JPH0474160A - Production of aromatic dithiol compound - Google Patents
Production of aromatic dithiol compoundInfo
- Publication number
- JPH0474160A JPH0474160A JP2186727A JP18672790A JPH0474160A JP H0474160 A JPH0474160 A JP H0474160A JP 2186727 A JP2186727 A JP 2186727A JP 18672790 A JP18672790 A JP 18672790A JP H0474160 A JPH0474160 A JP H0474160A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- aromatic
- sulfur
- hydrosulfide
- iron
- 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
- -1 aromatic dithiol compound Chemical class 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- 159000000014 iron salts Chemical class 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 21
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 abstract description 6
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 abstract description 4
- 239000000975 dye Substances 0.000 abstract description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 abstract description 2
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 abstract description 2
- 239000006096 absorbing agent Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000010992 reflux Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Polymers SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-N 0.000 description 2
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000004662 dithiols Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 2
- GBDZXPJXOMHESU-UHFFFAOYSA-N 1,2,3,4-tetrachlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1Cl GBDZXPJXOMHESU-UHFFFAOYSA-N 0.000 description 1
- QLVKECUOHNDWOI-UHFFFAOYSA-N 2-oxo-1,3,2$l^{5}-diazaphosphonan-2-amine Chemical compound NP1(=O)NCCCCCCN1 QLVKECUOHNDWOI-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- ONPIOWQPHWNPOQ-UHFFFAOYSA-L barium(2+);dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Ba+2].[O-]S([O-])(=O)=S ONPIOWQPHWNPOQ-UHFFFAOYSA-L 0.000 description 1
- ZDVYABSQRRRIOJ-UHFFFAOYSA-N boron;iron Chemical compound [Fe]#B ZDVYABSQRRRIOJ-UHFFFAOYSA-N 0.000 description 1
- FAYYUXPSKDFLEC-UHFFFAOYSA-L calcium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Ca+2].[O-]S([O-])(=O)=S FAYYUXPSKDFLEC-UHFFFAOYSA-L 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- ANVWDQSUFNXVLB-UHFFFAOYSA-L copper;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Cu+2].[O-]S([O-])(=O)=S ANVWDQSUFNXVLB-UHFFFAOYSA-L 0.000 description 1
- LQQMGWKYFSXQOO-UHFFFAOYSA-H dibismuth;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=S.[O-]S([O-])(=O)=S.[O-]S([O-])(=O)=S LQQMGWKYFSXQOO-UHFFFAOYSA-H 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- FKPGNMBJYBPNHL-UHFFFAOYSA-L dioxido-oxo-sulfanylidene-$l^{6}-sulfane;lead(2+) Chemical compound [Pb+2].[O-]S([O-])(=O)=S FKPGNMBJYBPNHL-UHFFFAOYSA-L 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- 229940062135 magnesium thiosulfate Drugs 0.000 description 1
- TZKHCTCLSRVZEY-UHFFFAOYSA-L magnesium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Mg+2].[O-]S([O-])(=O)=S TZKHCTCLSRVZEY-UHFFFAOYSA-L 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- IHYNKGRWCDKNEG-UHFFFAOYSA-N n-(4-bromophenyl)-2,6-dihydroxybenzamide Chemical compound OC1=CC=CC(O)=C1C(=O)NC1=CC=C(Br)C=C1 IHYNKGRWCDKNEG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- CEOCDNVZRAIOQZ-UHFFFAOYSA-N pentachlorobenzene Chemical compound ClC1=CC(Cl)=C(Cl)C(Cl)=C1Cl CEOCDNVZRAIOQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は芳香族ジチオール化合物の製造方法に関し、詳
しくは染料、医薬、光安定化材、近赤外線吸収材等の中
間体として有用な芳香族ジチオール化合物の製造方法に
関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing aromatic dithiol compounds, and more specifically, aromatic dithiol compounds useful as intermediates for dyes, medicines, light stabilizers, near-infrared absorbing materials, etc. The present invention relates to a method for producing a dithiol compound.
芳香族ジチオール化合物は強力な金属キレート化能を有
し、芳香族ジチオレート金属錯体を製造するための中間
体として有用であり、該金属錯体は染料、医薬、光安定
化材、近赤外線吸収材として有用であることが知られて
いる。Aromatic dithiol compounds have strong metal chelating ability and are useful as intermediates for producing aromatic dithiolate metal complexes, and these metal complexes can be used as dyes, medicines, light stabilizers, and near-infrared absorbing materials. Known to be useful.
また、芳香族ジチオール化合物の製造方法としては１例
えばヘキサクロロベンゼンと水硫化ナトリウムとを、鉄
粉の存在下、ジメチルホルムアミド中で加熱反応させて
１，２，３．４−テトラクロロベンゼン−５，６−ジチ
オールを得る方法（ジャーナル・オブ・ジ・アミリカン
・ソサイエティ、８８．４８７０．１９６６）が知られ
ている。しかし、この方法は、広範囲のポリハロゲン化
ベンゼンジチオールの製造に適用できる方法とはいえな
い。In addition, as a method for producing an aromatic dithiol compound, 1, for example, hexachlorobenzene and sodium hydrogen sulfide are heated and reacted in dimethylformamide in the presence of iron powder to produce 1,2,3.4-tetrachlorobenzene-5,6 - A method for obtaining dithiols (Journal of the American Society, 88.4870.1966) is known. However, this method cannot be said to be applicable to the production of a wide range of polyhalogenated benzenedithiols.
近年、その点を解決する方法として、ポリハロゲン化ベ
ンゼンと水硫化物を、硫黄及び鉄粉又は鉄塩類の存在下
、極性有機溶媒中で反応させるハロゲン置換−オルソ−
ベンゼンジチオールの製造法（特開昭５８−１０５９６
０号公報）が提案されている。In recent years, as a method to solve this problem, halogen-substituted -ortho-
Method for producing benzenedithiol (JP-A-58-10596
Publication No. 0) has been proposed.
ところが、上記方法には、反応溶媒中の微量成分や微妙
な反応条件の違いによって収率が影響されるとか、得ら
れるジチオールの純度が低く、再結晶化を行なっても思
うように純度があがらないというような問題点がある。However, with the above method, the yield is affected by trace components in the reaction solvent and subtle differences in reaction conditions, and the purity of the dithiol obtained is low, and even with recrystallization, the purity cannot be increased as expected. There is a problem that there is no such thing.
従って、本発明の目的は、安定した高収率で得られると
共に、再結晶化を行なわなくても高純度品が得られる芳
香族ジチオール化合物の製造方法を提供することにある
。Therefore, an object of the present invention is to provide a method for producing an aromatic dithiol compound that can be obtained in a stable and high yield and that can also produce a highly purified product without recrystallization.
本発明によれば、芳香族ポリハロゲン化化合物と水硫化
物を、硫黄及び鉄粉又は鉄塩類の存在下、極性有機溶媒
中で反応させる芳香族ジチオール化合物の製造方法にお
いて、反応試剤として更にチオ硫酸化合物を添加するこ
とを特徴とする芳香族ジチオール化合物の製造方法が提
供される。According to the present invention, in the method for producing an aromatic dithiol compound in which an aromatic polyhalogenated compound and a hydrosulfide are reacted in a polar organic solvent in the presence of sulfur and iron powder or iron salts, thiol is further added as a reaction agent. A method for producing an aromatic dithiol compound is provided, which comprises adding a sulfuric acid compound.
すなわち、本発明においては、芳香族ポリハロゲン化化
合物からの芳香族ジチオール化合物の製造において、反
応試剤として水硫化物／チオ硫酸化合物混合物を使用す
ることを特徴とするが、該反応試剤を使用することによ
って、高収率でしかも純度の高い芳香族ジチオール化合
物を安定して製造することができる。That is, the present invention is characterized in that a hydrosulfide/thiosulfate compound mixture is used as a reaction reagent in the production of an aromatic dithiol compound from an aromatic polyhalogenated compound; By doing so, it is possible to stably produce an aromatic dithiol compound with high yield and high purity.
本発明で原料として用いる芳香族ポリハロゲン化化合物
としては、下記一般式（Ｉ）で表わされる化合物が適用
される。As the aromatic polyhalogenated compound used as a raw material in the present invention, a compound represented by the following general formula (I) is applied.
Ｔ？１ （式中、Ｘは塩素原子又は臭素原子を示し、Ｈｌ。T? 1 (In the formula, X represents a chlorine atom or a bromine atom, and Hl.
Ｒ２，Ｒ’及びＲ４は水素原子、ハロゲン原子、アルキ
ル基、アミノ基又はアルコキシ基を示し、また隣接する
置換基残基と結合し５員環若しくは６員環の芳香環を形
成してもよい。）
なお、本発明の方法によって、前記一般式（Ｉ）で表わ
される化合物から得られる芳香族ジチオール化合物は、
下記一般式（ｎ）で表わされる化合物である。R2, R' and R4 represent a hydrogen atom, a halogen atom, an alkyl group, an amino group or an alkoxy group, and may also be combined with adjacent substituent residues to form a 5-membered or 6-membered aromatic ring. . ) The aromatic dithiol compound obtained from the compound represented by the general formula (I) by the method of the present invention is
It is a compound represented by the following general formula (n).
（式中、Ｒ” 、Ｒ” 、Ｒ３及びＲ４は水素原子、ハ
ロゲン原子、アルキル基、アミノ基又はアルコキシ基を
示し、また隣接する置換基残基と結合し５員環若しくは
６員環の芳香環を形成してもよい。）本発明においては
、反応試剤として、水硫化物とチオ硫酸化合物とが併用
されるが、この場合、水硫化物としては、水硫化ナトリ
ウム、水硫化カリウムを用いるのが好ましい。水硫化物
は、原料の芳香族ポリハロゲン化化合物に対して少なく
とも０．５倍モル使用され、特に１倍モルから３倍モル
の範囲で使用するのが好ましい。水硫化物が０．５倍モ
ル未満になると、収率、純度ともに低くなる。(In the formula, R'', R'', R3 and R4 represent a hydrogen atom, a halogen atom, an alkyl group, an amino group or an alkoxy group, and are bonded to adjacent substituent residues to form a 5- or 6-membered aromatic ring. A ring may be formed.) In the present invention, a hydrosulfide and a thiosulfate compound are used together as a reaction reagent, but in this case, as the hydrosulfide, sodium bisulfide or potassium hydrosulfide is used. is preferable. Hydrosulfide is used in an amount of at least 0.5 times the mole of the aromatic polyhalogenated compound as a raw material, and preferably in a range of 1 to 3 times the mole. If the amount of hydrosulfide is less than 0.5 times the mole, both the yield and the purity will be low.
また、３倍モルを超える量を添加しても、収率は向上し
ない。Moreover, even if an amount exceeding 3 times the mole is added, the yield does not improve.
また、チオ硫酸化合物としては、チオ硫酸ナトリウム、
チオ硫酸カリウム、チオ硫酸カルシウム、チオ硫酸バリ
ウム、チオ硫酸アンモニウム、チオ硫酸ビスマス、チオ
硫酸マグネシウム、チオ硫酸銅、チオ硫酸鉛などが使用
される。これらは無水物であっても水和物であってもよ
い。この中で原料入手性や価格を考慮すると、チオ硫酸
ナトリウムの５水塩が好適である。In addition, thiosulfate compounds include sodium thiosulfate,
Potassium thiosulfate, calcium thiosulfate, barium thiosulfate, ammonium thiosulfate, bismuth thiosulfate, magnesium thiosulfate, copper thiosulfate, lead thiosulfate, and the like are used. These may be anhydrous or hydrated. Among these, sodium thiosulfate pentahydrate is preferred in consideration of raw material availability and price.
これらのチオ硫酸化合物は、芳香族ポリハロゲン化化合
物に対して少なくとも（１，１倍モル以上使用される。These thiosulfate compounds are used in an amount of at least 1.1 times the amount of the aromatic polyhalogenated compound.
好ましくは０．２倍モルから２倍モルの範囲で使用され
る。０．１倍モルより少ない場合は、収率及び純度の低
下を招く。また、２倍モルを超える量を添加しても、収
率は向上しない。It is preferably used in a range of 0.2 to 2 moles. If it is less than 0.1 times the mole, the yield and purity will decrease. Moreover, even if an amount exceeding twice the mole is added, the yield will not improve.
また、本発明において、硫黄としては一般の硫黄粉末が
使用される。添加される硫黄の量は、芳香族ポリハロゲ
ン化化合物に対して０．１倍モル以上であり、特に０．
２倍モルから０．７倍モルの範囲が好ましい、硫黄の添
加量が０．１倍モル未満になると収率が低下するし、逆
に０．７倍モルを超えても収率は向上しない。Further, in the present invention, general sulfur powder is used as sulfur. The amount of sulfur added is 0.1 times the mole or more relative to the aromatic polyhalogenated compound, particularly 0.1 times the mole or more relative to the aromatic polyhalogenated compound.
A range of 2 times mole to 0.7 times mole is preferable. If the amount of sulfur added is less than 0.1 times mole, the yield will decrease, and conversely, if it exceeds 0.7 times mole, the yield will not improve. .
更に、本発明で用いる鉄粉及び鉄塩類としては、通常の
鉄粉や還元鉄粉、電解鉄粉などと、塩化鉄、臭化鉄、硼
化鉄、燐酸鉄などが挙げられる。これらは芳香族ポリハ
ロゲン化化合物に対して、鉄原子換算で０．５倍モル以
上使用するのが好ましい。Furthermore, the iron powder and iron salts used in the present invention include ordinary iron powder, reduced iron powder, electrolytic iron powder, iron chloride, iron bromide, iron boride, iron phosphate, and the like. It is preferable to use these in an amount of 0.5 times or more in terms of iron atoms based on the amount of the aromatic polyhalogenated compound.
また、本発明で用いる極性有機溶媒としては。Further, as the polar organic solvent used in the present invention.
ｎ−ブタノールのようなアルコール系溶媒、ジメチルホ
ルムアミド、ヘキサメチレンホスホルアミドのようなア
ミド系溶媒、ジメチルスルホキシドのような硫黄系溶媒
などが挙げられるが、水硫化物の溶解性１反応生成物の
溶解性、１２０℃以上の反応温度等を考慮すると、ジメ
チルホルムアミドが特に好ましい。なお、ジメチルホル
ムアミドにモレキュラシーブを添加して、微量成分を除
去したものを使用することもできる。Examples include alcohol solvents such as n-butanol, amide solvents such as dimethylformamide and hexamethylene phosphoramide, and sulfur solvents such as dimethyl sulfoxide. Considering solubility, reaction temperature of 120° C. or higher, etc., dimethylformamide is particularly preferred. Note that it is also possible to use dimethylformamide obtained by adding molecular sieve to remove trace components.
本発明の実施に当たっては、まず鉄粉又は鉄塩類と硫黄
と水硫化物とチオ硫酸化合物とを反応釜に入れ、窒素等
の不活性ガスを流しながら極性有機溶媒を注入する。し
ばらく撹拌した後、芳香族ポリハロゲン化化合物を固体
のまま、あるし）はスラリー状ないし溶液状にして、ゆ
っくり添加する。In carrying out the present invention, first, iron powder or iron salts, sulfur, hydrosulfide, and a thiosulfate compound are placed in a reaction vessel, and a polar organic solvent is injected while flowing an inert gas such as nitrogen. After stirring for a while, the aromatic polyhalogenated compound is added slowly, either as a solid or in the form of a slurry or solution.
芳香族ポリハロゲン化化合物を添加した後、室温でしば
らく撹拌する。その後、ゆっくりと昇温し還流させる。After adding the aromatic polyhalogenated compound, the mixture is stirred for a while at room temperature. Thereafter, the temperature is slowly raised to reflux.
反応時間は還流してから数時間から１５時間である。The reaction time is from several hours to 15 hours after reflux.
反応終了後、注水して濾過することにより黒色の反応物
が得られる。これを酸化亜鉛と塩基の存在下で加熱還流
し、更に酸析することにより、所望の芳香族ジチオール
化合物を得ることができる。After the reaction is completed, a black reaction product is obtained by pouring water and filtering. The desired aromatic dithiol compound can be obtained by heating and refluxing this in the presence of zinc oxide and a base, and further performing acid precipitation.
なお、最初の仕込みにおいて、極性有機溶媒を注入する
前に、芳香族ポリハロゲン化化合物を他の反応試剤と共
に反応釜に入れておき、後から極性有機溶媒をゆっくり
と注入してもよい。In addition, in the initial charging, before injecting the polar organic solvent, the aromatic polyhalogenated compound may be placed in the reaction vessel together with other reaction reagents, and the polar organic solvent may be slowly injected later.
本発明の方法によると、従来法に比べて高収率で、高純
度の芳香族ジチオール化合物が、安定して得られる。According to the method of the present invention, a highly purified aromatic dithiol compound can be stably obtained in a higher yield than in the conventional method.
次に、本発明を実施例により更に詳細に説明する。なお
、以下において示す％及び部は何れも重量基準である。Next, the present invention will be explained in more detail with reference to Examples. Note that all percentages and parts shown below are based on weight.
実施例１
四つロフラスコに窒素ガスをゆるやかに通じながら鉄粉
１．７部、硫黄０．８部、７０％水硫化ナトリウム６．
３部、チオ硫酸ナトリウム５水塩５．４８部を入れ、更
にジメチルホルムアミド３５部を加えて撹拌した。Example 1 1.7 parts of iron powder, 0.8 parts of sulfur, and 6.7 parts of 70% sodium hydrogen sulfide were added to a four-loaf flask while slowly passing nitrogen gas.
3 parts of sodium thiosulfate pentahydrate and 5.48 parts of sodium thiosulfate pentahydrate were added thereto, and further 35 parts of dimethylformamide were added and stirred.
その後水冷しながら、１０部のペンタクロロベンゼンを
撹拌しつつ、少しずつ加えた。添加終了後、３０分間撹
拌し、その後ゆっくりと加熱し、５時間後に１２０℃に
なる様に連続的に昇温させた。その後、１０時間加熱還
流した。反応終了後放冷し、水７２部を加えて撹拌し、
黒色の沈殿物を吸引濾過して取り出した。Thereafter, while cooling with water, 10 parts of pentachlorobenzene was added little by little with stirring. After the addition was completed, the mixture was stirred for 30 minutes, then slowly heated, and the temperature was continuously raised to 120° C. after 5 hours. Thereafter, the mixture was heated under reflux for 10 hours. After the reaction was completed, the mixture was allowed to cool, and 72 parts of water was added and stirred.
The black precipitate was filtered off with suction.
次に、得られた固体を三角フラスコに移し、メタノール
７５部、酸化亜鉛５．５部及び水酸化ナトリウム１５部
を水７５部に溶解した水溶液を加え、１時間加熱還流し
た。その後放冷して反応液を吸引濾過し、濃赤色の濾液
を得た。この濾液を、濃硫酸７５部を水１５０部に溶解
したものに多量のクロロホルムを加えた水溶液に、水冷
しながらゆっくりと滴下した。滴下終了後、析出した黄
色の結晶を吸引濾過し、濾液のクロロホルム相を水洗し
、その後クロロホルム相を蒸発乾固して、淡黄色の１，
２゜４−トリクロロベンゼン−５，６−ジチオール８．
３４部を得た。融点は１１４．５〜１１６．０℃で、収
率は８５．０％であった。Next, the obtained solid was transferred to an Erlenmeyer flask, and an aqueous solution of 75 parts of methanol, 5.5 parts of zinc oxide, and 15 parts of sodium hydroxide dissolved in 75 parts of water was added, and the mixture was heated under reflux for 1 hour. Thereafter, the reaction solution was allowed to cool and was suction-filtered to obtain a deep red filtrate. This filtrate was slowly added dropwise to an aqueous solution prepared by dissolving 75 parts of concentrated sulfuric acid in 150 parts of water and adding a large amount of chloroform while cooling with water. After the dropwise addition, the precipitated yellow crystals were suction-filtered, the chloroform phase of the filtrate was washed with water, and the chloroform phase was evaporated to dryness to give pale yellow 1,
2゜4-Trichlorobenzene-5,6-dithiol8.
Obtained 34 copies. The melting point was 114.5-116.0°C, and the yield was 85.0%.
実施例２
４つロフラスコにアルゴンガスをゆるやかに通じながら
鉄粉１．９部、硫黄０．９部、７０％水硫化ナトリウム
７．２部及びチオ硫酸ナトリウム５水塩６．２８部を入
れ、ジメチルホルムアミド４０部を加えて撹拌した。そ
の後水冷しながら、１０部のテトラクロロベンゼンを撹
拌しつつ少しずつ加えた。添加終了後、３０分間撹拌し
、その後ゆっくりと加熱し、５時間後に１１８℃になる
様に連続的に昇温させた。Example 2 1.9 parts of iron powder, 0.9 parts of sulfur, 7.2 parts of 70% sodium hydrosulfide, and 6.28 parts of sodium thiosulfate pentahydrate were placed in a four-bottle flask while slowly passing argon gas. 40 parts of dimethylformamide was added and stirred. Thereafter, while cooling with water, 10 parts of tetrachlorobenzene was added little by little with stirring. After the addition was completed, the mixture was stirred for 30 minutes, then slowly heated, and the temperature was continuously raised to 118° C. after 5 hours.
その後、１０時間加熱還流した。反応終了後放冷し、水
８０部を加えて撹拌し、黒色の沈殿物を吸引濾過して取
り出した。Thereafter, the mixture was heated under reflux for 10 hours. After the reaction was completed, the mixture was allowed to cool, 80 parts of water was added and stirred, and the black precipitate was taken out by suction filtration.
次に、得られた固体を三角フラスコに移し、メタノール
８６部、酸化亜鉛６．６部及び水酸化ナトリウム１７部
を水８６部に溶解した水溶液を加え、１時間加熱還流し
た。その後放冷して反応液を吸引濾過し、濃赤色の濾液
を得た。この濾液を、濃硫酸８６部を水１７２部に溶解
したものに多量のクロロホルムを加えた水溶液に、水冷
しながらゆっくりと滴下した。滴下終了後、析出した黄
色の結晶を吸引濾過し、濾液のクロロホルム相を水洗し
、その後クロロホルム相を蒸発乾固して、淡黄色の１，
４ジクロロベンゼン−５，６−ジチオール８．０２部を
得た。Next, the obtained solid was transferred to an Erlenmeyer flask, and an aqueous solution of 86 parts of methanol, 6.6 parts of zinc oxide, and 17 parts of sodium hydroxide dissolved in 86 parts of water was added, and the mixture was heated under reflux for 1 hour. Thereafter, the reaction solution was allowed to cool and was suction-filtered to obtain a deep red filtrate. This filtrate was slowly added dropwise to an aqueous solution prepared by dissolving 86 parts of concentrated sulfuric acid in 172 parts of water and adding a large amount of chloroform while cooling with water. After the dropwise addition, the precipitated yellow crystals were suction-filtered, the chloroform phase of the filtrate was washed with water, and the chloroform phase was evaporated to dryness to give pale yellow 1,
8.02 parts of 4-dichlorobenzene-5,6-dithiol were obtained.
融点は５７．５〜５８．０℃であり、収率は８２．０％
であった。Melting point is 57.5-58.0°C, yield is 82.0%
Met.
比較例
実施例１において、チオ硫酸ナトリウム５水塩を添加し
なかった以外は、実施例１同様にして反応を行なったと
ころ、結晶５．０４部を得た。収率りま５１．４％で、
融点は８５〜１０５℃であった。Comparative Example The reaction was carried out in the same manner as in Example 1, except that sodium thiosulfate pentahydrate was not added, and 5.04 parts of crystals were obtained. Yield lima 51.4%,
The melting point was 85-105°C.
特許出願人 株式会社 リ コPatent applicant Rico Co., Ltd.
Claims (1)
及び鉄粉又は鉄塩類の存在下、極性有機溶媒中で反応さ
せる芳香族ジチオール化合物の製造方法において、反応
試剤として更にチオ硫酸化合物を添加することを特徴と
する芳香族ジチオール化合物の製造方法。(1) A method for producing an aromatic dithiol compound in which an aromatic polyhalogenated compound and a hydrosulfide are reacted in a polar organic solvent in the presence of sulfur and iron powder or iron salts, in which a thiosulfate compound is further added as a reaction reagent. 1. A method for producing an aromatic dithiol compound, characterized in that the aromatic dithiol compound is added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2186727A JPH0474160A (en) | 1990-07-13 | 1990-07-13 | Production of aromatic dithiol compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2186727A JPH0474160A (en) | 1990-07-13 | 1990-07-13 | Production of aromatic dithiol compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0474160A true JPH0474160A (en) | 1992-03-09 |
Family
ID=16193583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2186727A Pending JPH0474160A (en) | 1990-07-13 | 1990-07-13 | Production of aromatic dithiol compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0474160A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102566074A (en) * | 2011-12-13 | 2012-07-11 | 深圳朗光科技有限公司 | Polarizer and optical fiber sensor comprising same |
-
1990
- 1990-07-13 JP JP2186727A patent/JPH0474160A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102566074A (en) * | 2011-12-13 | 2012-07-11 | 深圳朗光科技有限公司 | Polarizer and optical fiber sensor comprising same |
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