JPS5993030A - Esterification - Google Patents
EsterificationInfo
- Publication number
- JPS5993030A JPS5993030A JP57200586A JP20058682A JPS5993030A JP S5993030 A JPS5993030 A JP S5993030A JP 57200586 A JP57200586 A JP 57200586A JP 20058682 A JP20058682 A JP 20058682A JP S5993030 A JPS5993030 A JP S5993030A
- Authority
- JP
- Japan
- Prior art keywords
- alcohol
- formula
- carboxylic acid
- 1mol
- dialkyl
- 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
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
- Catalysts (AREA)
- 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】
本発明は新規なエステル化方法、四に詳細には、次の一
般式（１）、
（式中、Ｒ１及びＲ２は低級アルキル基を、Ｘは）・ロ
ゲン原子を示す）
で表わされる１、３−ジアルキル−２−ノ・コゲノー３
．４，５．６−チトラヒドロピリミジニウム・ハロゲニ
ドを縮合剤として使用するエステル化方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel esterification method, in particular, the following general formula (1), (wherein R1 and R2 are lower alkyl groups, and X is a rogene atom) 1,3-dialkyl-2-no-cogeno3 represented by
．． The present invention relates to an esterification method using 4,5,6-titrahydropyrimidinium halide as a condensing agent.
従来、アルコール類とカルボン酸類とからエステルを製
造する方法としては種々の方法が知られており、その一
つには縮合剤を使用する方法があり、その縮合剤として
も多くのものが報告されている。Conventionally, various methods have been known to produce esters from alcohols and carboxylic acids, one of which is a method using a condensing agent, and many condensing agents have been reported. ing.
一方、医薬品等として有用な有機化合物中にはエステル
化反応によって得られるものが多いことから、本発明者
は、エステル化反応について鋭意研究を行っていたとこ
ろ、上記一般式（１）で表わされる化合物がエステル化
反応の縮合剤として優れていることを見出し、本発明を
完成した。On the other hand, since many organic compounds useful as pharmaceuticals etc. can be obtained by esterification reactions, the present inventors have been conducting intensive research on esterification reactions and found that the compound represented by the above general formula (1) The present invention was completed based on the discovery that the compound is excellent as a condensing agent for esterification reactions.
すなわち、本発明は、アルコール類（町とカルボンｅｔ
ａＧＶ）を１，３−ジアルキル−２−ハロゲノ−３，４
，５，６−チトラヒドロピリミジニウム・ハロゲニド（
１）を縮合剤として使用して反応させることを％９とす
るエステル化方法であり、次の反応式で示される。That is, the present invention provides alcohols (machi and carbon et al.
aGV) to 1,3-dialkyl-2-halogeno-3,4
,5,6-titrahydropyrimidinium halide (
This is an esterification method using 1) as a condensing agent at a rate of 9%, and is shown by the following reaction formula.
（ｉｌｌ） （Ｉｔ／） （１）
（Ｖ）（式中、Ｒ３はアルコール残基、
Ｒ４はカルボン酸残基、Ｂは塩基を示し、Ｒ，、Ｒ２及
びＸは前記した意味を有する）
本発明で縮合剤として使用される（１）式の化合物は、
例えば入手容易な溶剤として知られている次の一般式（
［）
（式中、Ｒ１及びＲ２は前記した意味を有する）で表わ
される１、３−ジアルキル−３＋ ４１５１６−チトラ
ヒドロー２（ＩＨ）−ピリミジノンにハロゲン化剤を反
応せしめることにより製造される。(ill) (It/) (1)
(V) (wherein R3 is an alcohol residue,
(R4 is a carboxylic acid residue, B is a base, R,, R2 and X have the meanings described above) The compound of formula (1) used as a condensing agent in the present invention is:
For example, the following general formula (
It is produced by reacting a halogenating agent with 1,3-dialkyl-3+ 41516-titrahydro-2(IH)-pyrimidinone represented by [] (wherein R1 and R2 have the above-mentioned meanings).
ここで使用されるハロゲン化剤としては、オキサリルハ
ロゲニト、三ハロゲン化リン、五ハロゲン化リン、オキ
シノ・ロゲン化リン、ホスゲン、トリクロロメチルクロ
ロポルメート等が挙げられる。Examples of the halogenating agent used here include oxalyl halide, phosphorus trihalide, phosphorus pentahalide, oxynophosphorus halide, phosgene, trichloromethylchloropormate, and the like.
反応は１，３−ジアルキル−３，４，５，６−チトラヒ
ドロー２（ＩＨ）−ピリミジノン又はノ飄ロゲン化剤の
何れか一方を四塩化炭素等の適当な溶媒にとかしてしき
、これに他方を少ｒｋずつ添加し、更に室温ないし７０
℃で数時間〜十数時間反応させることによって行われる
。The reaction is carried out by dissolving either 1,3-dialkyl-3,4,5,6-titrahydro-2(IH)-pyrimidinone or the chlorogenating agent in a suitable solvent such as carbon tetrachloride, and then adding the other to this. Add rk in small increments, and then heat to room temperature or 70°C.
This is carried out by reacting at a temperature of several hours to over ten hours.
斯くして得られる１、３−ジアルキル−２−ノーログノ
ー３．４，５．６−チトラヒドロピリミジニウム・・・
ロゲニドは単離することもできるが、単ｍすることなく
、その反応液を本発明のエステル化反応に使用すること
もできる。The 1,3-dialkyl-2-nologno3.4,5.6-titrahydropyrimidinium thus obtained...
Although rogenide can be isolated, its reaction solution can also be used in the esterification reaction of the present invention without isolation.
本発明方法を実施するには、アルコール類（ｌｉｔ）、
カルボン酸類（１■）、１，３−ジアルキル−２−ノ・
コゲノー３．４，５．６−チトラヒドロビリミジニウム
・ハロゲニド（Ｉ）の各１モルとピリジン、トリエアル
アミン、トリブチルアミン等の塩基（Ｖ） ２モルを混
和して室温で反応させればよく、かくするとき、反応は
有利に進行して、高収率でエステル（ＶＤを与える。To carry out the method of the invention, alcohols (lit),
Carboxylic acids (1■), 1,3-dialkyl-2-no.
Cogeno 3. If 1 mole each of 4,5,6-titrahydrobirimidinium halide (I) and 2 moles of a base (V) such as pyridine, triearamine, or tributylamine are mixed and reacted at room temperature, Often, when doing so, the reaction proceeds favorably to give the ester (VD) in high yield.
次にお考例及び実施例を挙げて説明する。Next, an explanation will be given with reference to examples and examples.
参考例１
四塩化炭素ｉｏｏｍｇに１，３−ジメチル−３゜、１，
５．６−７″′）ラヒドロ−２（Ｉ Ｈ）−ピリミジノ
ン４０Ｉを溶かし、これにトリクロロメチルクロロホル
メート２６１を滴下し、その４ ｔ ２０時間攪拌した
。析出した結晶をｔ取し、四塩化炭素で洗浄後乾燥して
２−クロロ−１，３−ジメチル−３，４，５，６−チト
ラヒドロピリミジニウム・クロライド３３．６Ｆ（収率
６９．９％）を得た。Reference example 1 Carbon tetrachloride ioomg 1,3-dimethyl-3°, 1,
5.6-7''') Lahydro-2(I H)-pyrimidinone 40I was dissolved, trichloromethyl chloroformate 261 was added dropwise thereto, and the mixture was stirred for 20 hours. The precipitated crystals were collected and After washing with carbon chloride and drying, 2-chloro-1,3-dimethyl-3,4,5,6-titrahydropyrimidinium chloride 33.6F (yield 69.9%) was obtained.
ＮＭＲ（δ、ｐＩ）ｍ、 ＣＤＣ−１３ｓ ） ：２．
３３ （２１（、ｑｕ ｉｎ ｔｅ ｔ 、 Ｊ ＝
５．８［（ｚ 、 −ＣＩ−１，、ｑ層ｌ−１２−）３
．５０ （６１４，ｓ、ＣＨ，−×２）３．９５
（４）１． ｔ ＋Ｊ＝５．８Ｈｚ 、 −Ｃ！１２Ｃ
ＩＩ２Ｃｐ−）実施例１
ε−グアニジノカプロン酸・塩酸塩２１．Ｏｆ−。NMR (δ, pI)m, CDC-13s): 2.
33 (21(, qu inte t, J =
5.8 [(z, -CI-1,, q layer l-12-)3
．． 50 (614,s,CH,-x2)3.95
(4)1. t+J=5.8Hz, -C! 12C
II2Cp-) Example 1 ε-guanidinocaproic acid hydrochloride 21. Of-.
ｐ−ヒドロキシ安息香酸エチル２０．（１’、ジクロル
メタン６０ｍ１の混合物中に、２−クロロ−１゜３−ジ
メチル−３，４，５，６−チトラヒドロピリミジニウム
クロライド２２．０７−を加え、次いでピリジン１９．
０Ｐを滴下し、更に一夜攪拌し、析出した結晶を濾過し
、ジクロルメタンで洗浄した。Ethyl p-hydroxybenzoate20. (1', into a mixture of 60 ml of dichloromethane, add 22.07 ml of 2-chloro-1°3-dimethyl-3,4,5,6-titrahydropyrimidinium chloride, then add 19.0 ml of pyridine.
0P was added dropwise, and the mixture was further stirred overnight, and the precipitated crystals were filtered and washed with dichloromethane.
Ｐ液及び洗液を合し、減圧下溶媒を留去し、残渣に水を
加えて溶かし、飽和炭酸水素ナトリウム水溶液１．５石
中に攪拌下加えた。析出晶をＰ取し、水、アセトンでμ
次洗浄後乾燥して、ε−グアニジノカプロン酸、・ｐ−
エトキンカルボニルフェニルエステルの炭酸塩２５．３
？（収率６６．１係）を得た。The P solution and the washing solution were combined, the solvent was distilled off under reduced pressure, and the residue was dissolved in water and added to 1.5 kg of a saturated aqueous sodium bicarbonate solution with stirring. Take the precipitated crystals and dilute them with water and acetone.
Next, after washing and drying, ε-guanidinocaproic acid, p-
Carbonate of Etquin carbonylphenyl ester 25.3
? (Yield 66.1%) was obtained.
実施例２
ジクロルメタン５０ｍ１にｎ−カプロン酸１３，９２−
、ベンジルアルコール１０．ｓｙ−及び２−りｏ。Example 2 N-caproic acid 13,92- in 50 ml of dichloromethane
, benzyl alcohol 10. sy- and 2-ri o.
−】１３−ジメチル−３，４，５，６−チトラヒドロビ
リミジニウムクロライド２２．０７４ｉ容１眸し、これ
にピリジン１９．（１−を滴下し、更に２時間攪拌した
。反応液に水を加え、ジクロルメタン層を分取し、飽和
炭酸水素ナトリウム水溶液で洗浄後、無水硫酸マグネシ
ウムで乾燥した。次いで溶媒を留去し、残渣を減圧蒸留
して、カプロン酸ベンジルエステル１７．７ Ｐ （収
率８５．９％）を得た。-] Add 1 volume of 22.074 i of 13-dimethyl-3,4,5,6-titrahydrobyrimidinium chloride, and add 19 g of pyridine. (1- was added dropwise and further stirred for 2 hours. Water was added to the reaction solution, the dichloromethane layer was separated, washed with saturated aqueous sodium bicarbonate solution, and dried over anhydrous magnesium sulfate. Then, the solvent was distilled off, The residue was distilled under reduced pressure to obtain 17.7 P of caproic acid benzyl ester (yield: 85.9%).
実施例３
ジクロルメタン１２０ｍ１に安息香酸２９．３Ｐ、エタ
ノール９．２ｇ−及び２−クロロ−１，３−ジメチル−
３，４，５，６−チトラヒドロビリミジニウムクロラ・
イド４３．９１−を溶解し、これにピリジン３７．９７
を滴下し、次いで反応液を実施例２と同様に処理し、安
息香酸エチルエステル２４６ｆ（収率８２．０％）を得
た。Example 3 29.3 P of benzoic acid, 9.2 g of ethanol and 2-chloro-1,3-dimethyl- in 120 ml of dichloromethane
3,4,5,6-titrahydrobirimidinium chlora・
Dissolve id 43.91- and add pyridine 37.97 to this.
was added dropwise, and then the reaction solution was treated in the same manner as in Example 2 to obtain ethyl benzoate 246f (yield: 82.0%).
以上 出願人 白鳥辺薬株式会社 ｉ゛−ｉ１’、！： 、ｊｌ’、ｊthat's all Applicant: Shiratoribenyaku Co., Ltd. i゛-i1',! : ,jl’,j
Claims (1)
原子を示す） で表わさノ］る１、３−ジアルキル−２−ハロゲノ−３
，４，５，６−チトラヒドロビリミジニウム・ハロゲニ
ドを縮合剤として使用して反応させることを特徴とする
エステル化方法。 ２、縮合剤が、１，３−ジメチル−２−クロロー：３．
４ 、５ 、６−チトラヒドロビリミジニウム・クロラ
イドである特許請求の範囲第１項記載のエステル化方法
。[Scope of Claims] (1) Alcohols and carboxylic acids are represented by the following general formula () (in the formula, R and H represent lower alkyl groups, and X represents a halogen atom). -Dialkyl-2-halogeno-3
, 4,5,6-titrahydrobirimidinium halide as a condensing agent. 2. The condensing agent is 1,3-dimethyl-2-chloro: 3.
The esterification method according to claim 1, wherein 4,5,6-titrahydrobirimidinium chloride is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57200586A JPS5993030A (en) | 1982-11-16 | 1982-11-16 | Esterification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57200586A JPS5993030A (en) | 1982-11-16 | 1982-11-16 | Esterification |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5993030A true JPS5993030A (en) | 1984-05-29 |
| JPH025737B2 JPH025737B2 (en) | 1990-02-05 |
Family
ID=16426803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57200586A Granted JPS5993030A (en) | 1982-11-16 | 1982-11-16 | Esterification |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5993030A (en) |
-
1982
- 1982-11-16 JP JP57200586A patent/JPS5993030A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH025737B2 (en) | 1990-02-05 |
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