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[ CAS No. 7235-40-7 ] {[proInfo.proName]}

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Cat. No.: {[proInfo.prAm]}
Chemical Structure| 7235-40-7
Chemical Structure| 7235-40-7
Structure of 7235-40-7 * Storage: {[proInfo.prStorage]}
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Product Details of [ 7235-40-7 ]

CAS No. :7235-40-7 MDL No. :MFCD00001556
Formula : C40H56 Boiling Point : -
Linear Structure Formula :- InChI Key :OENHQHLEOONYIE-JLTXGRSLSA-N
M.W : 536.87 Pubchem ID :5280489
Synonyms :
Provitamin A;beta-Carotene;Solatene;Provatene;NSC 62794;Lucarotin;KPMK;Food Orange 5

Calculated chemistry of [ 7235-40-7 ]

Physicochemical Properties

Num. heavy atoms : 40
Num. arom. heavy atoms : 0
Fraction Csp3 : 0.45
Num. rotatable bonds : 10
Num. H-bond acceptors : 0.0
Num. H-bond donors : 0.0
Molar Refractivity : 184.43
TPSA : 0.0 Ų

Pharmacokinetics

GI absorption : Low
BBB permeant : No
P-gp substrate : Yes
CYP1A2 inhibitor : No
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : 0.04 cm/s

Lipophilicity

Log Po/w (iLOGP) : 7.89
Log Po/w (XLOGP3) : 13.54
Log Po/w (WLOGP) : 12.61
Log Po/w (MLOGP) : 8.96
Log Po/w (SILICOS-IT) : 12.65
Consensus Log Po/w : 11.13

Druglikeness

Lipinski : 2.0
Ghose : None
Veber : 0.0
Egan : 1.0
Muegge : 2.0
Bioavailability Score : 0.17

Water Solubility

Log S (ESOL) : -11.04
Solubility : 0.0000000049 mg/ml ; 0.0 mol/l
Class : Insoluble
Log S (Ali) : -13.6
Solubility : 0.0 mg/ml ; 0.0 mol/l
Class : Insoluble
Log S (SILICOS-IT) : -7.59
Solubility : 0.0000138 mg/ml ; 0.0000000256 mol/l
Class : Poorly soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 1.0 alert
Leadlikeness : 3.0
Synthetic accessibility : 6.19

Safety of [ 7235-40-7 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 7235-40-7 ]

* 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.

  • Downstream synthetic route of [ 7235-40-7 ]

[ 7235-40-7 ] Synthesis Path-Downstream   1~69

  • 1
  • [ 128-08-5 ]
  • [ 92-53-5 ]
  • [ 64-17-5 ]
  • [ 67-66-3 ]
  • [ 7235-40-7 ]
  • [ 514-78-3 ]
  • 2
  • [ 7235-40-7 ]
  • [ 514-78-3 ]
YieldReaction ConditionsOperation in experiment
98.05% With sulfuric acid; copper(II) sulfate; potassium iodide; In dichloromethane; water; at -5 - 45℃; under 760.051 Torr; for 4h;Green chemistry; 5.36 g (10 mmol) of <strong>[7235-40-7]beta-carotene</strong> was placed in a 500 ml three-necked flask, 100 ml of dichloromethane was added , stirred at -5 C, 0.17 g (1 mmol) of catalyst potassium iodide was added, 0.17g of sulfuric acid aqueous solution was added as 5wt% auxiliary and mixed evenly, then, 1.29 g (10 mmol) of copper sulfate was dissolved in 15 ml of water, and the mixture was added dropwise to the flask (dropping time 1.5 h), at -5 C, the reaction pressure was atmospheric pressure, the reaction time was 2h, the heating rate of rC/min was raised to 45 C for 2 h, filtered, washed three times with water, the organic phase was separated, dried, and then recrystallized from acetone to give 5.53 g of an amaranth colored canthaxanthin, and the yield was 98.05%.
98.05% With dihydrogen peroxide; potassium iodide; lithium hydroxide; In dichloromethane; water; at -5 - 45℃; under 760.051 Torr; for 5.5h;Green chemistry;Catalytic behavior; 5.36 g (10 mmol) of <strong>[7235-40-7]beta-carotene</strong> was placed in a 500 ml three-necked flask, and 100 ml of dichloromethane was added thereto, and the mixture was stirred at -5 C, 0.17 g (1 mmol) of potassium iodide catalyst was added, and 0.34 g of lithium hydroxide auxiliary was added to the mixture, and the mixture was uniformly mixed. Then take 2.00g of 50% aqueous solution of hydrogen peroxide, drop into the flask (addition time 1.5h), -5 C, The reaction pressure is atmospheric pressure, the reaction time was 2h,The heating rate of 1 C / min was raised to 45 C for 2 h. filtered, washed 3 times with water, the organic phase was separated, dried, and then recrystallized from acetone to obtain a purple-red solid. The content was 5.53 g, and the yield was 98.05%.
98.05% With sodium nitrate; carbon dioxide; potassium iodide; In dichloromethane; water; at -5 - 45℃; for 4h; 5.36 g (10 mmol) of <strong>[7235-40-7]beta-carotene</strong> was placed in a 500 ml three-necked flask.The carbon dioxide gas was replaced 3 times, 125 g of dichloromethane was added, and the mixture was stirred at -5 C.Carbon dioxide is introduced into the reaction system at 300 ml/min.Adding catalyst potassium iodide 0.17g (1mmol),Then take 3.18 g of sodium nitrate aqueous solution (sodium nitrate: water = 1:6).Then added to the flask, -5 C, reaction pressure and pressure, The reaction time was 2 h, and the heating rate was raised to 45 C for 2 h at 1 C / min.The reaction process system is pH 6.5-6.8, filtered, and washed 3 times with water.The organic phase is separated, and the solvent is removed by spin drying under a heating condition of 5 KPaA and 30 C water bath.Then, it was dissolved in 50 mL of acetone, and heated in a 75 C oil bath for 10 h.Cool down to 25 C at 15 C / h, filter the sand core funnel,Drying in a vacuum oven at 100 PaA for 12 h gave a purple-red canthaxanthin of 5.53 g.The <strong>[7235-40-7]beta-carotene</strong> conversion rate was 100.00%, the canthaxanthin selectivity was 98.05%, and the yield was 98.05%.
89.05% With C26H28CoN2O12; oxygen; sodium iodide; In ethyl acetate; at 30℃; under 1500.15 Torr;Sealed tube; 0.1 mol of <strong>[7235-40-7]beta-carotene</strong> was dissolved in 3.6 L of ethyl acetate in a 2 L reactor, and then 0.0001 mol of the catalyst (compound Ih) and 0.0001 mol of sodium iodide were added.The temperature of the reaction liquid was adjusted to 30 C in a sealed state, oxygen was introduced under stirring, the reaction gauge pressure was controlled to 0.2 MPa, and the reaction temperature was controlled to 30 C.The reaction was stirred until the reaction solution <strong>[7235-40-7]beta-carotene</strong> was completely converted, that is, the reaction was stopped, and the content of canthaxanthin in the reaction solution was measured, and the yield of cantharidin was calculated to be 89.05%.
85.67% With calcium hypochlorite; urea hydrogen peroxide adduct; Aliquat 336; In tetrachloromethane; water; at 0 - 5℃; for 6h; In a 500 ml four-necked flask, 6 g of <strong>[7235-40-7]beta-carotene</strong> (99%, 0.01106 mol) and 120 ml of carbon tetrachloride were added.Add 3.64g of urea peroxide (0.03869mol) and 0.045g of trioctylmethylammonium chloride, vacuum three times, and cool to 0~5 C.19.63 g of an aqueous calcium hypochlorite solution precooled to 5 C (very effective chlorine content of 3 wt%, 0.01659 mol, pH adjusted to 7) was added very slowly.The temperature of the dropping process is controlled at 0 to 5 C, and the temperature is kept at this temperature for 6 hours.The oil layer and the water layer were obtained by standing layering, and the water layer was extracted once with 50 ml of carbon tetrachloride. The carbon tetrachloride layer obtained by the extraction was combined with the oil layer, and then washed once with 100 ml of a 2% w/v aqueous solution of sodium sulfite, and washed once with 100 ml of water. Concentrated to dryness,50 ml of isopropanol was added and the isomerization reaction was carried out at 80 C for 24 h.Drop to room temperature, filter, vacuum dry,Have a yellow solid 5.60g,The content was 95.43%, and the molar yield was 85.67%.
84.2% With oxygen; copper diacetate; glycine; In 1,2-dichloro-ethane; at 70℃; under 18751.9 Torr; for 13h;Autoclave; 16.08 g (0.03 mol) of <strong>[7235-40-7]beta-carotene</strong> and 960 g of dichloroethane were sequentially added to a 1 L autoclave.0.2% (molar ratio relative to <strong>[7235-40-7]beta-carotene</strong>) copper acetate,0.2% (molar ratio relative to <strong>[7235-40-7]beta-carotene</strong>) glycine,0.2% (molar ratio relative to <strong>[7235-40-7]beta-carotene</strong>) aminocyclodextrin was charged with a mixture of nitrogen and oxygen (volume ratio nitrogen: oxygen = 9:1) to an absolute pressure of 2.5 MPa,Heating to 70 C reaction, reaction 13h,The reaction solution is taken in a small amount for high performance liquid chromatography analysis.The reaction conversion rate was 92.6%, and the selectivity was 97.6%.The reaction was stopped, the reaction solution was filtered to remove the catalyst, and then the filtrate was heated to reflux.Add 960g of ethanol to the system,Cooling to -20 C suction filtration, the yield of canthaxanthin 84.2%
78.5% With sodium chlorate; iodine; In ethanol; chloroform; water; EXAMPLE 2 10 g of <strong>[7235-40-7]beta-carotene</strong> are dissolved in 500 ml of chloroform under a nitrogen atmosphere, and 60 g of sodium chlorate in 80 ml of water are added. The pH of the aqueous phase was brought to 3-4 with glacial acetic acid. 200 mg of iodine, dissolved in 100 ml of chloroform, are then added and the mixture is stirred for 20 hours at 25 C. The organic phase is then washed with four 200 ml portions of water and is dried, and the solvent is stripped off under reduced pressure. 500 ml of ethanol are added to the oily residue and the mixture is left to stand for 25 hours at -10 C. 8.2 g of crude canthaxanthin of 80.5% purity are obtained by filtration. Yield, 78.5%.
A solution of 40 mg sodium iodide in 10 ml water is added to 4 g <strong>[7235-40-7]beta-carotene</strong> in 270 ml dichloromethane in a nitrogen atmosphere at 0-5C. 20 ml chlorine bleach solution (NaOCl, ca 12% active chlorine content) is then added drop by drop at this temperature within 30 minutes. Before this, the chlorine bleach solution is slightly acidified (pH 6) with 1 N H2SO4 and used within 10 minutes. After addition, the mixture is stirred for a further 30 minutes at 0C. During this time, the color of the organic phase darkens increasingly. The mixture is diluted with water and the phases are separated. The organic phase is washed with water, dried over sodium sulfate and the solvent is removed in a vacuum. 4.9 g of the raw product with a canthaxanthin content of 72 surface percent is obtained. The all-trans content of the canthaxanthin measured by HPLC is 65%. For isomerization, 25 ml acetone and 40 mg iodine are added to the residue, which is refluxed until a z-isomer signal no longer occurs in HPLC.
A solution of 55 mg iodine in 30 ml dichloromethane is added to 4 g <strong>[7235-40-7]beta-carotene</strong> in 270 ml dichloromethane in a nitrogen atmosphere at 0-5C. 20 ml chlorine bleach solution (NaOCl, ca 12% active chlorine content) is then added drop by drop at this temperature within 30 minutes. Before this, the chlorine bleach solution is slightly acidified (pH 6) with 1 N H2SO4 and is used within 10 minutes. After addition, the mixture is stirred for a further 30 minutes at 0C. During this time, the organic phase darkens increasingly. The mixture is diluted with water and the phases are separated. The organic phase is washed with water, dried over sodium sulfate and the solvent is removed in a vacuum. 4.8 g of the raw product with a canthaxanthin content of 80 surface percent is obtained. The all-trans content of the canthaxanthin measured by HPLC is 71%. For isomerization, 25 ml acetone and 40 mg iodine are added to the residue, which is refluxed until a z-isomer signal no longer occurs in HPLC. The canthaxanthin can be separated out of the reaction mixture by the usual methods for the separation of constituents of a mixture. For example, the solvent can be removed by distillation at reduced pressure and the canthaxanthin can be isolated by recrystallization.
With sodium chlorate; iodine; In ethanol; dichloromethane; water; EXAMPLE 4 10 g of <strong>[7235-40-7]beta-carotene</strong> are dissolved in 1 l of methylene chloride under a nitrogen atmosphere and treated with 50 g of sodium chlorate in 200 ml of water. The pH of the aqueous phase is 2-3. After adding 200 mg of iodine, the mixture is stirred for 2 days at 25 C., the organic phase is then washed with four 200 ml portions of water and is dried, and the solvent is removed. 500 ml of ethanol are added to the residue and after the mixture has stood for 2 hours, the product is filtered off. Yield, 7.8 g of pure canthaxanthin, corresponding to 73.5%.

  • 3
  • [ 7235-40-7 ]
  • [ 116-31-4 ]
YieldReaction ConditionsOperation in experiment
89% With oxygen; In water; under 760.051 Torr; for 8h; In a 500 ml reaction bottle, 200 mL of solvent water, 54 g (0.1 mol) of <strong>[7235-40-7]beta-carotene</strong>, and 0.24 g (0.001 mol) of catalyst were added in sequence. Oxygen was maintained and the pressure was maintained at 1 atmosphere. After 8 hours of reaction under sunlight It was extracted three times with water and ethyl acetate. The aqueous layer was removed and the organic layer was dried over anhydrous sodium sulfate. The solvent was removed on a rotary evaporator to obtain 50.5 g of retinal with a yield of 89%.
  • 5
  • [ 7235-40-7 ]
  • [ 2790-54-7 ]
  • [ 2423-77-0 ]
  • 7
  • [ 5056-17-7 ]
  • [ 3917-39-3 ]
  • [ 7235-40-7 ]
  • 8
  • [ 7235-40-7 ]
  • [ 15356-74-8 ]
  • [ 79-77-6 ]
  • [ 3917-41-7 ]
  • [ 36340-49-5 ]
  • 9
  • [ 7235-40-7 ]
  • [ 15356-74-8 ]
  • [ 79-77-6 ]
  • [ 17974-57-1 ]
  • [ 36340-49-5 ]
  • 10
  • [ 7235-40-7 ]
  • [ 15356-74-8 ]
  • [ 1638-05-7 ]
  • trans/cis-15,15'-epoxy-β-carotene [ No CAS ]
  • [ 1923-89-3 ]
  • [ 864-94-8 ]
  • [ 36340-49-5 ]
  • 12
  • [ 21499-97-8 ]
  • [ 7235-40-7 ]
  • [ 18526-49-3 ]
  • 13
  • [ 251291-82-4 ]
  • [ 7235-40-7 ]
YieldReaction ConditionsOperation in experiment
75% With sodium; In ethanol; for 10h;Heating / reflux; Sodium (674 mg, 29.3 mmol) was added to a stirred solution of 11,20-di(benzenesulfonyl)-11,12,19,20-tetrahydro-? -carotene (F) (602 mg, 0.73 mmol) in EtOH (20 mL) under argon atmosphere. The reaction mixture was heated under reflux for 10 h with vigorous stirring. When the reaction was completed, the reaction mixture was concentrated under reduced pressure to remove most of the solvent. Toluene (50 mL) was added thereto to dissolve the residue, and the resultant mixture was washed with 1 M HCl, dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by flash chromatography over silica gel to give exclusively trans-? -carotene of Chemical Formula 3 (295 mg, 0.55 mmol) in 75% yield. ???NMR spectrum (JEOL, 300 MHz) data of trans-?-carotene is shown in Fig. 1b. The NMR data of the synthetic sample was identical to that of the authentic sample, shown in Fig. 1a
  • 14
  • [ 56798-08-4 ]
  • [ 75-24-1 ]
  • [ 111917-89-6 ]
  • [ 7235-40-7 ]
  • 15
  • [ 5056-17-7 ]
  • [ 55497-47-7 ]
  • [ 7235-40-7 ]
  • 16
  • [ 138846-06-7 ]
  • (1E,3E,5E,7E,9E)-1,10-bis(tri-n-butylstannyl)-3,8-dimethyldeca-1,3,5,7,9-pentaene [ No CAS ]
  • [ 7235-40-7 ]
  • 17
  • [ 7235-40-7 ]
  • [ 15356-74-8 ]
  • [ 79-77-6 ]
  • [ 36340-49-5 ]
  • 18
  • [ 870636-64-9 ]
  • [ 7235-40-7 ]
  • 13-cis-β,β-carotene [ No CAS ]
  • 19
  • [ 870636-68-3 ]
  • [ 7235-40-7 ]
  • 13-cis-β,β-carotene [ No CAS ]
  • 20
  • [ 870636-67-2 ]
  • [ 7235-40-7 ]
  • 13-cis-β,β-carotene [ No CAS ]
  • 21
  • [ 870636-66-1 ]
  • [ 7235-40-7 ]
  • 13-cis-β,β-carotene [ No CAS ]
  • 22
  • 2,17-dibromo-1,9,18-tris(benzenesulfonyl)-3,7,12,16-tetramethyl-1,18-bis(2,6,6-trimethyl-1-cyclohexen-1-yl)-3,7,11,15-octadecatetraene [ No CAS ]
  • [ 7235-40-7 ]
YieldReaction ConditionsOperation in experiment
50% With potassium methanolate; In cyclohexane; benzene; at 70 - 80℃; for 21h; Method A: Elimination Reaction from the Compound (P-1); To a stirred suspension of the crude (see Example 11) C40 dibromide (P-1) (0.15 g, 0.13 mmol) in cyclohexane (10 mL) and benzene (5 mL) was added KOMe (0.28 g, 3.99 mmol). The mixture was heated to 7080 C. for 21 h, cooled to room temperature, and 1 M HCl (10 mL) was carefully added. The reaction mixture was extracted with a 9:1 (v:v) solution (30 mL) of hexane and benzene, dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The resulting red solid was diluted with hexane (30 mL) and washed with CH3CN (10 mL×3). The combined CH3CN solution was extracted again with hexanes. The hexane layers were combined and concentrated under reduced pressure to give beta-carotene of the Chemical Formula 2 (56 mg, 0.10 mmol) in 77% crude yield. The crude product was purified by recrystallization from MeOH and THF to provide all-(E)-beta-carotene (36 mg, 0.067 mmol) in 50% yield as a dark red crystal.
50% With potassium methanolate; In cyclohexane; benzene; at 70 - 80℃; for 21h;Product distribution / selectivity; 136] Example 15. beta-carotene (Chemical Formula 2). [137] Method A: Elimination reaction from the compound (P-I) [138] To a stirred suspension of the crude (see Example 11) C 40 dibromide (P-I) (0.15 g,0.13 mmol) in cyclohexane (10 mL) and benzene (5 mL) was added KOMe (0.28 g, 3.99 mmol). The mixture was heated to 70-80 C for 21 h, cooled to room temperature, and 1 M HCl (10 mL) was carefully added. The reaction mixture was extracted with a 9:1 (v:v) solution (30 mL) of hexane and benzene, dried over anhydrous Na SO , filtered, and concentrated under reduced pressure. The resulting red solid was diluted with hexane (30 mL) and washed with CH CN (10 mL X 3). The combined CH CN solution was extracted again with hexanes. The hexane layers were combined and concentrated under reduced pressure to give beta-carotene of the Chemical Formula 2 (56 mg, 0.10 mmol) in 77% crude yield. The crude product was purified by recrystallization from MeOH and THF to provide all-(E)-beta-carotene (36 mg, 0.067 mmol) in 50% yield as a dark red crystal.
  • 23
  • 1,9,18-tris(benzenesulfonyl)-3,7,12,16-tetramethyl-1,18-bis(2,6,6-trimethyl-1-cyclohexen-1-yl)-3,7,11,15-octadecatetraene-2,17-diol, bis(tetrahydropyranyl) ether [ No CAS ]
  • [ 7235-40-7 ]
YieldReaction ConditionsOperation in experiment
81% With potassium methanolate; In cyclohexane; benzene; at 70 - 80℃; for 18h; Method B: Elimination Reaction from the Compound (P-2); To a stirred suspension of the bis(tetrahydropyranyl)ether (P-2) (0.55 g, 0.47 mmol) in cyclohexane (20 mL) and benzene (10 mL) was added KOMe (0.66 g, 9.40 mmol). The mixture was heated to 7080 C. for 18 h, cooled to room temperature, and 1 M HCl (20 mL) was carefully added. The reaction mixture was extracted with a 9:1 (v:v) solution (40 mL) of hexane and benzene, dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The resulting red solid was diluted with hexane (30 mL) and washed with CH3CN (10 mL×3). The combined CH3CN solution was extracted again with hexanes. The hexane layers were combined and concentrated under reduced pressure to give beta-carotene of the Chemical Formula 2 (0.25 g, 0.47 mmol) in 100% crude yield. The crude product was purified by recrystallization from MeOH and THF to provide all-(E)-beta-carotene (0.20 g, 0.38 mmol) in 81% yield as a dark red crystal.
81% With potassium methanolate; In cyclohexane; benzene; at 70 - 80℃; for 18h;Product distribution / selectivity; [139] Method B: Elimination reaction from the compound (P-2) [140] To a stirred suspension of the bis(tetrahydropyranyl) ether (P-2) (0.55 g, 0.47 mmol) in cyclohexane (20 mL) and benzene (10 mL) was added KOMe (0.66 g, 9.40 mmol). The mixture was heated to 70-80 C for 18 h, cooled to room temperature, and 1 M HCl (20 mL) was carefully added. The reaction mixture was extracted with a 9:1 (v:v) solution (40 mL) of hexane and benzene, dried over anhydrous Na SO , filtered, and concentrated under reduced pressure. The resulting red solid was diluted with hexane (30 mL) and washed with CH CN (10 mL X 3). The combined CH CN solution was <n="23"/>extracted again with hexanes. The hexane layers were combined and concentrated under reduced pressure to give beta-carotene of the Chemical Formula 2 (0.25 g, 0.47 mmol) in 100% crude yield. The crude product was purified by recrystallization from MeOH and THF to provide all-(E)-beta-carotene (0.20 g, 0.38 mmol) in 81% yield as a dark red crystal.
  • 24
  • 1,9,18-tris(benzenesulfonyl)-3,7,12,16-tetramethyl-1,18-bis(2,6,6-trimethyl-1-cyclohexen-1-yl)-3,7,11,15-octadecatetraene-2,17-diol, bis(1-ethoxyethyl) ether [ No CAS ]
  • [ 7235-40-7 ]
YieldReaction ConditionsOperation in experiment
70% With potassium methanolate; In cyclohexane; benzene; at 70 - 80℃; for 17h; Method C: Elimination Reaction from the Compound (P-3); To a stirred suspension of the bis(1-ethoxyethyl)ether (P-3) (0.10 g, 0.09 mmol) in cyclohexane (10 mL) and benzene (5 mL) was added KOMe (0.18 g, 2.60 mmol). The mixture was heated to 7080 C. for 17 h, cooled to room temperature, and 1 M HCl (5 mL) was carefully added. The reaction mixture was extracted with a 9:1 (v:v) solution (20 mL) of hexane and benzene, dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The resulting red solid was diluted with hexane (30 mL) and washed with CH3CN (10 mL×3). The combined CH3CN solution was extracted again with hexanes. The hexane layers were combined and concentrated under reduced pressure to give beta-carotene of the Chemical Formula 2 (46 mg, 0.086 mmol) in 99% crude yield. The crude product was purified by recrystallization from MeOH and THF to provide all-(E)-beta-carotene (32 mg, 0.059 mmol) in 70% yield as a dark red crystal.
70% With potassium methanolate; In cyclohexane; benzene; at 70 - 80℃; for 17h;Product distribution / selectivity; [141] Method C: Elimination reaction from the compound (P-3) [142] To a stirred suspension of the bis(l-ethoxyehtyl) ether (P-3) (0.10 g, 0.09 mmol) in cyclohexane (10 mL) and benzene (5 mL) was added KOMe (0.18 g, 2.60 mmol). The mixture was heated to 70-80 C for 17 h, cooled to room temperature, and 1 M HCl (5 mL) was carefully added. The reaction mixture was extracted with a 9:1 (v:v) solution (20 mL) of hexane and benzene, dried over anhydrous Na SO , filtered, and concentrated under reduced pressure. The resulting red solid was diluted with hexane (30 mL) and washed with CH CN (10 mL X 3). The combined CH CN solution was extracted again with hexanes. The hexane layers were combined and concentrated under reduced pressure to give beta-carotene of the Chemical Formula 2 (46 mg, 0.086 mmol) in 99% crude yield. The crude product was purified by recrystallization from MeOH and THF to provide all-(E)-beta-carotene (32 mg, 0.059 mmol) in 70% yield as a dark red crystal.
  • 25
  • 1,9,18-tris(benzenesulfonyl)-3,7,12,16-tetramethyl-1,18-bis(2,6,6-trimethyl-1-cyclohexen-1-yl)-3,7,11,15-octadecatetraene-2,17-diol, bis(methoxymethyl) ether [ No CAS ]
  • [ 7235-40-7 ]
YieldReaction ConditionsOperation in experiment
71% With potassium methanolate; In cyclohexane; benzene; at 70 - 80℃; for 18h; Method D: Elimination Reaction from the Compound (P-4); To a stirred solution of the bis(methoxymethyl)ether (P-4) (0.16 g, 0.14 mmol) in cyclohexane (10 mL) and benzene (5 mL) was added KOMe (0.19 g, 2.76 mmol). The mixture was heated to 7080 C. for 18 h, cooled to room temperature, and 1 M HCl (10 mL) was carefully added. The reaction mixture was extracted with a 9:1 (v:v) solution (30 mL) of hexane and benzene, dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The resulting red solid was diluted with hexane (30 mL) and washed with CH3CN (10 mL×X3). The combined CH3CN solution was extracted again with hexanes. The hexane layers were combined and concentrated under reduced pressure to give beta-carotene of the Chemical Formula 2 (67 mg, 0.13 mmol) in 91% crude yield. The crude product was purified by recrystallization from MeOH and THF to provide all-(E)-beta-carotene (53 mg, 0.10 mmol) in 71% yield as a dark red crystal.
71% With potassium methanolate; In cyclohexane; benzene; at 70 - 80℃; for 18h;Product distribution / selectivity; [143] Method D: Elimination reaction from the compound (P-4) [144] To a stirred solution of the bis(methoxymethyl) ether (P-4) (0.16 g, 0.14 mmol) in cyclohexane (10 mL) and benzene (5 mL) was added KOMe (0.19 g, 2.76 mmol). The mixture was heated to 70-80 C for 18 h, cooled to room temperature, and 1 M HCl (10 mL) was carefully added. The reaction mixture was extracted with a 9:1 (v:v) solution (30 mL) of hexane and benzene, dried over anhydrous Na SO , filtered, and concentrated under reduced pressure. The resulting red solid was diluted with hexane (30 mL) and washed with CH CN (10 mL X X3). The combined CH CN solution was extracted again with hexanes. The hexane layers were combined and concentrated under reduced pressure to give beta-carotene of the Chemical Formula 2 (67 mg, 0.13 mmol) in 91% crude yield. The crude product was purified by recrystallization from MeOH and THF to provide all-(E)-beta-carotene (53 mg, 0.10 mmol) in 71% yield as a dark red crystal.[145] The H NMR spectra of all-(E)-beta-carotene, which were prepared according to the above methods A-D, were identical to that of the authentic sample.
  • 26
  • 11,20-di(benzenesulfonyl)-11,12,19,20-tetrahydro-β-carotene [ No CAS ]
  • [ 7235-40-7 ]
YieldReaction ConditionsOperation in experiment
75% With sodium; In ethanol; toluene; Synthetic Example 6 beta-Carotene Sodium (674 mg, 29.3 mmol) was added to a stirred solution of 11,20-di(benzenesulfonyl)-11,12,19,20-tetrahydro-beta-carotene (F) (602 mg, 0.73 mmol) in EtOH (20 mL) under argon atmosphere. The reaction mixture was heated under reflux for 10 h with vigorous stirring. When the reaction was completed, the reaction mixture was concentrated under reduced pressure to remove most of the solvent. Toluene (50 mL) was added thereto to dissolve the residue, and the resultant mixture was washed with 1 M HCl, dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by flash chromatography over silica gel to give exclusively trans-beta-carotene of Chemical Formula 3 (295 mg, 0.55 mmol) in 75% yield.
  • 27
  • marigold oleoresin [ No CAS ]
  • cis-luteins [ No CAS ]
  • [ 7235-40-7 ]
  • [ 144-68-3 ]
  • [ 127-40-2 ]
  • [ 472-70-8 ]
YieldReaction ConditionsOperation in experiment
With potassium hydroxide; water; In ethanol; at 73 - 75℃; for 0.5h;Product distribution / selectivity; 25 Kgs of Marigold Oleoresin having 92.19gm/Kg or 9.22% of Xanthophylls is taken in 100 litres capacity reactor with an agitator. The Oleoresin is homogenised for 10 minutes under stirring at a temperature of 40 C with either steam or hot water in the jacket of the reactor as heating medium. Ethanolic KOH is prepared by taking 5Kgs of KOH with purity of 95% and dissolving it in 35 litres of Ethyl alcohol (1: 1.4 volumes). The prepared ethanolic KOH is added into reaction vessel slowly, containing the homogenised mass. The saponification reaction is carried out at a temperature of 75 C for 30 minutes. After ensuring the degree of saponification to be more than 99% by HPLC, 40 litres of demineralised hot water maintained at a temperature of 70 C is added to the reacted mass and the stirring is continued for 10 minutes. The diluted mass with carotenoid crystals is then pumped into a filter press to recover the crystals. Around 250 litres of additional hot water is pumped through the filter press to wash the unwanted impurities and bring down the pH of the effluent to neutral around 7.0. After ensuring the neutralisation, positive pressure of Nitrogen is applied to the filter press at pressure 1.25 Kg to squeeze the crystals trapped inside the filter. The wet crystals are then collected from the filter press plates into trays in a thin layer and dried in a tray drier at a temperature around 550C for 3 hours under normal pressure.The physical recovery of the final product is 6.76%. The Carotenoid crystals obtained contained 91.28% carotenoids (determined by spectrophotometer) of which 91.99% is all trans-Lutein, 6.90% all trans- EPO <DP n="12"/>Zeaxanthin, 0.27% cis-Luteins, 0.23% Beta Carotene and 0.5% Cryptoxanthin (determined by HPLC). The chemical recovery of the final product is 66.9%.The final product contained a moisture content of 0.57% and could not be detected for any traces of residual hexanes by gas chromatography analysis.; EXAMPLE 2:25.5Kgs of Marigold Oleoresin having 102.18gm/Kg or 10.22% of Xanthophylls is taken in 100 litres capacity reactor with an agitator.The Oleoresin is homogenised for 10 minutes under stirring at a temperature of 45C with either steam or hot water in the jacket of the reactor as heating medium. Ethanolic KOH is prepared by taking 5.1 Kgs of KOH with purity of 95% and dissolving it 40 litres of Ethyl alcohol (1: 1.56 volumes).The prepared Ethanolic KOH is added into reaction vessel slowly, containing the homogenised mass. The saponification reaction is carried out at a temperature of 73C for 30 minutes. After ensuring the degree of saponification to be more than 99% by HPLC, 45 litres of demineralised hot water maintained at a temperature of 65C is added to the reacted mass and the stirring is continued for 10 minutes. The diluted mass with carotenoid crystals is then pumped into a filter press to recover the crystals. Around 275 litres of additional hot water is pumped through the filter press to wash the unwanted impurities and bring down the pH of the effluent to neutral around 7.0. After ensuring the neutralisation, positive pressure of Nitrogen is applied to the filter press at pressure 1.2 Kg to squeeze the crystals trapped inside the filter. The wet crystals are then EPO <DP n="13"/>collected from the filter press plates into trays in a thin layer and dried in a tray drier at a temperature around 45C for 2 hours under vacuum at 600mm Hg.The physical recovery of the final product is 7.67%. The Carotenoid crystals obtained contained 93.76% carotenoids (determined by spectrophotometer) of which 92.86% is all trans-Lutein, 6.14% all trans- Zeaxanthin, 0.12% cis-Luteins, 0.22% Beta Carotene and 0.52% Cryptoxanthin (determined by HPLC). The chemical recovery of the final product is 70.53%.The final product contained a moisture content of 0.63% and could not be detected for any traces of residual hexanes by gas chromatography analysis.
  • 28
  • aqueous sodium chloride [ No CAS ]
  • [ 186194-14-9 ]
  • [ 5056-17-7 ]
  • beat-carotene [ No CAS ]
  • [ 7235-40-7 ]
YieldReaction ConditionsOperation in experiment
61% With potassium tert-butylate; In tetrahydrofuran; EXAMPLE XV Preparation of Beta-Carotene To a solution of 192 mg (0.564 mmole) of 3-methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4-pentadienylphosphonic acid, diethyl ester (produced in accordance with Example X) and 41 mg (0.25 mmole) of 2,7-dimethyl-2,4,6-octatrienedial (produced in accordance with Example XIV) in 2.25 mL of 8:1 (v/v) anhydrous tetrahydrofuran:dimethyl sulfoxide, protected from atmospheric moisture and maintained at a temperature of approximately 5 C. by use of an external ice water bath, was added 59 mg (0.526 mmole) of potassium tert-butoxide. This mixture was subsequently stirred in the cold for 15 minutes and then at room temperature for 3.5 hours. The product was isolated by dilution of the mixture with 25 mL of 4:1 (v/v) ether:dichloromethane and subsequent washing of the organic layer with 25 mL portions of 10% aqueous sodium chloride (3*25 mL). The organic layer was then dried over anhydrous magnesium sulfate and filtered. Removal of the volatile organic solvents by evaporation at reduced pressure, followed by filtration through a small column of silica gel (10 mL, 60-200 mesh, elution with 40 mL of 3:1 (v/v) hexane:benzene) to remove any unreacted starting materials afforded 82 mg (61% yield) of deep-purple crystals, identified by NMR analysis as beat-carotene: mp 183-185 C.
  • 29
  • [ 116-31-4 ]
  • [ 15647-89-9 ]
  • [ 7235-40-7 ]
YieldReaction ConditionsOperation in experiment
With sodium; In methanol; ethanol; dichloromethane; EXAMPLE 9 13.6 parts by weight of triphenyl-phosphonium chloride are dissolved in 100 parts by volume of absolute ethanol and, while stirring in a nitrogen atmosphere, simultaneously treated dropwise with a solution of 7 parts by weight of vitamin A aldehyde in 100 parts by volume of absolute ethanol and a solution of 0.6 parts by weight of sodium in 15 parts by volume of absolute methanol. After 2 hours the resulting red precipitate is filtered off, washed with water and dissolved in methylene chloride. The methylene chloride solution is filtered after drying over sodium sulfate and carefully evaporated. By spraying in ethanol there are obtained violet crystals of beta-carotene. After recrystallization from benzene/ethanol, there are obtained 9.4 parts by weight of beta-carotene of melting point 177-179 (abs. max. 453, 480 mmu, E11 = 2510, 2185 in petroleum ether).
  • 30
  • 5-(4-ethylenedioxy-2,6,6-trimethyl-1-cyclohexen-1-yl)-3-methyl-2,4-pentadienal [ No CAS ]
  • 2,7-dimethyl-2,4,6-octatrienylene bis(triphenyl-phosphonium bromide) [ No CAS ]
  • [ 7235-40-7 ]
YieldReaction ConditionsOperation in experiment
With sodium methylate; In methanol; A. 2.5 g. of sodium methoxide was added over 1 hour at 0-5 to a solution containing 6 g. of 5-(4-ethylenedioxy-2,6,6-trimethyl-1-cyclohexen-1-yl)-3-methyl-2,4-pentadienal and 7.5 g. of 2,7-dimethyl-2,4,6-octatrienylene bis(triphenyl-phosphonium bromide) dissolved in 50 ml. of methanol. After the addition, the resulting mixture was stirred under nitrogen for 2 hours. After this period, 2 g. more of this phosphonium bromide salt and another 0.5 g. of sodium methoxide were added to the mixture. Stirring was continued for an additional 4 hours at 0-5. The precipitated carotene was collected, washed with methanol and water, and recrystallized from benzene-methanol solvent mixture. This product was identified as 3,3,3',3'-Bis(ethylenedioxy)-trans-beta-carotene.
  • 31
  • aqueous sodium thiosulphate [ No CAS ]
  • [ 7235-40-7 ]
  • [ 108-90-7 ]
  • [ 514-78-3 ]
YieldReaction ConditionsOperation in experiment
With dihydrogen peroxide; iodine; In water; Example 2 Production of canthaxanthin from beta-Carotene with monochlorobenzene as solvent A three neck flask, equipped with a dropping funnel, a thermometer and a reflux condenser, was charged beta-Carotene (1 g, 1.863 mmol, 97%), monochlorobenzene (20 ml, 22.14 g), hydrogen peroxide (30% wt; 4.2 eq; 7.823 mmol, 0.90 ml, 0.99 g). The reaction mixture was then stirred at ambient temperature and solid iodine (0.25 eq, 0.4655 mmol, 118 mg) was then added in one portion. The resulting mixture was stirred for 90 minutes. At this time, beta-Carotene disappeared and the pH of the solution was 7. The resulting reaction mixture was allowed to stand still to separate into the 2 phases (upper phase = water; lower phase = organic phase). The organic phase was collected and washed successively with 15 ml of 2% aqueous sodium thiosulphate solution and 15 ml of water. The solvent was removed under reduced pressure affording 1.1 g of the crude crystalline product that was identified as canthaxanthin (mixture of isomers) by HPLC (Figure 2).
  • 32
  • thiosulphate [ No CAS ]
  • [ 7235-40-7 ]
  • [ 514-78-3 ]
YieldReaction ConditionsOperation in experiment
With dihydrogen peroxide; iodine; In chlororform; chloroform; Example 1 Production of canthaxanthin from beta-Carotene with chloroform as solvent A three neck flask, equipped with a dropping funnel, a thermometer and a reflux condenser, was charged beta-Carotene (1.988g, 3.59mmol, 97%), chloroform (70 ml, 103.7 g), hydrogen peroxide (30% wt; 4.09 eq; 14.69 mmol, 1.5ml, 1.665g). The reaction mixture was then stirred at ambient temperature and iodine solution (0.25 eq, 0.90 mmol, 0.228g in 6ml of chlororform) was then added in one portion. The resulting mixture was stirred for 5 hours. At this time, the beta-Carotene disappeared and the pH of the solution was 7. 20ml of thiosulphate solution was then added and the resulting mixture stirred for 15 minutes. The mixture was then allowed to stand still to allow separation into the 2 phases (upper phase = water; lower phase = organic phase). The organic phase was collected and the solvent removed under reduced pressure affording the crude crystalline product. This crude product was mixed with 7.5ml of acetone and heated under refluxed over night. After cooling to 4C, the cristalline canthaxanthine was collected by filtration (837mg, Yield 40%, all trans>98%) Analysis by HPLC verified that the product was canthaxanthine (Figure 1). The mother liquor contained canthaxanthine as a mixture of isomers (trans/cis ratio 50/50).
  • 33
  • [ 870636-66-1 ]
  • [ 7235-40-7 ]
  • [ 18526-49-3 ]
YieldReaction ConditionsOperation in experiment
29% With potassium methanolate; In cyclohexane; at 50 - 60℃; for 6h;Product distribution / selectivity; Method B.; To a stirred solution of the C40 THP diether (G-2) (1.50 g, 1.46 mmol) in cyclohexane (50 mL) was added KOMe (2.05 g, 29.25 mmol). The mixture was heated to 50 C.60 C. for 6 h, and cooled to room temperature. The mixture was then diluted with hexanes/benzene, washed with 1 M HCl solution, dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude product (1.26 g), which was consisted of a 4:1 mixture of all-(E) and 13-(Z) stereoisomers, was purified by SiO2 flash column chromatography (hexanes:EtOAc=32:1) to give all-(E)-beta-carotene (228 mg, 0.42 mmol) in 29% yield as a red solid.
  • 34
  • [ 870636-68-3 ]
  • [ 7235-40-7 ]
  • [ 18526-49-3 ]
YieldReaction ConditionsOperation in experiment
84% With potassium methanolate; In cyclohexane; at 80℃; for 16h;Product distribution / selectivity; Method D.; To a stirred solution of the C40 MOM diether (G-4) (0.945 g, 1.0 mmol) in cyclohexane (25 mL) was added KOMe (1.403 g, 20.0 mmol). The mixture was heated to 80 C. for 16 h, and cooled to room temperature. The mixture was then diluted with hexanes, washed 3 times with H2O, dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude product (0.548 g), which was consisted of a 4:1 mixture of all-(E) and 13-(Z) stereoisomers, was purified by recrystallization (THF:MeOH=1:5) to give all-(E)-beta-carotene (0.453 g, 0.84 mmol) in 84% yield as a red solid.
  • 35
  • [ 870636-64-9 ]
  • [ 7235-40-7 ]
  • [ 18526-49-3 ]
YieldReaction ConditionsOperation in experiment
38% With potassium methanolate; In cyclohexane; at 60 - 80℃; for 8.5h;Product distribution / selectivity; EXAMPLE 11; beta-carotene (Chemical Formula 2); Method A.; To a stirred suspension of the crude C40 dibromide (G-1) (1.34 g, 1.36 mmol) in cyclohexane (40 mL) was added KOMe (2.00 g, 28.48 mmol). The mixture was heated to 60 C.80 C. for 8.5 h, and cooled to room temperature. The mixture was then diluted with hexanes/benzene, washed with H2O and 1 M HCl solution, dried over Na2SO4, filtered, and concentrated under reduced pressure to give a dark-red solid (779 mg). The crude product was purified by dissolving in hexanes (60 mL) and washing with MeCN (30 mL×3). The MeCN layer was extracted again with hexanes, and the combined hexanes layer was concentrated under reduced pressure to give beta-carotene (584 mg, 1.09 mmol) in 80% yield as a red solid, which was consisted of a 4:1 mixture of all-(E) and 13-(Z) stereoisomers. The product was further purified by SiO2 flash column chromatography to give all-(E)-beta-carotene in 38% yield
  • 36
  • all-(E)-5,14-bis(benzenesulfonyl)-3,7,12,16-tetramethyl-1,18-bis(2,6,6-trimethyl-1-cyclohexenyl)octadeca-1,3,9,15,17-pentene-6,13-diol bis(1-ethoxyethyl)ether [ No CAS ]
  • [ 7235-40-7 ]
  • [ 18526-49-3 ]
YieldReaction ConditionsOperation in experiment
70% With potassium methanolate; In cyclohexane; at 80℃; for 16h;Product distribution / selectivity; Method C.; To a stirred solution of the C40 1-ethoxyethyl diether (G-3) (0.6 g, 0.6 mmol) in cyclohexane (20 mL) was added KOMe (0.842 g, 12.0 mmol). The mixture was heated to 80 C. for 16 h, and cooled to room temperature. The mixture was then diluted with hexanes, washed 3 times with H2O, dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude product (0.317 g), which was consisted of a 4:1 mixture of all-(E) and 13-(Z) stereoisomers, was purified by recrystallization (THF:MeOH=1:5) to give all-(E)-beta-carotene (0.226 g, 0.42 mmol) in 70% yield as a red solid.
  • 37
  • [ 7235-40-7 ]
  • [ 247257-17-6 ]
  • [ 1225465-67-7 ]
  • 38
  • [ 7235-40-7 ]
  • [ 247257-17-6 ]
  • C74H90O9S [ No CAS ]
  • 39
  • [ 7235-40-7 ]
  • [ 17092-92-1 ]
  • [ 7500-42-7 ]
  • [ 79-77-6 ]
  • [ 432-25-7 ]
  • [ 36340-49-5 ]
YieldReaction ConditionsOperation in experiment
With dihydrogen peroxide; sodium acetate In water at 27℃; for 1h; Enzymatic reaction;
  • 40
  • [ 7235-40-7 ]
  • [ 24951-77-7 ]
  • [ 1332483-34-7 ]
  • [ 1332483-20-1 ]
  • cholesteryl (12Z)-14'-apo-β-caroten-14'-oate [ No CAS ]
  • [ 1332483-25-6 ]
YieldReaction ConditionsOperation in experiment
With Hoveyda-Grubbs catalyst second generation; In toluene; at 20℃; for 24h;Inert atmosphere; General procedure: To the solution of a polyene (c=9.7×10-2 or 4.9×10-2 M) and of Hoveyda (Grubbs) second generation catalyst (15 mol %) in dry toluene (or dichloromethane or methanol) olefin (1-4 equiv) was added dropwise. The reaction mixture was stirred at rt under argon atmosphere. Then the mixture was analyzed by HPLC and purified by semipreparative HPLC or column chromatography.
  • 41
  • [ 7235-40-7 ]
  • [ 1332483-19-8 ]
  • [ 1332483-22-3 ]
  • [ 1332483-27-8 ]
YieldReaction ConditionsOperation in experiment
22%; 32% With Hoveyda-Grubbs catalyst second generation; In toluene; at 20℃; for 96h;Inert atmosphere; General procedure: To the solution of a polyene (c=9.7×10-2 or 4.9×10-2 M) and of Hoveyda (Grubbs) second generation catalyst (15 mol %) in dry toluene (or dichloromethane or methanol) olefin (1-4 equiv) was added dropwise. The reaction mixture was stirred at rt under argon atmosphere. Then the mixture was analyzed by HPLC and purified by semipreparative HPLC or column chromatography.
  • 42
  • [ 7235-40-7 ]
  • [ 1332483-18-7 ]
  • [ 133784-86-8 ]
  • [ 1332483-24-5 ]
YieldReaction ConditionsOperation in experiment
33%; 57% With Hoveyda-Grubbs catalyst second generation; In toluene; at 20℃; for 96h;Inert atmosphere; General procedure: To the solution of a polyene (c=9.7×10-2 or 4.9×10-2 M) and of Hoveyda (Grubbs) second generation catalyst (15 mol %) in dry toluene (or dichloromethane or methanol) olefin (1-4 equiv) was added dropwise. The reaction mixture was stirred at rt under argon atmosphere. Then the mixture was analyzed by HPLC and purified by semipreparative HPLC or column chromatography.
  • 43
  • [ 1968-40-7 ]
  • [ 7235-40-7 ]
  • ethyl (11Z)-13-nor-13,14-dihydroretinoate [ No CAS ]
  • [ 1332483-21-2 ]
  • ethyl (15Z)-12'-apo-13'-nor-13',14'-dihydro-β-caroten-12'-oate [ No CAS ]
  • [ 1332483-26-7 ]
YieldReaction ConditionsOperation in experiment
With Hoveyda-Grubbs catalyst second generation; In toluene; at 20℃; for 96h;Inert atmosphere; General procedure: To the solution of a polyene (c=9.7×10-2 or 4.9×10-2 M) and of Hoveyda (Grubbs) second generation catalyst (15 mol %) in dry toluene (or dichloromethane or methanol) olefin (1-4 equiv) was added dropwise. The reaction mixture was stirred at rt under argon atmosphere. Then the mixture was analyzed by HPLC and purified by semipreparative HPLC or column chromatography.
  • 44
  • [ 7235-40-7 ]
  • [ 1733-40-0 ]
  • N-phenyl-13-apo-β-caroten-13-amide [ No CAS ]
  • [ 1332483-23-4 ]
  • N-phenyl-14'-apo-β-caroten-14'-amide [ No CAS ]
  • [ 1332483-28-9 ]
YieldReaction ConditionsOperation in experiment
With Hoveyda-Grubbs catalyst second generation; In dichloromethane; toluene; at 20℃; for 72h;Inert atmosphere; General procedure: To the solution of a polyene (c=9.7×10-2 or 4.9×10-2 M) and of Hoveyda (Grubbs) second generation catalyst (15 mol %) in dry toluene (or dichloromethane or methanol) olefin (1-4 equiv) was added dropwise. The reaction mixture was stirred at rt under argon atmosphere. Then the mixture was analyzed by HPLC and purified by semipreparative HPLC or column chromatography.
  • 45
  • [ 7235-40-7 ]
  • [ 1483-88-1 ]
  • [ 1332483-23-4 ]
  • N-phenyl-14'-apo-β-caroten-14'-amide [ No CAS ]
  • [ 1332483-28-9 ]
YieldReaction ConditionsOperation in experiment
13% With Hoveyda-Grubbs catalyst second generation; In toluene; at 20℃; for 72h;Inert atmosphere; General procedure: To the solution of a polyene (c=9.7×10-2 or 4.9×10-2 M) and of Hoveyda (Grubbs) second generation catalyst (15 mol %) in dry toluene (or dichloromethane or methanol) olefin (1-4 equiv) was added dropwise. The reaction mixture was stirred at rt under argon atmosphere. Then the mixture was analyzed by HPLC and purified by semipreparative HPLC or column chromatography.
  • 46
  • (1E,3E,5E,7E)-2-(3,7-dimethyldeca-1,3,5,7,9-pentaenyl)-1,3,3-trimethylcyclohex-1-ene [ No CAS ]
  • [ 22255-47-6 ]
  • [ 7235-40-7 ]
  • [ 43219-55-2 ]
  • [ 70244-78-9 ]
  • 47
  • (1E,3E,5E,7E)-2-(3,7-dimethyldeca-1,3,5,7,9-pentaenyl)-1,3,3-trimethylcyclohex-1-ene [ No CAS ]
  • [ 7235-40-7 ]
  • [ 43219-55-2 ]
  • [ 70244-78-9 ]
  • 48
  • [ 1427286-50-7 ]
  • [ 256518-16-8 ]
  • [ 7235-40-7 ]
  • 49
  • [ 1427286-50-7 ]
  • [ 1427286-52-9 ]
  • [ 7235-40-7 ]
  • 50
  • [ 5056-17-7 ]
  • [ 62285-98-7 ]
  • [ 7235-40-7 ]
YieldReaction ConditionsOperation in experiment
65 g [(2E,4E)-3-methyl-5-(2,6,6-trimethyl-l-cyclohexenyl)-2,4-pentadienyl]triphenyl- phosphonium bromide (182.8 g), 2, 7-dimethyl-2,4,6-octatrien-l , 8-dial (25 g) was added to methylene chloride (1000 mL) at 15-25C and stirred for 15 min. Sodium methoxide solution (20.53g/82.1 mL) was added to the reaction mass in 2 hr at 15-25C then stirredU for 3 hr at 25-35C. After reaction completion, 10% ammonium chloride solution (500 mL) was added to the reaction mass at 25-35C and stirred for 15 min. The reaction mass was filtered through celite and washed with methylene chloride. The organic and aqueous layers were separated from filtrate and separated organic layer was washed with water. In another flask arranged with downward distillation, DM water (625 mL) was added and heated to 75-80C. The above separated organic layer was added into the hot water under slow purge of nitrogen at 75-80C and simultaneously solvent from the reaction mass was distilled off. The reaction mass was further heated to 85-95C and maintained for 30 min to remove of methylene chloride traces by distillation under slow nitrogen purging. Then the reaction mass was cooled to 50C, methanol (1250 mL) was added and stirred for an hour at reflux. The reaction mass was cooled to 25-35C. The solid obtained was filtered, washed with methanol, suck dried for an hour and finally dried at 60-65C under vacuum for 4 hr. The above dried material was added into n-butanol (250 mL) at 25-35C, heated the reaction mass to 100-105C and stirred for an hour at reflux. The reaction mass was cooled to 45-55C and methanol (750 mL) was added to it. Then the reaction mass was heated to 65-70C and stirred at reflux for an hour. Finally the reaction mass was cooled to 25-35C, filtered off the solid, washed with methanol and suck dried for an hour. The solid was further dried under vacuum at 60-65 C for 6 hr to get 65 g of beta-carotene. Total isomer content by HPLC: 99.22%.
  • 51
  • [ 7235-40-7 ]
  • [ 461-11-0 ]
YieldReaction ConditionsOperation in experiment
106.9 g With oxygen; In ethyl acetate; at 68℃; for 66h; <strong>[7235-40-7]beta-carotene</strong> (80 g) was placed in a 3-neck flask with stir bar, reflux condenser, O2 inlet (glass tube), and a temperature probe connected to a heating mantle to monitor and adjust the temperature as needed. Ethyl acetate (2 L) was added, O2 was bubbled through and the mixture was stirred and heated to 68C. After 66 h, the absorbance of a sample was measured as 0.36 at 380 nm using a 1 mm cuvette at ca.lO g/L, indicating the reaction was complete13. The reaction was stopped and the clear, light orange liquid was cooled to room temp and split between two 1-L round bottom flasks. Solvent was removed on the rotary evaporator at 40 C down to a pressure of 30 mm Hg, and the resulting syrup was dried under vacuum for 10 h to give a sticky orange solid (106.9 g) as OxBC.
  • 52
  • (1E,3E,5E,7E)-2-(3,7-dimethyldeca-1,3,5,7,9-pentaenyl)-1,3,3-trimethylcyclohex-1-ene [ No CAS ]
  • methyl (2E,4E)-4-methylocta-2,4,6-trienoate [ No CAS ]
  • [ 7235-40-7 ]
  • [ 69774-12-5 ]
YieldReaction ConditionsOperation in experiment
58%; 24% With Hoveyda-Grubbs catalyst second generation; In toluene; at 25℃; for 7h; General procedure: To a solution of (1E,3E,5E,7E)-2-(3,7-dimethyldeca-1,3,5,7,9-pentaenyl)-1,3,3-trimethylcyclohex-1-ene 12 (14 mg, 0.049 mmol) and butyl (E)-but-2-enoate 13 (46.4 muL, 0.294 mmol) in toluene (0.25mL), 2nd generation Hoveyda-Grubbs catalyst (0.46 mg, 0.0073 mmol) was added and the reaction mixture was thoroughly degassed. After stirring at 25C for 4.5h, the mixture was filtered through a Celite pad, which was washed with Et2O and the solvent was evaporated. The residue was purified by column chromatography (silica gel, 99:1 hexane/EtOAc) to afford, in order of elution, 2.2 mg (16%) of a red solid identified as beta,beta-carotene 1, 11.8 mg (62%) of a red oil identified as butyl (2E,4E,6E,8E,10E)-5,9-dimethyl-11-(2,6,6-trimethylcyclohex-1-en-1-yl)undeca-2,4,6,8,10-pentaenoate 15 and 0.2 mg (1%) of a yellow oil identified as butyl (2E,4E,6E)-5-methyl-7-(2,6,6-trimethylcyclohex-1-en-1-yl)hepta-2,4,6-trienoate 14. Data for beta,beta-carotene (1)
  • 53
  • [ 591-63-9 ]
  • (1E,3E,5E,7E)-2-(3,7-dimethyldeca-1,3,5,7,9-pentaenyl)-1,3,3-trimethylcyclohex-1-ene [ No CAS ]
  • [ 7235-40-7 ]
  • butyl (2E,4E,6E,8E,10E)-5,9-dimethyl-11-(2,6,6-trimethylcyclohex-1-en-1-yl)undeca-2,4,6,8,10-pentaenoate [ No CAS ]
  • butyl (2E,4E,6E)-5-methyl-7-(2,6,6-trimethylcyclohex-1-en-1-yl)hepta-2,4,6-trienoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
16%; 62%; 1% With Hoveyda-Grubbs catalyst second generation; In toluene; at 25℃; for 4.5h; To a solution of (1E,3E,5E,7E)-2-(3,7-dimethyldeca-1,3,5,7,9-pentaenyl)-1,3,3-trimethylcyclohex-1-ene 12 (14 mg, 0.049 mmol) and butyl (E)-but-2-enoate 13 (46.4 muL, 0.294 mmol) in toluene (0.25mL), 2nd generation Hoveyda-Grubbs catalyst (0.46 mg, 0.0073 mmol) was added and the reaction mixture was thoroughly degassed. After stirring at 25C for 4.5h, the mixture was filtered through a Celite pad, which was washed with Et2O and the solvent was evaporated. The residue was purified by column chromatography (silica gel, 99:1 hexane/EtOAc) to afford, in order of elution, 2.2 mg (16%) of a red solid identified as beta,beta-carotene 1, 11.8 mg (62%) of a red oil identified as butyl (2E,4E,6E,8E,10E)-5,9-dimethyl-11-(2,6,6-trimethylcyclohex-1-en-1-yl)undeca-2,4,6,8,10-pentaenoate 15 and 0.2 mg (1%) of a yellow oil identified as butyl (2E,4E,6E)-5-methyl-7-(2,6,6-trimethylcyclohex-1-en-1-yl)hepta-2,4,6-trienoate 14. Data for beta,beta-carotene (1): 1H NMR (400MHz, C6D6): delta 6.79 (dd, J=14.8, 11.4Hz, 2H, 2H11), 6.70-6.67 (m, 2H, H15), 6,49 (d, J=14.8Hz, 2H, H12), 6.42-6.31 (m, 8H, 2H7+2H8+ 2H10+2H14), 1.99 (t, J=5.6Hz, 4H, 2× CH2), 1.94 (s, 6H, 2× CH3), 1.88 (s, 6H, 2× CH3), 1.82 (s, 6H, 2× CH3), 1.64-1.56 (m, 4H, 2× CH2), 1.52-1.49 (m, 4H, 2× CH2), 1.16 (s, 12H, 4× CH3) ppm. HRMS (ESI+): Calcd. for C40H56 ([M+H]+), 536.4376; found, 536.4376. UV (MeOH): lambdamax 449, 241nm. Data for butyl (2E,4E,6E,8E,10E)-5,9-dimethyl-11-(2,6,6-trimethylcyclohex-1-en-1-yl)undeca-2,4,6,8,10-pentaenoate (15): 1H NMR (400MHz, CO(CD3)2): delta 7.71 (dd, J=15.0, 12.0Hz, 1H, H15), 7.02 (dd, J=15.0, 11.4Hz, 1H, H11), 6.48 (d, J=15.0Hz, 1H, H12), 6.34 (d, J=11.8Hz, 1H, H14), 6.42-6.18 (m, 3H, H7+H8+H10), 5.97 (d, J=15.0Hz, 1H, H15?), 4.16 (t, J=6.6Hz, 2H, O-CH2-), 2.13 (s, 3H, CH3), 2.10-2.06 (m, 2H, CH2), 2.06 (s, 3H, CH3), 1.75 (s, 3H, CH3), 1.72-1.61 (m, 4H, 2× CH2), 1.54-1.48 (m, 2H, CH2), 1.47-1.39 (m, 2H, CH2), 1.07 (s, 6H, 2× CH3), 0.97 (t, J=7.4Hz, 3H, CH2CH3) ppm. 13C NMR (100MHz, (CD3)2CO): 167.4 (s), 145.2 (s), 140.8 (d), 138.8 (s), 138.7 (s), 138.6 (d), 137.0 (d), 131.4 (d), 130.1 (s), 129.5 (d), 129.4 (d), 128.4 (d), 121.4 (d), 64.4 (t), 40.4 (t), 34.9 (s), 33.6 (t), 31.6 (t), 29.3 (q, 2×), 21.9 (q), 19.9 (t), 19.8 (t), 14.0 (q), 13.1 (q), 12.9 (q) ppm. HRMS (ESI+): Calcd. for C26H39O2 ([M+H]+), 383.2945; found, 383.2946. IR (NaCl): nu 2957 (m, C-H), 2928 (m, C-H), 2866 (w, C-H), 1708 (s, C=O), 1615 (m), 1563 (m), 1135 (s), 970 (m)cm-1. UV (MeOH): lambdamax 394nm. Data for butyl (2E,4E,6E)-5-methyl-7-(2,6,6-trimethylcyclohex-1-en-1-yl)hepta-2,4,6-trienoate (14): 1H NMR (400MHz, CDCl3): delta 7.71 (dd, J=15.0, 11.8Hz, 1H, H3), 6.38 (d, J=16.1Hz, 1H, H6 or H7), 6.18-6.10 (m, 2H, H6 or H7+H4), 5.87 (d, J=15.5Hz, 1H, H2), 4.16 (t, J=6.7Hz, 2H, O-CH2), 2.04 (s, 3H, CH3), 2.05-1.95 (m, 2H, CH2), 1.71 (s, 3H, CH3), 1.68-1.58 (m, 4H, 2× CH2), 1.50-1.37 (m, 4H, 2× CH2), 1.03 (s, 6H, 2× CH3), 0.95 (t, J=7.4Hz, 3H, CH2CH3) ppm. 13C NMR (100MHz, CDCl3): delta 167.8 (s), 144.4 (s), 140.7 (d), 137.6 (s), 136.9 (d), 130.9 (s), 130.8 (d), 127.4 (d), 120.2 (d), 64.3 (t), 39.7 (t), 34.4 (s), 33.3 (t), 30.9 (t), 29.1 (q, 2×), 21.9 (q), 19.4 (t), 19.3 (t), 13.9 (q), 13.2 (q) ppm. HRMS (ESI+): Calcd. for C21H33O2 ([M+H]+), 317.2475; found, 317.2472. IR (NaCl): nu 2958 (m, C-H), 2929 (m, C-H), 1711 (s, C=O), 1598 (m), 1144 (m), 977 (m)cm-1. UV (MeOH): lambdamax 329nm.
  • 54
  • [ 122057-55-0 ]
  • (1E,3E,5E,7E)-2-(3,7-dimethyldeca-1,3,5,7,9-pentaenyl)-1,3,3-trimethylcyclohex-1-ene [ No CAS ]
  • [ 7235-40-7 ]
  • methyl (2E,4E,6E,8E,10E,12E)-2,7,11-trimethyl-13-(2,6,6-trimethylcyclohex-1-en-1-yl)trideca-2,4,6,8,10,12-hexaenoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
10%; 40% With Hoveyda-Grubbs catalyst second generation; In toluene; at 25℃; for 7h; General procedure: To a solution of (1E,3E,5E,7E)-2-(3,7-dimethyldeca-1,3,5,7,9-pentaenyl)-1,3,3-trimethylcyclohex-1-ene 12 (14 mg, 0.049 mmol) and butyl (E)-but-2-enoate 13 (46.4 muL, 0.294 mmol) in toluene (0.25mL), 2nd generation Hoveyda-Grubbs catalyst (0.46 mg, 0.0073 mmol) was added and the reaction mixture was thoroughly degassed. After stirring at 25C for 4.5h, the mixture was filtered through a Celite pad, which was washed with Et2O and the solvent was evaporated. The residue was purified by column chromatography (silica gel, 99:1 hexane/EtOAc) to afford, in order of elution, 2.2 mg (16%) of a red solid identified as beta,beta-carotene 1, 11.8 mg (62%) of a red oil identified as butyl (2E,4E,6E,8E,10E)-5,9-dimethyl-11-(2,6,6-trimethylcyclohex-1-en-1-yl)undeca-2,4,6,8,10-pentaenoate 15 and 0.2 mg (1%) of a yellow oil identified as butyl (2E,4E,6E)-5-methyl-7-(2,6,6-trimethylcyclohex-1-en-1-yl)hepta-2,4,6-trienoate 14. Data for beta,beta-carotene (1)
  • 55
  • [ 68-26-8 ]
  • [ 7235-40-7 ]
YieldReaction ConditionsOperation in experiment
64.42% 120.1 g of vitamin A alcohol mother liquor (135.92 million IU/g, 0.171 mol) and 20.7 ml of pyridine (0.257 mol) were dissolved in 500 ml of methanol to prepare a vitamin A alcohol-methanol solution. In a three-necked flask, 89.7 g (0.342 mol) of triphenylphosphine and 700 ml of methanol were respectively added, and the temperature was lowered to 5C. 39.5 ml of HBr (mass concentration 47%, 0.342 mol) was slowly added dropwise to the dropping funnel to control the dropping temperature at 5C, stirring was continued for 5 h after the addition was completed, and a vitamin A alcohol-methanol solution was added, and the temperature was raised to 35 C for 30 h to obtain a vitamin A triphenylphosphonium bromide reaction solution. Take 81.4g of sodium persulfate (0.342mol) and 407 g water was added. The above-mentioned vitamin A triphenylphosphonium bromide reaction solution is pumped with nitrogen for three times and the temperature is lowered to 8C. Then sodium persulfate solution is added dropwise, and the stirring is completed for 15 minutes. Afterwards, 15% w/w sodium carbonate solution (544 g, 0.770 mol) was added dropwise. The stirring was continued for 3 h at 10 C., then the temperature was raised to 20 C. and stirring was continued for 3 h to stop the reaction. The temperature was raised to 40C and filtered. The filter cake was added with 600 ml of ethyl propionate. The nitrogen was evacuated three times, and the temperature was raised to reflux. The reaction was allowed to proceed for 18 hours. The reaction was cooled to room temperature, filtered, and vacuum dried at 50 C. to obtain 29.6 g of beta-carotene. Positive red crystalline solid. Analysis using GB5009.83-2016 showed that the content of beta-carotene was 99.91% and the yield was 64.42%.
  • 56
  • [ 127-47-9 ]
  • [ 7235-40-7 ]
YieldReaction ConditionsOperation in experiment
90.6% Add 49 g of 98% vitamin A acetate (2.8 million IU, 0.147 mol), 40.5 g of triphenylphosphine (0.154 mol), and 300 g of methanol to a 1 L three-necked flask, and cool to 0 C in an ice-water bath with stirring. 15.8 g of concentrated sulfuric acid (0.16 mol) was slowly added dropwise below 5 C, and the dripping was completed in about 0.5 h. After that, the temperature was kept under stirring for 10 h, and the reaction liquid became an orange transparent liquid. Add 150g of deionized water and extract with n-hexane (100g * 3 times). The lower layer is a reaction solution containing vitamin A triphenylphosphine salt (a methanol-aqueous solution of VA triphenylphosphine salt). It is 15.8% of vitamin A triphenylphosphine salt, 54.0% of methanol, 27.0% of water, 3.2% of undefined impurities; the conversion rate of raw material vitamin A acetate is more than 99%.An ethanol-water solution of VA triphenylphosphine salt (181.5 g, of which VA triphenylphosphine salt 22.1 g, 0.035 mol) obtained in Example 2 was added to a 1 L autoclave, and the coupling was performed according to the conditions in Example 5. The reaction is different in that 330 g of dichloromethane, 15.7 mg of palladium acetate (molar amount is 0.2% of VA triphenylphosphine salt), and 198.5 mg of beta-cyclodextrin (molar amount of VA triphenyl) 0.5% of phosphine salt), reacted in the kettle for 8h, after the reaction was completed, 17.4g of red beta-carotene product was obtained, and the purity was 98.4% by HPLC.The beta-carotene selectivity was 92%. Based on the vitamin A acetate of the raw material of Example 2, the total beta-carotene yield was 90.6%.
58.75% Take 90g Vitamin A acetate (2,213,000 IU / g, 0.208mol) and 48.4 g of aniline (0.52 mol) was dissolved in 1100ml of ethanol, dubbed vitamin A acetate-ethanol solution. In a three-necked flask were added triphenylphosphine 218.2g (0.832mol), respectively, 2300 ml of ethanol, cooled to 10C, the dropping funnel was slowly added dropwise 51.5 ml of concentrated hydrochloric acid (concentration of 37.5%, 0.624mol), was added dropwise a temperature controlled 10C, dropwise addition continued stirred for 2h. vitamin A acetate -ethanol solution was added, 25C for 24 h, to give vitamin A triphenyl phosphine chloride solution. Vitamin A solution of triphenyl phosphine chloride was evacuated three times with nitrogen up, down to 5 , was slowly added dropwise 1% w / w of the peracetic acid solution (3164g, 0.416mol), dropwise with stirring after the dropwise addition of 30% w 15min / w solution of sodium hydroxide (138.7g, 1.04mol), dropwise stirring was continued for 5 2h, then warmed to 20 stirring was continued for 3h, the reaction was stopped.Warmed to 40 filtered, the filter cake was added to 500ml of ethanol, was evacuated fill nitrogen three times, heated at reflux, the reaction for 20 h, cooled to room temperature, filtered, and dried 50 deg.] C under vacuum to afford beta- carotene 33.53g, appearance of a dark red crystalline solid GB 5009.83-2016 method of analysis, the results indicate that beta- carotene content of 97.83%, a yield of 58.75%.
  • 57
  • C38H44ClP [ No CAS ]
  • (R)-9-cis-13,14-dihydro-retinal [ No CAS ]
  • [ 7235-40-7 ]
YieldReaction ConditionsOperation in experiment
67% To a solution of phosphonium salt (VII) (24.9 mg, 0.044 mmol) in THF (0.20 nt) at -78 C was added hBuLi (0.027 mL, 0.044 mmol, 1.6 M in hexane) and the mixture was stirred for 30 mm. Then a solution of 9-cis-retinal V (9.0 mg, 0.03 1 mmcl) in THF (0.13 mL) was added and the mixture was stirred for 1 h at -78 C and 30 mm at 25 C. Water was added and the mixture was extracted with Et20 (3x). Thecombined organic layers were washed with brine (2x) and dried (Na2SO4) and the solvent was evaporated. The residue was purified by column chromatography (C 18-silica gel, CH3CN) to afford 11.3 mg (67%) of a red foam identified as 9-cis-B,B-carotene (VIII). The spectroscopic data are identical to those previously published (LIT).
  • 58
  • [ 7235-40-7 ]
  • [ 79-77-6 ]
  • [ 640-49-3 ]
  • [ 432-25-7 ]
  • [ 1107-26-2 ]
  • [ 36340-49-5 ]
YieldReaction ConditionsOperation in experiment
With tert.-butylhydroperoxide; mu-carbido-bis[(5,10,15,20-tetraphenyl-21H,23H-porphyrinato)iron(IV)]; In benzene; at 24.84℃;Kinetics; The apparent rate constants kapp and the rate constantsk of carotene oxidation at 298 K were determinedby changes in absorbance (A) of the reactionmixture at a working wavelength that corresponded tothe maximum of carotene absorption band lambdamax =463 nm at constant concentrations of initial compounds1, 2, and tBuOOH and different concentrationsof carotene by least-squares optimization of thedependence log(A0 - A?)/(Atau - A?)-tau and logkapp -CtBuOOH(A0, Atau, and A? are absorbances at a workingwavelength at the initial, current and final moment oftime, respectively).
With tert.-butylhydroperoxide; mu-carbido bis(2,3,7,8,12,13,17,18-octapropyl-5,10,15,20-tetraazaporphinato)iron(IV); In benzene; at 25℃;Kinetics; The degradation of beta carotene (CCar=(1.64-8.05)10-4 M) was conductedin the presence of 1 (C1=1.610-6 M) and tBuOOH (CtBuOOH =2.7310-2 M) in benzene solution at 25 C. The experiments were controlledspectrophotometrically by decrease in the intensity of absorptionband of carotene at 462 nm. It should be noted that UV-visspectrum of <strong>[7235-40-7]beta-carotene</strong> remains unchanged in pure benzene. In thepresence of tBuOOH for 5 h the intensity of absorption bands onlyslightly decreased and the conversion of beta carotene was limited to ?5%(Table 1). There were no changes observed when 1 was added tobeta carotene benzene solution. When beta carotene, tBuOOH and 1 were simultaneously placed in solution, the disappearance of the beta caroteneabsorption band occurred within 4 min designating that the 1-tBuOOHsystem mediates the process.
  • 59
  • Vitamin A triphenylphosphonium sulfate [ No CAS ]
  • [ 7235-40-7 ]
YieldReaction ConditionsOperation in experiment
With bis(acetylacetonate)oxovanadium; 18-crown-6 ether; oxygen; potassium carbonate; In toluene; at 40℃; for 6h;Molecular sieve; Green chemistry;Catalytic behavior; Vitamin A sulfate triphenylphosphine (1.0mmol), VO(acac)2 (0.1mmol), 3A molecular sieves (0.3g), 18-crown-6 (2.0mmol) and K2CO3 (2.0 mmol) was added toluene (20ml), the reaction was stirred under normal pressure while passing oxygen to maintain the reaction at 40 C, 6h. The reaction solution was cooled to room temperature, the solid residue was removed by filtration, and the filtrate concentrated in vacuo. The resulting solid is the desired product beta-carotene crude product. The crude product was dissolved in n-hexane under nitrogen was heated under reflux for 12h in various cis to all-trans compound of structural isomerization process, after cooling and filtering, and drying to obtain deep red crystal; GB5009.83-2016 analyzed using the method (method for detecting the same below), content 99.0% (HPLC); 84% overall yield.
  • 60
  • Vitamin A triphenylphosphine hydrochloride [ No CAS ]
  • [ 7235-40-7 ]
YieldReaction ConditionsOperation in experiment
With bis(acetylacetonate)oxovanadium; 15-crown-5; oxygen; potassium carbonate; In hexane; at 40℃; for 5h;Molecular sieve; Vitamin A triphenyl phosphine hydrochloride (1.0mmol), VO(OAc)2 (0.1mmol), 4A molecular sieves (0.3g), 15-crown-5 (2.0mmol) and K2CO3 (2.0 mmol) was added n-hexane (20ml), the reaction solution was stirred at normal pressure while passing oxygen to maintain the reaction at 40 C for 5h. Thereafter, until the reaction was cooled to room temperature, the solid residue was removed by filtration, and the filtrate concentrated in vacuo. The resulting solid is the desired product beta-carotene crude product. The crude product was dissolved in n-hexane under nitrogen was heated under reflux for 12h in various cis to all-trans compound of structural isomerization process, after cooling and filtering, and drying to obtain deep red crystal, content of 98.5% (HPLC); overall yield 74%.
  • 61
  • Vitamin A triphenylphosphine hydrobromide [ No CAS ]
  • [ 7235-40-7 ]
YieldReaction ConditionsOperation in experiment
With bis(acetylacetonate)oxovanadium; 18-crown-6 ether; oxygen; potassium hydroxide; In toluene; at 40℃; for 4h;Molecular sieve; Vitamin A hydrobromide salt of triphenylphosphine (1.0mmol), VO(acac)2 (0.1mmol), 3A molecular sieves (0.3g), 18-crown-6 (2.0mmol) and KOH (2.0mmol) was added toluene (20ml), the reaction was incubated at 40 C in the case of holding through atmospheric oxygen. The reaction was stirred for 4h. Thereafter, until the reaction was cooled to room temperature, the solid residue was removed by filtration, and the filtrate concentrated in vacuo. The resulting solid is the desired product beta-carotene crude product. The crude product was dissolved in n-hexane under nitrogen was heated under reflux for 12 h in various cis to all-trans compound of structural isomerization process, after cooling and filtering, and drying to obtain deep red crystal, content of 99.0% (HPLC); overall yield 91%.
  • 62
  • Vitamin A triphenylphosphonium benzenesulfonate [ No CAS ]
  • [ 7235-40-7 ]
YieldReaction ConditionsOperation in experiment
With 18-crown-6 ether; oxygen; vanadia; sodium butanolate; In dichloromethane; at 40℃; for 6h;Molecular sieve; Vitamin A benzenesulfonate triphenylphosphine (1.0mmol), V2O5 (0.1mmol), 3A molecular sieves (0.3g), 18-crown-6 (2.0mmol) and BuONa (2.0mmol) was added dichloromethane (20ml), the reaction solution 40 C in the case of holding through atmospheric oxygen the reaction was stirred at 6h C. The reaction solution was cooled to room temperature, the solid residue was removed by filtration, and the filtrate concentrated in vacuo. The resulting solid is the desired product beta-carotene crude product. The crude product was dissolved in n-hexane under nitrogen was heated under reflux for 12h in various cis to all-trans compound of structural isomerization process, after cooling and filtering, and drying to obtain deep red crystal, content of 99.2% (HPLC); overall yield 68%.
  • 63
  • [ 5056-17-7 ]
  • [ 59057-30-6 ]
  • [ 603-35-0 ]
  • [ 7235-40-7 ]
YieldReaction ConditionsOperation in experiment
95% 131.1 g (0.5 mol) of triphenylphosphine, 110.1 g (0.5 mol) of vinyl ionyl alcohol, and 500 g of methanol were placed in a three-necked flask, and dissolved by stirring at 45 C. 52.2 g (1.03 mol, 36 wt%) of hydrochloric acid was added dropwise to the three-necked bottle, and the dropping time was controlled at 30 to 50 min.After the completion of the dropwise addition, the reaction was kept at 45 C for 1 hour.After the completion of the reaction, the methanol solvent was removed by vacuum distillation at a temperature of 60 C in a three-necked flask, and 300 g of ethyl acetate was added to the three-necked flask, and the mixture was stirred at 45 C for 1 hour, cooled to room temperature, crystallized, filtered, and dried to obtain 2, 4 -pentadiene tenThe carbon phosphate was 240.5 g, the yield was 96%, and the purity was >98%. 55.13 g (0.11 mol) of 2,4-pentadienylpentadecyl phosphate, 8.21 g (0.05 mol) of 2,7-dimethyl-2,4,6-octanetriene-1,8- Dialdehyde, 12.8 g (0.12 mol) of sodium carbonate, 150 g of anhydrous methanol, stirred and dissolved under a nitrogen atmosphere;0.11 g (0.5 mmol) of No. 1 ionic liquid was mixed with 10 g of methanol, and a methanol solution of the ionic liquid was dropwise added to the reaction system at 10 C for 20 min, and the reaction was continued at 10 C for 3 h after the completion of the dropwise addition; After completion, the mixture was filtered, washed with water and dried to give 25.46 g of all-trans-beta-carotene in a yield of 95%, and the content of HPLC was 97%.
  • 64
  • [ 7235-40-7 ]
  • [ 17092-92-1 ]
YieldReaction ConditionsOperation in experiment
With 1H-imidazole; tert.-butylhydroperoxide; mu-carbido bis(2,3,7,8,12,13,17,18-octapropyl-5,10,15,20-tetraazaporphinato)iron(IV); In benzene; at 25℃;Kinetics; The degradation of beta carotene (CCar=(1.64-8.05)10-4 M) was conductedin the presence of 1 (C1=1.610-6 M) and tBuOOH (CtBuOOH =2.7310-2 M) in benzene solution at 25 C. The experiments were controlledspectrophotometrically by decrease in the intensity of absorptionband of carotene at 462 nm. It should be noted that UV-visspectrum of <strong>[7235-40-7]beta-carotene</strong> remains unchanged in pure benzene. In thepresence of tBuOOH for 5 h the intensity of absorption bands onlyslightly decreased and the conversion of beta carotene was limited to ?5%(Table 1). There were no changes observed when 1 was added tobeta carotene benzene solution. When beta carotene, tBuOOH and 1 were simultaneously placed in solution, the disappearance of the beta caroteneabsorption band occurred within 4 min designating that the 1-tBuOOHsystem mediates the process.
  • 65
  • (1E,3E,5E,7E,9E)-1,10-di(benzyldimethylsilyl)-3,8-dimethyldeca-1,3,5,7,9-pentaene [ No CAS ]
  • [ 138846-06-7 ]
  • [ 7235-40-7 ]
  • 66
  • C23H34OSi2 [ No CAS ]
  • [ 138846-06-7 ]
  • [ 7235-40-7 ]
  • 67
  • C35H48Si [ No CAS ]
  • [ 138846-06-7 ]
  • [ 7235-40-7 ]
  • 68
  • [ 7235-40-7 ]
  • [ 71-00-1 ]
  • C6H9N3O2*(x)C40H56 [ No CAS ]
YieldReaction ConditionsOperation in experiment
In ethanol; water; at 20℃; for 3h;Sealed tube; General procedure: A 30 mg/mL solution of L-His (> 99%, Sigma-Aldrich) was prepared by dissolving L-His powder in milli-Q water using a vortex mixer at ambient temperature in a Corning 15 mL centrifuge tube with a closed cap. Then 500 pL of the aqueous solution of L- His and 500 pL of 200 proof ethanol (KOPTEC, PA, US) was added to 200 pL of the small molecule solution (2 mg/mL). The small molecules used in this study were Nile red (> 98%, Sigma-Aldrich), pyrene (> 98%, Sigma-Aldrich), b-carotene (> 97%, Sigma-Aldrich), and doxorubicin HC1 (DOX, > 98%, Fluka, Mexico City, Mexico). The solution was vortexed for 15 seconds and kept static at ambient temperature. After 3 hours, crystals were collected and washed with ethanol to remove the free small molecules from the surface of the crystals and the supernatant was collected to measure the concentration of non-entrapped small molecules using HPLC. An Agilent 1200 LC System with a Binary SL Pump & Diode Array Detector, Shodex RI-501 Refractive Index Detector (single channel), and an Agilent 1100 Column Compartment (G1316) was utilized to carry out the analysis. Each individual sample of small molecules was quantified based on an optimized method reported in the literature for b-carotene (Etzbach et ah, ?Characterization of Carotenoid Profiles in Goldenberry (Physalis peruviana L.) Fruits at Various Ripening Stages and in Different Plant Tissues by HPLC-DAD-APCI-MSn,? Food Chem. 245:508-517 (2018), which is hereby incorporated by reference in its entirety), Nile red (Wu et ah,?Drug Delivery to the Skin from Sub-Micron Polymeric Particle Formulations:
  • 69
  • [ 20930-45-4 ]
  • [ 7235-40-7 ]
YieldReaction ConditionsOperation in experiment
93.6% With tert.-butylhydroperoxide; copper (I) iodide; sodium hydroxide In methanol; water monomer at -15 - 20℃; for 6.5h; Inert atmosphere; 1-5 Example 1 Under nitrogen protection, 12.56g (20mmol) of C20 phosphorus salt was placed in a 500ml three-necked flask, and 120g of water was added to dissolve,Then add tert-butyl hydroperoxide 3.6g (40mmol)and cuprous iodide 0.19g (1mmol),The reaction temperature was lowered to -15°C,Then 3.2g (80mmol) of sodium hydroxide was added dropwiseThe methanol solution (mass fraction 5%),The dropping time was 0.5h,The reaction system was then warmed to room temperature,The reaction was stirred and reacted at room temperature for 6 hours. After the reaction was completed, the reaction solution was filtered, washed and dried to obtain 5.02 g of β-carotene solid with a yield of 93.6%.
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