JPH03264547A - Production of long chain acyl derivatives of tartaric acid - Google Patents
Production of long chain acyl derivatives of tartaric acidInfo
- Publication number
- JPH03264547A JPH03264547A JP2061852A JP6185290A JPH03264547A JP H03264547 A JPH03264547 A JP H03264547A JP 2061852 A JP2061852 A JP 2061852A JP 6185290 A JP6185290 A JP 6185290A JP H03264547 A JPH03264547 A JP H03264547A
- Authority
- JP
- Japan
- Prior art keywords
- long chain
- tartaric acid
- dibenzyl
- long
- chain acyl
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 title abstract description 9
- 235000002906 tartaric acid Nutrition 0.000 title abstract description 9
- 239000011975 tartaric acid Substances 0.000 title abstract description 9
- 125000002252 acyl group Chemical group 0.000 title abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- -1 acyl tartrate dibenzyl ester derivative Chemical class 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 abstract description 24
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 abstract description 12
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 abstract description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 abstract description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- LCKIPSGLXMCAOF-UHFFFAOYSA-N dibenzyl 2,3-dihydroxybutanedioate Chemical compound C=1C=CC=CC=1COC(=O)C(O)C(O)C(=O)OCC1=CC=CC=C1 LCKIPSGLXMCAOF-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- 125000001165 hydrophobic group Chemical group 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 63
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- LPWCRLGKYWVLHQ-UHFFFAOYSA-N tetradecanoyl chloride Chemical compound CCCCCCCCCCCCCC(Cl)=O LPWCRLGKYWVLHQ-UHFFFAOYSA-N 0.000 description 2
- CSJCEQXZVMIHRX-UHFFFAOYSA-N 2,3-dibenzyl-2,3-dihydroxybutanedioic acid Chemical compound C=1C=CC=CC=1CC(O)(C(O)=O)C(O)(C(=O)O)CC1=CC=CC=C1 CSJCEQXZVMIHRX-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-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
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000002953 preparative HPLC Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000080 wetting agent Substances 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
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、同一分子内に親水基と親油基をあわせもつ界
面活性剤であり、また、気水界面−Ｌではカルボキシル
基を水面に向りて単分子膜を形成し、さらに、結晶中に
種々の有機溶媒を包接できるという特徴を有している酒
石酸長鎖アシル誘導体の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is a surfactant that has both a hydrophilic group and a lipophilic group in the same molecule. The present invention relates to a method for producing a long-chain acyl tartaric acid derivative, which is characterized in that it forms a monomolecular film and can include various organic solvents in the crystal.
この発明の産業上の利用分野としては、食品、化粧品、
染料などの乳化剤、安定剤、分散剤、湿潤剤として、ま
た、縮合系高分子材料、有機薄膜材料、半導体関連の有
機基板材料としてさらには、染料、香料等の包接材料と
して好適と考えられ、その工業的利用範囲は多岐にわた
っている。Industrial applications of this invention include foods, cosmetics,
It is considered suitable as an emulsifier, stabilizer, dispersant, wetting agent for dyes, etc., as a condensation polymer material, organic thin film material, semiconductor-related organic substrate material, and as an inclusion material for dyes, fragrances, etc. , its industrial applications are wide-ranging.
（式中のＲは、７〜１７の長鎖アルキル基従来の技術
従来の技術としては、酒石酸に長鎖カルボン酸塩化物を
作用させることにより、
一般式
（式中のＲは、７〜１７の長鎖アルギル基である）
で表される酒石酸長鎖アシル誘導体を製造できることが
知られている（米国特許 第２，０２５゜９８４号特許
明細誉；ブリチイン オブ ザ ケミカル ソサエティ
オブ ジャパン （１３ｕｌ＋、Ｃｈｅｍ、Ｓｏｃ、
’Ｊ ｐｎ、）第５１巻、１８７７頁）。しかしながら
、この製造方法は、長鎖カルボン酸が副生じて目的物に
混入（約４ ｍ 。(R in the formula is a long chain alkyl group of 7 to 17 It is known that it is possible to produce a long-chain acyl tartaric acid derivative represented by ,Soc,
'J pn, ) Vol. 51, p. 1877). However, in this production method, a long-chain carboxylic acid is produced as a by-product and mixed into the target product (approximately 4 m2).
１％）するため、元素分析の実測値が計算値と大きく異
なることとなり、しかも、目的物とこの長鎖カルボン酸
の結晶性、反応性などがよく似ているため、分離精製が
再結晶、再沈澱、カラムクロマトグラフィー、分取高速
液体り［１マドグラフイー等を用いても非常に困難であ
るという欠点を有している。そのため、従来、酒石酸長
鎖アシル誘導体を高純度かつ高収率で得ることは困難と
されていた。1%), the actual values of elemental analysis differ greatly from the calculated values.Moreover, since the crystallinity and reactivity of the target substance and this long-chain carboxylic acid are very similar, separation and purification may require recrystallization, It has the disadvantage that it is extremely difficult to use even if reprecipitation, column chromatography, preparative high-performance liquid chromatography [1], etc. are used. Therefore, it has conventionally been difficult to obtain long-chain acyl tartaric acid derivatives with high purity and high yield.
発明が解決しようとする課題
本発明者は、分離精製が容易で酒石酸長鎖アシル誘導体
を高純度かつ高収率で与える製造方法を開発するため鋭
意研究を重ねた結果、酒石酸ジベンジルエステル長鎖ア
シル誘導体を合成中間体として経由することを特徴とす
る酒石酸長鎖アシル誘導体の製造方法がその目的に適合
しうろことを見い出し、この知見に基づいてこの発明を
なすに至った。Problems to be Solved by the Invention The present inventor has conducted intensive research to develop a manufacturing method that is easy to separate and purify and provides long-chain tartaric acid acyl derivatives with high purity and high yield. The inventors have discovered that a method for producing long-chain acyl tartaric acid derivatives, which is characterized by using an acyl derivative as a synthetic intermediate, is suitable for the purpose, and based on this knowledge, the present invention has been accomplished.
課題を解決するための手段
すなわち、本発明は、一般式
（式中のＲは、７〜１７の長鎖アルギル基である）
で表わされる酒石酸長鎖アルキル誘導体の製造方法を提
供するものである。一般式（ＩＩ）におけるＲは炭素数
７〜１０の長鎖アルキル基であり、このようなものとし
てヘプチル基、ノニル基、ウンデシル基、トリデシル基
、ペンタデシル基、ヘプタデシル基などがある。Means for Solving the Problems, That is, the present invention provides a method for producing a long-chain alkyl tartrate derivative represented by the general formula (R in the formula is a long-chain argyl group of 7 to 17). . R in the general formula (II) is a long-chain alkyl group having 7 to 10 carbon atoms, such as a heptyl group, a nonyl group, an undecyl group, a tridecyl group, a pentadecyl group, a heptadecyl group, and the like.
この一般式（１１）で表わされる化合物は、一般式
％式％
（）
（式中のＲは、炭素数７〜１７の長鎖アルキル基である
）
で表される酒石酸ジベンジルエステル長鎖アシル誘導体
を合成中間体として経由することにより、高純度でかつ
高収率で製造することができる。The compound represented by this general formula (11) is a long-chain acyl tartrate dibenzyl ester represented by the general formula % (R in the formula is a long-chain alkyl group having 7 to 17 carbon atoms). By using a derivative as a synthetic intermediate, it can be produced with high purity and high yield.
この際の合成中間体として用いられる前記一般式（１）
の酒石酸ジベンジルエステル長鎖アシル誘導体は、酒石
酸ジベンジルエステルにピリジンと４−ジメチルアミノ
ピリジン存在下、長鎖カルボン酸塩化物を作用させるこ
とにより得られる。The general formula (1) used as a synthetic intermediate in this case
The long-chain acyl tartrate dibenzyl ester derivative can be obtained by reacting tartrate dibenzyl ester with a long-chain carboxylic acid chloride in the presence of pyridine and 4-dimethylaminopyridine.
この化合物は、アルコールから再結晶することにより、
高純度の針状結晶として精製することができる。この化
合物の精製の段階で、副生ずる長鎖カルボン酸エステル
を完全に除くことができるので、以後の操作では長鎖カ
ルボン酸および相当するエステルが混入することがなく
なり、その結果、最終目的物である前記一般式（Ｉ）の
酒石酸長鎖アシル誘導体を高純度で得ることができる。By recrystallizing this compound from alcohol,
It can be purified as highly pure needle-like crystals. During the purification of this compound, long-chain carboxylic acid esters that are produced as by-products can be completely removed, so that long-chain carboxylic acids and corresponding esters will not be contaminated in subsequent operations, and as a result, the final target product will not be contaminated with long-chain carboxylic acids and corresponding esters. A certain long-chain acyl tartrate derivative of general formula (I) can be obtained with high purity.
前記一般式（１１）で表される酒石酸長鎖アシル誘導体
は、一般式（Ｉ）の化合物を水素化分解することにより
、純度高くしかも高収率で得られる。The long-chain acyl tartaric acid derivative represented by the general formula (11) can be obtained with high purity and high yield by hydrogenolyzing the compound of the general formula (I).
一般式（１）の化合物の水素化分解は、この化合物を有
機溶媒中に溶解させ十分かくはんしながら、これに、触
媒量のパラジウム／活性炭を添加し、続いて、水素雰囲
気下、室温でかくはんする。その後、濾過して触媒を除
いたのち、溶媒を留去することによって、目的物を単一
生成物として得ることができる。Hydrogenolysis of the compound of general formula (1) is carried out by dissolving this compound in an organic solvent and stirring thoroughly, adding a catalytic amount of palladium/activated carbon to this, and then stirring at room temperature under a hydrogen atmosphere. do. Thereafter, the target product can be obtained as a single product by filtering to remove the catalyst and then distilling off the solvent.
反応溶媒としては、溶解性から、エタノール、塩化メチ
レン、クロロホルム、ベンゼン、酢酸エチルなどが用い
られる。このなかでも、原料と生成物の両方を良好に溶
解するエタノール／ベンゼン（７／３、容積比）混合溶
媒が望ましい。反応時間は、５時間で十分である。水素
圧は常圧以上が適当である。Ethanol, methylene chloride, chloroform, benzene, ethyl acetate, etc. are used as the reaction solvent in view of solubility. Among these, a mixed solvent of ethanol/benzene (7/3, volume ratio) is desirable because it dissolves both the raw material and the product well. A reaction time of 5 hours is sufficient. The appropriate hydrogen pressure is normal pressure or higher.
このようにして得られる反応混合物から目的化合物を精
製単離するためには、反応混合物にクロロホルム、ベン
ゼンなどの有機溶媒を加え、濾過により触媒を除いた後
、溶媒を減圧除去することにより、一般式（１１）の化
合物を単一生成物として高収率で得ることができる。高
純度試料を得るためには、ざらに、ナトリウムで充分乾
燥したヘキサンから再結晶することが望ましい。In order to purify and isolate the target compound from the reaction mixture obtained in this way, an organic solvent such as chloroform or benzene is added to the reaction mixture, the catalyst is removed by filtration, and the solvent is removed under reduced pressure. The compound of formula (11) can be obtained as a single product in high yield. In order to obtain a high-purity sample, it is desirable to recrystallize from hexane that has been thoroughly dried with sodium.
本発明の製造法で得た一般式（１１）の化合物は、赤外
線吸収スペクトルでは、１７２３〜１７２８ｃｍ−’に
カルボキシル基、１７４５〜１７５０ｃｍ −’にエス
テル基に由来する特性吸収を示し、ＩＨ−ＮＭＲにおい
ては、δ値が０．９ｐｐｍ、１゜２−１． ４ｐｐｍ、
１． ６−１． ”ｉｐｐｍ、 ２゜４−２
．５ｐｐｍ、５．８ｐｐｍの位置にそれぞれ、長鎖アル
キル基のメチル基の水素原子に、メチレン基の水素原子
に、酒石酸部位のメチン基の水素原子に帰属されるシグ
ナルが観測でき、これらによって生成物を同定すること
ができる。The compound of general formula (11) obtained by the production method of the present invention shows characteristic absorption derived from a carboxyl group at 1723 to 1728 cm-' and an ester group at 1745 to 1750 cm-' in an infrared absorption spectrum, and in IH-NMR. , the δ value is 0.9 ppm, 1°2-1. 4ppm,
1. 6-1. ”ippm, 2゜4-2
．． Signals assigned to the hydrogen atom of the methyl group of the long-chain alkyl group, the hydrogen atom of the methylene group, and the hydrogen atom of the methine group of the tartaric acid moiety can be observed at positions 5 ppm and 5.8 ppm, respectively, and these indicate that the product can be identified.
発明の効果
本発明の製造方法により得られる一般式（１１）の化合
物は、実測の元素分析値が誤差範囲で計算値と一致する
。また、この製造方法によって得られる化合物は、ＩＨ
−ＮＭＲスペクトル中に、長鎖カルボン酸に由来する２
、 ３−２． ４．ｐｐｍが現れないことから、長鎖
カルボン酸を混入していないことがわかる。以上のこと
から、この製造方法が高純度の目的化合物を高収率で与
えることがわかる。Effects of the Invention In the compound of general formula (11) obtained by the production method of the present invention, the actually measured elemental analysis value agrees with the calculated value within the error range. Moreover, the compound obtained by this production method is IH
-2 in the NMR spectrum derived from long-chain carboxylic acids.
, 3-2. 4. Since ppm does not appear, it can be seen that no long chain carboxylic acid is mixed. From the above, it can be seen that this production method provides a highly purified target compound in high yield.
次に、本発明を実施例によりざらに詳細に説明する。Next, the present invention will be roughly explained in detail using examples.
参考例 １
ジベンジル（２Ｒ，３Ｒ）−ジテトラデカノイル酒石酸
の製造
ジベンジル酒石酸８．４．ｇ （０，０２６ｍｏ ｌ）
とピリジン４．０ｍｌ （０，０４６ｍｏ １．）をベ
ンゼン５０ｍ１に溶解させ、少量の４．−Ｎ、Ｎ−ジメ
チルアミノピリジンを加え、０°Ｃに冷却した後、かく
はんしながらテトラデカン酸塩化物１２．５ｇ （５０
，６ｇ）を滴下した。室温で一夜かくはんした後、反応
混合物を細かく砕いた氷に注いだ。この液に酢酸エチル
を加えて抽出した後、有機層を飽和食塩水で洗浄し無水
硫酸ナトリウムで乾燥した。ついで減圧下で溶媒を除去
し、これにトルエンを加えて減圧下でトルエンを留去し
、室温で放置すると固化した。これをエタノールから再
結晶することにより白色針状結晶として目的物１０．５
１ｇ（収率、５４％）を得た。このものの物理的性質は
次の通りである。Reference Example 1 Production of dibenzyl (2R,3R)-ditetradecanoyltartaric acid Dibenzyltartaric acid 8.4. g (0,026mol)
and 4.0 ml (0,046 mo 1.) of pyridine were dissolved in 50 ml of benzene, and a small amount of 4. -N,N-dimethylaminopyridine was added, and after cooling to 0°C, 12.5 g of tetradecanoic acid chloride (50
, 6 g) was added dropwise. After stirring overnight at room temperature, the reaction mixture was poured onto finely crushed ice. After extraction by adding ethyl acetate to this liquid, the organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. Then, the solvent was removed under reduced pressure, toluene was added thereto, the toluene was distilled off under reduced pressure, and the mixture solidified when left at room temperature. By recrystallizing this from ethanol, the desired product 10.5 was obtained as white needle-like crystals.
1 g (yield, 54%) was obtained. The physical properties of this material are as follows.
融点 ６４６Ｃ
９
薄層クロマトグラフィーのＲｆ値
（展開溶媒 クロロホルム）０．８
参考例１の（Ａ）におけるテトラデカン酸塩化物の代わ
りに、各々該当する酸塩化物を用いて同様な操作によっ
て、次に示す化合物を得た。Melting point: 646C 9 Rf value of thin layer chromatography (developing solvent: chloroform) 0.8 In place of the tetradecanoic acid chloride in (A) of Reference Example 1, the corresponding acid chloride was used to perform the following procedure in the same manner. The compound shown was obtained.
ジベンジル（２Ｒ，３Ｒ）−ジオクタノイル酒石酸
（融点３７．５−３８．２°Ｃ）ジベンジル（２Ｒ，３
Ｒ）−ジベンジル酒石酸 （融点４４．０−４５．３
°Ｃ）ジベンジル（２Ｒ，３Ｒ）−シトデカノイル酒石
酸 （融点５４．５−５５．５’ Ｃ）ジベンジル（
２Ｒ，３Ｒ）−ジオクタデカノイル酒石酸 （融点７
５．５−７６．５°Ｃ）ジベンジルｍ ｅ ｓ ｏ−ジ
テトラデカノイル酒石酸 （融点４３．０−
４４．０°Ｃ）実施例１
（２Ｒ，３Ｒ）−ジテトラデカノイル酒石酸の製造
１０
密閉性の容器内でジベンジル（２Ｒ，３Ｒ）−ジテトラ
デカノイル酒石Ｍ１．２ｇ （０，ｏｏ１６ｍｏｌ）を
エタノール／ベンセン（７／３、容積比）混合溶媒１０
ｍ１に溶解させ、これに５％パラジウム／活性炭を０．
１５ｇ加え、ついで２〜３秒間減圧したのち、水素を容
器内に導入した。Dibenzyl (2R,3R)-dioctanoyltartaric acid
(melting point 37.5-38.2°C) dibenzyl (2R, 3
R)-dibenzyltartaric acid (melting point 44.0-45.3
°C) dibenzyl (2R,3R)-cytodecanoyltartaric acid (melting point 54.5-55.5'C) dibenzyl (
2R,3R)-dioctadecanoyltartaric acid (melting point 7
5.5-76.5°C) dibenzyl meso-ditetradecanoyltartaric acid (melting point 43.0-
44.0°C) Example 1 Production of (2R,3R)-ditetradecanoyl tartaric acid 10 Dibenzyl (2R,3R)-ditetradecanoyl tartaric acid M1.2 g (0,0016 mol) in a sealed container ethanol/benzene (7/3, volume ratio) mixed solvent 10
ml, and add 5% palladium/activated carbon to it.
After adding 15 g and then reducing the pressure for 2 to 3 seconds, hydrogen was introduced into the container.
室温で５時間かくはんし、クロロホルム１０ｍ１を加え
触媒を濾過で除去した。溶媒を減圧上留去し、更にベン
ゼン５ｍｌを加えペンセンを減圧上留去した。得られた
白色粉末なヘキサンから再結晶することにより白色りん
片状結晶として目的化合物０．５６ｇ（収率、６２％）
を得た。この化合物は’Ｈ−ＮＭＲスペクトルで
δ（ｐｐｍ）＝０．９，１．２０−１．２５゜１、５５
−１．６５．２． ／１ｏ−２，５０゜５．７５
に吸収があった。このものの物理的性質は次の通りであ
る。The mixture was stirred at room temperature for 5 hours, 10 ml of chloroform was added, and the catalyst was removed by filtration. The solvent was distilled off under reduced pressure, 5 ml of benzene was further added, and pentene was distilled off under reduced pressure. By recrystallizing from the obtained white powder hexane, 0.56 g of the target compound was obtained as white flaky crystals (yield, 62%).
I got it. The 'H-NMR spectrum of this compound shows that δ (ppm) = 0.9, 1.20-1.25°1, 55
-1.65.2. There was absorption at /1o-2,50°5.75. The physical properties of this material are as follows.
融点 ８１．４−８１．８°Ｃ
元素分析値（Ｃ３２■］５８０８として）１１
ＣＨ
計算値（％） ６７．３４ １０．２４実測値（％）
６７．２０ １０．５５このものの’Ｈ−ＮＭＲスペ
クトルを第１図に示す。Melting point 81.4-81.8°C Elemental analysis value (as C32■]5808) 11 CH Calculated value (%) 67.34 10.24 Actual value (%)
67.20 10.55 The 'H-NMR spectrum of this product is shown in Figure 1.
実施例２
（２Ｒ，３Ｒ）−ジオクタノイル酒石酸の製造密閉性の
容器内でジベンジル（２Ｒ，３Ｒ）−ジオクタノイル酒
石酸１．ＯＯｇ （０，００１７ｍｏｌ）をエタノール
／ベンゼン（７／３、容積比）混合溶媒９ｍｌに溶解さ
せ、これに５％パラジウム／活性炭を０．１５ｇ加え、
ついで２〜３秒間減圧したのち、水素を容器内に導入し
た。室温で５時間かくはんし、クロロホルム１０ｍ１を
加え触媒を濾過で除去した。溶媒を減圧上留去し、更に
ベンゼン５ｍｌを加えベンゼンを減圧上留去することに
より油状の一水和物として目的化合物０．４４ｇ （収
率、６０％）を得た。このものの１２−
物理的性質は次の通りである。Example 2 Preparation of (2R,3R)-dioctanoyltartaric acid Dibenzyl (2R,3R)-dioctanoyltartaric acid 1. OOg (0,0017 mol) was dissolved in 9 ml of ethanol/benzene (7/3, volume ratio) mixed solvent, and 0.15 g of 5% palladium/activated carbon was added thereto.
Then, after reducing the pressure for 2 to 3 seconds, hydrogen was introduced into the container. The mixture was stirred at room temperature for 5 hours, 10 ml of chloroform was added, and the catalyst was removed by filtration. The solvent was distilled off under reduced pressure, 5 ml of benzene was added, and the benzene was distilled off under reduced pressure to obtain 0.44 g (yield, 60%) of the target compound as an oily monohydrate. 12- The physical properties of this are as follows.
元素分析値（Ｃ２ｏＩ■３６０９として）ｃ
Ｈ
計算値（％） ６７．１２ ８．２９実測値（％）
５６．９８ ８．２９実施例３
（２Ｒ，３Ｒ）−ジデカノイル酒石酸の製造密閉性の容
器内でジベンジル（２Ｒ，３Ｒ）−ジデカノイル酒石酸
１．１ ｇ （０，００１６ｍ。Elemental analysis value (as C2oI■3609)c
H Calculated value (%) 67.12 8.29 Actual value (%)
56.98 8.29 Example 3 Preparation of (2R,3R)-didecanoyltartaric acid 1.1 g (0,0016 m.
１）をエタノール／ベンゼン（７／３、容積比）混合溶
媒１０ｍ１に溶解させ、これに５％パラジウム／活性炭
を０．１５ｇ加え、ついで２〜３秒間減圧したのち、水
素を容器内に導入した。室温で５時間かくはんし、クロ
ロホルム１０ｍ１を加え触媒を濾過で除去した。溶媒を
減圧上留去し、更にベンゼン５ｍｌを加えベンゼンを減
圧上留去した。得られた白色粉末をヘキサンから再結晶
することにより白色りん片状結晶として目的化合物０．
４７ｇ（収率、６０％）を得た。このものの物理的性質
は次の通りである。1) was dissolved in 10 ml of ethanol/benzene (7/3, volume ratio) mixed solvent, 0.15 g of 5% palladium/activated carbon was added thereto, the pressure was reduced for 2 to 3 seconds, and hydrogen was introduced into the container. . The mixture was stirred at room temperature for 5 hours, 10 ml of chloroform was added, and the catalyst was removed by filtration. The solvent was distilled off under reduced pressure, and 5 ml of benzene was further added and benzene was distilled off under reduced pressure. The obtained white powder was recrystallized from hexane to obtain the desired compound as white flaky crystals.
47 g (yield, 60%) was obtained. The physical properties of this material are as follows.
融点 ５６．５−５７．０°Ｃ
元素分析値（Ｃ２Ａ Ｈ４２０ｅとして）ＣＨ
計算値（％） ６２．８６ ９．２３実測値（％）
６２．６６ ９．２５実施例４
（２Ｒ，３Ｒ）−シトデカノイル酒石酸の製造密閉性の
容器内でジベンジル（２Ｒ，３Ｒ）−シトデカノイル酒
石酸１．５ｇ （０，００２１ｍｏ１）をエタノール／
ベンゼン（７／３、容積比）混合溶媒１０ｍ１に溶解さ
せ、これに５％パラジウム／活性炭を０．１５ｇ加え、
ついで２〜３秒間減圧したのち、水素を容器内に導入し
た。室温で５時間かくはんし、クロロホルム１０ｍ１を
加え触媒を濾過で除去した。溶媒を減圧上留去し、更に
ベンゼン５ｍｌを加えベンゼンを減圧上留去した。得ら
れた白色粉末なヘキサンから再結晶することにより白色
りん片状結晶として目的化合物１３−
１４−
０．７４ｇ（収率、６５％）を得た。この化合物は’Ｈ
−ＮＭＲスペクトルで
δ（ｒ）Ｉ）ｍ）＝０．９，１．２５−１．４０゜１．
６０−１．７０，２．４０−２．５０゜５．７５
に吸収があった。このものの物理的性質は次の通りであ
る。Melting point 56.5-57.0°C Elemental analysis value (as C2A H420e) CH Calculated value (%) 62.86 9.23 Actual value (%)
62.66 9.25 Example 4 Production of (2R,3R)-cytodecanoyltartaric acid 1.5 g (0,0021 mo1) of dibenzyl (2R,3R)-cytodecanoyltartaric acid was mixed with ethanol/in a sealed container.
Dissolve in 10 ml of benzene (7/3, volume ratio) mixed solvent, add 0.15 g of 5% palladium/activated carbon,
Then, after reducing the pressure for 2 to 3 seconds, hydrogen was introduced into the container. The mixture was stirred at room temperature for 5 hours, 10 ml of chloroform was added, and the catalyst was removed by filtration. The solvent was distilled off under reduced pressure, and 5 ml of benzene was further added and benzene was distilled off under reduced pressure. By recrystallizing from the obtained white powder hexane, 0.74 g (yield, 65%) of the target compound 13-14- was obtained as white flaky crystals. This compound is 'H
-NMR spectrum δ(r)I)m)=0.9,1.25-1.40°1.
There was absorption at 60-1.70, 2.40-2.50°5.75. The physical properties of this material are as follows.
融点 ６７−６８°Ｃ
元素分析値（Ｃ２ｅＨ５ｓＯｎとして）Ｃ、Ｈ
計算値く％） ６５．３４ ９．７９実測値（％’）
６４．８９ ９．５９このものの１Ｈ
す。Melting point 67-68°C Elemental analysis value (as C2eH5sOn) C, H calculated value (%) 65.34 9.79 Actual value (%')
64.89 9.59 1H of this thing.
ＮＭＲスペクトルを第２図に示
実施例５
（２Ｒ，３Ｒ）−ジオクタデカノイル酒石酸の製造
密閉性の容器内でジベンジル（２Ｒ，３Ｒ） −ジオク
タデカノイル酒石酸１．□ｇ （０，００１２ｍｏｌ）
をコータノール／ベンゼン（７／３、容積比）混合溶媒
１０ｍ１に溶解させ、これに５％パラジウム／活性炭を
０．１５ｇ加え、ついで２〜３秒間減圧したのち、水素
を容器内に導入した。The NMR spectrum is shown in FIG. 2. Example 5 Preparation of (2R,3R)-Dioctadecanoyltartaric acid Dibenzyl (2R,3R)-dioctadecanoyltartaric acid 1. □g (0,0012mol)
was dissolved in 10 ml of a mixed solvent of Cortanol/benzene (7/3, volume ratio), 0.15 g of 5% palladium/activated carbon was added thereto, the pressure was reduced for 2 to 3 seconds, and then hydrogen was introduced into the container.
室温で５時間かくはんし、クロロボルム１０ｍ１を加え
触媒を濾過で除去した。溶媒を減圧下留去し、更にベン
ゼン５ｍｌを加えベンゼンを減圧下留去した。得られた
白色粉末をヘキサンから再結晶することにより白色りん
片状結晶として目的化合物０．４３ｇ（収率、５５％）
を得た。この化合物はＩＨ−ＮＭＲスペクトルで
δ（１）Ｉ）ｍ）＝０．９，１．２０−１．４０゜１．
６０−１．７０，２．４０−２．５０゜５．７５
に吸収があった。このものの物理的性質は次の通りであ
る。The mixture was stirred at room temperature for 5 hours, 10 ml of chloroborum was added, and the catalyst was removed by filtration. The solvent was distilled off under reduced pressure, and 5 ml of benzene was further added and benzene was distilled off under reduced pressure. The obtained white powder was recrystallized from hexane to obtain 0.43 g of the target compound as white flaky crystals (yield, 55%).
I got it. The IH-NMR spectrum of this compound shows that δ(1)I)m)=0.9,1.20-1.40°1.
There was absorption at 60-1.70, 2.40-2.50°5.75. The physical properties of this material are as follows.
融点 ９５．５−９６．５９Ｃ
元素分析値（０４８■ｌ７４０８として）ＣＨ
１５−
１６−
計算値（％） ７０．３／１１０．９２実測値（％）
６９．７４ １０．７９融点 ９０．０−９１．
５°に
のものの’Ｈ−ＮＭＲスペクトルを第３図に示す。Melting point 95.5-96.59C Elemental analysis value (as 048■l7408) CH 15- 16- Calculated value (%) 70.3/110.92 Actual value (%)
69.74 10.79 Melting point 90.0-91.
The 'H-NMR spectrum at 5° is shown in FIG.
実施例６
ｍ ｅ ｓ ｏ−ジオクタデカノイル酒石酸の製造密閉
性の容器内でジベンジルｍ ｅ ｓ ｏ−ジテトラデカ
ノイル酒石ＭＯ，７６ｇ （０，ＯＯ１３ｍｏｆ）をエ
タノール／ベンゼン（７／３、容積比）混合溶媒８ｍｌ
に溶解させ、これに５％パラジウム／活性炭を０．１５
ｇ加え、ついで２〜３秒間減圧したのち、水素を容器内
に導入した。室温で５時間かくはんし、クロロホルム１
０ｍ１を加え触媒を濾過で除去した。溶媒を減圧下留去
し、更にベンゼン５ｍｌを加えベンゼンを減圧下留去し
た。得られた白色粉末をヘキサンから再結晶することに
より白色りん片状結晶として目的化合物０゜４９ｇ（収
率、６５％）を得た。このものの物理的性質は次の通り
である。Example 6 Preparation of m e s o -dioctadecanoyl tartaric acid In a sealed container, dibenzyl m e s o -ditetradecanoyl tartaric acid, MO, 76 g (0,0013 mof) was mixed with ethanol/benzene (7/3, Volume ratio) mixed solvent 8ml
5% palladium/activated carbon in 0.15%
After adding g and then reducing the pressure for 2 to 3 seconds, hydrogen was introduced into the container. Stir at room temperature for 5 hours, add chloroform 1
0ml was added and the catalyst was removed by filtration. The solvent was distilled off under reduced pressure, and 5 ml of benzene was further added and benzene was distilled off under reduced pressure. The obtained white powder was recrystallized from hexane to obtain 0.49 g (yield, 65%) of the target compound as white flaky crystals. The physical properties of this material are as follows.
第１図は本発明の化合物のうち、実施例１のＩＨ−ＮＭ
Ｒスペクトル図（重クロロホルム中、２５℃）、第２図
は実施例４の ’Ｈ−ＮＭＲスペクトル図（重クロロホ
ルム中、２５°Ｃ）、第３図は実施例５の ’Ｈ−ＮＭ
Ｒスペクトル図（重クロロホルム中、２５°Ｃ）である
。Figure 1 shows IH-NM of Example 1 among the compounds of the present invention.
R spectrum (in deuterated chloroform, 25°C), Figure 2 is the 'H-NMR spectrum of Example 4 (in deuterated chloroform, 25°C), and Figure 3 is 'H-NMR spectrum of Example 5.
It is an R spectrum diagram (in deuterated chloroform, 25°C).
Claims (1)
を合成中間体として経由することを特徴とする 一般式 ▲数式、化学式、表等があります▼・・・・・（II） （式中のＲは、７〜１７の長鎖アルキル基 である） で表わされる酒石酸長鎖アシル誘導体の製 造方法。[Claims] Represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ ...... (I) (R in the formula is a long-chain alkyl group with 7 to 17 carbon atoms) A general formula characterized by using a long-chain acyl tartrate dibenzyl ester derivative as a synthetic intermediate ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (R in the formula is 7 to 17 long-chain alkyl group) A method for producing a long-chain acyl tartaric acid derivative represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2061852A JPH0768164B2 (en) | 1990-03-13 | 1990-03-13 | Method for producing long-chain acyl tartrate derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2061852A JPH0768164B2 (en) | 1990-03-13 | 1990-03-13 | Method for producing long-chain acyl tartrate derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03264547A true JPH03264547A (en) | 1991-11-25 |
| JPH0768164B2 JPH0768164B2 (en) | 1995-07-26 |
Family
ID=13183042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2061852A Expired - Lifetime JPH0768164B2 (en) | 1990-03-13 | 1990-03-13 | Method for producing long-chain acyl tartrate derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0768164B2 (en) |
-
1990
- 1990-03-13 JP JP2061852A patent/JPH0768164B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0768164B2 (en) | 1995-07-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |