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[ CAS No. 114790-39-5 ]

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Chemical Structure| 114790-39-5
Chemical Structure| 114790-39-5
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CAS No. :114790-39-5 MDL No. :MFCD13184754
Formula : C12H17NO4 Boiling Point : -
Linear Structure Formula :- InChI Key :N/A
M.W :239.27 g/mol Pubchem ID :10800009
Synonyms :

Safety of [ 114790-39-5 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P264-P270-P301+P312-P330 UN#:N/A
Hazard Statements:H302 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 114790-39-5 ]

  • Downstream synthetic route of [ 114790-39-5 ]

[ 114790-39-5 ] Synthesis Path-Downstream   1~15

  • 1
  • [ 501-53-1 ]
  • [ 22483-09-6 ]
  • [ 114790-39-5 ]
YieldReaction ConditionsOperation in experiment
98% Preparation 22 [0100] [0101] A solution of aminoacetaldehyde dimethyl acetal (25 mL, 229 mmol) in toluene (120 mL) is treated at 0 C. with a 4.85 M sodium hydroxide solution (70.8 mL, 343.5 mmol). The mixture is stirred at 0 C. for 10 minutes and benzyl chloroformate (33.8 mL, 229 mmol) is added keeping the internal temperature below 20 C. during the addition. The mixture is warmed to room temperature over 4 hours. The organic layer is separated, washed with brine, dried over sodium sulfate, and concentrated to dryness to give the title compound (54 g, 98%). ES/MS (m/e): 240 (M+H).
98% With sodium hydroxide; In toluene; at 0 - 20℃; for 4h; A solution of aminoacetaldehyde dimethyl acetal (25 mL, 229 mmol) in toluene (120 mL) is treated at 0 C with a 4.85 M sodium hydroxide solution (70.8 mL, 343.5 mmol). The mixture is stirred at 0 C for 10 minutes and benzyl chloroformate (33.8 mL, 229 mmol) is added keeping the internal temperature below 20 C during the addition. The mixture is warmed to room temperature over 4 hours. The organic layer is separated, washed with brine, dried over sodium sulfate, and concentrated to dryness to give the title compound (54 g, 98 %). ES/MS (m/e): 240 (M+H).
93% With sodium hydroxide; In water; toluene; at 0 - 20℃; for 4h;Inert atmosphere; To a 500 ml_ round-bottomed flask equipped with temperature probe and nitrogen inlet were added aminoacetaldehyde dimethyl acetal (25 g, 238 mmol) in aq. NaOH (4.85 M, 69 ml_) and toluene (125 ml_). The mixture was cooled to 0 C in an ice bath and benzylchloroformate (40.6 g, 238 mmol) was added at such a rate that the internal temperature was maintained below 20C. The reaction mixture was stirred for 4 h at room temperature. The layers were separated, and the organic layer was washed with brine (2 x 20 ml_), dried with sodium sulfate, filtered, and concentrated to a colorless oil (53.24 g, 93% yield). 1H-NMR (CDCI3, 500 MHz): 7.30 (m, 5H), 5.1 1 (s, 2H), 4.37 (t, J=6.0 Hz, 1 H), 3.39 (s, 6H), 3.33 (t, J=6.0 Hz, 2H). MS (electrospray): exact mass calculated for Ci2Hi7NO4, 239.12; m/z found, 240 [M+H]+.
93% With sodium hydroxide; In water; toluene; at 0 - 20℃; Step A. (2,2-Dimethoxy-ethyl)-carbannic acid benzyl ester. To a 500 ml_ round-bottomed flask equipped with temperature probe and nitrogen inlet were added aminoacetaldehyde dimethyl acetal (25 g, 238 mmol) in aq. NaOH (4.85 M, 69 ml_) and toluene (125 ml_). The mixture was cooled to 0 C in an ice bath and benzylchloroformate (40.6 g, 238 mmol) was added at such a rate that the internal temperature was maintained below 20 C. The reaction mixture was stirred for 4 h at room temperature. The layers were separated, and the organic layer was washed with brine (2 x 20 ml_), dried with sodium sulfate, filtered, and concentrated to a colorless oil (53.24 g, 93% yield). 1H-NMR (CDCIs, 500 MHz): 7.30 (m, 5H), 5.1 1 (s, 2H), 4.37 (t, J=6.0 Hz, 1 H), 3.39 (s, 6H), 3.33 (t, J=6.0 Hz, 2H). MS (electrospray): exact mass calculated for Ci2Hi7NO4, 239.12; m/z found, 240 [M+H]+.
90% With sodium hydroxide; In water; toluene; EXAMPLE 38A benzyl 2,2-dimethoxyethylcarbamate Benzyl chloroformate (231.3 g, 1.3 mol) was added gradually to a mixture of aminoacetaldehyde dimethyl acetal (152.0 g, 1.3 mol) in toluene (750 mL) and aqueous NaOH (72.8 g, 1.82 mol; in 375 mL of water) at 10-20 C. After the addition was completed, the mixture was stirred at ambient temperature over 4 hours. The organic layer was separated, washed with brine (2*100 mL) and concentrated to provide the title compound as an oil (281.5 g, 90% yield). 1H NMR (CDCl4, 300 MHz) delta 3.33 (t, J=6.0Hz, 2H), 3.39 (s, 6H), 4.37 (t, J=6.0 Hz, 1H), 5.11 (s, 2H), 7.30 (m, 5H); MS (DCI/NH3) m/z 257 (M+NH4)+, 340 (M+H)+.
90% With sodium hydroxide; In water; toluene; at 10 - 20℃; for 4h; EXAMPLE 33A (2,2-Dimethoxy-ethyl)-carbamic Acid Benzyl Ester Benzyl chloroformate (Aldrich, 231.3 g, 1.3 mol) was added gradually to a mixture of aminoacetaldehyde dimethyl acetal (Aldrich, 152.0 g, 1.3 mol) in toluene (750 mL) and aqueous NaOH (72.8 g, 1.82 mol; in 375 mL of water) at 10-20 C. After the addition was complete, the mixture was stirred at ambient temperature for 4 h. The layers were separated and the organic layer was washed with brine (2*100 mL) and concentrated under reduced pressure to provide the title compound as an oil (281.5 g, 90% yield). 1H NMR (CDCl4, 300 MHz) delta 3.33 (t, J=6.0 Hz, 2H), 3.39 (s, 6H), 4.37 (t, J=6.0 Hz, 1H), 5.11 (s, 2H), 7.30 (m, 5H); MS (DCI/NH3) m/z 257 (M+NH4)+, 240 (M+H)+.
90% With sodium hydroxide; In water; toluene; at 10 - 20℃; for 4h; Example 7A (2,2-Dimethoxy-ethyl)-carbamic Acid Benzyl Ester Benzyl chloroformate (Aldrich, 231.3 g, 1.3 mol) was added gradually to a mixture of aminoacetaldehyde dimethyl acetal (Aldrich, 152.0 g, 1.3 mol) in toluene (750 mL) and aqueous NaOH (72.8 g, 1.82 mol; in 375 mL of water) at 10-20 C. After the addition was complete, the mixture was stirred at ambient temperature for 4 h. The layers were separated and the organic layer was washed with brine (2*100 mL) and concentrated under reduced pressure to provide the title compound as an oil (281.5 g, 90% yield). 1H NMR (CDCl4, 300 MHz) delta 3.33 (t, J=6.0 Hz, 2H), 3.39 (s, 6H), 4.37 (t, J=6.0 Hz, 1H), 5.11 (s, 2H), 7.30 (m, 5H); MS (DCl/NH3) m/z 257 (M+NH4)+, 240 (M+H)+.
60.4% With triethylamine; In dichloromethane; at 0 - 20℃; for 4h; Benzyl (2, 2-dime I box ye th yl ) car ham ate : To a mixture of 2,2-dimethoxyethan-l- amine (8 g, 76.2 mmol) and Et3N (23.1 g, 228.6 mmol) in DCM (80 mL) was added dropwise benzyl chloroformate (14.3 g,83.8 mmol) at 0 C. The mixture was stirred at room temperature for 4 hrs. TLC showed the reaction was completed. The reaction was quenched with water (100 mL), extracted with DCM (3 x 100 mL). The combined organic layer was dried over anhydrous sodium sulfate and concentrated in vacuo to give a crude product. The crude product was purified by chromatography on silica gel (petroleum ether: EtOAc = 4: 1 to 2: 1 ) to afford benzyl (2,2-dimethoxyethyl)carbamate (11 g, yield: 60.4%) as a colorless oil.
With sodium hydroxide; In water; toluene; at 10 - 20℃; for 4h; Benzyl chloroformate (231.3 g, 1.3 mol) was added gradually to a mixture of aminoacetaldehyde dimethyl acetal (152.0 g, 1.3 mol) in toluene (750 mL) and aqueous NaOH (72.8 g, 1.82 mol; in 375 mL of water) at 10-20 C. After the addition was completed, the mixture was stirred at ambient temperature about 4 hours. The organic layer was separated, washed with brine (2*100 mL) and concentrated to provide the title compound. 1H NMR (CDCl3, 300 MHz) delta 3.33 (t, J=6.0 Hz, 2H), 3.39 (s, 6H), 4.37 (t, J=6.0 Hz, 1H), 5.11 (s, 2H), 7.30 (m, 5H); MS (DCI/NH3) m/z 257 (M+NH4)+, 240 (M+H)+.
With sodium hydroxide; In water; toluene; at 10 - 20℃; for 4h; Benzyl chloroformate (231.3 g, 1.3 mol) was added gradually to a mixture of aminoacetaldehyde dimethyl acetal (152.0 g, 1.3 mol) in toluene (750 mL) and aqueous NaOH (72.8 g, 1.82 mol; in 375 mL of water) at 10-20 C. After the addition was complete, the mixture was stirred at ambient temperature for 4 h. The organic layer was separated, washed with brine (2×100 mL) and concentrated to provide the title compound.
With sodium hydroxide; In water; toluene; at 10 - 20℃; for 4h; Benzyl chloroformate (231.3 g, 1.3 mol) was added gradually to a mixture of aminoacetaldehyde dimethyl acetal (152.0 g, 1.3 mol) in toluene (750 mL) and aqueous NaOH (72.8 g, 1.82 mol; in 375 mL of water) at 10-20 C. After the addition was complete, the mixture was stirred at ambient temperature for 4 h. The organic layer was separated, washed with brine (2×100 mL) and concentrated to provide the title compound. MS (DCl/NH3): m/z 240 (M+1)+, 257 (M+18)+.
With sodium hydroxide; In water; toluene; at 10 - 20℃; for 16h; Compound BB-29-1 (4.56g, 43.37mmol) was dissolved in toluene (24mL), sodium hydroxide (2.19 g of,54.65mmol) was dissolved in water (12mL), and then an aqueous solution of sodium hydroxide was slowly added to the reaction in.Then benzyl chloroformate(6.96g, 40.77mmol) was slowly added dropwise to the reaction mixture, the reaction temperature was controlled at 10-20 , after the completion of dropwise addition, the reactionwas stirred at room temperature for 16 hours.After completion of the reaction the organic layer was separated, washed with brine (50 mL x 2), dried over sodium sulfatedrying, filtered, and concentrated to give the title compound BB-29-2 (yellow oil, 11g, crude) was used directly in the next step
With sodium hydroxide; In water; toluene; at 10 - 20℃; for 4h; EXAMPLE 1A benzyl 2,2-dimethoxyethylcarbamate Benzyl chloroformate (231.3 g, 1.3 mol) was added gradually to a mixture of aminoacetaldehyde dimethyl acetal (152.0 g, 1.3 mol) in toluene (750 mL) and aqueous NaOH (72.8 g, 1.82 mol; in 375 mL of water) at 10-20 C. After the addition was completed, the mixture was stirred at ambient temperature about 4 hours. The organic layer was separated, washed with brine (2*100 mL) and concentrated to provide the title compound. 1H NMR (CDCl3, 300 MHz) delta 3.33 (t, J=6.0 Hz, 2H), 3.39 (s, 6H), 4.37 (t, J=6.0 Hz, 1H), 5.11 (s, 2H), 7.30 (m, 5H); MS (DCI/NH3) m/z 257 (M+NH4)+, 240 (M+H)+.
With sodium hydroxide; In water; toluene; at 20℃; for 4h; A solution of 2,2-dimethoxyethan-1-amine (1600 g, 15.22 mol) in toluene (8 L), was added a solution of NaOH (858 g, 21.45 mol) in water (4.42 L). This was followed by the addition of CbzCl (2598 g, 15.23 mol) dropwise with stirring at <20 C. The resulting solution was stirred for 4 h at room temperature. The organic layer was separated and washed with 3x5 L of brine. The organic layer was dried over anhydrous sodium sulfate and concentrated under vacuum to afford benzyl N-(2,2-dimethoxyethyl)carbamate as a white solid.

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  • 2
  • [ 114790-39-5 ]
  • [ 67561-03-9 ]
YieldReaction ConditionsOperation in experiment
50% With oxalic acid; In tetrahydrofuran; hexane; water; ethyl acetate; N-Benzyloxycarbonyl Aminoacetaldehyde To a solution of 80 ml THF, 40 ml water, and 800 mg oxalic acid was added 9.6 g (40 mmol) of N-benzyloxycarbonyl aminoacetaldehyde dimethyl acetal, and refluxed for 4 days. The THF was removed under reduced pressure and the remaining solution was extracted with ether (3*100 ml), the ether fractions were combined and dried over anhydrous sodium sulfate. The ether was removed under reduced pressure and the remaining solution was purified by flash chromatography (hexane and ethyl acetate 3:1 then 1:1) to yield 3.88 g, 50% yield.
  • 3
  • [ 114790-39-5 ]
  • [ 106-95-6 ]
  • [ 569682-60-6 ]
YieldReaction ConditionsOperation in experiment
98% With potassium hydroxide;N-benzyl-N,N,N-triethylammonium chloride; In toluene; at 50℃; for 48h;Inert atmosphere; To a 500 ml_ round-bottomed flask equipped with thermocouple probe, nitrogen inlet, reflux condenser, heating mantle, and mechanical stirring was added (2,2- dimethoxy-ethyl)-carbamic acid benzyl ester (50 g, 209 mmol) in toluene (180 ml_). To the resulting solution was added powdered KOH (51 .6 g, 920 mmol) and triethylbenzylammonium chloride (0.810 g, 3.55 mmol). A solution of allyl bromide (33.0 g, 275 mmol) in toluene (50 ml_) was added dropwise over 10 minutes. The mixture was heated to 50 C and stirred for 2 days. To the reaction mixture was added water (230 ml_) over ten minutes. The layers were separated and the aqueous was extracted with toluene (2 x 200 ml_). The combined organics were washed with brine (1 x 200 ml_), dried withmagnesium sulfate, filtered, and concentrated to afford the title compound (57.8 g, 98%). 1 H-NMR (CDCI3, 500 MHz): 7.31 (m, 5H), 5.76 (m, 1 H), 5.15 (m, 4H), 4.51 (m, 1 H), 3.98 (d, J=9.48, 2H), 3.36 (m, 8H).
98% With N-benzyl-N,N,N-triethylammonium chloride; potassium hydroxide; In toluene; at 50℃; for 48h; Step B. Allyl-(2,2-dimethoxy-ethyl)-carbamic acid benzyl ester. To a 500 ml_ round-bottomed flask equipped with thermocouple probe, nitrogen inlet, reflux condenser, heating mantle, and mechanical stirring was added (2,2- dimethoxy-ethyl)-carbamic acid benzyl ester (50 g, 209 mmol) in toluene (180 ml_). To the resulting solution was added powdered KOH (51 .6 g, 920 mmol) and triethylbenzylammonium chloride (0.810 g, 3.55 mmol). A solution of allyl bromide (33.0 g, 275 mmol) in toluene (50 ml_) was added dropwise over 10 minutes. The mixture was heated to 50 C and stirred for 2 days. To the reaction mixture was added water (230 ml_) over ten minutes. The layers were separated and the aqueous was extracted with toluene (2 x 200 ml_). The combined organics were washed with brine (1 x 200 ml_), dried withmagnesium sulfate, filtered, and concentrated to afford the title compound (57.8 g, 98%). 1 H-NMR (CDCI3, 500 MHz): 7.31 (m, 5H), 5.76 (m, 1 H), 5.15 (m, 4H), 4.51 (m, 1 H), 3.98 (d, J=9.48, 2H), 3.36 (m, 8H).
96% With potassium hydroxide; N-benzyl-N,N,N-triethylammonium chloride; In water; toluene; EXAMPLE 38B benzyl allyl(2,2-dimethoxyethyl)carbamate The product of Example 38A (281.0 g, 1.18 mol) in dry toluene (1.0 L) was treated with powdered KOH (291.2 g, 5.20 mol) and triethylbenzylammonium chloride (4.4 g, 0.02 mol). A solution of allyl bromide (188.7 g, 1.56 mol) in toluene (300 mL) was then added dropwise over 1 hour at 20-30 C. The mixture was stirred overnight at room temperature and then water (300 mL) was added over 20 minutes at 20-30 C.. The layers were separated and the aqueous phase was extracted with toluene (2*300 mL). The organic phases were combined, washed with brine (2*100 mL), dried (K2CO3), filtered and the filtrate concentrated to provide the title compound as oil (315.6 g, 96%, yield). 1H NMR (MeOH-d4, 300 MHz) delta 3.32 (s, 3H) 3.37 (m, 5H), 3.97 (d, J=5.4Hz, 2H), 4.50-4.40 (m, 1H), 5.15 (m, 4H), 5.75 (m, 1H), 7.23 (m, 5H); MS (DCI/NH3) m/z 297 (M+NH4)+, 280 (M+H)+.
96% With potassium hydroxide; N-benzyl-N,N,N-triethylammonium chloride; In water; toluene; at 20 - 30℃; for 19.3333h; EXAMPLE 33B Allyl-(2,2-dimethoxy-ethyl)-carbamic Acid Benzyl Ester The product of Example 33A (281.0 g, 1.18 mol) in dry toluene (1.0 L) was treated with powdered KOH (291.2 g, 5.20 mol) and triethylbenzylammonium chloride (Aldrich, 4.4 g, 0.02 mol). A solution of allyl bromide (Aldrich, 188.7 g, 1.56 mol) in toluene (300 mL) was then added dropwise over 1 hour at 20-30 C. The mixture was stirred for -18 h at ambient temperature and then water (300 mL) was added over 20 minutes at 20-30 C. The layers were separated and the aqueous phase was extracted with toluene (2*300 mL). The organic phases were combined, washed with brine (2*100 mL), dried (K2CO3), filtered and the filtrate concentrated under reduced pressure to provide the title compound as an oil (315.6 g, 1.13 mol, 96%, yield). 1H NMR (MeOH-d4, 300 MHz) delta 3.32 (s, 3H) 3.37 (m, 5H), 3.97 (d, J=5.4 Hz, 2H), 4.50-4.40 (m, 1H), 5.15 (m, 4H), 5.75 (m, 1H), 7.23 (m, 5H); MS (DCI/NH3) m/z 297 (M+NH4)+, 280 (M+H)+.
96% With potassium hydroxide; N-benzyl-N,N,N-triethylammonium chloride; In toluene; at 20 - 30℃; for 19h; Example 7B Allyl-(2,2-dimethoxy-ethyl)-carbamic Acid benzyl Ester The product of Example 7A (281.0 g, 1.18 mol) in dry toluene (1.0 L) was treated with powdered KOH (291.2 g, 5.20 mol) and triethylbenzylammonium chloride (Aldrich, 4.4 g, 0.02 mol). A solution of allyl bromide (Aldrich, 188.7 g, 1.56 mol) in toluene (300 mL) was then added dropwise over 1 hour at 20-30 C. The mixture was stirred for ~18 h at ambient temperature and then water (300 mL) was added over 20 minutes at 20-30 C. The layers were separated and the aqueous phase was extracted with toluene (2*300 mL). The organic phases were combined, washed with brine (2*100 mL), dried (K2CO3), filtered and the filtrate concentrated under reduced pressure to provide the title compound as an oil (315.6 g, 1.13 mol, 96%, yield). 1H NMR (MeOH-d4, 300 MHz) delta 3.32 (s, 3H) 3.37 (m, 5H), 3.97 (d, J=5.4 Hz, 2H), 4.50-4.40 (m, 1H), 5.15 (m, 4H), 5.75 (m, 1H), 7.23 (m, 5H); MS (DCl/NH3) m/z 297 (M+NH4)+, 280 (M+H)+.
75% Preparation 23 Benzyl N-allyl-N-(2,2-dimethoxyethyl)carbamate A solution of <strong>[114790-39-5]benzyl N-(2,2-dimethoxyethyl)carbamate</strong> (50 g, 208.9 mmol) in toluene (180 mL) is treated with solid potassium hydroxide (51.6 g, 919.69 mmol) under nitrogen. After 10 minutes, benzyltriethylammonium chloride (0.8 g, 3.1 mmol) is added. After another 10 minutes a solution of allyl bromide (33 g, 272.8 mmol) in toluene (50 mL) is added drop wise over 10 minutes. The resultant mixture is stirred at 50 C. for 48 hours. The mixture is cooled to room temperature and quenched with water. The organic layer is separated, washed with brine, dried over magnesium sulfate, and concentrated to dryness to give the title compound (44 g, 75%). ES/MS (m/e): 280 (M+H).
75% With N-benzyl-N,N,N-triethylammonium chloride; potassium hydroxide; In toluene; at 50℃; for 48h;Inert atmosphere; A solution of <strong>[114790-39-5]benzyl N-(2,2-dimethoxyethyl)carbamate</strong> (50 g, 208.9 mmol) in toluene (180 mL) is treated with solid potassium hydroxide (51.6 g, 919.69 mmol) under nitrogen. After 10 minutes, benzyltriethylammonium chloride (0.8 g, 3.1 mmol) is added. After another 10 minutes a solution of allyl bromide (33 g, 272.8 mmol) in toluene (50 mL) is added drop wise over 10 minutes. The resultant mixture is stirred at 50 C for 48 hours. The mixture is cooled to room temperature and quenched with water. The organic layer is separated, washed with brine, dried over magnesium sulfate, and concentrated to dryness to give the title compound (44 g, 75 ). ES/MS (m/e): 280 (M+H).
75% A solution of <strong>[114790-39-5]benzyl N-(2,2-dimethoxyethyl)carbamate</strong> (50 g, 208.9 mmol) in toluene (180 mL) is treated with solid potassium hydroxide (51.6 g, 919.69 mmol) under nitrogen. After 10 minutes, benzyltriethylammonium chloride (0.8 g, 3.1 mmol) is added. After another 10 minutes a solution of allyl bromide (33 g, 272.8 mmol) in toluene (50 mL) is added drop wise over 10 minutes. The resultant mixture is stirred at 50 C for 48 hours. The mixture is cooled to room temperature and quenched with water. The organic layer is separated, washed with brine, dried over magnesium sulfate, and concentrated to dryness to give the title compound (44 g, 75%). ES/MS (m/e): 280 (M+H).
75% A solution of <strong>[114790-39-5]benzyl N-(2,2-dimethoxyethyl)carbamate</strong> (50 g, 208.9 mmol) in toluene (180 mL) is treated with solid potassium hydroxide (51.6 g, 919.69 mmol) under nitrogen. After 10 minutes, benzyltriethylammonium chloride (0.8 g, 3.1 mmol) is added. After another 10 minutes a solution of allyl bromide (33 g, 272.8 mmol) in toluene (50 mL) is added dropwise over 10 minutes. The resultant mixture is stirred at 50 C for 48hours. The mixture is cooled to room temperature and quenched with water. The organic layer is separated, washed with brine, dried over magnesium sulfate, and concentrated to dryness to give the title compound (44 g, 75%). ES/MS (mlz): 280 (M+H).
With potassium hydroxide;N-benzyl-N,N,N-triethylammonium chloride; In toluene; at 20 - 30℃; The product of Example 1A (281.0 g, 1.18 mol) in dry toluene (1.0 L) was treated with powdered KOH (291.2 g, 5.20 mol) and triethylbenzylammonium chloride (4.4 g, 0.02 mol). A solution of allyl bromide (188.7 g, 1.56 mol) in toluene (300 mL) was then added dropwise over 1 hour at 20-30 C. The mixture was stirred overnight at room temperature and then water (300 mL) was added over 20 minutes at 20-30 C. The layers were separated and the aqueous phase was extracted with toluene (2*300 mL). The organic phases were combined, washed with brine (2*100 mL), dried (K2CO3), filtered and the filtrate concentrated to provide the title compound. 1H NMR (MeOH-d4, 300 MHz) delta 3.32 (s, 3H) 3.37 (m, 5H), 3.97 (d, J=5.4 Hz, 2H), 4.40-4.50 (m, 1H), 5.15 (m, 4H), 5.75 (m, 1H), 7.23 (m, 5H); MS (DCI/NH3) m/z 297 (M+NH4)+, 280 (M+H)+.
The solution of Example 4A in toluene (343 Kg) was charged to a 200-gallon reactor followed by addition of allyl bromide (41.5 Kg) and methyltributylammonium chloride (8.3 Kg). The mixture was stirred for 15 minutes, cooled to 16 C., and treated with 50% NaOH solution (296.9 Kg) slowly over 1 hour while maintaining the internal temperature below 30 C. The mixture was stirred at room temperature until there remained no more than 1.0% 1, as determined by HPLC. The mixture was allowed to settle and the layers were separated. The organic layer was washed with phosphate buffer solution made of 10 mM KH2PO4 and 10 mM K2HPO4 (2×260 Kg), followed by a water wash (256 Kg).
With potassium hydroxide; N-benzyl-N,N,N-triethylammonium chloride; In water; toluene; Example 1B benzyl allyl(2,2-dimethoxyethyl)carbamate The product of Example 1A (281.0 g, 1.18 mol) in dry toluene (1.0 L) was treated with powdered KOH (291.2 g, 5.20 mol) and triethylbenzylammonium chloride (4.4 g, 0.02 mol). A solution of allyl bromide (188.7 g, 1.56 mol) in toluene (300 mL) was then added dropwise over 1 hour at 20-30 C. The mixture was stirred overnight at room temperature and then water (300 mL) was added over 20 minutes at 20-30 C. The layers were separated and the aqueous phase was extracted with toluene (2*300 mL). The organic phases were combined, washed with brine (2*100 mL), dried (K2CO3), filtered and the filtrate concentrated to provide the title compound. 1H NMR (MeOH-d4, 300 MHz) delta 3.32 (s, 3H) 3.37 (m, 5H), 3.97 (d, J=5.4 Hz, 2H), 4.40-4.50 (m, 1H), 5.15 (m, 4H), 5.75 (m, 1H), 7.23 (m, 5H); MS (DCI/NH3) m/z 297 (M+NH4)+, 280 (M+H)+.
With potassium hydroxide; N-benzyl-N,N,N-triethylammonium chloride; In toluene; at 20 - 30℃; The product of Example 19A (281.0 g, 1.18 mol) in dry toluene (1.0 L) was treated with powdered potassium hydroxide (291.2 g, 5.20 mol) and triethylbenzylammonium chloride (4.4 g, 0.02 mol). A solution of allyl bromide (188.7 g, 1.56 mol) in toluene (300 mL) was then added dropwise over 1 h at 2030 C. The mixture was stirred overnight at room temperature and then water (300 mL) was added over 20 min at 20-30 C. The layers were separated and the aqueous phase was extracted with toluene (2×300 mL). The organic phases were combined, washed with brine (2×100 mL), dried (K2CO3), filtered and the filtrate concentrated to provide the title compound.
With potassium hydroxide; N-benzyl-N,N,N-triethylammonium chloride; In toluene; at 20 - 30℃; for 1h; The product of Example 19A (281.0 g, 1.18 mol) in dry toluene (1.0 L) was treated with powdered potassium hydroxide (291.2 g, 5.20 mol) and triethylbenzylammonium chloride (4.4 g, 0.02 mol). A solution of allyl bromide (188.7 g, 1.56 mol) in toluene (300 mL) was then added dropwise over 1 h at 20-30 C. The mixture was stirred overnight at room temperature and then water (300 mL) was added over 20 min at 20-30 C. The layers were separated and the aqueous phase was extracted with toluene (2×300 mL). The organic phases were combined, washed with brine (2×100 mL), dried (K2CO3), filtered and the filtrate concentrated to provide the title compound. MS (DCl/NH3): m/z 280 (M+1)+, 297 (M+18)+.
With benzyltrimethylammonium chloride; potassium hydroxide; In toluene; at 20 - 30℃; Compound BB-29-2 (5.62g, 23.49mmol) ,potassium hydroxide (2.64g, 46.98mmol) and benzyl trimethylammonium chloride (0.088g, 0.474mmol) was suspended in toluene (20 mL), and then slowly 3-bromo-propene (5.68g of,46.98mmol) in toluene (6mL), control the temperature of the reactants at 20-30 degrees.The reaction was stirred Gexiao at RT for 16, the reaction at 30 degrees after 24 hours.After completion of the reaction, 20mL of water was added, the organic phase was separated, dried over anhydrous sodiumsulfate, filtered, and concentrated under reduced pressure to give the title compound BB-29-3 (yellow oil, with 5.20 g of, crude product).
EXAMPLE 1B benzyl allyl(2,2-dimethoxyethyl)carbamate The product of Example 1A (281.0 g, 1.18 mol) in dry toluene (1.0 L) was treated with powdered KOH (291.2 g, 5.20 mol) and triethylbenzylammonium chloride (4.4 g, 0.02 mol). A solution of allyl bromide (188.7 g, 1.56 mol) in toluene (300 mL) was then added dropwise over 1 hour at 20-30 C. The mixture was stirred overnight at room temperature and then water (300 mL) was added over 20 minutes at 20-30 C. The layers were separated and the aqueous phase was extracted with toluene (2*300 mL). The organic phases were combined, washed with brine (2*100 mL), dried (K2CO3), filtered and the filtrate concentrated to provide the title compound. 1H NMR (MeOH-d4, 300 MHz) delta 3.32 (s, 3H) 3.37 (m, 5H), 3.97 (d, J=5.4 Hz, 2H), 4.40-4.50 (m, 1H), 5.15 (m, 4H), 5.75 (m, 1H), 7.23 (m, 5H); MS (DCI/NH3) m/z 297 (M+NH4)+, 280 (M+H)+.
With N-benzyl-N,N,N-triethylammonium chloride; potassium hydroxide; In toluene; at 20℃; for 24h; To a solution of <strong>[114790-39-5]benzyl N-(2,2-dimethoxyethyl)carbamate</strong> (1700 g, 7.10 mol), KOH (1755 g, 31.28 mol) and benzyltriethylammonium chloride (32.37g, 142.1 mmol) in toluene (7.82 L) was added 3-bromoprop-1-ene (1117.4 g, 9.24 mol) dropwise with stirring at room temperature. The resulting solution was stirred for 24 h at room temperature. Two batches were thus run in parallel. The reaction was then quenched by the addition of 10 L of water. The resulting solution was extracted with 2x7 L of toluene and the organic layers combined. The organic phase was washed with 2x10 L of brine. The mixture was dried over anhydrous sodium sulfate and concentrated under vacuum to afford benzyl N-(2,2-dimethoxyethyl)-N-(prop-2-en- 1 -yl)carbamate as pale yellow oil.

  • 4
  • [ 4549-74-0 ]
  • [ 114790-39-5 ]
  • (2,2-dimethoxy-ethyl)-(1,2-dimethyl-but-2-enyl)-carbamic acid benzyl ester [ No CAS ]
  • 6
  • [ 114790-39-5 ]
  • [ 569682-63-9 ]
  • 7
  • [ 114790-39-5 ]
  • [ 569682-65-1 ]
  • 8
  • [ 114790-39-5 ]
  • [ 569682-64-0 ]
  • 9
  • [ 114790-39-5 ]
  • benzyl 4-(1H-indol-3-yl)-2-oxopyrrolidine-1-carbamate [ No CAS ]
  • 10
  • [ 114790-39-5 ]
  • [ 307002-11-5 ]
  • 11
  • [ 114790-39-5 ]
  • [ 182207-32-5 ]
  • 12
  • [ 13139-17-8 ]
  • [ 22483-09-6 ]
  • [ 114790-39-5 ]
YieldReaction ConditionsOperation in experiment
With triethylamine; In toluene; at 5 - 30℃; for 1.25h; N-(Benzyloxycarbonyloxy)succinimide (74.5 Kg) was charged to a 200-gallon reactor, followed by toluene (235.1 Kg). The mixture was stirred for 15 minutes and cooled to 5 C. A solution of aminoacetaldehyde dimethylacetal (30 Kg) and triethylamine (28.9 Kg) in toluene (26.1 Kg) was charged slowly to the reactor over a 1 hour period while maintaining the internal temperature below 30 C. The mixture was stirred at 20 C. until there remained no more than 1.0% CbzOSu, as determined by HPLC. Water (150 Kg) was charged to the reactor and the contents of the reactor were stirred for 15 minutes. The layers were separated and the organic layer was washed with 5% ammonium chloride (2×151 Kg) followed by a water wash (150 Kg). The product was taken onto the next step as a solution, without isolation.
  • 15
  • [ 114790-39-5 ]
  • [ 1017789-40-0 ]
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