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US3923897A Expired / Lapsed US ⏱️ 0.0 years remaining

Production of hoplike beverage bittering materials

Assignee: Kalamazoo Spice Extraction Co
•
Filing: 1973-04-02
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Granted: 1975-12-02
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Expires: 1993-04-02
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Abstract

Abstract 2,4-DIACYL-5-ALKYL-4-HYDROXYCYCLOPENTANE-1,3-DIONES (TETRAHYDROISO-ALPHA ACIDS) (TETRAHYDROISOHUMULONES) R1, R2, and R3 are various alkyl groups which may or may not be identical, e.g., in the formulas above, if R2 R3 CH2CH2CH(CH3)2 isopentyl and R1 -CH2CH(CH3)2 isobutyl, the compound I becomes desoxytetrahydrohumulone 3'',5''-diisopentyl2'',4'',6''-trihydroxyisovalerophenone and III becomes tetrahydroisohumulone. Similarly, when R2 and R3 are isopentyl and R1 is -CH(CH3)CH2CH3 or -CH(CH3)2, the starting material (I) is respectively desoxytetrahydroadhumulone and desoxytetrahydrocohumulone, the intermediates II become tetrahydroadhumulone and tetrahydrocohumulone, and the end products III become tetrahydroisoadhumulone and tetrahydroisocohumulone. For clarity, it should be stated here that desoxytetrahydroalpha acids are herin designated by I and may also be designated a 3'',5''-dialkyl-2'',4'',6''-trihydroxyacylphenone, that the intermediate tetrahydrohumulone is herein designated by II and may also be designated a tetrahydro-alpha acid or a 6-acyl-2,4dialkyl-2-hydroxycyclohexane-1,3,5-trione, and that the ultimate end product, the tetrahydroisohumulone, is herein designated III and may sometimes be designated a tetrahydroiso-alpha acid or a 2,4-diacyl-5-alkyl-4-hydroxycyclopentane-1,3-dione. Moreover, sometimes the terms ''''alpha acids'''' and ''''iso-alpha acids'''' are employed herein without the ''''tetrahydro'''' prefix, without any intention, however, to define a different material when such abbreviation is employed. Such abbreviation, when employed, will be apparent to one skilled in the art. To conform with current nomenclature practice, lupulones are usually referred to herein as beta acids; tetrahydrohumulones (II) as tetrahydro-alpha acids; and tetrahydroisohumulones (III) as tetrahydroiso-alpha acids. It should be recognized, however, that the terms alpha acids, ''''beta acids,'''' and ''''iso-alpha acids'''' are used herein in a generic sense and are not meant to limit the various alkyl groups R1,R2, and R3 (Chart I) to groups found in naturallyoccurring substances, the present invention being equally applicable to synthetically derived materials. 6-ACYL-2,4-DIALKYL-2-HYDROXYCYCLOHEXANE-1,3,5-TRIONES (TETRAHYDROHUMULONES) (TETRAHYDRO-ALPHA ACIDS) 3'',5''-DIALKYL-2'',4'',6''-TRIHYDROXYACYLPHENONES (DESOXYTETRAHYDROALPHA ACIDS) Production of hoplike beverage bittering materials by the peracid oxidation of 3'',5''-dialkyl-2'',4'',6''trihydroxyacylphenones to 6-acyl-2,4-dialkyl-2hydroxycyclohexane-1,3,5-triones (tetrahydrohumulones or tetrahydro-alpha acids) and isomerization thereof to 2,4-diacyl5-alkyl-4-hydroxycyclopentane-1,3-diones (tetrahydroisohumulones or tetrahydroiso-alpha acids). CHART I: Conversion of beta acids into flavoring materials in the tetrahydro-alpha acids family

Inventors

  • 👤 Leonard R Worden

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-08 11:36
CPC Classifications
C; C12; C12C; C12C3/00; C12C3/12; C12C5/00; C12C5/008; C12C5/02; C12C5/026; C12C3/04; C12C3/08

Claims Analysis

Total Claims: 16
Claim 1
Independent Claim 48 words
THE PROCESS FOR THE OXIDATION OF A 3'',5''-DIALKYL-2'',4'',6''TRIHYDROXYALKANOYLPHENONE TO A 6-ALKANOYL-2,4-DIALKYL-2HYDROXYCYCLOHEXANE-1,3,5-TRIONE, AN ALPHA ACID, SAID ALKANOYL AND ALKYL GROUPS CONTAINING A MAXIMUM OF 8 CARBON ATOMS, COMPRISING THE STEP OF CONTACTING AN ORGANIC PERACID OXIDIZING AGENT WITH THE STARTING 3'',5''-DIALKYL-2'',4'',6''-TRIHYDROXYALKANOYLPHENONE IN THE LIQUID PHASE TO PRODUCE SAID 6-ALKANOYL2,4-DIALKYL-2-HYDROXYCYCLOHEXANE-1,3,5-TRIONE.
Claim 2
Dependent Claim 48 words
THE PROCESS FOR THE OXIDATION OF A 3'',5''-DIALKYL-2'',4'',6''TRIHYDROXYALKANOYLPHENONE TO A 6-ALKANOYL-2,4-DIALKYL-2HYDROXYCYCLOHEXANE-1,3,5-TRIONE, AN ALPHA ACID, SAID ALKANOYL AND ALKYL GROUPS CONTAINING A MAXIMUM OF 8 CARBON ATOMS, COMPRISING THE STEP OF CONTACTING AN ORGANIC PERACID OXIDIZING AGENT WITH THE STARTING 3'',5''-DIALKYL-2'',4'',6''-TRIHYDROXYALKANOYLPHENONE IN THE LIQUID PHASE TO PRODUCE SAID 6-ALKANOYL2,4-DIALKYL-2-HYDROXYCYCLOHEXANE-1,3,5-TRIONE.
Claim 3
Dependent Claim 12 words
A process of claim 1 which utilizes peracetic acid as oxidizing agent.
Claim 4
Dependent Claim 12 words
A process of claim 1 which utilizes perbenzoic acid as oxidizing agent.
Claim 5
Dependent Claim 12 words
A process of claim 1 which utilizes monoperphthalic acid as oxidizing agent.
Claim 6
Dependent Claim 21 words
A process of claim 1 in which both alpha acids and iso-alpha acids aRe present at the start of the reaction.
Claim 7
Dependent Claim 16 words
The process of claim 1 wherein the oxidation is carried out in a water-immiscible organic solvent.
Claim 8
Dependent Claim 100 words
A PROCESS OF CLAIM 1 WHICH FURTHER INCLUDES THE PRODUCTION AOOF A 2,4-DIALKANOYL-5-ALKYL-4-HYDROXYCYCLOPENTANE-1,3DIONE AS ISO-ALPHA ACID, BY CARRYING OUT SAID OXIDATION OF SAID PHENONE WITH A PERACID IN THE PRESENCE OF A WATER-IMMISCIBLE ORGANIC SOLVENT, AND ISOMERIZING THE SAID THUS-FORMED TRIONE, AN ALPHA ACID, INTO AN ISO-ALPHA ACID WITHOUT ISOLATION OF THE TRIONE BY ADDING SUFFICIENT SALT OF A METAL, SELECTED FROM THE GROUP CONSISTING OF SODIUM, POTASSIUM, MANGANESE, NICKEL, CERIUM, AND GROUP IIA AND GROUP IIB ELEMENTS OF THE PERIODIC TABLE, TO MAINTAIN THE ALPHA ACID IN THE WATER-IMMISCIBLE ORGANIC SOLVENT, THE PH BEING MAINTAINED AT 13 OR BELOW.
Claim 9
Dependent Claim 12 words
A process of claim 7 which utilizes peracetic acid as oxidizing agent.
Claim 10
Dependent Claim 24 words
A process of claim 7 in which a metal ion taken from the class consisting of calcium and magnesium is present during the isomerization.
Claim 11
Dependent Claim 40 words
A process of claim 7 comprising carrying out the said oxidation of said phenone with a peracid in the presence of a water-immiscible solvent, and isomerizing the thus-formed trione at a pH above about 7 without removal of water-immiscible solvent.
Claim 12
Dependent Claim 76 words
A process of claim 10 comprising the step of conducting the oxidation using a peracid in the presence of a water-immiscible solvent and, after said conversion, adjusting the pH to above about 7 in the presence of sufficient metal ion to drive the 6-alkanoyl-2,4-dialkyl-2-hydroxycyclohexane-1,3,5-trione-alpha acid product into the water-immiscible solvent, holding the mixture until the alpha acid has isomerized to an iso-alpha acid, and separating the iso-alpha acid or a metal complex thereof from the solvent.
Claim 13
Dependent Claim 12 words
A process of claim 10 in which the peracid is peracetic acid.
Claim 14
Dependent Claim 22 words
A process of claim 10 in which the solvent is taken from the class consisting of methylene chloride, ethylene dichloride, and trichloroethylene.
Claim 15
Dependent Claim 24 words
A process of claim 10 in which the metal ion is a polyvalent metal ion taken from the class consisting of calcium and magnesium.
Claim 16
Dependent Claim 20 words
A process of claim 14 in which the iso-alpha acid is subsequently treated with acid to substantially remove metal ions.

References Cited (Backward Citations)

US3552975A Cited
US3536762A Cited
US3686316A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1978-12-01 1979-06-02 1979-12-02 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1982-12-01 1983-06-02 1983-12-02 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1986-12-01 1987-06-02 1987-12-02 $7700.00 Window Closed / Lapsed

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