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CAS No. : | 112-38-9 | MDL No. : | MFCD00004442 |
Formula : | C11H20O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | FRPZMMHWLSIFAZ-UHFFFAOYSA-N |
M.W : | 184.28 | Pubchem ID : | 5634 |
Synonyms : |
Undecylenic acid
|
Num. heavy atoms : | 13 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 0.73 |
Num. rotatable bonds : | 9 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 1.0 |
Molar Refractivity : | 56.29 |
TPSA : | 37.3 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -4.68 cm/s |
Log Po/w (iLOGP) : | 2.62 |
Log Po/w (XLOGP3) : | 3.86 |
Log Po/w (WLOGP) : | 3.38 |
Log Po/w (MLOGP) : | 2.76 |
Log Po/w (SILICOS-IT) : | 3.06 |
Consensus Log Po/w : | 3.13 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.85 |
Log S (ESOL) : | -2.82 |
Solubility : | 0.279 mg/ml ; 0.00151 mol/l |
Class : | Soluble |
Log S (Ali) : | -4.34 |
Solubility : | 0.00842 mg/ml ; 0.0000457 mol/l |
Class : | Moderately soluble |
Log S (SILICOS-IT) : | -2.94 |
Solubility : | 0.212 mg/ml ; 0.00115 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 3.0 |
Synthetic accessibility : | 1.89 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P273-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335-H412 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1.34 kg | With hydrogen bromide In toluene at 18℃; for 1 h; Industrial scale | The use of a melting point of 23 ° C, a purity of more than 98.5percent 10-undecenoic acid 1kg, raw material ratio of 10-undecenoic acid and toluene mass ratio of 1:3, according to 10-undecenoic acid and The molar ratio of hydrogen bromide is 1:1.20, and hydrogen bromide gas is fed into the bottom of the addition column, and then the feed liquid and hydrogen bromide are continuously added to maintain the ratio.Through the cooling water control reactor reaction temperature at 18 °C, after a reaction for 1 hour,Recovery of toluene by distillation, washing oil phase 2-3 times, and cooling the system to 15 ~ 20 ° C, after sufficient crystallization, vacuum filtration to obtain white crystal 11-bromo undecanoic acid 1.34kg; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With monoammonium 12-tungstophosphate for 12h; Heating; | |
100% | With sulfuric acid In methanol for 6h; Reflux; | Synthesis of methyl undec-10-enoate (1): 10-Undecenoic acid(10 g, 54.34 mmol), was added to methanol (17.6 mL) andsulfuric acid (0.1 mL, 2 wt % 10-undecenoic acid) and stirred at refluxing temperature of methanol for 6 h. After completion ofthe reaction as shown by TLC (hexane/ethyl acetate 80:20, v/v),excess methanol was removed under reduced pressure and theproduct was diluted with ethyl acetate (30 mL), washed with5% aqueous NaHCO3 solution (3 × 30 mL), and dried over anhydrous Na2SO4. The organic solvent was removed underreduced pressure to afford crude methyl ester of 10-undecenoicacid. The product was purified by column chromatography withbasic alumina and hexane as the eluent to get 99% pure methylundec-10-enoate (1) as indicated by GC. The product wasanalyzed by 1H NMR, 13C NMR, ESIMS, and FTIR and thestructure was confirmed by comparing the data with those reported in the literature [14]. |
99% | Stage #1: methanol; 10-undecenoic acid With thionyl chloride at 10 - 20℃; for 12h; Stage #2: With potassium carbonate In water |
99% | With sulfuric acid for 24h; Reflux; | |
98% | With boron trifluoride diethyl etherate | |
97% | With sulfuric acid Reflux; | 4.1 Step 1. Methyl undec-10-enoate (17). A stirred mixture of undec-10-enoic acid (16) (20 g, 108.53 mmol, 1.0 eq) and sulfuric acid (5 mL) in methanol (200 mL) was heated to reflux for one night. The resulting mixture was concentrated and the residue was diluted with ethyl acetate (200 mL) and aqueous solution of NaHCC (100 mL). The aqueous layer was extracted with additional ethyl acetate (2 x 100 mL). The combined organic layer was dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to give methyl undec-10-enoate (17) (21g, 97%). The compound was used without further purification. |
95% | With sulfuric acid at 65℃; for 16h; | |
93% | In toluene for 8h; Heating / reflux; | 1 Example 1-Methyl ester of undecylenic acid In a two-necked 100 ml flask, 7 ml of methanol and a spatula tip of [P-TOLUENESULPHONIC] acid are added to 15 g of unde- cylenic acid (81.4 mmol) dissolved in 35 ml of anhydrous toluene. The whole is heated under reflux for 8 hours with a Dean Stark or Markusson distilling apparatus separating the water of esterification. All of the glassware used has been dried beforehand in an oven at [120°C.] The progress of the re- action is monitored by TLC (silica gel plates), eluant hex- ane/EtOAc 7: 3. Rf ester = 0.64. Work-up: the product is diluted with EtOAc, washed twice with a mixture of [NAHCO3/H2O] 1: 1, then with [H20] and saturated NaCl solution and dried over [NA2SO4. 15] g (73.0 mmol) are ob- tained, (yield 93%). Any traces of starting acid can be re- moved by filtration over a bed of alumina. |
93% | With sulfuric acid Reflux; | 5.1.1.2. Methyl 10-undecenoate (3) To a solution of 5.00 g (27.1 mmol) of 10-undecenoic acid in 100 mL of methanol, 1 mL of concentrated H2SO4 was added. The resulting mixture was stirred at reflux overnight. The solution was cooled to room temperature and 200 mL of petroleum ether was added. The combined organic extracts were washed with a saturated NaHCO3 aqueous solution, with brine and dried over MgSO4, filtered and concentrated under vacuum. The new product was dried under vacuum overnight to give 5.00 g (93%) of 3 as a yellow oil. TLC: Rf = 0.4 (9:1 Cyclohexane/EtOAc); NMR 1H (400 MHz; CDCl3) δ 5.83-5.77 (ddt, 1H, J = 17.1;10.1;6.8), 5.01-4.91 (m, 2H), 3.66 (s, 3H), 2.29 (t, 2H, J = 7.6), 2.04 (q, 2H, J = 7.0), 1.61 (quint, 2H, J = 7.3), 1.38-1.29 (m, 10H); NMR 13C (100 MHz; CDCl3) δ 174.9, 139.8, 114.8, 52.0, 34.8, 34.4, 29.8, 25.6. MS calcd for C12H23O2 = 199.2, found 199.2. |
92% | With chloroformic acid ethyl ester; potassium carbonate for 12h; Ambient temperature; | |
91% | With dmap; dicyclohexyl-carbodiimide at 20℃; | I.A To a solution of starting undecylenic acid in methanol is added DCC and 4- DMAP. The reaction mixture is stirred overnight at room temperature. |
90% | With toluene-4-sulfonic acid for 12h; | |
90% | In methanol for 7h; | |
90% | With sulfuric acid for 6h; Reflux; | |
90% | With toluene-4-sulfonic acid In dichloromethane for 48h; Reflux; | Methyl 10-Undecenoate 1 Initially, 184.28 g (1.00 mol) methyl undec-10-enoic acid, 82 mL (2.00 mol) methanol und 4.52 g (26 mmol) p-toluenesulfonic acid were dissolved in 200 mL dichloromethane and heated under reflux for 48 h. After cooling to room temperature, the organic phase was was washed with 100 mL distilled water, 100 mL of a 5 % solution of sodium bicarbonate, and with another 100 mL of distilled water consecutively. The solvent was removed under reduced pressure after drying with sodium sulfate. Finally, a fractional distillation (83 °C, 10-3 mbar) was carried out to isolate 178.87 g of methyl 10-undecenoate 1 (0.90 mol, 90 %) with a purity of about 99 % in the form of a clear, colorless liquid. |
90% | With sulfuric acid at 65℃; for 13h; | |
80% | for 4h; Ambient temperature; | |
77% | With dmap; oxalyl dichloride; Tropone; triethylamine In dichloromethane at 20℃; for 14h; | |
With sulfuric acid | ||
With hydrogenchloride | ||
With sulfuric acid In dichloromethane | ||
With sulfuric acid Heating; | ||
With toluene-4-sulfonic acid In toluene | ||
With sulfuric acid for 4h; Heating; | ||
With thionyl chloride 1.) reflux, 3.0 h; 2.) room temp., overnight; Yield given. Multistep reaction; | ||
With sulfuric acid | ||
With toluene-4-sulfonic acid for 3h; Heating; | ||
With sulfuric acid for 3h; Heating; | ||
With hydrogen cation | ||
With hydrogen cation | ||
With sulfuric acid for 3h; Heating; | ||
With sulfuric acid | ||
With sulfuric acid for 6h; Reflux; | ||
With sulfuric acid Reflux; | ||
With sulfuric acid | ||
With toluene-4-sulfonic acid In dichloromethane for 48h; Reflux; | ||
With toluene-4-sulfonic acid | ||
With sulfuric acid Heating; | ||
With sulfuric acid Reflux; | ||
With sulfuric acid for 10h; Reflux; | 2.1a Synthesis of methyl undec-10-enoate (2) To a stirred solution of undec-10-enoic acid (73.45 mmol) inmethanol (100 mL), a few drops of concentrated H2SO4 wereadded. The reactionmixturewas refluxed for 10 h. Progress of the reaction was monitored by micro TLC. After completion the reaction, methanol was removed under reduced pressure and water was added and the title compound was extracted with ethyl acetate, dried over anhydrous sodium sulphate and concentrated under vacuum to afford the title compound.1H NMR (300 MHz, CDCl3): (δ, ppm) = 5.75-5.85 (m,-CH = CH2-, 1H), 4.91-5.01 (m, -CH = CH2-, 2H), 3.66(s,-OCH3, 2H), 2.28-2.31(t, -CH2-, J = 7.4 Hz, 2H), 2.01-2.06(m, -CH2-, 2H), 1.59-1.65(m, -CH2-, 2H), 1.26-1.39(m,-(CH2)5-, 10H).ESI-mass: [M+ H]+m/z = 199. | |
With toluene-4-sulfonic acid | ||
With toluene-4-sulfonic acid In toluene for 5h; Reflux; | ||
With sulfuric acid for 3h; Reflux; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With monoammonium 12-tungstophosphate for 12h; Heating; | |
97% | In toluene for 8h; Heating / reflux; | 1a Example 1a - Ethyl ester of undecylenic acid In a 100 ml two-necked flask, 8 ml of ethanol and a spatula tip of p-toluenesulphonic acid are added to 15 g of undecylenic acid (81.4 mmol) dissolved in 35 ml of anhydrous toluene. The whole is heated under reflux for 8 hours with a Dean Stark or Markusson distilling apparatus separating the water of esterification. All of the glassware used has previously been dried in an oven at [120°C.] The progress of the reaction is monitored by TLC (silica gel plates), eluant hexane/EtOAc 7: 3. Rf ester = 0.67. Work-up: the product is diluted with EtOAc, washed twice with a mixture of [NAHCO3/H2O] 1: 1, then with [H20] and a saturated NaCl solution and dried over [NA2SO4. 16.] 7 g (78.9 mmol) are obtained (Yield 97%). Any traces of starting acid can be eliminated by filtration over a bed of alumina. |
97% | With dimethyl sulfoxide In dichloromethane at 0 - 20℃; Inert atmosphere; |
95% | With sulfuric acid for 20h; Inert atmosphere; Reflux; | |
90% | With K5<CoW12O40> In toluene at 85℃; for 5h; | |
With hydrogenchloride | ||
(i) (COCl)2, DMF, MeCN, (ii) /BRN= 1718733/, Py; Multistep reaction; | ||
With toluene-4-sulfonic acid for 6h; Heating; | ||
With toluene-4-sulfonic acid In toluene for 5h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With ozone; sodium hydroxide In methanol; dichloromethane at -78 - 20℃; for 6h; | |
85% | With sodium periodate; RuCl3*2.9H2O In water at 20℃; for 0.75h; Sonication; | |
83% | Stage #1: 10-undecenoic acid With ozone; acetic acid In dichloromethane Inert atmosphere; Stage #2: With semicarbazide hydrochloride at 0 - 20℃; for 48h; Inert atmosphere; |
80% | Stage #1: 10-undecenoic acid With oxygen; ozone In dichloromethane; acetic acid at 0℃; Stage #2: With toluene-4-sulfonic acid hydrazide In dichloromethane; acetic acid at 20℃; Inert atmosphere; | Ozonolysis of alkenes (1-3). General procedure. General procedure: Through a solution of 10.0 mmol of alkene 1-3 in 25 mL of anhydrous alcohol (MeOH or i-PrOH) or in a mixture of 25 mL of CH2Cl2 and 5.7 mL of AcOH at 0 °C was bubbled the ozone-oxygen mixture till 10 mmol of ozone was consumed. The reaction mixture was flushed with argon. At 0 °C 6.51 g (35.0 mmol) of TsNHNH2 was added, the reaction mixture was stirred at room temperature till disappearance of preoxides (monitoring by the starch iodide test), the solvent was distilled off, the residue was dissolved in 150 mL of CHCl3, washed with brine (4 × 35 mL), dried with Na2SO4, and evaporated. |
78% | With sodium periodate In water; ethyl acetate; acetonitrile for 2h; | |
With ammonium vanadate; nitric acid | ||
14 Oxidation of 10-undecenoic acid EXAMPLE 14 Oxidation of 10-undecenoic acid The procedure of Example 2 was followed, except that 0.03 mole 10-undecenoic acid (5.7 g) was employed as substrate. Decanoic acid ethyl ester was used as gas chromatographic internal standard. Yield of decane dioic acid: 67% of the theoretical based on the undecenoic acid used. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With thionyl chloride | |
95% | With thionyl chloride; N,N-dimethyl-formamide In benzene Reflux; | |
90% | With oxalyl dichloride In benzene for 3h; Ambient temperature; |
88% | With thionyl chloride for 2h; Heating; | |
84% | With thionyl chloride In dichloromethane for 4h; Reflux; | |
83% | With thionyl chloride; N,N-dimethyl-formamide at 80℃; for 10h; Inert atmosphere; Sealed tube; | |
83% | With thionyl chloride; N,N-dimethyl-formamide at 80℃; for 10h; Inert atmosphere; Schlenk technique; | |
61% | With thionyl chloride at 20 - 60℃; for 5h; | |
55% | With thionyl chloride; hydroquinone at 65℃; for 6h; | 3.2.2.1 (2.1) Preparation of intermediate undecenoyloxybenzoyl chloride: Dissolve 18.43g (0.10mol) of undecylenic acid and 16mL (0.20mol) of thionyl chloride in a 100mL three-necked flask, add a small amount of hydroquinone as a polymerization inhibitor, heat to reflux at 65°C for 6h, after the reaction is complete At 65°C, vacuum distillation was performed to remove excess thionyl chloride. The temperature was continued to increase, and the fractions at 139.0157.0°C/1.30KPa were collected to obtain the product undecenoyl chloride with a yield of 55%. In a 250mL three-necked flask, dissolve 16.57g (0.12mol) of p-hydroxybenzoic acid in 150mL of THF and 9.5mL of pyridine, stir until clear, and slowly add 0.10mol of undecenoyl chloride in THF solution at room temperature. Reaction for 10h, heating and refluxing for 10h. After the reaction is completed, pour the reaction solution into 1000 mL of water, add 37% concentrated hydrochloric acid to acidify the system, make the system appear strongly acidic, let stand overnight, filter with suction, wash the filter cake to neutral, then wash with hot water, and wait for the filter cake After drying, it was recrystallized with ethanol to obtain powder undecenoyloxy benzoic acid with a yield of 80%. In a 100mL round bottom flask, dissolve 9.13g (0.03mol) of undecenoyloxybenzoic acid in 20mL of thionyl chloride, and heat to reflux for 6h at 65°C in an oil bath. After the reaction is completed, vacuum distillation is carried out. A light yellow transparent liquid undecenoyloxy benzoyl chloride was obtained with a yield of 68%. |
With thionyl chloride | ||
With phosphorus pentachloride | ||
With thionyl chloride In benzene | ||
With oxalyl dichloride | ||
With thionyl chloride; N,N-dimethyl-formamide at 40℃; for 2h; | ||
With phosphorus pentachloride In benzene Heating; | ||
With oxalyl dichloride for 3h; | ||
With thionyl chloride for 12h; Heating; | ||
With oxalyl dichloride In toluene | ||
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane | ||
With thionyl chloride for 4h; Ambient temperature; | ||
With oxalyl dichloride In dichloromethane at 20℃; for 2h; | ||
With thionyl chloride In dichloromethane for 10h; Heating; | ||
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane for 1h; | ||
With oxalyl dichloride In dichloromethane at 20℃; for 1h; | ||
With oxalyl dichloride In dichloromethane at 20℃; for 2h; | ||
With thionyl chloride at 80℃; for 2h; | ||
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 0 - 25℃; Inert atmosphere; | ||
With phosphorus trichloride at 70℃; for 2h; | ||
With thionyl chloride | ||
With phosphorus trichloride at 70℃; for 3h; | 4.1.8. General procedure for the synthesis of aurone fatty acid esters General procedure: A solution of fatty acid (3.75 mmol) and PCl3 (1.5 mmol) was stirred at 70 °C for 3 h, and a yellow solution containing fatty acid chloride could be gotten.A solution of aurone (1.86 mmol) and anhydrous pyridine (1 mL) in CH2Cl2 (10 mL) was stirred at boiling temperature, and the above reaction mixture was added slowly. Then the reaction continued for 1-2 h at boiling temperature. Washing with dilute hydrochloric acid (10% v/v aqueous solution), saturated NaHCO3 solution, drying (Na2SO4) and removal of solvent under reduced pressure gives the crude product. The product was further purified either by flash column chromatography or recrystallization. | |
With oxalyl dichloride In tetrahydrofuran at 0℃; for 2h; Inert atmosphere; | ||
With thionyl chloride In toluene for 1.5h; Reflux; | 23 A mixture of toluene (12 mL) and SOCl2 (7.75 g, 65 mmol) and undec-10-enoic acid (1.00 g, 5.43 mmol) were refluxed for 1.5 h. The solvent and remaining SOCl2 were distilled off and the product (X) was further used in the thioester synthesis. | |
With oxalyl dichloride; N,N-dimethyl-formamide In tetrahydrofuran at 0 - 23℃; for 1.08333h; Inert atmosphere; | ||
With thionyl chloride at 55℃; | ||
With thionyl chloride for 1.5h; Reflux; | ||
With thionyl chloride for 1.5h; Reflux; | ||
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 0℃; for 3h; Inert atmosphere; | General procedure for the synthesis of fatty acid chlorides (10a-h): General Procedure: General procedure: To a stirred solution of fatty acid in DCM, catalytic amount of DMF was added. The contents were stirred at 0 °C. Oxalyl chloride was added under nitrogen atmosphere. The reaction mixture was further stirred at 0 °C for 3 h. Then reaction mixture was concentrated under reduced pressure to remove dichloromethane and excess of oxalyl chloride traces. Later crude acid chloride dissolved in DCM was used for the next step directly under nitrogen atmosphere. | |
With thionyl chloride for 3h; Heating; | 9 Reference Production Example 9 (Trans-10-undecenoic acid methyl ester, compound 22) Trans-10-undecenoic acid was dissolved in thionyl chloride (10 ml) and treated in water bath for 3 hours to distill off excess thionyl chloride. Methanol (30 ml) was added to chloride of trans-10-undecenic acid and refluxed in water bath for 2 hours. After cooling, the reaction mixture was added to 1N HCl (80 ml) to be acidic and distributed with EtOAc. The distributed liquid was purified with column chromatography (developing solvent: C6H14-EtOAc (3:1)) after concentration, and trans-10-undecenoic acid methyl ester shown in the following was isolated. Colorless oily substance, C12H22O2 MW 198, EIMS m/z (%): 198 (M+, 0), 166 (M+ - CH3OH, 22), 149 (13), 124 (36), 87 (53), 74 (100) | |
With thionyl chloride; N,N-dimethyl-formamide; sodium hydroxide In dichloromethane; water for 1.5h; Reflux; | ||
With thionyl chloride for 1.5h; Reflux; | ||
With thionyl chloride for 2h; Reflux; | 1 10-undecenoic acid (3.7 g, 0.02 mol), the thionyl chloride and (8 mL) was added, and refluxed in water bath for 2 hours.Then, the excess of thionyl chloride was distilled off under reduced pressure to give the 10-undecenoic acid chloride | |
With oxalyl dichloride In N,N-dimethyl-formamide at 20℃; | ||
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 0℃; for 3h; Inert atmosphere; | General Procedure for the Synthesis of Fatty Acid Chlorides (2a-2j) To a stirred solution of fatty acid in dichloromethane (DCM), catalytic amount of dimethyl formamide (DMF) was added and the contents were stirred at 0 °C. Oxalyl chloride was added under nitrogen atmosphere and the reaction mixture was further stirred at 0 °C for 3 h. Then reaction mixture was concentrated under reduced pressure to remove DCM and excess oxalyl chloride. Later crude acid chloride dissolved in DCM was used for the next step directly under nitrogen atmosphere. | |
With thionyl chloride In N,N-dimethyl-formamide at 80℃; for 4h; Inert atmosphere; | ||
With thionyl chloride; N,N-dimethyl-formamide In toluene at 70℃; for 3h; | ||
With oxalyl dichloride at 20 - 35℃; for 3.5h; Inert atmosphere; Green chemistry; | 21 Synthesis of undecylenoyl chloride by chlorination of undecylenic acid Using Catalyst of Example 9 To a stirred mixture of undecylenic acid (37 g,200.8 mmol) and the polymeric catalyst of Example 9 (0.75 g) at room temperature under nitrogen atmosphere, oxalyl chloride (28 g, 220.5 mmol) is added over 30 minutes. The reaction is continued at 30-35° C. and the progress of the reaction is monitored by estimating the unconverted fatty acid. The reaction was stopped after 3 hours when the free undecylenic acid was found to be less than 1.0% by weight. | |
With oxalyl dichloride In dichloromethane; N,N-dimethyl-formamide at 20 - 22℃; for 1h; | ||
With thionyl chloride | ||
With thionyl chloride In dichloromethane at 10℃; | 2.1 Step one amidation At room temperature, the reaction vessel was added 1250ml of dichloromethane and 50g 10-undecenoic acid, while stirring 129.1g of thionyl chloride was added dropwise, the reaction was completed at 10 ° C, the reaction was completed, concentration, to obtain A; | |
With thionyl chloride In tetrahydrofuran for 2h; Reflux; | ||
With oxalyl dichloride In dichloromethane at 0 - 20℃; for 3.16667h; Inert atmosphere; | ||
With thionyl chloride | ||
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 0 - 20℃; | ||
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 0 - 20℃; | Acyl chlorides General procedure: The acid (5 mmol) was dissolved in anhydrous CH2Cl2 (10 mL) and DMF (a few drops) added.Oxalyl chloride (6 mmol, 1.2 equiv.) was added dropwise to the solution, that was cooled in an icewater bath. The resulting mixture was allowed to stir at room temperature for an additional 4 h andthe solvent was evaporated to afford the crude acyl chloride, which was used directly in the nextstep. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With bromine In chloroform | |
99% | With bromine In chloroform at 0℃; for 1h; | |
97% | With bromine In tetrachloromethane for 1.5h; |
94% | With bromine In diethyl ether at 5℃; for 2h; | |
94% | With bis(1,3-dimethyl-2-imidazolidinone) hydrotribromide In dichloromethane at 20℃; for 1h; | 4.2 Typical procedure for the bromination of olefins with 3a General procedure: To a solution of 1-tetradecene (7a, 408mg, 2.08mmol) in CH2Cl2 (4mL) was added 44 3a (990mg, 2.11mmol), and the mixture was stirred at 20°C for 1h. The reaction mixture was then diluted with hexane (50mL) and washed with water (20mL×2). The organic layer was dried over Na2SO4 (15g) and concentrated in vacuo. The crude residue (690mg) was purified using silica gel column chromatography (eluent: hexane) to afford 1,2-dibromotetradecane (8a, 683mg, 92%) [23] as a colourless liquid; |
94% | With bromine In dichloromethane at 0 - 5℃; for 1h; | 17.A Step A: 10, 11-dibromoundecanoic acid To a solution undec-10-enoic acid (2.00 g, 10.9 mmol) in CHCI3 (7 mL) stirred at 0 °C, a solution of bromine (0.590 ml_, 1 1 .4 mmol), in CHCI3 (9 mL) was added below 5 °C and the mixture was stirred for 1 h at 0 °C. LCMS indicated complete reaction. The reaction mixture was washed with sat. Na2S203 (2x), sat. NaCI (1 x). The organic phase was dried over Na2S04 and concentrated under vacuum to give the desired product (3.6 g, 94%) as yellow oil (upon storing at 4 °C, the oil solidified). LCMS (ESI) m/z calcd for CnH20Br2O2: 342. Found: 341 (M-1) . 1H NMR (400 MHz, Chloroform-d) d 1 1 .39 (br, 1 H), 4.32 - 4.01 (m, 1 H), 3.87 (dd, J = 10.2, 4.4 Hz, 1 H), 3.64 (t, J = 10.0 Hz, 1 H), 2.37 (t, J = 7.5 Hz, 2H), 2.24 - 2.04 (m, 1 H), 1 .93 - 1 .74 (m, 1 H), 1 .74 - 1 .50 (m, 3H), 1 .50 - 1 .25 (m, 9H). |
61% | With 1,1,1,3',3',3'-hexafluoro-propanol; N,N,N,N-tetraethylammonium tetrafluoroborate; ethylene dibromide In acetonitrile at 20℃; Inert atmosphere; Electrolysis; | |
With chloroform; bromine | ||
With carbon disulfide; bromine | ||
With bromine | ||
With bromine at 0℃; | ||
With bromine; potassium bromide In acetic acid at 25℃; | ||
With bromine In diethyl ether at 0 - 20℃; | 2.2.1. Synthesis of 10-undecynoic acid In a 1000 ml two-necked round bottom flask provided with a Teflon-coated magnetic bar and a pressure equalized dropping funnel, 10-undecenoic acid (46.0 g, 0.25 mol) and diethyl ether (500 mL) were placed. To this solution, bromine (48 g, 300 mmol) was added with stirring at 0 °C during 75 min. The mixture was allowed to warm up gradually to room temperature and after stirring overnight, the solvent and the excess of bromine were removed at reduced pressure. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With lithium aluminium tetrahydride In tetrahydrofuran at 0 - 20℃; for 0.5h; Inert atmosphere; | Synthesis of 10-undecene-1-ol (3): To a stirred solution of LiAlH4 (1.50 g, 40.76 mmol) in dry THF (100 mL) was added dropwise 10-undecenoic acid (5.0 g, 27.17 mmol) in dry THF (10 mL) with vigorous stirring at 0 °C and the mixture was stirred for 30 min at room temperature. The reaction mixture was quenched with ethyl acetate. The solution was filtered and the organic layer was washed with H2O, brine and dried over Na2SO4. After removal of the solvent, the residue was purified by column chromatography (4% ethyl acetate in hexane) afforded (3) as a colorless oil (4.48 g, 97%). Spectroscopic data were consistent with the literature data.11 IR (neat) max: 3370, 3076, 2926, 1639, 1460, 1054, 908 cm-1; 1H NMR (300 MHz, CDCl3) : 1.24-1.41 (12H, m, H-3, H-4, H-5, H-6, H-7, H-8), 1.49-1.59 ( 2H, m, H-2), 1.98-2.07 (2H, m, H-9), 3.59 (2H, t, J = 6.79 Hz, H-1), 4.87-4.99 (2H, m, H-11), 5.68-5.83 (1H, m, H-10); m/z ( EI) 152 [M+-18]. |
96% | With lithium aluminium tetrahydride In diethyl ether for 3h; Heating; | |
95% | With lithium aluminium tetrahydride In tetrahydrofuran for 12h; Heating; |
95% | With lithium aluminium tetrahydride In tetrahydrofuran for 12h; Heating; | |
93% | With lithium aluminium tetrahydride In tetrahydrofuran for 2h; Heating; | |
92% | With indium(III) bromide; 1,1,3,3-Tetramethyldisiloxane In chloroform at 60℃; for 1h; Inert atmosphere; | |
90% | With sodium bis(2-methoxyethoxy)aluminium dihydride In benzene for 1h; Heating; | |
90% | With samarium diiodide; water; triethylamine In tetrahydrofuran at 20℃; for 2h; Inert atmosphere; | |
88% | With lithium aluminium tetrahydride In tetrahydrofuran at 0 - 50℃; | |
79% | Stage #1: 10-undecenoic acid With trimethylphenylsilane; C69H55ClP3Ru In tetrahydrofuran at 60℃; for 16h; Glovebox; Stage #2: With hydrogenchloride In tetrahydrofuran; water at 20℃; for 1h; Glovebox; chemoselective reaction; | |
77% | With lithium aluminium tetrahydride In diethyl ether for 16h; Ambient temperature; | |
65% | With lithium aluminium tetrahydride In tetrahydrofuran at -10 - 70℃; for 66h; | 10-Undecen-1-ol (6) LiAlH4 (1.04 g, 27.4 mmol, 3 eq) was added slowly in portions to a solution of 10-undecenoic acid (5) (1.70 g, 9.22 mmol, 1 eq) in dry THF (92 mL, 0.10 M) at -10°C. The reaction mixture was allowed to warm to rt and then stirred at 70°C for 66 h. The reaction mixture was cooled to 0 °C and then quenched by the slow addition of water (50 mL) followed by 1 M aqueous HCl (25 mL). The mixture was allowed to warm to rt and the separated aqueous layer was extracted twice with diethyl ether (100 mL). The combined organic extracts were dried over sodium sulphate, filtered and then concentrated in vaccuo. The crude residue was purified by flash column chromatography on silica using a gradient of 15-20% ethyl acetate in petroleum ether as eluent to give the alcohol 6 (1.02 g, 65%) as a colourless oil; δH (300 MHz, CDCl3) 5.80 (1H, ddt, J 17.0, 10.2 and 6.7, H2C=CH), 5.02-4.86 (2H, m, H2C=CH), 3.62 (2H, t, J 6.6, CH2OH), 2.07-1.97 (2H, m, H2C=CHCH2), 1.58-1.49 (3H, m, CH2 and OH), 1.39-1.23 (12H, m, 6x CH2). The 1H NMR data recorded for 6 was identical to the data reported in the literature [2]. |
49% | With sodium tetrahydroborate; benzene-1,2-diol; trifluoroacetic acid In tetrahydrofuran at 25℃; for 4h; | |
With lithium aluminium tetrahydride; diethyl ether | ||
With sodium bis(2-methoxyethoxy)aluminium dihydride | ||
With lithium aluminium tetrahydride | ||
With sodium tetrahydroborate; iodine 1) THF, r.t. 2) THF, 1 h, 0 deg C; Yield given. Multistep reaction; | ||
With sodium tetrahydroborate; N,N-dimethylchloromethyleniminium chloride 1.) acetonitrile, THF, -30 deg C, 1 h; 2.) acetonitrile, THF, N,N-dimethylformamide, -78 deg C to -20 deg C, 2 h; Yield given. Multistep reaction; | ||
With lithium aluminium tetrahydride In diethyl ether | ||
With zirconium(IV) borohydride In tetrahydrofuran at 25℃; for 1h; | ||
Multi-step reaction with 2 steps 1: H2SO4 / Heating 2: LiAlH4 / diethyl ether | ||
67 %Spectr. | With samarium diiodide; water; triethylamine In tetrahydrofuran at 20℃; Inert atmosphere; | |
Multi-step reaction with 2 steps 1: <i>tert</i>-butyl alcohol / Acidic conditions 2: sodium | ||
Multi-step reaction with 2 steps 1: sulfuric acid / 24 h / Reflux 2: diisobutylaluminium hydride / tetrahydrofuran; hexane / 5 h / -78 °C | ||
With hydrido(phosphonite)cobalt(I); 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane In 2-methyltetrahydrofuran for 16h; Sealed tube; Darkness; Schlenk technique; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With hydrogen bromide at 115℃; for 0.5h; | |
With hydrogen bromide; Petroleum ether | ||
With hydrogen bromide; toluene im Vakuum; |
With Perbenzoic acid; hydrogen bromide; Petroleum ether bei Ausschluss von Sauerstoff; | ||
With 9-(oxiran-2-yl)nonanoic acid; hydrogen bromide; Petroleum ether bei Ausschluss von Sauerstoff; | ||
With hydrogen bromide | ||
With diethyl ether; hydrogen bromide | ||
With hydrogen bromide; hydrogen; toluene at 0℃; | ||
With hydrogen bromide; Petroleum ether; dibenzoyl peroxide bei Ausschluss von Sauerstoff; | ||
With air; hydrogen bromide; Petroleum ether | ||
With hydrogen bromide In acetic acid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With hydrogen bromide In 1,4-dioxane; hexane at 20℃; for 1h; | |
67% | With hydrogen bromide In Petroleum ether at 15℃; for 0.75h; | |
67% | With 2,2'-azobis(isobutyronitrile); hydrogen bromide In Petroleum ether for 0.5h; Irradiation; |
With air; hydrogen bromide; toluene | ||
With hydrogen bromide; toluene; dibenzoyl peroxide unter Luftausschluss; | ||
With air; hydrogen bromide; benzene | ||
With Perbenzoic acid; hydrogen bromide; Petroleum ether bei Anwesenheit von Luftsauerstoff; | ||
With hydrogen bromide; Petroleum ether; dibenzoyl peroxide bei Anwesenheit von Luftsauerstoff; | ||
With 9-(oxiran-2-yl)nonanoic acid; hydrogen bromide; Petroleum ether bei Anwesenheit von Luftsauerstoff; | ||
With hydrogen bromide; toluene | ||
With 2,2’-azobis(4-methoxy-2,4-dimethyl)valeronitrile; hydrogen bromide | ||
With hydrogen bromide In toluene; benzene at 18 - 20℃; for 0.75h; | 1 Using 10-undecylenic acid having a melting point of 23 ° C and a purity of more than 98% as a raw material, the volume ratio of 10-undecenoic acid to toluene and benzene was 1: 3: 2, 1% of the mass of undecenoic acid, the reaction apparatus is shown in Fig. 1, and then the raw material liquid is supplied to the addition vessel in an amount of about 1/2 volume, and then the mixture of 10-undecenoic acid and hydrogen bromide Molar ratio of 1: 1 .1 to the bottom of the reactor into the hydrogen bromide gas, and then keep the feedstock and hydrogen bromide ratio of continuous feeding, cooling water or frozen salt water control reactor temperature 18 ~ 20 , through the discharge Adjust the reaction volume of the reactor to control the reaction residence time of about 45 minutes.Curing kettle jacket through the steam control maturation temperature of 75 to 80 ° C, steamed to return to the addition of hydrogen bromide reactor to continue the reaction.The yield of 11-bromoundecanoic acid was 132.6%.Take the above reaction liquid, add 28% ammonia water according to the molar ratio of 11-bromoundecanoic acid and ammonia molecule 1:10, add 2% tetrabutyl ammonium bromide as phase transfer catalyst, the reaction temperature should be controlled between 28-30 , stirring reaction for 36 hours, vacuum filtration, the cake is 11-amino undecanoic acid crude.The crude 11-amino undecanoic acid is added into ion-free water at a mass ratio of 1: 5, and heated to 120C for dissolution. After being kept for 1 hour, the crystals are cooled and filtered at 20C to obtain 11-amino undecanoic acid product.Drying, weighing, product yield (10-undecenoic acid) 92.6%. | |
1.34 kg | With hydrogen bromide In toluene at 18℃; for 1h; Industrial scale; | 1.1 (1) Synthesis of 11-bromoundecanoic acid: The use of a melting point of 23 ° C, a purity of more than 98.5% 10-undecenoic acid 1kg, raw material ratio of 10-undecenoic acid and toluene mass ratio of 1:3, according to 10-undecenoic acid and The molar ratio of hydrogen bromide is 1:1.20, and hydrogen bromide gas is fed into the bottom of the addition column, and then the feed liquid and hydrogen bromide are continuously added to maintain the ratio.Through the cooling water control reactor reaction temperature at 18 °C, after a reaction for 1 hour,Recovery of toluene by distillation, washing oil phase 2-3 times, and cooling the system to 15 ~ 20 ° C, after sufficient crystallization, vacuum filtration to obtain white crystal 11-bromo undecanoic acid 1.34kg; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | at 140 - 165℃; for 5h; Inert atmosphere; | 1 Preparation of N-Undecylenoyl Monoethanol Amide (MEA Amide of Undecylenic Acid) Preparation of N-Undecylenoyl Monoethanol Amide (MEA Amide of Undecylenic Acid) A mixture of undecylenic acid (500 g, 2.71 mol) and monoethanol amine (166 g, 2.71 mol) is stirred under nitrogen blanket in pressure vessel at 140° C. for 4 hr and then the temperature is raised to 165° C. for additional one hour. At this stage, acid value is normally found to be around 10° C. or less. Cool the reaction mass to 60° C. and the molten mass are converted into off white flakes (610 g, 99%) by pouring it on glass plate. (Melting point 56-58° C., acid value, less than 10, IR (KBr):1640 cm-1 carbonyl amide, 1556 cm-1, 2919 cm -1, 3289 cm-1 (NH of amide). |
99% | at 140 - 165℃; for 5h; Inert atmosphere; Sealed tube; | Preparation ofN-undecylenoyl monoethanol amide (ME A amide of undecylenic acid): Preparation ofN-undecylenoyl monoethanol amide (ME A amide of undecylenic acid): A mixture of undecylenic acid (500g, 2.71mol) and monoethanol amine (166g, 2.71mol) is stirred under nitrogen blanket in pressure vessel at 140°C for 4 hr and then the temperature is raised to 165°C for additional one hour. At this stage, acid value is normally found to be around 10°C or less. Cool the reaction mass to 60°C and the molten mass are converted into off white flakes (610 g, 99 %) by pouring it on glass plate. (Melting point 56-58 °C, acid value, less than 10, IR (KBr): 1640 cm"1 carbonyl amide , 1556 cm"1, 2919 cm"1, 3289 cm"1 (ΝΗ of amide). |
99% | at 140 - 165℃; for 5h; Inert atmosphere; | 1 Preparation of N-Undecylenoyl Monoethanol Amide (MEA Amide of Undecylenic Acid): Preparation of N-Undecylenoyl Monoethanol Amide (MEA Amide of Undecylenic Acid): A mixture of undecylenic acid (500 g, 2.71 mol) and monoethanol amine (166 g, 2.71 mol) is stirred under nitrogen blanket in pressure vessel at 140° C. for 4 hr and then the temperature is raised to 165° C. for additional one hour. At this stage, acid value is normally found to be around 10° C. or less. Cool the reaction mass to 60° C. and the molten mass are converted into off white flakes (610 g, 99%) by pouring it on glass plate. (Melting point 56-58° C., acid value, less than 10, IR (KBr):1640 cm-1 carbonyl amide, 1556 cm-1, 2919 cm-1, 3289 cm-1 (NH of amide). |
97% | at 50 - 180℃; for 4h; | 1 Into a 100 ml three-necked flask fitted with a mechanical stirrer, thermometer, distillation condenser, 20.2 g (0.107 moles) of 10-undecenoic acid is placed. The reaction flask is heated to 50 C, followed by the slow addition of 9.8 g (0.16 moles) ofethanolamine. The reaction temperature is slowly increased to180 C and held at this temperature for 4 hours. The progress of the reaction is followed by gas chromatography. After 4 hours 1.8 g (95 % of theoretical value) of water is collected. The reaction mixture is cooled to room temperature; the tan colored product is dissolved in ethanol, and then poured into water. The white precipitate of amidealkanol obtained is filtered, washed with water and dried to give 24.0 g (Yield = 97 %) of a white powder. H NMR6 : 5.85 (m, 1H), 5.0 (m, 1H), 4.9 (m, 1H), 3.6 (t, 2H), 3.3 (m, 2H), 2.2 (2H), 2.1 (q, 2H), 1.6 (b, 2H), 1.4 (t, 2H), 1.35 (8H) ppm. 13C NMR : 173, 140,115, 62,43, 36,34, 30,29. 8,25 ppm. |
Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | Stage #1: 10-undecenoic acid With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane at 0℃; for 0.0833333h; Inert atmosphere; Stage #2: aniline In dichloromethane at 0 - 20℃; for 24h; Inert atmosphere; | 2-5 Example 2-5 This example is a further invention on the basis of Example 2-2, and provides an application of a multifunctional aromatic amine compound in the later modification of the optically active urea compound undecylenic acid. The preparation method of the compound is as follows: Filled with argon, a flame-dried round bottom flask was filled with 2.0 mL of DCM, 0.52 mmol, 1.3 eq of EDC-HCl and 0.56 mmol, 1.4 eq of DMAP, and then the reaction flask was cooled in an ice bath to zero degrees and add 0.4mmol, 1.0eq of undecylenic acid (VI-3), after stirring for five minutes, add 0.48mmol, 1.2eq of aniline (II-2), then remove the ice bath, and stir the reaction mixture at room temperature for 24 hours. Until TLC detects the complete consumption of the raw materials, the reaction was quenched with 5 mL of 1M HCl, and the organics were separated. Finally, the aqueous layer was extracted with DCM (2×5 mL), and the organic layers were combined, dried over Na2SO4 and concentrated to obtain the product (II- 5). The final yield is 97%. |
94% | With magnesium In toluene at 160℃; for 2h; | Typical amidation procedure General procedure: In a 50 cm3 flat-bottomed one-necked flask, 0.91 g dodecanoicacid (4.54 mmol) was dissolved in 3 cm3 of toluene. Then, 0.42 g aniline (4.54 mmol) and Mg powder(30 mmol %) was added. The flask was attached to a reflux condenser and heated under atmospheric conditions in anoil bath at 160 C for 2 h. After the reflux period, the reaction mixture was cooled slightly, 10 cm3 of acetone was added and the magnesium powder filtered off under vacuum. The clear filtrate was concentrated in vacuo andthe residue crystallized from MeOH/acetone/H2O to give white bright needles (0.98 g). |
94% | With dmap In dichloromethane at 0 - 20℃; for 24h; Inert atmosphere; |
76% | With triethylamine; trichlorophosphate In dichloromethane |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With 2,2-dimethoxy-2-phenylacetophenone In dichloromethane at 20℃; for 0.166667h; Irradiation; | 1 2.1. Thioether-containing u-hydroxyacid (TEHA) 2.1. Thioether-containing u-hydroxyacid (TEHA) An equimolar mixture of 10-undecenoic acid (1.0 g, 5.43 mmol)and 2-mercaptoethanol (0.4 g, 5.43 mmol) was irradiated indichloromethane solution at l 365 nm in the presence of DMPA(2% mol respect to C]C) as photoinitiator. The completion of thereaction was conrmed after 10 min by the completely disap-pearance of C]C double bonds from 1H NMR. The thioether con-taining u-hydroxyacid was quickly obtained. (yield % 100, mp:54 C, LC-(ESI) MS: m/z calcd: 262.16; found: 262.16).1H NMR (CDCl3, d, ppm): 3.72 (t, 2H, eCH2eOH), 2.72 (t, 2H,eCH2eSe), 2.50 (t, 2H, eCH2eSe), 2.34 (t, 2H, eCH2eCO),1.69e1.27 (m, 16H, eCH2e).13C NMR (CDCl3, d, ppm): 179.9 (s), 60.3 (t), 35.4 (t), 34.1 (t), 31.7(t), 29.9e29.0 (t), 24.8 (t). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With dicyclohexyl-carbodiimide In tetrahydrofuran at 0 - 20℃; Inert atmosphere; | |
72% | ||
71% | With dicyclohexyl-carbodiimide In acetonitrile at 25℃; for 1h; |
46% | With dicyclohexyl-carbodiimide In ethyl acetate for 16h; Ambient temperature; | |
With dicyclohexyl-carbodiimide In ethyl acetate at 20℃; Inert atmosphere; Cooling with ice; | ||
With dicyclohexyl-carbodiimide In dichloromethane at 0 - 23℃; for 16h; Inert atmosphere; | 4.1.1. General procedure for synthesis of NHS esters (method A) General procedure: To a solution of the appropriate fatty acid 9b, 13b-37b (1.0equiv) in CH2Cl2 (0.1 M) at 0°C was added N-hydroxysuccinimide (NHS, 1.0 equiv) and N,N'-dicyclohexylcarbodiimide (1.0 equiv). The reaction mixture was warmed to 23°C and stirred 16 h. Theresulting mixture was filtered and the filtrate was concentrated under reduced pressure to provide NHS esters 9c, 13c-37c without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With tris[2-(4,6-difluorophenyl)pyridinato-C2,N]-iridium(III); oxygen In acetonitrile at 20℃; Irradiation; Sealed tube; Green chemistry; chemoselective reaction; | Synthesis of carboxylic acids General procedure: An oven-dried resealable test tube equipped with a magnetic stir bar was charged withaldehyde (1.0 mmol), Ir(dFppy)3 (0.005-0.01 mmol), and MeCN (4.0 mL, 0.25 M). Oxygen wasthen bubbled through the reaction mixture and sealed with a silicone septa screw-cap. A balloonfilled with oxygen was attached to the tube, and the test tube was placed under blue LEDs atroom temperature. The reaction was allowed to proceed for 3-12 h, and reaction progress waschecked by TLC. The solvent was removed under vacuum, and the corresponding carboxylic acidwas purified by flash silica gel chromatography. |
87% | With tetrabutyl-ammonium chloride; dihydrogen peroxide; potassium carbonate In tetrahydrofuran Ambient temperature; without CeCl3*7H2O; | |
87% | With tetrabutyl-ammonium chloride; dihydrogen peroxide; potassium carbonate In tetrahydrofuran Ambient temperature; |
84% | With dipyridinium dichromate | |
73% | With sodium chlorite; sodium dihydrogenphosphate; 2-methyl-but-2-ene In <i>tert</i>-butyl alcohol at 0℃; for 2h; Inert atmosphere; | |
70% | With 1-hydroxycyclohexyl phenyl ketone; sodium hydroxide In 1,2-dimethoxyethane at 80℃; Sealed tube; | |
With sodium hydroxide 1.) 19 h reflux; 2.) 24 h reflux; Yield given. Multistep reaction; | ||
85 % Spectr. | With dihydrogen peroxide In water at 90℃; for 2h; | |
With poly[4-(diacetoxyiodo)styrene]; 2,2,6,6-tetramethyl-piperidine-N-oxyl In acetone at 20℃; for 24h; | ||
Multi-step reaction with 2 steps 1: 92 percent / trityl perchlorate / CH2Cl2 / 3 h / -45 °C 2: 76 percent / piperidine / H2O / 3 h / 90 °C | ||
90 %Chromat. | With dihydrogen peroxide In water at 90℃; for 2h; | 10 Example 10 Example 10 Nafion NR50 (500 mg), 30% aqueous hydrogen peroxide solution (1.3 mL, 11 mmol), and 10-undecenaldehyde (2.1 mL, 10 mmol) were mixed and stirred at 90° C. for 2 hours. After the reaction solution was cooled to room temperature, the yield of 10-undecenoic acid by measurement of GLC was 90%. |
With alcohol dehydrogenase from Escherichia coli; nicotinamide adenine dinucleotide In dimethyl sulfoxide at 25℃; Enzymatic reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With water; oxygen; copper(l) chloride In tetrahydrofuran at 20℃; for 36h; | |
60% | With oxygen; sodium chloride; palladium dichloride In water; N,N-dimethyl-formamide at 90℃; for 15h; | 3 Example 3 10-Undecenoic acid (4.7 g), DMF (30 ml), and water (3 ml) were added to the container. PdCl2 (2.0 mol %) and NaCl (0.17 eq.) were added thereto, and the inside of the container was placed in an oxygen atmosphere. Thereafter, by heating at 90° C. for 15 hours, 10-oxoundecanoic acid, which was a target product, was obtained with a yield of 60%. |
60% | With oxygen; sodium chloride; palladium dichloride In water; N,N-dimethyl-formamide at 90℃; for 15h; |
With jones reagent; mercury(II) diacetate 1) water, acetone, rt, 2) rt, 20 h; Yield given. Multistep reaction; | ||
3.2 g | With p-benzoquinone; palladium dichloride In water; N,N-dimethyl-formamide at 90℃; for 12h; | 2 Example 2 A mixture of 10-undecenoic acid (4.7 g), 1,4-benzoquinone (0.63 g), DMF (50 mL), water (5 mL), and PdCl2 (0.09 g) was heated and stirred at 90° C. for 12 hours. (0356) The solvent was then evaporated under reduced pressure. The resulting residue was mixed with a solution of sodium methoxide in methanol and the mixture was filtered. The solid residue was mixed with hydrochloric acid and the mixture was extracted with ethyl acetate. The extract was dried over sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by column chromatography, whereby 10-oxoundecanoic acid (3.2 g) was obtained. (0357) The spectrum data of the resulting 10-oxoundecanoic acid are the following. (0358) 1H-NMR (CDCl3) δppm: 1.27-1.37 (m, 8H), 1.51-1.60 (m, 4H), 2.11 (s, 3H), 2.29-2.42 (m, 4H) (0359) The resulting 10-oxoundecanoic acid (0.73 g) was added to a 2 M solution of ammonia in methanol and water was evaporated. Thereby, ammonium 10-oxoundecanoate (0.57 g) was obtained. (0360) The spectrum data of the resulting ammonium 10-oxoundecanoate are the following. (0361) 1H-NMR (CDCl3) δppm: 1.05 (m, 8H), 1.31 (m, 4H), 1.96-2.02 (m, 5H), 2.28-2.34 (t, J=7.3, 4H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With borane-ammonia complex In 5,5-dimethyl-1,3-cyclohexadiene for 12h; Reflux; | |
96% | With magnesium In toluene at 160℃; for 2h; | Typical amidation procedure General procedure: In a 50 cm3 flat-bottomed one-necked flask, 0.91 g dodecanoicacid (4.54 mmol) was dissolved in 3 cm3 of toluene. Then, 0.42 g aniline (4.54 mmol) and Mg powder(30 mmol %) was added. The flask was attached to a reflux condenser and heated under atmospheric conditions in anoil bath at 160 C for 2 h. After the reflux period, the reaction mixture was cooled slightly, 10 cm3 of acetone was added and the magnesium powder filtered off under vacuum. The clear filtrate was concentrated in vacuo andthe residue crystallized from MeOH/acetone/H2O to give white bright needles (0.98 g). |
92% | at 160℃; for 2h; Molecular sieve; Neat (no solvent); |
78% | With triethylamine; trichlorophosphate In dichloromethane |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With [Cl(C6F13C2H4)2SnOSn(C2H4C6F13)2Cl]2 In various solvent(s) at 150℃; for 16h; | |
70% | With 5,5'-dimethyl-3,3′-azoisooxazole; triphenylphosphine In acetonitrile for 9h; Reflux; | |
64% | With magnesium sulfate; toluene-4-sulfonic acid In dichloromethane for 36h; Inert atmosphere; Reflux; |
64% | With magnesium sulfate; toluene-4-sulfonic acid In dichloromethane for 36h; Inert atmosphere; Reflux; | |
With 2,2'-dipyridyldisulphide; 4 A molecular sieve; triphenylphosphine; methyl iodide 1.) CH2Cl2 , rt, 30 min; 2.) rt, 2 h; Yield given. Multistep reaction; | ||
With toluene-4-sulfonic acid In toluene for 5h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | Stage #1: 10-undecenoic acid With oxalyl dichloride In dichloromethane; N,N-dimethyl-formamide at 0 - 20℃; for 1.5h; Stage #2: With ammonia In dichloromethane; N,N-dimethyl-formamide at 0 - 20℃; Further stages.; | |
89% | With urea | |
63% | With urea at 170 - 180℃; for 4h; |
60% | With urea at 170 - 180℃; for 4h; | 1 Synthesis of 10-undecenamide Urea (15 g, 0.25 mol) and undecylenic acid (23.01 g, 0.125 mol) were taken in a two-necked flask and heated to 170-180 ° C.Heating was stopped after 4 h of reaction.When the temperature drops to 110-120 ° C,The reaction was stopped by adding a 5% Na2CO3 solution (100-150 ml), and the mixture was placed in an ice water bath, and the solid was precipitated, filtered, and recrystallized twice with 95% ethanol.Drying in vacuo gave a colorless solid in 60% yield. 1H NMR(400MHzCDCl3)δ5.80(1Hm)5.47(2Hs)2.22(2Ht)2.04(2Hm)1.63(2Hm)1.38-1.29(10Hm) |
Multi-step reaction with 2 steps 1: 1,8-diazabicyclo[5.4.0]undec-7-ene / neat (no solvent) / 24 h / 160 °C / Green chemistry 2: ammonia / methanol / 3 h / 20 °C / Green chemistry |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99.4% | In toluene at 80℃; for 3h; | 8 A 1 L flask equipped with a reflux tube was charged with 184.0 g (1.0 mol) of 10-undecylenic acid and 150.0 g of toluene and heated at 80° C. Then 100.6 g (0.625 mol) of hexamethyldisilazane was added dropwise to the solution, which was heated at 80° C. for a further 3 hours. The volatile component was removed by heating at 100° C. in vacuum, obtaining CH3═CH(CH2)8COOSiMe2 (Silylated product A) (254.4 g, yield 99.4%). |
In tetrahydrofuran | ||
at 80 - 90℃; for 4h; Inert atmosphere; | Preparation of TMS Protected 10-Undecylenic Acid (UATMS) To a 500 mL round bottom flask 200 g of undecylenic acid was charged. The flask was heated to 80° C. and 109.5 g of hexamethyldisilazane (HMDZ) was added dropwise via an addition funnel Once all the HMDZ was added the reaction temperature was increased to 90° C. and stirred under nitrogen for 4 hrs, cooled to room temperature and stirred overnight. The reaction was determined to be complete by the disappearance of the UA peak in the GC chromatogram. The material was stripped at 135° C. at 50 torr with a nitrogen sparge through a short path distillation head. A clear brown low viscosity fluid was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
23 % Chromat. | Stage #1: 10-undecenoic acid With aluminum oxide; potassium permanganate; water for 0.166667h; Stage #2: diazomethane In diethyl ether |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With dicyclohexyl-carbodiimide In acetonitrile at 25℃; for 1h; | |
98% | With dmap; diisopropyl-carbodiimide In dichloromethane at 20℃; | I.A To a solution of starting undecylenic acid (4.1 g, 22.2 mmol, 1.1 equiv.) in anhydrous DCM (120 ml) was added paranitrophenol (2.9 g, 20.9 mmol). In the presence of DIC (3.6 ml, 1.2 equiv.) and 4-DMAP (60 mg), the reaction mixture was stirred at rt overnight, whereupon t.l.c (PE-EA 6:1, Rf 0.52) indicated the reaction was finished. The suspension was diluted with DCM and filtered through celite. The filtrate was concentrated to afford a residue. The residue was purified by flash column chromatography (Petroether- CHCl3 2:1) to provide ester 2 (6.23 g, 98 %).1H NMR (300 MHz, CDCl3) 8.31 (d, J = 9.2 Hz, 2 H), 7.32 (d, J = 9.2 Hz, 2 H), 5.84 (m, 1 H, H-IO), 5.03 (m, 2 H, H-I l), 2.64 (t, J = 7.5 Hz, 2 H, H-2), 2.09 (m, 2 H, H-9), 1.80 (m, 2 H, H-3), 1.48-1.35 (m, 10 H, H-4-8), 3.96 (br s, 1 H), 3.87 (dd, J = 9.8, 2.4 Hz, 1 H), 3.51 (m, 2 H), 2.50 (d, J = 2.1 Hz, 1 H). 13 C NMR (75 MHz, CDCl3): 171.1, 155.5, 145.2, 139.0, 125.1, 122.3, 114.2, 34.4, 33.8, 29.3, 29.2, 29.1, 29.0, 24.9. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With jones reagent In acetone at 0℃; for 0.5h; | |
83% | With Oxone; 2-Iodobenzoic acid; tetra(n-butyl)ammonium hydrogensulfate In ethyl acetate at 70℃; for 7h; | |
80% | With 1-hydroxycyclohexyl phenyl ketone; sodium hydroxide In 1,2-dimethoxyethane at 80℃; Sealed tube; chemoselective reaction; |
Multi-step reaction with 2 steps 1: pyridinium chlorochromate / dichloromethane / 16 h / 23 °C / Inert atmosphere; Molecular sieve 2: sodium dihydrogenphosphate; sodium chlorite; 2-methyl-but-2-ene / <i>tert</i>-butyl alcohol / 2 h / 0 °C / Inert atmosphere | ||
With chromium (VI) oxide; periodic acid In water; acetonitrile at 20℃; for 1h; chemoselective reaction; | General Procedure for Oxidation of Alcohols General procedure: Chemicals and reagents were purchased fromAldrich or Fisher and used without further purification unless noted. The required amount of H5IO6(see Table 2) and CrO2 (0.042 g, 0.5 mmol) were ground together in amortar to produce a uniform gray-black mixture, which was then transferred to a50 mL round-bottomed flask along with a magnetic stir bar. Water (5.0 mL) was added, and the mixture wasstirred for 5-10 minutes to dissolve the H5IO6. Then 20.0 mL acetonitrile (ACN) was added andthe mixture was stirred vigorously to disperse the black CrO2solid. At this point the solution phasewas dark yellow. The alcohol reactant(5.0 mmol, weighed if solid, via pipette if liquid) was added in one portionwith vigorous stirring, and within one minute the solution phase became muchlighter (although it gradually darkened during the reaction period). | |
With alcohol dehydrogenase from Escherichia coli; nicotinamide adenine dinucleotide In dimethyl sulfoxide at 25℃; Enzymatic reaction; | ||
Multi-step reaction with 2 steps 1: alcohol dehydrogenase from Escherichia coli; nicotinamide adenine dinucleotide / dimethyl sulfoxide / 25 °C / pH 7 / Enzymatic reaction 2: alcohol dehydrogenase from Escherichia coli; nicotinamide adenine dinucleotide / dimethyl sulfoxide / 25 °C / pH 7 / Enzymatic reaction |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With propylphosphonic anhydride; triethylamine In dichloromethane at 0 - 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With AS2053 nitro-Grela-I2SIPr In toluene at 40 - 80℃; for 7h; | 1 Example 1: Eicos-10-endioic acid An inert reactor was charged with 65 g of 10-undecenoic acid and 195 g of toluene. At 40 ° C, in a slight nitrogen100mg of AS2053 nitro-Grela-I2SIPr (purchased from under conditions of continuous purging of headspace air)A solution of Apeiron) in 65 g of toluene was added to the first solution over 5 hours. The reaction was aged for 2 hours and then heatedUntil a clear solution (about 80 ° C) is formed. Finally, the solution was cooled to room temperature (about 20 ° C), and the precipitated product was separated and dried.53.0 g of the title compound were obtained. GC-MS analysis of samples (with BSTFA (N,O-bis(trimethylsilyl)trifluoroacetyl)The amine) derivatization treatment showed that the product contained 97.5% of the title product in the form of a mixture of E and Z isomers, 1.0% tenN-carbenedicarboxylic acid, 0.3% 10-undecenoic acid and a small amount of other impurities (mainly homologues of the product). |
87% | With 2,2-Dimethyl-1-oxa-2-silacyclohexan In methanol; water at 100℃; for 4h; | |
67 %Chromat. | In dichloromethane at 30℃; for 2h; | 2 EXAMPLE 2; This example illustrates the synthesis of the C20 diacid starting from ricinoleic acid. During the first stage, methyl ricinoleate is subjected to a pyrolysis at a temperature of 550° C. to form methyl 10-undecenoate, which is converted to the acid form by hydrolysis. In the second homometathesis stage, use is made of the ruthenium complex (3) catalyst described in the publication by Stefan Randl et al., Synleft (2001), 10, 430, which is very stable and does not decompose when it is exposed to air or to water. The homometathesis reaction is carried out in CH2Cl2, at a 0.15M 10-undecenoic acid concentration, at a temperature of 30° C. and for 2 hours with a catalyst concentration of 0.5 mol %. The yields are determined by chromatographic analysis. The yield of diacid HOOC-(CH2)8-CHCH-(CH2)8-COOH is 67 mol %. This product can be hydrogenated according to a conventional process with a yield of 100%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: tetrahydrofuran 2: 1.) BH3, 2.) H2O2, NaOH / 1.) THF |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: petroleum ether; 10.11-epoxy-undecanoic acid (1); HBr / bei Anwesenheit von Luftsauerstoff 2: ethanol / Verseifen mit wss.-alkoh.NaOH |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | Candida antarctica-derived lipase; In 1,4-dioxane; dimethyl sulfoxide; at 40℃; for 168h;Molecular sieve;Product distribution / selectivity; | <strong>[497-76-7]Arbutin</strong> (327 mg) and 10-undecylenic acid (885 mg) were dissolved in 4.0 ml of a 1,4-dioxane/DMSO (=9:1) mixed solvent in an Erlenmeyer flask. After adding 0.4 g of activated molecular sieves 4A, 40 mg of immobilized Candida antarctica-derived lipase (manufactured by Novozymes) was added, followed by stirring at 40C and 130 rpm for 1 week. The molecular sieve had been activated by a simple process using a microwave oven. Specifically, molecular sieves 4A placed in a flask had been heated in a microwave oven for 1 minute, and immediately thereafter, allowed to cool to room temperature under reduced pressure using a vacuum pump; this process was conducted three times. TLC analysis of the enzymatic reaction product revealed that only a monoester was produced. The enzymatic reaction mixture was filtered to remove the enzyme and molecular sieves, and then the filtrate was concentrated under reduced pressure. Methanol (4 ml) and water (2.5 ml) were added to the concentrate, and hexane (5 ml) was further added to extract unreacted undecylenic acid into the hexane layer. Such hexane extraction was carried out 6 times, and the aqueous layer was concentrated using an evaporator. After adding 8 mL of water to the concentrate to form a white precipitate, the supernatant liquid was removed by centrifugation. Such aqueous extraction was performed 3 times to remove DMSO and unreacted <strong>[497-76-7]arbutin</strong>. The white precipitate was collected and dried under reduced pressure, to give 287 mg of powder. TLC analysis of the purified product using 100% ethyl acetate confirmed that unreacted 10-undecylenic acid had been removed and that a single ester compound had been produced. The purified product was subjected to NMR analysis to thereby find that the it was the same compound as the ester obtained in Example 1-1, i.e., 6-O-(10-undecylenoyl) <strong>[497-76-7]arbutin</strong>. The yield of the ester was 91%. The process used in this Example does not involve purification with a silica gel column, and thus easy and simple. |
Candida antarctica-derived lipase; In 1,4-dioxane; at 40℃; for 168h;Molecular sieve;Product distribution / selectivity; | <strong>[497-76-7]Arbutin</strong> (33 mg) and 10-undecylenic acid (89 mg) were dissolved in 4.0 ml of 1,4-dioxane in an Erlenmeyer flask. After adding 0 to 15 wt.% of activated molecular sieves 4A, 40 mg of immobilized Candida anterctica-derived lipase (manufactured by Novozymes) was added, followed by stirring at 40C and 130 rpm for 1 week. The molecular sieve had been activated by the same method as in Example 1-5. The change over time in <strong>[497-76-7]arbutin</strong> conversion ratio was determined by HPLC analysis. The conditions for the HPLC analysis were as follows: Device; Shimazu LC-10, Column; TSK gel Amide-80, Mobile phase solvent; acetonitrile/water (=90:10), Flow rate; 1.0 ml, Detection; differential refraction. Fig. 1 shows the results. The addition of molecular sieves, which act as a dehydrating agent, remarkably improved the <strong>[497-76-7]arbutin</strong> conversion ratio (reaction ratio). The higher the concentration of molecular sieves, the higher the conversion ratio. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With potassium carbonate In N,N-dimethyl-formamide at 20℃; Cooling with ice; | 1-1 Synthesis of 10-undecenoic acid benzyl ester 10-undecenoic acid (10.025 g, 54.5 mmol) was placed in a recovery flask,Dimethylformamide (hereinafter referred to as DMF) as a solvent.30 mL) was added and dissolved.After dissolution,Potassium carbonate (15.067 g, 109.5 mmol) was added,Then benzyl bromide (8 mL, 60.0 mmol) was gradually added under ice cooling, and the mixture was stirred at room temperature overnight.After neutralization with 1N HCl, hexane extraction was carried out, and the organic layer was dried with sodium sulfate, filtered, and concentrated under reduced pressure using an evaporator. The obtained residue was purified by column chromatography to give benzyl 10-undecenoate (yield: 14.62 g, yield: 98%). External appearance and 1 H-NMR measurement results of the obtained 10-undecenoic acid benzyl ester are shown in Table 1 |
86% | With potassium carbonate In acetone at 70℃; for 12h; | |
65% | With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 12h; Inert atmosphere; |
61% | Stage #1: 10-undecenoic acid With potassium carbonate In DMF (N,N-dimethyl-formamide) Stage #2: benzyl bromide for 3h; | 2.1 Example 2 [00344] The following example sets forth the synthesis and characterization of Compound 13. [00345] 2.1 Benzylation of Undecelinic Acid to Form Compound 4 Undecelinic acid (105.5 g, 1.05 moles) was placed in a 3-neck round bottomed flask with dimethylformamide (500 mL) and potassium carbonate (249.0 g, 1.8 moles) and was stirred overnight while in a N2 atmosphere. Benzyl bromide (100 g, 0.545 moles) was then added over 1 hour after which the solution was stirred for 2 hours. TLC (1:12; isopropyl ether/hexane on SiO2/glass) showed that the undecelinic acid had been consumed. [00347] The product solution was then filtered via Celite, washed twice with water (2300 mL) and the organic phases extracted with hexane (2700 mL). The combined product solution was then dried with magnesium sulfate, filtered and weighed to give 177 g (61 % crude yield). 1H NMR showed that the product solution was benzylated undecelinic acid. |
With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 36h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | In dichloromethane at 45℃; for 2h; | 2 The ruthenium complex catalyst (3) described in the publication by Stefan Randl et al., Synlett (2001) 10, 430 is used. This compound is very stable and does not decompose when it is exposed to air or water. The synthesis is performed in CH2Cl2, at a concentration of 0.05 M of reagent, at a temperature of 45° C., and for 2 hours. The yields are determined by chromatographic analysis. In the present case, the reagent is 10-undecenoic acid and 2 equivalents of acrylonitrile are used (2 mol of acrylonitrile per mole of acid) and with a catalyst concentration of 5 mol %. The yield of acid nitrile CN-CHCH-(CH2)8-COON is 67%. |
With Hoveyda-Grubbs catalyst second generation In toluene at 100℃; for 1h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With tin(ll) chloride; In 5,5-dimethyl-1,3-cyclohexadiene; at 145 - 150℃; for 8h;Inert atmosphere; | General procedure: This procedure was adapted from the literature (Padmajaet al., 2012). In general, the polyol (TMP, PEME, or TMT, 1.0 eq.), UA (6.0 eq.), and xylene were mixed together at 145-150 C under an inert atmosphere in the presence of tin chloride as a catalyst (SnCl2 0.1% wt. in relation to total reagent mass). The reaction mixture was allowed to stir for 8 h. Afterward, the mixture was washed with saturated NaCl solution, dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure to remove the solvent. The final products were purified by flash column chromatography using basic alumina or silica as the stationary phase and hexane/ethyl acetate as an eluent. DG tetraundecylenate was synthesized as mentioned above, but using 8.0 eq. of UA. The esters of UA with TMP, PEME, TMT, and DG are identified as 1, 2, 3, and 4, respectively. |
di(n-butyl)tin oxide; at 160 - 215℃; for 5.5h;Inert atmosphere; | The polyol, 10-decenoic acid, and the catalyst oxide were charged to a 500 mL round-bottomed flask equipped with a heating mantle, thermocouple, magnetic stirrer, and Dean-Stark trap. The reaction mixture was heated to refluxing and maintained at reflux to allow the reaction to proceed. Table 3 provides reaction information for Experiments 5-9.The reaction mixture was then vacuum distilled to remove most of the unreacted 10-undecenoic acid. The product was subjected to wiped film evaporation (at <2 mmHg and 155 C. using a 60 mL/min feed rate) to remove residual 10-decenoic acid. Table 4 provides the distillation information for Experiments 5-9. Within Tables 1, 2, 3 and 4, GC conversion provides the percentage of polyol hydroxyl groups that were converted to 10-decenoate esters as determined by GC area.All heating stages of the reaction and product isolation were conducted under a nitrogen atmosphere or under vacuum (with the vacuum bleed valve attached to nitrogen). | |
tin(ll) chloride; at 190℃;Inert atmosphere; | EXAMPLE 1; Preparation of Trimethylolpropane Triesters of 10- Undecenoic Acid; Trimethylolpropane (67 g, 0.5 mole) and 10-undecenoic acid (920 g, 5.0 mole) were charged in a 4-necked reaction flask equipped with stirrer, thermometer, water condenser and a nitrogen purger. The reaction mixture was heated to 19O0C under nitrogen atmosphere in presence of stannous chloride (1.0 g). The esterification was allowed to continue until theoretical amount of water was collected. The crude product was distilled at 1430C temperature and 3 mm vacuum to remove excess 10-undecenoic acid and passed over basic alumina to remove acidic impurities to yield the product (304 g) with acid value 0.05. The product was evaluated for viscosity, viscosity index (Vl.), pour point, flash point and copper strip corrosion and the data is provided in the following table. <n="13"/>The structure of the title product was established by 1H NMR studies.1H NMR (CDCl3, delta ppm): 0.9 [t, -CH3], 1.2-1.5 [m, CH3-CH2-, 3 x (-CH2-)5], 1.5-1.7 [m, 3 x (-CO-CH2-CH2)], 2.0 [q, 3 x (-CH2-CH=CH2)], 2.3 [t, 3 x (-CO-CH2-)], 4.0 [s, 3 x (-O- CH2-)], 4.9-5.0 [m, 3 x (-CH=CH2)], 5.7-5.8 [ m, 3 x (-CH=CH2)]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47.5% | With dmap; dicyclohexyl-carbodiimide In dichloromethane at 20℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With 2Zn(2+)*(CH3)3NC2H4OH(1+)*5Cl(1-)=[HOC2H4N(CH3)3]Zn2Cl5; at 130℃; for 8h; | (a) gamma-undecalactone: A mixture of 10-undecenylic acid (2.0 g; 10.8 mmol) and IL (2.23 g; 5.4 mmol) was stirred at 130 C. After 8 h, the product was separated from IL by extracting first with ethyl acetate then with hexane. The organic solvent was evaporated using rotary evaporator and dried under vacuum to get 1.88 g of peach flavored gamma-undecalactone as clear oil (isolated yield, 94%). The structure of the product was confirmed by 1H and 13C NMR, ESI-Mass and matched well with literature report.81H NMR (300 MHz, CDCl3, delta): 4.46 (tt, 1H, CH-O), 2.51 (dd, 2H, alpha-CH2), 2.31-2.26 (m, 1H, beta-CH2), 1.90-1.75 (m, 1H, beta-CH2), 1.75-1.60 (m, 1H, delta-CH2), 1.60-1.50 (m,1H, delta-CH2), 1.40-1.20 (m, 10H, 5CH2), 0.85 (t, 3H, CH3). 13C NMR (75 MHz, CDCl3, delta):14.0-29.5 (CH2), 31.8 (beta-CH2), 35.5 (alpha-CH2), 81.1 (CH-O), 177.1 (C=O). ESI-Mass m/z: [m++Na] 207, [m++1+Na] 208. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35% | With D-glucose; sodium hydroxide In hydrogenated sunflower oil; water at 30℃; for 150h; Microbiological reaction; Enzymatic reaction; | 2 7 g/l of 9-decen-2-one is obtained.Example 2; Conversion with Aspergillus oryzae (B); Aspergillus oryzae [origin=tube frozen at -80° C.] is seeded onto malt agar, and incubated at 30° C. for 72 hours.The preceding preculture is seeded into 3.5 l of malt medium (same concentration as in Example 1).The mixture is incubated at 30° C., 600 rpm, 0.5 vvm of air, free pH, for 24 hours. A dry weight of 11 g/l is obtained.The undecylenic acid is then dispensed at a feed rate of 0.5 g/l/h for 6 hours and then at a feed rate of 0.9 g/l/h for 48 hours: i.e. a total of 46 g/l. This undecylenic acid is dispensed as a mixture with hydrogenated sunflower oil (¼ acid-¾ oil); this oil is thus dispensed at feed rates of 1.5 g/l/h and then 2.7 g/l/h. Glucose is dispensed in parallel continuously at a feed rate of 0.36 g/l/h for 48 hours. The pH is regulated at 6 throughout the conversion with 5N NaOH. The speed is increased to 900 rpm and the mixture is aerated at a rate of 0.3 vvm. The conversion is continued for 48 hours.A production of 16.5 g/l of 9-decen-2-one is obtained, i.e. a bioconversion yield of 35%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With dmap In <i>tert</i>-butyl alcohol at 20℃; for 20h; | |
58% | With dmap In <i>tert</i>-butyl alcohol at 20℃; for 20h; | 2 An oven-dried 50 mL round bottom flask was charged with 10-undeceneoic acid (5 mmol), di-tert-butyl dicarbonate (10 mmol) and tert-butanol (10 mL). N,N-dimethylaminopyridine (1.5 mmol) was added to the stirred mixture and the reaction was allowed to stir for 20 h at R.T.. The reaction mixture was concentrated in vacuo and the residue purified by silica gel chromatography using ethyl acetate/hexanes (2:8) to afford the product as a light yellow oil (58%). RJ=0.98. iHNMR (400 MHz, CDCb): δ = 5.81 (m, 1H), 4.96 (dq, 1H, SJHH = 17.1 Hz, 4JHH = 1.6 Hz), 4.91 (dq, 1H, 10.2 Hz, 4JHH= 1.2 Hz), 2.19 (t, 2H, 7.7 Hz), 2.02 (q, 2H, 3JHH = 7.0 Hz), 1.28-1.56 (m, 21H) ppm. isCNMR (400 MHz, CDCb): δ = 173.3, 139.2, 114.1, 79.9, 35.6, 33.8, 29.3, 29.2, 29.0, 28.9, 28.1, 25.1 ppm. GC/MS EI): Calculated [M-C4H9]+: 184.1; found: 184.1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | Stage #1: 10-undecenoic acid; 3-tert-butyl-2,5-dihydroxybenzaldehyde In tetrahydrofuran; N,N-dimethyl-formamide at 0℃; Inert atmosphere; Stage #2: With diisopropyl-carbodiimide In tetrahydrofuran; N,N-dimethyl-formamide at 0 - 20℃; | Synthesis of 10-undecenoic Acid, 3-tert-butyl-5-formyl-4-hydroxyphenylester (2)A Schlenk flask equipped with a stir bar was charged with 3-tert-butyl-2,5-dihydroxybenzaldehyde (2.730 g, 14.06 mmol), 10-undecenoic acid (2.590 g, 14.06 mmol) and N,N-dimethylaminopyridine (0.172 g, 1.406 mmol). The flask was purged with N2 and THF (12 mL) and N,N-dimethylformamide (0.6 mL) were added. The mixture was cooled to 0° C. in an ice bath and N,N'-diisopropylcarbodiimide (1.86 mL, 14.76 mmol) was added. The mixture was stirred for 5 minutes at 0° C. then allowed to warm up to room temperature and stir overnight. The precipitated urea was filtered off and the mixture washed with 6 mL. THF was then removed under vacuum. The crude orange liquid was purified by flash chromatography using hexane:ethyl acetate (4:1) to give 4.354 g (86%) of a yellow-orange liquid. 1H NMR (RT, 500 MHz, C6D6): δ=12.09 (s, 1H), 9.08 (s, 1H), 7.30 (d, JHH=5 Hz, 1H), 6.77 (d, JHH=5 Hz, 1H), 5.79 (m, 1H), 5.02 (m, 2H), 2.33 (t, JHH=13 Hz, 2H), 1.99 (m, 2H), 1.65 (m, 2H), 1.37 (s, 9H), 1.35-1.17 (m, 10H). 13C NMR (RT, 126 MHz, C6D6): δ=196.3, 171.6, 158.9, 143.1, 139.9, 139.1, 123.6, 120.5, 114.6, 35.25, 34.52, 34.30, 29.82, 29.72, 29.57, 29.55, 29.42, 29.27, 29.25, 25.37. |
86% | With diisopropyl-carbodiimide In tetrahydrofuran; N,N-dimethyl-formamide at 0 - 20℃; Inert atmosphere; | Synthesis of 10-undecenoic acid, 3-tert-butyl-5-formyl-4-hydroxyphenylester (2) A Schlenk flask equipped with a stir bar was charged with 3-tert-butyl-2,5-dihydroxybenzaldehyde (2.730 g, 14.06 mmol), 10-undecenoic acid (2.590 g, 14.06 mmol) and N,N-dimethylaminopyridine (0.172 g, 1.406 mmol). The flask was purged with N2 and THF (12 mL) and N,N-dimethylformamide (0.6 mL) were added. The mixture was cooled to 0° C. in an ice bath and N,N'-diisopropylcarbodiimide (1.86 mL, 14.76 mmol) was added. The mixture was stirred for 5 minutes at 0° C. then allowed to warm up to room temperature and stir overnight. The precipitated urea was filtered off and the mixture washed with 6 mL water. THF was then removed under vacuum. The crude orange liquid was purified by flash chromatography using hexane:ethyl acetate (4:1) to give 4.354 g (86%) of a yellow-orange liquid. 1H NMR(RT, 500 MHz, C6D6): δ=12.09 (s, 1H), 9.08 (s, 1H), 7.30 (d, JHH=5 Hz, 1H), 6.77 (d, JHH=5 Hz, 1H), 5.79 (m, 1H), 5.02 (m, 2H), 2.33 (t, JHH=13 Hz, 2H), 1.99 (m, 2H), 1.65 (m, 2H), 1.37 (s, 9H), 1.35-1.17 (m, 10H). 13C NMR (RT, 126 MHz, C6D6): δ=196.3, 171.6, 158.9, 143.1, 139.9, 139.1, 123.6, 120.5, 114.6, 35.25, 34.52, 34.30, 29.82, 29.72, 29.57, 29.55, 29.42, 29.27, 29.25, 25.37. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | Stage #1: 10-undecenoic acid With oxalyl dichloride In dichloromethane; N,N-dimethyl-formamide at 0 - 20℃; for 1.75h; Inert atmosphere; Stage #2: 1-indoline With triethylamine In dichloromethane; N,N-dimethyl-formamide Inert atmosphere; | Procedure B General procedure: Carboxylic acid (10 mmol) was dissolved in 40 mL DCM in a flame-dried round bottom flask andcooled to 0 °C. Then, oxalyl chloride (1.27 mL, 15 mmol, 1.5 eq.) was added and a few drops of dry DMF. The mixture was stirred for 45 minutes at 0 °C until gas formation ceased followed by 1 hour at room temperature. Then, Et3N (2.79 mL, 2 eq.) and indoline (1.68 mL, 1.5 eq.) were added, the ice bath was removed and the slurry was stirred overnight. The mixture was poured into 1 N HCl (100 mL), and extracted with DCM (3 x 50 mL). The combined organic layers were dried with MgSO4, concentrated and purified via column chromatography (silica gel, 20-25%EtOAc in heptane) and additionally recrystallized from DCM/heptane to afford the pure amide. |
With dmap; dicyclohexyl-carbodiimide In dichloromethane at 0 - 20℃; for 20h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | Stage #1: 10-undecenoic acid With n-butyllithium; diisopropylamine In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide; hexane at -25 - 20℃; for 0.5h; Inert atmosphere; Stage #2: carbon dioxide In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide; hexane at -25 - 22℃; Inert atmosphere; | 1 Synthesis of non-8-enyl-malonic acid (1): An oven-dried 500 mL 2-neck flask equipped with magnetic stirbar and addition funnel was charged with diisopropylamine (12.8 mL, 91.1 mmol) and THF (180 mL) under nitrogen. The solution was chilled to -25° C. in a dry ice/water/ethanol bath, and n-butyllithium (34 mL of a 2.65 M solution in hexanes, 89.0 mmol) was added dropwise via addition funnel. The solution was stirred for 30 min, after which a degassed solution of undecenoic acid (8.0 g, 43.4 mmol) in THF (44 mL) was added dropwise via addition funnel, causing the solution to become turbid. HMPA (8 mL, 43.4 mmol) was added via addition funnel. The cooling bath was then removed to allow the solution to warm to room temperature over 30 min, during which time the solution turned clear and yellow. The solution was cooled again to -25° C. A second 500 mL 2-neck flask under N2(g) purge was charged with CO2(s) (200 g, 4.5 mol) and chilled to -25° C. The enolate solution was cannula transferred onto the CO2(s) under N2(g) purge, causing the solution to become clear and colorless. The solution was stirred at -25° C. for 30 minutes then the cooling bath was removed and stirring continued at 22° C. overnight, during which time the reaction gelled. The reaction was quenched by the addition of 10% HCl (aq) (100 mL), causing two layers to form. This biphasic mixture was transferred to a reparatory funnel, and the organic layer was collected and the aqueous layer was extracted with ether (3×75 mL). The combined organic layers were then washed successively with 2M HCl (aq) (3×50 mL), water (75 mL), saturated NaCl (aq) (75 mL), and then dried over anhydrous MgSO4 (s). The solvent was removed on a rotary evaporator to yield 9.5 g of white solid. The crude product was recrystallized from heptane to yield white crystals. Yield: 9.07 g (92% yield). 1H NMR (300 MHz, DMSO-d6, 22° C.): δ (ppm) 12.62 (s, 2H, CH(COOH)2), 5.78 (ddt, JH-H3=17.0, 10.3, 6.8 Hz, 1H, CH2═CHCH2), 4.98 (ddt, JH-H3=17.2, 1.6 Hz, JH-H32.2 Hz, 1H, CH2═CHCH2), 4.93 (ddt, JH-H3=10.2, 1.2 Hz, JH-H2=2.3 Hz, 1H, CH2═CHCH2), 3.17 (t, JH-H3=7.5 Hz, 1H, CH(COOH)2), 2.00 (dt, JH-H3=7.0, 6.8 Hz, 2H, CH2═CHCH2), 1.73-1.63 (m, 2H, CH2CH(COOH)2), 1.40-1.16 (m, 10H, CH2═CHCH2(CH2)5CH2CH(COOH)2). 13C NMR (75 MHz, DMSO-d6, 22° C.): δ (ppm) 170.90, 138.82, 114.64, 51.60, 33.18, 28.69, 28.64, 28.41, 28.24, 26.79. ESI-MS: calcd. for C12H20O4Na [M+Na]+251.1, found 251.1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85.9% | With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 0 - 20℃; for 96h; Inert atmosphere; | 2.3.6 Synthesis of symmetric azobenzene diene monomer (M1) General procedure: To a Schlenk flask, azobenzene chromophore, 4 (4.53 g, 15.0 mmol), 10-undecenoic acid (7.74 g, 42.0 mmol), and DMAP (0.44 g, 3.6 mmol) were discharged and dissolved in 50 mL of dried DMF (50 mL) under a nitrogen atmosphere, and then EDCI (6.89 g, 36.0 mmol) was added at 0 °C with rapid stirring. The reaction mixture was allowed to warm to room temperature and stirred for an additional time. After 4 days, the reaction mixture was poured into water and red solid precipitated. The crude product was further purified by recrystallization from ethanol/ethyl acetate (1:1 v/v) to give a red crystal M1 (8.17 g, 85.9% yield). 1H NMR (CDCl3): δ (ppm) 7.86-7.77 (m, 4H, o-ArH-N=N-ArH), 7.04-6.93 (m, 4H, m-ArH-N=N-ArH), 5.79-5.72 (m, 2H, CH2=CH), 5.01-4.89 (m, 4H, CH2=CH), 4.52-4.47 (m, 4H, OCH2CH2OCO), 4.19-4.11 (m, 4H, OCH2CH2OCO), 2.20-2.13 (m, 4H, OCOCH2), 2.00-1.96 (m, 4H, CH2=CHCH2), 1.73-1.68 (m, 4H, OCOCH2CH2), 1.43-1.21 (m, 10H, CH2). 13C NMR (CDCl3): δ (ppm) 171.2, 161.6, 143.9, 139.2, 124.3, 116.8, 114.5, 72.7, 64.4, 33.1, 30.6, 25.4. LC: single peak observed. EI/MS: calcd. for C38H54N2O6: 634.3; Found: 634.2. Anal. calcd for C: 71.92, H: 8.52, O: 15.14; Found C: 71.95, H: 8.53, O: 15.11. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83.2% | With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 0 - 20℃; for 96h; Inert atmosphere; | 2.3.6 Synthesis of symmetric azobenzene diene monomer (M1) General procedure: To a Schlenk flask, azobenzene chromophore, 4 (4.53 g, 15.0 mmol), 10-undecenoic acid (7.74 g, 42.0 mmol), and DMAP (0.44 g, 3.6 mmol) were discharged and dissolved in 50 mL of dried DMF (50 mL) under a nitrogen atmosphere, and then EDCI (6.89 g, 36.0 mmol) was added at 0 °C with rapid stirring. The reaction mixture was allowed to warm to room temperature and stirred for an additional time. After 4 days, the reaction mixture was poured into water and red solid precipitated. The crude product was further purified by recrystallization from ethanol/ethyl acetate (1:1 v/v) to give a red crystal M1 (8.17 g, 85.9% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 85% 2: 10% | Stage #1: methanol; 10-undecenoic acid With ozone at 0 - 20℃; Inert atmosphere; Stage #2: With hydroxylamine hydrochloride Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | Stage #1: methanol; 10-undecenoic acid With ozone at 0℃; Inert atmosphere; Stage #2: With semicarbazide hydrochloride at 0 - 20℃; for 48h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75.7% | Stage #1: 10-undecenoic acid; C37H51BrN2O9S With dmap In tetrahydrofuran; dichloromethane at 0℃; for 0.25h; Inert atmosphere; Stage #2: With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In tetrahydrofuran; N,N-dimethyl-formamide at 0 - 20℃; for 72h; Inert atmosphere; | 7 2.7. Synthesis of the azobenzene-containing a,x-diene inimer (4) Compound 3 (3.90 g, 5 mmol), 10-undecenoic acid (1.11 g, 6 mmol), DMAP (0.08 g, 0.6 mmol), CH2Cl2 (22 mL), and THF (8 mL) were charged into a 100-mL round-bottom flask equipped with a magnetic stirrer under a nitrogen atmosphere, and the mixture was stirred at 0 °C for 15 min. EDCI (1.12 g, 6 mmol) was then added to the former solution, which was stirred for 3 days after the solution warmed to room temperature. The resulting solution was washed three times with deionized water (3 * 80 mL), and the organic layer was dried over anhydrous Na2SO4. The solvent was then evaporated and the crude product was purified by silica gel chromatography eluted with methylene chloride/petroleum ether (10/1, Rf = 0.6) to give a dark red solid (3.58 g, 75.7% yield). 1H NMR (500 MHz, CDCl3, δ): 8.04-7.76 (m, 4H, o-ArH-N=N-ArH), 7.05-6.83 (m, 4H, m-ArH-N=N-ArH), 5.85-5.72 (d, 1H, CH2=CH), 5.02-4.94 (m, 2H, CH2=CH), 4.90-4.72 (CH2CHOCOCH2OCO), 4.53-4.46 (m, 2H, CH2CH2OCO), 4.37-4.07 (m, 4H, CH2CH2OCO + CH2CHOCOCH2OCO), 2.73-2.50 (m, 6H, CH2CH2SCH2), 2.32-2.11 (m, 4H, OCOCH2), 2.08-1.79 (m, 10H, CH2=CHCH2 + OCOCCH3BrCH3), 1.71-1.52 (m, 4H, OCOCH2CH2), 1.50-1.16 (m, 24H, CH2). 13C NMR (125 MHz, CDCl3, δ): 175.6, 172.0, 161.4, 145.0, 139.7, 122.9, 115.2, 77.1, 72.8, 69.3, 66.4, 53.2, 36.5, 33.6, 29.9, 28.5, 26.8, 25.2. LC: single peak was observed. EI/MS: Calcd. for C48H69O10N2SBr: 946.02; found: 945.99. Anal. calcd. for C48H69O10N2SBr: C 60.94, H 7.35, O 16.91; Found: C 60.91, H 7.36, O 16.87. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | Stage #1: dibromodifluoromethane; 10-undecenoic acid With tetrahydrofuran; eosin at 20℃; for 5h; Irradiation; Inert atmosphere; Schlenk technique; Stage #2: With potassium hydrogencarbonate for 5h; Inert atmosphere; Irradiation; Cooling with ice; Schlenk technique; | |
71% | With eosin y In tetrahydrofuran at 20℃; for 10h; Inert atmosphere; | 6 In 25 ml reaction tube add catalyst (16.2 mg, 0 . 025mmol, 5 µM %), (92 mg, 0 . 5mmol, 1.0 equiv.) and THF (15 ml), sealed by a rubber plug, and the 3M adhesive tape seal, then adding CF2Br2(630 mg, 6.0 equiv. , 3.0mmol), liquid nitrogen freezing, oil pump pumping the oxygen, nitrogen, thawing, so cycle three times. The final blue LED lamp is placed at a distance of 2 cm at, room temperature reaction 10h. After the reaction, the solvent is removed under reduced pressure directly, the obtained crude product by column chromatography (hexane: ethyl acetate=2:1), to obtain the product (112 mg), yield: 71%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | Stage #1: 10-undecenoic acid With dmap; dicyclohexyl-carbodiimide In dichloromethane at 0℃; for 0.5h; Stage #2: (±)-3-(4-methoxybenzyloxy)propane-1,2-diol In dichloromethane at 20℃; for 18h; | 1 3-((4-Methoxybenzyl)oxy)propane-1,2-diyl bis(undec-10-enoate) (19) General procedure: N,N’-dicyclohexylcarbodiimide (DCC) (3.0 eq) and 4 (dimethylamino)pyridine (DMAP) (0.4 eq) were sequentially added to a solution of the carboxylic acid (2.2 eq) in CH2Cl2 (0.25 M) at 0 °C and stirred for 30 min. A solution of the diol (1.0 eq) in CH2Cl2 (0.13 M) was added to the reaction mixture which was then stirred at RT for 18 h. The reaction mixture was filtered through celite, washed with CH2Cl2, and then concentrated in vaccuo.3-((4-Methoxybenzyl)oxy)propane-1,2-diyl bis(undec-10-enoate) (19). Following the general procedure using DCC (2.90 g, 14.1 mmol, 3.0 eq), DMAP (240 mg, 1.98 mmol, 0.4 eq), 10-undecenoic acid (2.08 mL, 10.3 mmol, 2.2 eq), the diol 18 (1.00 g, 4.70 mmol, 1.0 eq) and CH2Cl2 (55.0 mL, 0.08 M), the resulting crude residue was purified by flash column chromatography on silica using 30% ethyl acetate in petroleum ether as eluent to give the bis-ester 19 (2.33 g, 91%) as a pale yellow oil; νmax (CDCl3/cm-1) 3077, 2930, 2856, 1735, 1639, 1465, 1442, 1416, 1248 and 1173; δH (300 MHz, CDCl3) 7.24-7.21 (2H, m, 2x ArH), 6.89-6.86 (2H, m, 2x ArH), 5.80 (2H, ddt, J 17.0, 10.2 and 6.2, 2x H2C=CH), 5.22 (1H, ddt, J 3.9, 6.4 and 5.1, COOCH), 5.02-4.92 (4H, m, 2x H2C=CH), 4.49 (1H, d, J 11.6, OCHHAr), 4.43 (1H, d, J 11.6, OCHHAr), 4.32 (1H, dd, J 3.9 and 11.8, COOCHH), 4.16 (1H, dd, J 6.4 and 11.8, COOCHH), 3.80 (3H, s, OCH3), 3.57 (1H, dd, J 5.1 and 10.8, CHHOPMB), 3.53 (1H, dd, J 5.1 and 10.8, CHHOPMB), 2.31 (2H, t, J 7.5, CH2COO), 2.27 (2H, t, J 7.4, CH2COO), 2.06-1.99 (4H, m, 2x H2C=CHCH2), 1.63-1.53 (4H, m, 2x CH2), 1.40-1.24 (20H, m, 10x CH2); δC (75 MHz, CDCl3) 173.5, 173.2, 159.4, 139.2, 114.2, 113.9, 73.1, 70.1, 68.0, 62.8, 55.4, 34.4, 34.2, 33.9, 29.4, 29.3, 29.2, 29.0, 25.07, 25.00; m/z (ES) 562.4095 (M++NH4, 100%, C33H56O6N requires 562.4102). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With hypophosphorous acid In 1,4-dioxane; water monomer at 180℃; for 1h; Microwave irradiation; Sealed tube; | General procedure A: Representative procedure for the hydrophosphinylation of unactivated terminalalkenes using hypophosphorous acid General procedure: 50% aq. H3PO2 (2 mmol), alkene (0.4 mmol) and dioxane (4 mL) were added into a 10 mL microwave vialcontaining a Teflon-coated stirrer bar and a septum. The vial was sealed and was heated under microwaveirradiation at 180 °C for 1 hour. After cooling to room temperature the reaction mixture was partitioned betweenCH2Cl2 (15 mL) and water (10 mL), the organic phase was dried over Na2SO4 and concentrated under reducedpressure. Chromatographic purification, if necessary, on silica gel using CH2Cl2-MeOH-CH3COOH: 9-1-0.5 aseluent affords the corresponding H-phosphinic acids 3. |
With tris-(dibenzylideneacetone)dipalladium(0); hypophosphorous acid; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In water monomer; N,N-dimethyl-formamide at 110℃; | Palladium-catalyzed hydrophosphinylation (general procedure) General procedure: Pd2dba3 (75%, 0.01 eq., 0.1 mmol, 122 mg) and Xantphos (0.022 eq., 0.22 mmol, 127 mg) weredissolved in 10 mL of DMF. Hypophosphorous acid (50% in H2O, 2 eq., 20 mmol, 2.35 mL) andthe olefin, or the allylic alkohol (1 eq., 10 mmol) were added. The reaction mixture was heatedto 110° C for 16 h The reaction mixture was then filtered and the solvent evaporated underreduced pressure. The residue was dissolved in 50 mL of 2 M aqueous HCl and 50 mL of EtOAc.The layers were separated and the aqueous layer extracted three times with 50 mL of EtOAc.The combined organic layers were washed with 50 mL of saturated NaCl-solution and driedover Na2SO4. Removal of the solvent gave the crude product which was oxidized or purifiedvia RP column chromatography as specified. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | In 1,4-dioxane; at 160℃; for 1h;Microwave irradiation; Sealed tube; | General procedure: Phenyphosphinic acid (0.2 mmol), alkene (0.4 mmol) and dioxane (4 mL) were added into a 10 mL microwavevial containing a Teflon-coated stirrer bar and a septum. The vial was sealed and was heated under microwaveirradiation at 160 C for 1 hour. After cooling to room temperature the reaction mixture was purified by columnchromatography on silica gel using CH2Cl2-MeOH-CH3COOH: 9-0.5-0.5 as eluent to give the corresponding<strong>[1779-48-2]phenyl phosphinic acid</strong>s 6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane at 0 - 20℃; Inert atmosphere; | 4.7. General procedures for synthesis of mono acid 1,2-O-diacyl-3-O-(b-D-20,30,40,6'-tetra-O-acetyl-glucopyranosyl)-sn-glycerols (6a-6d) General procedure: 3-O-(b-D-20,30,40,6'-tetra-O-acetyl-glucopyranosyl)-sn-glycerol(5) (0.23 mmol) was dissolved in anhydrous dichloromethane(5 mL), fatty acid (0.47 mmol), N-(3-Dimethylaminopropyl)-0Nethylcarbodiimide hydrochloride (EDC) (0.47 mmol) and DMAP(catalytic amount) were added under nitrogen at 0 C. The reactionmixture was stirred for overnight at RT. After all the starting materials have been used, the reaction mixture was dissolved in CHCl3and washed with water and brine solution. The organic layer wasdried over anhydrous sodium sulphate and evaporated underreduced pressure. The mixture was purified by silica gel columnchromatography using hexane: EtOAc (4: 1, v/v) solvent mixture togive title compounds (6a-6d) in 88e92% yields. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | Stage #1: 10-undecenoic acid With oxygen; ozone In isopropyl alcohol at 0℃; Stage #2: toluene-4-sulfonic acid hydrazide In isopropyl alcohol at 20℃; Inert atmosphere; | Ozonolysis of alkenes (1-3). General procedure. General procedure: Through a solution of 10.0 mmol of alkene 1-3 in 25 mL of anhydrous alcohol (MeOH or i-PrOH) or in a mixture of 25 mL of CH2Cl2 and 5.7 mL of AcOH at 0 °C was bubbled the ozone-oxygen mixture till 10 mmol of ozone was consumed. The reaction mixture was flushed with argon. At 0 °C 6.51 g (35.0 mmol) of TsNHNH2 was added, the reaction mixture was stirred at room temperature till disappearance of preoxides (monitoring by the starch iodide test), the solvent was distilled off, the residue was dissolved in 150 mL of CHCl3, washed with brine (4 × 35 mL), dried with Na2SO4, and evaporated. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dicyclohexyl-carbodiimide; In ethanol; acetic acid; at 60℃; for 5h; | Undecyl- <strong>[9012-76-4]chitosan</strong> was synthesized by coupling of amine group of <strong>[9012-76-4]chitosan</strong> to carboxyl group of fatty acid adopting previous method with slight modification (Lee et al., 2011). In brief, increasing volume of (5mL, 10mL, 15mL and 20mL of 1mg/mL w/v) undec-10-enoic acid dissolved in ethanol were added to the 50mL <strong>[9012-76-4]chitosan</strong> dissolved in acetic acid solution (2mg/mL w/v). Both the solutions were mixed at 60C under constant stirring for 10min. DCC (23.0mg) was then added to carry out coupling reaction for 5h at 60 C under constant stirring. After completion of reaction (monitored by TLC), the reaction mixture was allowed to cool, extracted by dichloromethane, washed with water (3×10mL), dried over anhydrous Na2SO4 and then evaporated under reduced pressure to afford the product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | Stage #1: 10-undecenoic acid With 4-methyl-morpholine; chloroformic acid ethyl ester In diethyl ether at 0 - 20℃; for 1h; Inert atmosphere; Stage #2: N-benzyl-O-(tert-butyldimethylsilyl)hydroxylamine In diethyl ether at 0 - 20℃; for 2h; Inert atmosphere; | [General procedure E]N-Benzyl-N-((tert-butyldimethylsilyl)oxy)octanamide (10a) General procedure: N-Methylmorpholine (300 μL, 2.7 mmol, 1.3 equiv) was added to a solution of octanoic acid (330 μL, 2.1 mmol) and Et2O (6.3 mL) at room temperature. After cooling to 0 °C, ethyl chloroformate (240 μL, 2.5 mmol, 1.2 equiv) was then added to the solution. The resulting suspension was stirred for 1 h at 0 °C, added to a solution of N-siloxyamine 47 (800 μL, 3.1 mmol, 1.5 equiv) and Et2O (3.3 mL) at 0 °C, and allowed to warm to room temperature. After stirring for 2 h at room temperature, the solution was quenched with saturated aqueous NaHCO3 (10 mL), and extracted with EtOAc (2x20 mL). The combined organic extracts were washed with brine (10 mL), dried over Na2SO4, and concentrated. The residue was purified by silica gel column chromatography (EtOAc/hexane 1:150) to give 764 mg of N-siloxyamide 10a (100%): |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With triethylamine In tetrahydrofuran at 0 - 25℃; for 1h; Inert atmosphere; | |
72% | With triethylamine In toluene at 23℃; for 7h; Cooling with ice; | 1 Example of Synthesis 1 In a separable flask having a capacity of 1,000 ml and equipped with a reflux tube, a dropping funnel, a stirrer and a thermometer, 184 g (1 mol) of 10-undecylenic acid, 119 g (1.1 mol) of trimethylchlorosilane and 500 ml of toluene were put, and 111 g (1.1 mol) of triethylamine was added dropwise thereto over one hour in an ice bath. After completion of the dropwise addition, a reaction was caused at room temperature (23° C., the same applies hereinafter) for six hours. Thereafter, a generated triethylamine hydrochloride was removed by filtration. Furthermore, toluene and unreacted substances were removed (distilled off) at 150° C. at 300 Pa, thus obtaining 10-undecylenic acid trimethylsilyl ester as a target product (collected amount: 226 g, yield: 72%).H-NMR (400 MHz, CDCl3) δ 5.46 (m, 3H), 2.48 (t, 2H), 1.88 (m, 2H), 1.08 (brs, 16H), 0.28 (s, 9H) |
Yield | Reaction Conditions | Operation in experiment |
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89% | Stage #1: 10-undecenoic acid With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane for 0.333333h; Cooling with ice; Stage #2: L-Tyr-OMe In dichloromethane at 20℃; for 12h; | 2.3 General procedure for synthesis of methyl N-fattyacyl-L-tyrosinate General procedure: A mixture of 12.3 mmol of fatty acid, 12.3 mmol of EDC and 15.38 mmol of HOBt dissolved in ice-cold anhydrous DCM (50 mL) was kept in ice for 20 min with stirring, followed bythe addition of 10.25 mmol of L-tyrosine methyl ester and the mixture was left at room temperature for 12 h with stirring. TLC (hexane/ethyl acetate 1:1, v/v) was used to monitor the reaction. At the end of the reaction, the mixture was dissolvedin 75 mL of CHCl3, which was then washed with 5% NaHCO3 solution and saturated NaCl solution. The chloroform layer was dried with anhydrous Na2SO4. The filtrate was then dried under vaccum. Then, the crude mixture was purified by silica gel chromatography by using solvent mixture (hexane/ethylacetate 70:30, v/v), with 80-89% yield of the title compound was obtained as a solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72.4% | With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane at 20℃; for 2h; | 4.2.3. General procedure for the preparation of 3 and 3a-3g General procedure: A mixture of sinomenine hydrochloride (365.1 mg, 1.0 mmol),paraformaldehyde (720.6 mg, 8 mmol), in HCl solution (2.0 M/L, 100.0 mL), was stirred at 60 C for 2 h. After reaction for 2 h, thereaction liquidwas cooled to room temperature. Then, the pH of themixed solution was adjusted to 9 using 10% NaOH solution untilwhite solid precipitated. Then the white solid was filtered, washedwith water, and dried in a vacuum constant temperature dryingbox. Finally, the compound 3, sinomenine benzyl alcohol intermediate(1-hydroxymethyl sinomenine), was gotten in a yield of85.7%.To a stirred solution of various carboxylic acid (2.5 mmol) inCH2Cl2 (5 mL) was added the compound 3 (359.1 mg, 1 mmol), EDC(766.8 mg, 4.0 mmol), DMAP (73.4 mg, 0.6 mmol) and then stirredfor 2 h at room temperature. The reaction mixturewaswashed withbrine, dried over anhydrous Na2SO4, filtered and concentrated. Theresidue was purified by flash column chromatography (DCM:MeOH 100: 4) to afford the compounds 3a-3g in a yield of 62.1%e72.4%. |
59% | With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane at 20℃; for 2h; | 4.2.17. 1-(10-undecenoyloxymethylene)-4-(10-undecenoyloxy)-7, 8-didehydro-3,7-dimethoxy-17-methylmorphinan-6-one (3c) General procedure: A mixture of sinomenine hydrochloride (1 mmol), Sorbic acid (1.5 eq), EDC(1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 2.0 eq), DMAP(4-dimethylaminopyridine) in CH2Cl2, was stirred at room temperature for 2 h, followedby addition of water, the solution was extracted with CH2Cl2. The combined extract wasdried with anhydrous NaSO4. The residue was separated by column chromatography togive the pure sample. Oily substance; yield 70%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | Stage #1: 10-undecenoic acid With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In tetrahydrofuran at 0℃; for 0.166667h; Stage #2: nalbuphine hydrochloride With dmap; trimethylamine In tetrahydrofuran at 0 - 20℃; | 1 3-(cyclobutylmethyl)-4a,7-dihydroxy-2,3,4,4a,5,6,7,7a-octahydro-1H-4,12-methanobenzofuro[3,2-e]isoquinolin-9-yl undec-10-enoate, Nalbuphino-undecelenoate, (NB-31). EDCI (1.04 g, 5.4 mmol) was added to undecylenic acid (1.0 g, 5.4 mmol) in THF (30 mL) at 0° C. with stirring. The reaction mixture was stirred for 10 min and Nalbuphine hydrochloride (2.13 g, 5.4 mmol), trimethylamine (1.1 g, 10.9 mmol) and 4-dimethylaminopyidine (0.22 g, 1.8 mmol) were added at 0° C. The stirring was continued for 1 h at 0° C. and at room temperature overnight. The reaction mixture was filtered, filtrate was evaporated, and the residue was purified by column chromatography (silicagel, EtOAc/Heptanes, 1:1). The white solid was formed after evaporation of selected fractions, yield 2.2 g (78%), purity 95% by HPLC. The structure was confirmed by NMR 1H. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride In methanol at 20℃; for 2h; | Lipid 1: 10-Undecenoic acid (850 mg, 4.6 mmol), DMT-MM (1650 mg, 5.1 mmol) and D-glucamine (920 mg, 5.1 mmol) were dissolved in methanol and reacted at room temperature (RT) for 2 h. The white reaction dispersion was cooled in ice bath, followed by filtration and washing with ice-cold methanol to yield 1580 mg of lipid 1 (yield 99%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | Stage #1: oxalyl dichloride; 10-undecenoic acid With N,N-dimethyl-formamide In dichloromethane at 0℃; for 1h; Inert atmosphere; Stage #2: 9-Decen-1-ol With triethylamine In dichloromethane at 20℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With iron(III)-acetylacetonate; phenylsilane In ethanol; ethylene glycol at 35℃; for 12h; Schlenk technique; Inert atmosphere; | 4.2. General Procedures of Iron-Catalyzed SOMOphilic Alkynylation General procedure: Flame-dried 10 mL Schlenk tube filled with N2, acetylenic sulfones 2 (0.2 mmol, 1.0 equiv) and Fe(acac)3 (21.2 mg, 0.06 mmol, 30 mol%) were added under N2, evacuated and purged with N2 three times. Afterwards, PhSiH3 (43.2 mg, 0.4 mmol, 2 equiv), nonactivted alkenes 1 (33.1 mg, 0.3 mmol, 1.5 equiv) and ethanol (0.8 mL) and ethylene glycol (0.2 mL) were added via syringe. The formed mixture was stirred at 35 °C under N2 for 12 h, as monitored by TLC. The solution was then cooled to room temperature, and the solution was diluted with ethyl acetate and transferred to a round bottom flask. The concentrated residue was purified by column chromatography using ethyl acetate/petroleum ether as an eluent to afford the corresponding products and 3 and 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | Stage #1: 10-undecylenic acid With 1-hydroxy-pyrrolidine-2,5-dione In ethanol at 20℃; for 4h; Stage #2: glucosamine Hydrochloride With N-[3-(N,N-dimethylamino)-propyl]-N'-ethyl-carbodiimide hydrochloride; triethylamine In ethanol; water monomer for 48h; | 2.1 Example 2 (1) Dissolve 2.9 mL of undecylenic acid and 1.65 g of N-hydroxysuccinimide (NHS) in 15 mL of ethanol, and stir at room temperature for 4 h; 2.70 g of glucosamine hydrochloride and 2.85 g of 1-(3-diol) Methylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC·HCl) was dissolved in 10 mL of distilled water. After fully dissolving, the two solutions were mixed and vigorously stirred, and 1 to 3 drops of triethylamine were added. The reaction was continued for 48 h. After the reaction was completed, the system was rotary evaporated to remove ethanol, extracted three times with dichloromethane, and the aqueous phase was taken and freeze-dried to obtain undecenoylated glucosamine with a yield of 80%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With triethylamine In toluene at 23℃; for 6.5h; Cooling with ice; | 2 Synthesis Example 2 In a separable flask having a capacity of 500 ml and equipped with a reflux tube, a dropping funnel, a stirrer and a thermometer, 25 g (0.045 mol) of the bis(10-undecylenic acid) diphenylsilyl ester obtained in Example of synthesis 2 and 0.05 g of 0.5% Karstedt catalyst (platinum olefin compound complex) toluene solution were put, and the resulting mixture was heated to 80° C. Next, 15 g (0.12 mol) of trimethoxysilane was added dropwise thereto over two hours while the temperature range was adjusted to 80 to 100° C. After completion of the dropwise addition, a reaction was caused at 80° C. for eight hours. Thereafter, unreacted substances were removed at 150° C. at 300 Pa, thus obtaining bis(11-trimethoxysilylundecanoic acid) diphenylsilyl ester as a target product, represented by the following chemical formula (10) (collected amount: 39 g, yield: 93%).H-NMR (400 MHz, CDCl3) δ 7.36 (m, 10H), 3.82 (s, 18H), 2.18 (t, 4H), 1.51 (m, 4H), 1.08 (brs, 28H), 0.78 (t, 4H), 0.28 (s, 18H) |
Tags: 112-38-9 synthesis path| 112-38-9 SDS| 112-38-9 COA| 112-38-9 purity| 112-38-9 application| 112-38-9 NMR| 112-38-9 COA| 112-38-9 structure
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