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CAS No. : | 929-77-1 | MDL No. : | MFCD00009347 |
Formula : | C23H46O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | QSQLTHHMFHEFIY-UHFFFAOYSA-N |
M.W : | 354.61 | Pubchem ID : | 13584 |
Synonyms : |
Methyl behenate
|
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P301+P312-P302+P352-P304+P340-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
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 |
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With diethyl ether | ||
In Petroleum ether Acidic conditions; |
Yield | Reaction Conditions | Operation in experiment |
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With sulfuric acid | ||
With sulfuric acid for 7h; Heating; | ||
With sulfuric acid Heating; |
Yield | Reaction Conditions | Operation in experiment |
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With hydrogen; nickel at 190 - 200℃; Hydrogenation; |
Yield | Reaction Conditions | Operation in experiment |
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With potassium hydroxide |
Yield | Reaction Conditions | Operation in experiment |
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45.2% | With sodium methylate In methanol at 35℃; electrolysis on Pt electrode, 0.05 amps, 50-60 volts; |
Yield | Reaction Conditions | Operation in experiment |
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With methanol; sulfuric acid for 6h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
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98% | With hydrogen In dichloromethane at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
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With hydrogenchloride at 90℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
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With hydrogenchloride at 90℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
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With lithium aluminium tetrahydride In tetrahydrofuran at 0 - 20℃; for 3h; | ||
With lithium aluminium tetrahydride In tetrahydrofuran |
Yield | Reaction Conditions | Operation in experiment |
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0.7 mg | With hydrogenchloride; methanol at 76℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
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With sulfuric acid In water for 4h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
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With diethyl ether |
Yield | Reaction Conditions | Operation in experiment |
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With diethyl ether |
Yield | Reaction Conditions | Operation in experiment |
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With diethyl ether |
Yield | Reaction Conditions | Operation in experiment |
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With diethyl ether |
Yield | Reaction Conditions | Operation in experiment |
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With diethyl ether |
Yield | Reaction Conditions | Operation in experiment |
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72% | With sodium methylate In methanol at 27℃; Electrochemical reaction; Pt anode; graphite cathode; |
Yield | Reaction Conditions | Operation in experiment |
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With sodium hydrogen sulfate; silica gel In hexane at 70℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
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With sodium hydrogen sulfate; silica gel In hexane at 70℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
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With hydrogenchloride at 74℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
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With hydrogenchloride at 90℃; for 15h; |
Yield | Reaction Conditions | Operation in experiment |
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91% | With sodium methylate In toluene | S.2 Synthesis of (2-morpholinoethyl) behenate (Quencher 2) Synthesis Example 2 Synthesis of (2-morpholinoethyl) behenate (Quencher 2) A mixture of 35.5 g of methyl behenate (18), 19.7 g of 2-morpholinoethanol (17), 270 mg of sodium methoxide and 150 g of toluene was heated under reflux for 6 hours while distilling off the methanol resulting from the reaction. The reaction solution was cooled. By standard aqueous work-up and distilling off toluene, 41.3 g of (2-morpholinoethyl) behenate (Quencher 2) was obtained (yield 91%). The target compound thus obtained was analyzed by IR and 1H-NMR spectroscopy. IR (KBr): v=2917, 2850, 1739, 1467, 1172, 1116 cm-1 |
Yield | Reaction Conditions | Operation in experiment |
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With sodium methylate at 20℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 3 steps 1: MeONa / methanol / Electrolysis; Pt anode; graphite cathode 2: Ba(OH)2 3: 72 percent / MeONa / methanol / 27 °C / Electrochemical reaction; Pt anode; graphite cathode |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: Ba(OH)2 2: 72 percent / MeONa / methanol / 27 °C / Electrochemical reaction; Pt anode; graphite cathode |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 3 steps 1: 1.) n-BuLi / 1.) THF, hexane, -10 deg C, 45 min, 2.) THF, hexane, room temperature, overnight 2: 86 percent / H2 / Pd/C / methanol / 6 h 3: H2SO4 / 7 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 3 steps 1: 1.) n-BuLi / 1.) THF, hexane, -10 deg C, 45 min, 2.) THF, hexane, room temperature, overnight 2: 86 percent / H2 / Pd/C / methanol / 6 h 3: H2SO4 / 7 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: 86 percent / H2 / Pd/C / methanol / 6 h 2: H2SO4 / 7 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: H2, 10percent Pd/C 2: HCl / 2 h / 90 °C |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 2: 45.2 percent / MeONa / methanol / 35 °C / electrolysis on Pt electrode, 0.05 amps, 50-60 volts |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 3 steps 1: KOH 2: 48.6 percent / MeONa / methanol / 35 °C / electrolysis on Pt electrode, 0.05 amps, 50-60 volts 3: 96 percent / LiAlH4 / tetrahydrofuran / 1.) -10 deg C -> room temperature, 1 h, 2.) room temperature, 4 h |
Yield | Reaction Conditions | Operation in experiment |
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Multi-step reaction with 2 steps 1: KOH 2: 48.6 percent / MeONa / methanol / 35 °C / electrolysis on Pt electrode, 0.05 amps, 50-60 volts |
Yield | Reaction Conditions | Operation in experiment |
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In methanol | II.A Step A--Preparation of Potassium Behenate Step A--Preparation of Potassium Behenate Methyl behenate (0.375 moles/mole of sucrose to be used in Step B) is saponified by stirring at reflux in methanol containing an equivalent amount of KOH. The reaction is stirred with heating until all methyl ester has been converted to soap as indicated by infrared analysis. The soap solution is used, as is in the next reaction step. |
Yield | Reaction Conditions | Operation in experiment |
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With potassium hydroxide; at 48 - 52℃; for 4h; | A 500 g quantity of soybean oil was added into temperature- and pressure- controlled water-jacketed reactor 2L all stainless steel pressure Reactor (Parr Instrument Company, Moline, IL, USA). The soybean oil was dried by a negative pressure of 110 mmHg(A) applied by vacuum, and then heating and maintaining the oil at 1000C + 50C under negative pressure while being maintained in a turbulent flow by agitation until there was no trace of bubbling at the oil surface after which, the oil was cooled to 500C + 2C.While the soybean oil was being dewatered, 100 g of absolute methanol (20% w/w of the oil) was added to a stirred vessel and then 5 g of KOH (1% w/w of the oil) was added while the methanol was vigorously agitated until the KOH was completely dissolved. The KOH-methanol mixture was added under vacuum to the 500 g dewatered soybean oil maintained in a turbulent flow by agitation after which, the negative pressure within the reactor was broken with nitrogen gas which was used to flush and then maintain the headspace within the reactor. Addition of the KOH-methanol mixture to the dewatered oil initiated an exothermic esterifcation reaction and therefore, the temperature within the water- jacketed reactor was carefully maintained at 500C + 20C during the reaction period. The esterifcation reaction proceeded for 4 hrs while the oil was maintained in a turbulent flow by agitation. At the end of this time period, agitation was ceased and the methylated soybean oil was transferred to a separation funnel where it was maintained for 18 hrs to allow the reaction mixture to separate into two phases comprising a top layer containing the methyl ester reaction product above a bottom layer containing the reaction by products, i.e., spent methanol and crude glycerol.After the phase separation was complete, the bottom layer containing the reaction by-products was removed from the separation funnel after which, the top methyl ester layer was removed into a separate container. The temperature of the methyl ester product was adjusted to about 75 after which water heated to 95C was added to the methyl ester phase until a ratio of 85 : 10 methyl ester: water was reached. The mixture was then vigorously agitated for 10 min and then EPO <DP n="19"/>centrifuged at 4,200 rpm for 10 min to separate the mixture into 2 phases comprising a top layer containing washed methyl ester reaction product above a bottom layer containing water-soluble by-products removed from the methyl ester reaction product. The top layer containing the washed methyl ester product was decanted and transferred to rotary evaporator flasks wherein any remaining water was removed.After dewatering was completed, the temperature of the methyl ester reaction product was adjusted to 600C +/- 3C after which, 2 % (w/w) TriSyl 615 adsorbent was added to the reaction product and mixed for 15 min to remove any remaining impurities. The adsorbent was removed from the methyl ester reaction product by recycling the methyl esters through a pressure filter apparatus until clarity was achieved. The methyl ester reaction product was then packaged and analyzed.Results: The data in Tables 5 and 6 show that the process of the present invention provided a 100 % conversion of the triglyceride compounds present in soybean oil into methyl esters, the purity of the final methyl ester product was 100%, and the recovery was 88.6 %, i.e., 500 g of soybean oil yielded 443 g of methyl ester product containing 443 g methyl esters. EPO <DP n="20"/>Table 5: Analysis of soybean methyl ester reaction product.Component ConcentrationSoap 0 ppmAcid value 0.04 mg KOH/gKarl Fisher moisture value 74 ppmFree glycerol <0.01 %Total glycerol <0.08 %Total methylated fatty acid content 1,000.0 mg/g productIndividual methylated fatty acidsC 14 - Myristic acid 0.7 mg/g productC16 - Palmitic acid 103.5 mg/g productC16:ln7 - Palmitoleic acid 1.0 mg/g productC 17:0 Margaric acid 1.0 mg/g productC 18 - Steric acid 45.0 mg/g productC18:ln9 - Oleic acid 218.6 mg/g productC 18:1 - Octadecenoic acid 12.7 mg/g productC18:2n6 - Linoleic acid 530.7 mg/g productC18:3n3 - alpha-linoleic acid 75.1 mg/g productC20 - Arachidic acid 3.7 mg/g productC20:ln9 - Eicosenoic acid 2.8 mg/g productC20:2n6 - Eicosadienoic acid - mg/g productC20:3n3 - Mead's acid - mg/g productC22 - Behenic acid 3.4 mg/g productC22: ln9 - Erucic acid - mg/g productC22:2n6 - Docosadienoic acid - mg/g productC21 :5n3 - Heneicosapentaenoic acid - mg/g productC22:4n6 - Docosatetraenoic acid - mg/g productC22:5n6 - Docosapentaenoic acid - mg/g productC24 - Lignoceric acid 0.8 mg/g productC24:ln9 - Nervonic acid - mg/g productOther fatty acids 3.8 mg/g productTable 6: Mass Balance calculation.Input: 500 g soybean oilOutput: 443 g washed and purified soybean methyl ester reaction productPercent recovery: 88.6 % |
Yield | Reaction Conditions | Operation in experiment |
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With potassium hydroxide; at 48 - 52℃; for 4h; | A 500 g quantity of canola oil was added into temperature- and pressure- controlled water-jacketed reactor 2L all Stainless Steel Pressure Reactor (Parr Instrument Company, Moline, IL, USA). The canola oil was dried by a negative pressure of 110 mmHg(A) applied by vacuum, and the oil was dewatered by heating to and maintenance at 1000C + 5C under negative pressure while being maintained in a turbulent flow by agitation until there was no trace of bubbling at the oil surface after which, the oil was cooled to 5O0C + 2C.While the oil was being dewatered, 100 g of absolute methanol (20% w/w of the oil) was added to a stirred vessel and then 5 g of KOH (1% w/w of the oil) was added while the methanol was vigorously agitated until the KOH was completely dissolved. The KOH-methanol mixture was added under vacuum to the 500 g dewatered oil maintained in a turbulent flow by agitation after which, the negative pressure within the reactor was broken with nitrogen gas which was used to flush and then maintain the headspace within the reactor. Addition of the KOH-methanol mixture to the dewatered oil initiated an exothermic esterifcation reaction and therefore, the temperature within the water-jacketed reactor was carefully maintained at 500C + 2C during the reaction period. The esterification reaction proceeded for 4 hrs while the oil was maintained in a turbulent flow by agitation. At the end of this time period, agitation was ceased and the methylated canola oil was transferred to a separation funnel where it was maintained for 18 hrs to allow the reaction mixture to separate into two phases comprising a top layer containing the methyl ester reaction product above a bottom layer containing the reaction by products, i.e., spent methanol and crude glycerol.After the phase separation was complete, the bottom layer containing the reaction by-products was removed from the separation funnel after which, the top methyl ester layer was removed into a separate container. The temperature of the methyl ester product was adjusted to about 75 after which water heated to 95C was added to the methyl ester phase until a ratio of 85: 10 methyl ester.water was reached. The mixture was then vigorously agitated for 10 min and then EPO <DP n="16"/>centrifuged at 4,200 rpm for 10 min to separate the mixture into 2 phases comprising a top layer containing washed methyl ester reaction product above a bottom layer containing water-soluble by-products removed from the methyl ester reaction product. The top layer containing the washed methyl ester product was decanted and transferred to rotary evaporator flasks wherein any remaining water was removed.After dewatering was completed, the temperature of the methyl ester reaction product was adjusted to 6O0C +/- 30C after which, 0.5 2% (w/w) TriSyl 615 adsorbent was added to the reaction product and mixed for 15 min to remove any remaining impurities. The adsorbent was removed from the methyl ester reaction product by recycling the methyl esters through a pressure filter apparatus until clarity was achieved. The methyl ester reaction product was then packaged and analyzed.Results: The data in Tables 3 and 4 show that the process of the present invention provided a 99% conversion of the triglyceride compounds present in canola oil into methyl esters, the purity of the final methyl ester product was 100 %, and the recovery was 85 % i.e., 500 g of canola oil yielded 425 g of methyl ester product containing 421 g methyl esters. EPO <DP n="17"/>Table 3 : Analysis of canola methyl ester reaction product.Component ConcentrationSoap O ppmAcid value 0.03 mg KOH/gKarl Fisher moisture value 65 ppmFree glycerol <0.01 %Total glycerol <0.10 %Total methylated fatty acid content 993.5 mg/g productIndividual methylated fatty acidsC 14 - Myristic acid 0.3 mg/g productCl 6 - Palmitic acid 41.5 mg/g productC16: ln7 - Palmitoleic acid 2.6 mg/g productC 17:0 Margaric acid 1.6 mg/g productC18 - Steric acid 17.0 mg/g productC18: ln9 - Oleic acid 558.7 mg/g productC 18: 1 - Octadecenoic acid 30.1 mg/g productC18:2n6 - Linoleic acid 1 19.6 mg/g productC18:3n3 - alpha-linoleic acid 106.1 mg/g productC20 - Arachidic acid 6.6 mg/g productC20: ln9 - Eicosenoic acid 15.1 mg/g productC20:2n6 - Eicosadienoic acid 0.6 mg/g productC20:3n3 - Mead's acid - mg/g productC22 - Behenic acid 3.6 mg/g productC22:ln9 - Erucic acid 1.4 mg/g productC22:2n6 - Docosadienoic acid - mg/g productC21 :5n3 - Heneicosapentaenoic acid - mg/g productC22:4n6 - Docosatetraenoic acid - mg/g productC22:5n6 - Docosapentaenoic acid - mg/g productC24 - Lignoceric acid 1.2 mg/g productC24: In9 - Nervonic acid 2.0 mg/g productOther fatty acids 5.4 mg/g productTable 4: Mass Balance calculation. Input: 50O g canola oilOutput: 425 g washed and purified canola methyl ester reaction productPercent recovery: 85 % |
Yield | Reaction Conditions | Operation in experiment |
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With potassium hydroxide; at 48 - 52℃; for 4.5h; | A 1 ,700 kg quantity of mustard oil was sprayed with a nozzle pressure of 10.0 + 5.0 psi into a temperature- and pressure-controlled water-jacketed reactor. After the mustard oil was added to the reactor, a negative pressure of 110 mmHg(A) was applied by vacuum, and the oil was dewatered by heating to and maintenance at 1000C + 5C under negative pressure while being maintained in a turbulent flow by agitation until there was no trace of bubbling at the oil surface after which, the oil was cooled to 5O0C +/- 20C.While the oil was being dewatered, 340.0 kg of absolute methanol (20% w/w of the oil) was added to a stirred vessel and then 17.0 kg of KOH (1% w/w of the oil) was added while the methanol was vigorously agitated until the KOH was completely dissolved. The KOH-methanol mixture was added under vacuum to the 1,700 kg of dewatered oil maintained in a turbulent flow by agitation after which, the negative pressure within the reactor was broken with nitrogen gas which was used to flush and then maintain the headspace within the reactor. Addition of the KOH-methanol mixture to the dewatered oil initiated an exothermic esterification reaction and therefore, the temperature within the water- jacketed reactor was carefully maintained at 5O0C + 2C during the reaction period. The esterification reaction proceeded for 4.5 hrs while the oil was maintained in a turbulent flow by agitation. At the end of this time period, agitation was ceased and the methylated mustard oil was maintained in the reactor for 2 hrs to allow the reaction mixture to separate into two phases comprising a top layer containing the methyl ester reaction product above a bottom layer containing the reaction by products, i.e., spent methanol and crude glycerol.After the phase separation was complete, the bottom layer containing the reaction by-products was removed from the reaction vessel after which the temperature of the retained methyl ester product was adjusted to 500C. Then, 500 L of water heated to 95C was added to the methyl ester phase under vacuum after which, the negative pressure was released and the mixture was agitated for 30 min at atmospheric pressure to wash water-soluble impurities out of the methyl ester reaction product after which, agitation was stopped. The mixture was allowed to EPO <DP n="13"/>separate over an 8-hr period into 2 phases comprising a top layer containing washed methyl ester reaction product above a bottom layer containing water- soluble by-products removed from the methyl ester reaction product.After the second phase separation was complete, the bottom layer was removed. A negative pressure of 110 mmHg(A) was then applied by vacuum to the washed methyl ester reaction product remaining in the reactor while the temperature of the reaction product was raised to 95C + 5C under agitation to dewater the washed methyl ester water product. After dewatering was completed, the temperature of the methyl ester reaction product was adjusted to 600C + 3C after which, 2 % (w/w) TriSyl 615 adsorbent (TriSyl is a registered trademark of W.R. Grace & Co.) was added to the reaction product and mixed for 30 min to remove any remaining impurities. The adsorbent was removed from the methyl ester reaction product by recycling the methyl esters through a pressure filter apparatus until clarity was achieved. The methyl ester reaction product was then packaged and analyzed.Results:The data in Table 1 show that the process of the present invention provided a 99% conversion of the triglyceride compounds present in mustard oil into methyl esters, the purity of the final methyl ester product was 98.95%, and the recovery was 91.8%, i.e., 1,700 kg of mustard oil yielded 1,560 kg of methyl ester product containing 1,531 kg methyl esters. The data in Table 2 show that the 91.8% of the starting raw material (i.e., crude mustard oil) was recovered and purified methyl ester reaction product. EPO <DP n="14"/>Table 1; Analysis of mustard methyl ester reaction product.Component ConcentrationSoap O ppmAcid value 0.12 mg KOH/gKarl Fisher moisture value 666 ppmFree glycerol O.001 %Total glycerol <0.01 %Total methylated fatty acid content 989.5 mg/g productIndividual methylated fatty acidsC14 - Myristic acid 0.5 mg/g productCl 6 - Palmitic acid 29.0 mg/g productC16:ln7 - Palmitoleic acid 1.5 mg/g productC17:0 Margaric acid - mg/g productC18 - Steric acid 14.4 mg/g productC18:ln9 - Oleic acid 216.2 mg/g productC 18:1 - Octadecenoic acid 11.1 mg/g productC18:2n6 - Linoleic acid 202.7 mg/g productC18:3n3 - alpha-linoleic acid 110.6 mg/g productC20 - Arachidic acid 8.3 mg/g productC20: ln9 - Eicosenoic acid 1 18.3 mg/g productC20:2n6 - Eicosadienoic acid 9.7 mg/g productC20:3n3 - Mead's acid 1.7 mg/g productC22 - Behenic acid 4.6 mg/g productC22:ln9 - Erucic acid 231.6 mg/g productC22:2n6 - Docosadienoic acid 1.7 mg/g productC21 :5n3 - Heneicosapentaenoic acid 4.2 mg/g productC22:4n6 - Docosatetraenoic acid 1.1 mg/g productC22:5n6 - Docosapentaenoic acid... |
Yield | Reaction Conditions | Operation in experiment |
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at 55℃; for 1.5h;Product distribution / selectivity; | Freeze-dried tissue samples were uniformly distributed by grinding for 10 -15 sec in a room-temperature coffee bean grinder. Samples of freeze-dried tissue (0.25g), or oils (20 mul) were placed into a 16 x 125 mm screw- cap Pyrex culture tube to which 1.0 ml methyl Cl 3:0 internal standard (0.5mg methyl C13:0/ml methanol) was added. Two ml of sodium methoxide (0.5 M) or 2 ml of boron trifluoride in methanol (14%, wt/vol) were added to the Pyrex tubes containing the samples. The tubes were incubated in a 55 0C water bath for 1.5 h with vigorous 5 sec hand-shaking every 20 min. Two ml of a saturated solution Of NaHCO3 and 3 ml hexane were then added and the tubes were vortex-mixed. After centrifugation, the hexane layer containing the FAME was placed into a GC vial. The vial was capped and placed at -20 C until GC analysis; The analysis of freeze-dried beef longissimus muscle fatty acids using sodium methoxide, boron trifluoride and direct FAME synthesis is presented in Table 4. Once again, there were striking differences among the three methods. Direct FAME synthesis recovered more fatty acids than did sodium methoxide and much more than did boron trifluoride. Since most of the fatty acids were esterified in longissimus muscle, as opposed to unesterified in the CLA capsule (Table 3), it was not surprising that sodium methoxide performed much better <n="23"/>in FAME synthesis of this sample, although it methylated only 78% of the fatty acids present. This sample also shows that boron trifluoride performed much better with the free fatty acid anions in the CLA sample (Table 3) than with the esterified fatty acids in muscle tissue. This latter result was surprising since boron trifluoride can methylate all families of fatty acids (Carrapiso and Garcia, 2000). Although boron trifluoride did methylate all of the different fatty acids present, as all of the peaks were identical to direct FAME synthesis, it did not do so quantitatively. It is unclear at this time why boron trifluoride gave such poor results. It can be mentioned that Bolte et al. reports satisfactory FAME synthesis results using boron trifluoride on freeze-dried lamb muscle tissue fatty acids by using much higher temperature and more concentrated effort, i.e., by incubating at 8O0C and vortex-mixing two to three times/min. However, our results do not seem to be due to the fact that boron trifluoride cannot permeate the meat sample, because similar results were observed when using a chloroform :methanol extract according to the method of Folch et al.(1956), where extraction of fatty acids by boron trifluoride would no longer be an issue (data not shown). Apparently, and unexpectedly, there are fatty acid structures in beef longissimus muscle that can be easily methylated by direct synthesis but not by boron trifluoride.When expressed as % FA, sodium methoxide and direct FAME synthesis were quite similar in their results, but boron trifluoride was different, and in this latter case the %FA values were higher when the concentration of fatty acid was lower. This difference could be explained by the fact that boron trifluoride methylated only 46% of the fatty acids present in longissimus muscle, and did so preferentially. With boron trifluoride, long chain unsaturated fatty acids appeared to be methylated more efficiently than short chain or saturated fatty acids, whereas, direct FAME synthesis methylated fatty acids without bias to chain length or structure. As a result, direct FAME synthesis consistently methylated more fatty acid, averaging 1.3 times that of sodium methoxide and 2.2 times that of boron trifluoride. |
Yield | Reaction Conditions | Operation in experiment |
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Samples were uniformly distributed by grinding for 10 -15 sec in a room-temperature coffee bean grinder. Samples could be processed in the state obtained, e.g., wet, dry, freeze- dried, or semi-frozen. Samples (0.5g wet, dry, or semi-frozen sample), (0.25g freeze-dried sample), or oils (20 mul) were placed into a 16 x 125 mm screw-cap Pyrex culture tube to which 1.0 ml Cl 3:0 internal standard (0.5mg C13:0/ml methanol), 0.7 ml 10 N KOH in water, and 5.3 ml methanol was added. The tube was incubated in a 55 C water bath for 1.5 h with vigorous 5 sec hand-shaking every 20 min to properly permeate, dissolve and hydrolyze the sample. After cooling below room temperature in a cold tap water bath, 0.58 ml of 24 N H2SO4 in water was added. (Care is taken in the preparation of the stock solutions IO N KOH and 24 N H2SO4, especially as the H2SO4 solution is extremely exothermic.) The tube was mixed by inversion, and with precipitated K2SO4 present, was incubated again in a 55 C water bath for 1.5 h with 5 sec hand-shaking every 20 min. After FAME synthesis, the tube was cooled in a cold tap water bath. Three ml of hexane was added and the tube was vortex-mixed for 5 min on a multi-tube vortex. The tube was centrifuged for 5 min in a tabletop centrifuge and the hexane layer, containing the FAME, was placed into a gas chromatography (GC) vial. The vial was capped and placed at -20 0C until GC analysis; The analysis of freeze-dried beef longissimus muscle fatty acids using sodium methoxide, boron trifluoride and direct FAME synthesis is presented in Table 4. Once again, there were striking differences among the three methods. Direct FAME synthesis recovered more fatty acids than did sodium methoxide and much more than did boron trifluoride. Since most of the fatty acids were esterified in longissimus muscle, as opposed to unesterified in the CLA capsule (Table 3), it was not surprising that sodium methoxide performed much better <n="23"/>in FAME synthesis of this sample, although it methylated only 78% of the fatty acids present. This sample also shows that boron trifluoride performed much better with the free fatty acid anions in the CLA sample (Table 3) than with the esterified fatty acids in muscle tissue. This latter result was surprising since boron trifluoride can methylate all families of fatty acids (Carrapiso and Garcia, 2000). Although boron trifluoride did methylate all of the different fatty acids present, as all of the peaks were identical to direct FAME synthesis, it did not do so quantitatively. It is unclear at this time why boron trifluoride gave such poor results. It can be mentioned that Bolte et al. reports satisfactory FAME synthesis results using boron trifluoride on freeze-dried lamb muscle tissue fatty acids by using much higher temperature and more concentrated effort, i.e., by incubating at 8O0C and vortex-mixing two to three times/min. However, our results do not seem to be due to the fact that boron trifluoride cannot permeate the meat sample, because similar results were observed when using a chloroform :methanol extract according to the method of Folch et al.(1956), where extraction of fatty acids by boron trifluoride would no longer be an issue (data not shown). Apparently, and unexpectedly, there are fatty acid structures in beef longissimus muscle that can be easily methylated by direct synthesis but not by boron trifluoride.When expressed as % FA, sodium methoxide and direct FAME synthesis were quite similar in their results, but boron trifluoride was different, and in this latter case the %FA values were higher when the concentration of fatty acid was lower. This difference could be explained by the fact that boron trifluoride methylated only 46% of the fatty acids present in longissimus muscle, and did so preferentially. With boron trifluoride, long chain unsaturated fatty acids appeared to be methylated more efficiently than short chain or saturated fatty acids, whereas, direct FAME synthesis methylated fatty acids without bias to chain length or structure. As a result, direct FAME synthesis consistently methylated more fatty acid, averaging 1.3 times that of sodium methoxide and 2.2 times that of boron trifluoride. | ||
Freeze-dried tissue samples were uniformly distributed by grinding for 10 -15 sec in a room-temperature coffee bean grinder. Samples of freeze-dried tissue (0.25g), or oils (20 mul) were placed into a 16 x 125 mm screw- cap Pyrex culture tube to which 1.0 ml methyl Cl 3:0 internal standard (0.5mg methyl C13:0/ml methanol) was added. Two ml of sodium methoxide (0.5 M) or 2 ml of boron trifluoride in methanol (14%, wt/vol) were added to the Pyrex tubes containing the samples. The tubes were incubated in a 55 0C water bath for 1.5 h with vigorous 5 sec hand-shaking every 20 min. Two ml of a saturated solution Of NaHCO3 and 3 ml hexane were then added and the tubes were vortex-mixed. After centrifugation, the hexane layer containing the FAME was placed into a GC vial. The vial was capped and placed at -20 C until GC analysis; The analysis of freeze-dried beef longissimus muscle fatty acids using sodium methoxide, boron trifluoride and direct FAME synthesis is presented in Table 4. Once again, there were striking differences among the three methods. Direct FAME synthesis recovered more fatty acids than did sodium methoxide and much more than did boron trifluoride. Since most of the fatty acids were esterified in longissimus muscle, as opposed to unesterified in the CLA capsule (Table 3), it was not surprising that sodium methoxide performed much better <n="23"/>in FAME synthesis of this sample, although it methylated only 78% of the fatty acids present. This sample also shows that boron trifluoride performed much better with the free fatty acid anions in the CLA sample (Table 3) than with the esterified fatty acids in muscle tissue. This latter result was surprising since boron trifluoride can methylate all families of fatty acids (Carrapiso and Garcia, 2000). Although boron trifluoride did methylate all of the different fatty acids present, as all of the peaks were identical to direct FAME synthesis, it did not do so quantitatively. It is unclear at this time why boron trifluoride gave such poor results. It can be mentioned that Bolte et al. reports satisfactory FAME synthesis results using boron trifluoride on freeze-dried lamb muscle tissue fatty acids by using much higher temperature and more concentrated effort, i.e., by incubating at 8O0C and vortex-mixing two to three times/min. However, our results do not seem to be due to the fact that boron trifluoride cannot permeate the meat sample, because similar results were observed when using a chloroform :methanol extract according to the method of Folch et al.(1956), where extraction of fatty acids by boron trifluoride would no longer be an issue (data not shown). Apparently, and unexpectedly, there are fatty acid structures in beef longissimus muscle that can be easily methylated by direct synthesis but not by boron trifluoride.When expressed as % FA, sodium methoxide and direct FAME synthesis were quite similar in their results, but boron trifluoride was different, and in this latter case the %FA values were higher when the concentration of fatty acid was lower. This difference could be explained by the fact that boron trifluoride methylated only 46% of the fatty acids present in longissimus muscle, and did so preferentially. With boron trifluoride, long chain unsaturated fatty acids appeared to be methylated more efficiently than short chain or saturated fatty acids, whereas, direct FAME synthesis methylated fatty acids without bias to chain length or structure. As a result, direct FAME synthesis consistently methylated more fatty acid, averaging 1.3 times that of sodium methoxide and 2.2 times that of boron trifluoride. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 2 mg 2: 2 mg | With hydrogenchloride at 90℃; for 15h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 2 mg 2: 0.5 mg | With hydrogenchloride at 90℃; for 15h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: sodium docosanoate With hydrogenchloride In methanol; water Stage #2: boron trifluoride methanol complex Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride In water for 5h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: methyl iodide With magnesium In diethyl ether at 20℃; for 0.5h; Inert atmosphere; Stage #2: behenic acid methyl ester In diethyl ether at 0 - 20℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: magnesium / diethyl ether / 0.5 h / 20 °C / Inert atmosphere 1.2: 0 - 20 °C / Inert atmosphere 2.1: sodium hydride / tetrahydrofuran / 4 h / Inert atmosphere; Reflux 2.2: Inert atmosphere; Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94.1% | With sodium ethanolate; In ethanol; at 55℃; | 1.68 g of methyl behenate (manufactured by Sigma Aldrich Co., LLC.), 1.00 of phytosphingosine (manufacturedby Cosmoferm B.V.), and 16 mL of ethanol (manufactured by Kanto Chemical Co. , Inc.) were added in a 30-mL eggplantflask and the mixture was stirred in a 55C hot water bath for 15 min. After it was confirmed that the reaction systemwas homogeneous, 124 mL of a 21% sodium ethoxide-ethanol solution (manufactured by Sigma Aldrich Co., LLC.) wasadded to the mixture. After 2 hours, a precipitate was confirmed and the mixture was continuously stirred during a wholeday and night. After the resulting reaction mixture was cooled to 0C, the precipitate was filtered and washed to obtain1.90 g of N-docosanoyl-phytosphingosine in the form of a white solid in a yield of 94.1% (purity > 98%).Melting point 120-122C IR (ATR, cm-1) 3326, 2913, 2849, 1613, 1556, 1467, 1075, 720MS (positive): [M + H]+ = 640.8, [M + Na]+ = 662.71H-NMR (deuterated pyridine, 500MHz, delta) 0.85 (3H, t, J = 7.1Hz), 0.85 (3H, t, J = 7.1Hz), 1.16-1.48 (58H, br), 1.69 (1H,m), 1.82 (2H, m), 1.94(2H, m), 2.24 (1H, m), 2.45 (2H, t, J=7.4Hz), 4.29 (1H, m), 4.40 (1H, ddd, J = 6.2, 6.2, 5.2Hz),4.49 (2H, m), 5.10 (1H, m), 6.19 (1H, d, J=6.9Hz), 6.53 (1H, d, J=6.9Hz), 6.62 (1H, t, J=5.0Hz), 8.51 (1H, d, J=8.3Hz) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrazine In ethanol Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: hydrazine / ethanol / Heating 2.1: potassium hydroxide; sodium dodecyl-sulfate / ethanol; water 2.2: 2 h / Reflux 2.3: 0 - 5 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium hydroxide; methanesulfonic acid In methanol; water | A Synthesis of Methyl Behenate EXAMPLE A Synthesis of Methyl Behenate A glass reactor equipped with a stirrer, thermometer, nitrogen inlet and water trap connected to a water cooled condenser is charged with 200 grams of Behenic acid, 150 grams of methanol, 0.4 grams of methanesulfonic acid (70%) and 0.2 grams of hypophosphorous acid (50%). The mixture is stirred and heated slowly to 130° C. to remove the water by-product along with methanol. After the distillation is stopped, the reaction mixture is treated dropwise with 150 grams of methanol under nitrogen sparge over a period of 2 hours at 130° C. to reduce the acid value to less than 1.10. The mixture is cooled to 80° C., neutralized with 0.6 grams of potassium hydroxide (45%) and stripped at 100° C. at 1 mm Hg vacuum for 15 minutes to remove water and unreacted methanol. The final produce is cooled to 80° C. and filtered through Whatman filter paper (Grade 42) to yielding 205 grams of methyl behenate as a white solid wax. GC-MS: Purity>98.7%; 1H-NMR (pyridine-d5): δ 0.89 ppm (t): 3H; δ 1.20-1.40 ppm (m): 36H; δ 1.65 ppm (m): 2H; δ 2.34 ppm (t): 2H; δ 3.64 ppm (s): 3H. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With triethylamine; at 160℃; for 5h;Autoclave; Green chemistry; | General procedure: Into a stainless steel pressure microreactor of capacity 17 mL was charged 5 wt % of zeolite NaY-Bf, 100 mmol of carboxylic acid, and 300-400 mmol of dimethyl carbonate, the reactor was hermetically closed, and the reaction mixture was heated at 180-200C for 5 h. On completion of the reaction the reactor was cooled to room temperature, opened, the reaction mixture was filtered through a bed of Al2O3. Unreacted dimethyl carbonate was distilled off, the residue was distilled at atmospheric pressure or in a vacuum, or it was crystallized from ethanol. |
With diiron nonacarbonyl; at 180℃; for 1h;Sealed tube; | General procedure: 1-3 mmol of catalyst Mn 2 (CO) 10 , 100 mmol of the carboxylic acid, and 300-400 mmol of dimethyl carbonate were placed into a 17 mL stainless steel microreactor. The reactor was sealed, and the reaction mixture was heated at 180 for 1 h. After the reaction was complete, the reactor was cooled to room temperature and opened. The reaction mixture was filtered through a layer of Al 2 O 3 . Unreacted dimethyl carbonate was distilled off, the residue was distilled at atmospheric or reduced pressure, or crystallized. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sulfuric acid at 70℃; for 4h; | Transesterification of compounds 3a-3l General procedure: To a mixture of 3a-3l (12 mg) were added 0.1 mL of concentrated H2SO4 and 5 mL of anhydrous MeOH. The system was heated with stirring at 70 °C during 4 h. After addition of 10 mL of saturated NaCl and extraction with EtOAc (3 × 10 mL), the organic phase was dried over MgSO4, filtered and analyzed by GC-FID.15 Identification of methyl esters of fatty acids was performed by comparison of retention times to each compound with those of authentic samples. |
Tags: 929-77-1 synthesis path| 929-77-1 SDS| 929-77-1 COA| 929-77-1 purity| 929-77-1 application| 929-77-1 NMR| 929-77-1 COA| 929-77-1 structure
[ 818-88-2 ]
10-Methoxy-10-oxodecanoic acid
Similarity: 1.00
[ 818-88-2 ]
10-Methoxy-10-oxodecanoic acid
Similarity: 1.00
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