Structure of 2-Decyltetradecan-1-ol
CAS No.: 58670-89-6
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| CAS No. : | 58670-89-6 |
| Formula : | C24H50O |
| M.W : | 354.65 |
| SMILES Code : | CCCCCCCCCCCCC(CCCCCCCCCC)CO |
| English Name : | 2-Decyltetradecan-1-ol |
| MDL No. : | MFCD00674096 |
| InChI Key : | CAYHVMBQBLYQMT-UHFFFAOYSA-N |
| Pubchem ID : | 93875 |
* 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 |
|---|---|---|
| 98% | Stage #1: 2-decylteradecanol With triphenylphosphine In dichloromethane at 0℃; for 0.0833333h; Inert atmosphere; Stage #2: With N-Bromosuccinimide In dichloromethane for 16h; | 1 Example 1 Synthesis of 1 -bromo-2-decyltetradecane (1) Under argon, triphenylphosphine (27.8 g, 70.5 mmol) was suspended in a flask with DCM (47 ml). The mixtures was cooled to 0°C before 2-decyltetradecan-1-ol (29.8 ml, 105.8 mmol) was introduced. After 5 minutes stirring, N-bromosuccinimide (18.8 g, 105.8 mmol) was added poration wise to the flask. The reaction mixture immediately turned yellow and continued to darken to orange. The reaction was stirred for 16 hours after which the solvent was removed by vacuum evaporation. The brown residue was diluted with petroleum ether and the solution flushed through a silica plug. The filtrate was evaporated to give a clear oil. Yield: 28.7 g, 98 %. 1H NMR(400 MHz, Chloroform-d) 6 3.44 (d, J = 4.7 Hz, 2H), 1.66 - 1.47 (m, 2H), 1.44 - 1.15 (m, 40H),0.88 (t, J= 6.6 Hz, 7H).13C NMR (101 MHz, ODd3) 639.72,39.70,32.75,32.10,29.97,29.82,29.77, 29.53, 26.74, 22.86, 14.26. |
| 97% | With N-Bromosuccinimide; triphenylphosphine In dichloromethane at 0 - 20℃; for 24h; | 1 -bromo-2-decyl-tetradecane (116) 2-decyltetradecan-1-ol (30 g, 84.5 mmol) and triphenylphosphine (45 g, 169 mmol) were dis30 solved in dichloromethane (100 ml) and cooled to 0 00 To the mixture N-bromosuccinimide(23 g, 127 mmol) was added slowly, then stirred at room temperature for 24 hours. After evaporation of solvents in vacuo the products were dissolved in hexane. Purification by column chromatography (silica gel, hexane) yielded compound 116. Colorless oil (yield = 97%). |
| 97% | With N-Bromosuccinimide; triphenylphosphine In dichloromethane at 0 - 20℃; for 72h; Inert atmosphere; |
| 95% | With N-Bromosuccinimide; triphenylphosphine In dichloromethane at 20℃; for 50h; Cooling with ice; | |
| 94% | With bromine; triphenylphosphine In dichloromethane at 20℃; Inert atmosphere; | |
| 91% | With carbon tetrabromide; triphenylphosphine In dichloromethane at 0℃; for 2h; | 14 EXAMPLE 14 1-Bromo-2-decyl-1-tetradecane was prepared by the bromonation of 2-decyl-1-tetradecanol according to a method described in the Journal of Organic Chemistry,42, 353, 1997. A solution of 2-decyl-1-tetradecanol (50.0 g, 0.14 mol) and CBr4 (58.0 g, 0.17 mol) in dichloromethane (150 mL) was stirred at 0º C and PPh3 (55.0 g, 0.21 mol) was added portionwise. After the addition of PPh3, the reaction mixture was stirred for additional 2 h at 0º C. Reaction solvent was then removed and the mixture was washed with methanol to remove the by-product phosphine oxide. The resulting viscous liquid was further purified by extracting with hexane to give 1-bromo-2-decyl-1-tetradecane (53.6 g, 91 %). This compound was shown by 1H NMR and GC-MS to have the following structural formula: |
| 89% | With N-Bromosuccinimide; triphenylphosphine In dichloromethane at 0℃; Schlenk technique; Inert atmosphere; | |
| 80% | With N-Bromosuccinimide; triphenylphosphine In dichloromethane at 20℃; for 12h; | |
| 80% | With N-Bromosuccinimide; triphenylphosphine In dichloromethane at 20℃; for 12h; | |
| 75.5% | With bromine; triphenylphosphine In dichloromethane at 0℃; for 16h; | 2 11-(6-bromomethyl)tricosane In a well dried 500 mL three-necked round bottom flask, Triphenylphosphine (23.72 g, 0.0862 mol) in MC, Bromine (13.84 g, 0.06544 mol) dissolved in MC added dropwise over 10 min at 0 °C. Then, 2-decyltetradecan-1-ol (25.5g, 0.0719 mol) was dropped and stirred for 16 hours. Then extracted with MC, dried with MgSO4, and then the organic layer was washed with water using a rotary evaporator to remove the solvent. Hexane as the impurity solid filtered (triphenylphosphine reaction unit) to melt glass the solvent, the material from melt in hexane using a rotary evaporator to remove the solvent. By using n-hexane separated by column chromatography the desired compound 11-(6-bromomethyl)tricosane (27.2 g, 75.5 %). |
| 75.5% | With bromine; triphenylphosphine In dichloromethane at 0℃; for 16h; | 2 Synthesis of 11-(bromomethyl)tricosane Triphenylphosphine (23.72 g, 0.0862 mol) was added to a well-dried 500 mL three-necked round-bottomed flask and dissolved in MC. The temperature was lowered to 0 ° C and bromine (13.84 g, 0.06544 mol) Followed by dropping and stirring for 10 minutes. Then, 2-decyltetradecan-1-ol (25.5 g, 0.0719 mol) dissolved in MC was dropped and stirred for 16 hours. MC. The organic layer was washed with water, dried over MgSO4, and then the solvent was removed using a rotary evaporator. The solvent was dissolved in hexane, and the impure solid (triphenylphosphine reactant) was distilled off freely. The material dissolved in hexane was removed using a rotary evaporator. The residue was subjected to column chromatography using n-hexane to obtain 11- (bromomethyl) tricoic acid as a target compound (27.2 g, 75.5%). |
| 70% | With N-Bromosuccinimide; triphenylphosphine In dichloromethane at 0 - 20℃; Inert atmosphere; | |
| With bromine; triphenylphosphine | ||
| With N-Bromosuccinimide; triphenylphosphine | ||
| With carbon tetrabromide; triphenylphosphine In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere; | ||
| With N-Bromosuccinimide; triphenylphosphine In dichloromethane at 20℃; for 12h; Inert atmosphere; | ||
| With N-Bromosuccinimide; triphenylphosphine In dichloromethane at 0 - 20℃; Inert atmosphere; Schlenk technique; | ||
| With bromine; triphenylphosphine In dichloromethane at 0 - 20℃; Inert atmosphere; | ||
| With carbon tetrabromide; triphenylphosphine In tetrahydrofuran at 20℃; Inert atmosphere; |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 95% | Stage #1: 2-decylteradecanol With trimethylamine hydrochloride; triethylamine In dichloromethane for 0.333333h; Cooling with ice; Stage #2: p-toluenesulfonyl chloride In dichloromethane at 0℃; for 3h; | |
| 88% | Stage #1: 2-decylteradecanol; p-toluenesulfonyl chloride With pyridine In dichloromethane at 0 - 20℃; for 3h; Stage #2: With water In dichloromethane at 0℃; | |
| 88% | With pyridine In dichloromethane at 20℃; for 3h; Cooling with ice; | 2 Example 2 2-Decyl-1-tetradecanol (compound 3) (9.7 g (0.0274 mol)) and pyridine (10.6 g (0.134 mol)) were dissolved in dichloromethane (100 ml), and tosyl chloride (15.5 g (0.0813 mol)) was added under stirring in an ice bath. After stirring for 3 hours at room temperature, ice water (20 ml) was added to the mixture to terminate the reaction. Hexane (200 ml) was added to the obtained reaction solution, and after washing the organic layer with 1 N HCl (3×100 ml), it was washed with a saturated sodium bicarbonate aqueous solution (3×100 ml), and further with a saturated NaCl solution three times. After drying over anhydrous magnesium sulfate, the solvent was distilled off under vacuum to obtain compound 4 (toluene-4-sulfonic acid 2-decyl-1-tetradecyl ester). The yield was 88%. (0179) 1H-NMR (300 MHz, CDCl3) (0180) δ 7.78 (d, J=8.25, 2H), 7.33 (d, J=8.44, 2H), 3.91 (d, J=5.14, 2H), 2.44 (s, 3H), 1.65-1.51 (m, 1H), 1.38-1.02 (m, 40H), 0.90-0.78 (m, 6H) |
| 82.6% | With pyridine at -10 - 0℃; for 4h; | |
| 33% | With pyridine In dichloromethane at 20℃; for 72h; | |
| Stage #1: 2-decylteradecanol With pyridine at 0℃; for 0.5h; Stage #2: p-toluenesulfonyl chloride for 2h; | 2.3.1. Synthesis of 2-Decyltetradecyl 4-Methylbenzenesulfonate (1) 2-Decyltetradecan-1-ol (23.5 g, 0.066 mol) was added andstirred at 10 C for 10 min. Pyridine (15.8 g, 0.198 mol)was added at 0 C and the mixture stirred for 30 min.Then, p-toluene sulfonyl chloride (13.9 g, 0.073 mol) wasadded and stirred for 2 h, and then cooled down to roomtemperature and kept at this temperature for 12 h. Thesolution was then diluted with water and extracted withethyl acetate. The organic extract was dried over MgSO4and the solvent was removed. Without further purificationfor following reaction proceeds. | |
| 83 % | Stage #1: 2-decylteradecanol With pyridine Inert atmosphere; Cooling with ice; Stage #2: p-toluenesulfonyl chloride Inert atmosphere; Cooling with ice; |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 90% | With C37H36Cl2NPRuS2; sodium hydroxide In neat (no solvent) at 135℃; Inert atmosphere; Sealed tube; | 2-Ethylhexan-1-ol (5a); Typical Procedure General procedure: An oven-dried 15 mL pressure tube was charged with BuOH (4mmol), catalyst 1 (0.5 mol%), and NaOH (25 mol%), and themixture was purged three times with argon. The tube wassealed with a screw cap and the mixture was heated at 135 °Cfor 36 h. The resulting mixture was passed through a plug ofCelite and then all the volatiles were evaporated. The crudemixture was then purified by column chromatography [silicagel (100-200 mesh)] to give a colorless liquid; yield: 195 mg(75%). |
| 86% | With [CpIrCl2]2; potassium <i>tert</i>-butylate; 1,7-Octadiene In para-xylene at 120℃; for 4h; | |
| 83% | With potassium <i>tert</i>-butylate In neat (no solvent) at 150℃; for 24h; |
| 80% | With potassium hydroxide at 240℃; for 5h; Inert atmosphere; Dean-Stark; Large scale; | 4 Example 4: In a four-necked flask equipped with a thermometer, water trap, reflux condenser, gas duct, and mechanical stirrer, 1000 kg of n-dodecanol and 2 kg of potassium hydroxide were added. Nitrogen was introduced for 30 minutes, and the temperature was raised to 60°C. 10 kg of mesoporous carbon sphere-supported nickel catalyst was then added, and the temperature was raised to 240°C. The reaction was allowed to react for 5 hours. After cooling, the reaction mixture was washed with hot water until neutral, dried over anhydrous magnesium sulfate, and filtered. Vacuum distillation was performed to obtain colorless, transparent 2-decyltetradecanol with a purity of 95% and a yield of 80%. The polymer content was less than 1 wt%. |
| With heptanal; potassium hydroxide at 250℃; for 4h; Dean-Stark; | ||
| 66 % | With potassium hydroxide In water at 240℃; Inert atmosphere; | 9 (Example 1) General procedure: Stirrer, thermometer, nitrogen blowing tube, sampling tube, and for separating reaction by-product water 600.0 g (3.79 mol) of 1-decanol (C10) (manufactured by Kao Corporation, product name: Calcol 1098) as a raw alcohol was placed in a 1 L five-neck glass flask equipped with a condenser and a dephlegmator. ), 13.3 g of 48% potassium hydroxide aqueous solution (manufactured by Kanto Kagaku Co., Ltd.) as the base catalyst (B) (3 parts by mole per 100 parts by mole of the total amount of raw alcohol), and Preparation Example 1 as the catalyst (A). 0.06g (0.01 parts by mass per 100 parts by mass of the total amount of raw material alcohol) of the Cu-Zn/Zeolite fired product prepared in step 1 was charged, and nitrogen gas was bubbled into the system at a flow rate of 6L/hr. The temperature inside was raised.After the system temperature reached 225° C., the flow rate of nitrogen gas was changed to 0.13 L/hr, and the reaction was carried out for 8 hours.The results are shown in Table 1. |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 90% | With 1H-imidazole; iodine; triphenylphosphine In toluene at 0 - 20℃; for 2h; | |
| 73% | With hydrogen iodide In water Heating / reflux; | 19.a 228.06g of 2-decyl-1-tetradecanol [58670-89-6] are mixed with 484.51 g 47% hydroiodic acid and the mixture is refluxed overnight. The product is extracted with t-butyl-methylether. Then the organic phase is dried and concentrated. The product is purified over a silica gel column to give 211.54 g of the desired compound 51 (73%). 1H-NMR (ppm, CDCI3): 3.26 2H d, 1.26-1.12 41 H m, 0.88 6H t. |
| 73% | With hydrogen iodide In water Reflux; | 1.a; 4.a a) 228.06 g of 2-decyl-1-tetradecanol [58670-89-6] are mixed with 484.51 g 47% hydroiodic acid [10034-85-2] and the mixture is refluxed overnight. The product is extracted with t-butyl-methylether. Then the organic phase is dried and concentrated. The product is purified over a silica gel column to give 211.54 g of the desired compound 1 (73%). 1H-NMR data (ppm, CDCl3): 3.26 2H d, 1.26-1.12 41H m, 0.88 6H t. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With dibutyltin(II) dilaurate In chloroform at 65℃; for 16h; Inert atmosphere; | 4 To a solution of 2-decyl-l-tetradecanol (19.62 g) in chloroform (50 mL) was added the compound of Example 2 (23. Ig) and 3 drops of DBTDL (dibutyl tin dilaurate). The reaction mixture was subsequently stirred at 65°C in an argon atmosphere for 16h. Hereafter, the solvent was removed by evaporation using a rotary evaporator. The resulting compound was redissolved in pentane (100 mL) and filtered over celite followed by removal of the solvent in vacuo, resulting in a slight yellowish glass. 1H NMR (400 MHz, CDCl3): δ 13.1 (IH), 11.9 (IH), 10.2 (IH), 5.8 (IH), 4.8-4.3 (IH), 4.2-3.6 (3H), 3.1-2.9 (2H), 2.2 (3H), 1.9-0.6 (62H). |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| Multi-step reaction with 3 steps 1: N-Bromosuccinimide; triphenylphosphine 2: potassium carbonate / N,N-dimethyl-formamide / Reflux 3: N-Bromosuccinimide |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 70.44% | Stage #1: 2-decylteradecanol With sodium In tetrahydrofuran at 70℃; for 2h; Stage #2: 1 ,6-dibromohexane In tetrahydrofuran at 80℃; for 8h; | 3 11-((6-bromohexyloxy)methyl)tricosane Well-dried 500 mL three-necked round bottom flask was charged with 2-decyltetradecan-1-ol (30 g, 0.085 mol), metal Na (2.1 g 0.0913 mol) is dissolved in THF (270 mL) refluxed for 2 hours at 70°C. And added dropwise to 1,6-dibromohexane (41 g, 0.168 mol) slowly and raising the temperature to 80°C and refluxed for 8 hours. After completion of reaction, and extracted with ether and the aqueous solution of Na2CO3, Dried over anhydrous MgSO4 and then, by the use of a rotary evaporator to remove the solvent. The objective compound obtained by column chromatography 11-((6-bromohexyloxy)methyl)tricosane (31 g, 70.44%). [Figure 4]. |
| 70.44% | Stage #1: 2-decylteradecanol With sodium In tetrahydrofuran at 70℃; for 2h; Stage #2: 1 ,6-dibromohexane With lithium chloride; copper(I) bromide In tetrahydrofuran at 80℃; for 8h; | 3 Synthesis of 11-((6-bromohexyloxy)methyl)tricosane 2-decyltetradecan-1-ol (30 g, 0.085 mol) was dissolved in THF (270 mL) and a metal Na (2.1 g, 0.0913 mol) was added to a well dried 500 mL three- ) Was added and the mixture was refluxed at 70 ° C for 2 hours. Then, 1,6-dibromohexane (41 g, 0.168 mol) was slowly added dropwise, the temperature was raised to 80 ° Cto 8 hours; Upon completion of the reaction, the reaction mixture was extracted with ether and Na2CO3 aqueous solution, dried over anhydrous MgSO4, and then the solvent was removed using a rotary evaporator. The desired compound 11 - ((6-bromohexyloxy) methyl) tricoic acid was obtained by column chromatography (31 g, 70.44%). |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| In neat (no solvent) at 119.84℃; for 4h; Sealed tube; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 68% | With Amberlyst 15 resin at 80℃; for 24h; | 2 - 1 l-(((2,3-dimethylbutan-2-yl)oxy)methyl)tricosane A solution of 2-decyl-l-tetradecanol (5 g, 0.014 mol) and 2,3-dimethyl-2-butene (16 g, 0.190 mol) was treated with Amberlyst 15 resin (200 mg (dry mass), pre-washed in deionised water and dried) and stirred at 80 °C for 24 h in a flask fitted with a reflux condensor. Progress of the reaction was monitored by analysing a sample using gas chromatography (GC) after 2 h of reaction and is shown in Figure 2. After this time the reaction mixture was filtered to remove the resin and purified by flash column (0140) chromatography using heptane as the eluent to yield the tertiary ether (4.2 g, 0.01 mol, 68 % yield) as a colourless oil. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| Stage #1: perylene-3,4,9,10-tetracarboxylic acid 3,4:9,10-dianhydride With sulfuric acid; bromine; iodine Stage #2: 2-decylteradecanol With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 14h; Inert atmosphere; Reflux; Overall yield = 1.4 g; | 2.2.3 Synthesis of 1,7(6)-di(2-decyl-1-tetradecanoyl)perylene-3,4,9,10-tetracarboxylic acid bisanhydride (6) 4 (1.00 g, 1.82 mmol), 2-decyl-1-tetradecanol (5, 1.88 g, 5.30 mmol), and K2CO3 (1.62 g, 4.50 mmol) were stirred under argon atmosphere and at room temperature in 200 mL DMF for a 2 h period. The reaction mixture was then heated to reflux and continued for 12 h. After cooling to room temperature, the solution was poured into a mixture of cold acetic acid/cold water (100 mL, 1:1 by volume). After allowing the mixture to cool at -8 °C overnight, the precipitate was filtered off, washed with hot water, and dried in vacuum oven to give the crude product. Finally, the dark purple crude product was purified by recrystallization from dimethylformamide/methanol to obtain pure product 6 as a dark purple powder (1.40 g, 70 %). M.p.:>400 °C. FTIR (Fig. 1 b, KBr, thin film, cm-1): ν = 3065 (aromatic CH- stretch), 2920 and 2850 (aliphatic CH- stretch), 1763 and 1731 (anhydride C=O stretch), 1590 (aromatic C=C stretch), 1244 and 1155 (CO- stretching), 1011 (C-OC- stretch), 806 and 738 (CH- bend). 1H NMR (400 MHz, CDCl3:CF3COOD (3:1)): δH (ppm) = 8.44-8.42 (d, J =8.0 Hz, 2Ar-H), 8.36-8.34 (d, J =8.0 Hz, 2Ar-H), 7.5 (s, 2Ar-H), 4.21 (d, J =7.8 Hz, 2CH2), 1.87 (m, 2CH), 1.63 (m, 4CH2), 1.32-1.15 (m, 36CH2), 0.86 (m, 4CH3). 13C NMR (100.6 MHz, CDCl3:CF3COOD (3:1)): δC (ppm) = 162.14, 160.92, 138.59, 131.75, 125.28, 123.07, 122.43, 110.22, 74.59, 42.78, 41.43, 41.30, 37.36, 34.04, 30.33, 29.33, 27.13, 22.71, 16.06. UV/Vis (Fig. 2 , DMF): λmax nm ε = 421, 484, 518 12,500, 551, 697 and 753. UV/Vis Fig. 3 a, solid state): λmax (nm) = 472, 498, 541 nm. Fluorescence (Fig. 2, DMF, λexc = 485 nm): λmax (nm) = 534 and 570. Fluorescence quantum yield (c = 1 × 10-6 M in TCE, reference N,N′-bis-dodecyl-3,4,9,10-perylenebis(dicarboximide) with f = 100 %, λexc. = 485 nm) = 30 %. Anal. Calcd. for C72H104O8 (Mw, 1097.59); C, 78.79; H, 9.55. Found: C, 78.62; H, 9.46. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 94% | Stage #1: 2-decylteradecanol With methanesulfonyl chloride; triethylamine In dichloromethane at -10 - 25℃; for 17.5h; Inert atmosphere; Stage #2: 1-(2,3-dihydroxy propyl)piperazine In ethanol at 150℃; for 13h; Inert atmosphere; | 7; 9 Example 9 Into a 1 L four-necked flask equipped with a stirring machine and a condenser tube, 70.9 g (0.20 mol) of 2-decyl-1-tetradecanol, 22.3 g (0.22 mol) of triethylamine and 1,320 g of dichloromethane were added, 25.2 g (0.22 mol) of methanesulfonyl chloride was dropwise added in a stream of nitrogen in a state cooled to -10° C. to 0° C., and the reaction mixture was aged at from -10 to 0° C. for 30 minutes and at 25° C. for 17 hours. Then, extraction with a saturated salt solution and removal of the solvent were carried out to obtain 93.0 g of an intermediate. Then, into a 1 L four-necked flask equipped with a stirring machine and a condenser tube, 92.6 g of the intermediate, 124.4 g (0.54 mol) of 3-(1-piperazinyl)-1,2-propanediol and 150 g of ethanol were added, followed by reaction at 150° C. for 13 hours in a stream of nitrogen. Then, only the oil layer was collected by extraction with chloroform, which was subjected to vacuum distillation and vacuum drying to obtain 81.8 g (yield: 94.0%) of pale yellow oil 3-(4-(2-decyltetradecyl)-1-piperazinyl)-1,2-propanediol. Identification was conducted from the results of 1H-NMR measurement, 13C-NMR measurement and elemental analysis.1H-NMR (CDCl3): 3.71-3.82 (m, 2H), 3.50-3.53 (dd, 1H), 2.12-2.66 (m, 12H), 1.48 (s, 1H), 1.20-1.26 (m, 40H), 0.86-0.90 (t, 6H) [ppm]. 13C-NMR (CDCl3): 66.76, 65.04, 63.40, 60.37, 53.71, 34.82, 32.37, 31.94, 30.11, 29.72, 29.69, 29.38, 26.61, 22.70, 14.13 [ppm]. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 71% | With pyridinium p-toluenesulfonate In 5,5-dimethyl-1,3-cyclohexadiene at 130℃; for 5h; Dean-Stark; | 12 Example 12 - synthesis of (Z)-ll-(((2-methylbut-l-en-l-yl)oxy)methyl)tricosane (reduced equivalents of aldehyde) To a 3-necked round bottom flask equipped with a Dean-Stark receiver and a thermometer was added 2-decyltetradecan-l-ol (50 g, 0.14 mol), xylenes (50 g), 2- methylbutanal (36.5 g, 0.42 mol, 3 equiv.) and pyridinium p-toluenesulfonate (177 mg, 0.7 mmol, 0.5 mol%). The reaction mixture was heated in an oil bath to a temperature of 130 °C resulting in vigorous reflux. The reaction progress was monitored by GC and after ca. 5 hr the reaction was cooled to room temperature overnight under an N2 atmosphere. K2CO3 (220 mg) was added and the mixture filtered. The volatiles were removed to give the (Z)-l l-(((2- methylbut-l-en-l-yl)oxy)methyl)tricosane product as a yellow oil, GC analysis of the mixture: 1% dehydrated alcohol (11-methylenetricosane + isomers), 6% alcohol, 71% of the (Z)-l l-(((2-methylbut-l-en-l-yl)oxy)methyl)tricosane and 20% acetal. Comparative |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 78% | With pyridinium p-toluenesulfonate at 20 - 135℃; Dean-Stark; Inert atmosphere; | 11 Comparative Example 11 - synthesis of (Z)-ll-(((2-ethylhex-l-en-l- yl)oxy)methyl)tricosane using 2-ethylhexanal dimethyl acetal as starting material To a 3-necked round bottom flask equipped with a Dean-Stark receiver and a thermometer was added 2-decyltetradecan-l-ol (40 g, 0.11 mmol), 2-ethylhexanal dimethyl acetal (29.5 g, 0.17 mol), and pyridinium p-toluenesulfonate (0.14 g, 0.5 mol%). The reaction mixture was heated in an oil bath at 135 °C with continuous removal of methanol. After ca. 5 hr the mixture was cooled to rt overnight under N2 before K2CO3 (220 mg) was added and the mixture filtered. The volatiles were removed to give a mixture comprised of 78% of the (Z)- l l-(((2-ethylhex-l-en-l-yl)oxy)methyl)tricosane, 18% alcohol, <1% dehydrated alcohol (11- methylenetricosane + isomers) and 3% acetal as a colourless oil. This comparative example demonstrates that the use of a dimethyl acetal, as opposed to a branched aldehyde, results in poorer alcohol conversion and increased by-product production when compared to Example 3, which is performed under similar conditions using the aldehyde reagent. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 98% | With pyridine; toluene-4-sulfonic acid In toluene at 145 - 150℃; for 5h; Dean-Stark; | 2-9; 19 Example 6 - synthesis of (Z)-ll-(((2-ethylhex-l-en-l-yl)oxy)methyl)tricosane using PTSA and pyridine To a 3-necked round bottom flask equipped with a Dean-Stark receiver and a thermometer was added 2-decyltetradecan-l-ol (62 g, 0.18 mmol), 2-ethylhexanal (57 g, 0.44 mmol), toluene (36 g), p-toluenesulfonic acid (0.16 g, 0.5 mol%), and pyridine (71 pL, 0.5 mol%). The reaction mixture was heated in an oil bath to a temperature of 145-150 °C with continuous removal of water. After ca. 5 hr the mixture was cooled to rt overnight under an N2 before K2C03 (220 mg) was added and the mixture filtered. The volatiles were removed to give a mixture comprised of 98% of the (Z)-l l-(((2-ethylhex-l-en-l-yl)oxy)methyl)tricosane, This example demonstrates that the PPTS catalyst may be formed in situ from PTSA and pyridine without significant changes in alcohol conversion and by-product formation when compared to Examples 3 to 5. |