JPH03255050A - Preparation of cis, cis-muconic acid chloride - Google Patents
Preparation of cis, cis-muconic acid chlorideInfo
- Publication number
- JPH03255050A JPH03255050A JP2050066A JP5006690A JPH03255050A JP H03255050 A JPH03255050 A JP H03255050A JP 2050066 A JP2050066 A JP 2050066A JP 5006690 A JP5006690 A JP 5006690A JP H03255050 A JPH03255050 A JP H03255050A
- Authority
- JP
- Japan
- Prior art keywords
- cis
- muconic acid
- acid chloride
- mol
- muconic
- 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.)
- Pending
Links
- TXXHDPDFNKHHGW-CCAGOZQPSA-N cis,cis-muconic acid Chemical compound OC(=O)\C=C/C=C\C(O)=O TXXHDPDFNKHHGW-CCAGOZQPSA-N 0.000 title claims abstract description 51
- TXXHDPDFNKHHGW-UHFFFAOYSA-N (2E,4E)-2,4-hexadienedioic acid Natural products OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000012320 chlorinating reagent Substances 0.000 claims abstract description 13
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 150000001408 amides Chemical class 0.000 claims abstract description 9
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 4
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 239000003905 agrochemical Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 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 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 5
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- TXXHDPDFNKHHGW-HSFFGMMNSA-N cis,trans-muconic acid Chemical compound OC(=O)\C=C\C=C/C(O)=O TXXHDPDFNKHHGW-HSFFGMMNSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical group OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- KVBQNFMTEUEOCD-UHFFFAOYSA-M 1-butylpyridin-1-ium;bromide Chemical compound [Br-].CCCC[N+]1=CC=CC=C1 KVBQNFMTEUEOCD-UHFFFAOYSA-M 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- IQNTUYCIRRCRDY-UHFFFAOYSA-N 2,5-dichlorobenzene-1,4-dicarbonyl chloride Chemical compound ClC(=O)C1=CC(Cl)=C(C(Cl)=O)C=C1Cl IQNTUYCIRRCRDY-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 241001315609 Pittosporum crassifolium Species 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 240000000581 Triticum monococcum Species 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- CELCMWUXMBTJRP-UHFFFAOYSA-N chlorobenzene;hydrochloride Chemical compound Cl.ClC1=CC=CC=C1 CELCMWUXMBTJRP-UHFFFAOYSA-N 0.000 description 1
- RVOJTCZRIKWHDX-UHFFFAOYSA-N cyclohexanecarbonyl chloride Chemical compound ClC(=O)C1CCCCC1 RVOJTCZRIKWHDX-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- PXYBXMZVYNWQAM-GLIMQPGKSA-N dimethyl (2z,4z)-hexa-2,4-dienedioate Chemical compound COC(=O)\C=C/C=C\C(=O)OC PXYBXMZVYNWQAM-GLIMQPGKSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 etc. Chemical compound 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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、高分子原料、医薬原料、農薬原料どして有用
なシス、シス−ムコン酸クロリドの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing cis, cis-muconic acid chloride, which is useful as a polymer raw material, a pharmaceutical raw material, an agricultural chemical raw material, etc.
例えば、ムコン酸クロリドは、末端が反応性を示すため
ジオール、ジアミン類と反応させることにより、高分子
となる。また、酸クロリドば、塩化アルミニウムを触媒
とするフリーデルタラフト反応により、多くの試薬と反
応性を示し医薬、農薬の原料として有用である。シス、
シス体は、立体異性体の一つで、二重結合を２つもった
構造を有するので、グラフト重合が容易に進むなどの利
点を有している。For example, muconic acid chloride becomes a polymer by reacting with diols and diamines because its terminals exhibit reactivity. In addition, acid chloride exhibits reactivity with many reagents through the Friedelta raft reaction using aluminum chloride as a catalyst, making it useful as a raw material for medicines and agricultural chemicals. Sis,
The cis isomer is one of the stereoisomers and has a structure with two double bonds, so it has advantages such as easy graft polymerization.
〈従来の技術及び発明が解決しようとする問題点〉従来
より、カルボン酸から酸クロリドを得る方法としてはカ
ルボン酸にチオニルクロリド、オキシ塩化リン、五塩化
リンあるいは三塩化リン等の塩素化剤を作用させるのが
一般的である。特にチオニルクロリドを塩素化剤として
用いる場合には、亜硫酸ガスの発生を促すために少量の
アミンもしくはア果ドを添加させる方法が知られている
。<Prior art and problems to be solved by the invention> Conventionally, as a method for obtaining acid chloride from carboxylic acid, a chlorinating agent such as thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, or phosphorus trichloride is added to the carboxylic acid. It is common to let it work. Particularly when thionyl chloride is used as a chlorinating agent, a method is known in which a small amount of amine or acid is added to promote the generation of sulfur dioxide gas.
しかしながら、上記の反応においては、少量のアミン、
アミドとはいえカルボン酸基１モルあたり、０．０７モ
ル％〜６モル％と比較的多量添加している。例えば、Ｏ
ｒｇａｎｉｃ ｆｕｎｃｔｔｏｎａｌ ｇｒｏｕｐ ｐ
ｒｅｐａｒａｔｉｏｎｓ（Ｓｅｃｏｎｄ Ｅｄｉｔｉｏ
ｎ）、５ｔａｎｌｅｙ Ｒ，５ａｎｄｌｅｒａｎｄ Ｗ
ｏｌｆ Ｋａｒｏ（ＡｃａｄｅｌｌＩｉｃ Ｐｒｅｓｓ
１９８３ ） 、 Ｐ １５６〜１５７によれば、
２，５−ジクロロテレフタル酸クロリドの合成に於いて
、カルボン酸基当たりのピリジン添加量は１．２５モル
％となっている。However, in the above reaction, a small amount of amine,
Although it is an amide, it is added in a relatively large amount of 0.07 mol % to 6 mol % per mol of carboxylic acid group. For example, O
rganic functtonal group p
reparations (Second Edition)
n), 5tanley R, 5andlerand W
olf Karo (AcadellIic Press
1983), pp. 156-157,
In the synthesis of 2,5-dichloroterephthalic acid chloride, the amount of pyridine added per carboxylic acid group is 1.25 mol%.
同様にトリメシン酸クロリド、無水ｌ・リメリト酸クロ
リドの場合それぞれ２．５モル％、６モル％である。Similarly, in the case of trimesic acid chloride and anhydrous 1-limellitic acid chloride, the amounts are 2.5 mol% and 6 mol%, respectively.
一方アごドの場合、精密有機合成実験マニュアル（南江
堂） 、 Ｌ、Ｆ、Ｔｉｅｔｚｅ、Ｔｈ、Ｅｉｃｈｅｒ
著、高野誠、小笠原国部 共訳、Ｐ１２６〜１２７によ
れば、シクロヘキサンカルボン酸クロリドの台底に於い
てカルボン酸基当たりのＤＭＦ比は０．０６８モル％と
なっている。On the other hand, in the case of Agodo, Precision Organic Synthesis Experiment Manual (Nankodo), L, F, Tietze, Th, Eicher.
According to the authors, Makoto Takano and Kunibu Ogasawara, co-translators, pages 126-127, the DMF ratio per carboxylic acid group in the base of cyclohexanecarboxylic acid chloride is 0.068 mol%.
同様に４−クロロベンゼンクロリドの場合にも０．０６
８モル％である。Similarly, in the case of 4-chlorobenzene chloride, 0.06
It is 8 mol%.
上記の反応で、カルボン酸を塩素化するには、チオニル
クロリド等の塩素化剤を多量使用し、長時間反応させる
ことが必要であるが、その際反応系にアミンあるいはア
ミドをカルボン酸基１モル当り約０．０７モル％以上存
在させると反応時間を短縮できる。In order to chlorinate carboxylic acid in the above reaction, it is necessary to use a large amount of a chlorinating agent such as thionyl chloride and to react for a long time. If the amount is present at about 0.07% by mole or more, the reaction time can be shortened.
しかしながら、これらの公知の酸クロリドの合成法をシ
ス、シス−ムコン酸に適用した場合には、得られた酸ク
ロリド体の立体配置が保持されずシス、トランス体ある
いはトランス、トランス体に異性化してしまい、目的の
シス、シス−ムコン酸クロリドを得ることが出来なかっ
た。However, when these known acid chloride synthesis methods are applied to cis, cis-muconic acid, the configuration of the resulting acid chloride is not maintained and isomerized into cis, trans or trans, trans forms. As a result, the desired cis, cis-muconic acid chloride could not be obtained.
すなわち、立体配置を変化させることなくシスシス−ム
コン酸からシス、シス−ムコン酸クロリドを収率よく得
る方法は知られていなかった。That is, no method was known for obtaining cis,cis-muconic acid chloride from cis-cis-muconic acid in good yield without changing the steric configuration.
く問題点を解決するための手段〉
そこで、本発明者等はかかる問題点を解決すべく鋭意検
討した結果、シス、シス−ムコン酸と塩素化剤を反応さ
せるに際し、反応系にアミンあるいはアミドを特定量存
在させると、かかる問題点を解決できることを見い出し
、本発明に到達した。Means for Solving the Problems> Therefore, as a result of intensive studies to solve these problems, the present inventors found that when reacting cis, cis-muconic acid with a chlorinating agent, an amine or an amide was added to the reaction system. It has been discovered that such problems can be solved by the presence of a specific amount of , and the present invention has been achieved.
すなわち、本発明の目的は、シス、シス−ムコン酸を出
発原料として、その立体配置を変えることなく収率よく
シス、シス−ムコン酸クロリドを製造する方法を提供す
ることにある。That is, an object of the present invention is to provide a method for producing cis, cis-muconic acid chloride in good yield without changing its steric configuration, using cis, cis-muconic acid as a starting material.
そして、その目的は、シス、シス−ムコン酸クロリドと
塩素化剤とを非極性溶媒の存在下もしくは溶媒の非存在
下アミンもしくはアミドをカルボン酸基１モルに当り０
．００１モル％〜０．０５モル％存在させて反応させる
ことを特徴とするシスシス−ムコン酸クロリドの製造方
法により容易に達成される。The purpose is to combine cis, cis-muconic acid chloride and a chlorinating agent in the presence of a non-polar solvent or in the absence of a solvent with 0% amine or amide per mole of carboxylic acid group.
．． This can be easily achieved by a method for producing cis-muconic acid chloride, which is characterized in that the reaction is carried out in the presence of 0.001 mol% to 0.05 mol%.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明で用いる塩素化剤としては、公知の塩素化剤であ
れば、特に限定されるものではなく、例えばチオニルク
ロリド、オキシ塩化リン、五塩化リンあるいはホスゲン
等が挙げられ、特にチオニルクロリドを用いるのがよい
。The chlorinating agent used in the present invention is not particularly limited as long as it is a known chlorinating agent, and examples thereof include thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, phosgene, etc. In particular, thionyl chloride is used. It is better.
そして、塩素化剤の使用量としては、反応基質であるシ
ス、シス−ムコン酸１モルに対して、通常２〜１０モル
好ましくは３〜９モルの範囲から選ばれる。The amount of the chlorinating agent to be used is usually selected from the range of 2 to 10 mol, preferably 3 to 9 mol, per 1 mol of cis, cis-muconic acid, which is the reaction substrate.
その際、ヘプタン、ヘキサン、トルエン、ベンゼン等の
非極性溶媒と上記の塩素化剤との混合溶液の状態で反応
を行なってもよく、あるいは塩素化剤のみで他の溶媒の
非存在下反応を行なってもよい。At that time, the reaction may be carried out in a mixed solution of a non-polar solvent such as heptane, hexane, toluene, benzene, etc. and the above chlorinating agent, or the reaction may be carried out with only the chlorinating agent in the absence of other solvents. You may do so.
本発明で用いるアごンとしては三級あるいは四級アミン
及びそれらの塩が用いられ、例えば四級アミンとしては
テトラブチルアンモニウムプロミド（ＴＢＡＢ）、 ブ
チルピリジニウムプロミド、ベンジルトリエチルアンモ
ニウムクロリド等が挙げられる。また、三級アミンとし
てはピリジン、トリエチルアミン、トリブチルアミン等
が挙げられる。好ましくはピリジン、ＴＢＡＢを用いる
のがよい。Tertiary or quaternary amines and their salts are used as the amines used in the present invention. Examples of quaternary amines include tetrabutylammonium bromide (TBAB), butylpyridinium bromide, benzyltriethylammonium chloride, etc. It will be done. Furthermore, examples of tertiary amines include pyridine, triethylamine, and tributylamine. Preferably, pyridine and TBAB are used.
またアミドとしては、ジメチルホルムアミド、ジエチル
ホルムアミド、メチルホルムアミド等が挙げられ、好ま
しくはジメチルホルムアミドを用いるのがよい。Further, examples of amides include dimethylformamide, diethylformamide, methylformamide, etc., and dimethylformamide is preferably used.
本発明においては、これらのアミンあるいはアミドの存
在量が重要であり、その量としては反応基質であるシス
、シス−ムコン酸におけるカルボン酸基１モルに対して
、通常０．００１−０．０５モル％、好ましくはＯ，Ｏ
Ｏ３〜０．０１モル％とするのがよい。これらの範囲を
越えるとシス、トランス体又はトランス、トランス体へ
の異性化が進行する等の点で好ましくない。In the present invention, the amount of these amines or amides present is important, and the amount is usually 0.001-0.05 per mole of carboxylic acid group in cis, cis-muconic acid, which is the reaction substrate. Mol%, preferably O, O
It is preferable that O3 to 0.01 mol%. Exceeding these ranges is unfavorable because isomerization to cis, trans or trans, trans isomers proceeds.
本発明における反応条件としては、反応圧力を常圧、反
応温度を４０〜９０°Ｃ１好ましくは６０〜８０℃とす
る。特に反応温度が高すぎると得られるシス、シス−ム
コン酸クロリドの収率が低下するので好ましくない。As for the reaction conditions in the present invention, the reaction pressure is normal pressure, and the reaction temperature is 40 to 90°C, preferably 60 to 80°C. In particular, if the reaction temperature is too high, the yield of cis, cis-muconic acid chloride obtained is undesirable.
〈実施例〉
以下、実施例により本発明を具体的に説明するが、本発
明の要旨を越えない限り、本発明は下記実施例に限定さ
れるものではない。<Examples> Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to the following Examples unless the gist of the present invention is exceeded.
実施例１
シス、シス−ムコン酸７．１ｇ、チオニルクロリド６５
ｍβ、テトラブチルアンモニウムプロミド（ＴＢＡ、Ｂ
）２■（対カルボン酸基モル比０．００６％）を混合し
７０℃で、３時間反応させた。Example 1 7.1 g of cis, cis-muconic acid, 65 g of thionyl chloride
mβ, tetrabutylammonium bromide (TBA, B
)2■ (molar ratio to carboxylic acid groups: 0.006%) were mixed and reacted at 70°C for 3 hours.
ムコン酸は、完全に熔解し酸クロリドが得られた。過剰
のチオニルクロリドを留去してＨ−Ｎ ＭＲにてシス、
シス体保持率をみたところ９５％であった。Muconic acid was completely dissolved and acid chloride was obtained. Excess thionyl chloride was distilled off, and cis,
The retention rate of cis form was 95%.
実施例２
シス、シス−ムコン酸７．１ｇ、 ヘプタン５０ｍ尼、
チオニルクロリド１４．５ｍｊ２テトラブチルアンモニ
ウムプロミド２ｍｇ（対カルボン酸基モル比０゜００６
モル％）を混合し７０°Ｃで、７時間反応させた。不溶
物を濾過したところ０．９ｇあった。Example 2 7.1 g of cis, cis-muconic acid, 50 m of heptane,
Thionyl chloride 14.5 mj2 Tetrabutylammonium bromide 2 mg (molar ratio to carboxylic acid group 0°006
(mol%) were mixed and reacted at 70°C for 7 hours. When the insoluble matter was filtered, 0.9 g was found.
これば、ＩＲにて確認したところ、原料のシス。I confirmed this through IR and found that the raw material was sys.
シス−ムコン酸であった。不溶物より反応率を算出する
と８７％となった。また、濾液は、Ｈ−ＮＭＲより′＠
認したところシス、シス−ムコン酸クロリドであった。It was cis-muconic acid. The reaction rate was calculated from the insoluble matter to be 87%. In addition, the filtrate was analyzed by H-NMR.
It was found to be cis, cis-muconic acid chloride.
この時のシス、シス体保持率は９３％であった。At this time, the retention rate of cis and cis forms was 93%.
実施例３〜１０
実施例２と同様の方法で、以下の条件を変更して行った
。結果を次に示す。Examples 3 to 10 Examples 3 to 10 were carried out in the same manner as in Example 2, with the following conditions changed. The results are shown below.
比較例１〜３
実施例２と同様の方法で、以下の条件を変更して比較実
験を行った。結果を次に示す。Comparative Examples 1 to 3 Comparative experiments were conducted in the same manner as in Example 2, with the following conditions changed. The results are shown below.
参考例
シス、シス−ムコン酸ジメチルエステルの合成実施例１
で合成したシス、シス−ムコン酸クロリド溶液より未反
応のチオニルクロリドを５０’Ｃ１１６Ｃ１１６Ｏで留
去した。残ったヘプタン溶液に４０°Ｃにおいてメタノ
ールｌ１ｍｆｉゆっくり滴下し１時間反応させた。水１
０ｍＲ添加し、水層を分液除去、酢酸メチル２５ｄ追加
後、重曹溶液で中和した。油層を取り出し濃縮したとこ
ろ、シス。Reference Example Synthesis of cis, cis-muconic acid dimethyl ester Example 1
Unreacted thionyl chloride was distilled off from the cis, cis-muconic acid chloride solution synthesized in 50'C116C116O. 1 mfi of methanol was slowly added dropwise to the remaining heptane solution at 40°C and reacted for 1 hour. water 1
0 mR was added, the aqueous layer was separated and removed, 25 d of methyl acetate was added, and the mixture was neutralized with a sodium bicarbonate solution. When the oil layer was taken out and concentrated, it yielded cis.
シス−ムコン酸ジメチルエステルが７．３ｇ得られた。7.3 g of cis-muconic acid dimethyl ester was obtained.
このもののシス、シス一体保持率は８２％であった。The cis-cis retention rate of this product was 82%.
〈発明の効果〉
本発明の方法によると、立体配置を変化させることなく
、シス、シス−ムコン酸からシス、シスムコン酸クロリ
ドを短時間かつ高収率で得ることができる。<Effects of the Invention> According to the method of the present invention, cis, cis-muconic acid chloride can be obtained from cis, cis-muconic acid in a short time and in high yield without changing the steric configuration.
Claims (1)
の存在下もしくは溶媒の非存在下アミンもしくはアミド
をカルボン酸基１モル当り０．００１モル％〜０．０５
モル％存在させて反応させることを特徴とするシス、シ
ス−ムコン酸クロリドの製造方法。(1) Cis, cis-muconic acid and a chlorinating agent in the presence of a nonpolar solvent or an amine or amide in the absence of a solvent from 0.001 mol % to 0.05 mol % of an amine or amide per mol of carboxylic acid group.
A method for producing cis, cis-muconic acid chloride, characterized in that the reaction is carried out in the presence of mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2050066A JPH03255050A (en) | 1990-03-01 | 1990-03-01 | Preparation of cis, cis-muconic acid chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2050066A JPH03255050A (en) | 1990-03-01 | 1990-03-01 | Preparation of cis, cis-muconic acid chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03255050A true JPH03255050A (en) | 1991-11-13 |
Family
ID=12848621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2050066A Pending JPH03255050A (en) | 1990-03-01 | 1990-03-01 | Preparation of cis, cis-muconic acid chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03255050A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010525006A (en) * | 2007-04-25 | 2010-07-22 | エフ．ホフマン−ラ ロシュ アーゲー | New synthesis method of acid chloride |
-
1990
- 1990-03-01 JP JP2050066A patent/JPH03255050A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010525006A (en) * | 2007-04-25 | 2010-07-22 | エフ．ホフマン−ラ ロシュ アーゲー | New synthesis method of acid chloride |
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