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Structure of 26734-09-8 * Storage: {[proInfo.prStorage]}
* 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.
Reference：
[1] Angewandte Chemie - International Edition, 1999, vol. 38, # 3, p. 351 - 354
9
[ 26734-09-8 ]
[ 24424-99-5 ]
[ 184357-44-6 ]
Yield
Reaction Conditions
Operation in experiment
100%
at 20℃; for 16 h;
Step 1: Synthesis of tert-butyl (3-hydroxy-2,2-dimethylpropyl)carbamate To a solution of 3-amino-2,2-dimethyl-l-propanol (1.50 g, 14.5 mmol) in CH2C12 (70 ml) is added di-tert-butyl dicarbonate (3.49 g, 16.0 mmol). The mixture is stirred at room temperature for 16 h. Saturated NH4C1 solution is added and the mixture is stirred for 10 min. The layers are separated and the organic phase is washed with saturated NaHC03 solution and is dried (Na2S04) and concentrated in vacuo to afford the title compound as a white solid (3.40 g, quantitative). LCMS: 226.20 (M+Na+).
94%
With sodium carbonate In 1,4-dioxane; water at 0℃;
To a solution of neopentanolamine (75 g, 728 mmol) and sodium carbonate (77.2 g, 728 mmol) in p-dioxane (1 L) and water (1 L) at 0 0C was added di-tert-butyl dicarbonate (175 g, 801 mmol). After stirring overnight, the solution was concentrated in vacuo and the residue was partitioned between ethyl acetate and water. The organic phase was washed again with brine and then dried with MgSOφ filtered, and concentrated in vacuo to give 139 g (94percent) of a thick, colorless syrup. 1NMR
71%
at 20℃; for 4 h;
To a solution of 3-amino-2,2-dimethylpropan-1 -ol (25 g, 242 mmol) in dichloromethane (DCM) (200 mL) was added di-tert-butyl dicarbonate (56.3 mL, 242 mmol) dropwise. It was stirred at ambient temperature for 4 h. The reaction mixture was filtered and the filtrate was concentrated. It was purified via flash column chromatography using 15 percent ethyl acetate in n-hexane as solvent to give the title compound (35 g, 172 mmol, 71 .0 percent yield) as an off white solid. LCMS: m/z 204.00 (M+)+, 1 .82 min (ret. time) tert-Butyl (2,2-dimethyl-3-oxopropyl)carbamate
11.86 g
With sodium hydrogencarbonate; sodium carbonate In tetrahydrofuran; water at 0 - 20℃; for 24 h;
To a mixture of 3-amino-2,2-dimethyl-1-propanol (5 g, 48.47 mmol), Na2C03 (0.5 g) and NaHC03 (0.5 g) in THF/H20 (3:1 , 30 mL) at 0°C was added dropwise a solution of Boc20 in THF/H20 (3:1 , 20 mL). The reaction was stirred at rt for 24 h. The mixture was extracted with DCM (x3). The combined organic layers were dried, filtered and evaporated. The residue (11.86 g) was used in the next experiment without further purification.1H NMR (300 MHz, CDCI3) δ 3.18 (s, 2H), 2.94 (s, 2H), 1.43 (s, 9H), 0.83 (s, 6H).
12.7 g
With sodium carbonate In 1,4-dioxane; water for 5 h; Cooling with ice
[Step 1] tert-Butyl (3-hydroxy-2,2-dimethylpropyl) carbamate A solution of 3-amino-2,2-dimethyl-1-propanol (6.98g) and sodium carbonate (7.18g) in 1,4-dioxane-H2O (1:1, 240 mL) was stirred under ice-cooling, and di-tert-butyl dicarbonate (14.77g) was added, and the mixture was stirred for 5 hours. Ethyl acetate was added, and the organic layer was separated, washed sequentially with water and brine, dried over magnesium sulfate and concentrated in vacuo to obtain the titled compound (12.7g) as a colorless solid.
12.7 g
With sodium carbonate In 1,4-dioxane; water for 5 h; Cooling with ice
A solution of 3-amino-2,2-dimethyl-1-propanol (6.98g) and sodium carbonate (7.18g) in 1,4-dioxane-H2O (1:1,240 mL) was stirred under ice-cooling, and di-tert-butyl dicarbonate (14.77g) was added, and the mixture was stirredfor 5 hours. Ethyl acetate was added, and the organic layer was separated, washed sequentially with water and brine,dried over magnesium sulfate and concentrated in vacuo to obtain the titled compound (12.7g) as a colorless solid.
254 mg
With triethylamine In dichloromethane at 0 - 25℃; for 16 h;
To a solution of 3-amino-2,2-dimethyl-propan-l-ol (400.00 mg, 3.88 mmol, 1.00 eq) in DCM (3.00 mL) were added triethylamine (1.18 g, 11.63 mmol, 1.61 mL, 3.00 eq) and Boc20 (1.27 g, 5.82 mmol, 1.34 mL, 1.50 eq) at 0 °C. The mixture was stirred at 25 °C for 16 h. The reaction mixture was concentrated and the residue was diluted with ethyl acetate (10 mL) and washed with H20 (10 mL * 3), dried over anhydrous Na2S04 and concentrated. The crude residue was purified by column chromatography (Si02, Petroleum ether/Ethyl acetate=20: l to 5: l)to afford tert-butyl N-(3-hydroxy-2,2-dimethyl-propyl)carbamate (254.00 mg). 1H NMR (400MHz, CHLOROFORM-d) δ = 3.69 (t, J=7.3 Hz, 1H), 3.18 (d, J=7.1 Hz, 2H), 2.95 (d, J=6.6 Hz, 2H), 1.44 (s, 9H), 0.84 (s, 6H)
0.658 g
at 20℃; for 2 h;
mixture of compound 29 (0.345 g), tert-butyl dicarbonate (0.730 g) and THF (50 ml) was stirred at room temperature for 2 hours.The reaction solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: chloroform / methanol = 95/5) to give the title compound 30 (0.658 g).
N-(3-chlorobenzyl)-2-(3-hydroxy-2,2-dimethylpropyl)-3-oxoisoindoline-1-carboxamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
23%
Stage #1: 3-amino-2,2-dimethylpropan-1-ol; o-carboxybenzaldehyde In methanol; acetonitrile at 20℃; for 0.5h;
Stage #2: 1-chloro-3-(isocyanomethyl)benzene In methanol; acetonitrile at 20℃;
26 N-(3-chlorobenzyl)-2-(3-hydroxy-2,2-dimethylpropyl)-3-oxoisoindoline-1-carboxamide
The 3-amino-2,2-dimethylpropan-1-ol (0.276 mmol) was dissolved in MeCN (1 mL) and added to 2-Formylbenzoic acid (0.276 mmol) dissolved in MeOH (1 mL), this was stirring for 30 min in r.t. 1-chloro-3-(isocyanomethyl)benzene (0.248 mmol) dissolved in MeCN (2 mL) was added to the mixture and the reaction was left stirring in r.t. over night. The reaction was finished the next morning and the solvent was evaporated. The crude was dissolved in DCM (4 mL) and extracted with water (3 mL), the organic phase was collected and the solvent was evaporated. The crude was dissolved in DMSO (1 ml), filtrated and purified by preparative HPLC using a Waters FractionLynx III HPLC system with a mass triggered fraction collector, equipped with an Xbridge Prep C18 150*19 mm column using a MeCN/0.2% NH3 buffer system with a gradient from 100% A (5% MeCN+95% 0.2% NH3) to 100% B (95% MeCN+5% 0.2% NH3) as mobile phase, followed by concentration in vacuo afforded the title compound (0.025 g, 23%). 1H-NMR* (600 MHz, DMSO-d6, DMSO*) δ 9.29-9.17 (m, 1H), 7.77-7.46 (m, 4H), 7.4-7.15 (m, 4H), 5.48-5.4 (s, 1H), 4.74-4.63 (m, 1H), 4.4-4 26 (m, 2H), 3.79-3.71 (d, 1H), 3.19-3.05 (m), 2.76-2.64 (d), 0.88-0.75 (s, 6H); HRMS calculated for (C21H23Cl N2O3+H)+, 387.1475 found (ES [M+H]+), 387.1475
2,2-dimethyl-3-(6-methyl-5-nitro-pyridin-2-ylamino)-propan-1-ol[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
27%
With N-ethyl-N,N-diisopropylamine; In dimethyl sulfoxide; at 180℃; for 0.25h;Microwave irradiation;
Example 101 2, 2-Dimethyl-3-(6-methyl-5-nitro-pyridin-2-ylamino)-propan-1-ol 6-Chloro-2-methyl-3-nitro-pyridine (40 mg, 0.232 mmol) was solved in 900 IlL DMSO. 3-Amino-2, 2-dimethyl-propan-1-ol (31 mg, 0.301 mmol) and DIPEA (52 p. L, 0.301 mmol) was added and heated to 180 °C in microwave for 15 min parameters: Normal absorption, hold time on, pre-stirring 30 sec). Crude mixture was diluted in CH2CI2 and washed several times with NH4CI (aq) and phases were separated on SPE Phase Separator. Organic phase was evaporated in vacuo and crude product mixture was then purified on silica column with 7: 1 n-heptane: EtOAc as mobile phase. This gave 15 mg (27 percent) of 2, 2-dimethyl-3-(6-methyl-5-nitro-pyridin-2-ylamino)-propan-1-ol.
Method 4 4-[N-(3-hydroxy-2.2-dimethylpropyl)sulphamoyl]aniline A mixture of sulphanilyl fluoride (1g, 5.7 mmol), 3-amino-2,2-dimethylpropan-1-ol (884 mg, 8.6 mmol) and triethylamine (0.876 ml, 6.3 mmol) in butan-1-ol (20 ml) was heated at reflux for 24 hours. The volatiles were removed by evaporation and residue was purified by chromatography on silica gel to give the title compound. NMR: 0.72 (s, 6H), 2.52 (d, 2H), 3.08 (d, 2H), 4.40 (t, 1H), 7.19 (t, 1H), 7.60 (s, 1H), 7.64 (d, 2H), 7.96 (d, 2H), 8.40 (s, 1H), m/z 259 (MN)+.
With hydrogenchloride; In dichloromethane; ethyl acetate;
EXAMPLE 67 N-(3-Hydroxy-2,2-dimethyl-propyl)-C-{4-[(7-oxo-6,7-dihydro-1-thia-3,6-diaza-as-indacen-8-ylidenemethyl)-amino]-phenyl}-methanesulfonamide (Z-isomer) A solution of 3.16 g (30.6 mmol) of 3-amino-2,2-dimethylpropanol in 10 mL of CH2Cl2 was added at once to a solution of 2.40 g (10.2 mmol) of 4-nitrophenylmethanesulphonyl chloride (Lee, et al., Journal of the American Chemical Society 1987, 109, 7472-7; Macor, et al., Tetrahedron Letters 1992, 33, 8011-4) in 40 mL of CH2Cl2. The mixture was stirred at rt for 15 min, the solvent was removed in vacuo and the residue was redissolved in 50 mL of EtOAc. The solution was washed with three 50-mL portions of 1.0 N HCl and concentrated in vacuo. Purification of the residue by flash chromatography on silica gel (hexane/EtOAc 1:1) afforded N-(3-hydroxy-2,2-dimethyl-propyl)-(4-nitrophenyl)-methanesulfonamide as a white solid (0.84 g, 27%): 1H NMR (DMSO-d6): delta0.74 (s, 6H), 2.78 (d, J=6.4 Hz, 2H), 3.11 (d, J=5.3 Hz, 2H), 4.47 (t, J=5.3 Hz, 1H), 4.52 (s, 2H), 7.02 (t, J=6.4 Hz, 1H), 7.65 (d, J=8.8 Hz, 2H), 8.25 (d, J=8.8 Hz, 2H); APCI-MS: m/z 301 (M-H)-.
1,5-bis[(3-hydroxy-2,2-dimethylpropyl)amino]anthraquinone[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
82%
In 2-ethoxy-ethanol; water;
EXAMPLE 1 A mixture of 1,5-dichloroanthraquinone (138.0 g, 0.5 mol), 3-amino-2,2-dimethylpropanol (206.0 g, 2.0 mol) and 2-ethoxyethanol (1L) is heated at about 130 C. for 22 hours with good agitation. The dark red reaction mixture is cooled to about 40 C. and demineralized water (3L) is added to precipitate the product, 1,5-bis-[(3-hydroxy 2,2-dimethylpropyl)amino]anthraquinone, which is collected by filtration, washed with demineralized water and air dried to yield 203.0 g of product (99% of theory). Highly crystalline product (168 g, 82% of theory) is obtained by reslurrying the crude product in hot methanol, cooling the slurry to room temperature, collecting the solids by filtration, washing with methanol and drying in air.
82%
In 2-ethoxy-ethanol; water;
EXAMPLE 1 A mixture of 1,5-dichloroanthraquinone (138.0 g, 0.5 mol), 3-amino-2,2-dimethylpropanol (206.0 g, 2.0 mol) and 2-ethoxyethanol (1 L) is heated at about 130C for 22 hours with good agitation. The dark red reaction mixture is cooled to about 40C and demineralized water (3 L) is added to precipitate the product, 1,5-bis-[(3-hydroxy 2,2-dimethylpropyl)amino]anthraquinone, which is collected by filtration, washed with demineralized water and air dried to yield 203.0 g of product (99% of theory). Highly crystalline product (168 g, 82% of theory) is obtained by reslurrying the crude product in hot methanol, cooling the slurry to room temperature, collecting the solids by filtration, washing with methanol and drying in air.
With potassium carbonate; In tetrahydrofuran; water; at 20℃; for 2h;
Example 7: Preparation of Compounds A14, A51, A52(sodium salt), BU, B51(bis(trifluoroacetate) salt) and B52a) Compound A51:Compound A51Step 1: To a mixture of commercial 3-amino-2,2-dimethyl-1-propanol (1.33 g, 13 mmol) in tetrahydrofuran (40 mL) and 1 M aqueous potassium carbonate (10 mL) was added a solution of N-Boc-Phe-O-Succinimide (4.60 g, 13 mmol). The reaction mixture was stirred vigorously at room temperature for 2 h. The two phases were separated and the organic layer was concentrated to afford 3-(N-Boc-L-phenylalaninarnido)-2,2-dimethylpropanol as a white solid ready for use without further purification.
Stage #1: Boc-Val-ONSu; 3-amino-2,2-dimethylpropan-1-ol With potassium carbonate In water; acetonitrile at 20℃; for 2h;
Stage #2: With hydrogenchloride In water; acetonitrile
21.1
Example 21: Preparation of Compound A64 Compound A64Step 1 : A solution of commercial 3-amino-2,2-dimethyl-1-propanol (1.7 g, 16.5 mmol), N-[(1 ,1-dimethylethoxy)carbonyl]-D- Valine, 2,5-dioxo-1-pyrrolidinyl ester (Giuntini F. et a/., J. Med. Chem. (2009), 52(13), 4026-4037, incorporated herein by reference) (4.7 g, 15.0 mmol) and 1M aqueous potassium carbonate (10 ml_, 10.0 mmol) in acetonitrile (30 mL) was stirred at room temperature for 2 h. The mixture was concentrated to about one third of its volume, diluted with 1M hydrochloric acid and extracted three times with ethyl acetate. The combined organic layers were washed with water, dried over magnesium sulfate, filtered and the filtrate evaporated to a residue. The crude product was purified by silica gel chromatography using hexane/ethyl acetate (50:50) to isolate 4g (88% yield) of tert-butyl N-[(1S)-1-[(3-hydroxy-2,2-dimethyl-propyl)carbamoyl]-2-methyl-propyl]carbamate.
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