USRE30339E - Conversion of acid S, produced by the organism Polyangium cellulosum var. fulvum into acid F - Google Patents
Conversion of acid S, produced by the organism Polyangium cellulosum var. fulvum into acid F Download PDFInfo
- Publication number
- USRE30339E USRE30339E US05/924,469 US92446978A USRE30339E US RE30339 E USRE30339 E US RE30339E US 92446978 A US92446978 A US 92446978A US RE30339 E USRE30339 E US RE30339E
- Authority
- US
- United States
- Prior art keywords
- acid
- methyl ester
- fulvum
- ester
- conversion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002253 acid Substances 0.000 title claims abstract description 58
- 241000862997 Sorangium cellulosum Species 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 title abstract description 4
- 150000004702 methyl esters Chemical class 0.000 claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229930194542 Keto Natural products 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- -1 keto ester Chemical class 0.000 claims abstract description 7
- 238000012746 preparative thin layer chromatography Methods 0.000 claims abstract description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 4
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 101150108015 STR6 gene Proteins 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000855 fermentation Methods 0.000 abstract description 7
- 230000004151 fermentation Effects 0.000 abstract description 7
- 230000003115 biocidal effect Effects 0.000 abstract description 4
- 150000002148 esters Chemical class 0.000 abstract description 4
- 229940121375 antifungal agent Drugs 0.000 abstract description 3
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 abstract description 2
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000843 anti-fungal effect Effects 0.000 abstract description 2
- 229910001958 silver carbonate Inorganic materials 0.000 abstract description 2
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000001793 charged compounds Chemical class 0.000 description 3
- 239000012230 colorless oil Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 244000166102 Eucalyptus leucoxylon Species 0.000 description 2
- 235000004694 Eucalyptus leucoxylon Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- WACQKHWOTAEEFS-UHFFFAOYSA-N cyclohexane;ethyl acetate Chemical compound CCOC(C)=O.C1CCCCC1 WACQKHWOTAEEFS-UHFFFAOYSA-N 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 241000400611 Eucalyptus deanei Species 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D309/18—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member containing only hydrogen and carbon atoms in addition to the ring hetero atom
Definitions
- the present invention is concerned with a process for the conversion of the major antifungal antibiotic (acid S) isolated from the fermentation of Polyangium cellulosum var. fulvum into the minor antibiotic (acid F) from the same fermentation.
- Acid F is isolated either in small amounts or in many cases not at all from the fermentation medium.
- Acid S and acid F are described in U.S. Pat. Nos. 3,651,216 and 3,804,948. As disclosed in these patents, both acid S and acid F are potent antifungal agents.
- U.S. Pat. No. 3,804,948 describes the chemical preparation of the methyl ester of acid S. Keto ester S, a derivative of acid S, disclosed in U.S. Pat. No. 3,932,620 is also used in the process of this invention.
- Keto ester S(III) in an alcoholic solvent such as methanol, is reduced with an alkali metal borohydride, typically sodium borohydride, to provide a mixture of acid S methyl ester II and acid F methyl ester IV.
- the reduction step may be conducted under nitrogen.
- alkali metal borohydride typically sodium borohydride
- the reduction step may be conducted under nitrogen.
- These esters are readily separated by preparative thin layer chromatography.
- a typical solvent system which may be used for this separation is ethyl acetate-cyclohexane in a ratio of 4:1. Variations of this solvent system, commonly used in thin layer chromatography separations are also suitable.
- the acid F methyl ester IV thus obtained is hydrolyzed to obtain acid F (V).
- the hydrolysis is conducted in an alcoholic solvent, such as methanol, using alkali metal hydroxide, typically sodium hydroxide.
- the hydrolysis step may be conducted under nitrogen.
- the diacetate VI of the semi-synthetic product was prepared.
- a sample of natural acid F (VII) obtained from the fermentation was also acetylated to obtain acid F diacetate VIII.
- the NMR spectra of the two diacetates VI and VIII were found to be identical in all respects, indicating that the semi-synthetic product VI is acid F diacetate.
- the semi-synthetic product V is identical to natural acid F (VII) isolated from the fermentation of Polyangium cellulosum var. fulvum.
- the infra-red spectra of semi-synthetic acid F (V) and natural acid F (VII) are also identical.
- Acid S Methyl Ester (most polar compound) is isolated as a colorless oil (86 mg., 37%), Acid F Methyl Ester (least polar compound) is isolated as a colorless oil (49 mg., 21%).
- Diagnostic TLC indicates both products to be homogeneous and both have the same Rf values as the corresponding esters derived from the natural acids.
- Acid F (Semi-synthetic) 1 N sodium hydroxide solution (3 ml) is added to a methanol solution of semi-synthetic acid F methyl ester (49 mg., 0.00001 mole). The reaction mixture is stirred at 90 under nitrogen for 30 minutes. The methanol is removed under pressure. The aqueous residue is acidified with 1 N hydrochloric acid and extracted with chloroform. The extracts are dried over magnesium sulfate and evaporated to give acid F as a colorless oil (25 mg., 53%).
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
A process for the conversion of the major antifungal antibiotic, acid S (ATCC No. 25532) isolated from the fermentation of Polyangium cellulosum var. fulvum into the minor antibiotic, acid F, from the same fermentation is described wherein acid S is methylated with diazomethane to provide acid S methyl ester which is then oxidized with silver carbonate on celite to obtain the corresponding keto ester S, which is subsequently reduced with sodium borohydride to give a mixture of acid S methyl ester and acid F methyl ester. These esters are readily separated by preparative thin layer chromatography and the acid F methyl ester is hydrolyzed with sodium hydroxide solution to provide acid F.
Description
The present invention is concerned with a process for the conversion of the major antifungal antibiotic (acid S) isolated from the fermentation of Polyangium cellulosum var. fulvum into the minor antibiotic (acid F) from the same fermentation. Acid F is isolated either in small amounts or in many cases not at all from the fermentation medium. Thus, in order to have an adequate supply of acid F, it has been found necessary to design a process for the conversion of the readily available acid S into acid F.
Acid S and acid F are described in U.S. Pat. Nos. 3,651,216 and 3,804,948. As disclosed in these patents, both acid S and acid F are potent antifungal agents. In addition, U.S. Pat. No. 3,804,948 describes the chemical preparation of the methyl ester of acid S. Keto ester S, a derivative of acid S, disclosed in U.S. Pat. No. 3,932,620 is also used in the process of this invention.
The process of the invention is shown in Scheme A as follows: ##STR1## Acid S (I) is methylated with diazomethane to provide acid S methyl ester II, which is oxidized with silver carbonate on celite to obtain keto ester S (III). Attempts to oxidize acid S directly to keto S yields tars, but selective oxidation of acid S methyl ester to keto ester S, following the procedure described in U.S. Pat. No. 3,932,620 is successful.
Keto ester S(III), in an alcoholic solvent such as methanol, is reduced with an alkali metal borohydride, typically sodium borohydride, to provide a mixture of acid S methyl ester II and acid F methyl ester IV. The reduction step may be conducted under nitrogen. These esters are readily separated by preparative thin layer chromatography. A typical solvent system which may be used for this separation is ethyl acetate-cyclohexane in a ratio of 4:1. Variations of this solvent system, commonly used in thin layer chromatography separations are also suitable.
The acid F methyl ester IV thus obtained is hydrolyzed to obtain acid F (V). The hydrolysis is conducted in an alcoholic solvent, such as methanol, using alkali metal hydroxide, typically sodium hydroxide. The hydrolysis step may be conducted under nitrogen.
To confirm the structure of acid F (V), the diacetate VI of the semi-synthetic product was prepared. A sample of natural acid F (VII) obtained from the fermentation was also acetylated to obtain acid F diacetate VIII. The NMR spectra of the two diacetates VI and VIII were found to be identical in all respects, indicating that the semi-synthetic product VI is acid F diacetate. Thus, the semi-synthetic product V is identical to natural acid F (VII) isolated from the fermentation of Polyangium cellulosum var. fulvum. The infra-red spectra of semi-synthetic acid F (V) and natural acid F (VII) are also identical.
The following examples are provided to further illustrate the invention and are not be construed as limiting the scope of the invention.
IR γ max broad 3600-3200 and 2800-2500 (OH), 1720 cm-1 (CO)
______________________________________
.Iadd.Mass Spectrum
______________________________________
Observed molecular ion 474.3010
Calculated for C.sub.28 H.sub.42 O.sub.5
474.2981
______________________________________
.Iaddend.
m/e (relative intensity) 474(14), 456(9), 445(29), 379(19), 361(8), 279(64), 245(19), 235(21), 195(75) and 193(100).
IR γ max broad 3500-3100 and 2800-2400(OH), 1745 (CO) and 1720 cm-1 (CO)
______________________________________
.Iadd.Mass Spectrum
______________________________________
Observed molecular ion 558.3295
Calculated for C.sub.32 H.sub.46 O.sub.8
558.3271
______________________________________
.Iaddend.
m/e (relative intensity) 558(17), 529(50), 463(21), 343(10), 305(10), 259(7), 245(23), 195(23) and 193(100).
NMR (CDCl3) δ 0.89 (s, 3H, CH3), 1.05 (m, 6H, 2CH3), 1.59 (s, 3H, CH3), 1.64 (s, 3H, CH3), 1.98 (s, 3H, CH3 CO), 2.14 (s, 3H, CH3 CO), 2.44 (q, 1H, CH2 CO), 2.65 (q, 1H, CH2 CO), 3.07 (m, 1H, bisallyl), 3.86 (q, 1H, CH--O), 4.07-4.29 (m, 3H, 3CH--O), 4.67 (q, 1H, CH--OAc), 5.06 (q, 1H, vinyl), 5.25 (d, 1H, vinyl), 5.32-5.52 (m, 4H, 3 vinyl and 1 CH--OAc) and 5.57 (d, 1H, vinyl).
IR γ max broad 3500-3100 and 2800-2400(OH), 1745(CO) and 1720 cm-1 (CO).
______________________________________
.Iadd.Mass Spectrum
______________________________________
Observed molecular ion 558.3249
Calculated for C.sub.32 H.sub.46 O.sub.8
558.3271
______________________________________
.Iaddend.
m/e (relative intensity) 558(26), 529(44), 463(30), 343(12), 305(14), 259(14), 245(21), 195(90) and 193(100)
NMR (CDCl3) δ 0.89 (s, 3H, CH3), 1.05 (m, 6H, 2CH3), 1.59 (s, 3H, CH3), 1.64 (s, 3H, CH3), 1.98 (s, 3H, CH3 CO), 2.14 (s, 3H, CH3 CO), 2.44 (q, 1H, CH2 CO), 2.65 (q, 1H, CH2 CO), 3.07 (m, 1H, bisallyl), 3.86 (q, 1H, CH--O), 4.07-4.29 (m, 3H, 3CH--O), 4.67 (q, 1H, CH--OAc), 5.06 (q, 1H, vinyl), 5.25 (d, 1H, vinyl), 5.32-5.52 (m, 4H, 3 vinyl and 1CH--OAc) and 5.57 (d, 1H, vinyl).
Claims (3)
1. A process for preparing the substance acid F (V) having the following formula: ##STR6## which comprises the following steps: A. Reducing an alcoholic solution of keto ester S (III) wherein the keto ester S has the following formula: ##STR7## with an alkali metal borohydride to obtain a mixture of acid S methyl ester II and acid F methyl ester IV having the following formulas: ##STR8## B. Separating acid S methyl ester II and acid F methyl ester IV by preparative thin layer chromatography;
C. Hydrolyzing acid F methyl ester IV to obtain the desired acid F (V).
2. A process according to claim 1 wherein in Step A, the reduction is conducted in methanol using sodium borohydride.
3. A process according to claim 1 wherein in Step C, the hydrolysis is conducted in methanol using sodium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/924,469 USRE30339E (en) | 1978-07-14 | 1978-07-14 | Conversion of acid S, produced by the organism Polyangium cellulosum var. fulvum into acid F |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/924,469 USRE30339E (en) | 1978-07-14 | 1978-07-14 | Conversion of acid S, produced by the organism Polyangium cellulosum var. fulvum into acid F |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/794,180 Reissue US4076940A (en) | 1977-05-05 | 1977-05-05 | Conversion of acid S, produced by the organism Polyangium cellulosum var. fulvum into acid F |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE30339E true USRE30339E (en) | 1980-07-15 |
Family
ID=25450239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/924,469 Expired - Lifetime USRE30339E (en) | 1978-07-14 | 1978-07-14 | Conversion of acid S, produced by the organism Polyangium cellulosum var. fulvum into acid F |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USRE30339E (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070015823A1 (en) * | 2004-12-16 | 2007-01-18 | Zong-Qiang Tian | Ambruticin VS compounds |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3651216A (en) * | 1970-05-11 | 1972-03-21 | Warner Lambert Co | Antibiotic substances produced by polyangium cellulosum var. fulvum |
| US3804948A (en) * | 1972-02-15 | 1974-04-16 | Warner Lambert Co | Antifungal substances from polyangium cellulosum var.fulvum |
| US4001398A (en) * | 1974-06-24 | 1977-01-04 | Warner-Lambert Company | Octahydro and decahydro derivatives of acid S, an antibiotic produced by Polyangium cellulosum var. fulvum |
| US4009261A (en) * | 1975-08-07 | 1977-02-22 | Warner-Lambert Company | 7-Substituted triol derivatives of acid S, an antibiotic produced by polyangium cellulosum var. fulvum |
| US4016257A (en) * | 1975-08-07 | 1977-04-05 | Warner-Lambert Company | Amide derivatives of acids, an antibiotic produced by Polyangium cellulosum var. fulvum |
-
1978
- 1978-07-14 US US05/924,469 patent/USRE30339E/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3651216A (en) * | 1970-05-11 | 1972-03-21 | Warner Lambert Co | Antibiotic substances produced by polyangium cellulosum var. fulvum |
| US3804948A (en) * | 1972-02-15 | 1974-04-16 | Warner Lambert Co | Antifungal substances from polyangium cellulosum var.fulvum |
| US4001398A (en) * | 1974-06-24 | 1977-01-04 | Warner-Lambert Company | Octahydro and decahydro derivatives of acid S, an antibiotic produced by Polyangium cellulosum var. fulvum |
| US4009261A (en) * | 1975-08-07 | 1977-02-22 | Warner-Lambert Company | 7-Substituted triol derivatives of acid S, an antibiotic produced by polyangium cellulosum var. fulvum |
| US4016257A (en) * | 1975-08-07 | 1977-04-05 | Warner-Lambert Company | Amide derivatives of acids, an antibiotic produced by Polyangium cellulosum var. fulvum |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070015823A1 (en) * | 2004-12-16 | 2007-01-18 | Zong-Qiang Tian | Ambruticin VS compounds |
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