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Chemical Structure| 131818-17-2 Chemical Structure| 131818-17-2

Structure of 131818-17-2

Chemical Structure| 131818-17-2

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CAS No.: 131818-17-2

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Product Details of [ 131818-17-2 ]

CAS No. :131818-17-2
Formula : C11H14BrNO2
M.W : 272.14
SMILES Code : O=C(OC(C)(C)C)NC1=CC=C(Br)C=C1
MDL No. :MFCD01006612
InChI Key :VLGPDTPSKUUHKR-UHFFFAOYSA-N
Pubchem ID :2773608

Safety of [ 131818-17-2 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Computational Chemistry of [ 131818-17-2 ] Show Less

Physicochemical Properties

Num. heavy atoms 15
Num. arom. heavy atoms 6
Fraction Csp3 0.36
Num. rotatable bonds 4
Num. H-bond acceptors 2.0
Num. H-bond donors 1.0
Molar Refractivity 64.39
TPSA ?

Topological Polar Surface Area: Calculated from
Ertl P. et al. 2000 J. Med. Chem.

38.33 ?2

Lipophilicity

Log Po/w (iLOGP)?

iLOGP: in-house physics-based method implemented from
Daina A et al. 2014 J. Chem. Inf. Model.

2.88
Log Po/w (XLOGP3)?

XLOGP3: Atomistic and knowledge-based method calculated by
XLOGP program, version 3.2.2, courtesy of CCBG, Shanghai Institute of Organic Chemistry

3.68
Log Po/w (WLOGP)?

WLOGP: Atomistic method implemented from
Wildman SA and Crippen GM. 1999 J. Chem. Inf. Model.

3.61
Log Po/w (MLOGP)?

MLOGP: Topological method implemented from
Moriguchi I. et al. 1992 Chem. Pharm. Bull.
Moriguchi I. et al. 1994 Chem. Pharm. Bull.
Lipinski PA. et al. 2001 Adv. Drug. Deliv. Rev.

3.06
Log Po/w (SILICOS-IT)?

SILICOS-IT: Hybrid fragmental/topological method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

2.35
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

3.11

Water Solubility

Log S (ESOL):?

ESOL: Topological method implemented from
Delaney JS. 2004 J. Chem. Inf. Model.

-3.88
Solubility 0.0361 mg/ml ; 0.000133 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Soluble
Log S (Ali)?

Ali: Topological method implemented from
Ali J. et al. 2012 J. Chem. Inf. Model.

-4.17
Solubility 0.0182 mg/ml ; 0.0000669 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Moderately soluble
Log S (SILICOS-IT)?

SILICOS-IT: Fragmental method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

-4.2
Solubility 0.0172 mg/ml ; 0.0000631 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Moderately soluble

Pharmacokinetics

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

 Yes
P-gp substrate?

P-glycoprotein substrate: SVM model built on 1033 molecules (training set)
and tested on 415 molecules (test set)
10-fold CV: ACC=0.72 / AUC=0.77
External: ACC=0.88 / AUC=0.94

 No
CYP1A2 inhibitor?

Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.83 / AUC=0.90
External: ACC=0.84 / AUC=0.91

 Yes
CYP2C19 inhibitor?

Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.80 / AUC=0.86
External: ACC=0.80 / AUC=0.87

 Yes
CYP2C9 inhibitor?

Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set)
and tested on 2075 molecules (test set)
10-fold CV: ACC=0.78 / AUC=0.85
External: ACC=0.71 / AUC=0.81

 Yes
CYP2D6 inhibitor?

Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set)
and tested on 1068 molecules (test set)
10-fold CV: ACC=0.79 / AUC=0.85
External: ACC=0.81 / AUC=0.87

 No
CYP3A4 inhibitor?

Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set)
and tested on 2579 molecules (test set)
10-fold CV: ACC=0.77 / AUC=0.85
External: ACC=0.78 / AUC=0.86

 No
Log Kp (skin permeation)?

Skin permeation: QSPR model implemented from
Potts RO and Guy RH. 1992 Pharm. Res.

-5.35 cm/s

Druglikeness

Lipinski?

Lipinski (Pfizer) filter: implemented from
Lipinski CA. et al. 2001 Adv. Drug Deliv. Rev.
MW ≤ 500
MLOGP ≤ 4.15
N or O ≤ 10
NH or OH ≤ 5

 0.0
Ghose?

Ghose filter: implemented from
Ghose AK. et al. 1999 J. Comb. Chem.
160 ≤ MW ≤ 480
-0.4 ≤ WLOGP ≤ 5.6
40 ≤ MR ≤ 130
20 ≤ atoms ≤ 70

 None
Veber?

Veber (GSK) filter: implemented from
Veber DF. et al. 2002 J. Med. Chem.
Rotatable bonds ≤ 10
TPSA ≤ 140

 0.0
Egan?

Egan (Pharmacia) filter: implemented from
Egan WJ. et al. 2000 J. Med. Chem.
WLOGP ≤ 5.88
TPSA ≤ 131.6

 0.0
Muegge?

Muegge (Bayer) filter: implemented from
Muegge I. et al. 2001 J. Med. Chem.
200 ≤ MW ≤ 600
-2 ≤ XLOGP ≤ 5
TPSA ≤ 150
Num. rings ≤ 7
Num. carbon > 4
Num. heteroatoms > 1
Num. rotatable bonds ≤ 15
H-bond acc. ≤ 10
H-bond don. ≤ 5

 0.0
Bioavailability Score?

Abbott Bioavailability Score: Probability of F > 10% in rat
implemented from
Martin YC. 2005 J. Med. Chem.

0.55

Medicinal Chemistry

PAINS?

Pan Assay Interference Structures: implemented from
Baell JB. & Holloway GA. 2010 J. Med. Chem.

0.0 alert
Brenk?

Structural Alert: implemented from
Brenk R. et al. 2008 ChemMedChem

0.0 alert: heavy_metal
Leadlikeness?

Leadlikeness: implemented from
Teague SJ. 1999 Angew. Chem. Int. Ed.
250 ≤ MW ≤ 350
XLOGP ≤ 3.5
Num. rotatable bonds ≤ 7

 No; 1 violation:MW<1.0
Synthetic accessibility?

Synthetic accessibility score: from 1 (very easy) to 10 (very difficult)
based on 1024 fragmental contributions (FP2) modulated by size and complexity penaties,
trained on 12'782'590 molecules and tested on 40 external molecules (r2 = 0.94)

 2.11

Application In Synthesis of [ 131818-17-2 ]

* 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.

  • Downstream synthetic route of [ 131818-17-2 ]

[ 131818-17-2 ] Synthesis Path-Downstream   1~32

  • 1
  • [ 40138-16-7 ]
  • [ 131818-17-2 ]
  • [ 870703-82-5 ]
  • 2
  • [ 1692-15-5 ]
  • [ 131818-17-2 ]
  • [ 197435-52-2 ]
YieldReaction ConditionsOperation in experiment
75% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 90℃; for 14h; Suzuki coupling reaction of tert-butyl 4-bromophenylcarbamate (800 mg, 2.95 mmol) with 4-pyridineboronic acid (300 mg, 2.46 mmol) in the presence of Pd(PPh3)4 (57 mg, 0.05 mmol) and K2C03 (678 mg, 4.9 mmol) in dioxane- H20 (4: 1, 10 mL) at 90 C for 14 hr. tert-Butyl 4-(pyridin-4- yl)phenylcarbamate (600 mg, 75%) was obtained after flash column chromatography (DCM:MeOH, 20: 1).
  • 3
  • [ 24424-99-5 ]
  • [ 106-40-1 ]
  • [ 131818-17-2 ]
YieldReaction ConditionsOperation in experiment
99% In neat (no solvent); at 80℃; for 0.166667h;Green chemistry; General procedure: The reactions were carried out in a 50 mL RB flask under reduced pressure for 10 min at 80C unless reported differently. In a typical experiment, 5 mmol of amine was added to 5 mmol of BOC anhydride, and the reaction was allowed to proceed for 10 min. The desired product was obtained in a rotary evaporator under vacuum conditions.
96% With iron(III) trifluoromethanesulfonate; In neat (no solvent); at 20℃; for 0.1h;Green chemistry; General procedure: Fe(OTf)3 (1 mol%) was added to a magnetically stirred mixture of anamine (1 mmol) and Boc2O (1 mmol) at room temperature. The mixturewas stirred until completion of the reaction (TLC), then diluted withEtOAc and washed with water. The organic layer was dried overanhydrous MgSO4, then the solvent was distillated off under vacuum toyield the highly pure N-Boc derivatives
95% In neat (no solvent); at 100℃; for 0.0833333h;Microwave irradiation; Green chemistry; General procedure: Amine (1 mmol) and di-tert-butyl dicarbonate [(Boc)2O] (1.1 mmol) were placed in a microwave reaction vial. The LG microwave oven MG 555f was programmed to 300 W at 100 C. The reaction was monitored using TLC. After the reaction, ice water was added to the reaction mixture which resulted in the precipitation of the product. The solid product was merely filtered off and washed with excess cold water. The product was pure enough for all practical purposes. For characterization purpose, it was further purified by column chromatography (Neutral Alumina as adsorbent, solvent system: Hexane: Ethyl acetate (7.5:2.5)).
95% With 1,3-disulfonic acid imidazolium hydrogen sulfate; In neat (no solvent); at 20℃; for 0.2h;Green chemistry; General procedure: Amine (1 mmol) was added to the mixture of (Boc)2O (1 mmol) and DSIMHS (6.5 mg, ~ 0.02 mmol) with constant stirring at room temperature under solvent-free conditions. After completion of the reaction (monitored by TLC), ethyl acetate (3 × 5 mL) was added to the reaction mixture and the catalyst was decanted and washed with ethyl acetate (2 × 5 mL) and dried. The product was purified by column chromatography, using ethyl acetate-petroleum ether (2:8) eluent.
95% With phenylsulfonic acid supported on mesoporous silica SBA-15; In neat (no solvent); at 20℃; for 0.25h;Green chemistry; General procedure: An amine (1 mmol) was added to a magnetically stirred mixture of SBA-15-Ph-SO3H (1 mol %, 4 mg) and (Boc)2O (1.1 mmol) at room temperature. The progressof the reaction was monitored by thin-layer chromatography (TLC). After completion of the reaction, the reaction mixture was diluted with EtOH (5 mL)and centrifuged. Then the clear liquid was separated, and the residue containing the catalyst was kept for recovery. EtOH was distilled off under vacuum to yield the highly pure N-Boc derivative.
94% With pyridinium trifluroacetate; In neat (no solvent); at 20℃; for 0.833333h;Green chemistry; General procedure: To a magnetically stirred mixture of amine (1mmol) and (Boc)2O (1mmol) a catalytic amount of ionic liquid (0.2mmol) was added under solvent-free conditions at room temperature for the specified period of time. The progress of the reaction was monitored by TLC and GC-MS. The mixture extraction was carried out using ethyl acetate (2×5mL). The organic layer was washed with water (2×10mL) and dried over anhydrous Na2SO4. The solvent was evaporated under vacuum to yield highly pure N-Boc derivatives. In some cases, the purification was done by column chromatography using silica gel (60-120) by hexane-ethyl acetate as eluent to get a pure product.
93% With guanidine hydrochloride; In ethanol; at 35 - 40℃; for 1h; General procedure: Amine (1 mmol) was added to a magnetically stirred solution of guanidine hydrochloride (15 mol%) and di-tert-butyl dicarbonate (1.2 mmol) in EtOH (1 mL), at 35-40C and stirred for appropriate time (Table 1). After completion of the reaction (followed by TLC or GC), EtOH was evaporated under vacuum and the residue either was washed with water to remove the catalyst or was dissolved in CH2Cl2 (or EtOAc) and filtered off to separate out the catalyst. Evaporation of the organic solvent (if used in work up) gives almost a pure product. In the cases of using an excess (Boc)2O the product was washed with petroleum ether or hexane to recover the residual (Boc)2O. If necessary, the product was further purified either by crystallization (hexane and dichloromethane, or diethyl ether and petroleum ether) or silica gel column chromatography using EtOAc-hexane (1: 6) as eluent.
92% With choline chloride; urea; at 50℃;Green chemistry; General procedure: A dried test tube, equipped with a magnetic stir bar, wascharged with 0.5 cm3 DES, amine derivatives(0.5 mmol), and Boc2O (0.5 mmol) and the mixture washeated at 50 C until the reaction was complete (monitoredby TLC and IR). After this time, 5 cm3 water wasadded and in the most cases a white solid was obtained.The solid product was collected by filtration and washedsuccessively with water and recrystallized from ethanolto get the pure final product [51-60]. The viscousproducts extracted with ethyl acetate and were purifiedby column chromatography, using ethyl acetate-petroleumether.
90% With dmap; triethylamine; In dichloromethane; at 0 - 20℃; To a mixture of 4-bromoaniline (950 mg, 5.6 mmol), triethylamine (678 mg, 6.7 mmol) and DMAP (73 mg, 0.56 mmol) in DCM (30 mL) was added Boc20 (1.22g, 5.6 mmol) at 0 C. The reaction mixture was allowed to warm to room temperature and stirred for 2 hr. After the reaction was quenched with 5% NaHC03, the mixture was extracted with DCM (3 x 20 mL). The organic layer was combined and dried over anhydrous MgS04. tert-Butyl 4-bromophenylcarbamate (1.36 g, 90%) was obtained after flash column chromatography (hexane:ethyl acetate, 4: 1).
90% For the N-boc protection of amines, to solution of diboc (1 mmol) in ethanol (5 ml) was added {K*18-crown-6]Br3}n (0.001 mmol). The solution was stirred at room temperature for 1 min. The amine (1 mmol) was then added and solution as stirred at room temperature for an appropriate time (table 1). After completion of the reaction, the solvent was removed by water bath distillation. To the residue was added ethyl acetate (5 ml) and the mixture was filtered (the catalyst is insoluble in n-hexane and ethyl acetate). The solid was washed with ethyl acetate ()10 ml*2) amd combined filtrates were reduced to dryness to yield the pure products.
89% With sulfonic acid-functionalized nanoporous titania catalyst; In neat (no solvent); at 20℃; for 0.583333h; General procedure: An amine (1 mmol) was added to a magnetically stirred mixture of TiO2-Pr-SO3H (10 mg) and di-tert-butyl dicarbonate (240 mg, 1.1 mmol) at room temperature. The mixture was stirred until completion of the reaction (TLC), then diluted with EtOAc (10 mL) and filtered. The residue contains only the catalyst and kept for recovery. The filtrate was washed with water (3 x 20 mL) and brine (2 x 20 mL) and dried over anhydrous MgSO4, then solvent was distillated off under vacuum to yield the highly pure N-Boc derivative.
83% In toluene; at 70℃; A solution of 4-bromoaniline (5.02 g, 29. 18 mmol) and DI-TERI-BUTYL dicarbonate (7.64 g, 35.02 mmol) in toluene (150 mL) was stirred at 70C overnight. After the removal of toluene under reduced pressure, the residue was dissolved with ethyl acetate. The solution was washed with 0. 1 M hydrochloric acid and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by recrystallization from hexane to give tert-butyl (4-bromophenyl) - carbamate (6.56 g, 83%) as colorless needle crystals.
81% at 20℃; for 3h;Green chemistry; General procedure: To (Boc)2O (1.0 mmol), was added an amine (1.0 mmol)and the mixture was stirred at room temperature for the time indicated in Table 1. The progress of the reaction was monitored by TLC. In most cases, the BOC protected product was found to be sufficiently pure and did not require any further purification. In some cases the product was purified by silica gel column chromatography (1:2; EtOAc/ Petrolium ether).All products were characterized by IR, 1H NMR and their physical properties.
80% With NaH; In tetrahydrofuran; Part C. Preparation of 1-Bromo-4-t-butoxycarbonylaminobenzene To a mixture of NaH (4.13, 0.14 mol) in THF was added 4-bromoaniline. The resulting mixture was refluxed under N2 for 1 h. It was then cooled and di-t-butyl dicarbonate (33 g, 0.15 mol) was added. After stirred for 1/2 h, more NaH (4.13 g, 0.14 mol) was added and the reaction mixture was ref luxed under N2 overnight. The reaction mixture was cooled and carefully quenched with water. The mixture was extracted with ether. The combined organic solution was washed with saturated aqueous NH4 Cl and saturated aqueous NaHCO3, dried over MgSO4, and concentrated. It was then purified by chromatography on silica gel eluted with hexane to yield 27.2 g of the desired product (80%). 1 H-NMR (CDCl3): d 1.52 (s, 9H); 6.48 (br s, 1H); 7.27 (d, 2H); 7.40 (d, 2H).
80% Part C. Preparation of 1-Bromo-4-t-butoxycarbonylaminobenzene To a mixture of NaH (4.13, 0.14 mol) in THF was added 4-bromoaniline.. The resulting mixture was refluxed under N2 for 1h.. It was then cooled and di-t-butyl dicarbonate (33 g, 0.15 mol) was added.. After stirred for 1/2h, more NaH (4.13 g, 0.14 mol) was added and the reaction mixture was refluxed under N2 overnight.. The reaction mixture was cooled and carefully quenched with water.. The mixture was extracted with ether.. The combined organic solution was washed with saturated aqueous NH4Cl and saturated aqueous NaHCO3, dried over MgSO4, and concentrated.. It was then purified by chromatography on silica gel eluted with hexane to yield 27.2 g of the desired product (80%).. 1HNMR (CDCl3): d 1.52 (s, 9H); 6.48 (br s, 1H); 7.27 (d, 2H); 7.40 (d, 2H).
80% With iron oxide; In ethanol; at 20℃; for 2h;Green chemistry; General procedure: A round-bottom flask (10 mL), which contains EtOH(5 mL), was charged with a solution of diboc (1-2 mmol),nano-Fe3O4 (3 mol%, 0.007 g) and the amine (1 mmol). The mixture was stirred at room temperature for the appropriate time (Table 3). After completion of the reaction, the catalyst was collected by a magnet and separated from the solution of product and the remaining starting materials.After drying and evaporation of the solvent, the resulting solid was recrystallized from n-hexane or ethyl acetate(5 mL) to give the pure product. The recovered catalyst was washed with EtOH, dried and reused for the next run. The catalyst was recovered and reused for six times without any significant changes in the yield and the reaction time.
80% With piperazine functionalized zirconium-Fe3O4-MCM-41 magnetic nanoparticles; In neat (no solvent); at 20℃; for 0.5h; General procedure: In a round-bottom flask (10 mL), 1 mmol of the amine as the substrate was added to a magnetically stirred mixture of di-tert-butyldicarbonate [(Boc)2O](1 mmol, 0.218 g) and Fe3O4atMCM-41atZr-piperazine nanocatalyst (0.03 g) at ambient temperature. When the reaction was fulfilled, as indicated by TLC (n-hexane:ethyl acetate; 7:3), the mixture was purified with ethanol. Afterward, in the presence of a magnetic stirrer bar, Fe3O4atMCM-41atZr-piperazine nanocatalyst was separated, concurrently turning clear the reaction mixture. Eventually, after washing the organic phase with 10% aqueous solution of sodium bicarbonate (2×20 mL), it was dried over Na2SO4. The solvent was removed under reduced pressure to acquire the favorable product in good to high yields.
64% In toluene; at 70℃; for 16h; Step-1: Synthesis of tert-butyl (4-bromophenyl)carbamate To a stirred solution of 4-bromoaniline (10 g, 58 mmol) in toluene (200 mL) was added boc anhydride (12.6 g, 58 mmol). The reaction mixture was stirred for 16 h at 70 C, after completion of reaction (monitored by TLC), excess of toluene was removed under reduced pressure. Residue was diluted with water (250 mL) solid obtained was filtered and dried under reduced pressure to obtain desired compound (10.2 g, 64%).
49% With triethylamine; In dichloromethane; at 18℃; for 16h; Into a 250 mL round bottom flask were added p-bromoaniline (5.16 g, 30 mmol), di(tert-butyl) carbonate (7.86 g, 36 mmol) and dichloromethane (100 mL). To the stirred solution triethylamine (1 mL, 7 mmol) was added dropwise in 6 h and stirring continued for additional 10 h at room temperature. The solvent was then removed under reduced pressure and the residual was submitted to a silica gel column, after eluted with CH2Cl2, 4 was obtained as a white solid (4.0 g, 49%). 1H NMR (400 MHz, DMSO-d6) delta 9.5 (s, 1H), 7.42(s, 4H), 1.47 (s, 9H).
With sodium hydrogencarbonate; In n-heptane; dichloromethane; water; ethyl acetate; a tert-butyl N-(4-bromophenyl)carbamate Di-tert-butyl-dicarbonate (16.5 g, 0.0756 mol) was dissolved in anhydrous dichloromethane (150 mL), cooled to 0 C. and the solution of 4-bromoaniline (9.75 g, 0.0567 mol) in anhydrous dichloromethane (50 mL) was added dropwise. The mixture was warmed up to ambient temperature and stirred under an atmosphere of nitrogen for sixteen hours. The organic phase was washed with saturated solution of sodium bicarbonate in water (120 mL), dried with magnesium sulfate and concentrated under reduced pressure to yield a yellow oil which was purified by flash chromatography on silica using ethyl acetate/n-heptane (3:97) as mobile phase to yield tert-butyl N-[(4-bromophenyl)carbamate (7.1 g, 0.0257 mol) as a colorless oil. 1H NMR (DMSO-d6, 400 MHz) delta 9.49 (s, 1H), 7.42 (s, 4H) 1.47 (s, 9H).
With sodium hydrogencarbonate; In chloroform; To a mixture of 34.4 g of p-bromoaniline in 400 ml of chloroform is added 200 ml of saturated sodium bicarbonate, followed by 51 g di-t-butyl dicarbonate in 50 ml of chloroform. The mixture is first stirred at room temperature for 4 hours and then heated under reflux overnight to yield 4-(t-butoxycarbonylamino)-bromobenzene, m.p. 101-103.
With sodium hydrogencarbonate; In n-heptane; dichloromethane; water; ethyl acetate; a) tert-butyl N-(4-bromophenyl)carbamate Di-tert-butyl-dicarbonate (16.5 g, 0.0756 mol) was dissolved in anhydrous dichloromethane (150 mL), cooled to 0 C. and the solution of 4-bromoaniline (9.75 g, 0.0567 mol) in anhydrous dichloromethane (50 mL) was added dropwise. The mixture was warmed up to ambient temperature and stirred under an atmosphere of nitrogen for sixteen hours. The organic phase was washed with saturated solution of sodium bicarbonate in water (120 mL), dried with magnesium sulfate and concentrated under reduced pressure to yield a yellow oil which was purified by flash chromatography on silica using ethyl acetate/n-heptane (3:97) as mobile phase to yield tert-butyl N-[(4-bromophenyl)carbamate (7.1 g, 0.0257 mol) as a colorless oil. 1H NMR (DMSO-d6, 400 MHz) delta 9.49 (s, 1H), 7.42 (s, 4H) 1.47 (s, 9H).
In tetrahydrofuran; at 50℃; for 5h; 5.0 mmol of 4-bromoaniline (0.86 g) is dissolved in 10 mL [OF THF ;] 1.09 g (5.0 mmol) of di-tert-butyl dicarbonate is added, and the resultant solution is warmed to [50 C FOR] 5 hours. The reaction is partitioned between water and ethyl acetate; the organic layer is washed with brine, dried over [NA2S04,] and and concentrated to give a white solid. This crude material is dissolved in 20 mL of dry THF and cooled in an ice [BATH ;] and 250 mg (1.25 eq) of NaH (60% oil dispersion) is added portionwise. Gas evolves, leaving a foamy semisolid after 15 min. Additional THF (10 mL) is added to break up the foam, followed by 0. [50] mL (1.6 eq) of [IODOMETHANE.] The resultant mixture is stirred overnight, warming slowly to ambient temperature. The reaction mixture is added carefully to aqueous IN [H3P04] (some gas evolves.), the resulting mixture is extracted with ethyl acetate. The organic layer is washed with brine and dried over [NA2S04.] The crude product is purified by silica gel chromatography, eluting with a gradient [OF 0->10%] ethyl [ACETATE/HEXANES,] providing 1.08 g (76% overall) of the title compound as a slightly yellowish oil.
In toluene; at 70℃; for 15h; p-Bromoaniline (13.0 g, 76 mmol) and Boc2O (19.8 g, 91 mmol) were dissolved in toluene (380 mL) and stirred at 70 C. for 15 h. The reaction mixture was cooled to RT, evaporated to dryness, re-dissolved in EtOAc and washed with 0.1M HCl and brine. The organic solution was dried over anhydrous MgSO4, evaporated to dryness and purified by flash column chromatography, using 5% to 10% EtOAc in hexane as the eluent, to obtain the Boc-protected aniline (23 g). The Boc-protected bromoaniline (10.7 g, 39.2 mmol) was dissolved in anhydrous THF (75 mL) in a flask equipped with an overhead stirrer. The solution was cooled to 0 C. and MeLi (1.2 M in Et2O, 33 mL, 39.2 mmol) was added drop wise while maintaining the internal temperature below 7 C. The reaction mixture was stirred at 0 C. for 15 min and then cooled to -78 C. before n-BuLi (2.4 M in hexane, 17 mL, 39.2 mmol) was added drop wise, maintaining the internal temperature below -70 C.). The reaction mixture was stirred at -78 C. for 1 h, B(OEt)3 (17 mL, 98 mmol) was added drop wise (internal temperature<-65 C.) and stirring was continued for 45 min at -78 C. and at 0. C. for 1 h. The reaction mixture was then treated with 5% aqueous HCl (100 mL, to pH 1) for 15 min and NaCl(s) was added to saturate the aqueous layer. The aqueous layer was extracted with 0.5 M NaOH (4×100 mL) and the combined aqueous layers were acidified with 5% HCl (150 mL, to pH 1) and extracted with Et2O (3×200 mL). The combined organic layers were dried over anhydrous MgSO4, filtered and concentrated to give the N-Boc carbamate of 4-aminophenylboronic acid as a solid (7.5 g).
With triethylamine; In tetrahydrofuran; at 0 - 20℃; for 20h; 2 mL (1.2 eq. ) Triethylamine are added to a solution of 2g (11.6 MMOL) p-bromo-aniline in 25 mL THF. The reaction mixture is cooled to 0C and treated with 2.66 g (1.05 eq. ) Boc20 under continuous stirring, then allowed to reach 20C, stirred for an additional 20 hours and extracted with water/ethyl acetate. The combined organic phases are washed with brine, dried over magnesium sulfate and evaporated. The residue is column chromatographed (hexane, HEXANE/ETHYL acetate 7: 1 then 4: 1) to yield after evaporation and recrystallization from hexane the desired product as a white powder.
16.73 g In tetrahydrofuran; at 80℃; for 24h; i) A solution of 4-bromoanilin (12.46 g) and di-tert-butyl dicarbonate (18.97 g) in THF (500 mL) was stirred at 80 C for 24 hours. After cooling to room temperature the solvent was removed under reduced pressure and the remaining solid was transferred to a filter and washed with heptane. The filtrate was concentrated under reduced pressure and the remaining solids were washed with heptanes one more time. The combined solids were dried under reduced pressure at 40 C to give tert-butyi (4- bromophenvDcarbamate (16.73 g) as a white solid.
With potassium carbonate; In tetrahydrofuran; at 20℃; To a solution of 4-bromoaniline (60A) (1.71 g, 10.0 mmol) in THF (100 mL) and water (10 mL) was added K2CO3 (4.14 g, 30.0 mmol) and di-ter/-butyl dicarbonate (3.27 g, 15.0 mmol). The mixture was stirred at room temperature overnight, diluted with water (50 mL), and extracted with ethyl acetate (50 mL x 3). The combined organic layers was washed with water (100 mL) and brine (100 mL), dried over anhydrous sodium sulfate, concentrated, and purified with flash column chromatography on silica gel (ethyl acetate in petroleum ether, 30% v/v) to afford Compound 333A. LC-MS (ESI) m/z: 216 [M-55]+; 'H-NMR (CDCh, 400 MHz): d (ppm) 1.52 (s, 9H), 6.48 (brs, 1H), 7.26 (d, J= 8.8 Hz, 2H), 7.39 (d, J= 8.8 Hz, 2H).

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  • 4
  • [ 500-22-1 ]
  • [ 131818-17-2 ]
  • [4-(hydroxy-pyridin-3-yl-methyl)-phenyl]-carbamic acid <i>tert</i>-butyl ester [ No CAS ]
  • 5
  • [ 100-54-9 ]
  • [ 131818-17-2 ]
  • [ 147696-69-3 ]
  • 6
  • [ 131818-17-2 ]
  • 2-benzenesulfonylamino-3-[(5-bromo-thiophene-2-carbonyl)-amino]-propionic acid <i>tert</i>-butyl ester [ No CAS ]
  • 2-benzenesulfonylamino-3-[5-(4-<i>tert</i>-butoxycarbonylamino-phenyl)-thiophene-2-carbonyl]-amino}-propionic acid <i>tert</i>-butyl ester [ No CAS ]
  • 7
  • [ 95-16-9 ]
  • [ 131818-17-2 ]
  • [ 6278-73-5 ]
  • (4-benzothiazol-2-yl-phenyl)-carbamic acid <i>tert</i>-butyl ester [ No CAS ]
  • 8
  • [ 2942-13-4 ]
  • [ 131818-17-2 ]
  • [ 43036-17-5 ]
  • [4-(6-methoxy-benzothiazol-2-yl)-phenyl]-carbamic acid <i>tert</i>-butyl ester [ No CAS ]
  • 9
  • [ 131818-17-2 ]
  • [ 10387-40-3 ]
  • [ 937737-95-6 ]
  • 10
  • [ 2213-43-6 ]
  • [ 131818-17-2 ]
  • C16H25N3O2 [ No CAS ]
  • 11
  • [ 59983-39-0 ]
  • [ 131818-17-2 ]
  • C17H27N3O3 [ No CAS ]
  • 12
  • [ 131818-17-2 ]
  • [ 312760-48-8 ]
  • 13
  • [ 131818-17-2 ]
  • [ 312760-49-9 ]
  • 14
  • [ 131818-17-2 ]
  • (S)-2-Benzenesulfonylamino-3-[5-(4-guanidino-phenyl)-thiophene-2-carbonyl]-amino}-propionic acid; compound with trifluoro-acetic acid [ No CAS ]
  • 15
  • [ 131818-17-2 ]
  • [4-(pyridine-3-carbonyl)-phenyl]-carbamic acid <i>tert</i>-butyl ester [ No CAS ]
  • 16
  • [ 131818-17-2 ]
  • [4-(hydroxyimino-pyridin-3-yl-methyl)-phenyl]-carbamic acid <i>tert</i>-butyl ester [ No CAS ]
  • 17
  • [ 131818-17-2 ]
  • 5-[1-(4-Amino-phenyl)-1-pyridin-3-yl-meth-(E)-ylideneaminooxy]-pentanoic acid ethyl ester [ No CAS ]
  • 18
  • [ 131818-17-2 ]
  • 2-pyridin-3-yl-thiazolidine-4-carboxylic acid [4-(pyridine-3-carbonyl)-phenyl]-amide [ No CAS ]
  • 19
  • [ 131818-17-2 ]
  • 2-Pyridin-3-yl-thiazolidine-4-carboxylic acid (4-[(Z)-hydroxyimino]-pyridin-3-yl-methyl}-phenyl)-amide [ No CAS ]
  • 20
  • [ 131818-17-2 ]
  • 3-pyridin-3-yl-1<i>H</i>-pyrrolo[1,2-<i>c</i>]thiazole-7-carboxylic acid [4-(pyridine-3-carbonyl)-phenyl]-amide [ No CAS ]
  • 21
  • [ 131818-17-2 ]
  • 3-pyridin-3-yl-1<i>H</i>-pyrrolo[1,2-<i>c</i>]thiazole-7-carboxylic acid [4-(hydroxyimino-pyridin-3-yl-methyl)-phenyl]-amide [ No CAS ]
  • 22
  • [ 131818-17-2 ]
  • 5-[1-(4-tert-Butoxycarbonylamino-phenyl)-1-pyridin-3-yl-meth-(E)-ylideneaminooxy]-pentanoic acid ethyl ester [ No CAS ]
  • 23
  • [ 131818-17-2 ]
  • 5-[1-Pyridin-3-yl-1-{4-[(2-pyridin-3-yl-thiazolidine-4-carbonyl)-amino]-phenyl}-meth-(E)-ylideneaminooxy]-pentanoic acid ethyl ester [ No CAS ]
  • 24
  • [ 131818-17-2 ]
  • 5-(pyridin-3-yl-{4-[(3-pyridin-3-yl-1<i>H</i>-pyrrolo[1,2-<i>c</i>]thiazole-7-carbonyl)-amino]-phenyl}-methyleneaminooxy)-pentanoic acid ethyl ester [ No CAS ]
  • 26
  • [ 131818-17-2 ]
  • 3-((Z)-3-Dimethylamino-propenyl)-4-methoxy-N-(4-pyridin-4-yl-phenyl)-benzamide [ No CAS ]
  • 27
  • [ 131818-17-2 ]
  • 3-((E)-3-Dimethylamino-propenyl)-4-methoxy-N-(4-pyridin-4-yl-phenyl)-benzamide [ No CAS ]
  • 28
  • [ 131818-17-2 ]
  • 3-(3-Dimethylamino-prop-1-ynyl)-4-methoxy-N-(4-pyridin-4-yl-phenyl)-benzamide [ No CAS ]
  • 29
  • [ 131818-17-2 ]
  • [ 3365-13-7 ]
  • 30
  • [ 131818-17-2 ]
  • 4'-Amino-biphenyl-2-carbaldehyde [ No CAS ]
  • 31
  • [ 131818-17-2 ]
  • [ 194664-63-6 ]
  • 32
  • [ 100-39-0 ]
  • [ 131818-17-2 ]
  • [ 693792-98-2 ]
YieldReaction ConditionsOperation in experiment
100% With sodium hydride; In tetrahydrofuran; at 0 - 60℃; for 5h; To a solution of tert-butyl (4-bromophenyl) carbamate (0.50 g, 1.84 mmol) and benzyl bromide (0.262 mL, 2.20 mmol) in tetrahydrofuran (20 mL) was added sodium hydride (60% in oil, 0. 11 g, 2.76 mmol) at 0C, and the mixture was stirred at room temperature for 1 hour and THEN-AT 60C for 4 hours. After cooled to room temperature, the reaction mixture was quenched with saturated ammonium chloride solution, and extracted with ethyl acetate. The separated organic phase was washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by column chromatography on silica-gel (hexane: ethyl acetate,. 9: 1) to give ter-butyl benzyl (4-bromophenyl) carbamate (0.68 g, 100%) as colorless oil.
 

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