JPH01316341A - Production of omega-hydroxy fatty acid - Google Patents
Production of omega-hydroxy fatty acidInfo
- Publication number
- JPH01316341A JPH01316341A JP63192692A JP19269288A JPH01316341A JP H01316341 A JPH01316341 A JP H01316341A JP 63192692 A JP63192692 A JP 63192692A JP 19269288 A JP19269288 A JP 19269288A JP H01316341 A JPH01316341 A JP H01316341A
- Authority
- JP
- Japan
- Prior art keywords
- borohydride
- monoester
- metallic salt
- alkaline earth
- acid
- 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.)
- Granted
Links
- 235000014113 dietary fatty acids Nutrition 0.000 title claims description 11
- 239000000194 fatty acid Substances 0.000 title claims description 11
- 229930195729 fatty acid Natural products 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- -1 boron hydride compound Chemical class 0.000 claims abstract description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 9
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 abstract description 6
- 150000002596 lactones Chemical class 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 3
- 229910010277 boron hydride Inorganic materials 0.000 abstract 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 abstract 1
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 239000002304 perfume Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 10
- 239000012279 sodium borohydride Substances 0.000 description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 description 7
- KWBXOAXXGSYUEH-UHFFFAOYSA-N 15-methoxy-15-oxopentadecanoic acid Chemical compound COC(=O)CCCCCCCCCCCCCC(O)=O KWBXOAXXGSYUEH-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910052788 barium Inorganic materials 0.000 description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 5
- 159000000009 barium salts Chemical class 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000011592 zinc chloride Substances 0.000 description 5
- 235000005074 zinc chloride Nutrition 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000012448 Lithium borohydride Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N 12-hydroxylauric acid Chemical compound OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- AKKQEFPXXLRKLT-UHFFFAOYSA-N 15-ethoxy-15-oxopentadecanoic acid Chemical compound CCOC(=O)CCCCCCCCCCCCCC(O)=O AKKQEFPXXLRKLT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OXXOYNFTOCTMGG-UHFFFAOYSA-N acetic acid;6-amino-2-[[2-(2,6-diaminohexanoylamino)-3-(4-hydroxyphenyl)propanoyl]amino]hexanoic acid Chemical compound CC(O)=O.NCCCCC(N)C(=O)NC(C(=O)NC(CCCCN)C(O)=O)CC1=CC=C(O)C=C1 OXXOYNFTOCTMGG-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野]
本発明は、ω−ヒドロキシ脂肪酸を製造する方法に関す
る。ω−ヒドロキシ脂肪酸は、医薬品の原料或いは香料
等として用いられる大環状ラクトンの合成原料として有
用なものであり。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing ω-hydroxy fatty acids. ω-Hydroxy fatty acids are useful as raw materials for the synthesis of macrocyclic lactones used as raw materials for pharmaceuticals or fragrances.
さらには、ポリマー原料として、その用途も広い。Furthermore, it has a wide range of uses as a polymer raw material.
[従来の技術]
ω−ヒドロキシ脂肪酸の製造方法としては、従来、ω−
ヒドロキシ−もしくは、ω−アシロキシ−アルキル−γ
−ブチロラク1〜ンを、水添分解触媒の存在下、水素ガ
スの共存下で接触反応せしめる方法(特公昭61−37
76号公報)或いは、13−オキサ−ビシクロ[10,
4゜0]−へキサデセン[1(12)]をラクトンに転
化し、当該ラクトンをウオルフーキシナー法又は、ファ
ンーミノロン法によりラクトン環を開環する方法(特公
昭61−21474号公報)等が提案されている。これ
らの方法は、いずれも複雑な化合物を出発原料とするた
め、高価な原料を用いることになり、延いては、′I5
造コストが高くなるという問題を有していた。[Prior Art] Conventionally, as a method for producing ω-hydroxy fatty acids, ω-
Hydroxy- or ω-acyloxy-alkyl-γ
- A method of catalytically reacting butyrolactone in the presence of a hydrogen cracking catalyst and in the coexistence of hydrogen gas (Japanese Patent Publication No. 61-37
76) or 13-oxa-bicyclo[10,
A method has been proposed in which 4゜0]-hexadecene [1(12)] is converted into a lactone and the lactone ring is opened by the Wolffukisiner method or the van-minolone method (Japanese Patent Publication No. 61-21474). has been done. All of these methods use complex compounds as starting materials, resulting in the use of expensive raw materials, and as a result, 'I5
The problem was that the manufacturing cost was high.
本発明者は、これに対して、比較的安価な長鎖二酸を出
発原料とし、この二酸をジエステルとし、次いで、これ
に例えば、水酸化バリウムを添加して、バリウムのモノ
塩とし、次いで、当該バリウムを酸で置換してモノエス
テル化し、当該モノエステルを銅−クロム酸化物触媒の
存在下に還元して、ω−ヒドロキシ脂肪酸を製造する方
法を提案した(特願昭61−231253号)。In contrast, the present inventor uses a relatively inexpensive long-chain diacid as a starting material, converts this diacid into a diester, and then adds, for example, barium hydroxide to this to obtain a monosalt of barium. Next, we proposed a method for producing ω-hydroxy fatty acids by substituting the barium with an acid to monoesterify the monoester and reducing the monoester in the presence of a copper-chromium oxide catalyst (Japanese Patent Application No. 61-231253). issue).
[発明が解決しようとする問題点]
本発明者は、上記方法をさらに簡便な工程とすべく研究
を進めた結果、上記の酸で置換する前の長鎖二酸モノエ
ステルのアルカリ金属塩又はアルカリ土類金属塩が、水
素化ホウ素化合物で還元されること、さらに、特に水素
化ホウ素リチウム、水素化ホウ素カルシウム、水素化ホ
ウ素マグネシウム、水素化ホウ素亜鉛等を還元剤として
用いると、高い選択性でエステル基のみが還元されるこ
とを見い出した。[Problems to be Solved by the Invention] As a result of conducting research to make the above method a simpler process, the present inventor discovered that the alkali metal salt of the long chain diacid monoester or Alkaline earth metal salts can be reduced with borohydride compounds, and in particular, when lithium borohydride, calcium borohydride, magnesium borohydride, zinc borohydride, etc. are used as reducing agents, high selectivity can be achieved. We found that only the ester group was reduced.
本発明は、上記知見に鑑みなされたもので、本発明の目
的は、安価な原料を用いて、比較的簡便な工程で、安価
に、しかも効率良く、ω−ヒドロキシ脂肪酸を製造する
方法を提案することにある。The present invention was made in view of the above findings, and an object of the present invention is to propose a method for producing ω-hydroxy fatty acids at low cost and efficiently using inexpensive raw materials and a relatively simple process. It's about doing.
[問題点を解決するための手段]
本発明は、長鎖二酸モノエステルのアルカリ金属塩又は
アルカリ土類金属塩を水素化ホウ素化合物で還元するこ
とからなるω−ヒドロキシ脂肪酸の製造方法である。[Means for solving the problems] The present invention is a method for producing ω-hydroxy fatty acids, which comprises reducing an alkali metal salt or alkaline earth metal salt of a long-chain diacid monoester with a borohydride compound. .
上記長鎖二酸モノエステルは、医薬品の原料或いは香料
のためのラクトンを得る場合は、炭素数9〜18のアル
カンニ酸のモノエステルを用いることが好ましいが、か
かる炭素数のものに限られるものではない。The long-chain diacid monoester mentioned above is preferably a monoester of alkanniic acid having 9 to 18 carbon atoms when obtaining a lactone for pharmaceutical raw materials or fragrances, but it is limited to those having such a carbon number. isn't it.
このモノエステルのアルカリ金属塩又はアルカリ土類金
属塩は、アルカンニ酸をアルコールでジエステル化し、
これにアルカリ金属又はアルカリ土類金属の水酸化物を
添加すると、エステル基の一方が、モノエステル塩とな
って固体として反応系外に析出し、これを固液分離する
ことにより得られる。この場合のアルカリ金属又はアル
カリ土類金属としては、リチウム、ナトリウム、カリウ
ム、ルビジウム、ベリリウム、マグネシウム、カルシウ
ム、ストロンチウム。The alkali metal salt or alkaline earth metal salt of this monoester is obtained by diesterizing an alkanioic acid with an alcohol,
When an alkali metal or alkaline earth metal hydroxide is added to this, one of the ester groups becomes a monoester salt and precipitates out of the reaction system as a solid, which is obtained by solid-liquid separation. In this case, the alkali metals or alkaline earth metals include lithium, sodium, potassium, rubidium, beryllium, magnesium, calcium, and strontium.
バリウム等を例示できるが、バリウムが、モノエステル
塩の収率を高くでき好ましい。Examples include barium, but barium is preferred because it can increase the yield of the monoester salt.
また、上記ジエステル化のためのアルコールは、炭素数
1〜4の低級アルコールを用いることが、エステル化物
の分離精製を容易にできるために好ましい。Moreover, it is preferable to use a lower alcohol having 1 to 4 carbon atoms as the alcohol for the above-mentioned diesterification, since the esterified product can be easily separated and purified.
尚、アルカンニ酸は、相当する炭素数のアルカンを微生
物の存在下に酸化することにより比較的安価に生産され
ている。Incidentally, alkaniic acid is produced relatively inexpensively by oxidizing an alkane having a corresponding number of carbon atoms in the presence of microorganisms.
上記の長鎖二酸モノエステルのアルカリ金属塩又はアル
カリ土類金属塩に水素化ホウ素化合物を還元剤として作
用させるが、この場合の使用量は、当該塩中の二酸モノ
エステル1モルに対し、0.5〜1モル程度とすること
が経済的に好ましい。尚、この水素化ホウ素化合物は、
水素化ホウ素リチウム、水素化ホウ素カルシウム、水素
化ホウ素亜鉛、水素化ホウ素マグネシウム、水素化ホウ
素カリウム、水素化ホウ素ベリリウム、水素化ホウ素バ
リウム等を用いることができるが、特には、還元を高い
選択率で行うことができる水素化ホウ素リチウム、水素
化ホウ素カルシウム、水素化ホウ素マグネシウム、水素
化ホウ素亜鉛が好ましい。さらに、水素化ホウ素化合物
は、他の化合物と混合して用いることができ1例えば、
水素化ホウ素ナトリウムは塩化アルミニウムとの混合物
として用いると還元反応の速度はより速くなる。また、
前記の水素化ホウ素化合物は、水素化ホウ、素ナトリウ
ムと対応するハロゲン化物との反応、例えば、水素化ホ
ウ素リチウムは水素化ホウ素ナトリウムと塩化リチウム
との反応により得られる。この場合、水素化ホウ素化合
物の種類はもとより、水素化ホウ素化合物の調製の方法
によっても活性及び選択性に差が生じ、水素化ホウ素ナ
トリウムとヨウ化亜鉛とを反応させて得られた水素化ホ
ウ素亜鉛は、極めて高い選択性と反応性を有しており、
特に好ましいものである。尚、これらの水素化ホウ素化
合物は、前もって調製し、還元反応を行う際に添加して
も良いが、還元反応の反応容器内で、調製して、そのま
ま反応に用いても良い。A borohydride compound is allowed to act as a reducing agent on the alkali metal salt or alkaline earth metal salt of the long-chain diacid monoester mentioned above. In this case, the amount used is per mole of the diacid monoester in the salt. , it is economically preferable to set the amount to about 0.5 to 1 mol. In addition, this borohydride compound is
Lithium borohydride, calcium borohydride, zinc borohydride, magnesium borohydride, potassium borohydride, beryllium borohydride, barium borohydride, etc. can be used, but especially those with high selectivity for reduction can be used. Lithium borohydride, calcium borohydride, magnesium borohydride, and zinc borohydride are preferred. Furthermore, the borohydride compound can be used in mixture with other compounds1, for example,
When sodium borohydride is used as a mixture with aluminum chloride, the rate of the reduction reaction becomes faster. Also,
The above-mentioned borohydride compounds can be obtained by reacting borohydride, sodium borohydride, and the corresponding halide; for example, lithium borohydride can be obtained by reacting sodium borohydride with lithium chloride. In this case, the activity and selectivity vary depending not only on the type of borohydride compound but also on the method of preparing the borohydride compound. Zinc has extremely high selectivity and reactivity,
This is particularly preferred. Note that these borohydride compounds may be prepared in advance and added when performing the reduction reaction, or they may be prepared in the reaction vessel for the reduction reaction and used as they are in the reaction.
この還元反応は、上記水素化ホウ素化合物を有機溶媒、
例えば、ジエチレングリコールジメチルエーテル、ジエ
チルエーテル、テトラヒドロフラン、ジオキサン、N、
N−ジメチルホルムアミド、ジメチルスルホキシド等に
1〜10重量%濃度で懸濁させ、これに上記モノエステ
ル塩を同様の溶媒に10〜30重量%濃度で懸濁した液
を滴下し、0〜100℃の温度で、1〜30時間撹拌反
応させることにより行うことができる。In this reduction reaction, the above-mentioned borohydride compound is treated with an organic solvent,
For example, diethylene glycol dimethyl ether, diethyl ether, tetrahydrofuran, dioxane, N,
It is suspended in N-dimethylformamide, dimethyl sulfoxide, etc. at a concentration of 1 to 10% by weight, and a solution prepared by suspending the above monoester salt in the same solvent at a concentration of 10 to 30% by weight is added dropwise to the suspension, and the mixture is heated at 0 to 100°C. The reaction can be carried out by stirring the reaction at a temperature of 1 to 30 hours.
反応終了後は、反応液を塩酸、硫酸、硝酸、酢酸等の酸
水溶液に加えて、未反応の水素化ホウ素化合物を潰し、
ついで酸性にして、ω−ヒドロキシ脂肪酸のバリウム塩
を加水分解し、析出した有機物を濾別除去することによ
り、ω−ヒドロキシ脂肪酸を得ることができる。After the reaction is complete, add the reaction solution to an aqueous acid solution such as hydrochloric acid, sulfuric acid, nitric acid, or acetic acid to crush the unreacted borohydride compound.
Next, the barium salt of the ω-hydroxy fatty acid is acidified, and the precipitated organic matter is removed by filtration to obtain the ω-hydroxy fatty acid.
[実施例]
(実施例1)
水素化ホウ素ナトリウム0.76g(20n+mol)
をジエチレングリコールジメチルエーテル20m1に懸
濁させ、これに塩化リチウム0.85g(20s mo
l)を加え、室温で30分間撹拌した。[Example] (Example 1) Sodium borohydride 0.76g (20n+mol)
was suspended in 20 ml of diethylene glycol dimethyl ether, and 0.85 g of lithium chloride (20 s mo
1) was added and stirred at room temperature for 30 minutes.
次に、これにペンタデカン二酸モノメチルエステルのバ
リウム塩7.18 g(二階として20mmol)をジ
エチレングリコールジメチルエーテル30m1に懸濁し
た液を滴下し、引き続き、80℃の温度で、22時間撹
拌した0反応終了後、濃塩酸11m1を含むイオン交換
水120m1に反応液を加え、室温で30分間撹拌し、
ω−ヒドロキシペンタデカン酸を析出させた。これを濾
別し、ω−ヒドロキシペンタデカン酸を得た。Next, a suspension of 7.18 g (20 mmol of barium salt of pentadecanedioic acid monomethyl ester) in 30 ml of diethylene glycol dimethyl ether was added dropwise to this, and the reaction was subsequently stirred at a temperature of 80° C. for 22 hours. After that, the reaction solution was added to 120 ml of ion-exchanged water containing 11 ml of concentrated hydrochloric acid, and stirred at room temperature for 30 minutes.
ω-hydroxypentadecanoic acid was precipitated. This was filtered to obtain ω-hydroxypentadecanoic acid.
ガスクロマトグラフィーにより分析した結果、純度84
%、収率76%であった。As a result of analysis by gas chromatography, the purity was 84.
%, yield was 76%.
(実施例2)
ペンタデカン二酸モノメチルエステルの代りにペンタデ
カン二酸モノエチルエステル7.36g(二階として2
0n mol)を用いた以外は、実施例1と同じ操作で
ω−ヒドロキシペンタデカン酸を得た。この場合の収率
は70%であった。(Example 2) Instead of pentadecanedioic acid monomethyl ester, 7.36 g of pentadecanedioic acid monoethyl ester (2
ω-hydroxypentadecanoic acid was obtained in the same manner as in Example 1 except that ω-hydroxypentadecanoic acid was used. The yield in this case was 70%.
(実施例3)
ペンタデカン二酸モノメチルエステルの代りにドデカン
二酸モノメチルエステル6.24g(二階として20r
1mol)を用いた以外は、実施例1と同じ操作でω−
ヒドロキシドデカン酸を得た。この場合の収率は70%
であった。(Example 3) 6.24 g of dodecanedioic acid monomethyl ester (20 r as the second floor) was used instead of pentadecanedioic acid monomethyl ester.
ω-
Hydroxydodecanoic acid was obtained. The yield in this case is 70%
Met.
(実施例4)
水素化ホウ素ナトリウム0.76g(20+mmol)
をジエチレングリコールジメチルエーテル20m1に懸
濁させ、これに塩化カルシウム2.22 g(20n
mol)を加え、室温で30分間撹拌した。(Example 4) Sodium borohydride 0.76g (20+mmol)
was suspended in 20ml of diethylene glycol dimethyl ether, and 2.22g of calcium chloride (20n
mol) and stirred at room temperature for 30 minutes.
次に、これにペンタデカン二酸モノメチルエステルのバ
リウム塩7.18 g(二階として20mmol)をジ
エチレングリコールジメチルエーテル30m1に懸濁し
た液を滴下し、引き続いて、80℃の温度で、9時間撹
拌した。反応終了後、実施例1と同様の操作を行い、ω
−ヒドロキシペンタデカン酸を、収率76%で得た。Next, a suspension of 7.18 g (20 mmol of barium salt of pentadecanedioic acid monomethyl ester) in 30 ml of diethylene glycol dimethyl ether was added dropwise thereto, followed by stirring at a temperature of 80° C. for 9 hours. After the reaction is completed, the same operation as in Example 1 is performed, and ω
-Hydroxypentadecanoic acid was obtained with a yield of 76%.
(実施例5)
実施例4において、塩化カルシウムの代りに塩化マグネ
シウム1.90g(20m mol)を用い。(Example 5) In Example 4, 1.90 g (20 mmol) of magnesium chloride was used instead of calcium chloride.
80℃、9時間に代えて、100℃、6時間撹拌した以
外は、実施例4と同様の操作を行い、ω−ヒドロキシペ
ンタデカン酸を得た。この場合の収率は88%であった
。The same operation as in Example 4 was performed except that stirring was performed at 100°C for 6 hours instead of at 80°C for 9 hours to obtain ω-hydroxypentadecanoic acid. The yield in this case was 88%.
(実施例6)
実施例4において、塩化カルシウムの代りに塩化亜鉛2
.73g(20mmol)を用い、80℃。(Example 6) In Example 4, zinc chloride 2 was used instead of calcium chloride.
.. 73 g (20 mmol) was used at 80°C.
9時間に代えて、80℃で3時間撹拌した以外は、実施
例4と同様の操作を行い、ω−ヒドロキシペンタデカン
酸を得た。この場合の収率は84%であった。The same operation as in Example 4 was performed except that stirring was performed at 80° C. for 3 hours instead of 9 hours to obtain ω-hydroxypentadecanoic acid. The yield in this case was 84%.
(実施例7)
実施例6において、塩化亜鉛の代りにヨウ化亜鉛3.1
9 g(10m mol)を加えた以外は、実施例6と
同様の操作を行い、ω−ヒドロキシペンタデカン酸を得
た。この場合の収率は94%であった。(Example 7) In Example 6, 3.1% of zinc iodide was used instead of zinc chloride.
Except for adding 9 g (10 mmol), the same operation as in Example 6 was performed to obtain ω-hydroxypentadecanoic acid. The yield in this case was 94%.
(実施例8)
実施例6において、塩化亜鉛の代りに臭化亜鉛2.25
g(10m mol)を加えた以外は、実施例6と同
様の操作を行い、ω−ヒドロキシペンタデカン酸を得た
。この場合の収率は46%であった。(Example 8) In Example 6, 2.25% of zinc bromide was used instead of zinc chloride.
The same operation as in Example 6 was performed except that g (10 mmol) was added to obtain ω-hydroxypentadecanoic acid. The yield in this case was 46%.
(実、流側9)
水素化ホウ素ナトリウム0.76 g(20m mol
)をジオキサン50m1に懸濁させ、これに塩化亜鉛5
.45 g(40+++ mol)を加え、室温で30
分間撹拌した。次に、これにペンタデカン二酸モノメチ
ルエステルのバリウム塩7.18 g(二階として20
n mol)をジオキサン50m1’に懸濁した液を滴
下し、引き続いて、80℃の温度で。(Actually, stream side 9) Sodium borohydride 0.76 g (20 m mol
) was suspended in 50 ml of dioxane, and 5 ml of zinc chloride was added to it.
.. Add 45 g (40+++ mol) and leave at room temperature for 30
Stir for a minute. Next, 7.18 g of barium salt of pentadecanedioic acid monomethyl ester (20 g as a second layer) was added to this.
n mol) in 50 ml of dioxane was added dropwise at a temperature of 80°C.
9時間撹拌した。反応終了後、実施例1と同様の操作を
行い、ω−ヒドロキシペンタデカン酸を、収率82%で
得た。Stirred for 9 hours. After the reaction was completed, the same operation as in Example 1 was performed to obtain ω-hydroxypentadecanoic acid in a yield of 82%.
(実施例10)
水素化ホウ素ナトリウム0.76g(20mmo1)を
ジメトキシエタン20m1に懸濁させ、これに塩化亜鉛
2.73 g(20m mol)を加え、室温で30分
間撹拌した。次に、これにペンタデカン二酸モノメチル
エステルのバリウム塩7.18g(二階として20n
mol)をジメトキシエタン30m1に懸濁した液を滴
下し、引き続いて、80℃の温度で、9時間撹拌した。(Example 10) 0.76 g (20 mmol) of sodium borohydride was suspended in 20 ml of dimethoxyethane, 2.73 g (20 mmol) of zinc chloride was added thereto, and the mixture was stirred at room temperature for 30 minutes. Next, add to this 7.18 g of barium salt of pentadecanedioic acid monomethyl ester (20n as a second layer).
mol) in 30 ml of dimethoxyethane was added dropwise, followed by stirring at a temperature of 80° C. for 9 hours.
反応終了後、実施例1と同様の操作を行い、ω−ヒドロ
キシペンタデカン酸を、収率35%で得た。After the reaction was completed, the same operation as in Example 1 was performed to obtain ω-hydroxypentadecanoic acid in a yield of 35%.
[発明の効果]
本発明は、長鎖二階モノエステルのアルカリ金属塩又は
アルカリ土類金属塩を直接、水素化ホウ素化合物で還元
するようにしたので、比較的簡便な工程で、製造コスト
が安く、しかも効率よく、ω−ヒドロキシ脂肪酸を製造
できるという格別の効果を奏するものである。[Effects of the invention] In the present invention, the alkali metal salt or alkaline earth metal salt of a long-chain second-order monoester is directly reduced with a borohydride compound, so the process is relatively simple and the manufacturing cost is low. Moreover, it has the special effect of being able to efficiently produce ω-hydroxy fatty acids.
Claims (1)
類金属塩を水素化ホウ素化合物で還元することを特徴と
するω−ヒドロキシ脂肪酸の製造方法。A method for producing ω-hydroxy fatty acids, which comprises reducing an alkali metal salt or alkaline earth metal salt of a long-chain diacid monoester with a borohydride compound.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63192692A JP2551464B2 (en) | 1987-12-07 | 1988-08-03 | Method for producing ω-hydroxy fatty acid |
EP89104300A EP0357865A3 (en) | 1988-07-18 | 1989-03-10 | Process for producing omega-hydroxy fatty acids |
US07/826,638 US5191096A (en) | 1987-12-07 | 1992-01-23 | Process for producing ω-hydroxy fatty acids |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62-307417 | 1987-12-07 | ||
JP30741787 | 1987-12-07 | ||
JP63192692A JP2551464B2 (en) | 1987-12-07 | 1988-08-03 | Method for producing ω-hydroxy fatty acid |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01316341A true JPH01316341A (en) | 1989-12-21 |
JP2551464B2 JP2551464B2 (en) | 1996-11-06 |
Family
ID=26507478
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63192692A Expired - Fee Related JP2551464B2 (en) | 1987-12-07 | 1988-08-03 | Method for producing ω-hydroxy fatty acid |
Country Status (1)
Country | Link |
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JP (1) | JP2551464B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5218138A (en) * | 1992-09-02 | 1993-06-08 | Rhone-Poulenc Rorer Pharmaceuticals Inc. | Stereoselective reduction of 3-hydroxyket-1-ones to 1,3-syn-dihydroxylated compounds |
-
1988
- 1988-08-03 JP JP63192692A patent/JP2551464B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5218138A (en) * | 1992-09-02 | 1993-06-08 | Rhone-Poulenc Rorer Pharmaceuticals Inc. | Stereoselective reduction of 3-hydroxyket-1-ones to 1,3-syn-dihydroxylated compounds |
Also Published As
Publication number | Publication date |
---|---|
JP2551464B2 (en) | 1996-11-06 |
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