* 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.
Stage #1: at 100℃; for 0.166667 h; Inert atmosphere Stage #2: for 6 h; Inert atmosphere
stearic acid 0.28percent of the composite antioxidant was added to the reaction kettle, and the mixture was slowly heated to 100 ° C after stirring for N2 and 10 min. The stearic acid was completely melted and the 0.20percent composite catalyst with the weight of ethylenediamine and stearic acid was added. Constant temperature reaction for 2 hours, And then slowly heated to 180 ° C, constant temperature reaction for 4 hours to dehydration reaction,The water generated during the reaction is taken out of N2 to stop the reaction, Cooled to 160 ° C discharge.Wherein the molar ratio of stearic acid to ethylenediamine is 1: 0.58; the antioxidant 1076 in the antioxidant,The ratio of the antioxidant DLTDP to the antioxidant T501 was 0.20: 0.36: 1; the composite catalyst was prepared by using the p-toluenesulfonic acid / SAPO-34 supported solid acid catalyst prepared in Example 1 and Example 2 and the phosphoric acid / SiO2-Al2O3 supported solid acid catalyst, the mass ratio of 1: 3.5. The yield of N,N'-ethylenebis(stearamide)
Reference:
[1] Patent: CN105777568, 2016, A, . Location in patent: Paragraph 0024; 0025
[2] Industrial and Engineering Chemistry, 1948, vol. 40, p. 1365
[3] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1976, p. 386 - 389
[4] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1983, p. 2197 - 2200
[5] Patent: CN105348128, 2016, A, . Location in patent: Paragraph 0015
Reference:
[1] Nippon Kagaku Zasshi, 1948, vol. 69, p. 154,156[2] Chem.Abstr., 1952, p. 3951
4
[ 57-11-4 ]
[ 3386-33-2 ]
Yield
Reaction Conditions
Operation in experiment
91%
at 150℃;
4-Dimethylaminopyridine Hydrochloride as Catalyst for Phosgene Synthesis To the reaction bottle, 80 g of stearic acid and 0.008 g of 4-dimethylaminopyridine hydrochloride were added and the mixture was heated to 150 ° C,When the molar ratio of phosgene to stearic acid to phosgene was 1: 6, the phosgene was stopped. Distillation under reduced pressure stearyl chloride, the chemical titration analysis of more than 98percent, the molar yield of 91percent.
Reference:
[1] Patent: CN105601502, 2016, A, . Location in patent: Paragraph 0061; 0062; 0063
5
[ 57-11-4 ]
[ 56-81-5 ]
[ 555-43-1 ]
Reference:
[1] JAOCS, Journal of the American Oil Chemists' Society, 2000, vol. 77, # 11, p. 1139 - 1145
[2] Journal of Agricultural and Food Chemistry, 2003, vol. 51, # 7, p. 2096 - 2099
[3] Agricultural and Biological Chemistry, 1987, vol. 51, # 8, p. 2153 - 2160
[4] Journal fuer Praktische Chemie (Leipzig), 1933, vol. <2>136, p. 309
[5] Ann.Chim.applic., vol. 25, p. 322[6] Chem. Zentralbl., 1935, vol. 106, # II, p. 3084
[7] Biochemische Zeitschrift, 1926, vol. 177, p. 166[8] Proceedings of the Imperial Academy (Tokyo), vol. 2, p. 343[9] Chem. Zentralbl., 1926, vol. 97, # II, p. 2451
[10] Gazzetta Chimica Italiana, 1912, vol. 42 II, p. 291
[11] Recueil des Travaux Chimiques des Pays-Bas, 1899, vol. 18, p. 193
[12] Industrial and Engineering Chemistry, 1929, vol. 21, p. 953[13] Chem. Zentralbl., 1930, vol. 101, # I, p. 3840
[14] Journal of the Chemical Society, 1934, p. 670[15] Journal of the Chemical Society, 1948, p. 987
[16] Chemistry and Physics of Lipids, 1995, vol. 77, # 2, p. 155 - 171
6
[ 638-66-4 ]
[ 57-11-4 ]
[ 555-43-1 ]
Reference:
[1] Ann.d.Physik, 1854, vol. 93, p. 436[2] Jahresbericht ueber die Fortschritte der Chemie und Verwandter Theile Anderer Wissenschaften, 1854, p. 447
[3] Annales de Chimie (Cachan, France), 1854, vol. <3> 41, p. 295[4] Annales de Chimie (Cachan, France), 1856, vol. 46, p. 482
7
[ 57-11-4 ]
[ 56-81-5 ]
[ 555-43-1 ]
[ 22610-63-5 ]
[ 51063-97-9 ]
[ 621-61-4 ]
[ 504-40-5 ]
Reference:
[1] Magnetic Resonance in Chemistry, 2012, vol. 50, # 6, p. 424 - 428
8
[ 504-40-5 ]
[ 57-11-4 ]
[ 555-43-1 ]
Reference:
[1] Z.B., 1903, vol. 44, p. 87
9
[ 555-43-1 ]
[ 4704-94-3 ]
[ 57-11-4 ]
Reference:
[1] Journal of Molecular Catalysis B: Enzymatic, 2014, vol. 102, p. 16 - 24
10
[ 100-02-7 ]
[ 57-11-4 ]
[ 14617-86-8 ]
Reference:
[1] Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1990, vol. 39, # 11, p. 2311 - 2316[2] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1990, # 11, p. 2555 - 2560
[3] Comptes Rendus Chimie, 2013, vol. 16, # 3, p. 229 - 238
[4] Journal of Molecular Catalysis B: Enzymatic, 2011, vol. 73, # 1-4, p. 22 - 26
[5] Australian Journal of Chemistry, 1975, vol. 28, p. 1011 - 1015
[6] Journal of Organic Chemistry, 1970, vol. 35, p. 2042 - 2043
[7] Chemische Berichte, 1963, vol. 96, p. 1747 - 1750
[8] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1988, p. 423 - 432
Reference:
[1] New Journal of Chemistry, 2018, vol. 42, # 18, p. 15127 - 15135
[2] Nature (London, United Kingdom), 1949, vol. 163, p. 441
[3] Nature (London, United Kingdom), [4] Nature (London, United Kingdom), 1949, vol. 164, p. 244 - 245
[5] Nature (London, United Kingdom), [6] Nature (London, United Kingdom), 1950, vol. 165, p. 612 - 613
[7] , Gmelin Handbook: Cu: MVol.B2, 44, page 715 - 717,
[8] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, [9] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1940, vol. 210, p. 533 - 534
[10] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, [11] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1941, vol. 213, p. 837 - 839
[12] , Gmelin Handbook: Cu: MVol.B2, 44, page 715 - 717,
[13] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, [14] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1940, vol. 210, p. 533 - 534
[15] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, [16] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1941, vol. 213, p. 837 - 839
[17] , Gmelin Handbook: Cu: MVol.B2, 44, page 715 - 717,
[18] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, [19] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1940, vol. 210, p. 533 - 534
[20] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, [21] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1941, vol. 213, p. 837 - 839
[22] , Gmelin Handbook: Cu: MVol.B2, 44, page 715 - 717,
[23] Journal of Physical Chemistry, [24] Journal of Physical Chemistry, 1911, vol. 15, p. 97 - 146
[25] Proceedings of the Royal Society of London, Series A: Mathematical, Physical and Engineering Sciences, [26] Proceedings of the Royal Society of London, Series A: Mathematical, Physical and Engineering Sciences, 1947, vol. 191, p. 243 - 252
[27] , Gmelin Handbook: Cu: MVol.B2, 44, page 715 - 717,
stearic acid 0.28% of the composite antioxidant was added to the reaction kettle, and the mixture was slowly heated to 100 C after stirring for N2 and 10 min. The stearic acid was completely melted and the 0.20% composite catalyst with the weight of ethylenediamine and stearic acid was added. Constant temperature reaction for 2 hours, And then slowly heated to 180 C, constant temperature reaction for 4 hours to dehydration reaction,The water generated during the reaction is taken out of N2 to stop the reaction, Cooled to 160 C discharge.Wherein the molar ratio of stearic acid to ethylenediamine is 1: 0.58; the antioxidant 1076 in the antioxidant,The ratio of the antioxidant DLTDP to the antioxidant T501 was 0.20: 0.36: 1; the composite catalyst was prepared by using the p-toluenesulfonic acid / SAPO-34 supported solid acid catalyst prepared in Example 1 and Example 2 and the phosphoric acid / SiO2-Al2O3 supported solid acid catalyst, the mass ratio of 1: 3.5. The yield of N,N'-ethylenebis(stearamide)
Equipped with a stirring rod in a 1L four-necked flask sealed 142g (0.5mol) of stearic acid and 0.3g of sodium borohydride was slowly stirred under nitrogen gas 2min, to ensure that the air was stopped after the drain nitrogen; was added 17.4 g of ( 0.290mol) ethylenediamine at a temperature of 100 forming a salt 1.5h; phosphoric acid was added 0.3g and 1.0g of phosphorous acid in the reactants, dehydrated under nitrogen and 190 temperature of the reaction 6h, after completion of the reaction a white ethylene bis stearic acid amide product, the product parameters: acid ?7mg / g, an amine value 0mg / g, mp148 , 3 color values.
at 100 - 200℃; for 4h;Inert atmosphere;
Add 100 g of stearic acid and 0.4 g of antioxidant to the reactor, and pass in nitrogen gas.The temperature was increased to 100 C, and 12.7 g of ethylenediamine was added.Add 0.7 g of (NH4) 0.5Ti0.5H0.5PW12O40 catalyst prepared in Example 1,Heated to 200 , dehydrated for 4 h,A white N,N'-ethylenedi(stearamide)product was obtained. The acid value of the product was 2.6 mg / g.Melting range: 145 to 150 C, whiteness value: 90.
Add 100 g of stearic acid and 0.4 g of antioxidant to the reactor, pass nitrogen gas, increase the temperature to 100 C, add 12.7 g of ethylenediamine, and neutralize the salt formation for 1.5 h, then add 0.7 g of the prepared in Example 1 Quaternary ammonium phosphotungstate titanium catalyst, heated to 200 C, and dehydrated for 4 h to obtain a white ethylenebisstearylamide product.
With 0.5C19H42N(1+)*0.5Zr(4+)*0.5H(1+)*O40PW12(3-); at 110 - 190℃; for 6h;Inert atmosphere;
Add 100 g of stearic acid and 0.3 g of antioxidant to the reactor, pass nitrogen gas, raise the temperature to 110 C, add 12.8 g of ethylenediamine, neutralize the salt-forming reaction for 1 h, add 1 g of the preparation prepared in Example 1 Compound doped heteropoly acid salt catalyst, heated to 190 C , dehydration reaction for 5 h, to obtain a white ethylene bis stearamide product, acid value of the product: 3.7 mg / g, melting range: 143 ~ 147 , whiteness Value: 90.
With trimethyloctylammonium methanesulfonate; toluene-4-sulfonic acid; at 60℃; under 760.051 Torr; for 6h;
According to the flow of Figure 1, the following processing is performed:2.5 mol of octadecanoic acid, 2.5 mol of ethanol and 0.75 mol of octyltrimethylammonium methanesulfonate-p-toluenesulfonic acidThe molten solvent (the molar ratio of trimethylcyclohexylammonium methanesulfonate to p-toluenesulfonic acid is 1:2) is added to the esterification reactor to form the ester.The reaction vessel was heated to 60 C, and the reaction was stirred at normal pressure for 6 hours, and the stirring speed was 1000 rpm. After the reaction, the reaction solution is introduced into the decantationThe device is statically phased and the rest time is 6h. The upper liquid (ester phase) and the lower liquid (water) obtained after phase separation in the decanterThe phase is introduced into the washing tank and the flash tank respectively to carry out product ester purification and raw materials (mainly eutectic solvents, carboxylic acids and alcohols).Received. The working pressure of the washing tank is normal pressure, the operating temperature is room temperature, and the mass fraction is taken from the top of the washing tank.97% product ethyl octadecanoate, a high purity ester, a mixture of eutectic solvent and water at the bottom, introduced into the flash tank; flashingThe tank has an operating pressure of 0.01 bar and an operating temperature of 250 C. The unreacted raw material is taken from the top of the flash tank and containsA mixture of water and ester with a eutectic solvent having a mass fraction of 99.99% at the bottom. Low eutectic solution obtained at the bottom of the flash tankThe agent is respectively exchanged to a temperature of 60 C through a heat exchanger and returned to the esterification reactor for recycling. Mixture produced at the top of the flash tankIntroduced into the alcohol recovery tower, the actual number of plates in the alcohol recovery column is 55, the operating pressure is atmospheric pressure, the operating reflux ratio is 6, and the alcohol recovery towerThe unreacted alcohol was obtained from the top, cooled to 60 C by a heat exchanger, and returned to the esterification reactor for recycling. Alcohol recovery towerThe material of the tower kettle is introduced into the carboxylic acid recovery tower, the actual number of trays of the carboxylic acid recovery tower is 60, the operating pressure is normal pressure, and the operation reflux ratio is operated.At 3.6, by-product water is obtained at the top of the acid recovery tower, and finally the water is removed from the esterification reaction system, and the acid recovery tower isThe kettle is obtained as a mixture containing unreacted carboxylic acid and a part of the product, and is cooled to 60 C by a heat exchanger to return to the esterification reaction.The kettle is recycled. The yield of ethyl octadecanoate in Example 19 was 98.7%, and the purity was 97%.
97%
With alumina methanesulfonic acid; at 120℃; for 0.333333h;Microwave irradiation;
General procedure: In a typical reaction, AMA 2:3 (332 g, 0.6 mol), the corresponding carboxylicacid (1 mol), and alcohol (1.5-2 mol) were mixed in the provided reaction glass tubeequipped with a screw cap and magnetic agitation until a wet mixture was achieved.The reaction mixture was irradiated with microwaves (Anton Parr Monowave 300reactor) at 80 C for 8 min or 120 C for 20 min. On cooling, the mixture was diluted with dichloromethane (41 mL), filtered under gravity, and washed with dichloromethane;then the filtrate was washed with Na2CO3 (ss) and water. The organic layerwas dried over Na2SO4, filtered, and concentrated under reduced pressure to give theester.
91.2%Chromat.
at 300℃; under 112511 Torr; for 0.25h;
An esterification reaction of a fatty acid and alcohol or a transesterification of rapeseed oil and alcohol was conducted using, as a raw material, fats and oils and alcohols shown in Table 7, under conditions of mole ratio, temperature, pressure and reaction time shown in Table 7. Since about 98.5% of rapeseed oil is composed of a tri-glyceride, the reaction from rapeseed oil can be judged to be a transesterification. The reaction product was subjected to HPLC analysis in the same manner as in Example 1, from the HPLC analysis result, conversion into a fatty acid alkyl ester from a fatty acid or rapeseed oil (=yield of alkyl ester) was obtained. The results are shown in Table 7 together with the reaction conditions. TABLE 7 Alcohol/fats and oils Temperature Pressure Reaction Example (mole ratio) Fats and oils Alcohol ( C.) (Mpa) time (min) Yield (%) Example 42/1C18-3 Methanol 300 20 8 96.2 5-1 Example 42/1C18-2 300 20 8 95.1 5-2 Example 42/1C18-1 300 20 8 95.8 5-3 Example 42/1C18-0 300 20 8 94.7 5-4 Example 42/1C16-0 300 20 8 94.0 5-5 Example 42/1 Rapeseed 300 20 15 98.0 5-6 oil Example 42/1 Rapeseed 350 43 4 98.0 5-7 oil Example 42/1C18-3 Ethanol 300 15 12 94.6 5-8 Example 42/1C18-2 300 15 14 97.4 5-9 Example 42/1C18-1 300 15 14 95.9 5-10 Example 42/1C18-0 300 15 15 91.2 5-11 Example 42/1C16-0 300 15 14 91.7 5-12 Example 42/1 Rapeseed 300 15 45 96.7 5-13 oil Example 42/1 Rapeseed 350 25 10 97.1 5-14 oil Example 42/1C18-3 1-propanol 300 10 15 97.0 5-15 Example 42/1C18-2 300 10 14 92.7 5-16 Example 42/1C18-1 300 10 14 92.3 5-17 Example 42/1C18-0 300 10 14 89.6 5-18 Example 42/1C16-0 300 10 14 90.1 5-19 Example 42/1 Rapeseed 300 10 45 96.1 5-20 oil Example 42/1 Rapeseed 350 23 14 98.8 5-21 oil Example 42/1C18-3 1-butonal 300 9 15 97.3 5-22 Example 42/1C18-2 300 9 14 92.4 5-23 Example 42/1C18-1 300 9 14 86.1 5-24 Example 42/1C18-0 300 9 14 82.5 5-25 Example 42/1C16-0 300 9 14 81.1 5-26 Example 42/1 Rapeseed 300 9 45 87.1 5-27 oil Example 42/1 Rapeseed 350 23 14 95.3 5-28 oil Example 42/1 Rapeseed 1-octanol 300 6 45 68.7 5-29 oil Example 42/1 Rapeseed 350 19 20 90.7 5-30 oil C16-0: palmitic acid, C18-0: stearic acid, C18-1: oleic acid, C18-2: linoleic acid, C18-3: linolenic acid
92%Chromat.
With sulfuric acid; for 4h;Reflux;
General procedure: General procedure for the synthesis of compounds (6a-p); organic acid (0.40 mmol.), and catalyst (0.0005 mmol.) was combined with 20 mL ethanol in a 50 mL round bottomed flask equipped with a stir bar. Reaction was allowed to stir at reflux temperature for the appropriate amount of time (4 h). After completion of reaction, the reaction mixture was concentrated in vacuum to give a crude product which was analyzed by 1H NMR and GC-MS.
With immobilized Candida antarctica Lipase B; In neat (no solvent); at 60℃; for 6h;Green chemistry; Enzymatic reaction;
The different experiments were performed by adding 1 g of SA, ethanol (1, 2, 3 or 6 equiv.) and 50 mg of Novozym 435 in a 12 ml vial. The mixture was kept in the shaker at 60 C and 300 rpm. The course of reaction was monitored by GC at defined times.
With acidic cation exchange resin Amberlyst 70; In water; at 50 - 145℃;Flow reactor; Green chemistry;
General procedure: Acetic acid and ethanol at a weight ratio of 1:2 or 1:3 were mixed at 30 C., and then introduced into the lower part of the vertical reactor at a liquid hourly space velocity (LHSV) of 3 hour-1. The reaction was performed at 115 C. The esterized mixture was output from the upper part of the vertical reactor, and collected to be analyzed by gas photography. The acid value of the product was determined by titration, and the conversion rate and the selectivity were analyzed. The results were shown in Table 1.
With zirconium containing 2-aminoterephthalate metal organic framework; at 78℃;Kinetics;
General procedure: In view of the good catalytic activity and recyclability of UiO-type MOFs for the esterification of lauric acid with MeOH and EtOH,we wanted to investigate the applicability of the MOFs to otherbiomass derived free fatty acids with longer chain lengths, bothsaturated and unsaturated. Thus, we extended our study to theesterification with MeOH and EtOH of palmitic (hexadecanoic acid,C16), Stearic (octadecanoic acid, C18), Oleic (cis-9-octadecenoicacid C18:1), linoleic (cis,cis-9,12-octadecadienoic acid, C18:2) and-linolenic acids (cis,cis,cis-9,12,15-octadecatrienoic acid, C18:3).For the sake of brevity, the complete catalytic data obtained for eachfatty acid and the comparison with other acid catalysts from theliterature is provided as Supporting Information (Tables S1-S10).In order to illustrate the dependence of the chain length andunsaturation degree of the fatty acid on reaction rate, Fig. 3 showsthe calculated pseudo-first order reaction rate constants, k, of ester-ification of various fatty acids with ethanol over UiO-66-NH2. Thesame tendency was also observed for UiO-66, although this mate-rial was in general less active than UiO-66-NH2(as already observed C12 for C12 esterification commented above). As it can be observed, thereaction rate decreases as the chain length and the degree of unsa-turation of the fatty acid increases. This is probably due to higheradsorption of the unsaturated fatty acid (or fatty ester) on the sur-face of the solid, which causes the progressive deactivativation ofthe catalyst. However, it is worth mentioning that this deactivationdue to product adsorption is fully reversible, and the activity of thecatalysts is completely recovered by simply washing with EtOH.In conclusion, the above experiments demonstrates that bothZr-containing UiOs can efficiently catalyze the esterification of var-ious fatty acids with MeOH and EtOH, being less active as the alkylchain length and degree of unsaturation of the acid increases. It isalso worth mentioning that in all the reactions tested, the Zr-MOFswere found to be stable and reusable without significant loss ofactivity, as we have previously demonstrated for the esterificationof C12 with EtOH over UiO-66-NH2.
74%Chromat.
With sulfuric acid; In water; at 55 - 70℃; for 13h;
Example 4 Esterification of Stearic Acid (0062) Commercially available stearic ac vas mixed with ethanol at a 1:3 molar ratio, and 1 mol % H2SO4 was added as a catalyst. The ethanol mixture used contained 5% methanol as denaturant. The mixture was heated at 70 C. with agitation for 5 hours and the temperature was then decreased to 55 C. with agitation for 8 hours. Agitation was then halted to allow the separation of the aqueous and ethyl stearate layers. GC analysis of the ethyl stearate layer revealed a fatty acid content of 94%, 86% of which was either in the methyl or ethyl ester form. [table-us-00006-en] Component Percentage by mass Ethyl Stearate 74 Methyl Stearate 8 Stearic Acid 11 Ethanol 1 Palmitic Acid 1 Unknown 5
With 3H(1+)*O40SiW12(4-)*C21H22O3PS(1+);Reflux; Dean-Stark;
General procedure: Acidic pseudo-IL (0.05 g) was loaded into a 50-mL threenecked flask with a magnetic stirrer, and a reflux condenser. A Dean-Stark apparatus was used to remove the water continuously from the reaction mixture. n-Butanol (14.8 g,0.2 mol) and aliphatic acid (with -OH/-COOH molar ratio = 1.5:1) were added and reaction was carried out under reflux condition. The reaction progress was monitored by the acid-base titration. The conversion of the reaction was calculated on the acidity using the following equation: Conversion (%) = [1 - (final acidity)/(initial acidity)] × 100%. Here, the acidity from acidic pseudo-IL was excluded. For final and initial acidity, the acidity from the pseudo-IL was subtracted. The products were confirmed using GC-MS analysis. After reaction, the IL was separated from the reaction mixture by cooling the temperature, which made the catalyst recovery quite simple.
82.5%Chromat.
at 300℃; under 67506.8 Torr; for 0.233333h;
An esterification reaction of a fatty acid and alcohol or a transesterification of rapeseed oil and alcohol was conducted using, as a raw material, fats and oils and alcohols shown in Table 7, under conditions of mole ratio, temperature, pressure and reaction time shown in Table 7. Since about 98.5% of rapeseed oil is composed of a tri-glyceride, the reaction from rapeseed oil can be judged to be a transesterification. The reaction product was subjected to HPLC analysis in the same manner as in Example 1, from the HPLC analysis result, conversion into a fatty acid alkyl ester from a fatty acid or rapeseed oil (=yield of alkyl ester) was obtained. The results are shown in Table 7 together with the reaction conditions. TABLE 7 Alcohol/fats and oils Temperature Pressure Reaction Example (mole ratio) Fats and oils Alcohol ( C.) (Mpa) time (min) Yield (%) Example 42/1C18-3 Methanol 300 20 8 96.2 5-1 Example 42/1C18-2 300 20 8 95.1 5-2 Example 42/1C18-1 300 20 8 95.8 5-3 Example 42/1C18-0 300 20 8 94.7 5-4 Example 42/1C16-0 300 20 8 94.0 5-5 Example 42/1 Rapeseed 300 20 15 98.0 5-6 oil Example 42/1 Rapeseed 350 43 4 98.0 5-7 oil Example 42/1C18-3 Ethanol 300 15 12 94.6 5-8 Example 42/1C18-2 300 15 14 97.4 5-9 Example 42/1C18-1 300 15 14 95.9 5-10 Example 42/1C18-0 300 15 15 91.2 5-11 Example 42/1C16-0 300 15 14 91.7 5-12 Example 42/1 Rapeseed 300 15 45 96.7 5-13 oil Example 42/1 Rapeseed 350 25 10 97.1 5-14 oil Example 42/1C18-3 1-propanol 300 10 15 97.0 5-15 Example 42/1C18-2 300 10 14 92.7 5-16 Example 42/1C18-1 300 10 14 92.3 5-17 Example 42/1C18-0 300 10 14 89.6 5-18 Example 42/1C16-0 300 10 14 90.1 5-19 Example 42/1 Rapeseed 300 10 45 96.1 5-20 oil Example 42/1 Rapeseed 350 23 14 98.8 5-21 oil Example 42/1C18-3 1-butonal 300 9 15 97.3 5-22 Example 42/1C18-2 300 9 14 92.4 5-23 Example 42/1C18-1 300 9 14 86.1 5-24 Example 42/1C18-0 300 9 14 82.5 5-25 Example 42/1C16-0 300 9 14 81.1 5-26 Example 42/1 Rapeseed 300 9 45 87.1 5-27 oil Example 42/1 Rapeseed 350 23 14 95.3 5-28 oil Example 42/1 Rapeseed 1-octanol 300 6 45 68.7 5-29 oil Example 42/1 Rapeseed 350 19 20 90.7 5-30 oil C16-0: palmitic acid, C18-0: stearic acid, C18-1: oleic acid, C18-2: linoleic acid, C18-3: linolenic acid
ethyl 6-O-octadecanoyl-D-glucopyranoside[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
90%
lipase;
EXAMPLE 6 Preparation of ethyl 6-O-octadecanoyl-D-glucopyranoside The title compound was obtained as a crude product (1310 g, 90% mon.COPYRGT.ester, 5% <strong>[3198-49-0]ethyl D-glucopyranoside</strong>, 5% diesters) according to example using a reaction temperature of 80 C., <strong>[3198-49-0]ethyl D-glucopyranoside</strong> (603 g, 2.9 mol), octadecanoic acid (1112 g, 3.9 mol) and immobilized lipase (30 g). The reaction was complete in 48 hours. NMR-spectra of the chromatographically purified product are in accordance with the 1 H and 13 C NMR-spectra given for the pure alpha and beta anomers in tables 4 a/4 b.
With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; triethylamine; In dichloromethane; ethyl acetate; at 0 - 20℃; for 0.5h;Inert atmosphere;
General procedure: <strong>[62-31-7]Dopamine hydrochloride</strong> (60.7 mg, 0.32 mmol) and palmitoleic acid (91.0 muL, 0.32 mmol) were mixed in dry CH2Cl2(1 mL) under an Ar atmosphere, and triethylamine (133 muL, 0.96 mmol) was added at 0C. PPACA (50% in ethyl acetate, 200 muL, 0.32 mmol) was slowly added over 30 min at the same temperature, and the reaction mixture was stirred at room temperature overnight. The mixture was worked up followed by evaporation, and the residue was purified by column chromatography (eluent; EtOAc-hexane=1 : 1-4 : 1) to give N-palmitoleoyl dopamine (22.6 mg, 18.1%) as a colorless oil.
PREPARATIVE EXAMPLE 1; Synthesis of CLA by Alcaline Isomerization of Grape Seed Oil in Glycerol (The following synthesis makes the object of a co-pending application); 1 kg glycerol, 235 g potassium hydroxide (KOH) and 1000 g of grape seed oil were added into a 4-neck round bottom flask (5000 ml) equipped with a mechanical stirrer, a thermometer, a reflux condenser, and a nitrogen inlet, the nitrogen being introduced in first run through two oxygen traps.Nitrogen was bubbled into the reaction mixture for 20 min and the temperature was then raised to 90-100 C., and kept under mechanical stirring for about 20 minutes to convert the trigliceride in the corresponding potassium salts. The double phase system disappears to form a glyceric soap suspension, then heated at 230 C. under inert atmosphere and stirred for 4 hours.The reaction mixture was cooled to about 100 C., and the stirring stopped as the reaction mixture tend to reach very high viscosity during cooling. 2 l of water was then slowly added, and the mixture kept at 95 C. for 2 hour. This operation becomes necessary because of the neglegible presence of water and high content of glycerol causing fatty acids to be present as mono- and diglyceride from 5% to 10% by weight of the total lipid content. As partial glyceride esters tend to form W/O emulsion, the water addition and re-heating provides full saponification of the residual esterified fatty acid.The mixture was transferred into a becker, then cooled to room temperature and 50% w/v sulfuric acid was added to the mixture which was stirred for 1 hour until the pH stabilized at about 3.The acidulated oil phase formed a lower hydroglyceric layer and an upper fatty acid oil layer containing CLA, which was separated by decantating. Noteworthy, in industrial operation the separation could be carried out by centrifugation.The CLA was washed with water and finally it was made anhydrous with sodium sulphate and filtered, then it is stored in a dark bottle at 4 C. until time of use. Total yield about 770 g af an amber oil, whose GC-analysis is shown in Table 1; The composition of CLA appears to be a complex mixture, i.e. 9c, 11t- and 8c, 10t-octadecadienoic acids at 30.90%, 11c, 13t-10t, 12c-octadecadienoic acids at 32.05%, 11t, 13c-8c, 10c-9c, 11c-octadecadienoic acid at 1.55%, 10c, 12c-11c, 13c-11t, 13t, 9t, 11t-10t, 12t-8t,10t-octadecadienoic acids making the remaining part.
With calcium hydroxide; water; In butan-1-ol; at 50 - 175℃; for 0.666667 - 1h;Reactivity;
An esterification reaction mixture (94 g), consisting of butanol (ca., 4.9% w/w), butyl stearate (95.1% w/w), residual stearic acid (trace), residual methanesulfonic acid catalyst (1383 ppm) and undesired <strong>[1912-32-9]butyl methanesulfonate</strong> (613 ppm) was treated with 45% aqueous KOH (229 mg, 1.84 mmol as compared to 1.74 mmol MSA originally charged to the reaction). The resulting mixture was heating at 50 C. for 40 minutes. Without wishing to be bound by any particular theory or explanation, it is believed that reaction of butyl stearate with KOH produced potassium stearate, which retains significant solubility in the butyl stearate medium. The formed potassium stearate then reacted with <strong>[1912-32-9]butyl methanesulfonate</strong> to produce potassium methanesulfonate and butyl stearate. After filtration of the by-product solid salts (0.6325 g), analysis of the mixture by gas chromatography revealed only 300 ppm unreacted <strong>[1912-32-9]butyl methanesulfonate</strong>, a 51% reduction. Repetition of the above KOH treatment at a higher temperature (175 C./60 min.) revealed complete reaction of the <strong>[1912-32-9]butyl methanesulfonate</strong>. Similarly, treatment with NaOH was found equally effective as treatment with KOH. Treatment with Ca(OH)2 proved ineffective, presumably due to formation of poorly soluble calcium salts. Treatment with acidic tin(II) or zirconium (IV) salts resulted in formation of additional <strong>[1912-32-9]butyl methanesulfonate</strong>.
37
[ 75-75-2 ]
[ 1912-32-9 ]
[ 123-95-5 ]
[ 57-11-4 ]
[ 822-16-2 ]
[ 2386-57-4 ]
Yield
Reaction Conditions
Operation in experiment
With sodium hydroxide; water; In butan-1-ol; at 50 - 175℃; for 0.666667 - 1h;Conversion of starting material;
An esterification reaction mixture (94 g), consisting of butanol (ca., 4.9% w/w), butyl stearate (95.1% w/w), residual stearic acid (trace), residual methanesulfonic acid catalyst (1383 ppm) and undesired <strong>[1912-32-9]butyl methanesulfonate</strong> (613 ppm) was treated with 45% aqueous KOH (229 mg, 1.84 mmol as compared to 1.74 mmol MSA originally charged to the reaction). The resulting mixture was heating at 50 C. for 40 minutes. Without wishing to be bound by any particular theory or explanation, it is believed that reaction of butyl stearate with KOH produced potassium stearate, which retains significant solubility in the butyl stearate medium. The formed potassium stearate then reacted with <strong>[1912-32-9]butyl methanesulfonate</strong> to produce potassium methanesulfonate and butyl stearate. After filtration of the by-product solid salts (0.6325 g), analysis of the mixture by gas chromatography revealed only 300 ppm unreacted <strong>[1912-32-9]butyl methanesulfonate</strong>, a 51% reduction. Repetition of the above KOH treatment at a higher temperature (175 C./60 min.) revealed complete reaction of the <strong>[1912-32-9]butyl methanesulfonate</strong>. Similarly, treatment with NaOH was found equally effective as treatment with KOH. Treatment with Ca(OH)2 proved ineffective, presumably due to formation of poorly soluble calcium salts. Treatment with acidic tin(II) or zirconium (IV) salts resulted in formation of additional <strong>[1912-32-9]butyl methanesulfonate</strong>.
With potassium hydroxide; water; In butan-1-ol; at 50 - 175℃; for 0.666667 - 1h;Conversion of starting material;
An esterification reaction mixture (94 g), consisting of butanol (ca., 4.9% w/w), butyl stearate (95.1% w/w), residual stearic acid (trace), residual methanesulfonic acid catalyst (1383 ppm) and undesired <strong>[1912-32-9]butyl methanesulfonate</strong> (613 ppm) was treated with 45% aqueous KOH (229 mg, 1.84 mmol as compared to 1.74 mmol MSA originally charged to the reaction). The resulting mixture was heating at 50 C. for 40 minutes. Without wishing to be bound by any particular theory or explanation, it is believed that reaction of butyl stearate with KOH produced potassium stearate, which retains significant solubility in the butyl stearate medium. The formed potassium stearate then reacted with <strong>[1912-32-9]butyl methanesulfonate</strong> to produce potassium methanesulfonate and butyl stearate. After filtration of the by-product solid salts (0.6325 g), analysis of the mixture by gas chromatography revealed only 300 ppm unreacted <strong>[1912-32-9]butyl methanesulfonate</strong>, a 51% reduction. Repetition of the above KOH treatment at a higher temperature (175 C./60 min.) revealed complete reaction of the <strong>[1912-32-9]butyl methanesulfonate</strong>. Similarly, treatment with NaOH was found equally effective as treatment with KOH. Treatment with Ca(OH)2 proved ineffective, presumably due to formation of poorly soluble calcium salts. Treatment with acidic tin(II) or zirconium (IV) salts resulted in formation of additional <strong>[1912-32-9]butyl methanesulfonate</strong>.
1-stearoyl-2-hydroxy-3-N,N-dimethylaminopropane[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In tetrahydrofuran; benzene;
A. Synthesis of 1-stearoyl-2-hydroxy-3-N,N-dimethylaminopropane (SHDAP) STR19 A solution of stearic acid (1 g) in benzene (100 mL) was treated with oxalyl chloride (6 mL) at room temperature for one hour. The solvent was removed under reduced pressure and the residue was dissolved in dry THF. The solution was cooled to 0° C. and slowly added to a solution of 3-N,N-dimethylaminopropan-1,2-diol, with stirring. The reaction mixture was stirred at 0° C. for 0.5 hour and then warmed to room temperature for two hours. The resulting solution was diluted with water, made basic with sodium hydroxide and extracted with methylene chloride. The organic extract was concentrated and chromatographed to provide SHDAP (0.39 g).
EXAMPLE 10; Preparation of Various Complexes Comprising Brimonidine and Selected CounterionsIn this experiment, various complexes comprising Brimonidine and counterions of one of the following acids were prepared: pamoic acid, capric acid, sebacic acid, hippuric acid, naproxen, 1-hydroxy-2-naphthoic acid, palmitic acid, and stearic acid. Variations of the procedure described in the following disclosure may be made within the skill of a person of ordinary skill in the art without departing from the scope of the present invention. Brimonidine free base in a preselected solvent was heated to about 60-70 C. The organic acid in another portion of the solvent was added into the heated mixture or was included in the original mixture before heating. The heating of the combined mixture was continued for an additional period, which was not critical. In certain embodiments, an antisolvent was added to the combined mixture, preferably at a lower temperature, to effect a precipitation of the complex of brimonidine and the counterion. It may be advantageous to remove a portion of the solvent and antisolvent to assist the precipitation. In certain other embodiments, the heated combined mixture was cooled down to a lower temperature, such as room temperature (or below) to effect the precipitation of the complex of brimonidine and the counterion. The precipitate was then filtered and dried to yield the final complex. The solubility of various complexes in water at the resulting pH is shown in Table 9.
With carbon dioxide; water; at 68 - 90℃; under 22801.5 - 29642 Torr; for 2 - 5h;Product distribution / selectivity;
Example 1 Sodium stearate and water at weight ratio of 15:85, were introduced into a pressure vessel, the temperature was adjusted to 90 C and CO2 was introduced. CO2 pressure was maintained at 30 atmospheres and mixing was applied. After 2 hours, mixing was stopped and the phases were separated. The organic phase was analyzed for free fatty acid and the aqueous phase for sodium bicarbonate. The analyses showed 30% conversion of the <strong>[822-16-2]sodium stearate</strong> to free stearic acid.Example 2 Example 1 was repeated at similar conditions, but the reaction time was doubled. The conversion yield was about 50%.Example 3 Example 1 was repeated with the following changes: the water proportion was increased to 97.5% of the starting mixture, the temperature was reduced to 68 C, the pressure was increased to 39 atmospheres and the reaction duration was 5 hours. The analyses at the end of the reaction showed conversion yield greater than 90%.
In water; acetone; at 0 - 30℃; for 1.66667h;Reflux;
2.00 g of desvenlafaxine base is suspended in a mixture of 17.0 ml of acetone and 5.4 ml of demineralised water and heated under reflux conditions. 2.38 g of stearic acid is added and the mixture is further stirred and heated under reflux conditions for 10 minutes, stirred at 30 C for another 30 minutes and finally stirred at 0 C for one hour. The product is filtered, washed with mother liquor and dried under vacuum at ambient temperature to yield 3.52 g (84.6%) of stearate salt.
at 70 - 180℃;Inert atmosphere;Product distribution / selectivity;
Example 1 Commercial Sodium Stearate and Slow Addition of L-Lactide In this Example, 395.47 g stearic acid and 426.30 g <strong>[822-16-2]sodium stearate</strong> were added to a 4-necked, 2,000 mL round bottom flask equipped with an overhead stirrer (PTFE paddle on a glass rod and Ace Glass trubore) through the center neck. One side neck was topped with a thermometer (-10 to 300 C.), and a second side neck was topped with a nitrogen sparge line (type ?A? glass frit on angled glass tube).A heating mantle attached to a rheostat was used to heat the flask. Once the stearic acid was melted (70 C.), the nitrogen sparge was set to 400 mL /min. The reaction at this point was a suspension of particles in liquid.The third side arm was topped with an addition funnel with equilibrating side arm wrapped in silicone heating tapes. The tapes were attached to an analog heat controller. Next, 202.12 g L-lactide was added to the addition funnel and allowed to melt.When the reaction temperature reached 179 C., the L-lactide was slowly added to the reaction (0.56 mol L-lactide :1 mol fatty acid :0.58 mol sodium). The addition was complete by t=1 hour 13 min., and the reaction temperature was maintained at 180 C.During and after the addition, a graduated pipet was used to withdraw small (2-5 mL each) samples to determine reaction composition over time. The small samples were transferred to 20 mL vials and allowed to cool on the bench.The heat was turned off at t=1 hour 44 min. The heating mantle was removed, and the mixture cooled to between 80-100 C. The mixture was poured onto a metal sheet to solidify.The resulting product was a shiny, brittle, orange - brown colored solid with caramel odor.The product had the following properties: (a) QC data: 90.39 Acid Value; 141.66 Ester Value; 3.14% sodium ; and 25.41% total recoverable lactic acid ; and(b) GC-FID: 13.36% palmitic ; 31.83% stearic ; 11.42% palmitoyl-1-lactylate ; 26.39% stearoyl-1-lactylate ; 3.13% palmitoyl-2-lactylate ; 7.27% stearoyl-2-lactylate ; 0.85% palmitoyl-3-lactylate ; 1.84% stearoyl-3-lactylate ; 0.46% palmitoyl-4-lactylate ; and 0.73% stearoyl-4-lactylate.The above results show that the inventive reaction proceeds much faster than the prior art reaction. The control reaction set forth above would require at least 5 hours to reach a similar composition as this Example.
With immobilized Candida antarctica Lipase B; In neat (no solvent); at 60℃; for 12h;Green chemistry; Enzymatic reaction;
General procedure: To a 1 g of SA (3.52 mmol), in a 12 ml vial, was added an alcohol donor (for DEC: 0.5, 1 or 2 molar ratio were used; for TEOF 1 molar ratio). Then 50 mg of Novozym 435 and 5 mul of ethanol were added to start the reaction. The mixture was kept in shaker at 60 C and 300 rpm. The course of reaction was monitored by GC at defined times.
With immobilized Candida antarctica Lipase B; In neat (no solvent); at 60℃; for 8h;Green chemistry; Enzymatic reaction;
General procedure: To a 1 g of SA (3.52 mmol), in a 12 ml vial, was added an alcohol donor (for DEC: 0.5, 1 or 2 molar ratio were used; for TEOF 1 molar ratio). Then 50 mg of Novozym 435 and 5 mul of ethanol were added to start the reaction. The mixture was kept in shaker at 60 C and 300 rpm. The course of reaction was monitored by GC at defined times.
General procedure: At room temperature, organic carbonyl acid 3 (R-COOH, 0.5 mmol) was added into a reaction tube equipped with a small magnet. Then a solution of tertiary amine 1 (R1CH2-NR2R3, 0.5 mmol ) in DCM (2.5 mL) was added dropwise in 2 min. After the mixture was stirred at room temperature for a few minutes, 1 equivalents of dimethyl acetylenedicarboxylate (DMAD, 2) was added. The reaction was stirred overnight at room temperature, and then monitored by TLC with silica gel coated plates. After being stirred for 14 h, the solvent was removed and the residue was purified by a flash column chromatography with silica gel with ethyl acetate/hexane (1:25-30) as eluent to give the desired products 4, 5, and 7. Most of compounds are known and confirmed by NMR, ESI-MS, IR.
With lipase from Pseudomonas stutzeri PS59; In aq. phosphate buffer; isopropyl alcohol; at 30℃; for 0.25h;pH 8.0;Enzymatic reaction;
General procedure: An assay mixture consisting of 1 ml of liquid ester or 1 g of solid ester, 3 ml of isopropanol, 5 ml of phosphate buffer (pH=8.0), and 1 ml of the lipase solution was incubated for 15 min at 30C with stirring at 180 rpm. The reaction was terminated by the addition of 95% ethanol, and the amount of liberated fatty acids after incubation was determined by titrating with 50 mM NaOH in the presence of two drops of phenolphthalein solution as the indicator. The control experiment was performed under the same conditions with the addition of 95% ethanol prior to the reaction. One unit of lipase activity was defined as the amount of enzyme required to liberate 1 mumol of free fatty acid per minute under the experimental conditions.
With Mg-Al hydrotalcite; hydrogen; at 325℃; under 21446.5 Torr;
[0058] As an example, FIG. 2 shows results from reacting triglycerides over a hydrotalcite catalyst according to the invention. To generate the data shown in FIG. 2, a feed containing the triglyceride tristearin was exposed to a hydrotalcite catalyst at a temperature of about 325C. and a hydrogen partial pressure of about 400 psig (about 2.8 MPag) in a batch environment. Although hydrogen was added to this experiment, it is believed that hydrogen is not required for ketone formation. The side chains in tristearin correspond to the fatty acid stearic acid, which is an 18-carbon saturated fatty acid.However, some side chains of other lengths were also present due to impurities in the tristearin feed. With the exception of such impurities, the feed contained approximately 100 wt % of tristearin.
With aluminum oxide; dilauryl thiodipropionate; 2,6-di-tert-butyl-4-methyl-phenol; Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; magnesium oxide; In water; at 100 - 130℃; under 5250.53 Torr; for 0.75h;
S1: Take Glycerol Tristearate, Stir while feeding, and keep the temperature at 100C. After the Glycerol Tristearate is completely melted, the Catalyst A, antioxidant, and water was added and at a temperature of 130C and a pressure of 0.7 MPa carried out the hydrolysis reaction. The hydrolyzed product was allowed to stand for 45 minutes, the oil and water were separated, and the catalyst was recovered by oil phase filtration to obtain stearic acid. wherein, According to the mass ratio, the amount of the magnesium oxide: Al2O3-MgO is 1: 8 in the catalyst A, and the dosage is 4% of the mass of the Glycerol Tristearate; the Al2O3-MgO is prepared through a precipitation method, and In molar ratio, Al2O3:MgO is 2:1; wherein, according to the mass ratio, antioxidant 1076: antioxidant DLTDP: antioxidant T501 is 0.5:0.65:1 in antioxidants. Wherein, Its amount is 0.5% of the mass of Glycerol Tristearate; According to the mass ratio, Glycerol Tristearate: water is 1:0.5;
Nα-(9-fluorenylmethyloxycarbonyl)-Nγ-2,2,4,6,7-pentamethyldihydrobenzofuran-5-sulfonyl-L-arginine[ No CAS ]
C75H130N14O24[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
The interaction of cyclic and linear RGD peptide ligands withalpha v beta 3 integrin receptor were studied using MolecularOperating Environment software (Details in SupplementaryMaterial). The peptide amphiphiles were synthesized by followingstandard solid phase peptide synthesis procedure. Thecyclic RGD amphiphile (C18-ADA5-cRGDfK) was synthesizedentirely on solid support. Several protocols for synthesisof the cyclic RGD (cRGDfV or cRGDfK) peptide have beenreported and modified for improved yields. The cyclic RGDpeptide was built on solid phase using the protocol reported byMcCusker et al. with some modifications [20]. The O-allylprotected aspartic acid, Fmoc-Asp-OAll (2.5 equivalents)was loaded on the 2-chloro trityl chloride resin in the presenceof 10 equivalents of N,N-diisopropylethylamine (DIPEA) for5 h. After washing the resin with DMF (3 times) and DCM (3times), the amino group was deprotected by treatment with20% piperidine in DMF for 30 min and the wash steps wererepeated. The Fmoc-Gly-OH was added in the presence of 2equivalents of HOBT (hydroxybenzotriazole), 2 equivalentsof HATU (2-(1H-7-azabenzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate) and 4 equivalents of DIPEA.The subsequent amino acids in the order of Fmoc-Arg(Pbf)OH, Fmoc-Lys-Dde and Fmoc-Phe-OH were conjugatedusing the same deprotection and conjugation protocol.Each conjugation step was performed for 2 h. Allyldeprotection was performed using chloroform and Nmethylmorpholinein the presence of palladium catalyst in aN2 atmosphere for 4 hours followed by amino groupdeprotection using 20% piperidine in DMF. Cyclization wascarried out overnight in the presence of PyBOP (benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate),DIPEA and DMF. This step was repeated for an additional6 h. Further, the 1-(4,4-Dimethyl-2,6-dioxocyclohexylidene)ethyl (Dde) group was specifically cleaved by using 2% hydrazinehydrate in DMF. For synthesis of the amphiphiles, the 8-amino-3,6 dioxaoctanoic acid (ADA) groups were conjugatedto the lysine side chain using the same protocol as for theamino acids. Finally, stearic acid was conjugated in the presenceof PyBOP (4 equivalents) and DIPEA (8 equivalents).The amphiphile was cleaved from the resin by treating withTFA:TIS: H2O (95:2.5:2.5) for 3 hrs. After removal of TFA,the amphiphile was precipitated using ether:hexane (50:50)mixture. The amphiphile was then separated by centrifugationand freeze dried before further analysis. The synthesis oflinear RGD amphiphile (C18-ADA5-RGD) was carried outusing the same protocol as previously reported [18] (SpecificDetails are provided in Supplementary Materials). All amphiphilessynthesized were characterized for molecular weightand purity using Matrix Assisted Laser Desorption/Ionization- Time of Flight (MALDI-TOF) and reversed phaseHPLC (RP-HPLC) respectively.
With toluene-4-sulfonic acid; In neat (no solvent); at 60℃; for 4.0h;
General procedure: The FFA (2.0 g), glycerol formal (GlyF: 1.5 molar equivalent respect to the FFA) andp-toluene-sulfonic acid (5percent w/w respect of the weight of the FFA) were charged in a conventionalround bottom flask with a magnetic stirrer. The mixture was heated at 60 C and stirred vigorously for4 h. The reaction was quenched by neutralizing the acid catalyst with saturated solution of sodiumcarbonate then filtered. The liquid phase was collected in a separatory funnel and partitioned betweenchloroform and water (3 x 20 mL). The organic layer was dried over sodium sulfate, filtered and thesolvent eliminated using a rotary evaporator. The sample was stored in a glass vial Table 2 summarizesthe experimental conditions and the results of reactions between GlyF and the FFAs.
With hydrogen; at 320℃; under 37503.8 Torr;Flow reactor;
Stearic acid was converted into stearyl alcohol using a fixed-bed reactor containing a CuCr/Al2O3 catalyst. Specifically, 6 g of a commercially available CuCr/Al2O3 catalyst was placed in a fixed-bed reactor, the top and bottom of the catalyst were closed with glass wool, the remaining portion of the reactor was filled with silica beads, and a thermocouple was disposed so as to be in contact with the catalyst. The reaction temperature was increased to about 400 C. at a rate of about 5 C./min under conditions of N2 flow rate of about 200 seem and H2 flow rate of 200 seem, and was then maintained for about 3 hr at a reaction pressure of about 50 bar. Thereafter, the reaction temperature was decreased to about 300 C., after which the mixed solution of C18 fatty acid and ethanol at a molar ratio of 1:5 was fed at about 0.13 sccm, and the reactor was operated at a space velocity (WHSV) of about 1 hr-1. Draining for the first 16 hr and then sampling at 8-hr intervals were performed, and hydrogenation activity and selectivity were measured. The reaction activity was measured at about 300 C., after which changes in the reaction activity were checked depending on changes in the reaction temperature and pressure. The stabilized product pattern results, observed two days after changes in the reaction conditions, were adopted, taking reaction stability into consideration. The conversion efficiency of the product was measured via SimDist analysis. The product selectivity and the presence or absence of side reactions were measured via GC-MS and SimDist analysis.
With phosgene; 4-(dimethylamino)pyridine hydrochloride; at 150℃;
4-Dimethylaminopyridine Hydrochloride as Catalyst for Phosgene SynthesisTo the reaction bottle, 80 g of stearic acid and 0.008 g of 4-dimethylaminopyridine hydrochloride were added and the mixture was heated to 150 C,When the molar ratio of phosgene to stearic acid to phosgene was 1: 6, the phosgene was stopped. Distillation under reduced pressure stearyl chloride, the chemical titration analysis of more than 98%, the molar yield of 91%.
Stearic acid (19. 7 Kg, 57.6 mol, 1.2 eq.) Was added to the 200 L autoclave, and thionyl chloride (145. OKg) was pumped and replaced with nitrogen. The first warming to 40 C, the reaction 1 hour, then heated to reflux 6-8 hours. Cooling to40 C, decompression steamed to remove thionyl chloride; when concentrated to no liquid, into the dichloromethane (20. OKg), and then concentrated to no liquid. (450. OKg), stirring for 15 minutes, into the 000L reactor, and then cooled to 10 ~ 15 C, the rapid addition of anhydrous aluminum chloride (13. 3Kg, 99.7 mol, 1.73 eq.). The starting material 10 was dissolved in DCM (450.0 OKg) and added dropwise to the kettle. The temperature was controlled at 10-15 C. After the addition, the temperature was maintained between 10 and 15 C for 1 hour. reaction. After completion of the reaction, 2M hydrochloric acid (330. OKg) was added dropwise. After completion of the addition, stirring was continued for 0.5 hour. Standing, liquid separation. The organic phase was washed with 0.6 M aqueous hydrochloric acid (300. OKgX); once with saturated aqueous sodium bicarbonate (300. OKg) and again with water (300. OKg). The organic phase was washed with water (300. OKg) ) Was added, and then sodium sulfate (75 kg) was added to the organic phase for drying for 2 hours. The desiccant was filtered and the filter cake was dried in a drying oven to give product 11 as a yellow solid powder (33.6 g, 100%).
3 mmol stearic acid was withdrawn in the reaction vessel,3 mmol of DCC, 3 mmol of DMAP,Add 20mL of anhydrous methylene chloride dissolved, ice bath conditions, stirring for 30 minutes;1 mmol of <strong>[38748-32-2]TP</strong> was dissolved in an appropriate amount of anhydrousMethylene chloride and slowly added dropwise to the reaction system,Ice bath conditions for 30 minutes,The reaction was continued overnight at room temperature,The reaction was separated and purified on a silica gel column to give 532.2 mg of <strong>[38748-32-2]triptolide</strong>. Yield 84.9%.
The method for preparing the fatty acyl taurine surfactant of this embodiment has the following steps:(1) Put 285g of stearic acid and 1000g of acetic anhydride into the reactor;(2) Slowly increase the temperature to 150 C and reflux for 10 hours;(3) Connect to vacuum -0.08 ~ -0.09MPa, temperature 150 , vacuum degassing for 4 hours;(4) Reduce the temperature to 90 ;(5) Add 132g of taurine (95% powder), and 146g of methyl taurine (95% powder) slowly warm up to 290 ;(6) Insulation at 290 , reaction for 6 hours;(7) The finished product of stearoyl methyl taurine and taurine is obtained by cooling down.