US7115786B2
Expired / Lapsed
US
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Method for production of β-cryptoxanthin and α-cryptoxanthin from commercially available lutein
Assignee: University of Maryland, College Park
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Filing: 2003-02-06
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Granted: 2006-10-03
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Expires: 2023-02-06
Abstract
Abstract The present invention relates to a method of reacting (3R,3′R,6′R)-lutein with a catalytic amount of an acid to obtain a mixture of anhydroluteins, rich in anhydrolutein III, with substantially no Z-isomers being formed. The mixture is converted to (3R)-β-cryptoxanthin (major product) and (3R,6′R)-α-cryptoxanthin (minor product) by reacting the anhydroluteins with borane-amine complexes (e.g. Me 3 N.BH 3 ) or other hydride donors and an acid in a chlorinated solvent, preferably dichloromethane, at ambient temperature to produce (3R)-β-cryptoxanthin and (3R,6′R)-α-cryptoxanthin.
Inventors
- 👤 Frederick Khachik
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-04 00:33
CPC Classifications
C; C07; C07C; C07C403/00; C07C403/24
Claims Analysis
Total Claims: 39
Claim 1
Independent Claim
98 words
A process for converting (a) (3R,3′R,6′R)-lutein (85% total carotenoids) or (b) purified lutein (97% total carotenoids) containing 5–7% (3R,3′R)-zeaxanthin or mixtures of (a) and (b) to a mixture of anhydroluteins I, II, and III at elevated temperature, comprising reacting (3R,3′R,6′R)-lutein in an alcohol or mixture of alcohols with a catalytic amount of an aqueous mineral acid or a strong organic acid at an elevated temperature of about 45° C. to about 100° C. to give a mixture of anhydroluteins comprising anhydrolutein III as the major product, anhydroluteins I and II as the minor products, and the recovered (3R,3′R)-zeaxanthin.
Claim 2
Dependent Claim
98 words
A process for converting (a) (3R,3′R,6′R)-lutein (85% total carotenoids) or (b) purified lutein (97% total carotenoids) containing 5–7% (3R,3′R)-zeaxanthin or mixtures of (a) and (b) to a mixture of anhydroluteins I, II, and III at elevated temperature, comprising reacting (3R,3′R,6′R)-lutein in an alcohol or mixture of alcohols with a catalytic amount of an aqueous mineral acid or a strong organic acid at an elevated temperature of about 45° C. to about 100° C. to give a mixture of anhydroluteins comprising anhydrolutein III as the major product, anhydroluteins I and II as the minor products, and the recovered (3R,3′R)-zeaxanthin.
Claim 3
Dependent Claim
17 words
The process of claim 1 , wherein said mixture of anhydroluteins comprises at least 80% anhydrolutein III.
Claim 4
Dependent Claim
15 words
The process of claim 2 , wherein said anhydrolutein III comprises substantially no Z-anhydrolutein III.
Claim 5
Dependent Claim
38 words
The process of claim 1 , wherein said alcohol is selected from the group consisting of ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol (n-amyl alcohol), 2-pentanol, n-hexyl alcohol, n-octyl alcohol, ethylene glycol, and propylene glycol.
Claim 6
Dependent Claim
28 words
The process of claim 1 , wherein said aqueous mineral acid is aqueous sulfuric, hydrochloric or phosphoric acid, and said strong organic acid is trifluoroacetic or trichloroacetic acid.
Claim 7
Dependent Claim
13 words
The process of claim 1 , wherein said elevated temperature is 78–100° C.
Claim 8
Dependent Claim
25 words
The process of claim 1 , further comprising adding water to convert Z(cis)-isomers of anhydroluteins at the elevated temperature to all-E-anhydrolutein rich in all-E-anhydrolutein III.
Claim 9
Dependent Claim
26 words
The process of claim 1 , further comprising isomerizing anhydroluteins I and II to anhydrolutein III at elevated temperatures in the presence of water and acid.
Claim 10
Dependent Claim
28 words
The method of claim 1 , further comprising cooling the mixture of anhydroluteins to ambient temperature or between 5–10° C. to precipitate the all-E-anhydroluteins as a crystalline product.
Claim 11
Dependent Claim
28 words
The method of claim 9 , further comprising filtering and washing the crystalline product with an alcohol or acetone and drying at about 60° C. under high vacuum.
Claim 12
Dependent Claim
29 words
The method of claim 9 , further comprising reacting all-E-anhydroluteins with a chlorinated solvent, hydride donor and a strong organic acid to give a mixture of all-E-(3R)-β-cryptoxanthin and all-E-(3R,6′R)-α-cryptoxanthin.
Claim 13
Dependent Claim
30 words
The method of claim 1 , wherein the mixture of anhydroluteins is neutralized with an aqueous or an organic base, extracted with an organic solvent, and crystallized from an alcohol.
Claim 14
Dependent Claim
19 words
The method of claim 12 , wherein the organic solvent is ethyl acetate, an ether, or a chlorinated solvent.
Claim 15
Dependent Claim
65 words
A process for converting (a) (3R,3′R,6′R)-lutein (85% total carotenoids) or (b) purified lutein (97% total carotenoids) containing 5–7% (3R,3′R)-zeaxanthin or mixtures of (a) and (b) to lutein 3′-alkyl ether, comprising reacting (3R,3′R,6′R)-lutein with an alcohol in the presence of a catalytic amount of an aqueous mineral acid or a strong organic acid at an elevated temperature to give all-E(trans)-lutein 3′-alkyl ether and the recovered (3R,3′R)-zeaxanithin.
Claim 16
Dependent Claim
65 words
A process for converting (a) (3R,3′R,6′R)-lutein (85% total carotenoids) or (b) purified lutein (97% total carotenoids) containing 5–7% (3R,3′R)-zeaxanthin or mixtures of (a) and (b) to lutein 3′-alkyl ether, comprising reacting (3R,3′R,6′R)-lutein with an alcohol in the presence of a catalytic amount of an aqueous mineral acid or a strong organic acid at an elevated temperature to give all-E(trans)-lutein 3′-alkyl ether and the recovered (3R,3′R)-zeaxanithin.
Claim 17
Dependent Claim
32 words
The process of claim 14 , wherein said alcohol is ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol (n-amyl alcohol), 2-pentanol, n-hexyl alcohol, n-octyl alcohol, ethylene glycol, or propylene glycol.
Claim 18
Dependent Claim
28 words
The process of claim 14 , wherein said aqueous mineral acid is aqueous sulfuric, hydrochloric or phosphoric acid, and said strong organic acid is trifluoroacetic or trichloroacetic acid.
Claim 19
Dependent Claim
13 words
The process of claim 14 , wherein said elevated temperature is 45–50° C.
Claim 20
Dependent Claim
61 words
The method of claim 14 , further comprising transforming the lutein 3′-alkyl ether in situ into a mixture of anhydroluteins, comprising reacting lutein 3′-alkyl ether with a catalytic amount of an aqueous mineral acid or a strong organic acid at an elevated temperature in water to give anhydrolutein III as the major product and anhydroluteins I and II as minor products.
Claim 21
Dependent Claim
26 words
The method of claim 18 , wherein the aqueous mineral acid is aqueous sulfuric, hydrochloric or phosphoric acid, and the strong organic acid is trifluoroacetic acid.
Claim 22
Dependent Claim
17 words
The process of claim 18 , wherein the elevated temperature is 78° C. to about 100° C.
Claim 23
Dependent Claim
26 words
The process of claim 18 , further comprising adding water thereby preventing E/Z(trans/cis)-isomerization of anhydroluteins at an elevated temperature of 78° C. to about 100° C.
Claim 24
Dependent Claim
27 words
The process of claim 18 , further comprising isomerizing anhydroluteins I and II to anhydrolutein III at elevated temperatures in the presence of water in 7–20 h.
Claim 25
Dependent Claim
28 words
The method of claim 18 , further comprising cooling said mixture of anhydroluteins to ambient temperature or between 5–10° C. to precipitate the all-E-anhydroluteins as a crystalline product.
Claim 26
Dependent Claim
30 words
The method of claim 18 , further comprising filtering said crystalline product, washing said product with an alcohol or acetone, and drying said product at 60° C. under high vacuum.
Claim 27
Dependent Claim
30 words
The method of claim 24 , further comprising reacting said product with a chlorinated solvent, hydride donor and a strong organic acid to give a mixture of all-E-(3R)-β-cryptoxanthin and all-E-(3R,6′R)-α-cryptoxanthin.
Claim 28
Dependent Claim
30 words
The method of claim 14 , wherein said all-E(trans)-lutein 3′-alkyl ether is neutralized with an aqueous or an organic base, extracted with an organic solvent, and crystallized from an alcohol.
Claim 29
Dependent Claim
19 words
The method of claim 26 , wherein the organic solvent is ethyl acetate, an ether or a chlorinated solvent.
Claim 30
Dependent Claim
65 words
A process for converting a mixture of all-E-anhydroluteins rich in all-E-anhydrolutein III, to a mixture of all-E-(3R)-β-cryptoxanthin and all-E-(3R,6′R)-α-cryptoxanthin, comprising reacting anhydroluteins containing 3–8% (3R,3′R)-zeaxanthin in a chlorinated solvent with about 1.3 equivalent of a hydride donor and about 3.5–4 equivalent of a strong organic acid at ambient temperature for about 1–5 hours to give a mixture of E/Z-(3R)-β-cryptoxanthin, E/Z-(3R,6′R)-α-cryptoxanthin, unreacted E/Z-anhydroluteins, and recovered E/Z-(3R,3′R)-zeaxanthin.
Claim 31
Dependent Claim
65 words
A process for converting a mixture of all-E-anhydroluteins rich in all-E-anhydrolutein III, to a mixture of all-E-(3R)-β-cryptoxanthin and all-E-(3R,6′R)-α-cryptoxanthin, comprising reacting anhydroluteins containing 3–8% (3R,3′R)-zeaxanthin in a chlorinated solvent with about 1.3 equivalent of a hydride donor and about 3.5–4 equivalent of a strong organic acid at ambient temperature for about 1–5 hours to give a mixture of E/Z-(3R)-β-cryptoxanthin, E/Z-(3R,6′R)-α-cryptoxanthin, unreacted E/Z-anhydroluteins, and recovered E/Z-(3R,3′R)-zeaxanthin.
Claim 32
Dependent Claim
16 words
The method of claim 28 , wherein said hydride ion donor is borane-trimethylamine, borane-dimethylamine, or borane-tert-butylamine.
Claim 33
Dependent Claim
14 words
The method of claim 28 , wherein said hydride ion donor is a trialkylsilanes.
Claim 34
Dependent Claim
11 words
The method of claim 30 , wherein said trialkylsilanes is triethylsilane.
Claim 35
Dependent Claim
14 words
The method of claim 28 , wherein said strong organic acid is trifluoroacetic acid.
Claim 36
Dependent Claim
44 words
The method of claim 28 , further comprising heating said mixture of E/Z-(3R)-β-cryptoxanthin, E/Z-(3R,6′R)-α-cryptoxanthin, unreacted E/Z-anhydroluteins, and recovered E/Z-(3R,3′R)-zeaxanthin in an alcohol at 78–87° C. to convert the Z-carotenoids to their all-E-isomers and obtain a mixture of all-E-(3R)-β-cryptoxanthin, all-E-(3R,6′R)-α-cryptoxanthin, unreacted all-E-anhydroluteins, and recovered all-E-(3R,3′R)-zeaxanthin.
Claim 37
Dependent Claim
14 words
The method of claim 33 , wherein said alcohol is ethanol, 1-propanol, or 2-propanol.
Claim 38
Dependent Claim
43 words
The method of claim 33 , further comprising neutralizing said all-E-isomers with an aqueous or an organic base, removing the aqueous layer, and displacing the chlorinated solvent with a higher boiling alcohol by distillation under reduced pressure until carotenoids crystallize from the alcohol.
Claim 39
Dependent Claim
30 words
The method of claim 35 , further comprising crystallizing carotenoids, collecting said carotenoids, washing said carotenoids with acetone or alcohol and drying said carotenoids under high vacuum at 60° C.
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