127.3, 124.8, 119.8, 69.1 |
91% | In pyridine; dichloromethane; for 1h; | Benzyl phenyl carbonateAccording to: Pittelkow, M.; Lewinsky, R.; and Christensen, J. B. Synthesis 2002, 15, 2195- 2202.Phenyl chloroformate (54.1 g, 500 mmol) was added dropwise to a mixture of benzyl alcohol (78.3 g, 500 mmol), dichloromethane (90 ml) and pyridine (50 ml) in a 1 l-f lask with condenser and addition funnel. The mixture was stirred for 1 h. Water (125 ml) was added. EPO <DP n="95"/>The phases were separated. The organic phase was washed with dilute sulfuric acid (2 M, 2x125 ml). Brine had to be added in the final wash in order to obtain good separation. The organic phase was dried over sodium sulfate, filtered, and concentrated in vacuo. The crude compound was vacuum destilled to yield a colourless liquid. Yield:104.3 g, 91 %1H-NMR (CDCI3) delta: 7.46-7.17 (2 multiplets, 10H), 5.27 (s, 2H)13C- NMR (CDCI3) delta: 152.5, 149.9, 133.5, 128.3, 127.6, 127.5, 127.3, 124.8, 119.8, 69.1 |
82% | With triethylamine; In dichloromethane; at 0 - 20℃; for 18h; | In a single-necked flask, benzyl alcohol 38 and triethylamine (1.1 eq) were added and dissolved in dichloromethane with stirring.Phenyl chloroformate 39 (1.0 eq) was weighed and slowly dropped at 0 C. After the addition was complete, stir at room temperature for 18h. The reaction solution was washed with water and dilute hydrochloric acid, and the pH was adjusted to 8 with NaHCO3. The organic phase was dried by adding anhydrous sodium sulfate.Filter and concentrate the filtrate to dryness to obtain the crude product. The crude product was passed through a silica gel column to obtain a transparent oily substance 40 with a yield of about 82% |
62% | With triethylamine; In dichloromethane; at 0 - 20℃; | General procedure: The alcohol, thiol, or amine starting material (1.0 equiv.) was combined with the phenyl chloroformate reagent (1.0 equiv.) in anhydrous CH2Cl2 (15mL) at 0C, followed by the addition of base (1.0 equiv.). The resultant solution was stirred at 0C for 20 min, after which the ice bath was removed, and the reaction mixture was stirred at r.t. until the completion of the reaction as indicated by TLC. The reaction was quenched by adding brine (30mL), and the aqueous solution was extracted with ethyl acetate (3×15 mL). The organic layers were combined, dried over MgSO4, and evaporated under vacuum. The crude products from each reaction were purified by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
31% | In ethanol; at 20℃; for 2h;Reflux; | A mixture of 1,6-diaminohexane 39 (39.15 g, 0.338 mol) and <strong>[28170-07-2]benzyl phenyl carbonate</strong> (35.7 g, 0.156 mol) inethanol (125 ml) was stirred for 2 hours at room temperature and subsequently heated for an additional hour atreflux to achieve full conversion. The reaction mixture was allowed to cool to room temperature, affording awhite precipitate. After removing the precipitate by filtration, the supernatant was evaporated to dryness anddissolved in 330 ml 2 M aqueous HCl. The resulting solution was extracted with dichloromethane (DCM)(2x150 ml). The aqueous phase was subsequently adjusted to pH = 10 with 6 M aqueous NaOH and extractedwith DCM (3x150 ml). All organic phases were combined, dried over Na2SO4, evaporated to dryness, anddissolved in 200 ml diethyl ether. The resulting solution was extracted with 1M aqueous NaOH (3x50 ml), driedover Na2SO4, and evaporated to dryness to afford crude 40. The product was recrystallized from diethyl ether at-18C to afford white crystals (12.0 g, 31 %). 1H NMR (400 MHz, CDCl3): delta 1.03 (br.s, 2H), 1.58-1.14 (m, 8H),2.66 (t, J = 6.9 Hz, 2H), 3.18 (q, J = 6.7 Hz, 2H), 4.83 (br.s, 1H), 5.08 (s, 2H), 7.45 - 7.19 (m, 5H) ppm. 13CNMR (400 MHz, CDCl3): delta 26.63, 26.68, 30.07, 33.83, 41.12, 42.25, 66.67, 128.17, 128.21, 128.61, 136.78,156.51 ppm. RP-LCMS: calc. Mw= 250.2 g/mol, found m/z: 251.3 [M+H]+.Synthesis of |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane; for 20h; | According to: Pittelkow, M.; Lewinsky, R.; and Christensen, J. B. Synthesis 2002, 15, 2195-2202.Benzyl phenylcarbonate (25,1 g, 1 10 mmol) was added dropwise to a solution of diethyl- enetriamine (5,16 g, 50 mmol) in dichloromethane (100 ml). The mixture was stirred for at least 20 h. The organic phase was washed with phosphate buffer (0.025 M K2HPO4, 0.025 MNaH2PO4, 2000 ml, pH adjusted to 3 with 2 M sulfuric acid). The organic phase was dried over sodium sulfate, filtered, and concentrated in vacuo.Yield: 25.2 g A portion (5 g) of the crude oil was mixed with hydrochloric acid (2 M, 15 ml). The mixture was stirred for 15 minutes. The mixture was filtered. The isolated solid was mixed with abs. ethanol (600 ml). The mixture was brought to reflux. The boiling mixture was decanted in order to remove insoluble impurities. The compound crystallized over night at 5 C.Yield: 2.84 g (white crystals) 1H-NMR (af-DMSO) delta: 8.96 (b, 2H), 7.51 (t, J = 5.56 Hz, 2H), 7.40-7.30 (b, 10H), 5,04 (s,4H), 3.33 (q, J = 6.06 Hz, 4H), 3.00 (b, 4H)13C- NMR (af-DMSO) delta: 156.6, 137.2, 128.7, 128.3, 128.2, 66.0, 46.8, 37.1LC-MS (ES-positive mode), m/z: 372.5 [M+H]+ | |
In dichloromethane; for 20h; | According to: Pittelkow, M.; Lewinsky, R.; and Christensen, J. B. Synthesis 2002, 15, 2195-2202.Benzyl phenylcarbonate (25,1 g, 1 10 mmol) was added dropwise to a solution of diethylenetriamine (5,16 g, 50 mmol) in dichloromethane (100 ml). The mixture was stirred for at least 20 h. The organic phase was washed with phosphate buffer (0.025 M K2HPO4,0.025 M NaH2PO4, 2000 ml, pH adjusted to 3 with 2 M sulfuric acid). The organic phase was dried over sodium sulfate, filtered, and concentrated in vacuo.Yield: 25.2 g A portion (5 g) of the crude oil was mixed with hydrochloric acid (2 M, 15 ml). The mixture was stirred for 15 minutes. The mixture was filtered. The isolated solid was mixed with abs. ethanol (600 ml). The mixture was brought to reflux. The boiling mixture was decanted in order to remove insoluble impurities. The compound crystallized over night at 5 C.Yield: 2.84 g (white crystals) 1H-NMR (af-DMSO) delta: 8.96 (b, 2H), 7.51 (t, J = 5.56 Hz, 2H), 7.40-7.30 (b, 10H), 5,04 (s,4H), 3.33 (q, J = 6.06 Hz, 4H), 3.00 (b, 4H)13C- NMR (Gf-DMSO) delta: 156.6, 137.2, 128.7, 128.3, 128.2, 66.0, 46.8, 37.1LC-MS (ES-positive mode), m/z: 372.5 [M+H]+ |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | Example 2: Synthesis of compound 22.28 g (10 mmol) benzyl phenylcarbonate was dissolved in 20 ml ethanol and 1.03 ml (10 mmol) 1,2-diamino-l-methylpropane was added dropwise and stirred at RT overnight. The mixture was diluted with 25 ml water and acidified with 1M HC1 until pH < 3 and extracted with DCM. The aqueous phase was basified with 4M NaOH and extracted with DCM. The extract was dried with MgS04 and concentrated in vacuo. This gave 1.93 g (87%) monoprotected diamine. This material was dissolved in 25 ml dioxane, 2.028 g (10.5 mmol) Boc20 and 0.12 g (1 mmol) DMAP were added and the reaction was stirred at RT overnight. The mixture was concentrated in vacuo and purified by column chromatography (Si02, ether/heptane, 1 :0 to 7:3) to give 1.13 g (40%) of diprotected diamine. The diprotected diamine was dissolved in 10 ml dry DMF, 1.1 ml (17.5 mmol) iodomethane was added and the reaction mixture cooled in ice. 0.50 g (10.5 mmol) sodium hydride (60% in oil) was added in portions and stirred in ice for 2 hrs. The mixture was warmed to RT, quenched with 10 ml saturated NH4C1 and 50 ml water, extracted with ethyl acetate, dried with MgS04 and concentrated in vacuo. The product was purified by column chromatography (Si02, DCM/ethyl acetate, 1 :0 to 50:1) to give 0.358 g (29%) of Cbz-protected compound 2. 1H-NMR (300 MHz, CDC13): delta = 1.29 (s, 3H, Me), 1.35 (s, 3H, Me), 1.46 (s, 9H, Boc), 2.82/2.86 (s, 3H, Me, Z/E), 2.93 (s, 3H, Me), 3.72 (s, 2H, CH2N), 5.12 (s, 2H, benzyl), 7.35 (m, 5H, Phe). This material was dissolved in 20 ml methanol, 0.04 g Pd/C was added, the mixture was stirred under hydrogen for 3 hrs, filtered, and the filtrate concentrated. This gave 0.21 g (100%) of compound 2. MS (ESI): m/z = 217.2 (M+H+). |