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Structure of 3163-27-7 * 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.
With ethyl 2,2-dibromoacetoacetate; triphenylphosphine In dichloromethane at 20℃; for 0.5 h;
General procedure: Ethyl α,α-dibromoacetoacetate 2a (0.41 mmol, 1.2 equiv), alcohols 1a-1s (0.34 mmol, 1.0 equiv) and Ph3P (0.68 mmol, 2.0 equiv) were added under ambient temperature to 3 mL of DCE in air. After stirred at room temperature for appropriate time (monitored by TLC), the reaction was quenched by addition of H2O (3 mL) and then extracted with ethyl acetate (3×3 mL). The combined organic layer was washed with brine, dried over Na2SO4, and concentrated. The crude product was purified by column chromatography on silica gel with petroleum ether or mixture of petroleum ether and ethyl acetate as eluent to afford the corresponding products 3a-3s.
53%
With pyridine; phosphorus tribromide In toluene at 0 - 20℃; for 1.25 h;
4-methyl-7-(naphthalene-1-ylmethoxy)-2H-chromen-2-one (4Z) l\\-Ε.-\\ΔΛ-SUQQΛP<; 1 -Naphthalene methanol (2.0 g, 12.7 mmol) was dissolved in toluene (30 ml_) and pyridine (1.02 mL, 12.7 mmol) was added. The solution was cooled to 0 0C. PBr3 (1.19 ml_, 12.7 mmol) was added dropwise over 15 min. The reaction mixture was then brought up to room temperature and stirred for 1 h. The mixture was washed with K2CO3 solution and extracted with EtOAc (3 x 30 mL). The EtOAc layer was washed with brine and dried (MgSO4). The solvent was evaporated off in-vacuo to give 1- (bromomethyl)naphthalene (1.5 g, 53percent) as a colourless oil, This intermediate was used in the following reaction.
Reference：
[1] Synthetic Communications, 2010, vol. 40, # 11, p. 1646 - 1649
[2] Organic Letters, 2003, vol. 5, # 8, p. 1167 - 1169
[3] Tetrahedron Letters, 2014, vol. 55, # 1, p. 90 - 93
[4] Canadian Journal of Chemistry, 1981, vol. 59, p. 2629 - 2641
[5] Tetrahedron, 2003, vol. 59, # 52, p. 10453 - 10463
[6] Bulletin of the Chemical Society of Ethiopia, 2012, vol. 26, # 2, p. 305 - 309
[7] Beilstein Journal of Organic Chemistry, 2011, vol. 7, p. 1648 - 1655
[8] Patent: WO2010/125350, 2010, A1, . Location in patent: Page/Page column 53-54
[9] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1922, vol. 175, p. 105
[10] Journal of the American Chemical Society, 1933, vol. 55, p. 2975,2976
[11] Journal of the Chemical Society, 1957, p. 2796,2799
[12] Journal of the American Chemical Society, 1953, vol. 75, p. 353
[13] Patent: US5859007, 1999, A,
[14] Polish Journal of Chemistry, 2007, vol. 81, # 5-6, p. 947 - 969
[15] Tetrahedron Letters, 2011, vol. 52, # 1, p. 13 - 16
[16] Organic and Biomolecular Chemistry, 2013, vol. 11, # 9, p. 1463 - 1467
[17] Chemical Communications, 2014, vol. 50, # 28, p. 3692 - 3694
[18] Organic Letters, 2014, vol. 16, # 2, p. 484 - 487
[19] Organic Letters, 2014, vol. 16, # 17, p. 4424 - 4427
2
[ 66-77-3 ]
[ 3163-27-7 ]
Reference：
[1] Tetrahedron Letters, 2000, vol. 41, # 27, p. 5161 - 5164
[2] Journal of the Chemical Society, 1957, p. 2796,2799
[3] Chemical Communications, 2014, vol. 50, # 28, p. 3692 - 3694
[4] Organic Letters, 2014, vol. 16, # 2, p. 484 - 487
[5] Organic Letters, 2014, vol. 16, # 17, p. 4424 - 4427
3
[ 90-12-0 ]
[ 3163-27-7 ]
Yield
Reaction Conditions
Operation in experiment
80%
With tribromo-isocyanuric acid In ethyl acetate for 6 h; Reflux; Green chemistry
General procedure: a solution of the arene (2.0 mmol) and TBCA (0.25 g, 0.68 mmol) in EtOAc (20 mL) was refluxed for 6 h with stirring. At the end of the reaction, the precipitated cyanuric acid was then separated by filtration and the filtrate was evaporated to dryness under reduced pressure. The residue was passed through a short chromatographic column (SiO2, eluted with 15:1 hexane–ethyl acetate) to give the purified products.
Reference：
[1] Bulletin of the Chemical Society of Japan, 1991, vol. 64, # 11, p. 3355 - 3362
[2] Advanced Synthesis and Catalysis, 2008, vol. 350, # 13, p. 2033 - 2038
[3] Tetrahedron Letters, 2009, vol. 50, # 16, p. 1861 - 1865
[4] Monatshefte fur Chemie, 2003, vol. 134, # 7, p. 991 - 1014
[5] Advanced Synthesis and Catalysis, 2018, vol. 360, # 21, p. 4197 - 4204
[6] Tetrahedron Letters, 2015, vol. 56, # 49, p. 6843 - 6845
[7] Journal of Organic Chemistry, 2017, vol. 82, # 2, p. 1114 - 1126
[8] Journal of Medicinal Chemistry, 2014, vol. 57, # 6, p. 2589 - 2600
[9] Organic and Biomolecular Chemistry, 2016, vol. 14, # 15, p. 3699 - 3714
[10] Canadian Journal of Chemistry, 1985, vol. 63, p. 3140 - 3146
[11] Journal of the Chemical Society, 1927, p. 3104
[12] Chemische Berichte, 1922, vol. 55, p. 1854
[13] Justus Liebigs Annalen der Chemie, 1924, vol. 436, p. 75
[14] Helvetica Chimica Acta, 1936, vol. 19, p. 581,586
[15] Recueil des Travaux Chimiques des Pays-Bas, 1937, vol. 56, p. 853,856
[16] Annales de Chimie (Cachan, France), 1948, vol. <12> 3, p. 62,84
[17] Journal of the Chemical Society, 1946, p. 830
[18] Chemische Berichte, 1916, vol. 49, p. 2823
[19] Chemische Berichte, 1909, vol. 42, p. 2381
[20] Chemische Berichte, 1926, vol. 59, p. 2511[21] Chemische Berichte, 1927, vol. 60, p. 2371
[22] Il Farmaco; edizione scientifica, 1974, vol. 29, # 3, p. 217 - 224
[23] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1976, p. 1104 - 1111
[24] Journal of the American Chemical Society, 1975, vol. 97, # 8, p. 2198 - 2205
[25] Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 1982, vol. 78, p. 3467 - 3476
[26] Chemical and pharmaceutical bulletin, 1994, vol. 42, # 3, p. 512 - 520
[27] Chemical and Pharmaceutical Bulletin, 1997, vol. 45, # 2, p. 297 - 304
[28] Polish Journal of Chemistry, 2001, vol. 75, # 3, p. 429 - 441
[29] Synlett, 2005, # 18, p. 2837 - 2842
[30] Patent: WO2007/27917, 2007, A2, . Location in patent: Page/Page column 28-29
[31] Synthetic Communications, 2010, vol. 40, # 17, p. 2617 - 2623
[32] Organic Letters, 2013, vol. 15, # 16, p. 4194 - 4197
[33] Biochemical and Biophysical Research Communications, 2013, vol. 437, # 4, p. 620 - 624
[34] European Journal of Organic Chemistry, 2014, vol. 2014, # 16, p. 3402 - 3410
[35] Patent: CN105218382, 2016, A, . Location in patent: Paragraph 0044-0046
4
[ 33250-32-7 ]
[ 3163-27-7 ]
Reference：
[1] Bulletin of the Chemical Society of Japan, 1991, vol. 64, # 4, p. 1410 - 1412
Reference：
[1] Journal of the Indian Chemical Society, 1999, vol. 76, # 4, p. 216 - 217
[2] Journal of Organic Chemistry, 1947, vol. 12, p. 760,761, 763
[3] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1936, vol. 202, p. 73
[4] Patent: 2212099, 1938, ,
7
[ 558-13-4 ]
[ 4780-79-4 ]
[ 3163-27-7 ]
Reference：
[1] Patent: US5576313, 1996, A,
8
[ 86-55-5 ]
[ 3163-27-7 ]
Reference：
[1] Canadian Journal of Chemistry, 1981, vol. 59, p. 2629 - 2641
[2] Journal of the Chemical Society, 1957, p. 2796,2799
With bromocyane; triphenylphosphine In dichloromethane at 20℃; Inert atmosphere;
99%
With dibromo sulfoxide In toluene for 7h;
99%
With ethyl α,α-dibromoacetoacetate; triphenylphosphine In dichloromethane at 20℃; for 0.5h;
General Procedure for the Synthesis of products
General procedure: Ethyl α,α-dibromoacetoacetate 2a (0.41 mmol, 1.2 equiv), alcohols 1a-1s (0.34 mmol, 1.0 equiv) and Ph3P (0.68 mmol, 2.0 equiv) were added under ambient temperature to 3 mL of DCE in air. After stirred at room temperature for appropriate time (monitored by TLC), the reaction was quenched by addition of H2O (3 mL) and then extracted with ethyl acetate (3×3 mL). The combined organic layer was washed with brine, dried over Na2SO4, and concentrated. The crude product was purified by column chromatography on silica gel with petroleum ether or mixture of petroleum ether and ethyl acetate as eluent to afford the corresponding products 3a-3s.
91%
With pyridine; phosphorus tribromide In benzene at 55℃; for 6h;
91%
With pyridine; phosphorus tribromide In toluene at 60℃; for 12h;
89%
With N-Bromosuccinimide; 1,1,1,3,3,3-hexamethyldisilazane potassium; (1,3,4)-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene In dichloromethane at 20℃; for 6h; Inert atmosphere;
85%
With phosphorus tribromide at 0 - 20℃; for 20h;
84%
With 1,1,1,2,2,2-hexamethyldisilane In chloroform for 3.5h; Reflux;
74%
With functionalised triphenylphosphine monolith In dichloromethane for 1h; Inert atmosphere;
74%
With phosphorus tribromide In tetrahydrofuran at 0 - 10℃; for 2h;
53%
With pyridine; phosphorus tribromide In toluene at 0 - 20℃; for 1.25h;
4-methyl-7-(naphthalene-1-ylmethoxy)-2H-chromen-2-one (4Z) l-Ε.-ΔΛ-SUQQΛP0C. PBr3 (1.19 ml_, 12.7 mmol) was added dropwise over 15 min. The reaction mixture was then brought up to room temperature and stirred for 1 h. The mixture was washed with K2CO3 solution and extracted with EtOAc (3 x 30 mL). The EtOAc layer was washed with brine and dried (MgSO4). The solvent was evaporated off in-vacuo to give 1- (bromomethyl)naphthalene (1.5 g, 53%) as a colourless oil, This intermediate was used in the following reaction.
With hydrogen bromide
With sulfuric acid; hydrogen bromide
With pyridine; phosphorus tribromide; benzene
With bromine; triphenylphosphine In Carbon tetrachloride; hexane; ethyl acetate
1-Bromomethylnaphthalene
1-Bromomethylnaphthalene To a stirring solution of 912 mg (3.48 mmol, 1.2 equiv) of triphenylphosphine in 10 mL of CCl4 at 0° C. is added 180 μL (3.48 mmol, 1.2 equiv) of Br2. The resulting orange-yellow suspension is stirred 10 min at 0° C., then a solution of 500 mg (3.16 mmol) of 1-Naphthalenemethanol in 5 mL of CCl4 is added over 2 min. The resulting solution is stirred 1.5 h at RT, and the solvent is removed in vacuo. Purification of the residue by silica gel flash column chromatography using hexane/EtOAc 10/1 as eluent afforded 670 mg of the title compound as a clear, colorless oil: 1 H NMR (CDCl3, 300 MHz) δ8.18 (d, 1H), 7.83 (m, 2H), 7.63-7.38 (m, 4H), 4.98 (s, 2H); Rf =0.65 in hexane/EtOAc 5/1.
With phosphorus tribromide
With 1,1,1,3,3,3-hexabromoacetone; triphenylphosphine In acetonitrile at 40℃; for 2h; Inert atmosphere;
3. General procedure for the synthesis of benzyl bromides
A mixture of alcohol (1.2 mmol) and triphenylphosphine (1.8 mmol) was stirred in dry acetonitrile (6 mL) for 15 min. Hexabromoacetone (0.6 mmol) was added and the stirring continued at 40° under a nitrogen atmosphere. Conversion of the alcohol into the bromide was followed by 1H NMR analysis on a sample previously quenched with cold water.
With phosphorus tribromide In dichloromethane at 20℃; for 1h;
With phosphorus tribromide In dichloromethane at 0℃; for 0.5h;
With hydrogen bromide; acetic acid at 0℃; for 0.5h;
With hydrogen bromide In acetic acid at 0℃; for 0.5h;
With 1-chloro-1-(dimethylamino)-2-methyl-1-propene; lithium bromide In [D3]acetonitrile at 20℃; Inert atmosphere;
Deoxyhalogenations of cyclopentanol and 1naphtalenemethanol (Table 1)
General procedure: TMCE (1 mmol) was syringed in a solution of 1 mmol of 1-naphthalenemethanol or cyclopentanol and dry LiBr, LiI or KI (2.5 mmol) in deuterated acetonitrile or chloroform under argon atmosphere. The suspension was stirred at room temperature for 15-30 min 13C NMR of the crude mixtures revealed the formationof the titled compounds through detection of the characteristic signals at δ 32.04 ppm, δ 4.17 ppm corresponding to naphthyl CH2-Br, CH2-I respectively and at δ 53.59 ppm, δ 29.81 ppm forcyclopentyl CH-Br, CH-I respectively.
With phosphorus tribromide In dichloromethane at 0℃; for 0.25h;
With nickel(II) nitrate hexahydrate; aluminium In water at 20℃; for 48h; Inert atmosphere;
2.1 General procedure for the homo-coupling ofbenzyl halides
General procedure: To a suspension of aluminium powder (1.2 eq) in water (5mL), Ni(NO3)2.6H2O (10 mol%) was added and the reaction mixture was degassed using argon. The suspension was stirred at room temperature for 5 min. Benzyl halide (3 mmol) was added slowly to the reaction mixture, and the mixture was stirred at room temperature for 48 h under argon. The mixture slowly turned into a clear solution and the bibenzyl crystals were seen to be floating on top of the solution. The mixture was quenched with hydrochloric acid (4M, 5 mL)and extracted with dichloromethane. The combined organic extract was washed with water and dried over Na2SO4.The solvent was removed and the residue was purified by chromatography or recrystallization. All products gave satisfactory spectroscopic data and were compared with authentic sample wherever available.
40%
With iodine; magnesium In tetrahydrofuran at 30℃; for 3h; Sonication; Inert atmosphere;
With water; iron
With water; nickel
With sodium; benzene
Multi-step reaction with 2 steps
1: 1) NaH / 1) THF, 15 min, 2) r.t., 20 h
2: 3 percent / NiCl2(dppe) / benzene / 18 h / 46 °C
Multi-step reaction with 2 steps
1: 1) NaH / 1) THF, 15 min, 2) r.t., 20 h
2: 3 percent / MeMgI / NiCl2(dppe) / benzene / 18 h / 46 °C
9.1 Step 1: diethyl (naphthalen-1-ylmethyl)phosphonate
Step 1: diethyl (naphthalen-1-ylmethyl)phosphonate[00225j A mixture of triethyl phosphite (955 mg, 5.75 mmol) and 1 -(bromomethyl)naphthalene (1.11 g, 5.00 mmol) was stirred under N2 at 87°C overnight. The mixture was cooled to room temperature. The reaction mixture was used directly for the next step without further operation. The compound was characterized by the following spectroscopic data:MS(ESI, pos.ion)m/z: 279.2 (M+1); exact mass of C15H1903P: 278.11.
2-Bromo-5-(1-naphthalenylmethoxy)-nitrobenzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
92%
With potassium carbonate; In N-methyl-acetamide;
A. 2-Bromo-5-(1-naphthalenylmethoxy)-nitrobenzene To a solution of 4.0 g (18.3 mmol) of <strong>[78137-76-5]4-bromo-3-nitrophenol</strong> in 25 mL of dimethylformamide, 4.87 g (22.0 mmol) of 1-bromomethyl naphthalene and 3.04 g (22.0 mmol) of potassium carbonate were added and the mixture was stirred at room temperature overnight. The mixture was poured into 250 mL of ice/water and the precipitate was filtered and dried to afford compound A as a tan solid (6.1 g, 92percent). Melting point: 124°-126° C.
Stage #1: (R,R)-1,2-diphenylethylenediamine With sodium t-butanolate In toluene at 20℃; for 1.5h; Inert atmosphere;
Stage #2: 2-(bromomethyl)naphthalene In toluene for 2h; Reflux; Inert atmosphere;
Stage #1: 1,1‐bis[(4S)‐4‐isopropyl‐4,5‐dihydrooxazol‐2‐yl]ethane With tert.-butyl lithium In tetrahydrofuran at -78℃; for 1h; Inert atmosphere;
Stage #2: 2-(bromomethyl)naphthalene In tetrahydrofuran at -78 - 20℃; Inert atmosphere;
Stage #1: ethyl 3-methyl-indole-2-carboxylate With sodium hydride In N,N-dimethyl-formamide at 22℃; for 0.5h;
Stage #2: 2-(bromomethyl)naphthalene In N,N-dimethyl-formamide at 50℃; for 3h;
B.2.1; 1
General Procedure B: Preparation of the 2-carboxylic acid derivative (I'); 2.1.; To a solution of the indole methyl- or ethylester (V) (9.0 mmole) in dimethylformamide (100 ml) was added at 22° C. NaH (55-65% in oil, 9.6 mmole) and stirring was continued until gas evolution ceased (30 min). The mixture was treated with the halogen-methyl derivatives (IV) (9.6 mmole) and stirring was continued at 50° C. for 3 h. The mixture was partitioned between aqueous NH4Cl and ethyl acetate, the organic layer was washed with water, dried and evaporated. The residue was chromatographed on silica (n-heptane/AcOEt, 4:1) to give the indole ester (VI).; Example 1; 3-Methyl-1-naphthalen-1-ylmethyl-1H-indole-2-carboxylic acid; Using general procedure B, 3-methyl-1H-indole-2-carboxylic acid ethyl ester was coupled with 1-bromomethyl-naphthalene and the product obtained was hydrolyzed to give the title compound as a white solid. MS: 314.1 ([M-H]-).
Stage #1: Indole-3-carboxaldehyde With potassium hydroxide In ethanol
Stage #2: 2-(bromomethyl)naphthalene In acetone for 0.333333h;
5.1.7. General procedure for the synthesis of 1-benzyl-1H-indole-3-carbaldehyde
General procedure: A mixture of 1H-indole-3-carbaldehyde(1 g, 6.9 mmol) and KOH (570.86 mg, 10.2 mmol) in EtOH (66 mL) was stirred at room temperature when the solid was dissolved. The solvent was evaporated in vacuo, then added acetone (66 mL) and 1-(bromomethyl)-2-fluorobenzene (1.22 mL, 10.2 mmol). The mixture was stirred at room temperature for 20 min, filtered, the filtrate was concentrated under reduced pressure. The residue was added a little water and put it in the refrigerator overnight. The precipitate was washed with water and vacuum dried to afford 11a (636 mg, 39.2%).
Stage #1: 3-methylbenzo[b]thiophene-2-carboxylic acid With lithium diisopropyl amide In tetrahydrofuran at -10℃; for 0.5h; Inert atmosphere;
Stage #2: 2-(bromomethyl)naphthalene In tetrahydrofuran at -10 - 20℃; Inert atmosphere;
Potassium carbonate (798 mg, 5.77 mmol) was added to a solution of 5,7-dichloro-1H-imidazo [4,5 -b]pyridine (350 mg, 1.862 mmol) (5 ,7-dichloro-3H-imidazo [4,5-b]pyridine, obtained as described in example 1) in N,N-Dimethylformamide (DMF) (6.5 mL) and the mixture was stirred for 25 min-(bromomethyl)naphthalene (576 mg, 2.61 mmol) was then added and the reaction mixture was stirred at rt overnight. The mixture was pouredonto water and the precipitate formed was collected by filtration. The residue was purified on silica gel (15 to 30% EtOAc in hexanes) to give 5,7-dichloro-3-(1- naphthalenylmethyl)-3H-imidazo[4,5-b]pyridine (160 mg, 0.488 mmol, 26.2 % yield) as a light yellow powder. MS(ES+) m/e 328 (MH+); 1H NMR (400 MHz, DMSO-d6) delta ppm 8.67 (s, 1 H), 8.25 (d, J=8.08 Hz, 1 H), 7.97 - 8.03 (m, 1 H), 7.92 (d, J=8.34 Hz, 1 H), 7.66-7.70 (m, 1 H), 7.56-7.66 (m, 2 H), 7.41-7.49 (m, 1 H), 7.11 (d,J=6.32 Hz, 1 H), 6.00 (s, 2 H)
Stage #1: 2-ethyl-butyric acid methyl ester With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at -78℃; for 1h;
Stage #2: 2-(bromomethyl)naphthalene In tetrahydrofuran; hexane at -78 - 25℃;
Stage #1: 4-phenyl-2-methyl-2-butanol With sodium hydride In N,N-dimethyl-formamide at 0℃; for 0.5h; Inert atmosphere;
Stage #2: 2-(bromomethyl)naphthalene In N,N-dimethyl-formamide at 20 - 70℃; for 26h; Inert atmosphere;
1-Naphthylmethyl ether 3b.
Under argon atmosphere, to a solution of 2-methyl-4-phenyl-2-butan- ol 3a (1.15 g, 7.00 mmol) in anhydrous DMF (7.0 mL) were added NaH (420 mg, 10.5 mmol) at 0 °C. The reaction mixture was stirred at 0 °C for 30 min, and then 1-naphthylmethyl bromide (1.70 g, 7.70 mmol) was added. After stirring at rt for 23 h, the reaction was heated to 70 °C with oilbath. After being stirred at 70 °C for 3 h, the reaction mixture was diluted with ether and quenched with saturated aqueous solution of NH4Cl at 0 °C. The residual mixture was extracted with ether and the organic layer was washed with saturated aqueous NaCl, dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by flash silica gel column chromatography (hexane/ethyl acetate = 40/1 → 10/1 → 3/1) to give NAPI ether 3b (1.24 g, 4.07 mmol, 58%) as a colorless oil with recovery of 2-methyl-4-phenyl-2-butanol 3a (378 mg, 2.30 mmol, 33%) as a pale yellow oil.
1-naphthylmethyl p-hydroxyphenylpropionate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
68%
Stage #1: 4-hydroxyphenylpropionic acid With sodium hydrogencarbonate In acetone at 20℃; for 1h;
Stage #2: 2-(bromomethyl)naphthalene With lithium iodide In acetone at 40℃; for 12h;
2 Example 2 Synthesis of 1-naphthylmethyl p-hydroxyphenylpropionate (PN2, abbreviated as Formula III)
1) Weigh 1.10 mmol of p-hydroxyphenylpropionic acid,Dissolved in 1.5mL acetone,After adding 2.2 mmol of NaHCO3 for 1 h at room temperature,2.2 mmol of lithium iodide and 2.2 mmol of 1- (bromomethyl) naphthalene were added successively.The reaction mixture was stirred at 40 ° C for 12 h (TLC end of the reaction).2) After the reaction was cooled to room temperature,Add saturated sodium chloride solution 10mL and ethyl acetate 5mL,Homogenize after mixing;The aqueous phase was extracted twice with ethyl acetate (3 mL × twice)The combined organic phase,Saturated sodium chloride solution (2mL × 2 times),Dried over anhydrous sodium sulfate,The solvent was removed by rotary evaporation (-0.08 MPa, 45 ° C) to give a solid crude product.3) The crude product was purified by column chromatography,Column chromatography (total volume of solid to crude product mass multiple:Gradient I is 20 times,1-naphthalene methyl p-hydroxyphenylpropionate (PN 229.6 mg, 68% yield) was obtained after 5 times gradient II and 5 times gradient III). Structure identification data as follows:
General procedure: The phase-transfer catalysts (C1-C11) were synthesized according to the proceduresbelow. To a solution of cinchonidine (1.00 g, 3.4 mmol) in THF (50 mL) was addedthe aryl benzyl bromides (3.4 mmol). The mixture was heated for 6-8 h at reflux.After cooling to room temperature, the mixture was poured into MTBE (150 mL)under stirring. The precipitated solid was filtrated and recrystallized fromCH3OH/MTBE to afford C1-C11
7-methyl-1-(naphthalen-1-ylmethyl)indoline-2,3-dione[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
82%
Stage #1: 7-methyl-1H-indole-2,3-dione With sodium hydride In N,N-dimethyl-formamide at 0 - 25℃; for 0.25h; Inert atmosphere;
Stage #2: 2-(bromomethyl)naphthalene In N,N-dimethyl-formamide at 0 - 20℃; for 1h; Inert atmosphere;
With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 0.833333h;
Synthesis of 1-cyclopropyl-6-fluoro-7-(4-(naphthalen-1-ylmethyl)piperazin-1-yl)-4-oxo-1,4-dihydro-1,8-naphthyridine-3-carboxylic acid (4.2)
Enoxacin (4.1; 250 mg, 0.78 mmol, 1 eq) was added to DMF (15 mL) and stirred for 20 minutes at 120°C. Then i-(bromomethyl)naphthalene (173 mg, 0.78 mmol, 1 eq) and potassium carbonate (324 mg, 2.34 mmol, 3 eq) were added and the mixture stirred for a further 30 minutes at reflux. The mixture was allowed to cool, then extracted withdichloromethane (2x5o mL) using a 1M solution of citric acid to neutralise the aqueous phase. Combined organic fractions were washed with distilled water (50 mL) followed by brine (so mL), dried over MgSO4, filtered and concentrated in vacuo to give the crude product. Purification was achieved using an SCX-2 catch and release cartridge (see Solid Phase Extraction method) to afford compound 4.2 (113.86 mg, 79.2 % yield)as a pale brown solid. 1H NMR (400 MHz, CDC13) 6 15.11 (br. s., 1H), 8.69 (s, 1H), 8.33 (dd, J = 1.64, 7.93 Hz,1H), 8.09 (d, J = 13.35 Hz, 1H), 7.86 - 7.91 (m, 1H), 7.80 - 7.86 (m, 1H), 7.49 - 7.58 (m,2H), 7.41 - 7.46 (m, 2H), 4.38 (q, J = 7.05 Hz, 2H), 3.99 (s, 2H), 3.84 - 3.90 (m, 4H),2.65 - 2.71 (m, 4H), 1.48 (t, J = 7.18 Hz, 3H); LC-MS Retention time 3.05 minutes, found461.1 [M+H] calculated for C26H25FN403 461.51 [M+H].
1-cyclopropyl-6-fluoro-8-methoxy-7-((4aS,7aS)-1-(naphthalen-1-ylmethyl)octahydro-6H-pyrrolo[3,4-b]pyridine-6-yl)-4-oxo-1,4-dihydroquinoline-3-carboxylic acid[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
84.6%
<strong>[186826-86-8]Moxifloxacin hydrochloride</strong> (6.1; 100 mg, 0.23 mmol, 1 eq) was added to a 1:1 mix of acetonitrile and distilled water (10 mL total). After stirring for minutes, potassiumcarbonate (?s mg, 0.69 mmol, 3 eq) was added and the mixture stirred for a further s minutes. Once fully dissolved, i-(bromomethyl)naphthalene (48 mg, 0.22 mmol, 0.95 eq) was added slowly over the course of 1 hour and the mixture subsequently stirred for 24 hours. Upon completion, the product was extracted with dichloromethane (2 x 20 mL) using a 1M solution of citric acid to neutralise the aqueous phase. Combinedorganic fractions were washed with distilled water (20 mL) and dried over MgSO4, filtered and concentrated in vacuo to give the crude product. Purification was achieved using an SCX-2 catch and release cartridge (see Solid Phase Extraction method) to afford 6 .2.
4-(3-(Naphthalen-1-yl)oxiran-2-yl)benzonitrile[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
88%
(131) 1.1 mmol in a nitrogen atmosphere at -78 CTrifluoroacetic anhydride is dissolved in 1mL of anhydrous dichloromethane.Slowly add 2.2 mmol of anhydrous dimethyl sulfoxide to the reaction system and stir for 10 min.Get A13;(132) dissolving 1.1 mmol of 4-cyanobenzyl alcohol in 0.5 mL of anhydrous dichloromethane,Slowly add to A13, stir for 1 h, and slowly add 5.5 mmol to the reaction system.N, N-diisopropylethylamine, stirred for 2h to obtain B13;(133) TLC (thin layer chromatography) detection, the raw materials disappear, the reaction is moved to room temperature,Add 1.1 mmol to B13 at room temperature1-bromomethylnaphthalene,5.5mmol lithium hydroxide, 0.2mL water and 0.5mL dimethyl sulfoxide,Reaction at 25 for 12h,TLC (thin layer chromatography) detection, the starting point disappeared, the reaction stopped,Get C13;(134) adding saturated aqueous sodium bicarbonate solution to C13 to quench the reaction,Add 40 mL of dichloromethane, wash the organic phase three times with water, and wash the organic phase once with saturated sodium chlorideIt was then dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography.238.4 mg of product, this compound is 13, the yield is 88%.
tert-butyl 7-(naphthalen-1-ylmethyl)-3,4-dihydroisoquinoline-2(1H)-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
39%
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate In water; acetone at 100℃; for 0.5h; Microwave irradiation; Inert atmosphere;
4.1.3. General Procedure C for Microwave Suzuki Coupling of Boronic Ester 6 and PendantBenzyl Bromide
General procedure: The appropriate benzyl bromide (1.5-2.0 eq), intermediate 6 (1.0 eq), Pd(dppf)Cl2 (0.1 eq), andK2CO3 (3.0 eq) were combined in a microwave vessel equipped with a teflon stirbar. The system wasflushed with argon. A degassed mixture of 3:1 acetone:water (2-3 mL) was added, and the reaction washeated in a microwave to 100 C for 30 min. The product was purified via silica gel chromatography inethyl acetate/hexanes.
6-bromo-1-(naphthalen-1-ylmethyl)-1H-benzo[d][1,3]oxazine-2,4-dione[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
51%
General procedure: To a stirred solution of 6-chloro-1H-benzo[d][1,3]oxazine-2,4-dione (13a), 6-bromo-1H- benzo[d][1,3]oxazine-2,4-dione (13b) or 1H-benzo[d][1,3]oxazine-2,4-dione (13c) (1 equiv.) in DMSO (10 mL/mmol), 60% sodium hydride (1.5 equiv.) was added and the resulting suspension was stirred for 15 min. at room temperature, until the evolution of gas ceased. Then, the appropriate halide (1.5 equiv.): methyl iodide for 13a, 1-(bromomethyl)naphthalene for 13b or benzyl bromide and 4-bromobenzyl bromide for 13c, was added and the resulting mixture was stirred at room temperature for 18 h. Next day, the reaction mixture was poured into water (100 mL/10mL DMSO) and extracted with ethyl acetate (3 × 100 mL/100mL H2O). Combined organic layers were washed with brine (100 mL/300 mL EtOAc) and dried over anhydrous magnesium sulfate. Crude products were crystallized from mixture of ethyl acetate and hexane.
With tetra-(n-butyl)ammonium iodide; sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃;
1-((but-2-yn-1-yloxy)methyl)naphthalene (1q)
To a stirred solution of but-2-yn-1-ol (252 mg, 3.6 mmol) in THF (20 mL) was added dropwise NaH (60% dispersion in oil, 214 mg, 5.3 mmol) at 0 °C. After the mixture was stirred at 0 °C for 3 h. The desired l-(bromomethyl)naphthalene (950 mg, 4.3 mmol) and a piece of tetrabutylammonium iodide were then added. The solution was stirred at room temperature for 15 h. The aqueous layer was extracted with Et20 and the combined organic layers were washed with water and brine, dried over anhydrous Na2SO4ri, then concentrated in vacuo. The residue was purified by silica gel column chromatography (hexane/EtOAc =30/1) to afford yellow solid 642.6 mg, yield: 85%. 1H NMR (400 MHz, CDCh): S (ppm) 7.81-7.82 (m, 4H), 7.45-7.47 (m, 3H), 4.74 (s, 2H), 4.16-4.18 (m, 2H), 1.88 (t, J = 2.2 Hz, 3H); 13C NMR (100 MHz, CDCh): d (ppm) 135.2, 133.3, 133.1, 128.2, 127.9, 127.7, 126.8, 126.1, 126.0, 125.9, 82.7, 75.1, 71.5, 57.8, 3.6; Ms (El): m/z = 210.1 [M+],
Stage #1: di-isopropylphosphine; 2-(bromomethyl)naphthalene In methanol at 50℃; for 48h; Inert atmosphere; Schlenk technique; Sealed tube;
Stage #2: With triethylamine In methanol at 20℃; for 0.5h; Inert atmosphere; Schlenk technique; Sealed tube;
Stage #1: 2,2’-methylenebis[(4S)-4-phenyl-4,5-dihydro-2-oxazole] With sodium hydride In tetrahydrofuran; mineral oil at 0℃; for 0.5h;
Stage #2: 2-(bromomethyl)naphthalene In tetrahydrofuran; mineral oil at 0 - 20℃; for 8h;
Stage #1: bis((S)-4-isopropyl-4,5-dihydrooxazol-2-yl)methane With sodium hydride In tetrahydrofuran; mineral oil at 25℃; Inert atmosphere;
Stage #2: 2-(bromomethyl)naphthalene In tetrahydrofuran; mineral oil at 55℃; enantioselective reaction;
Stage #1: bis((S)-4-benzyl-4,5-dihydrooxazol-2-yl)methane With lithium hexamethyldisilazane In tetrahydrofuran at -40℃;
Stage #2: 2-(bromomethyl)naphthalene In tetrahydrofuran at -40 - 20℃;
63 %
Stage #1: bis((S)-4-benzyl-4,5-dihydrooxazol-2-yl)methane With sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; Schlenk technique; Inert atmosphere;
Stage #2: 2-(bromomethyl)naphthalene In tetrahydrofuran Schlenk technique; Inert atmosphere;
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