There will be a HazMat fee per item when shipping a dangerous goods. The HazMat fee will be charged to your UPS/DHL/FedEx collect account or added to the invoice unless the package is shipped via Ground service. Ship by air in Excepted Quantity (each bottle), which is up to 1g/1mL for class 6.1 packing group I or II, and up to 25g/25ml for all other HazMat items.
Type
HazMat fee for 500 gram (Estimated)
Excepted Quantity
USD 0.00
Limited Quantity
USD 15-60
Inaccessible (Haz class 6.1), Domestic
USD 80+
Inaccessible (Haz class 6.1), International
USD 150+
Accessible (Haz class 3, 4, 5 or 8), Domestic
USD 100+
Accessible (Haz class 3, 4, 5 or 8), International
USD 200+
Structure of 629-03-8 * 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.
With potassium <i>tert</i>-butylate In tetrahydrofuran for 16 h; Inert atmosphere; Reflux
General procedure: To a stirred solution of n-dibromoalkane (1 equiv.) in anhydrous THF (0.1M) under an argon atmosphere was added tert-BuOK (1.15 equiv.) in portionwise over 30 min. After being stirred under reflux for 16h, the reaction was cooled and subsequently quenched with water. The resulting mixture was then diluted with diethylether, and the layers were separated. The aqueous layer was extracted several times with diethylether, and the combined organic layers were washed with brine, dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The resultant crude product was purified by flash column chromatography over silica gel using petroleum ether as eluent to afford the desired product. 2.3.1 6-Bromo-1-hexene 3 The title compound was synthesized from 1,6-dibromohexane (8.1 g, 33.6 mmol) following the above protocol. Yield: 4.3 g (79percent), colorless oil. Rf: 0.71 (n-hexane 100percent, visualized with KMnO4 solution). 1H NMR (CDCl3, 500 MHz, ppm): δ 5.79 (ddt, J = 17.0, 10.2, 6.7 Hz, 1H), 5.02 (ddd, J = 17.1, 3.5, 1.6 Hz, 1H), 4.97 (ddt, J = 10.2, 2.2, 1.2 Hz, 1H), 3.41 (t, J = 6.8 Hz, 2H), 2.13 – 2.05 (m, 2H), 1.92 – 1.83 (m, 2H), 1.54 (tt, J = 9.3, 6.6 Hz, 2H). 13C NMR (CDCl3, 126 MHz, ppm): δ 138.27, 115.14, 33.87, 32.95, 32.29, 27.48.
Reference:
[1] Bioorganic and Medicinal Chemistry, 2018, vol. 26, # 14, p. 4047 - 4057
[2] Synthetic Communications, 2001, vol. 31, # 9, p. 1367 - 1371
[3] Synthesis, 1984, # 10, p. 885
[4] Journal of the American Chemical Society, 1992, vol. 114, # 8, p. 3044 - 3051
[5] Chemistry - A European Journal, 2013, vol. 19, # 3, p. 1002 - 1012
[6] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1986, p. 1431 - 1438
[7] Journal of the American Chemical Society, 2006, vol. 128, # 14, p. 4506 - 4507
[8] Journal of the American Chemical Society, 2007, vol. 129, # 10, p. 2938 - 2953
[9] Journal of Organic Chemistry, 1995, vol. 60, # 8, p. 2456 - 2460
[10] Patent: US5932075, 1999, A,
[11] Chemische Berichte, 1992, vol. 125, # 9, p. 2119 - 2128
[12] Chemistry - A European Journal, 2009, vol. 15, # 34, p. 8533 - 8541
[13] Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, 2010, vol. 65, # 3, p. 414 - 424
[14] Molecular Crystals and Liquid Crystals, 2012, vol. 552, p. 33 - 42
[15] Dalton Transactions, 2017, vol. 46, # 1, p. 221 - 226
2
[ 629-03-8 ]
[ 1608-26-0 ]
[ 2695-47-8 ]
Reference:
[1] Patent: US5495037, 1996, A,
3
[ 629-11-8 ]
[ 629-03-8 ]
Yield
Reaction Conditions
Operation in experiment
97%
With N-Bromosuccinimide; triphenylphosphine In dichloromethane at -78 - 20℃; for 12 h; Darkness
General procedure: NBS (534 mg, 3 mmol) was dissolved in CH2Cl2 (10 mL) contained in a 50 mL flask. Ph3P (786 mg, 3 mmol) and 9 (1 mmol) were added sequentially dropwise into the NBS solution at –78 °C. The reaction mixture was stirred in the dark at r.t. for 12 h and the progression of the reaction was monitored by TLC (eluent: PE–EtOAc, 20:1). The mixture was then concentrated in vacuo and the product 11 was isolatedby flash chromatography on a silica gel column (eluent: PE–EtOAc, 30:1).
Reference:
[1] Synthesis (Germany), 2015, vol. 47, # 8, p. 1154 - 1162
[2] Journal of the American Chemical Society, 1936, vol. 58, p. 488
[3] Archiv der Pharmazie (Weinheim, Germany), 1935, p. 323[4] Zhurnal Obshchei Khimii, 1935, vol. 5, p. 1508
[5] Journal of the Chemical Society, 1948, p. 46
[6] Org.Synth.Coll.Vol.III<1955>228,
[7] Monatshefte fuer Chemie, 1932, vol. 61, p. 221
[8] Chemische Berichte, 1944, vol. 77/79, p. 669,673[9] Monatshefte fuer Chemie, 1947, vol. 77, p. 259,262
[10] Monatshefte fuer Chemie, 1927, vol. 48, p. 524,729
[11] Journal fuer Praktische Chemie (Leipzig), 1960, vol. 10, p. 265 - 289
[12] Journal of the American Chemical Society, 1944, vol. 66, p. 1821
[13] Chemical and Pharmaceutical Bulletin, 1961, vol. 9, p. 485 - 491
[14] Bulletin of the Chemical Society of Japan, 1971, vol. 44, p. 177 - 184
[15] Tetrahedron, 1977, vol. 33, p. 19 - 25
4
[ 32315-10-9 ]
[ 292638-85-8 ]
[ 349553-73-7 ]
[ 629-03-8 ]
Yield
Reaction Conditions
Operation in experiment
40%
With N-ethyl-N,N-diisopropylamine In dichloromethane
Triphosgene (1.3 g, 4.3 mmol) was dissolved in anhydrous CH2Cl2 (20 mL). A mixture of 6-azidohexylamine (1) (1.6 g, 12 mmol) and N,N-diisopropylethylamine (DIEA, 2.4 mL, 13.8 mmol) in anhydrous CH2Cl2 (35 mL) was added dropwise to the stirred solution of triphosgene over a period of 7 h using a syringe pump. After further stirring for 2 h, a solution of (2) (6.4 g, 13 mmol) and DIEA (2.7 mL, 15.2 mmol) in anhydrous CH2Cl2 (20 mL) was added. The reaction mixture was stirred for 4 h at room temperature under nitrogen, and washed with 0.5 M HCl and brine. The organic layer was then dried over anhydrous MgSO4, and the solvent was removed by evacuation. Purification with column chromatography (silica, 1:1 EtOAc/hexane) yielded colorless oil (3.0 g, 40percent). 1H NMR (CDCl3, 300 MHz): δ 1.45 (s, (CH3)3C, 27H); 1.36-1.58 (m, CH2CH2CH2CH2, 8H); 2.46 (t, CH2CH2O, J=6.4 Hz, 6H), 3.13 (m, CONHCH2, 2H), 3.26 (t, N3CH2, J=6.9 Hz, 2H), 3.64-3.76 (m, CCH2O and CH2CH2O, 12H); 5.00 (t, CH2NHCO, J=6.7 Hz, 1H), 5.29 (s, CONHC, 1H). 13C NMR (CDCl3, 75 MHz): δ 26.52, 26.54, 28.81, 30.26 (CH2CH2CH2CH2); 28.14 ((CH3)3C); 36.20 (CH2CH2O); 39.86 (CONHCH2); 51.40 (N3CH2); 58.81 (CCH2O); 67.16 (CH2CH2O); 69.23 (CCH2O); 80.58 ((CH3)3C); 157.96 (NHCONH); 171.26 (COOt-Bu). FAB-MS: 674.26 (M+).
Reference:
[1] Bulletin de la Societe Chimique de France, 1910, vol. <4> 7, p. 330[2] Bulletin de la Societe Chimique de France, 1913, vol. <4> 13, p. 520
Reference:
[1] Journal of the Chinese Chemical Society, 2012, vol. 59, # 3, p. 389 - 393
[2] Synthetic Communications, 1994, vol. 24, # 11, p. 1557 - 1564
22
[ 629-03-8 ]
[ 17696-11-6 ]
Reference:
[1] Bulletin de la Societe Chimique de France, 1956, p. 1345,1350
23
[ 629-03-8 ]
[ 29823-21-0 ]
Reference:
[1] Bulletin de la Societe Chimique de France, 1956, p. 1345,1350
24
[ 629-03-8 ]
[ 829-85-6 ]
[ 19845-69-3 ]
Reference:
[1] Tetrahedron Letters, 2003, vol. 44, # 46, p. 8373 - 7377
[2] Phosphorus, Sulfur and Silicon and the Related Elements, 2004, vol. 179, # 2, p. 277 - 283
(Method D) K2CO3 (1.38 g, 10 mmol, 1 equiv.) was added to a suspension of 3- hydroxybenzamide (1.37 g, 10 mmol, 1 equiv.) in CH3CN (100 ml). The mixture stirred for 10 min at room temperature, before 1 ,6-dibromo-hexane (9.76 g, 40 mmol, 4 equiv.) was added. The resulting mixture was stirred at 600C for 16 h. After this time, the reaction was cooled to room temperature, any undissolved solids were filtered off and the filtrate evaporated under reduced pressure to dryness. The residue was taken-up in EtOAc and water. The organic phase was separated and washed consecutively with K2CO3 solution, water and brine. Dried with MgSO4 and evaporated under reduced pressure to a small volume. The precipitant solid was filtered and washed with EtOAc/pentane, to give the desired compound as a white solid (2.0 g, 67%), mp 115-1170C. HPLC-MS (method 1): m/z 300 [M]+, 302 [M+2H]+, Rt = 4.08 min.
55.4%
With potassium carbonate; In acetonitrile; at 60℃;
General procedure: To a solution of 3 (1.37 g, 10 mmol) in DMF (foralkyl dichloride) or CH3CN (for alkyl dibromide) (75 mL) were added K2CO3 (1.80 g, 13 mmol) and NaI (0.45 g, 3 mmol), CH3CN (for alkyldibromide) and then, saturated dihalide (30 mmol). The resulting reaction mixturewas warmed to 60 C and stirred for 16-20 h. After cooling to room temperature, the reaction mixturewas filtered and evaporated under reduced pressure to dryness. After theresidue was taken up in EtOAc (60 mL) and water (10 mL), the organic phase was separated and washed consecutively with saturated K2CO3 solution (2 × 4ml), water (10 mL) and brine (2 × 10 mL). After the washed organic phase was dried over anhydrous Na2SO4, filtered and evaporated under reduced pressure, the residue was purified by flash chromatography (petroleum ether/ethyl acetate, 1:1) to give the target compounds 4-15 in yields ranging from 55.4% to 73.6%.
Example 18 Preparation of C6 bis-L-Lactate Diol (Compound 19a) 33.60 g 1,6-dibromo hexane (Compound 18a; 0.15 mol) was added to a solution of 33.62 g <strong>[867-56-1]sodium L-lactate</strong> (Compound 17a; 0.3 mol) in 60 ml anhydrous DMF, and the mixture was heated at 60 C. for 3 days. The reaction mixture was cooled to room temperature and poured into 500 ml cold water, acidified to about pH 4 with 1N HCl, and extracted 4 times with 75 ml ethyl acetate. The organic layers were combined and washed with water, dried over anhydrous sodium sulfate, and the solvent removed in vacuo to obtain a slightly brownish oily product. The product was filtered over silica gel with 1:1 (v:v) ethyl acetate-hexane. Thirty-two g of pure product were obtained. The structure of the product was confirmed by 1H NMR.
In N,N-dimethyl-formamide; at 60℃; for 72h;
Example 18: Preparation of C6 bis-L-Lactate Diol (Compound 19a) [0134] 33.60 g 1,6-dibromo hexane (Compound 18a; 0.15 mol) was added to a solution of 33.62 g sodium L- lactate (Compound 17a; 0.3 mol) in 60 ml anhydrous DMF, and the mixture was heated at 60C for 3 days. The reaction mixture was cooled to room temperature and poured into 500 ml cold water, acidified to about pH 4 with 1N HC1, and extracted 4 times with 75 ml ethyl acetate. The organic layers were combined and washed with water, dried over anhydrous sodium sulfate, and the solvent removed in vacuo to obtain a slightly brownish oily product. The product was filtered over silica gel with 1: 1 (v: v) ethyl acetate-hexane. Thirty-two g of pure product were obtained. The structure of the product was confirmed by'H NMR.
With sodium hydroxide; tetrabutylammomium bromide; In hexane; water; for 5h;Heating / reflux;
To a solution consisting of sodium hydroxide (50 percent in water, 50 g), hexane (50 ml) and tetrabutylamonium bromide (0.7 g) was added 3- ethyl-3-oxetanemethanol (5.0 g, 43.0 mmol) and 1,6-dibromohexane (30 g, 122.9 mmol). This mixture was heated at reflux for 5 h. After cooling to room temperature, the resulting mixture was diluted with water (100 ml) and extracted with ethyl acetate (3 x 100 ml). The extracts were combined and dried over sodium sulphate. The solvent was removed under reduced pressure and the residue was purified by column chromatography, eluting with petrol / ethyl acetate (9 : 1 ), to give a colourless oil (6.65 g, 55percent). 1H NMR (300 MHz, CDCl3) : No. (ppm) 4.44 (d, J = 5.8 Hz, 2H, OCH2), 4.37 (d, J = 5.8 Hz, 2H, OCH@), 3.52 (s, 2H, OCH2), 3.46 (t, J = 6.4 Hz, 2H, OCH@), 3.40 (t, J = 6.8 Hz 2H, BrCH@), 1.35-1.91 (m, 10H, CH2), 0.88 (t, J = 7.5 Hz, 6H, CH3) ; 13C NMR (75 MHz, CDCI3): No. (ppm) 78.5 (OCH2), 73.4 (OCH2), 71.3 (OCH2), 43.4 (quat. ), 33.8 (CH2), 32.7 (CH2), 29.3 (CH2), 27.9 (CH2) 26.8 (CH2), 25.4 (CH2), 8.2 (CH3). MS (m/e): 279 (MH+, 0.1 percent)0281 (MH+ , 0.1 percent), 248 (3), 250 (3), 83 (89), 55 (100), 41 (86)
60 g
50 g of 3-ethyloxetanylmethanol and 172 g of sodium hydroxide were added to 500 ml of DMF, The mixture was stirred at 50 °C DEG under a nitrogen atmosphere. Then, 158 g of 1,6-dibromohexane Was added dropwise. After the addition, the mixture was stirred for 6 hours at 80 DEG 50 °C . After cooling to room temperature, 500 ml of water and 500 ml of toluene were added to separate the organic layer. The obtained organic layer was washed with saturated aqueous sodium hydrogencarbonate and water, and dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure. The residue was purified by vacuum distillation, 60 g of a colorless liquid (ex-4) was obtained
With sodium iodide; In diethyl ether; ethanol; water; acetone; Petroleum ether;
Example 5 Synthesis of diethyl-2,5-bis-(6-bromohexoxy)terephthalate 25.4 g (0.1 mol) diethyl-2,5-dihydroxyterephthalate, 232 ml (1.5 mol) 1,6-dibromohexane, 130 g (0.94 mol) K2 CO3 and 200 mg NaI in 200 ml acetone are heated under reflux for 12 hours. The initially yellow suspension decolorizes. After distilling off the solvent, 1200 ml diethyl ether are added to the reaction mixture and the whole is washed twice, each time with 200 ml water. The organic phase is then dried over Na2 SO4 and the solvent is distilled off. The colourless product which crystallized out after adding 250 ml petroleum ether at -20 C. is recrystallized once from petroleum ether and twice from ethanol. Yield: 52.6 g (91%) colourless crystals Melting point: 58 to 60 C. C24 H36 Br2 O6 (580.35): Calc. C 49.67 H 6.25 Found C 49.94 H 6.28
(a) [(6-Bromohexyl)oxy]methylcyclohexane From cyclohexylmethanol (5.0 g) and 1,6-dibromohexane (20 ml) by the method of (1a) to give (2a) (7.78 g) b.p. 182/0.8 Torr.
General procedure: To a stirred solution of monovalent beta-carbolines 1-17 (2.0 mmol) in anhydrous DMF (30 ml) was added 60% NaH (0.4 g, 10 mmol). After stirring for 20 min at room temperature, the appropriate dibromoalkane (1.0 mmol) was added. And then the reaction mixture was stirred at room temperature for 8-20 h. After completion of the reaction as indicated by TLC, the solution was poured into ice-water and extracted with CH2Cl2. The combined organic layer was washed with water and brine, dried over anhydrous Na2SO4, filtered and evaporated in vacuum. The residue was purified by column chromatography with CH2Cl2/MeOH (50:1) to successfully afford the desirable target products.
With potassium hydroxide; In dimethyl sulfoxide; at 10℃; for 24h;
(1) Synthesis of 4, 4-bis (6-bromohexyl) -4H-cyclopenta [2, 1-b: 3, 4-b'] dithiophene (compound 23)[0305]4H-cyclopenta [2, 1-b: 3, 4-b'] dithiophene (2.0 g, 11.23 mmol) and 1, 6-Dibromhexane (13.27 g, 55 mmol) were dissolved in 30 mL DMSO at 10 . Then KOH (1.8 g, 33 mmol) was added in several portions. After stirring for 24 h, the mixture was poured into water and extracted twice with ethyl acetate, the combined organic phase was dried with MgSO4and the crude product was subjected to column chromatography on silica gel to afford compound 23 as a light yellow oil (4.8 g, 86 ) .[0306]1H NMR (400 MHz, CDCl3) delta 7.53 (d, 2H) , delta 6.90 (d, 2H) , 3.52 -3.41 (t, 4H) , 1.80 -1.68 (m, 4H) , 1.43 (d, J 4.0 Hz, 4H) , 1.33 -1.23 (m, 4H) , 1.15 (m, 4H) , 0.89 -0.85 (m, 4H) .
General procedure: To a mixture of dry diisopropylamine (1.70 mL, 12.0 mmol, 2.40 equiv) and dry THF (12 mL) was10 added dropwise n-butyllithium (1.63 M n-hexane solution, 6.13 mL, 10.0 mmol, 2.00 equiv) at -78 oC under a nitrogen atmosphere. The solution was stirred for 30 min at 0 oC and 5-methyl-2,2-bipyridine(9) (855 mg, 5.02 mmol, 1.00 equiv) in dry THF (50 mL) was added at -78 oC. The temperature wasallowed to raise gradually over 4 h to -40 oC. The solution was recooled to -78oC and 1,10-dibromodecane (7.50 g, 25.0 mmol, 5.00 equiv) in dry THF (25 mL) was added. The solution was allowed to warm up to room temperature and stirred overnight. After the addition of water, THF wasevaporated under reduced pressure. Sodium hydrogen carbonate solution was added and the mixturewas extracted with dichloromethane. The extract was washed with brine and dried over sodium sulfate.After filtration, the solvent was removed under reduced pressure. The crude product was purified bycolumn chromatography on basic aluminum oxide (toluene) to give 10a as a white powder (1.10 g,20 56%). Analytically pure sample was obtained by recrystallization from hexane.
7-[(4-bromohexyl)oxy]-2-phenyl-4H-1-benzopyran-4-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
75.5%
With potassium carbonate; In acetone; for 4h;Reflux;
General procedure: A mixture of 3a-f/5-6 (5mmol) with suitable alpha,omega-dibromoalkanes (50mmol) and anhydrous K2CO3 (1.4g, 10mmol) in acetone (15mL) was refluxed under stirring for 4h. After cooling, the reaction mixture was filtered and the filtrate was evaporated under reduced pressure. The obtained residue was purified by silica gel chromatography with hexane/acetone (20:1) as eluent to give compounds 4a-f, 4h-k, 7a, and 7c.
Example given for n = 7: An oven dried round bottom flask, equipped with magnetic stir bar was sealed under argon. To the flask, THF (10 mL) and n-BuLi (2.4 M in hexanes, 2.0 mL, 4.8 mmol) were added and cooled to 0 oC. To this flask, <strong>[63071-03-4]2-methoxy-6-methylpyridine</strong> (0.50 mL, 4.1 mmol) was added drop wise via syringe, which resulted in a yellow color that intensified to brown over a few min. After 10 min, 1,6-dibromohexane (2.0 mL, 13 mmol) was added in one portion and the color rapidly dissipated. After an additional 2 h, the reaction was quenched upon addition of water. The phases were separated and the aqueous phase was extracted with ethyl acetate. The combined organic phases were washed with brine, dried (MgSO4) and concentrated in vacuo. Final purification by column chromatography (0% -15% ethyl acetate in hexanes) afforded the desired compound (397 mg, 34%) along with the dimer 1,8-bis(6-methoxypyridin-2-yl)octane (180 mg, 27%).
With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 6h;
General procedure: To a solution of BA (500 mg, 1.09mmol)in DMF (20 ml), 1,3-dibromo-propane(0.5 ml, 4.3 mmol) and K2CO3 (593 mg,4.3mmol) were added. The reactionmixture was stirred for 6 h at roomtemperature, then poured into water(100 ml) and extracted with EtOAc (3£ 40 ml). The combined organic layer waswashed with water and saturated NaCl solution sequentially. The dried (Na2SO4)organic layer was evaporated in vacuo.The product was purified by columnchromatography (petroleum ether (PE)-EtOAc; 15:1) to give compound 2a(440 mg, 70%). Compounds 8a-d were prepared from7 and the corresponding dibromopropaneas described for 2a in 81%, 79%, 70%, and75% yields, respectively.
65%
With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 6h;
General procedure: To a solution of BA (500 mg, 1.09 mmol) in DMF (20 ml), 1,3-dibromo-propane(0.5 ml, 4.3 mmol) and K2CO3(593 mg, 4.3 mmol) were added. Then the reaction mixture was stirred for 6 h at room temperature, poured into water (100 ml) and extracted with EtOAc (3× 40 ml). The combined organic layer was washed with water and saturated NaCl solution sequentially. The dried (Na2SO4) organic layer was evaporated in vacuo. The product was purified by column chromatography (petroleum ether (PE):EtOAc = 15:1) to give compound 2a (440 mg, 70%).
To a cooled suspension (0 oC) of sodium hydride, 60 % w/w in mineral oil (1.22 g, 30.6 mmol) in DMF (8 mL) was added a solution of 2-(2-(benzyloxy)ethoxy)ethanol (commercially available from for example Aldrich) (4 g, 20.4 mmol) in DMF (8 mL). After stirring for 25 minutes, 1,6- dibromohexane (commercially available from for example Aldrich) (14.1 mL, 92 mmol) dissolved in (DMF) (8 mL) was added dropwise to the mixture. The reaction was stirred under an atmosphere of nitrogen for 30 minutes. A further aliquot of sodium hydride, 60 % w/w in mineral oil (1.22 g, 30.6 mmol) was added and the reaction was stirred at room temperature for an additional 1 hour. The reaction mixture was filtered through celite and the solid was washed with DCM. The filtrate was partitioned between DCM (50 mL) and water (50 mL). The organic extract was separated, washed with brine (2 x 50 mL), dried using a hydrophobic frit and concentrated under reduced pressure. The product was purified by chromatography on silica using a gradient elution from 0% to 85% methyl tert-butyl ether in cyclohexane to afford the title compound (3.91 g, 10.3 mmol, 51% yield). LCMS RT= 1.30 min, ES+ve m/z 359.3./361.3 [M+H]+.
With potassium carbonate; In N,N-dimethyl-formamide; at 20 - 25℃; for 3h;
1,6-Dibromohexane (manufactured by Tokyo Chemical Industry) (6.0 g, 24.6 mmol) was dissolved in DMF (12.7 ml), 3-(methylamino)-1-propanol (manufactured by Tokyo Chemical Industry) (6.6 g, 73.7 mmol) and potassium carbonate (1.7 g, 12.3 mmol) were added, and the mixture was stirred at 20 - 25°C for 3 hr. The progress of the reaction was confirmed by TLC (eluent: chloroform/methanol/28percent aqueous ammonia solution = 80/20/2(v/v/v)). Potassium carbonate in the reaction mixture was filtered off using filter paper (5A), and the solvent was evaporated by an evaporator to give a brown liquid. The obtained brown liquid was dissolved in chloroform (20 ml), and the mixture was extraction-washed with water (30 g). The solvent in the organic layer was evaporated by an evaporator to give a brown liquid (3.6 g).
With potassium carbonate; In N,N-dimethyl-formamide; at 80℃;
General procedure: To a solution of compound 2 (1.12 g, 5 mmol) and K2CO3 (2.07 g,15 mmol) in DMF (15 mL), an appropriate amount of a,x-dibromoalkanewas added. After stirring at 80 C for 2?10 h until thematerial 2 disappeared, the solvent was poured into ice water(100 mL), extracted with EtOAc (2 70 mL) and washed with saturatedaq NaCl solution (2 80 mL). The organic layer was driedover anhydrous Na2SO4 and concentrated in vacuum. Then the residuewas purified by a silica-gel column chromatography to affordproduct.
General procedure: A mixture of the ditertiary amine (Compound 2) (11.52 g, 0.05 mol) and water (15 g) was charged into a reaction flask fitted with thermometer, stirrer and reflux condenser and heated to 65°C. Epichlorohydrin (4.63 g, 0.05 mol) was then added into the reactor. The temperature was gradually raised to 76°C and the reaction was carried out for 3 h. After the reaction, the resulted product was purified via vacuum distillation to remove unreacted reactants. The product was a clear and yellowish liquid (15.10 g, yield: 93.49percent).
3-(6-bromohexyl)-1-octylimidazolium bromide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
85%
In acetonitrile; for 24h;Reflux; Inert atmosphere;
1,6-Dibromohexane (10.00 g, 42 mmol) was dissolved in anhydrous acetonitrile (10 mL) and introduced into a three-neck round-bottom flask. After the solution was heated gently to reflux, a solution of 1 (0.50 g, 2.80 mmol) in anhydrous acetonitrile (5 mL) was added dropwise under N2 atmosphere. The reaction mixture was stirred for 24 h at reflux and then cooled to room temperature. The solvent was removed to give a residue, which was purified by washing with anhydrous diethyl ether (35 mL), and concentrated under reduced pressure. The residue was dried under vacuum to afford 2 as a puce oil (1.01 g,85 percent). deltaH (CDCl3, 400 MHz) 10.32 (1H, s), 7.62 (1H, s), 7.50 (1H, s), 4.40 (2H, t, J 7.2), 4.34 (2H, t, J 7.6), 3.43?3.40 (4H, m), 2.03?1.84 (6H, m), 1.51?1.23 (12H, m), 0.87 (3H, t, J 6.8). deltaC (CDCl3, 100 MHz) 136.3, 122.1, 121.8, 49.9, 49.6, 33.7, 32.3,32.1, 31.5, 30.1, 30.0, 28.9, 27.2, 26.1, 25.1, 22.4, 14.0. m/z (ESI) 345 ([M]+). m/z 345.1733. HRMS (ESI) Anal. Calc. for C17H32BrN2 ([M]+) 345.1728.
With potassium carbonate; In butanone; for 16h;Reflux;
Synthesis of diethyl-2,5-di(bromohexyl)oxyterephthalate (compound 38); K2CO3 (3.26 g, 23.6 mmol) was added portionwise to a stirred solution of diethyl-2,5-dihydroxyterephthalate (1 .00 g, 3.93 mmol) and 1 ,6-dibromohexane (6.1 mL, 39.3 mmol) in 2-butanone (20 mL). The reaction mixture was stirred at reflux for 16 h, after which the K2CO3 and salt were filtered off and washed with dichloromethane (20 mL). The filtrate was then evaporated to dryness under reduced pressure and the crude product was purified by flash chromatography (10% ethyl acetate in hexane). This yielded the product 38 as a white solid (1 .91 g, 3.29 mmol, 84%). 1 H N MR (400 MHz, CDCb), delta = 1.39 (6 H, t, J = 7.1 Hz, CH3), 1 .50-1.52 (8 H, m, CH2), 1 .79-1.93 (8 H, m, CH2), 3.42 (4 H, t, J = 6.8 Hz, CH2), 4.01 (4 H , t, J = 6.4 Hz, CH2), 4.37 (4 H , q, J = 7.1 Hz, CH2), 7.34 (2 H , s, Ar-H).
10-(6-bromohexyl)-10H-benzo[b]pyrido[2,3-e][1,4]thiazine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
55%
General procedure: To a stirred solution of KOH (10.0 mmol, 560 mg) in dry DMF (10 mL), <strong>[261-96-1]10H-benzo[b]pyrido[2,3-e][1,4]thiazine</strong> (1a) (5.0 mmol, 1.0 g), 7-bromo-<strong>[261-96-1]10H-benzo[b]pyrido[2,3-e][1,4]thiazine</strong> (1b) (5.0 mmol, 1.4 g), 7-chloro-<strong>[261-96-1]10H-benzo[b]pyrido[2,3-e][1,4]thiazine</strong> (1c) (5.0 mmol, 1.2 g) or 7-fluoro-<strong>[261-96-1]10H-benzo[b]pyrido[2,3-e][1,4]thiazine</strong> (1d) (5.0 mmol, 1.1 g) in DMF (5 mL) was added slowly over an interval of 10-15 minutes under a nitrogen atmosphere. This mixture was stirred for 15 more minutes at room temperature and then 1,6-dibromohexane (15 mmol, 3.65 g) in DMF (5 mL) was added. The reaction mixture was kept under nitrogen atmosphere for another 15-20 minutes and then was allowed to stir at room temperature for 12-14 h. Progress of the reaction was monitored on TLC. On completion of the reaction, the contents were poured in ice cold water and extracted with ethylacetate thrice (20 mL-10 mL-10 mL). The combined organic layers was dried using anhydrous sodium sulphate and solvent was removed under vacuum. The residue was purified on column chromatography using silica gel as an adsorbent and eluted with n-Hex/EtOAC to furnish pure products 2a-d.
General procedure: <strong>[442-51-3]Harmine</strong> 7 (2 mmol) and NaH (3 mmol) were dissolved in anhydrous DMF (10 mL). RX, RX2 or ArCH2Cl (3 mmol) was added and then stirred at room temperature until the reaction is completed. Then the reaction solution was quenched with cool water (20 mL), the organic compounds were extracted with EtOAc (30 mL × 3) and washed sequentially with water (30 mL), brine (50 mL), then dried over anhydrous Na2SO4 and concentrated. The residue was purified by column chromatography with petroleum ether (60-90 C) / acetone (1 : 1, v : v) to afford the target products.
1,6-bis(5-(benzyloxy)-2-(4-(benzyloxy)phenyl)-3-methyl-1H-indol-1-yl)hexane[ No CAS ]
C35H36BrNO2[ No CAS ]
C35H36BrNO2[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
26%; 66%; 12%
General procedure: The indole (5) dissolved in THF (10 mL) was added dropwise toa stirring mixture of NaH in THF (10 mL) at 0 C under N2 atmosphere.The mixture was stirred for 10 min, at which point theappropriate dibromoalkane (6)-(10) was added and the mixturewas stirred for 30 min at 0 C. The reaction was refluxed for a further30 min under N2 atmosphere, the mixture was allowed to coolat which point water was added dropwise until the solutionbecame clear. The solvent was then evaporated under reducedpressure to obtain a brown oil. The resin was dissolved in DCM(50 mL) and washed with water (3 50 mL), brine (50 mL) anddried over Na2SO4. The solvent was evaporated under reducedpressure to obtain a brown oil. The material was purified via flashchromatography over silica gel to afford the desired product.
1,6-hexamethylenebis(N,N-dihydroxyethyl-N-octadecylammonium) dibromide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
65%
In acetonitrile; for 69.0h;Heating;
G6-MOH-18 and G6-DOH-18 were synthesized by reaction of 1equivalent of 1,6-dibromohexane (25 mmol, 6.1 g) (Aldrich) with 2equivalents of N-hydroxyethyl-N-methyl-N-octadecylamine (50 mmol,16.35 g) or <strong>[10213-78-2]N,N-dihydroxyethyl-N-octadecylamine</strong> (50 mmol, 17.85 g),by heating in acetonitrile for 60 h and 69 h, respectively. White solidswere obtained. The crude products were crystallized from a mixture ofchloroform/methanol and dried over P4O10, yield: G6-MOH-18: 60%,G6-DOH-18: 65%;
General procedure: The synthetic route is shown in Scheme 2. For example, to a stirred solution of <strong>[26687-82-1]arctigenin</strong> (372 mg, 1 35 mmol) in 20 mL acetone were added anhydrous K2CO3 (110 mg, 0.8 mmol) at room temperature. After 36 stirring at room temperature for 30 min, 1,4-dibromobutane (323 mg, 1.5 mmol) was added to the 37 reaction mixture, and whole was refluxed at 60 for 24 h. The precipitate was filtered off and washed 38 with acetone (4×30 mL). The solvent was evaporated under reduced pressure, and the residue was treated 39 with water (50 mL) and extracted with dichloromethane (4×30 mL). The organic layer were combined, 40 dried with anhydrous Na2SO4, and concentrated under reduced pressure. The crude product was purified 41 via silica gel column chromatography with mixed petroleum ether and ethyl acetate (4:3, v/v) as eluent,and resulted in a white solid.
With potassium carbonate; In N,N-dimethyl-formamide; at 80℃; for 24h;
General procedure: A mixture of <strong>[42523-29-5]2,7-dihydroxyfluorenone</strong> (1) (23.34 g, 0.11 mol), 1,4-dibromobutane (216 g, 1.00 mol) and anhydrous K2CO3 (64 g,0.46 mol) in DMF (150 mL) was stirred at 80 °C for one day. Upon completion of reaction, the mixture was diluted with H2O (600 mL).The precipitate was filtered and recrystallized from EtOH to give a solid; (39.25 g, yield: 74percent);