GB2031885A - Microbiological production of carboxylic acid mixtures containing omega , ( omega -1)-dihydroxy carboxylic acids - Google Patents
Microbiological production of carboxylic acid mixtures containing omega , ( omega -1)-dihydroxy carboxylic acids Download PDFInfo
- Publication number
- GB2031885A GB2031885A GB7931897A GB7931897A GB2031885A GB 2031885 A GB2031885 A GB 2031885A GB 7931897 A GB7931897 A GB 7931897A GB 7931897 A GB7931897 A GB 7931897A GB 2031885 A GB2031885 A GB 2031885A
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- Prior art keywords
- carboxylic acid
- omega
- dihydroxy
- carboxylic acids
- dihydroxy carboxylic
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6409—Fatty acids
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/14—Fungi; Culture media therefor
- C12N1/16—Yeasts; Culture media therefor
- C12N1/165—Yeast isolates
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
- C12P7/42—Hydroxy-carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
- C12P7/44—Polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12R—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES C12C - C12Q, RELATING TO MICROORGANISMS
- C12R2001/00—Microorganisms ; Processes using microorganisms
- C12R2001/645—Fungi ; Processes using fungi
- C12R2001/72—Candida
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Health & Medical Sciences (AREA)
- Biotechnology (AREA)
- Genetics & Genomics (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Health & Medical Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Microbiology (AREA)
- Biochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mycology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Botany (AREA)
- Medicinal Chemistry (AREA)
- Tropical Medicine & Parasitology (AREA)
- Virology (AREA)
- Biomedical Technology (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Carboxylic acids containing omega , ( omega - 1)-dihydroxy carboxylic acid as a chief ingredient are produced by a method wherein omega , ( omega -1)-dihydroxy carboxylic acid-producing microorganism which belongs to Candida genus is cultured with alpha-olefins having 12 to 18 carbon atoms in a medium, or cells of said microorganism which has been grown in advance is allowed to react on alpha- olefins having 12 to 18 carbon atoms as substrate thereby forming carboxylic acids having omega , ( omega -1)-dihydroxy carboxylic acid as a chief ingredient and recovering the carboxylic acids from the broth.
Description
SPECIFICATION
The production of carboxylic acids containing o; (w-l) dihydroxy carboxylic acid as a chief ingredient.
This invention relates to a method for the production of carboxylic acids containing o, (0)-1 )-dihydroxy acid as a chief ingredient from alpha-olefins of C12 to C18 using a microorganism.
The (o, (w-1)-dihydroxy carboxylic acids referred to herein and in the claims means carboxylic acids having the formula 1 in which n is an integer of from 12 to 18.
HOOC(CH2)n.3CH(OH)CH2OH (1)
The method of the invention, however, produces a mixture of acids containing more or less of the formulae 2 to 5,
HOCC(CH2)n.2COOH (2) HOOC(CH2)n 3CH(OH)COOH (3) HOOC(CH2)n 2CH2OH (4) HOOC(CH2)n 3CH(OH)CH2OCH3 (5) in which n is an integer of from 12 to 18.
Of the carboxylic acids expressed in the equations from (1) to (5) shown above, this invention produces carboxylic acid of (1) having o,o-l -dihydroxy carboxylic acid as a chief ingredient of the mixture, but the production of at least one or more from (2) to (5) is/are also included.
Heretofore there have been some reports published on the productions of various compounds from alpha-olefins as substrate; for example, Japanese patent publication 38-15608 discloses the production of dicarboxylic acid from corresponding alpha-olefin and Japanese patent Kokal 51-51390, the production of alpha-hydroxy carboxylic acid respectively. Also J. Bruyn etc. report on the on the production of 1,2-hexadecenediol from 1-hexadecene (J. Bruyn Koninkl. Ned. Akad. Watenschap Proc. Ser., 57c41 (1954);
J.E. Stewart. W.R. Finnerty, R.E. Kallia and D.P. Stevenson, Science, 132 1251 (1960); T. Ishikawa and J.W.
Foster, Nature, 192 892 (1961)).
However, the production of any substance, except dicarboxylic acid, which possesses a functional group such as carboxylic group or hydroxyl group at the terminal and adjacent carbon of the chain is not mentioned in these reports.
Generally, intra-molecular condensation and inter-molecular condensation tend to occur in long-chain hydrocarbons possessing a carboxylic group/groups at a terminal or terminals of the chains and a hydroxy group/groups at a terminal, terminals or near the terminals. Specifically, long-chain hydrocarbons which possess methylene groups in their carbon chains are promising raw materials of polymers, medicine, anti-corrosive agents and perfumery, and especially, 15-hydroxypentadecanoic acid is useful as a raw material of synthesis of large cyclic lactone which is an expensive perfume.
It is, therefore, an object of this invention to provide a process for producing carboxylic acids having o, (o-l )-dihydroxy carboxylic acid as a chief ingredient.
According to the present ivention there is provided a method of producing a carboxylic acid mixture containing o, ((0-1 )-dihydroxy carboxylic acid as the main component, comprising cultivating a microorganism of the genus Candida or cells thereof with an a-olefin of from 12 to 18 carbon atoms.
The alpha-olefin used in this invention is, preferably a straight chain hydrocarbon having 12 to 18 carbon atoms. Selection of carbon number depends on the desired carboxylic acid but it is possible to use simultaneously alpha-olefins having two or more different carbon numbers.
The microorganism utilized in this invention belongs to the Candida genus and is able to assimilate or react on alpha-olefins to produce carboxylic acids have o, ((0-1 )-dihydroxy carboxylic acid as a chief ingredient as shown in the above formula (1) or to produce along with said (1) at least one from the compounds expressed in the above mentioned formulae (2) to (5).
Candida tropicalis BR-254 used in the examples of this invention which will be described below has been deposited with Fermentation Research Institute, Agency of Industrial Science and Technology with a deposit number FERM P-4604.
Following are the microbiological properties of this strain: (1) Size and shape: Short oval (4x8)"x(5-11), Forming of spores Negative (2) Cultural characteristics:
Streak culture on an agar medium containing glucose, yeast extract and peptone:
The colony is light yellowish white, dull and smooth on the surface.
(3) Fermentation of sugars:
Glucose + Trehalose +
Galactose + Lactose
Sucrose + Melibiose
Maltose + Raffinose
Cellobiose - Melezitose
Inulin (4) Assimilation of carbon compounds:
Glucose + Ethanol +
Galactose + Glycerol +
D-Ribose - Erythrytol +
L-Rhamnose - Ribotol +
L-Sorbose + Galactitol
Sucrose + D-Mannitol +
Maltose + D-Glunitol +
Cellobiose - a-Methyl-D-Glucoside +
Melibiose - Salicin +
Raffinose - DL-Lactic acid 42
Inulin - Succinic acid +
Soluble starch + Citric acid +
D-Xylose + Inositol
L-Arabinose +
D-Arabinose (5) Assimilation of KNO3: Negative (6) Vitamin requirement: Biotin (7) Growth in a medium lacking
vitamin:Weak (8) NaCltolerance: 11-13% (9) Maximum temp. for growth: 41 - 43"C (10) Guanosine-cytosine content: 35.3%
Pre-cultivation of said microorganism may be carried out with assimilable carbon source, for example, a-olefins, sugars and other carbon compounds to grow a cell mass and then the grown cells may be cultured in a medium with alpha-olefin as a substrate, or so called resting cell reaction may be carried out with the alpha-olefin as a substrate in a medium aerobically.
Carbon sources appropriate to a growth medium can include, besides alpha-olefin, glucose, sucrose, maltose, trehalose or substances containing these ingredients.
Nitrogen sources can include ammonium chloride, ammonium sulfate, ammonia in solution, urea, amino acids or substances containing these ingredients.
Trace growth stiumlants and minerals needed for growth can include zinc sulfate, ferrous sulfate, magnesium sulfate, manganese sulfate, potassium phosphate and sodium phosphate as minerals and vitamins and nucleic acids as trace growth stimulants. In addition, compounds such as peptone and corn steep liquor may be included. In short, the media should contain assimilable and nutrient substances selected in a wide range for the production of the desired product. Amounts of these additives can be appropriately determined according to the well known method employed for fermentation.
In this invention, said microorganism is cultured in the medium described above at a pH about 7 and temperature of about 30"C for 72 to 96 hours aerobically by shaking so that said microorganism can contact the substrate and other components of the medium sufficiently. When foaming is observed during the cultivation, an appropriate amount of defoaming agent is added to control foaming and prevent cells from mixing in foams. The thus produced products contain (o,(u)-1)-dihydroxy carboxylic acid as shown in formula 1 above and in addition, one or more components shown in formulae 2 to 5 above.
In order to separate and recover each compound from the mixture of products the following procedure may be used: cells are removed from the mixture of the cultivation or reaction products and resultant liquid is adjusted to pH 2, the obtained white crystalline precipitate is methylated and separated into individual compounds through a silica gel column or by fractional distillation.
The present invention will now be described by way of example.
EXAMPLE 1
Preparation ofseeds:
Cadida tropicalis BR-254 (FERM P-4604) was streak-cultured on malt extract agar (manuf. by Oxoid, Code
CM 59) slant at 30"C for 24 hours. Separately, 30g of sucrose, 10g of sodium acetate of Nl14CI, 29 of K2HPO4, 0.6g of MgSO4. 7H2O, lOmg of FeSO4.7H.20,8mg of MnSO4.4-5H20,8mg of ZnS04. 7H20 and 5ill9 of biotin were dissolved in 1 liter of deionized water, adjusted to pH 6.5, sterilized at 115"C for 15 minutes and 50ml of it was placed in a 500ml Erlenmeyer flask to which two loopfuls of cells of said strain were inoculated in order to carry out cultivation by reciprocal shaking at 28"C for 24 hours.As a result, 50ml of seed solution was obtained.
Cultivation:
One litre of a medium containing 5 grams of Na2HPO4.12H2O, 4g of NH4Cl, 0.6g of MgSO4.7H2O, lOmg of FeSO4. 7H2O, 8 mg of MnSO4.4-5H2O,8mg of ZnSO4.7H2O and 5F9 of biotin which were dissolved in 1 liter deionized water and adjusted to pH7 and added to a 2 litre jar fermentor along with 100ml tetradecene, and sterilized at 1150for 15 min. To said medium 50ml of seeds prepared as described above was inoculated; then cultivation was carried out for 24hr at 30"C with aeration at 0.6L/min and agitation at 800rpm, and pH was controlled at pH7 using 2N KOH.Further cultivation was followed at 30"C, agitation at 600rpm and aeration at 0.9L/min for 48hr.
Separation ofproducts: The produced broth was adjusted at pH 9.0 with 2N KOH, centrifuged at 6000rpm for 15min in order to remove cells and resultant water layer was adjusted to pH 2.0 with concentrated hydrochloric acid. Obtained white crystalline precipitate was filtered with suction and dissolved in 200ml of 1 N KOH to carry out extraction with ether. Resultant water layer was adjusted to pH 2.0 with concentrated hydrochloric acid to conduct extraction with ether and then the ether was removed by distillation under reduced pressure. As a result, 4.5g of white crystalline matter was obtained.When 500mg of said mixture was methylated with diazomethane, placed on the column filled with silica gel and eluted with 10% ethyl acetate in chloroform, 4 kinds of compounds were eluted. Further elution was carried out with ethyl acetate and one kind of compound was eluted. Table 1 shows the weight of these five products and their weight percentage.
TABLE 1
Compound by number 1) Weight (mg) Weight percentage
No.1 48 11.2
No. 2 23 5.4
No.3 32 7.5
No.4 51 11.9
No. 5 274 64.2 1) indicates elution numbers.
Identification of the products:
The compound of No. 5 in Table 1 was examined by elemental analysis as well as by mass spectrometry,
I.R. and '3C-NMR. The results are in Table 2.
TABLE 2
Experimental Calculated (%) Elemental Analysis C 65.76 65.66
H 11.24 11.02 JR absorption
C=O 1740cm-1
-O-H 3320cm-1(broad) Polyol 3480cm-1 13C-NMR absorption
(ppm) 51.9 1758 34.4 26.0 30.1 26.7 34.7 73.2 67.4
30.8
Mass spectrometry (measured as trimethylsilylether) M+ - CH3 m/e 403
M+ - OCH3 m/e 387 Me - (CH2OTMS) m/e315 From the above results, the compound of (5) is identified as methyl 13,14-dihydroxytetradecanoate.
The compounds of Nos. 1 to 4 were analyzed in the same manner as above, and it was confirmed that these compounds had following structures: No. 1: Dimethyltetradecanedioate No. 2: Dimethyl-2-hydroxytetradecanedioate No. 3: Methyl-l 4-hydroxytetradecanoate No. 4: Methyl-13-hydroxy-14-methoxytetradecanoate
Table 3 shows the results of 13C-NMR
TABLE 3
Compound No. 1
Compound No. 2
Compound No. 3
Compound No. 4
EXAMPLE 2
Cultivation was carried out in the same manner as in Example 1 except that dodecene-1, hexadecene-1 and octadecene-l were used respectively instead of tetradecene-l.
Seeds prepared as described in Example 1 was inoculated to a 20ml medium in a 500ml flask consisting of the same compounds as in Example 1 and added with 2ml of tridecene-l, pentadecene-l and heptadecene-1 respectively. A cultivation was conducted by reciprocal shaking (opm :155) at 30"C for 96 hours. The produced broth was adjusted to pH 2 after removing cells and filtered to obtain precipitate which was dissolved in IN KOH solution and extracted by ether. The resultant water layer was adjusted to pH 2 with concentrated hydrochloric acid and extracted with ether. After removing the ether the precipitate was weighed, methylesterified andtrimethylsilylated (using TMS-HT manuf. by Tokyo Kasei Co.) in order to analyze the product by gas chromatography equipped with hydrogen flame ionization detector.
Table 4 shows the obtained ratio of area expressed in precentage.
As shown in the table, the total of each ratio of area did not reach 100%, because there was/were some ingredients that could not be identified.
TABLE 4
Total ratio of each area in
gas chromatographic analysis (%)
Weight I II ill IV V Total
Substrate Recovered (%) (%) (%) (%) (%) n-Dodecene-1 2.5g 60.3 8.8 5.2 6.6 9.0 89.9 n-Hexadecene-l 5.49 61.2 10.3 4.9 6.5 10.8 93.7 n-Octadecene-l 2.99 57.6 10.1 4.7 6.2 10.0 88.6 n-Tridecene-1 0.055g 60.3 10.4 4.6 6.8 8.1 90.2 n-Pentadecene-1 0.063g 58.5 10.1 5.0 6.9 6.3 86.8 n-Heptadecene-1 0.058g 55.8 10.2 5.0 6.4 9.9 87.3 I HOOC (CH2)n 3-CH(OH)CH2(OH) II HOOC (CH2)n 2-COOH Ill HOOC (CH2)n 3-CH(OH)COOH IV HOOC (CH)n 2-CH2OH V HOOC (CH2)n 3-CH(OH)CH2OCH3
Claims (7)
1. A method of producing a carboxylic acid mixture containing 0),(0)-1 )-dihydroxy carboxylic acid as the main component, comprising cultivating a microorganism of the genus Candida or cells thereof with an x-olefin of from 12 to 18 carbon atoms.
2. A method according to Claim 1, in which the microorganism in Candida tropicalis BR-254 (FERM
P-4604).
3. A method according to Claim 1 or Claim 2 in which the cultivation is conducted at a temperature of 30"C and a pH of 7 for a period of from 72 to 96 hours.
4. A method according to Claim 1 or 2 or 3, in which the cultivation product is processed to nearer the acids by removal of the cells and separation by fractional distillation or by chromatography.
5. A method of producing a carboxylic acid mixture containing 0),(0)-1 )-dihydroxy carboxylic acid, according to Example 1 or Example 2 hereinbefore.
6. A method of producing a carboxylic acid mixture containing W,(0)-1 )-dihydroxy carboxylic acid, according to Claim 1, substantially as hereinbefore described.
7. An co,(eo-1) dihydroxy carboxylic acid and acid mixtures containing same whenever produced by the method claimed in any of Claims 1 to 6.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11337378A JPS5539778A (en) | 1978-09-14 | 1978-09-14 | Microbial preparation of carboxylic acid composed mainly of omega,omega-1-dihydroxy acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2031885A true GB2031885A (en) | 1980-04-30 |
| GB2031885B GB2031885B (en) | 1983-02-02 |
Family
ID=14610635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7931897A Expired GB2031885B (en) | 1978-09-14 | 1979-09-14 | Microbiological production of carboxylic acid mixtures containing(1)-dihydroxy carboxylic acid |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5539778A (en) |
| BE (1) | BE878774A (en) |
| DE (1) | DE2937292A1 (en) |
| FR (1) | FR2436184A1 (en) |
| GB (1) | GB2031885B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0199972A1 (en) * | 1985-04-23 | 1986-11-05 | Hüls Aktiengesellschaft | 3-Hydroxy-dicarboxylic acids and process for their preparation |
| CN103555308A (en) * | 2013-11-05 | 2014-02-05 | 河南省科学院高新技术研究中心 | Application of sophorolipid in biological corrosion inhibitor for oil field produced water |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56134991A (en) * | 1980-03-26 | 1981-10-22 | Baiorisaac Center:Kk | Preparation of 2-hydroxy diacid by utilizing microorganism |
| WO1991014781A1 (en) * | 1990-03-19 | 1991-10-03 | Henkel Research Corporation | METHOD FOR INCREASING THE OMEGA-HYDROXYLASE ACTIVITY IN $i(CANDIDA TROPICALIS) |
| CA2349868C (en) | 1998-10-05 | 2010-07-20 | Cognis Corporation | Cytochrome p450 monooxygenase and nadph cytochrome p450 oxidoreductase genes and proteins related to the omega hydroxylase complex of candida tropicalis and methods relating thereto |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5019630B1 (en) * | 1969-11-10 | 1975-07-08 |
-
1978
- 1978-09-14 JP JP11337378A patent/JPS5539778A/en active Granted
-
1979
- 1979-09-13 FR FR7922930A patent/FR2436184A1/en active Pending
- 1979-09-13 BE BE0/197135A patent/BE878774A/en unknown
- 1979-09-14 DE DE19792937292 patent/DE2937292A1/en not_active Withdrawn
- 1979-09-14 GB GB7931897A patent/GB2031885B/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0199972A1 (en) * | 1985-04-23 | 1986-11-05 | Hüls Aktiengesellschaft | 3-Hydroxy-dicarboxylic acids and process for their preparation |
| US4827030A (en) * | 1985-04-23 | 1989-05-02 | Huels Aktiengesellschaft | 3-hydroxydicarboxylic acids and process for their production |
| CN103555308A (en) * | 2013-11-05 | 2014-02-05 | 河南省科学院高新技术研究中心 | Application of sophorolipid in biological corrosion inhibitor for oil field produced water |
| CN103555308B (en) * | 2013-11-05 | 2015-12-02 | 河南省科学院高新技术研究中心 | The application of sophorolipid in oil field extracted water Biologic inhibitor |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2436184A1 (en) | 1980-04-11 |
| JPS5539778A (en) | 1980-03-19 |
| JPS5644716B2 (en) | 1981-10-21 |
| GB2031885B (en) | 1983-02-02 |
| BE878774A (en) | 1980-03-13 |
| DE2937292A1 (en) | 1980-04-03 |
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| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |