JPH0352885A - Production of thiophenedicarboxylic acid diester - Google Patents
Production of thiophenedicarboxylic acid diesterInfo
- Publication number
- JPH0352885A JPH0352885A JP1188546A JP18854689A JPH0352885A JP H0352885 A JPH0352885 A JP H0352885A JP 1188546 A JP1188546 A JP 1188546A JP 18854689 A JP18854689 A JP 18854689A JP H0352885 A JPH0352885 A JP H0352885A
- Authority
- JP
- Japan
- Prior art keywords
- acid diester
- metal
- ion
- dicarboxylic acid
- formula
- 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
- -1 thiophenedicarboxylic acid diester Chemical class 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000654 additive Substances 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 230000002140 halogenating effect Effects 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims abstract description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 3
- 229910001432 tin ion Inorganic materials 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 229910021645 metal ion Inorganic materials 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 3
- 238000005658 halogenation reaction Methods 0.000 claims description 2
- 238000005695 dehalogenation reaction Methods 0.000 claims 1
- 230000026030 halogenation Effects 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 7
- 150000005690 diesters Chemical class 0.000 abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract description 2
- 229910052794 bromium Inorganic materials 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 7
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- HIHKYDVSWLFRAY-UHFFFAOYSA-N thiophene-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=CSC=1C(O)=O HIHKYDVSWLFRAY-UHFFFAOYSA-N 0.000 description 3
- YCGAZNXXGKTASZ-UHFFFAOYSA-N thiophene-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)S1 YCGAZNXXGKTASZ-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000007033 dehydrochlorination reaction Methods 0.000 description 2
- LHLAKFBPFFJRPV-UHFFFAOYSA-N dibutyl thiolane-2,5-dicarboxylate Chemical compound CCCCOC(=O)C1CCC(C(=O)OCCCC)S1 LHLAKFBPFFJRPV-UHFFFAOYSA-N 0.000 description 2
- KWZUUCHRIBVBJW-UHFFFAOYSA-N dibutyl thiophene-2,5-dicarboxylate Chemical compound CCCCOC(=O)C1=CC=C(C(=O)OCCCC)S1 KWZUUCHRIBVBJW-UHFFFAOYSA-N 0.000 description 2
- UBSQOGXCPUUNJW-UHFFFAOYSA-N dimethyl thiolane-2,5-dicarboxylate Chemical compound COC(=O)C1CCC(C(=O)OC)S1 UBSQOGXCPUUNJW-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 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 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- VZKPHLAASBCFGX-UHFFFAOYSA-N thiolane-2,5-dicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)S1 VZKPHLAASBCFGX-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- UCRQTPGCFCBLOX-UHFFFAOYSA-N thiophene-2,5-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)S1 UCRQTPGCFCBLOX-UHFFFAOYSA-N 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- AVRWEULSKHQETA-UHFFFAOYSA-N Thiophene-2 Chemical compound S1C=2CCCCCC=2C(C(=O)OC)=C1NC(=O)C1=C(F)C(F)=C(F)C(F)=C1F AVRWEULSKHQETA-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- CYUGNCLRGFKPAE-UHFFFAOYSA-N dimethyl thiophene-2,5-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)S1 CYUGNCLRGFKPAE-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- NBNBICNWNFQDDD-UHFFFAOYSA-N sulfuryl dibromide Chemical compound BrS(Br)(=O)=O NBNBICNWNFQDDD-UHFFFAOYSA-N 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Landscapes
- Heterocyclic Compounds Containing Sulfur Atoms (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）
本発明はチオフエンジカルボン酸ジエステルを製造する
方法に関する。チオフエンジカルボン酸ジエステルは、
機能性材料、医薬、農薬等を製造する際の重要な中間体
として広く知られている。例えば、チオフエンジカルボ
ン酸ジエステルとアミノフェノール誘導体を反応して得
られるジベンズオキサゾリル化合物は、プラスチック用
の蛍光増白剤として従来からよく使用されている。また
該ジエステルは加水分解により容易に公知の有用物質で
あるチオフエンジカルボン酸に導くことができる。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing thiophene dicarboxylic acid diester. Thiophene dicarboxylic acid diester is
It is widely known as an important intermediate in the production of functional materials, medicines, agricultural chemicals, etc. For example, a dibenzoxazolyl compound obtained by reacting a thiophene dicarboxylic acid diester with an aminophenol derivative has been commonly used as an optical brightener for plastics. Furthermore, the diester can be easily converted into thiophenedicarboxylic acid, a known useful substance, by hydrolysis.
（従来の技術）
（発明が解決しようとする問題点）
従来、チオフエンジカルボン酸誘導体を製造する方法は
いくつか知られている。例えば（１）アジピン酸と塩化
チオニルをピリジン触媒の存在下に反応せしめ、チオフ
ェン２．５−ジカルボン酸ジクロライドとし、これを加
水分解してチオフエン２．５−ジカルボン酸とする方法
。(Prior Art) (Problems to be Solved by the Invention) Conventionally, several methods for producing thiophenedicarboxylic acid derivatives are known. For example, (1) a method in which adipic acid and thionyl chloride are reacted in the presence of a pyridine catalyst to form thiophene 2,5-dicarboxylic acid dichloride, which is then hydrolyzed to form thiophene 2,5-dicarboxylic acid.
一・・・東独特許第１２９４８８号
（２）α，α′−ジクロロアジピン酸から得られるテト
ラヒド口チオフエン２．５−ジカルボン酸にオキシ塩化
リンと三塩化リンを反応させ、引き続き塩素を作用させ
、ジクロロテトラヒド口チオフエン２．５−ジカルボン
酸ジクロライドとし、これよりチオフエン２．５−ジカ
ルボン酸を得る方法。1... East German Patent No. 129488 (2) Tetrahydrothiophene 2,5-dicarboxylic acid obtained from α,α'-dichloroadipic acid is reacted with phosphorus oxychloride and phosphorus trichloride, and then chlorine is applied, A method for obtaining thiophene 2,5-dicarboxylic acid from dichlorotetrahydride and thiophene 2,5-dicarboxylic acid dichloride.
特公昭３９−３４３４
（３）α，α′−ジクロロアジピン酸のナトリウム塩と
硫化ナトリウムを水中で反応させ、そのまま系内に塩素
を吹き込み、チオフエン２．５−ジカルボン酸を得る方
法。Japanese Patent Publication No. 39-3434 (3) A method for obtaining thiophene 2,5-dicarboxylic acid by reacting sodium salt of α,α'-dichloroadipic acid with sodium sulfide in water, and directly blowing chlorine into the system.
特公昭３９−３８４２
（４）テトラヒドロチオフエン２．５−ジカルボン酸ジ
メチルエステルとイオウ原子を反応させ、チオフエン２
．５−ジカルボン酸ジメチルエステルを得る方法。Japanese Patent Publication No. 39-3842 (4) Tetrahydrothiophene 2,5-dicarboxylic acid dimethyl ester is reacted with a sulfur atom to form thiophene 2.
．． Method for obtaining 5-dicarboxylic acid dimethyl ester.
・−チェコスロバキア特許第１４０８７８号（５）テト
ラヒドロチオフエン２．５−ジカルボン酸ジメチルエス
テルを塩素化し、３，４−ジクロロテトラヒド口チオフ
ェン２．５−ジカルボン酸ジメチルエステルとし、さら
に加熱することにより、チオフエン２．５−ジカルボン
酸ジメチルエステルを得る方法。・-Czechoslovakia Patent No. 140878 (5) By chlorinating tetrahydrothiophene 2,5-dicarboxylic acid dimethyl ester to form 3,4-dichlorotetrahydride-thiophene 2,5-dicarboxylic acid dimethyl ester, and further heating. , a method for obtaining thiophene 2,5-dicarboxylic acid dimethyl ester.
〜 −チェコスロバキア特許第１３７０３２号等が知ら
れている。~ -Czechoslovakia Patent No. 137032 etc. are known.
しかしながら、何れの方法も、反応時間が長く収率が悪
い等、コスト的に満足できるものはなく、中には、塩化
水素、二酸化イオウが廃ガスとして副生するものもあり
、工業的に実施するには、有利な方法とはいえない。However, none of these methods is cost-satisfactory due to long reaction times and poor yields, and some methods produce hydrogen chloride and sulfur dioxide as by-products as waste gas, making it difficult to implement them industrially. This is not an advantageous way to do so.
前記状況に鑑みて本発明者らは、チオフエンジカルボン
酸ジエステルの工業的に有利な製造方法について鋭意検
討した結果、原料としてテトラヒドロチオフエンジカル
ボン酸ジエステルを用い、これをハロゲン化した後に、
脱ハロゲン化水素反応を行えば、容易に、チオフェンジ
カルボン酸ジエステルが得られることを見い出し、平戒
１年３月１３日に「チオフエンジカルボン酸ジエステル
およびその製造方法」として特許出願した。（特願平１
６１１８５）特願平１−６１１８５記載の方法は、
一般式（Ｉ′）で表されるチオフエンジカルボン酸ジ（
式中Ｒ′はＣエ〜Ｃ８のアルキル基、フェニル基、核置
換フェニル基またはベンジル基を示す。）
を製造するに際し、一般式（■′）で表されるテトラヒ
ド口チオフェンジカルボン酸ジエステ（式中Ｒ′は上記
定義と同じである。）をハロゲン化して一般式（ＩＩＩ
）で表される（式中ＸはＣＩまたはＢｒを示し、Ｒ′は
上記定義と同じである。）
ジハロテトラヒドロチオフェンジカルボン酸ジエステル
となし、引き続き、添加剤の存在下に脱ハロゲン化水素
反応を行うことを特徴とする一般式（工′）で表される
化合物の製造方法である。In view of the above-mentioned circumstances, the present inventors conducted intensive studies on an industrially advantageous manufacturing method for thiophenedicarboxylic acid diester, and as a result, using tetrahydrothiophenedicarboxylic acid diester as a raw material, after halogenating it,
They discovered that thiophenedicarboxylic acid diester could be easily obtained by carrying out a dehydrohalogenation reaction, and filed a patent application for ``thiophenedicarboxylic acid diester and method for producing the same'' on March 13, 1997. (Special application Hei 1
61185) The method described in Japanese Patent Application No. 1-61185 is
Thiophene dicarboxylic acid di(
In the formula, R' represents a C-C8 alkyl group, a phenyl group, a nuclear-substituted phenyl group, or a benzyl group. ), the tetrahydro-thiophene dicarboxylic acid diester represented by the general formula (■') (wherein R' is the same as defined above) is halogenated to produce the general formula (III
) (In the formula, X represents CI or Br, and R' is the same as defined above.) Dihalotetrahydrothiophene dicarboxylic acid diester, followed by dehydrohalogenation reaction in the presence of an additive. This is a method for producing a compound represented by the general formula (E), which is characterized by carrying out the following steps.
（■′）
（ｍ）
（１′ ）
本発明者らは、前記反応についてさらに検討を加えた結
果、脱ハロゲン化水素反応の際に添加剤として金属ある
いは金属イオンを用いれば触媒量の使用量で、より温和
な条件で上記反応が進行し、高純度のチオフエンジカル
ボン酸ジエステルが収率よく得られることを見出し、本
発明に到達した。脱ハロゲン化水素反応は単に加熱のみ
で行うことができるのであるが、この場合、反応を約１
５０℃の高温で行わなければならないため、熱履歴によ
るタール化が起こり、収率の低下を避けることができな
い。しかるに本発明の触媒量の安価な金属または金属イ
オンの添加によって後記実施例に示すような収率が得ら
れたことは驚くべき効果である。(■') (m) (1') As a result of further study on the above reaction, the present inventors found that if a metal or metal ion is used as an additive during the dehydrohalogenation reaction, the amount used in a catalytic amount can be reduced. The inventors have now discovered that the above reaction can proceed under milder conditions and that highly purified thiophenedicarboxylic acid diester can be obtained in good yield, leading to the present invention. The dehydrohalogenation reaction can be carried out simply by heating, but in this case, the reaction is
Since it must be carried out at a high temperature of 50° C., tar formation occurs due to thermal history, and a decrease in yield cannot be avoided. However, it is a surprising effect that the addition of a catalytic amount of an inexpensive metal or metal ion according to the present invention resulted in yields as shown in the Examples below.
金属としては銅、鉄、亜鉛、錫等が使用できる。また金
属イオンとしてはｌ価．２価の銅イオン、２価，３価の
鉄イオン、２価の亜鉛イオン、２価，４価の錫イオン等
が使用できる。これらの金属イオンは、実用上塩酸塩、
硫酸塩、硝酸塩等として使用されるため、使用する塩の
具体例としては、塩化第一銅、塩化第二銅、硫酸第二銅
、塩化第二鉄、塩化亜鉛、塩化第二錫等を挙げることが
できる。Copper, iron, zinc, tin, etc. can be used as the metal. Also, as a metal ion, it has a valence of l. Divalent copper ions, divalent and trivalent iron ions, divalent zinc ions, divalent and tetravalent tin ions, etc. can be used. These metal ions are practically hydrochloride,
Since it is used as a sulfate, nitrate, etc., specific examples of the salts used include cuprous chloride, cupric chloride, cupric sulfate, ferric chloride, zinc chloride, tin chloride, etc. be able to.
金属あるいは金属イオンの添加量はジハロテトラヒドロ
チオフェンジカルボン酸ジエステルに対してｏ．ｏｏｉ
〜０．１倍モル、好ましくは０．００５〜０．０５倍モ
ル使用する。The amount of metal or metal ion added is o. ooi
It is used in an amount of 0.1 to 0.1 times the mole, preferably 0.005 to 0.05 times the mole.
使用量が少なすぎると添加効果が認められず、多すぎて
もそれに見合う効果がなく、有利な効果は得られない。If the amount used is too small, no effect will be observed, and if it is too large, there will be no commensurate effect and no advantageous effect will be obtained.
反応温度は７０〜１３０℃の範囲であり、好ましくは８
０〜１２０℃の範囲で行う。反応温度が１３０゜Ｃを超
える時は、副反応のため収率が低下し、一方反応温度が
７０℃未満の時は、反応速度が事実上遅すぎるので好ま
しくない。The reaction temperature is in the range of 70 to 130°C, preferably 8
It is carried out in the range of 0 to 120°C. When the reaction temperature exceeds 130°C, the yield decreases due to side reactions, while when the reaction temperature is below 70°C, the reaction rate is actually too slow, which is undesirable.
一方、反応原料として用いるテトラヒドロチオフェンジ
カルボン酸ジエステルについては、種々の製造方法が公
知であるが、特願平１−６１１８５記載の方法を用いる
ことにより有利に製造することができる。本願発明にお
いては、先ずテトラヒドロチオフエンジカルボン酸ジエ
ステルをハロゲン化するのであるが、この時に用いるハ
ロゲン化剤としては、塩素、臭素、塩化スルフリル、臭
化スルフリル等を用いることができ、その使用量はテト
ラヒド口チオフエンジカルボン酸ジエステルに対し、２
．０〜４，０倍モル、好ましくは２． ０〜３．０倍
モルである。ハロゲン化剤の使用量が少なすぎると収率
が低く、逆に多すぎると副反応が起きるので前記範囲内
で使用するのが好ましい。ハロゲン化反応は、無溶媒あ
るいは溶媒の存在下で行うことができる。溶媒を用いる
場合、特に限定されるものではないが、ベンゼン、トル
エン、キシレン、クロルベンゼン、ジクロルベンゼン等
の芳香族化合物、ｎ−へキサン、シクロヘキサン、ｎ−
へブタン等の脂肪族炭化水素、クロロホルム、ジクロル
エタン、四塩化炭素等のハロゲン化炭化水素等を挙げる
ことができる。反応温度は通常−２０℃〜４０℃の範囲
であり、好ましくは、−１５℃〜３０℃の範囲で行う。On the other hand, various production methods are known for the tetrahydrothiophene dicarboxylic acid diester used as a reaction raw material, but it can be advantageously produced by using the method described in Japanese Patent Application No. 1-61185. In the present invention, the tetrahydrothiophene dicarboxylic acid diester is first halogenated, and as the halogenating agent used at this time, chlorine, bromine, sulfuryl chloride, sulfuryl bromide, etc. can be used, and the amount used is For tetrahydride thiophene dicarboxylic acid diester, 2
．． 0 to 4.0 times mole, preferably 2. It is 0 to 3.0 times the mole. If the amount of the halogenating agent used is too small, the yield will be low, and if it is too large, side reactions will occur, so it is preferable to use it within the above range. The halogenation reaction can be carried out without a solvent or in the presence of a solvent. When using a solvent, there are no particular limitations, but aromatic compounds such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, n-hexane, cyclohexane, n-
Examples include aliphatic hydrocarbons such as hebutane, halogenated hydrocarbons such as chloroform, dichloroethane, and carbon tetrachloride. The reaction temperature is usually in the range of -20°C to 40°C, preferably in the range of -15°C to 30°C.
反応温度が４０℃をこえるときは副反応のため目的物の
収率は低下し、一方反応温度が−２０℃未満のように低
くても特に有利な効果を得ることはできない。When the reaction temperature exceeds 40°C, the yield of the target product decreases due to side reactions; on the other hand, even if the reaction temperature is as low as less than -20°C, no particularly advantageous effects can be obtained.
かくして得られたジハロテトラヒド口チオフエンジカル
ボン酸ジエステルを前記した添加剤の存在下に脱ハロゲ
ン化水素反応を行うことにより、目的とするチオフエン
ジカルボン酸ジエステルを高純度で収率よく製造するこ
とができる。By subjecting the thus obtained dihalotetrahydride-thiophenedicarboxylic acid diester to a dehydrohalogenation reaction in the presence of the above-mentioned additives, the desired thiophenedicarboxylic acid diester can be produced with high purity and high yield. .
（実施例） 以下実施例により本発明をさらに詳細に説明寸る。(Example) The present invention will be explained in more detail with reference to Examples below.
実施例１
（チオフエン２．５−ジカルボン酸ジーｎ−プチルエス
テルの合成）
テトラヒドロチオフエン２．５−ジカルボン酸ジーｎ−
ブチルエステルを塩素化し、引き続き添加剤として触媒
量の金属あるいは金属イオンの存在下で、脱塩化水素反
応させることによりチオフエンジカルボン酸ジーｎ−ブ
チルエステルを得た。すなわち、攪拌機、温度計、ガス
吹込管および冷却器を備えた３００ｍｌ４ツロフラスコ
に、テトラヒドロチオフエン２，５−ジカルボン酸ジー
ｎ−ブチルエステル２８．８ｇ（０．１０モル）および
シクロヘキサン１００ｍｌを仕込み、攪拌下−１０℃〜
−５℃にて塩素１４．９ｇ （０．２１モル）をｌ時間
で導入した。その後同温度で１時間熟成し、塩素化反応
を行った。添加剤として、銅粉末０．３１８ｇ（０．０
０５０モル）を加え、溶媒であるシクロヘキサンを留出
させながら１０５℃にて８時間攪拌し、脱塩化水素反応
を行った。反応終了後、残留物を減圧蒸留することによ
り、無色の液体であるチオフエン２．５−ジカルボン酸
ジーｎ−ブチルエステル２７．３ｇを得た。テトラヒド
ロチオフェン２．５−ジカルボン酸ジーｎーブチルエス
テルに対する収率は、９６．０％、ガスクロマトグラフ
ィーによる純度測定結果は９９．０％以上であった。Example 1 (Synthesis of thiophene 2,5-dicarboxylic acid di-n-butyl ester) Tetrahydrothiophene 2,5-dicarboxylic acid di-n-
Thiophenedicarboxylic acid di-n-butyl ester was obtained by chlorinating the butyl ester and then subjecting it to a dehydrochlorination reaction in the presence of a catalytic amount of metal or metal ions as an additive. That is, 28.8 g (0.10 mol) of tetrahydrothiophene 2,5-dicarboxylic acid di-n-butyl ester and 100 ml of cyclohexane were charged into a 300 ml 4-tube flask equipped with a stirrer, a thermometer, a gas blowing tube, and a condenser, and the mixture was stirred. Below -10℃~
At -5 DEG C., 14.9 g (0.21 mol) of chlorine were introduced in 1 hour. Thereafter, the mixture was aged at the same temperature for 1 hour to carry out a chlorination reaction. As an additive, copper powder 0.318g (0.0
050 mol) was added thereto, and the mixture was stirred at 105° C. for 8 hours while distilling off the solvent cyclohexane to perform a dehydrochlorination reaction. After the reaction was completed, the residue was distilled under reduced pressure to obtain 27.3 g of thiophene 2,5-dicarboxylic acid di-n-butyl ester as a colorless liquid. The yield based on tetrahydrothiophene 2,5-dicarboxylic acid di-n-butyl ester was 96.0%, and the purity measurement result by gas chromatography was 99.0% or more.
実施例２〜１２
第１表に示すテトラヒドロチオフエンジカルボン酸ジエ
ステル（０．１０モル）、反応溶媒（１００ｍｌ）、ハ
ロゲン化剤（０．２１モル）を用い、添加剤としての金
属あるいは金属イオンの種類、使用量を変えた以外は、
実施例１と同様な操作を行い、目的物が液体のものは減
圧蒸留により単離し、固体のものは、反応終了後濾過、
精製することによりチオフエンジカルボン酸ジエステル
を得た。結果を表１に示した。Examples 2 to 12 Using tetrahydrothiophene dicarboxylic acid diester (0.10 mol), reaction solvent (100 ml), and halogenating agent (0.21 mol) shown in Table 1, metal or metal ion was added as an additive. Other than changing the type and amount used,
The same operation as in Example 1 was carried out, and if the target product was liquid, it was isolated by vacuum distillation, and if it was solid, it was filtered after the reaction was completed.
Thiophenedicarboxylic acid diester was obtained by purification. The results are shown in Table 1.
なお、得られたチオフエンジカルボン酸ジエステルの純
度は、すべて９９．０％以上であった（発明の効果）
テトラヒドロチオフエンジカルボン酸ジエステルをハロ
ゲン化し、その後、脱ハロゲン化水素反応してチオフエ
ンジカルボン酸ジエステルを製造する際に、各種の金属
または金属イオンを添加することにより該ジエステルを
収率よく高純度で得ることができた。銅、鉄、亜鉛、錫
等の安価な金属またはその塩を触媒量用いるだけで前記
の効果を得ることができるため、本発明の方法は工業的
利用価値の極めて大きいものである。The purity of the obtained thiophenedicarboxylic acid diesters was all 99.0% or higher (effect of the invention).The tetrahydrothiophenedicarboxylic acid diesters were halogenated and then dehydrohalogenated to produce thiophenedicarboxylic acid diesters. When producing acid diesters, by adding various metals or metal ions, the diesters could be obtained in good yield and with high purity. Since the above-mentioned effects can be obtained simply by using catalytic amounts of inexpensive metals such as copper, iron, zinc, and tin, or their salts, the method of the present invention has extremely high industrial utility value.
Claims (1)
、核置換フェニル基またはベンジル基を示す。） で表されるチオフェンジカルボン酸ジエステルを製造す
るに際し、 一般式（II′） ▲数式、化学式、表等があります▼（II′） （式中Ｒ′は上記定義と同じである。） で表されるテトラヒドロチオフェンジカルボン酸ジエス
テルをハロゲン化して 一般式（III） ▲数式、化学式、表等があります▼（III） （式中ＸはＣｌまたはＢｒを示し、Ｒ′は上記定義と同
じである。） で表されるジハロテトラヒドロチオフェンジカルボン酸
ジエステルとなし、引き続き添加剤の存在下に脱ハロゲ
ン化水素反応させることを特徴とする一般式（ I ′）
で表されるチオフェンジカルボン酸ジエステルを製造す
る方法。 （２）ハロゲン化温度が−１５〜３０℃である請求項（
１）記載の方法。 （３）脱ハロゲン化反応の際に用いる添加剤が金属ある
いは金属イオンである請求項（１）記載の方法。 （４）金属あるいは金属イオンが銅あるいは銅イオンで
ある請求項（３）記載の方法。 （５）金属あるいは金属イオンが鉄あるいは鉄イオンで
ある請求項（３）記載の方法。 （６）金属あるいは金属イオンが亜鉛または亜鉛イオン
である請求項（３）記載の方法。（７）金属あるいは金
属イオンが錫または錫イオンである請求項（３）記載の
方法。 （８）金属あるいは金属イオンの添加量が、ジハロテト
ラヒドロチオフェンジカルボン酸ジエステルに対して０
．００１〜０．１倍モルである請求項（３）記載の方法
。[Claims] (1) General formula (I') ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I') (In the formula, R' is an alkyl group of C_1 to C_8, a phenyl group, a nuclear-substituted phenyl group, or When producing a thiophenedicarboxylic acid diester represented by the general formula (II') ▲Mathematical formula, chemical formula, table, etc.▼(II') (In the formula, R' is the same as the above definition. The general formula (III) is obtained by halogenating the tetrahydrothiophene dicarboxylic acid diester represented by The general formula (I') is characterized in that it is formed with a dihalotetrahydrothiophene dicarboxylic acid diester represented by
A method for producing a thiophene dicarboxylic acid diester represented by (2) Claim in which the halogenation temperature is -15 to 30°C (
1) The method described. (3) The method according to claim (1), wherein the additive used in the dehalogenation reaction is a metal or a metal ion. (4) The method according to claim (3), wherein the metal or metal ion is copper or a copper ion. (5) The method according to claim (3), wherein the metal or metal ion is iron or iron ion. (6) The method according to claim (3), wherein the metal or metal ion is zinc or zinc ion. (7) The method according to claim (3), wherein the metal or metal ion is tin or a tin ion. (8) The amount of metal or metal ion added is 0 to the dihalotetrahydrothiophene dicarboxylic acid diester.
．． The method according to claim 3, wherein the amount is 0.001 to 0.1 times by mole.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1188546A JPH082895B2 (en) | 1989-07-19 | 1989-07-19 | Method for producing thiophene dicarboxylic acid diester |
| EP90104556A EP0387725B1 (en) | 1989-03-13 | 1990-03-09 | Production of thiophene-2,5-dicarboxylic acid diesters and tetrahydrothiophene-2,5-dicarboxylic acid diesters |
| DE69029754T DE69029754T2 (en) | 1989-03-13 | 1990-03-09 | Production of thiophene-2,5-dicarboxylic acid diesters and tetrahydrothiophene-2,5-dicarboxylic acid diesters |
| EP96101671A EP0719774B1 (en) | 1989-03-13 | 1990-03-09 | A method for production of dibenzoxazolyl thiophenes |
| DE69032378T DE69032378T2 (en) | 1989-03-13 | 1990-03-09 | A process for the preparation of dibenzoxazolylthiophenes |
| KR1019900003361A KR0142667B1 (en) | 1989-03-13 | 1990-03-12 | Production of thiophene-2,5-dicarboxylic acid diesters, tetrahydrothiophene-2,5-dicarboxylic acid diesters and dibenzoxazolyl-thiophenes |
| US07/492,072 US5093504A (en) | 1989-03-13 | 1990-03-12 | Production of thiophene-2,5-dicarboxylic acid diesters, tetrahydrothiophene-2,5-dicarboxylic acid diesters and dibenzoxazolylthiophenes |
| CA002011948A CA2011948C (en) | 1989-03-13 | 1990-03-12 | Production of thiophene-2, 5-dicarboxylic acid diesters, tetrahydrothiophene-2, 5-dicarboxylic acid diesters and dibenzoxazolylthiophenes |
| US07/753,088 US5221749A (en) | 1989-03-13 | 1991-08-30 | Production of dibenzoxazolylthiophenes |
| US08/005,463 US5310940A (en) | 1989-03-13 | 1993-01-19 | Production of thiophene-2,5-dicarboxylic acid diesters, tetrahydrothiophene-2,5-dicarboxylic acid diesters and dibenzoxazolylthiophenes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1188546A JPH082895B2 (en) | 1989-07-19 | 1989-07-19 | Method for producing thiophene dicarboxylic acid diester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0352885A true JPH0352885A (en) | 1991-03-07 |
| JPH082895B2 JPH082895B2 (en) | 1996-01-17 |
Family
ID=16225593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1188546A Expired - Fee Related JPH082895B2 (en) | 1989-03-13 | 1989-07-19 | Method for producing thiophene dicarboxylic acid diester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH082895B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5543129A (en) * | 1978-09-22 | 1980-03-26 | Asahi Chem Ind Co Ltd | Dechlorination of chlorine-containing polymer |
-
1989
- 1989-07-19 JP JP1188546A patent/JPH082895B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5543129A (en) * | 1978-09-22 | 1980-03-26 | Asahi Chem Ind Co Ltd | Dechlorination of chlorine-containing polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH082895B2 (en) | 1996-01-17 |
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