JPH04124170A - Polyfunctional thiol compound and its production - Google Patents
Polyfunctional thiol compound and its productionInfo
- Publication number
- JPH04124170A JPH04124170A JP24450490A JP24450490A JPH04124170A JP H04124170 A JPH04124170 A JP H04124170A JP 24450490 A JP24450490 A JP 24450490A JP 24450490 A JP24450490 A JP 24450490A JP H04124170 A JPH04124170 A JP H04124170A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- thiazolidine
- formula
- dimethyl
- general 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.)
- Pending
Links
- -1 thiol compound Chemical class 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 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 claims abstract description 7
- SNPQRYOQWLOTFA-UHFFFAOYSA-N 2,2-dimethyl-1,3-thiazolidine Chemical compound CC1(C)NCCS1 SNPQRYOQWLOTFA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 4
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 150000003548 thiazolidines Chemical class 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000002738 chelating agent Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 3
- 239000000976 ink Substances 0.000 abstract description 3
- 239000003973 paint Substances 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 150000001455 metallic ions Chemical class 0.000 abstract 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 229960003151 mercaptamine Drugs 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003586 protic polar solvent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000001984 thiazolidinyl group Chemical group 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ZLYYJUJDFKGVKB-OWOJBTEDSA-N (e)-but-2-enedioyl dichloride Chemical compound ClC(=O)\C=C\C(Cl)=O ZLYYJUJDFKGVKB-OWOJBTEDSA-N 0.000 description 1
- OGYGFUAIIOPWQD-UHFFFAOYSA-N 1,3-thiazolidine Chemical compound C1CSCN1 OGYGFUAIIOPWQD-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IRXBNHGNHKNOJI-UHFFFAOYSA-N butanedioyl dichloride Chemical compound ClC(=O)CCC(Cl)=O IRXBNHGNHKNOJI-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000010422 internal standard material Substances 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- UWBHMRBRLOJJAA-UHFFFAOYSA-N oxaluric acid Chemical compound NC(=O)NC(=O)C(O)=O UWBHMRBRLOJJAA-UHFFFAOYSA-N 0.000 description 1
- YVOFTMXWTWHRBH-UHFFFAOYSA-N pentanedioyl dichloride Chemical compound ClC(=O)CCCC(Cl)=O YVOFTMXWTWHRBH-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- SXYFKXOFMCIXQW-UHFFFAOYSA-N propanedioyl dichloride Chemical compound ClC(=O)CC(Cl)=O SXYFKXOFMCIXQW-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は一般式（Ｉ）
Ａ−Ｅ−ＮＨＣＨＳＨ］ ・・・ （ＩＩ２４
ｎ
（式中、Ａはカルボン酸化合物反応残基を、またｎは２
．３を表す）
で示される多官能チオール化合物およびその製法に関す
るものである。Detailed Description of the Invention (Industrial Application Field) The present invention relates to the general formula (I) A-E-NHCHSH] ... (II24
n (wherein A is a carboxylic acid compound reactive residue, or n is 2
．． 3) and a method for producing the same.
本発明によって提供される前記−数式（Ｉ）で示される
新規多官能チオール化合物は、繊維、塗料、接着剤、イ
ンキ等の種々の分野における架橋剤、硬化剤として、ま
た金属イオンとの反応性を利用したキレート化剤として
有用な化合物である。The novel polyfunctional thiol compound represented by formula (I) provided by the present invention can be used as a crosslinking agent and a curing agent in various fields such as fibers, paints, adhesives, and inks, and has a high reactivity with metal ions. This compound is useful as a chelating agent using
（従来の技術）
本発明による一般式（Ｉ）で示される多官能チオール化
合物は今まで報告されていない新規な化合物である。(Prior Art) The polyfunctional thiol compound represented by general formula (I) according to the present invention is a novel compound that has not been reported so far.
（発明が解決しようとする課題）
本発明の目的は、新規化合物である一般式（Ｉ）で示さ
れる多官能チオール化合物を提供することにある。(Problems to be Solved by the Invention) An object of the present invention is to provide a novel compound, a polyfunctional thiol compound represented by general formula (I).
また、本発明の他の目的は、多官能チオール化合物の製
法を提供することにある。Another object of the present invention is to provide a method for producing a polyfunctional thiol compound.
（課題を解決するための手段）
本発明は一般式（Ｉ）
Ａ−Ｅ−ＮＨＣＨＳＨ］ −（ＩＩ２４
ｎ
（式中、Ａはカルボン酸化合物反応残基を、またｎは２
．３を表す）
で示される多官能チオール化合物に関するものである。(Means for Solving the Problems) The present invention has the general formula (I) A-E-NHCHSH] -(II24
n (wherein A is a carboxylic acid compound reactive residue, or n is 2
．． 3) is related to a polyfunctional thiol compound represented by
また、本発明は一般式（ＩＩ）
ＣＨ−ＣＨ２
で示される２、２−ジメチル−１゜
３−チアゾリ
ジンと多官能酸クロライド化合物の反応生成物である一
般式（ＩＩＩ）
（式中、Ａはカルボン酸化合物反応残基を、またｎは２
．３を表す）
で示されるチアゾリジン誘導体を加水分解することを特
徴とする一般式（１）
％式％］
（式中、Ａはカルボン酸化合物反応残基を、またｎは２
．３を表す）
で示される多官能チオール化合物の製法に関するもので
ある。Furthermore, the present invention relates to the general formula (III) which is a reaction product of 2,2-dimethyl-1゜3-thiazolidine represented by the general formula (II) CH-CH2 and a polyfunctional acid chloride compound (wherein A is carboxylic acid compound reactive residue, or n or 2
．． General formula (1) characterized by hydrolyzing a thiazolidine derivative represented by
．． The present invention relates to a method for producing a polyfunctional thiol compound represented by:
＋ ｎ Ｈ２ Ａ −Ｅ−ＮＨＣ２Ｈ４Ｓ Ｈコ 。+ n H2 A -E-NHC2H4S H co.
＋
ｎ ＣＨ３
０ＣＨ３
（式中、
Ａはカルボン酸化合物反応残基を、
また
ｎは２．
３を表す）
（作 用）
本発明による一般式（１）で示される多官能チオール化
合物は、２．２−ジメチル−１，３−チアゾリジンと多
官能酸クロライド化合物との反応物である一般式（ＩＩ
Ｉ）
（式中、Ａはカルボン酸化合物反応残基を、またｎは２
．３を表す）
で示されるチアゾリジン誘導体を加水分解することによ
り得られる。多官能酸クロライド化合物の例としては、
テレフタロイルジクロライド、イソフタロイルジクロラ
イド、オキサルジクロライド、マロニルジクロライド、
琥珀酸ジクロリド、グルタリルジクロライド、アジポイ
ルクロライド、フマル酸ジクロライド等の化合物かあげ
られる。+ n CH3 0CH3 (In the formula, A represents a carboxylic acid compound reactive residue, and n represents 2.3) (Function) The polyfunctional thiol compound represented by the general formula (1) according to the present invention has the following properties. General formula (II
I) (wherein A is a carboxylic acid compound reactive residue, or n is 2
．． 3) is obtained by hydrolyzing a thiazolidine derivative represented by: Examples of polyfunctional acid chloride compounds include:
Terephthaloyl dichloride, isophthaloyl dichloride, oxal dichloride, malonyl dichloride,
Compounds such as succinic acid dichloride, glutaryl dichloride, adipoyl chloride, and fumaric acid dichloride can be mentioned.
本発明による、２．２−ジメチル−１，３−チアゾリジ
ンと多官能酸クロライド化合物の反応は無溶媒または、
適当な溶媒中、例えば、トルエン、キシレンのような芳
香族系溶媒中、四塩化炭素、クロロホルム、塩化メチレ
ン等の塩素系溶媒中、アセトン、メチルエチルケトン、
メチルイソブチルケトン等のケトン系溶媒中、Ｎ、Ｎ−
ジメチルホルムアミド、Ｎ−メチルピロリドン、ジメチ
ルスルホキシド等の非プロトン性溶媒中、ジオキサン、
テトラヒドロフラン等のエーテル系溶媒中、水溶媒中、
アルコール類、グリコールエーテル類のようなプロトン
性溶媒も使用できる。また前記混合溶媒中、場合によっ
ては、前記の内の水不溶性の溶媒と水との混合溶媒を用
い２層系で反応を行なうことができる。According to the present invention, the reaction between 2,2-dimethyl-1,3-thiazolidine and a polyfunctional acid chloride compound can be carried out without a solvent or by
In an appropriate solvent, for example, in an aromatic solvent such as toluene or xylene, in a chlorinated solvent such as carbon tetrachloride, chloroform, or methylene chloride, acetone, methyl ethyl ketone,
In a ketone solvent such as methyl isobutyl ketone, N, N-
In an aprotic solvent such as dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, dioxane,
In ether solvents such as tetrahydrofuran, in water solvents,
Protic solvents such as alcohols and glycol ethers can also be used. In addition, in some cases, a mixed solvent of water and a water-insoluble solvent among the above may be used to carry out the reaction in a two-layer system.
反応の際、副生する塩酸捕捉剤として、トリエチルアミ
ンのような有機アミン化合物や、水酸化ナトリウム、炭
酸ナトリウム等の無機塩基が使用される。During the reaction, an organic amine compound such as triethylamine or an inorganic base such as sodium hydroxide or sodium carbonate is used as a by-product hydrochloric acid scavenger.
反応温度は特に制限はないが、通常−２０℃から使用す
る溶媒の沸点までで実施される。The reaction temperature is not particularly limited, but it is usually carried out from -20°C to the boiling point of the solvent used.
２．２−ジメチル−１，３−チアゾリジンと多官能酸ク
ロライド化合物との反応のモル比は、特に限定されるこ
とはないが通常、酸クロライド基に対して２，２−ジメ
チル−１，３−チアゾリジンを等モル用いるのが好まし
い。The molar ratio of the reaction between 2.2-dimethyl-1,3-thiazolidine and the polyfunctional acid chloride compound is not particularly limited, but is usually 2,2-dimethyl-1,3 to the acid chloride group. - It is preferred to use equimolar amounts of thiazolidine.
反応時間は使用する原料の種類１．溶媒の種類、また反
応温度により異なる。通常１〜２４時間である。The reaction time depends on the type of raw materials used. It varies depending on the type of solvent and reaction temperature. Usually 1 to 24 hours.
本発明による２、２．−ジメチル−１，３−チアゾリジ
ンと多官能酸クロライド化合物の反応物である一般式（
Ｉ［［）
（式中、Ａはカルボン酸化合物反応残基を、またｎは２
．３を表す）
で示されるチアゾリジン誘導体の加水分解は、チアゾリ
ジン環に対する当モルまたはそれ以上の水の存在下であ
れば、無溶媒または適当な溶媒中、例えば、トルエン、
キシレンのような芳香族系溶媒中、四塩化炭素、クロロ
ホルム、塩化メチレン等の塩素系溶媒中、アセトン、メ
チルエチルケトン、メチルイソブチルケトン等のケトン
系溶媒中、Ｎ、Ｎ−ジメチルホルムアミド、Ｎ−メチル
ピロリドン、ジメチルスルホキシド等の非プロトン性溶
媒中、ジオキサン、テトラヒドロフラン等のエチル系溶
媒中、水溶媒中、アルコール類、グリコールエーテル類
のようなプロトン性溶媒も使用できる。2. According to the present invention. - General formula (
I[[) (wherein A is a carboxylic acid compound reactive residue, and n is 2
．． Hydrolysis of the thiazolidine derivative represented by 3) can be carried out without a solvent or in a suitable solvent, for example, toluene, in the presence of water in an amount equivalent to or more than the thiazolidine ring.
In aromatic solvents such as xylene, in chlorinated solvents such as carbon tetrachloride, chloroform, methylene chloride, in ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, N,N-dimethylformamide, N-methylpyrrolidone. , in an aprotic solvent such as dimethyl sulfoxide, in an ethyl solvent such as dioxane or tetrahydrofuran, in an aqueous solvent, or in a protic solvent such as alcohols or glycol ethers.
また、加水分解触媒として、塩酸、硫酸、硝酸、リン酸
などの無機酸、ギ酸、酢酸、プロピオン酸、などの有機
酸、硝酸銀、酢酸銀などの銀塩を使用してもよい。Further, as a hydrolysis catalyst, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, organic acids such as formic acid, acetic acid, and propionic acid, and silver salts such as silver nitrate and silver acetate may be used.
加水分解温度は特に制限はないが、通常、常温から一般
式（ＩＩＩ）て示されるチアゾリジン誘導体の分解温度
以下の範囲で実施される。The hydrolysis temperature is not particularly limited, but it is usually carried out in a range from room temperature to the decomposition temperature of the thiazolidine derivative represented by the general formula (III).
一般式（ＩＩＩ）て示されるチアゾリジン誘導体と水の
モル比は、特に限定されることはないが通常、チアゾリ
ジン環に対し等モルまたはそれ以上が好ましい。The molar ratio of the thiazolidine derivative represented by general formula (III) to water is not particularly limited, but is usually preferably equimolar or more relative to the thiazolidine ring.
加水分解に必要な時間は使用する原料の種類、溶媒の種
類、また反応温度により異なるが通常１〜２４時間であ
る。The time required for hydrolysis varies depending on the type of raw materials used, the type of solvent, and the reaction temperature, but is usually 1 to 24 hours.
（実 施 例）
つぎに、実施例に基すいて本発明をより詳細に説明する
が、本発明は、下記実施例のみに限定されるものではな
い。(Examples) Next, the present invention will be explained in more detail based on Examples, but the present invention is not limited to the following Examples.
実施例】−
テレフタロイル−ジ−メルカプトエチルアミンの合成
２１の３つロアラスコに、クロロホルム１０００ｇ、２
．２−ジメチル−１，３−チアシリシフ７０ｇ（０，６
モル）およびトリエチルアミン６７ｇ （０，６６モル
）を仕込み、１０℃以下、約３０分てテレフタロイルジ
クロライト６１．ｇ（０゜３モル）を滴下した。その後
２５〜３０℃で２時間反応させた。反応終了後、反応液
に水を加え抽出を行ない、クロロホルム層からクロロホ
ルムを留去することにより、白色結晶のテレフタロイル
−ジー（２，２−ジメチル−１，３−チアゾリジン）９
５ｇ （０，２６モル）が得られた。この化合物の融点
は２３７〜２３９℃であった。この化合物の元素分析、
ＮＭＲスペクトルおよび赤外吸収スペクトルの分析結果
を下記に示す。Example]-Synthesis of terephthaloyl-di-mercaptoethylamine 21 1000 g of chloroform, 2
．． 70g of 2-dimethyl-1,3-thiasilicif (0,6
mol) and triethylamine (67 g (0.66 mol)) and heated below 10°C for about 30 minutes to form terephthaloyl dichlorite 61. g (0.3 mol) was added dropwise. Thereafter, the mixture was reacted at 25 to 30°C for 2 hours. After the reaction is completed, water is added to the reaction solution for extraction, and chloroform is distilled off from the chloroform layer to obtain white crystals of terephthaloyl-di(2,2-dimethyl-1,3-thiazolidine) 9.
5 g (0.26 mol) were obtained. The melting point of this compound was 237-239°C. Elemental analysis of this compound,
The analysis results of NMR spectrum and infrared absorption spectrum are shown below.
また、第１図にＮＭＲスペクトルのチャートを示す。第
２図に赤外吸収スペクトルのチャートを示す。Further, FIG. 1 shows a chart of the NMR spectrum. FIG. 2 shows a chart of the infrared absorption spectrum.
［元素分析値］
（％）
（Ｘｌ
（％）
（％）
理論値
１７．５９
分析値
７．４２
［ＮＭＲスペク
トルコ
−ＮＭＲ
（溶媒：ＣＤＣｌ
内部標準物質
ＴＭＳ）
δ ＝３
７６〜３
Ｈ
−Ｎ Ｃ）Ｉ２ＣＤ２
Ｓ−
δ ＝７
４５〜７
Ｈ
フェニル環
つぎにテレフタロイル−ジー（２，２−ジメチル−１，
３−チアゾリジン）３６．４ｇ （０，１０モル）およ
び０．ＩＮ−塩酸水溶液１０００ ｍｌ、クロロホルム
１０００ ｍｌを反応フラスコに仕込み攪拌下、６０℃
、２４時間、加水分解を行なった。[Elemental analysis value] (%) (Xl (%) (%) Theoretical value 17.59 Analytical value 7.42 [NMR spectrum-NMR (solvent: CDCl Internal standard material TMS) δ = 3 76~3 H -N C) I2CD2 S- δ = 7 45-7 H phenyl ring then terephthaloyl-di(2,2-dimethyl-1,
3-thiazolidine) 36.4 g (0.10 mol) and 0.3-thiazolidine). 1000 ml of IN-hydrochloric acid aqueous solution and 1000 ml of chloroform were placed in a reaction flask and heated to 60°C with stirring.
The hydrolysis was carried out for 24 hours.
反応終了後、クロロホルム層を蒸発乾固し、メタノール
洗浄後、乾燥を行なった。その結果テレフタロイル−ジ
−メルカプトエチルアミン２２．７ｇ（０，０８モル）
が得られた。この化合物の元素分析、ＮＭＲスペクトル
および赤外吸収スペクトルの分析結果を下記に示す。ま
た、第３図にＮＭＲスペクトルのチャートを示す。第４
図に赤外吸収スペクトルのチャートを示す。After the reaction was completed, the chloroform layer was evaporated to dryness, washed with methanol, and then dried. As a result, 22.7 g (0.08 mol) of terephthaloyl-di-mercaptoethylamine
was gotten. The results of elemental analysis, NMR spectrum, and infrared absorption spectrum of this compound are shown below. Further, FIG. 3 shows a chart of the NMR spectrum. Fourth
The figure shows a chart of the infrared absorption spectrum.
［元素分析値］
Ｃ（％）Ｈ（％）Ｎ（％）Ｓｆ％）
理論値 ５０，７０ ５，６３ ９．８６ ２２
．５４分析値 ５１．ＯＱ ５．９０ ９．７
２ ２２．４５［ＮＭＲスペクトル］
’ Ｈ−ＮＭＲ（溶媒：ＣＤＣｌ３゜
内部標準物質： ＴＭＳ）
δ＝２．４９ｐｐｍ ２ｔｌ −５ｏｌδ＝
２．７０ｐｐｍ ４Ｈ−ＣＨ２−３δ＝３．
４５ｐｐｍ ４Ｈ−Ｃｌ４２ ＣＨ２ＳＨδ＝
７．９６ｐＤｍ ４Ｈ７エ＝ル環δ＝ ８．８１
ｐｌ’ｍ ２ｔｌ −ＣＯＮｆｉＣＨ２［
赤外吸収スペクトル
（ＫＢｒ
。ｍｌ）
］
３２９０．３２４４．３０５８．２９３５．２５４９．
１６２７．１５４４．１４９６＋３１９．１２９４．１
１９４． ８６６、 ６８６（発明の効果）
本発明によって提供される前記−数式（１）で示される
多官能チオール化合物は、今まで報告されていない新規
な化合物であり、繊維、塗料、接着剤、インキ等の種々
の分野における架橋剤、硬化剤として、また金属イオン
との反応性を利用したキレート化剤として有用な化合物
である。[Elemental analysis value] C (%) H (%) N (%) Sf%) Theoretical value 50,70 5,63 9.86 22
．． 54 Analysis value 51. OQ 5.90 9.7
2 22.45 [NMR spectrum] 'H-NMR (solvent: CDCl3° internal standard: TMS) δ=2.49ppm 2tl -5olδ=
2.70ppm 4H-CH2-3δ=3.
45ppm 4H-Cl42 CH2SHδ=
7.96pDm 4H7 el ring δ = 8.81
pl'm 2tl -CONfiCH2[
Infrared absorption spectrum (KBr.ml)] 3290.3244.3058.2935.2549.
1627.1544.1496+319.1294.1
194. 866, 686 (Effects of the Invention) The polyfunctional thiol compound represented by formula (1) provided by the present invention is a novel compound that has not been reported so far, and can be used in fibers, paints, adhesives, inks, etc. It is a compound useful as a crosslinking agent and curing agent in various fields, and as a chelating agent using its reactivity with metal ions.
第１図は、テレフタロイル−ジー（２，２−ジメチル−
１，３−チアゾリジン）のＮＭＲスペクトルのチャート
を示す。
第２図は、テレフタロイル−ジー（２，２−ジメチル−
１３
クトル図を示す。
チアゾリジン）の赤外吸収スペ
第３図は、テレフタロイル−ジ−メルカプトエチルアミ
ンのＮＭＲスペクトルのチャートを示す第４図は、テレ
フタロイル−ジ−メルカプトエチルアミンの赤外吸収ス
ペクトル図を示す。Figure 1 shows terephthaloyl di(2,2-dimethyl-
1,3-thiazolidine) is shown. Figure 2 shows terephthaloyl di(2,2-dimethyl-
13 shows the vector diagram. Figure 3 shows a chart of the NMR spectrum of terephthaloyl-di-mercaptoethylamine. Figure 4 shows an infrared absorption spectrum of terephthaloyl-di-mercaptoethylamine.
Claims (2)
、３を表す） で示される多官能チオール化合物。(1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) (In the formula, A is the carboxylic acid compound reaction residue, and n is 2
, 3) A polyfunctional thiol compound represented by:
多官能酸クロライド化合物の反応生成物である一般式（
III） ▲数式、化学式、表等があります▼・・・（III） （式中、Ａはカルボン酸化合物反応残基を、またｎは２
、３を表す） で示されるチアゾリジン誘導体を加水分解することを特
徴とする一般式（ I ） ▲数式、化学式、表等があります▼・・・（ I ） （式中、Ａはカルボン酸化合物反応残基を、またｎは２
、３を表す） で示される多官能チオール化合物の製法。(2) General formula (II) ▲Mathematical formulas, chemical formulas, tables, etc.▼...(II) is a reaction product of 2,2-dimethyl-1,3-thiazolidine and a polyfunctional acid chloride compound represented by General formula (
III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) (In the formula, A is the carboxylic acid compound reaction residue, and n is 2
, 3) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(I) residue, and n is 2
, 3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24450490A JPH04124170A (en) | 1990-09-13 | 1990-09-13 | Polyfunctional thiol compound and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24450490A JPH04124170A (en) | 1990-09-13 | 1990-09-13 | Polyfunctional thiol compound and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04124170A true JPH04124170A (en) | 1992-04-24 |
Family
ID=17119663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24450490A Pending JPH04124170A (en) | 1990-09-13 | 1990-09-13 | Polyfunctional thiol compound and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04124170A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003506337A (en) * | 1999-07-28 | 2003-02-18 | バンティコ アクチエンゲゼルシャフト | Amine curing agent for epoxide resin |
| JP2013505963A (en) * | 2009-09-28 | 2013-02-21 | ユニヴァーシティ オブ ケンタッキー リサーチ ファウンデイション | Thiol-containing compounds for removing elements from contaminated environments and methods of use |
-
1990
- 1990-09-13 JP JP24450490A patent/JPH04124170A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003506337A (en) * | 1999-07-28 | 2003-02-18 | バンティコ アクチエンゲゼルシャフト | Amine curing agent for epoxide resin |
| JP2013505963A (en) * | 2009-09-28 | 2013-02-21 | ユニヴァーシティ オブ ケンタッキー リサーチ ファウンデイション | Thiol-containing compounds for removing elements from contaminated environments and methods of use |
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