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Product Details of [ 7693-46-1 ]

CAS No. :7693-46-1 MDL No. :MFCD00007321
Formula : C7H4ClNO4 Boiling Point : -
Linear Structure Formula :- InChI Key :NXLNNXIXOYSCMB-UHFFFAOYSA-N
M.W : 201.56 Pubchem ID :82129
Synonyms :

Calculated chemistry of [ 7693-46-1 ]

Physicochemical Properties

Num. heavy atoms : 13
Num. arom. heavy atoms : 6
Fraction Csp3 : 0.0
Num. rotatable bonds : 3
Num. H-bond acceptors : 4.0
Num. H-bond donors : 0.0
Molar Refractivity : 47.14
TPSA : 72.12 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -5.71 cm/s

Lipophilicity

Log Po/w (iLOGP) : 1.36
Log Po/w (XLOGP3) : 2.56
Log Po/w (WLOGP) : 2.33
Log Po/w (MLOGP) : 0.84
Log Po/w (SILICOS-IT) : -0.24
Consensus Log Po/w : 1.37

Druglikeness

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

Water Solubility

Log S (ESOL) : -2.85
Solubility : 0.287 mg/ml ; 0.00143 mol/l
Class : Soluble
Log S (Ali) : -3.72
Solubility : 0.0382 mg/ml ; 0.00019 mol/l
Class : Soluble
Log S (SILICOS-IT) : -2.09
Solubility : 1.64 mg/ml ; 0.00815 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 3.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 1.82

Safety of [ 7693-46-1 ]

Signal Word:Danger Class:8
Precautionary Statements:P261-P280-P305+P351+P338-P310 UN#:3261
Hazard Statements:H314-H335 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 7693-46-1 ]

* 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.

  • Upstream synthesis route of [ 7693-46-1 ]
  • Downstream synthetic route of [ 7693-46-1 ]

[ 7693-46-1 ] Synthesis Path-Upstream   1~30

  • 1
  • [ 75-44-5 ]
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Reference: [1] Synthetic Communications, 2013, vol. 43, # 17, p. 2365 - 2369
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[3] Journal of Organic Chemistry, 1960, vol. 25, p. 1118 - 1123
[4] Journal of Organic Chemistry, 1978, vol. 43, p. 2410 - 2414
[5] Advanced Synthesis and Catalysis, 2010, vol. 352, # 18, p. 3339 - 3347
  • 2
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Reference: [1] Journal of Labelled Compounds and Radiopharmaceuticals, 2009, vol. 52, # 5, p. 166 - 172
[2] European Journal of Medicinal Chemistry, 2012, vol. 54, p. 690 - 696
  • 3
  • [ 100-02-7 ]
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Reference: [1] Patent: WO2007/38669, 2007, A2, . Location in patent: Page/Page column 171
  • 4
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Reference: [1] Patent: US5220018, 1993, A,
  • 5
  • [ 100-02-7 ]
  • [ 503-38-8 ]
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Reference: [1] Synthesis, 1993, # 1, p. 103 - 106
[2] Journal of Organic Chemistry, 2003, vol. 68, # 23, p. 8750 - 8766
  • 6
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Reference: [1] Journal of the American Chemical Society, 1968, vol. 90, p. 6199 - 6207
  • 7
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  • 8
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  • [ 5070-13-3 ]
  • [ 173604-87-0 ]
YieldReaction ConditionsOperation in experiment
81% With pyridine; hydrogenchloride In sodium hydroxide; chloroform EXAMPLE 5
Preparation of (5-methyl-1,3-dioxolene-2-one-4-yl)-methyl p-nitrophenyl carbonate STR16
4-Hydroxymethyl-5-methyl-1,3-doxolene-2-one (5.59 g) and pyridine (3.74 g) were dissolved in 50 mL of chloroform and cooled in an ice bath. 4-Nitrophenylchloroformate (9.46 g) dissolvedin chloroform (50 mL) was added dropwise to the above solution.
The mixture was stirred for 16 hours at room temperature.
The reaction mixture was cooled in ice and washed with ice cold 1percent sodium hydroxide, 1N hydrochloric acid, water and brine and dried over sodium sulfate.
Evaporation of the organic layer resulted in 11.2 g of crude product, which was crystallized from chloroform/hexane.
The crystals formed were filtered and washed with ice cold hexane/chloroform (1:1), to obtain the pure 4-nitrophenyl carbonate (9.11 g, 81percent); mp 116°-117°; 1 H NMR (CDCl3) δ2.23 (s, 3H), 5.05 (s,2H), 7.41 (d, 2H), 8.3 (s, 2H); 13 C NMR (CDCl3), δ9.43, 58.07, 121.69, 121.35, 132.15, 141.42, 145.57, 151.66, 152.19, 155.05; IR (KBr) 1779, 1811, 1525, 1247, 1221, 1207 cm-1.
Reference: [1] Patent: US5466811, 1995, A,
  • 9
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  • [ 5070-13-3 ]
Reference: [1] Journal of Organic Chemistry, 1960, vol. 25, p. 1118 - 1123
[2] Patent: US2004/13728, 2004, A1,
  • 10
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  • [ 602-09-5 ]
  • [ 5070-13-3 ]
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Reference: [1] Chemistry Letters, 1991, # 12, p. 2091 - 2094
  • 11
  • [ 93350-13-1 ]
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  • [ 5070-13-3 ]
  • [ 93350-09-5 ]
Reference: [1] Journal of Organic Chemistry, 1984, vol. 49, # 26, p. 5113 - 5116
  • 12
  • [ 29526-99-6 ]
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  • [ 1046817-22-4 ]
  • [ 5070-13-3 ]
Reference: [1] Synthesis (Germany), 2013, vol. 45, # 17, p. 2481 - 2484
  • 13
  • [ 100-02-7 ]
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  • [ 5070-13-3 ]
Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2010, vol. 20, # 19, p. 5933 - 5935
  • 14
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  • [ 5070-13-3 ]
Reference: [1] Journal of the American Chemical Society, 2011, vol. 133, # 8, p. 2749 - 2759
  • 15
  • [ 2018-66-8 ]
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  • [ 1738-87-0 ]
Reference: [1] Journal of Organic Chemistry, 1985, vol. 50, # 5, p. 560 - 565
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  • [ 57-11-4 ]
  • [ 14617-86-8 ]
Reference: [1] Organometallics, 2017, vol. 36, # 15, p. 2956 - 2964
  • 17
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  • [ 100-51-6 ]
  • [ 13795-24-9 ]
Reference: [1] Chemische Berichte, 1966, vol. 99, # 12, p. 3914 - 3924
[2] Bioorganic and medicinal chemistry letters, 2002, vol. 12, # 15, p. 2027 - 2030
[3] Patent: WO2010/31789, 2010, A1, . Location in patent: Page/Page column 27
[4] Angewandte Chemie - International Edition, 2016, vol. 55, # 10, p. 3364 - 3368[5] Angew. Chem., 2016, vol. 128, p. 3425 - 3429,5
[6] Chemistry and Biology, 2015, vol. 22, # 10, p. 1347 - 1361
  • 18
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  • [ 80149-80-0 ]
Reference: [1] Bioorganic and Medicinal Chemistry Letters, 1998, vol. 8, # 7, p. 735 - 738
[2] Journal of Organic Chemistry, 1983, vol. 48, # 9, p. 1539 - 1541
[3] Beilstein Journal of Organic Chemistry, 2013, vol. 9, p. 608 - 612
[4] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1986, p. 2181 - 2186
[5] Patent: WO2018/149419, 2018, A1, . Location in patent: Paragraph 001255
  • 19
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  • [ 97682-44-5 ]
Reference: [1] Chemistry - A European Journal, 1998, vol. 4, # 1, p. 67 - 83
  • 20
  • [ 72-40-2 ]
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  • [ 85622-93-1 ]
Reference: [1] Patent: US2002/133006, 2002, A1,
  • 21
  • [ 38585-74-9 ]
  • [ 7693-46-1 ]
  • [ 144163-97-3 ]
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[2] Journal of Medicinal Chemistry, 1998, vol. 41, # 4, p. 602 - 617
[3] Patent: EP1170289, 2002, A2, . Location in patent: Page 45
  • 22
  • [ 109-02-4 ]
  • [ 38585-74-9 ]
  • [ 7693-46-1 ]
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Reference: [1] Patent: US5914332, 1999, A,
[2] Patent: US5461067, 1995, A,
[3] Patent: US5559158, 1996, A,
[4] Patent: US5484801, 1996, A,
[5] Patent: US5773625, 1998, A,
  • 23
  • [ 7693-46-1 ]
  • [ 144163-97-3 ]
Reference: [1] Patent: US5773625, 1998, A,
  • 24
  • [ 159857-80-4 ]
  • [ 7693-46-1 ]
  • [ 159857-81-5 ]
Reference: [1] Patent: WO2017/66668, 2017, A1, . Location in patent: Sheet 3
  • 25
  • [ 111625-28-6 ]
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  • [ 874302-76-8 ]
YieldReaction ConditionsOperation in experiment
96% With pyridine In dichloromethane at 20℃; for 15 h; EXAMPLE 2; Example 2 was prepared according to Scheme 4; Scheme 4(a) pyridine, CH2C12; 2-(2-pyridyldithio)ethanol hydrochloride (compound (Ib); 8.8 g; 39.33mL) was dissolved in 78 mL CBbCk, and 2 eqs. of pyridine (CsHsN; 80.88 mL) wasadded. para-Nitrophenyl chloroformate (compound (6); 8.08 g; 40 mmol) wasdissolved in 80 mL CHaCLz, and the solution was added to mixture of 2-(2-pyridyldithio)ethanol hydrochloride and pyridine over a 15 minutes period. Theresultant clear solution was stirred at room temperature for 15 hours. TLC analysisfor the above mixture after 15 hours stirring indicated completion of the reaction. Themixture was then filtered to remove precipitated pyridine hydrochloride. The lightyellow clear filtrate was washed with deionized water (2x50 mL) to remove thedissolved pyridine hydrochloride, dried (Na2SO4), filtered, and concentrated withvacuum (13.8 g). Silica gel 60 (250 g) in CH.2C\\2 was used to from a 50 cm x 4.2 cmof silica gel bed with 250 mL solvent reservoir. The product compound (7), ca. 13.8g, was dissolved in 15 mL (10 mL + 5 mL) of CHaQ/z and the solution was loadedwith an elution ratio of 30 mL/min with standard collection of 30 mL fractionscoupled with UV- detection and gave 13.3 g (96percent yield).
85% With triethylamine In acetonitrile at -15 - 20℃; Inert atmosphere To a solution of 2-(pyridin-2-yldisulfanyl)ethanol (50 mg, 0.27 mmol) in dry acetonitirle (ACN) (2 ml_) and triethylamine (40 μΙ_), at -15°C under argon, was added 4-nitrophenyl chloroformate (62 mg, 0.31 mmol). As the solution turned yellow, the mixture was stirred overnight at room temperature. After removing the solvent under vacuum, the crude product was purified by chromatography on silica gel (EtOAc/Cyclohexane, 10/90) to give compound as light oil (80 mg, 85 percent). Rf: 0.3 (EtOAc/Cyclohexane : 40/60) 1H NMR (300 MHz, CDCI3): 8.46 (d, 1 H, J = 4.8 Hz, Py6), 8.27 (d, 2H, J = 9.2 Hz, Phenol- N02), 7.76 (m, 2H, Py4 and Py5), 7.37 (d, 2H, J = 9.1 Hz, Phenol-O), 7.17 (m, 1 H, Py3), 4.54 (t, 2H, J = 6.4 Hz, S-CH2-), 3.15 (t, 2H, J = 6.4 Hz, -CH2-OH). 13C NMR (75 MHz, CDCI3): 162.69 (Py2), 154.85 (Phenol-O-C-), 149.35 (Py6), 145.45 (Phenol-C-N02), 137.51 (Py4), 125.54 (2H, Phenol- N02), 122.03 (3H, Py3 and Phenol-O), 120.63 (Py5), 66.63 (S-CH2-), 36.78 (- CH2-OH). IR (cm-1): 1766, 1521 ,1203, 1110. MS (IC): m/z = 353 [M+H]+
85% With triethylamine In acetonitrile at 0 - 20℃; for 16 h; Inert atmosphere A solution of 8a (50 mg, 0.367mmol), Et3N (40 μL, 1.1 eq) in ACN (2 mL) was cooled to 0 °C. The solution turned yellow as 4-nitrophenylchloroformate (62 mg, 1.1 eq) was added, and was stirred for 16 hat rt. After concentration in vacuo, the residue was purified by column chromatography on silica gel (EtOAc/Cyclohexane 10percent–30percent) to afford the title compound as a pale yellow oil (80 mg, ρ=85percent). Rf (EtOAc/Cyclohexane 40percent)=0.30 1H NMR (300 MHz, CDCl3): δ 8.46 (d, 1H, J=4.7Hz), 8.27 (d, 2H, J=9.2Hz), 7.76 (m, 2H), 7.37 (d, 2H, J=9.1Hz), 7.17 (m, 1H), 4.54 (t, 2H, J=6.4Hz), 3.15 (t, 2H, J=6.4Hz). 13C NMR (75 MHz, CDCl3): δ 162.7, 154.9, 150.4, 149.4, 145.5, 137.5, 125.5, 122.0, 121.7, 120.4, 66.6, 36.8. IR, ν (cm−1): 1766, 1522, 1203, 1111. MS (ESI+): m/z=353 [M+H+], calculated 353.
82% With pyridine In dichloromethane p-Nitrophenylchloroformate was reacted with alcohol 52 (see Jones, L. R. et al., J. Am. Chem. Soc. 2006, 128, 6526-6527) according to the procedure described by Anderson, G. W. and McGregor, A. C, J. Am. Chem. Soc. 1957, 79, 6180-6183, to afford carbonate 53 in 82percent yield. 1H NMR (500 MHz, CD3OD): δ= 8.47 (m, IH), 8.24 (dd, Ji = 7.0Hz, J2 = 2.0Hz 2H), 7.74- 7.66 (m, 2H), 7.36 (dd, Ji = 7.0Hz, J2 = 2.0Hz 2H), 7.14 (m, IH), 4.54 (t, J = 6.0Hz, 2H), 3.15 (t, J = 6.0Hz, 2H) ppm. 13C NMR(125 MHz, CD3Cl3): δ= 159.3, 155.6, 152.5, 149.8, 145.6, 137.8, 125.6, 122.1, 121.6, 120.6, 66.9, 37.0 ppm. EI-MS (m/z): [M+l] calculated for [Ci4Hi3N2OsS2] 353.02 found 353.0.
81% With N-ethyl-N,N-diisopropylamine In dichloromethane Example 114. Synthesis of 4-nitrophenyl 2-(2-(Pyridin-2-yl)disulfanyl)ethyl carbonateIn a 250 mL round bottom flask, 4-nitrophenyl chloroformate (2.0 g, 10 mmol) was dissolved in dichloromethane (20 mL). 2-(2-(Pyridin-2- yl)disulfanyl)ethanol (1.9 g, 10 mmol) and N,N-diisopropylethylamine (1.0 g, 10 mmol) were dissolved in dichloromethane (100 mL) and added dropwise to the mixture and stirred overnight. The solution was then pumped down to dryness to yield a yellow oil. The crude product was purified by flash column chromatography (dichloromethane: acetone = 30:1) to produce a yellow oil (2.9 g, 81percent yield).
81% With N-ethyl-N,N-diisopropylamine In dichloromethane Example 8. Synthesis of 4-nitrophenyl 2-(2-(Pyridin-2-yl)disulfanyl)ethyl carbonateIn a 250 mL round bottom flask, 4-nitrophenyl chloroformate (2.0 g, 10 mmol) was dissolved in dichloromethane (20 mL). 2-(2-(Pyridin-2-yl)disulfanyl)ethanol (1.9 g, 10 mmol) and N,N-diisopropylethylamine (1.0 g, 10 mmol) were dissolved indichloromethane (100 mL) and added dropwise to the mixture and stirred overnight. The solution was then pumped down to dryness to yield a yellow oil. The crude product was purified by flash column chromatography (dichloromethane: acetone = 30:1) to produce a yellow oil (2.9 g, 81percent yield).
81% With N-ethyl-N,N-diisopropylamine In dichloromethane Example 8
Synthesis of 4-nitrophenyl 2-(2-(Pyridin-2-yl)disulfanyl)ethyl carbonate
In a 250 mL round bottom flask, 4-nitrophenyl chloroformate (2.0 g, 10 mmol) was dissolved in dichloromethane (20 mL) 2-(2-(Pyridin-2-yl)disulfanyl)ethanol (1.9 g, 10 mmol) and N,N-diisopropylethylamine (1.0 g, 10 mmol) were dissolved in dichloromethane (100 mL) and added dropwise to the mixture and stirred overnight.
The solution was then pumped down to dryness to yield a yellow oil.
The crude product was purified by flash column chromatography (dichloromethane:acetone=30:1) to produce a yellow oil (2.9 g, 81percent yield).

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[7] Patent: US2013/196946, 2013, A1, . Location in patent: Paragraph 1670
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[14] Patent: US2016/74528, 2016, A1, . Location in patent: Paragraph 0306-0307
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Reference: [1] Patent: US2017/95570, 2017, A1, . Location in patent: Paragraph 0593; 0594
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  • [ 1046817-22-4 ]
YieldReaction ConditionsOperation in experiment
84% With pyridine In dichloromethane at 0℃; for 1.5 h; A solution of pyridine (1.7 mL) in 10 mL of CH2Cl2 was added dropwise over 10 min to a 0 °C solution of (1-methyl)cyclopropanol (1300 mg, 17 mmol) and 4-nitrophenyl chloroformate (3842 mg, 19 mmol) in 50 mL of CH2Cl2. The mixture was stirred for 90 min, then quenched with 50 mL of 0.1 M*H2SO4. The CH2Cl2 phase was washed with water, NaHCO3, brine, and dried (MgSO4). The MgSO4 was filtered and the filtrate was diluted with twice its volume of hexane. A solid precipitate formed gradually. The mixture was filtered and the filtrate was concentrated to dryness to afford a colorless semisolid. This residue was digested with 50 mL of hexane, filtered while hot and the solid was washed with 2 .x. 10 mL of boiling hexane. The filtrate was concentrated to afford 2 as a white solid, mp 46-48 °C. 1H NMR (CDCl3) δ 0.72-0.82 (m, 2H), 1.02-1.15 (m, 2H), 1.66 (s, 3H), 7.38 (m, 2H), 8.27 (m, 2H). Calcd for C11H11NO5: C 55.70percent; H 4.67percent; N 5.90percent. Found: C 55.52percent, H 4.52percent, N 5.94percent. It is important that Et3N not be used in this reaction as it reacts with the chloroformate
20.8 g With dmap; triethylamine In dichloromethane at 0 - 20℃; for 14 h; B) 1 -Methylcvclopropyl 4-nitrophenyl carbonateA solution of 1 -methylcyclopropanol (10 g, 137 mmol), 4-nitrophehyl chloroformate (32 g, 152 mmol), and a few crystals of 4-dimethylaminopyridine (150 mg, 1 .2 mmol) in dichloromethane (462 mL), was cooled to zero degree Celsius. Triethylamine (36.5 g, 361 mmol) was added drop-wise. After 10 minutes, the ice bath was removed and the reaction was allowed to stir at room temperature for 14 hours. The reaction mixture was washed twice with saturated aqueous sodium carbonate. The aqueous phase was extracted with dichloromethane. The combined organic extracts were washed with water, dried over magnesium sulfate, filtered and the filtrate concentrated in vacuo. The residue was purified by flash silica gel chromatography, eluting with a gradient mixture of ethyl acetate in heptane (0 to 5percent ethyl acetate over the first 10 minutes, then isocratic at 5percent ethyl acetate to heptane) to give 20.8 g of the desired carbonate as a clear oil. This oil solidified upon standing.1 H NMR (500 MHz, deuterochloroform) delta 0.77 (app. t, =6.59 Hz, 2 H), 1 .09 (app. t, J=7.07 Hz, 2 H), 1.67 (s, 3 H), 7.40 (app. dt, J=9.27, 3.17 Hz, 2 H), 8.29 (app. dt, J=9.27, 3.17 Hz, 2 H).
3.21 g With pyridine In dichloromethane at 5℃; for 1.66667 h; 4-Nitrophenyl chloroformate (3; 3.84 g, 19 mmol) was dissolved in CH2Cl2 (40 mL) and cooled to <5 °C. To this was added a cold solution of 1 (1.30 g, 17 mmol) in CH2Cl2 (10 mL), previously dried with Na2SO4. A solution of pyridine (1.7 mL, 21 mmol) in CH2Cl2 (10 mL) was added dropwise with stirring over 10 min with continued cooling. The mixture was stirred for an additional 90 min, then quenched with 0.1 M H2SO4 (50 mL). The CH2Cl2 layer was washed with H2O (25 mL), aq NaHCO3 (25 mL), brine (25 mL), and dried (MgSO4). After filtration, the CH2Cl2 layer was diluted with twice its volume of hexane. A white precipitate of bis(4-nitrophenyl)carbonate formed gradually. This was filtered and discarded. The filtrate was concentrated to dryness to afford 3.99 g of a colorless semisolid. This was digested with hexane (50 mL) under reflux, filtered while hot, and the precipitate was washed with boiling hexane (2 × 10 mL). The filtrate was concentrated to give 3.42 g of a white solid, which was recrystallized from hexane (5 mL) to afford 3.21 g (79percent) of analytically pure 2; mp 46–48 °C. IR (film): 1770, 1524, 1349 cm–1. 1H NMR (400 MHz, CDCl3): δ = 0.72–0.82 (m, 2 H), 1.02–1.15 (m,2 H), 1.66 (s, 3 H), 7.38 (d, J = 9.4 Hz, 2 H), 8.27 (d, J = 9.4 Hz, 2H). 13C NMR (100 MHz, CDCl3): δ = 12.85, 20.48, 60.64, 121.67, 125.19, 145.24, 151.89, 155.41. Anal. Calcd for C11H11NO5: C, 55.70; H, 4.67; N, 5.90. Found: C,55.52; H, 4.52; N, 5.94.
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Reference: [1] Synthesis (Germany), 2013, vol. 45, # 17, p. 2481 - 2484
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YieldReaction ConditionsOperation in experiment
49% With pyridine In tetrahydrofuran; N,N-dimethyl-formamide at 0℃; Dissolve Fmoc-val-cit-pab-OH (1 eq) in THF: DMF (5: 1) and slowly add pyridine (4eq) at 0 ° C.4-nitrophenyl carbonochloridate (3 eq) is added and stirred at 0 ° C.The reaction is confirmed by HPLC. After completion of the reaction, the solvent is dried and then columed. Yield: yellow solid 49percent.
Reference: [1] Journal of Controlled Release, 2012, vol. 160, # 3, p. 618 - 629
[2] Patent: KR2017/41562, 2017, A, . Location in patent: Paragraph 0434-0435
[3] Nature Communications, 2017, vol. 8, # 1,
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