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CAS No. : | 112-89-0 | MDL No. : | MFCD00000231 |
Formula : | C18H37Br | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | WSULSMOGMLRGKU-UHFFFAOYSA-N |
M.W : | 333.39 | Pubchem ID : | 8218 |
Synonyms : |
|
Num. heavy atoms : | 19 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 1.0 |
Num. rotatable bonds : | 16 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 96.51 |
TPSA : | 0.0 Ų |
GI absorption : | Low |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -1.01 cm/s |
Log Po/w (iLOGP) : | 5.38 |
Log Po/w (XLOGP3) : | 10.31 |
Log Po/w (WLOGP) : | 7.64 |
Log Po/w (MLOGP) : | 6.35 |
Log Po/w (SILICOS-IT) : | 7.69 |
Consensus Log Po/w : | 7.47 |
Lipinski : | 1.0 |
Ghose : | None |
Veber : | 1.0 |
Egan : | 1.0 |
Muegge : | 3.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -7.35 |
Solubility : | 0.000015 mg/ml ; 0.000000045 mol/l |
Class : | Poorly soluble |
Log S (Ali) : | -10.25 |
Solubility : | 0.0000000188 mg/ml ; 0.0000000001 mol/l |
Class : | Insoluble |
Log S (SILICOS-IT) : | -7.97 |
Solubility : | 0.00000356 mg/ml ; 0.0000000107 mol/l |
Class : | Poorly soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 4.43 |
Signal Word: | Danger | Class: | N/A |
Precautionary Statements: | P301+P310-P331-P405-P501 | UN#: | N/A |
Hazard Statements: | H304 | Packing Group: | N/A |
GHS Pictogram: |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With potassium hydrogencarbonate; potassium iodide In acetonitrile for 3 h; Heating / reflux | In a 500 ml Erlenmeyer flask, 10 g (95 mmol) of diethanolamine, 37.96 g (0.114 mol) of octadecane bromide, 39.33 g (0.285 mol) of potassium bicarbonate and 0.5 g of potassium iodide in 200 ml of acetonitrile were mixed. The reaction mixture was stirred and heated under reflux for 3 hours. At the end of the reaction, the solvent was evaporated and the residue was taken up in dichloromethane. The organic phase was washed two times with water, dried over MgSO4, filtered, and concentrated under vacuum. The residue was crystallized from acetone, to obtain 33 g of white crystal. Yield: quantitative. Melting point: 49° C. Rf: 0.20 (CH2Cl2/MeOH, 90:10 v/v). IR (KBr): 3310 (O-H) cm-1 1H NMR (200 MHz, CDCl3, HMDS) δ ppm: 3.53 (t, 4H, J=5.43 Hz, CH2-O), 3.27 (s1, 2H, OH), 2.57 (t, 4H, J=5.43 Hz, N-CH2-C-O), 2.44 (t, 2H, J=7.06 Hz, CH2-N), 1.34 (m, 2H, CH2-C-N), 1.18 (s1, 30H, CH2), 0.80 (t, 3H, J=5.85 Hz, CH3) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | for 5 h; | 1) 20 g of octabromohydrin was added to a 1000 ml single-necked flask, 250 ml of dichloropropane and 17.7 g of triethylamine were added, and 16.65 g of methacryloyl chloride was added dropwise with stirring. After completion of the dropwise addition, stirring was continued for 5 hours. After completion of the reaction, the system was washed with water and saturated sodium carbonate and saturated brine, respectively. The organic phase was dried over anhydrous sodium sulfate, concentrated, and chromatographed. 18.4 g of octadecyl methacrylate was obtained in a yield of 76percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With potassium hydrogencarbonate; potassium iodide; In acetonitrile; for 3.0h;Heating / reflux; | In a 500 ml Erlenmeyer flask, 10 g (95 mmol) of diethanolamine, 37.96 g (0.114 mol) of octadecane bromide, 39.33 g (0.285 mol) of potassium bicarbonate and 0.5 g of potassium iodide in 200 ml of acetonitrile were mixed. The reaction mixture was stirred and heated under reflux for 3 hours. At the end of the reaction, the solvent was evaporated and the residue was taken up in dichloromethane. The organic phase was washed two times with water, dried over MgSO4, filtered, and concentrated under vacuum. The residue was crystallized from acetone, to obtain 33 g of white crystal. Yield: quantitative. Melting point: 49 C. Rf: 0.20 (CH2Cl2/MeOH, 90:10 v/v). IR (KBr): 3310 (O-H) cm-1 1H NMR (200 MHz, CDCl3, HMDS) delta ppm: 3.53 (t, 4H, J=5.43 Hz, CH2-O), 3.27 (s1, 2H, OH), 2.57 (t, 4H, J=5.43 Hz, N-CH2-C-O), 2.44 (t, 2H, J=7.06 Hz, CH2-N), 1.34 (m, 2H, CH2-C-N), 1.18 (s1, 30H, CH2), 0.80 (t, 3H, J=5.85 Hz, CH3) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With thallium (I) ethoxide In N,N-dimethyl-formamide at 70℃; for 48h; | |
With thallium (I) ethoxide In N,N-dimethyl-formamide |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | In acetonitrile at 100℃; for 20h; analogous reaction with and without other phase-transfer catalysts; analogous reaction of other diols; | |
69% | In acetonitrile at 100℃; for 20h; analogous reaction with other alcohols; analogous reation without and with other phase-transfer catalysts; | |
69% | In acetonitrile at 100℃; for 20h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With lithium bromide In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide for 3h; Heating; Yield given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88.1% | With potassium hydroxide In ethanol for 18h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With 2,2'-azobis(isobutyronitrile); sodium cyanoborohydride In acetonitrile; <i>tert</i>-butyl alcohol for 3h; Heating; | |
89% | With triethylsilane; dilauryl peroxide In cyclohexane for 1h; Heating; | |
80% | With sodium tetrahydroborate; 2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-benzopentaoxacyclopentadecin; tributyltin chloride In toluene at 110℃; for 36h; other alkyl and aryl halides; other catalysts; also without cocatalyst or phase-transfer catalysts; |
80% | With sodium tetrahydroborate; 2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-benzopentaoxacyclopentadecin; tributyltin chloride In toluene at 110℃; for 36h; | |
With sodium tetrahydroborate; 2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-benzopentaoxacyclopentadecin; tributyltin chloride In toluene at 110℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With potassium hydroxide; Aliquat 336 at 198℃; for 0.166667h; Irradiation; | |
35% | Stage #1: 2,5-bis-(hydroxymethyl)furan With potassium <i>tert</i>-butylate In dimethyl sulfoxide at -10℃; for 0.5h; Stage #2: 1-Bromooctadecane In dimethyl sulfoxide at -10 - 20℃; Inert atmosphere; | 12 Example 12: Synthesis of 2,5-bis((octadecyloxy)methyl)furan, B Example 12: Synthesis of 2,5-bis((octadecyloxy)methyl)furan, B Experimental: An oven dried, single neck 10 mL round bottomed flask equipped with a PTFE coated magnetic stir bar was charged with 100 mg of FDM A (0.780 mmol) and 5 mL of anhydrous DMSO. The flask was then immersed in an ice-brine bath (- 10°C) and, while stirring, 219 mg of potassium t- butoxide (1.95 mmol) added in portions and the mixture stirred for 30 minutes at this temperature. At this time, the neck was stoppered with a rubber septum and an argon gas inlet affixed via a 14" needle. While vigorously stirring and under an argon blanket, 586 of 1 -bromooctadecane (1.72 mmol) was added via syringe. The mixture was then warmed to room temperature and continued to react overnight. After this time, an aliquot was removed and spotted on a silica gel TLC plate, which exhibited a single band (cerium molybdate stain) after developing in 11 : 1 hexanes/ethyl acetate. The signature band for FDM A (baseline) was noticeably absent, suggesting this reagent had fully converted. Here, the mixture was diluted with 5 mL of water and 5 mL of methylene chloride and partitioned and the aqueous layer extracted with 3-5 mL volumes of methylene chloride. The organic phases were combined, dried with anhydrous magnesium sulfate, filtered and concentrated under vacuum. The oily residue was dissolved in a minimum amount of methylene chloride and added to 20 g of silica gel, which was then dried under vacuum, furnishing product adsorbed silica gel. This material was added to a pre-fabricated silica gel column, where flash chromatography with hexanes to 6% ethyl acetate in hexanes afforded 171 mg of a B as an off- white solid after concentration (35% of theoretical). NMR (400 MHz, CDC13), δ (ppm) 6.40 (s, 2H), 4.52 (s, 4H), 3.41-3.38 (m, 4H), 2.08 (m, 2H), 1.65 (m, 2H), 1.48 (t, J= 6.2 Hz, 4H), 1.41 (m, 4H), 1.40-1.28 (m, 58H), 0.89 (t, J= 6.8 Hz, 6H); 13C NMR (100 MHz, CDCI3) δ (ppm) 152.7, 108.6, 73.6, 69.0, 33.0, 31.2, 30.9, 29.8, 28.7, 26.2, 25.4, 24.9, 24.1, 23.8, 23.3, 22.9, 22.5, 22.1, 21.7, 21.3, 13.3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With 18-crown-6 ether; potassium carbonate In butanone Heating; | |
With potassium carbonate In acetonitrile Heating; | ||
With potassium carbonate In N,N-dimethyl-formamide at 70℃; |
With potassium carbonate; potassium iodide In acetone Reflux; | ||
With potassium carbonate In N,N-dimethyl-formamide at 170℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77.1% | With potassium hydroxide In benzene for 12h; Heating; | |
63% | Stage #1: (R)-3-benzyloxy-1,2-propanediol With sodium hydride In tetrahydrofuran; N,N-dimethyl-formamide; mineral oil at 0℃; for 0.333333h; Stage #2: 1-Bromooctadecane In tetrahydrofuran; N,N-dimethyl-formamide; methylamine at 0 - 20℃; | (R)-[2,3-Bis(octadecyloxy)propoxy]methylbenzene (9) (R)-3-Benzyloxy-1,2-propanediol (8; 8.0 g, 44.0 mmol) was co-evaporated with toluene twice and then dissolved in anhydrous THF/DMF (1:1, 180 mL). After the solution was cooled in an ice bath, NaH (60 % in mineral oil, 4.9 g, 133 mmol) was added in portions. After the bubbling ceased, the suspension was stirred at 0 °C for an additional 20 min, followed by dropwise addition of 1-bromooctadecane (36.7 g,110 mmol) dissolved in THF (20 mL). Thereafter, the reaction mixture was kept in an ice bath for 1 h and gradually warmed to rt. The mixture was stirred overnight and then cooled in an ice bath, followed by addition of sat. NH4Cl aq solution (150 mL). The mixture was extracted with EtOAc, and the organic phases were combined, washed with brine, dried with anhydrous Na2SO4, filtrated, and condensed under vacuum. The crude product was purified by column chromatography (silica gel, hexane/EtOAc, 15:1); this gave 9. Yield: 19.0 g (27.6 mmol, 63 %); white solid; Rf = 0.40 (hexane/EtOAc,12:1). 1H NMR (600 MHz, CDCl3): δ = 7.33 (d, J = 4.4 Hz, 4 H), 7.29-7.26 (m, 1H), 4.55 (s, 2 H), 3.62-3.46 (m, 7 H), 3.42 (t, J = 6.7 Hz, 2 H), 1.60-1.50 (m, 4 H), 1.25 (br, 60 H), 0.88 (t, J = 7.0 Hz, 6 H). 13C NMR (151 MHz, CDCl3): δ = 128.3, 127.6, 127.5, 77.9, 77.2, 77.0, 76.8, 73.4, 71.7, 70.8, 70.6, 70.3, 31.9, 30.1, 29.7, 29.7, 29.5, 29.4, 26.1,26.1, 22.7, 14.1. HRMS (ESI-TOF): m/z [M + Na]+ calcd for C46H86O3Na: 709.6469; found: 709.6485. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | In acetonitrile at 20℃; Reflux; | |
In acetonitrile | ||
In toluene; acetonitrile at 89.84℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84.5% | With potassium hydroxide In cyclohexanol for 3h; Heating; | |
57% | With potassium carbonate In N,N-dimethyl-formamide at 90℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With silver tetrafluoroborate; In acetonitrile; at 65℃; for 17h; | The reaction of thioarabinitol 63 (500 mg, 1.19 mmol) with the bromide 55 (436 mg, 1.31 mmol) and AgBF4 (255 mg, 1.31 mmol) in dry CH3CN (12 mL) gave compound 68 as a colorless syrup (465 mg, 73%, based on the isolation of 30% unreacted starting material 63): [alpha]D +6.67 (c 0.3, MeOH); 1H NMR (CDCl3): delta 7.37-7.29 (m, 9H, Ar), 7.25-7.18 (m, 6H, Ar), 4.63 and 4.52 (2d, each 1H, Ja,b=11.9 Hz, CH2Ph), 4.60 and 4.44 (2d, each 1H, Ja,b=11.8 Hz, CH2Ph), 4.58 (br s, 1H, H-2), 4.53 and 4.48 (2d, each 1H, Ja,b=11.7 Hz, CH2Ph), 4.32 (d, 1H, J1a,1b=13.2 Hz, H-1a), 4.18 (br s, 1H, H-3), 3.81-3.78 (m, 2H, H-4 and H-5a), 3.67-3.62 (m, 1H, H-1'a), 3.64 (dd, 1H, J5b,5a=J5b,4=11.0 Hz, H-5b), 3.64 (dd, 1H, J1b,1a=13.2 Hz, J1b,2=3.6 Hz, H-1b), 3.28-3.20 (m, 1H, H-1'b), 1.77-1.71 (m, 2H, H-2'), 1.50-1.20 (m, 30H, H-3'-H-17'), 0.88 (dd, 3H, J18',17'a=J18',17'b=6.8 Hz, H-18'); 13C NMR (CD3Cl3): delta 136.6, 136.1, 135.9 (3Cipso), 128.8-127.8 (15CAr), 82.8 (C-3), 82.0 (C-2), 73.6, 72.6, 71.8 (3 CH2Ph), 66.9 (C-5), 66.7 (C-4), 46.8 (C-1), 45.3 (C-1'), 31.9-22.6 (15C, C-3'-C-17'), 25.6 (C-2'), 14.1 (C-18'); MALDI-TOF MS: m/z 673.57 [M-BF4]+. Anal. Calcd for C44H65BF4O3S: C, 69.46; H, 8.61. Found: C, 69.64; H, 8.53. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium carbonate; In methanol; water; ethyl acetate; N,N-dimethyl-formamide; acetone; | Example 2 Preparation and analysis of <strong>[480-41-1]naringenin</strong> 7-O-stearyl ether(compound 7) 10 g(36.73 mmol) of <strong>[480-41-1]naringenin</strong> was dissolved in a mixture of 20 ml of acetone and 20 ml of DMF. 1.5 ml of octadecanyl bromide and 470 mg of sodium carbonate were added to the mixture and stirred in a water bath at 80C. for 19 hours. The resulting solution was cooled, and then, 20 ml of water and 200 ml of EtOAc were added thereto and the mixture was extracted with EtOAc. The extract thus obtained was washed with water and concentrated under a reduced pressure. A small amount of MeOH was added to the solid thus formed and the mixture was stirred with glass stick. The solid thus obtained was filtered and washed with EtOAc to give 1.25g of <strong>[480-41-1]naringenin</strong> 7-O-stearyl ether as a very pale yellow solid. m.p.: 117-119C 1H NMR (CDCl3)delta 12.0 (s, 1H), 7.32 (d, J=8.4 Hz, 2H), 6.87 (d, J=8.4 Hz, 2H), 6.04 (d, J=2.0 Hz, 1H), 6.02 (d, J=2.0 Hz, 1H), 5.34 (dd, J=12.8, 2.8 Hz, 1H), 3.94 (t, J=6.8 Hz, 2H), 3.07 (dd, J=17.2, 12.8 Hz, 1H), 2.77 (dd, J=17.2, 2.8 Hz, 1H), 1.75 (quin, J=6.8 Hz, 2H), 1.44-1.36 (m, 2H), 1.34-1.22 (m, 28H), 0.89 (t, J=6.8 Hz, 3H) ppm. 13C-NMR(CDCl3) delta 195.8, 167.5, 164.0, 162.7, 156.0, 130.6, 127.9, 115.6, 103.0, 95.5, 94.6, 78.9, 68.6, 43.2, 32.0, 29.74-29.65 (8 carbons), 29.62, 29.57, 29.4, 29.3, 28.9, 25.9, 22.7, 14.2 ppm. 1D NOESY: NOE contacts were observed between H (6.04 and 6.02 ppms) and H (3.94 ppm). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With acetic acid; In water; N,N-dimethyl-formamide; | EXAMPLE 63 4-(Octadecyloxy)-alpha-oxobenzeneacetic acid To 0.325 g (8.1 mmol) of a 60% oil dispersion of NaH suspended in 15 ml of anhydrous DMF and stirred under an argon atmosphere at room temperature was added 1.5 g (7.73 mmol) of <strong>[70080-54-5]4-hydroxyalpha-oxobenzeneacetic acid ethyl ester</strong>. The reaction mixture was stirred at room temperature for 20 minutes and a solution of 3.2 g (9.66 mmol) of 1-bromooctadecane in 20 ml of anhydrous DMF was added dropwise over 15 minutes. After stirring at reflux for 16 hours, 5 ml of acetic acid was added and the solvent was removed at reduced pressure. Water was added to the residue and the product was extracted with methylene chloride. The dried extract was concentrated at reduced pressure and the solid residue was purified by HPLC using 50% methylene chloride-hexane to give 2.9 g (84% yield, mp 46-48) of 4-(octadecyloxy)-alpha-oxobenzeneacetic acid ethyl ester. Anal. Calcd for C28 H46 O4: C, 75.29; H, 10.38. Found: C, 75.48; H, 10.35. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With potassium carbonate; In N,N-dimethyl-formamide; acetone; | EXAMPLE 47 2-Hydroxy-5-(octadecyloxy)benzoic acid methyl ester A mixture of 1 g (5.95 mmol) of 2,5-dihydroxybenzoic acid methyl ester, 1.98 g (5.95 mmol) of 1-bromooctadecane and 0.825 g (5.95 mmol) of potassium carbonate in 20 ml of acetone and 1 ml of DMF was stirred at reflux for 20 hours. The usual workup followed by purification by HPLC using 1% ethyl acetate-hexane gave 1.8 (72% yield, mp 61-64) of 2-hydroxy-5-(octadecyloxy)benzoic acid methyl ester. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With potassium carbonate; In water; acetone; | EXAMPLE 58 2-Hydroxy-5-(octadecyloxy)benzoic acid methyl ester A mixture of 2.0 g (11.9 mmol) of 2,5-dihydroxybenzoic acid methyl ester, 4.55 g (13.1 mmol) of 1-bromooctadecane and 1.9 g (13.7 mmol) of potassium carbonate in 50 ml of acetone was stirred at reflux for 24 hours. The solvent was removed at reduced pressure and the residue was treated with water. The product was extracted with ethyl acetate and the dried extract was concentrated to a solid which was recrystallized from ethyl acetate-hexane to give 3.5 g (70% yield, mp 53-54) of 2-hydroxy-5-(octadecyloxy)benzoic acid methyl ester. Anal. Calcd for C26 H44 O4: C, 74.24; H, 10.54. Found: C, 74.45; H, 10.89. |
With sodium methylate; In methanol; | EXAMPLE 14 2-Hydroxy-4-n-octadecoxy benzoic hydrazide hydrochloride Methyl-2,5-dihydroxy benzoate 16.8 g. (0.1 m.) was added to sodium methoxide (5.9 g. 0.11 m.) in methanol (100 ml.). 1-Octadecyl bromide (33.4 g., 0.1 m.) was added slowly, and the reaction mixture refluxed for 18 hours. The mixture was poured into water and shaken with ether. The ethereal extracts were washed with water, dried with magnesium sulphate, and the solvent was removed to give crude methyl 2-hydroxy-5-octadecoxy benzoate (41 g.). Distillation under reduced pressure gave the pure ester (10 g.) which had a boiling point of 232-242C at 0.07 mm. Hg. pressure, and a melting point of 62-63.5C after crystallisation from ethanol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium sulfite; In water; | Example 9 1,3-dimethyl-1-octadecyl-4-sulfomethyl-pyrrolidinium betaine; R1 =CH3; R2 =C18 H37 in the general formula I Methyl-n-octadecyl-diallylammonium bromide was produced by reacting <strong>[2424-01-3]methyldiallylamine</strong> with n-octadecylbromide. 1.26 g (0.01 mol) sodium sulfite are dissolved in 300 ml tap water in a sulfonation flask equipped with a stirrer, gas-inlet tube and thermometer and heated at 30 C. Then two aqueous solutions of 200 ml each are prepared. The first is prepared from 9.5 g (0.05 mol) sodium metabisulfite, 6.3 g (0.05 mol) sodium sulfite; the other one from 44.44 g (0.1 mol) crystallized methyl-n-octadecyl-diallylammonium bromide through heating with tap water and cooling to 30-35 C. in order to prevent recrystallization of the ammonium salt. The prepared solutions are then added, drop by drop, from two dripping funnels during the course of 40 minutes under vigorous stirring and simultaneous introduction of air oxygen, wherein care should be taken that the temperature of the reaction mixture does not fall below 30 C. The sulfobetaine starts already to crystallize upon dripping of the solutions from the reaction mixture as a snow-white substance. The pH value of the reaction mixture is kept at 7 during the entire dripping phase. After a post-reaction time of approximately 10 minutes, the sulfobetaine is suctioned off from the reaction mixture and dried. The yield is nearly quantitative. The recrystallization from ethanol confirms that the raw sulfobetaine accumulates practically free from neutral salts. Melting point 165 C. The product exhibits the following 13 C-NMR spectrum in DMSOD6 (indications as above). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In acetonitrile | 1 Cis-2-[(octadecylaminocarbonyl)oxy]methyl-5-hydroxymethyl tetrahydrofuran STR11 EXAMPLE 1 Cis-2-[(octadecylaminocarbonyl)oxy]methyl-5-hydroxymethyl tetrahydrofuran STR11 A suspension of 2.64 g (20 mmol) of cis-2,5-bis(hydroxymethyl)tetrahydrofuran, 7.99 g (24 mmol) of octadecyl bromide, 2.43 g (30 mmol) of potassium cyanate and 0.966 g (3 mmol) of tetrabutyl ammonium bromide in 100 ml of dry acetonitrile was refluxed, with stirring, at 100° C. for 20 hours. The resultant mixture was then diluted with hot methylene chloride, filtered and the filtrate concentrated in vacuo. The crude product was then purified by flash silica gel chromatography employing successive mixtures of petroleum ether and ethyl acetate in ratios of 4:1, 2.33:1 and 1:1 as the eluent to yield the title compound as a solid, m.p. 79°-80° C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene; | EXAMPLE 70 A mixture of 17.10 parts of 1,2,2,6,6-pentamethylpiperidin-4-ol and 3.50 parts of metallic sodium in 125 parts of toluene was heated under reflux conditions for 24 hours. The toluene solution was decanted off from the excess sodium and then refluxed for a further 24 hours with 36.60 parts of n-octadecyl bromide. The cooled solution was filtered to remove the sodium bromide which was formed during the reaction and the toluene solvent was removed by distillation under reduced pressure. Fractional distillation of the residue gave 4-octadecyloxy-1,2,2,6,6-pentamethylpiperidine having a boiling point of 184 C. at 0.25 m.m. of Hg. and the following elemental analysis by weight: Table 5 gives a list of ethers prepared using the procedure of Example 70. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With potassium hydroxide In N,N-dimethyl-formamide at 20 - 50℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With potassium carbonate; In N,N-dimethyl acetamide; water; | EXAMPLE (A-8) Preparation of 1,2-bis[octadecyloxy]anthraquinone 20 g of 1,2-dihydroxy-anthraquinone and 34.4 g of K2CO3 are added in a 500 ml round-bottom flask equipped with mechanical stirrer, thermometer and reflux condenser containing 250 ml N,N-dimethylacetamide. The mixture is heated to 80 C. and subsequently stirred for 60 minutes. Then, 82.9 g of 1-bromo-octadecane are added portionwise within one hour. The reaction is left to continue for 6 hours. After cooling to ambient temperature, a dense precipitate is formed. 100 ml of additional solvent are added to render the mixture filterable. The filter cake is washed with 50 ml of N,N-dimethylacetamide and 200 ml of water. The residue is taken up again in N,N-dimethylacetamide, filtered and washed with 200 ml of water. The desired product is obtained as a yellow powder. Melting point: 100-107 C. (Yield: 93%) |
93% | 20 g of 1,2-dihydroxy-anthraquinone and 34.4 g of K2CO3 are added in a 500 ml round-bottom flask equipped with mechanical stirrer, thermometer and reflux condenser containing 250 ml N,N-dimethylacetamide. The mixture is heated to 80 C. and subsequently stirred for 60 minutes. Then, 82.9 g of 1-bromo-octadecane are added portionwise within one hour. The reaction is left to continue for 6 hours. After cooling to ambient temperature, a dense precipitate is formed. 100 ml of additional solvent are added to render the mixture filterable. The filter cake is washed with 50 ml of N,N-dimethylacetamide and 200 ml of water. The residue is taken up again in N,N-dimethylacetamide, filtered and washed with 200 ml of water. The desired product is obtained as a yellow powder.Melting point: 100-107 C. (Yield: 93%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | Synthesis is carried out in a 500 ml round-bottom flask equipped with mechanical stirrer, thermometer and reflux condenser. In 200 ml of N,N'-dimethylacetamide, 9.14 g of KHCO3 and 20 g of 1,2-dihydroxy-anthraquinone (alizarin) are mixed and heated to 80 C. for one hour. 27.6 g of 2-ethylhexyl bromide are added dropwise within 30 min. After 6 hours the reaction is completed. Subsequently, 0.9 equivalent of KHCO3 are added and the mixture is heated to 100 C. and held at this temperature. After 4 hours, 27.6 g of 1-bromo-octadecane are added to the mixture with another equivalent of KHCO3 within 30 minutes. After two hours the temperature is increased to 125 C. for another two hours and successively 0.5 equivalent of 1-bromo-octadecane are added. The reaction is left to continue for two hours. After completion, the reaction mixture is cooled to room temperature and the precipitated product is filtered and washed with 500 ml of water. The obtained 45 g of crude product are recrystallized from isopropanol and washed with hot acetone to give 32 g of the desired compound as yellow crystals (95% HPLC (High Pressure Liquid Chromatography).Melting point: 61-68 C. (Yield: 64%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | Stage #1: p-hydoroxybenzenesulfonic acid; 1-Bromooctadecane With potassium carbonate In acetone for 24h; Reflux; Inert atmosphere; Stage #2: With hydrogenchloride In tetrahydrofuran Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
153 g | Step 1 : /V-(3-(Dioctadecylamino)-4-methoxyphenyl)acetamide N-(3-Amino-4-methoxyphenyl)acetamide (42 g, 0.23 mol), 1 - bromooctadecane (194 g, 0.583 mol), sodium bicarbonate (49 g, 0.583 mol) and A/-methyl-2-pyrrolidone (140 ml) are charged and heated at 80C for 16 hours. Acetic anhydride (15 ml) is added and stirring continued at 105C for 1 hour, before methanol (10 ml) is added. After stirring overnight, the reaction is allowed to cool to 25C before water (1 L) is added. The resultant solid is filtered off and then dissolved in methylene chloride (1 L). The organic solution is washed with water (500 ml), dried over MgS04 and treated with ca 20 g of activated charcoal for 15 minutes. The solution is filtered through a silica pad, washing with methylene chloride (2 x 500 ml). The combined organic layers are evaporated to a thick brown oil. This oil is suspended in acetonitrile (1 L) whist still hot (40-45C) and stirred rapidly overnight to give a fine suspension. The solid is filtered and washed with acetonitrile (500 ml), then dried at 40C to give N-(3-(dioctadecylamino)-4- methoxyphenyl)acetamide as a pale brown solid (153.0 g). H NMR analysis showed the presence of ca 20 mol% residual 1 -bromooctadecane in the solid; therefore, organic content estimated at 80%. Strength adjusted yield 122.4 g, 78%; (CDCI3, 300 MHz): delta 0.9 (6H, t), 1.2-1.6 (64H, m), 2.2 (3H, s), 3.1 (4H, br. t), 3.8 (3H, s), 6.8 (1 H, d), 7.1 (2H, br. m); MS (ES+): [M+Hf = 685.6 (70%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
20% | In di-isopropyl ether at 30℃; for 120h; | 3 Synthesis of 18-N(CH3)2-6-N(CH3)2 A solution of 0.5 g (1 eq.) Of 1-bromooctadecane (TCI, 97%) and 5.17 g (20 eq.)N, N, N ', N'-Tetramethyl-1,6-diaminohexane (TCI, 98%) in a 100 mL round bottom flask. Add 50 mL of diisopropyl ether (Aldrich, 98.5%), and stir in a water bath at 30 ° C for 120 hours. The state of the reaction mixture before the start of the reaction is a clear colorless solution. When the reaction is complete, 18-N (CH3) 2-6-N (CH3) 2 precipitates from the reaction mixture, precipitating a white product and sinking to the bottom. After cooling to 0 ° C, the product is filtered and recovered using a filter. The reactants that did not participate in the reaction were washed thoroughly with additional diisopropyl ether,Remove the diisopropyl ether. 1H-Liquid NMR analysis was performed using the thus obtained product as a CD3OD solvent (Fig. 3). As a result, 18-N (CH3) 2-6-N (CH3) 2-18, which is an addition product, was found to be pure 18-N (CH3) 2-6-N (CH3) 2 that was not produced. The selectivity is 99.9% or more, and the yield is about 20%. Reactants that do not participate in the reaction are completely soluble in diisopropyl ether and can be reused. |
In chloroform at 59.84℃; for 12h; | ||
In toluene; acetonitrile at 60℃; for 12h; |
In toluene; acetonitrile at 89.84℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With potassium carbonate In N,N-dimethyl-formamide at 140℃; | S1 4-Octadecyloxy-phenylacetate (1a) 4-Octadecyloxy-phenylacetate (1a) A mixture of K2CO3 (8.31 g, 60.2 mmol), methyl 4-hydroxy-phenylacetate (5.00 g, 30.0 mmol) and 1-bromoctadecane (13.04 g, 39.11 mmol) in DMF (80 mL) was stirred at 140° C. overnight. After cooling to rt, K2CO3 was removed by filtration, and the filtrate was diluted with H2O and acidified with 2 M HCl. The aqueous layer was extracted with CH2Cl2 (3*250 mL). The organic layers were combined and washed with H2O (3*50 mL), dried over MgSO4 and concentrated to dryness to afford the crude product. The crude product was taken up in CH2Cl2 and then cold MeOH was added to precipitate 1a (11.30 g, 27.01 mmol, 90%) as white powder. 1H NMR (500 MHZ, CDCl3): δ 0.87 (t, J=6.9 Hz, ArOCH2CH2(CH2)15CH3, 3H), 1.26-1.41 (m, ArOCH2CH2(CH2)15CH3, 30H), 1.73 (pent, J=7.4 Hz, ArOCH2CH2(CH2)15CH3, 2H), 3.56 (s, ArCH2COOCH3, 2H), 3.68 (ArCH2COOCH3, 3H), 3.93 (t, J=6.9 Hz, ArOCH2CH2(CH2)15CH3, 2H), 6.85 (d, J=8.6 Hz, ArH, 2H), 7.17 (d, J=8.6 Hz, ArH, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
18 g | With potassium carbonate; In 1-methyl-pyrrolidin-2-one; at 20℃; for 48h;Inert atmosphere; | To a mixture of 2,2-Bis(hydroxymethyl)butyric acid (49 grams), Potassium carbonate (52 grams) in N-Methyl-2-pyrrolidone (200 ml) was added Stearyl bromide (50 grams) in small lots and stirred at room temperature under Nitrogen atmosphere for 48 hours. The reaction mixture poured onto cold water, extracted with Diisopropyl ether, washed with water (300 ml), dried over Sodium sulphate, distilled under reduced pressure, purified by column chromatography using Hexane: Ethyl acetate (8:2) followed by precipitating in Hexane to give pure 2,2-Bis-hydroxymethyl-butyric acid octadecyl ester (18 grams) as a white powder with a melting point of 46-48 C. The product was characterized by IH NMR (CDCl3) delta 0.82 (m, 6H, CH3X2), 1.25 (m, 32H, CH2X16), 1.50 (q, 2H, CH2), 2.75 (bs, 2H, OH), 3.72 (d, 2H, CH2), 4.05 (d, 2H, CH2), 4.20 (t, 2H, CH2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With potassium carbonate; In acetone;Reflux; | General procedure: Ethyl 4-((4-hydroxyphenyl)diazenyl)benzoate (0.001 mol) was dissolved in acetone (20 mL) and added potassium carbonate (3 eq), to this reaction mixture respective alkyl halide (1.0 eq) was added and the reaction mixture was subjected to reflux and the completion of the reaction monitored by TLC. After completion the reaction mixture was poured into coldwater and the precipitated solid was filtered, dried and recrystallzied from ethanol water. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | General procedure: General Procedure for Preparation of Solenopsin Analogs [0180] 2,6-Dimethylpyridine or <strong>[108-75-8]2,4,6-trimethylpyridine</strong> (1.35 equiv.) was added dropwise to a stirred solution of n-BuLi (2M, 1.5 equiv.) in cyclohexane at 0 C. After 30 min of stirring at 0 C., the alkylbromide (1.0 equiv) was added dropwise and the reaction mixture was allowed to reach room temperature. The slurry was stirred at room temperature for another 4 h, followed by addition of ice water. The obtained water-mixture was extracted three times with ethyl acetate. The organic layers were combined and washed with brine, dried over MgSO4, filtered, and concentrated under reduced pressure. The crude compounds were purified by flash chromatography on silica gel. The resulting substituted pyridines (1.0 g) were reduced to the corresponding piperidines through catalytic hydrogenation at 50 psi for 12 hours in the presence of palladium (10 mol %) and rhodium on carbon (10 mol %) in absolute ethanol (80 mL). The mixture was filtered through Celite and concentrated under vacuum. The residue was passed through a short pad of silica, eluting with 20% (10% NH4OH:MeOH) in ethyl acetate, to give the products after concentration. 1H NMR of compounds S11-S14 showed the presence of a single diastereomer.Compound S11 was prepared from 2.5 mL of <strong>[108-75-8]2,4,6-trimethylpyridine</strong> (19 mmol) and 4.8 mL of 1-bromooctadecane (14 mmol) according to the general procedure. The crude 2,4-dimethyl-6-nonadecylpyridine was purified by flash chromatography (silica: ethyl acetate/hexanes 1:19), which afforded 2,4-dimethyl-6-nonadecylpyridine, the S11 precursor, as an off-white solid (3.71 g, 71% yield). _1H NMR (CDCl3) delta: 6.76 (d, 2H, J=6.4), 2.67 (t, 2H, J=8.0), 2.46 (s, 3H), 2.25 (s, 3H), 1.70-1.57 (m, 2H), 1.37-1.15 (m, 32H), 0.86 (t, 3H, J=7.0). UPLC-MS (ESI): 374.4 (M+H+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | In acetonitrile; for 22h;Reflux; | To a solution of <strong>[96556-05-7]1,4,7-trimethyl-1,4,7-triazacyclononane</strong> (0.214 g, 1.25 mmol) in acetonitrile (4 mL) was added 1-bromooctadecane (0.435 g, 1.30 mmol).The resulting colorless solution was heated at reflux with stirring for 22 hours, duringwhich time the solution turned yellow. The reaction mixture was concentrated invacuo, resulting in a yellow-white crude solid, which was triturated with hot hexanes(35 mL), then washed with cold hexanes (50 mL), resulting in C-18,0,0 (0.490 g,78%) as a white powder; mp=161-172 C; ?H NMR (300 MI-Tz, CDC13) oe 4.40-4.28(m, 2H), 4.13-3.99 (m, 2H), 3.62-3.55 (m, 2H), 3.32 (s, 3H), 2.95-2.72 (m, 4H), 2.52(s, 4H), 2.43 (s, 6H), 1.78-1.64 (m, 2H), 1.42-1.22 (m, 30H), 0.89-0.83 (m, 3H); ?3CNMR (75 MHz, CD3OD) oe 63.2, 60.1, 59.3, 54.3, 47.5, 46.7, 31.7, 29.4, 29.3, 29.2,29.1, 28.9, 26.1, 22.4, 21.6, 13.1; high resolution mass spectrum(ESI)m/z 424.4622([Mf calculated for [C27H58N3f: 424.4625). ?H and ?3C NMR spectra of compoundC- 18,0,0 can be found in Figure 39. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | In acetonitrile; for 23h;Reflux; | To a solution of tris(2-dimethylaminoethyl)amine (0.326 g, 1.41 mmol) in acetonitrile (4 mL) was added 1-bromooctadecane (1.41g, 4.23 mmol). The resulting mixture was heated at reflux with stirring for 23 hours, during which time a white solid was observed. After cooling, and the addition of a cold hexanes/acetonemixture (15 mL, 1:1), to the reaction flask, the precipitate was filtered with a Buchner funnel, and rinsed with a cold hexanes/acetone mixture (20 mL, 1:1), resulting in T-18,18,18 (1.48 g, 85%) as a white powder; mp=227-259 C; ?H NMR (300 JVII-Tz, CDC13) oe 4.13-4.02 (m, 6H), 3.65-3.58 (m, 6H), 3.46-3.38 (m, 6H), 3.35 (s, 18H), 1.78-1.66 (m, 6H), 1.41-1.37 (m, 90H), 0.89-0.82 (m, 9H); high resolutionmass spectrum (ESI) in/z 330.0376 ([Mj3 calculated for [C66H,4,N4j3: 330.0380). ?H spectmm of compound T-18,18,18 can be found in Figure 55. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | Synthesis of DSDMA and DODMA: (0248) DSDMA and DODMA were synthesized using the respective alkyl bromides with methodology derived from that of a DOTMA precursor (Feigner et al, PNAS USA, 84, 7413-7417 (1987)). 3-(Dimethylamino)-1,2-propanediol (714 mg, 6 mmol) and 95percent sodium hydride (NaH, 1.26 g, 50 mmol) were stirred in benzene (30 mL) under argon for 30 minutes. The correct (either oleyl or stearyl) alkyl bromide (5.0 g, 15 mmol) was added and the reaction refluxed under argon for 18 hours. The reaction mixture was then cooled in an ice bath while quenching via the slow addition of ethanol. Following dilution with a further 150 mL of benzene, the mixture was washed with distilled water (2×150 mL) and brine (150 mL), using ethanol (20 mL) to aid phase separation if necessary. The organic phase was dried over magnesium sulphate and evaporated. The crude product was purified on a silica gel (Kiesel Gel 60) column eluted with chloroform containing 0-5percent methanol. Column fractions were analyzed by thin layer chromatography (TLC) (silica gel, chloroform/methanol 9:1 v/v, visualized with molybdate) and fractions containing pure product (Rf=0.5) were pooled and concentrated. The product was decolorized by stirring for 30 minutes in a suspension of activated charcoal (1 g) in ethanol (75 mL) at 60° C. The charcoal was removed by filtration through Celite, and the ethanol solution concentrated to typically yield 2.4 g (65percent) of pure product. 1H-NMR (DSDMA): deltaH 3.65-3.32 (m, 7H, OCH, 3×OCH2), 2.45-2.31 (m, 2H, NCH2), 2.27 (s, 6H, 2×NCH3), 1.61-1.45 (m, 4H, OCH2CH2), 1.40-1.17 (m, 60H, Hstearyl), 0.86 (t, 6H, CH2CH3). 1H-NMR (DODMA): deltaH 5.4-5.27 (m, 4H, 2×CH?CH), 3.65-3.35 (m, 7H, OCH, 3×OCH2), 2.47-2.33 (m, 2H, NCH2), 2.28 (s, 6H, 2×NCH3), 2.06-1.94 (m, 8H, 4×CH2CH?CH), 1.61-1.50 (m, 4H, OCH2CH2), 1.38-1.20 (m, 48H, Holeyl), 0.88 (t, 6H, CH2CH3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine; In acetonitrile; at 97℃; for 7.5h; | 2-Pyridyl carbonitrile (12.5 g, 0.12 mol) was charged to a 2 L, three neck round bottomed flask equipped with condenser with attached N2 inlet-outlet, mechanical stirrer and thermocouple. Solid NH4Cl (6.4 g, 0.12 mol) was added. DMF (880 mL) then water (6.27 g) was added followed by sodium azide (7.8 g, 0.12 mol). The reaction was refluxed at approximately 137 C. overnight. A new very polar spot was seen by TLC but some starting material remained. NaN3 and NH4Cl, (each 0.05 mol/mol, based on the amount of substance of the 2-pyridyl carbonitrile) was added followed by a small amount of water. The reaction was complete after a total of about 65 h at 137 C. The mixture was carefully concentrated to remove DMF (CAUTION; a small amount of azide remains). The residue was dissolved in aqueous Na2CO3 (8 g, 0.075 mol in 0.3 L of aqueous solution). This aqueous layer was washed with ethyl acetate (2×200 mL). The aqueous layer was carefully brought to a pH of from 4 to 5 under good ventilation as traces of hydrazoic acid may form. The solid product (7 g) precipitated out of solution. The pH was then brought to between 1 and 2, and another batch of crystals was collected (3.8 g). These batches were shown to be the same substance by NMR. The resulting 2-pyridyl tetrazole (10.24 g, 0.07 mol) was allowed to react with bromooctadecane (25.2 g, 0.077 mol) and triethylamine (7.8 g, 0.077 mol) in acetonitrile (80 mL) at 97 C. for about 7.5 h. The solvent was removed under reduced pressure. The isomers were isolated by automated flash chromatography (120 g column; eluted with a gradient of from 0% to 25% ethyl acetate/hexanes over thirty minutes. The flow was 85 mL per minute.) The less polar spot had a mass of 8.3 g. The more polar spot had a mass of 13.6 g. The total yield of the reaction was 81%. HMBC NMR analysis led to the following structural assignments: (0184) Pyr-Ttz-1-C18: Less polar spot: 1H NMR (400 MHz, CDCl3) delta 8.7 (dd, 1H, ArH), 8.3 (d, 1H, ArH), 7.9 (t, 1H, ArH), 7.4 (m, 1H, ArH), 5.0 (t, 2H, NCH2), 1.9 (m, 2H, NCH2CH2), 1.4-1.2 (m, 28H, aliph), 0.85 (t, 3H, Me). Melting point: 67.6-68.9 C. Pyr-Ttz-2-C18: More polar spot: 1H NMR NMR (400 MHz, CDCl3) delta 8.8 (dd, 1H, ArH), 8.3 (d, 1H, ArH), 7.8 (t, 1H, ArH), 7.4 (m, 1H, ArH), 4.7 (t, 2H, NCH2), 2.1 (m, 2H, NCH2CH2), 1.4-1.2 (m, 28H, aliph), 0.9 (t, 3H, Me). Melting temperature was between 66.4 C. and 67.9 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With triethylamine; for 5h; | 1) 20 g of octabromohydrin was added to a 1000 ml single-necked flask, 250 ml of dichloropropane and 17.7 g of triethylamine were added, and 16.65 g of methacryloyl chloride was added dropwise with stirring. After completion of the dropwise addition, stirring was continued for 5 hours. After completion of the reaction, the system was washed with water and saturated sodium carbonate and saturated brine, respectively. The organic phase was dried over anhydrous sodium sulfate, concentrated, and chromatographed. 18.4 g of octadecyl methacrylate was obtained in a yield of 76%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68.4% | Stage #1: 15-hydroxylpentadecanoic acid With N,N,N,N,N,N-hexamethylphosphoric triamide; sodium hydride In tetrahydrofuran at 0℃; for 1h; Stage #2: 1-Bromooctadecane In tetrahydrofuran | 9.2 Synthesis of 15-(octadecyloxy)pentadecanoic acid 100 g (0.31 mol) of 15-hydroxypentadecanoic acid is dissolved in 150 ml of THF and 150 ml of HMPA, and 32 g (0.80 mol) of 60% sodium hydride (NaH) is slowly added at a reaction temperature of 0 ° C or lower. After stirring for 1 hour, add 100 g (0.30 mol) of octadecylbromide in 50 ml of THF and slowly add it. When the reaction is complete, the reaction is quenched with water, the THF is firstly blown off under reduced pressure, the organic layer extracted with ethyl acetate is washed three times with water, treated with anhydrous Na2SO4, filtered and the ethyl acetate is removed by distillation under reduced pressure. The obtained solid was recrystallized from n-hexane and dried under reduced pressure at 40 to obtain a yield of 68.4% and a white powder of 108.3 g of 15- (octadecyloxy) pentadecanoic acid as a white powder. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate In acetone Reflux; | ||
With potassium carbonate In acetone Reflux; | 2.3.1. Synthesis of 3,4-dioctyloxy acetophenone (A) 3,4-dioctadecyloxy acetophenone was synthesized by refluxing 3,4-dihydroxy acetophenone(1 equiv.) with corresponding n-octadecyl bromides (C18H37Br) (2 equiv.) in the presence ofAnhy.K2CO3 (1.2 equiv.) in dry acetone as a solvent [36]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | Methyl 2- (2-hydroxyphenyl) acetate (1a, 0.50 g, 3.01 mmol) was dissolved in N, N-dimethylformamide (5 mL)Potassium carbonate (1.25 g, 9.03 mmol) is added at room temperature and stirred for 30 minutes.Then 1-bromo octadecane (1.32 g, 3.97 mmol) was added to a solution ofAnd the temperature is refluxed at 60 C.When the reaction is completed, the reaction mixture is cooled to room temperature, distilled water is added, extracted three times with ethyl acetate, and washed with brine. The organic layer was dried over anhydrous MgSO4 and the solvent was removed under reduced pressure. The mixture was then separated by silica gel column chromatography (ethyl acetate / hexane = 1: 20) to give the title compound (0.57 g, 45%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
6.5% | With N-ethyl-N,N-diisopropylamine; In N,N-dimethyl-formamide; at 40℃; | PPDSA (0.3 g, 1.59 mmol, 1 eq) is dissolved in 20 ml of DMF. 1-Bromooctadecane (2.12 g, 6.36 mmol, 4 eq) and Hunig base (2.78, ml, 15.9 mmol, 10 eq) were added thereto and stirred overnight at 40 C. The reaction-completed compound was lyophilized, and the dried compound was subjected to silica gel chromatography to obtain a pure compound (72 mg, 6.5%) represented by the following formula (14) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1-Bromooctadecane 1.35 mL (4 e.q.),NaI 0.60 g (4 e.q.),Anhydrous acetonitrile 20 mL,Place in a sealed high pressure reaction flask and react at 80 C for 24 h.Add 1b 0.34g (1 mmol, 1 e.q.), charge N2 for 15 min, and react for 12 h.Thereafter, it was heated to reflux at 60 C for 2 h to be sufficiently oxidized.Cool to room temperature and filter.The filtrate was spun dry and passed through three columns in sequence: a neutral alumina column (petroleum ether-n-butanol 500:65), a silica gel column (the supernatant of n-butanol-water-glacial acetic acid 50:3:3),Gel column (methanol-dichloromethane-anhydrous ether 1:1:1).A yellow crystal 10 was obtained with a yield of about 10%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | With tetra-(n-butyl)ammonium iodide; potassium carbonate; In acetone; for 18h;Reflux; | To a solution of Methyl 4-mercaptobenzoate (466 mg, 2.77 mmol) in acetone (20 mL) was added K2CO3 (613 mg, 4.44 mmol) and 1-bromooctadecane (1.48 g, 4.44 mmol), and TBAI (143 mg, 0.44 mmol) and the resulting solution was stirred at reflux overnight. The reaction mixture was concentrated under red uced pressure and purified by silica-gel column chromatography (1 :0-3 : 2, pet. ethen EtOAc, v/v) to give the title compound as a white solid (460 mg, 1.09 mmol, 40%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | In acetonitrile; for 24h;Reflux; | The mixture containing 1.0 g (8.9 mmol) of 1-(2-hydroxyethyl)imidazole and 3.59 g (9.8 mmol) of 1-octadecyl bromide dissolved in 10 mL of acetonitrile was boiled with reflux condenser for 24 h. The precipitate formed during cooling was filtered, purified by recrystallization from ethyl acetate and dried under vacuum. Yield: 3.00 g (69%). Mp=56-58 C. IR-spectrum (KBr), cm-1: 3325, 3140, 3080, 2915, 2850, 1565, 1472,1378, 1165,1071, 871, 721. 1H NMR spectrum, 400 MHz (CDCl3), delta,ppm, J/Hz: 0.87 t (3H, J=7.0), 1.24-1.32m (30 H), 1.89-1.92m (2 H),3.98 t (2H, J=4.27), 4.26 t (2H, J=7.6), 4.53 t (2H, J=4.90), 7.31 s(1 H), 7.63 s (1 H), 9.73 s (1 H). ESI MS, m/z: 365.5 [M-Br]+.Calculated, %: C23H45 N2 OBr: C 62.00; H 10.18; N 6.29; Br 17.93;found, %: C 61.75; H 10.43; N 6.22; Br 17.58. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
General procedure: To a solution of 3-amino 7-hydroxycoumarin (1.0 eq) in dimethylformamide (DMF) (20 mL) was added anhy. K2CO3 (2.5 eq) and stirredat room temperature for 10-15 min. To this mixture, alkyl bromide(1.0 mmol) was added and resulting solution was stirred at room temperature(rt) for 22-24 h. The completion of reaction was checked byTLC. After completion of reaction, the reaction mixture was pouredinto ice-cold water to give solid. The solid was filtered, washed withwater, dried and recrystallized from ethanol to give compound 13 asoffwhite solid. These compounds 14a-lwere directly used for next step. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: tert.-butyl lithium / tetrahydrofuran; n-heptane / 2 h / -80 °C / Inert atmosphere 1.2: 48 h / -80 - 20 °C / Inert atmosphere 1.3: 2 h / 20 °C / Inert atmosphere 2.1: boron tribromide / dichloromethane / 12 h / -80 - 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With potassium carbonate In N,N-dimethyl-formamide at 60℃; for 6h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
36% | Stage #1: Sudan III With potassium carbonate In N,N-dimethyl-formamide at 25℃; for 0.166667h; Stage #2: 1-Bromooctadecane In N,N-dimethyl-formamide at 60 - 80℃; for 96h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With N-ethyl-N,N-diisopropylamine for 96h; Reflux; | 28 Example 28: Preparation of quaternized bis(3-trimethoxysilylpropyl)dialkylammonium bromide Bis(3-trimethoxysilylpropyl)amine (1 eq.) is treated with an alkyl halide (2 eq.), such as a C18-C22 alkyl bromide, in isopropanol and heated at reflux for 96 h to produce bis(3- trimethoxysilylpropyl)-N,N-dialkyllammonium bromide. An exemplary reaction scheme is depicted in FIG.11A and FIG.11B. FIG.17 illustrates an IR spectrum of bis(3- trimethoxysilyl)propyl-N,N-dioctadecyl ammonium bromide. Bis(3-trimethoxysilyl)propyl-N,N- dihexadecyl ammonium bromide can also be prepared using similar methods using bromohexadecane instead of bromooctadecane. | |
With N-ethyl-N,N-diisopropylamine for 96h; Reflux; | 28 Example 28: Preparation of quaternized bis(3-trimethoxysilylpropyl)dialkylammonium bromide Bis(3-trimethoxysilylpropyl)amine (1 eq.) is treated with an alkyl halide (2 eq.), such as a C18-C22 alkyl bromide, in isopropanol and heated at reflux for 96 h to produce bis(3- trimethoxysilylpropyl)-N,N-dialkyllammonium bromide. An exemplary reaction scheme is depicted in FIG.11A and FIG.11B. FIG.17 illustrates an IR spectrum of bis(3- trimethoxysilyl)propyl-N,N-dioctadecyl ammonium bromide. Bis(3-trimethoxysilyl)propyl-N,N- dihexadecyl ammonium bromide can also be prepared using similar methods using bromohexadecane instead of bromooctadecane. |
Tags: 112-89-0 synthesis path| 112-89-0 SDS| 112-89-0 COA| 112-89-0 purity| 112-89-0 application| 112-89-0 NMR| 112-89-0 COA| 112-89-0 structure
Precautionary Statements-General | |
Code | Phrase |
P101 | If medical advice is needed,have product container or label at hand. |
P102 | Keep out of reach of children. |
P103 | Read label before use |
Prevention | |
Code | Phrase |
P201 | Obtain special instructions before use. |
P202 | Do not handle until all safety precautions have been read and understood. |
P210 | Keep away from heat/sparks/open flames/hot surfaces. - No smoking. |
P211 | Do not spray on an open flame or other ignition source. |
P220 | Keep/Store away from clothing/combustible materials. |
P221 | Take any precaution to avoid mixing with combustibles |
P222 | Do not allow contact with air. |
P223 | Keep away from any possible contact with water, because of violent reaction and possible flash fire. |
P230 | Keep wetted |
P231 | Handle under inert gas. |
P232 | Protect from moisture. |
P233 | Keep container tightly closed. |
P234 | Keep only in original container. |
P235 | Keep cool |
P240 | Ground/bond container and receiving equipment. |
P241 | Use explosion-proof electrical/ventilating/lighting/equipment. |
P242 | Use only non-sparking tools. |
P243 | Take precautionary measures against static discharge. |
P244 | Keep reduction valves free from grease and oil. |
P250 | Do not subject to grinding/shock/friction. |
P251 | Pressurized container: Do not pierce or burn, even after use. |
P260 | Do not breathe dust/fume/gas/mist/vapours/spray. |
P261 | Avoid breathing dust/fume/gas/mist/vapours/spray. |
P262 | Do not get in eyes, on skin, or on clothing. |
P263 | Avoid contact during pregnancy/while nursing. |
P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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