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CAS No. : | 112-89-0 | MDL No. : | MFCD00000231 |
Formula : | C18H37Br | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | WSULSMOGMLRGKU-UHFFFAOYSA-N |
M.W : | 333.39 | Pubchem ID : | 8218 |
Synonyms : |
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Signal Word: | Danger | Class: | |
Precautionary Statements: | P301+P310-P331-P405-P501 | UN#: | |
Hazard Statements: | H304 | Packing Group: | |
GHS Pictogram: |
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* 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 |
---|---|---|
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 |
---|---|---|
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. |
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