JPH0920751A - Production of disulfides - Google Patents
Production of disulfidesInfo
- Publication number
- JPH0920751A JPH0920751A JP7196172A JP19617295A JPH0920751A JP H0920751 A JPH0920751 A JP H0920751A JP 7196172 A JP7196172 A JP 7196172A JP 19617295 A JP19617295 A JP 19617295A JP H0920751 A JPH0920751 A JP H0920751A
- Authority
- JP
- Japan
- Prior art keywords
- alkali metal
- metal hydroxide
- mol
- disulfides
- hydroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、脂肪族、脂環族および
芳香族ジスルフィド類の製造方法に関するものである。
更に詳しくは、本発明は、高収率でかつ、品質のよい前
記ジスルフィド類を効率的に製造する方法に関するもの
である。FIELD OF THE INVENTION The present invention relates to a method for producing aliphatic, alicyclic and aromatic disulfides.
More specifically, the present invention relates to a method for efficiently producing the above-mentioned disulfides with high yield and quality.
【０００２】[0002]
【従来の技術および発明が解決する課題】脂肪族または
芳香族ジスルフィド類の一般的合成法としては、チオー
ル類を酸化する方法、二硫化ナトリウムとハロゲン化ア
ルキルあるいはハロゲン化アリールと反応させる方法、
二硫化ナトリウムとアルキル硫酸エステル塩あるいはア
ルキルジアゾニウム塩とを反応させる方法、などが知ら
れている〔有機化学のハンドブック−有機合成化学協会
編（１９７９）〕。BACKGROUND OF THE INVENTION As a general method for synthesizing aliphatic or aromatic disulfides, a method of oxidizing thiols, a method of reacting sodium disulfide with an alkyl halide or an aryl halide,
A method of reacting sodium disulfide with an alkyl sulfate ester salt or an alkyl diazonium salt is known [Handbook of Organic Chemistry-Organic Synthetic Chemistry Society (1979)].
【０００３】また、脂環式炭化水素のジスルフィド類を
得る公知方法としては、シクロヘキセンと硫化水素を硫
黄の存在下で１５０℃で反応させる方法〔Ｊ．Ｃｈｅ
ｍ．Ｓｏｃｙ．，１９４７、１５３２（１９４７）〕、
シクロヘキサノールと多硫化アンチモンをジオキサンの
存在下、２００℃で反応させる方法〔日本化学雑誌、７
２、３７２（１９５１）〕、シクロヘキサノンと硫化水
素を９００〜１０００気圧、１３０℃で反応させる方法
〔Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，７４、３９８２（１
９５２）〕などがあるが、いずれも苛酷な条件で収率が
低く、工業的な製造方法としては問題がある。Further, as a known method for obtaining alicyclic hydrocarbon disulfides, a method in which cyclohexene and hydrogen sulfide are reacted at 150 ° C. in the presence of sulfur [J. Che
m. Soc. , 1947, 1532 (1947)],
Method of reacting cyclohexanol and antimony polysulfide in the presence of dioxane at 200 ° C. [Nippon Kagaku Shimbun, 7
2, 372 (1951)], a method of reacting cyclohexanone and hydrogen sulfide at 900 to 1000 atm and 130 ° C. [J. Am. Chem. Soc. , 74, 3982 (1
952)] and the like, but all of them have a low yield under severe conditions and are problematic as an industrial production method.
【０００４】また、ジシクロヘキシルジスルフィドは、
ゴム、プラスチックの製造に欠くことのできない各種添
加剤の原料を始めとして、界面活性剤、染料、医農薬な
ど各種合成薬品の原料として有用な化合物であるが、こ
れを工業的に製造する方法に関する報告例は少ない。Further, dicyclohexyl disulfide is
It is a compound useful as a raw material for various synthetic chemicals such as surfactants, dyes, pharmaceuticals and agrochemicals, as well as raw materials for various additives that are indispensable for the production of rubber and plastics. There are few reports.
【０００５】クロルシクロヘキサンを原料とするジシク
ロヘキシルジスルフィドの製造方法としては、エタノー
ル溶媒下での二硫化ナトリウムとの反応方法（チェコス
ロバキア国特許ＣＳ７７−２３７６号公報）、界面活性
剤を含む水を溶媒とする過剰の二硫化ナトリウムとの反
応方法（チェコスロバキア国特許ＣＳ８１−４３０９号
公報）などが提案されているが、生成物の組成や廃液処
理などに問題があり、経済的に製造しようとする目的か
らは満足できるものでなかった。As a method for producing dicyclohexyl disulfide using chlorocyclohexane as a raw material, a reaction method with sodium disulfide in an ethanol solvent (Czechoslovak Patent CS77-2376), water containing a surfactant as a solvent is used. Although a reaction method with excess sodium disulfide (Czech Slovak Patent No. CS81-4309) has been proposed, there is a problem in the composition of the product and the treatment of the waste liquid, and the purpose is to economically produce the product. I was not satisfied with it.
【０００６】また、特公昭６０−３０６６７号公報にお
いて、メタノールと水の混合溶媒下、クロルシクロヘキ
サン、硫化ナトリウム、硫黄を厳密なモル比設定下で反
応させる方法が提案された。この方法は、工業的な製造
方法としては有意義な方法ではあるが、さらに生産性を
向上させるため、溶媒使用量を低減させたりすると生成
物の純度不良や収率の低下を伴うなどの欠点を抱えてお
り、前述の目的達成に至るものではなかった。Further, Japanese Patent Publication No. 60-30667 proposed a method of reacting chlorocyclohexane, sodium sulfide and sulfur in a mixed solvent of methanol and water under a strict molar ratio setting. Although this method is a meaningful method as an industrial manufacturing method, in order to further improve the productivity, when the amount of solvent used is reduced, there are drawbacks such as poor purity of the product and a decrease in yield. I had it, and did not reach the purpose mentioned above.
【０００７】[0007]
【課題を解決するための手段】本発明者らは前述の特公
昭６０−３０６６７号公報に記載されている発明のさら
なる改良を図り、より経済的にかかるジスルフィド類を
製造する方法について鋭意検討の結果、アルカリ金属水
酸化物を共存させて反応せしめることにより、上記課題
を解決し得ることを見出して本発明に到達した。DISCLOSURE OF THE INVENTION The inventors of the present invention have made intensive studies on a method for producing such disulfides more economically with the aim of further improving the invention described in Japanese Patent Publication No. 60-30667. As a result, they have reached the present invention by finding that the above problems can be solved by reacting them in the presence of an alkali metal hydroxide.
【０００８】すなわち、本発明は、モノクロル置換化合
物を溶媒の存在下、アルカリ金属硫化物またはそれを含
む混合物と反応させるに際し、アルカリ金属水酸化物を
共存させ反応せしめることを特徴とするジスルフィド類
の製造方法を提供するものである。本発明をその具体的
実施態様として示せば、本発明は、クロルシクロヘキサ
ンをメタノール等の溶媒下、アルカリ金属硫化物あるい
はそれを含む混合物と反応せしめるに際し、アルカリ金
属水酸化物を、好ましくはクロルシクロヘキサン１モル
に対して０．１〜０．６モルの範囲で共存させることを
特徴とするジシクロヘキシルジスルフィドを効率的に製
造する方法である。ジシクロヘキシルジスルフィドは、
下記構造式によって示される。That is, according to the present invention, when a monochloro-substituted compound is reacted with an alkali metal sulfide or a mixture containing the same in the presence of a solvent, the disulfides are characterized by reacting with an alkali metal hydroxide. A manufacturing method is provided. Illustrating the present invention as a specific embodiment thereof, the present invention comprises reacting chlorcyclohexane with an alkali metal sulfide or a mixture containing the same in a solvent such as methanol. This is a method for efficiently producing dicyclohexyl disulfide, which is characterized in that it is allowed to coexist in the range of 0.1 to 0.6 mol with respect to 1 mol. Dicyclohexyl disulfide is
It is represented by the following structural formula.
【０００９】[0009]
【化１】 以下、本発明について詳細に説明する。Embedded image Hereinafter, the present invention will be described in detail.
【００１０】本発明の実施において、反応で共存させる
アルカリ金属水酸化物としては、水酸化リチウム、水酸
化ナトリウム、または水酸化カリウムあるいはそれを含
む水溶液が好適である。水溶液としては、５％〜４８％
程度の濃度のものが好ましく、特に安価で、かつ、取扱
いやすい面から４８％水酸化ナトリウム水溶液を用いる
ことが最も好ましい。In the practice of the present invention, the alkali metal hydroxide coexisted in the reaction is preferably lithium hydroxide, sodium hydroxide, potassium hydroxide or an aqueous solution containing the same. 5% to 48% as an aqueous solution
It is preferable to use a 48% aqueous solution of sodium hydroxide, since it is preferable to use a 48% aqueous solution of sodium hydroxide because it is inexpensive and easy to handle.
【００１１】このアルカリ金属水酸化物の共存量は、例
えばジシクロヘキシルジスルフィドを得るの場合、クロ
ルシクロヘキサン１モルに対して約０．１〜約０．６モ
ルの範囲、特に０．２〜０．４モルの範囲が好ましく、
同一反応条件下の共存なしに比べ、クロルシクロヘキサ
ン基準のジシクロヘキシルジスルフィドの収率が３〜８
％向上し、副生成物であるジシクロヘキシルトリスルフ
ィドの副生率が約１／３に減少する。In the case of obtaining dicyclohexyl disulfide, for example, the amount of the alkali metal hydroxide coexisting is in the range of about 0.1 to about 0.6 mol, particularly 0.2 to 0.4, relative to 1 mol of chlorocyclohexane. A molar range is preferred,
The yield of dicyclohexyl disulfide based on chlorocyclohexane is 3 to 8 as compared with the case without coexistence under the same reaction conditions.
%, The by-product ratio of dicyclohexyl trisulfide as a by-product is reduced to about 1/3.
【００１２】本発明ではアルカリ金属水酸化物の共存量
が、モノクロル置換化合物１モルに対して０．１モル未
満の場合は、収率や品質向上への効果は小さくなる傾向
があり、逆に、０．６モルを超えると効果は頭打ちにな
る一方、産廃量が増加していくので好ましくない。In the present invention, when the amount of the alkali metal hydroxide coexisting is less than 0.1 mol with respect to 1 mol of the monochloro-substituted compound, the effect on yield and quality improvement tends to be small. If the amount exceeds 0.6 mol, the effect will reach the ceiling, but the amount of industrial waste will increase, which is not preferable.
【００１３】本発明の実施においては、アルカリ金属水
酸化物を共存させる際、溶媒を使用する。本発明におい
て使用する溶媒は、炭素数１〜３の脂肪族アルコール類
あるいはそれを５０％程度以上含む水溶液等であり、安
価でかつ汎用的であり、さらには収率が高く副生物の生
成率が少ないなどの観点から、メタノールが特に好まし
い。In the practice of the present invention, a solvent is used when the alkali metal hydroxide is allowed to coexist. The solvent used in the present invention is an aliphatic alcohol having 1 to 3 carbon atoms or an aqueous solution containing about 50% or more thereof, which is inexpensive and versatile, and has a high yield and a by-product production rate. Methanol is particularly preferable from the viewpoint of low content.
【００１４】メタノール溶媒は、例えばジシクロヘキシ
ルジスルフィドを得るの場合、クロルシクロヘキサン１
モルに対して約０．８〜約３．０モルの範囲、特に１．
２〜２．０モルの範囲で使用することが好ましい。０．
８モル未満の場合は、ジシクロヘキシルジスルフィドの
収率が低下し、３．０モルを超えると、副生成物である
ジシクロヘキシルモノスルフィドの生成率が増加するの
で好ましくない。The methanol solvent is, for example, chlorocyclohexane 1 in the case of obtaining dicyclohexyl disulfide.
The range is from about 0.8 to about 3.0 moles, especially 1.
It is preferably used in the range of 2 to 2.0 mol. 0.
When the amount is less than 8 mol, the yield of dicyclohexyl disulfide decreases, and when the amount exceeds 3.0 mol, the production rate of the by-product dicyclohexyl monosulfide increases, which is not preferable.
【００１５】本発明の実施において、反応温度および圧
力は、溶媒その他が還流する温度、すなわち、７２〜１
１０℃の範囲と常圧〜２．１ｋｇ／ｃｍ2 Ｇの範囲、特
に９０〜１００℃の温度の範囲、１．２〜１．８ｋｇ／
ｃｍ2 Ｇの圧力の範囲が好ましく、常圧、還流下の反応
に比べ、反応時間が約１／３に短縮できる。In the practice of the present invention, the reaction temperature and pressure are such that the solvent or the like is refluxed, that is, 72 to 1
10 ° C. range and atmospheric pressure to 2.1 kg / cm 2 G range, especially 90 to 100 ° C. temperature range, 1.2 to 1.8 kg /
The pressure range of cm 2 G is preferable, and the reaction time can be shortened to about 1/3 as compared with the reaction under normal pressure and reflux.
【００１６】反応する温度が溶媒その他が還流する温度
以下、すなわち、７２℃未満では、同等の収率を得るに
は長時間の反応を必要とし、また１１０℃を超えるとク
ロルシクロヘキサンの脱塩酸によるシクロへキセンの副
生が顕著になるので好ましくない。When the reaction temperature is lower than the reflux temperature of the solvent or the like, that is, less than 72 ° C., it takes a long time to obtain an equivalent yield, and when it exceeds 110 ° C., dechlorination of chlorocyclohexane is required. It is not preferable because the by-product of cyclohexene becomes remarkable.
【００１７】本発明のように、反応系にアルカリ金属水
酸化物を共存させると、加圧下、高温で反応させても、
アルカリ金属水酸化物が共存しない場合に見られるよう
なシクロヘキシルメルカプタン、ジシクロヘキシルトリ
スルフィドの著しい副生が、抑制される。また、反応も
加速されるので品質のよいジシクロヘキシルジスルフィ
ドを短時間に高収率で得ることができる。When an alkali metal hydroxide is allowed to coexist in the reaction system as in the present invention, even if the reaction is carried out at high temperature under pressure,
A significant by-product of cyclohexyl mercaptan and dicyclohexyl trisulfide, which is observed when alkali metal hydroxide does not coexist, is suppressed. In addition, since the reaction is also accelerated, high quality dicyclohexyl disulfide can be obtained in a short time in a high yield.
【００１８】本発明で使用できるアルカリ金属硫化物と
しては、硫化ナトリウム、硫化カリウムなどがあり、特
に安価でかつ工業的に出回っている硫化ナトリウムが好
ましく用いられる。かかる硫化ナトリウムの種類として
は、、無水物、二水塩、９水塩などがあり、特に安価で
かつ水の含有率が比較的少ない二水塩が好ましく用いら
れる。Examples of the alkali metal sulfide usable in the present invention include sodium sulfide and potassium sulfide, and sodium sulfide, which is inexpensive and industrially available, is preferably used. Examples of such sodium sulfide include anhydrides, dihydrates, and 9-hydrates, and dihydrates that are inexpensive and have a relatively low water content are preferably used.
【００１９】アルカリ金属硫化物の使用量は、例えばジ
シクロヘキシルジスルフィドを得るの場合、クロルシク
ロヘキサン１モルに対して約０．５〜約０．８モルの範
囲であり、特にクロルシクロヘキサンと硫化ナトリウム
からのジシクロヘキシルモノスルフィドの効率のよい収
率を考えると、０．６５〜０．７０モルノ範囲で使用す
ることが望ましい。The amount of the alkali metal sulfide used is, for example, in the case of obtaining dicyclohexyl disulfide, in the range of about 0.5 to about 0.8 mol, based on 1 mol of chlorocyclohexane, and particularly from chlorocyclohexane and sodium sulfide. Considering the efficient yield of dicyclohexyl monosulfide, it is desirable to use it in the range of 0.65 to 0.70 mol.
【００２０】また、使用するイオウの量は、クロルシク
ロヘキサン１モルに対して約０．４〜約０．６モルの範
囲であり、特に副生物のシクロヘキシルメルカプタン、
ジシクロヘキシルモノスルフィド、ジシクロヘキシルト
リスルフィドの生成を抑制し、高純度のジシクロヘキシ
ルジスルフィドを得るには、０．４５〜０．５０モルの
範囲で使用することが好ましい。The amount of sulfur used is in the range of about 0.4 to about 0.6 mol per mol of chlorocyclohexane, especially by-product cyclohexyl mercaptan,
In order to suppress the formation of dicyclohexyl monosulfide and dicyclohexyl trisulfide and obtain high-purity dicyclohexyl disulfide, it is preferable to use it in the range of 0.45 to 0.50 mol.
【００２１】以下、実施例を示し本発明を具体的に説明
するが、本発明はこれらに限定されるものではない。Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
【００２２】[0022]
（実施例１）逆流コンデンサ、温度計、滴下ロート、攪
拌機を備えた５００ｍｌ容の四つ口フラスコにメタノー
ル６５．６ｇ（２．１モル）、硫化ナトリウム１０７．
０ｇ（６０％含量として０．８２モル）、硫黄１９．０
ｇ（０．５９モル）、４８％水酸化ナトリウム水溶液２
０．０ｇ（０．２４モル）を仕込み、加熱して、液温６
０〜６５℃を保持しながら３０分間撹拌した。次いで、
この液が還流するまで加熱し、純度９７．５％のクロル
シクロヘキサン１５０．０ｇ（１．２３モル）を滴下ロ
ートから少量ずつ添加した。添加終了後、還流状態を維
持しながら、１５時間反応を続けた。液温を５０℃以下
にした後、析出する塩化ナトリウムを小型遠心分離機を
用いて濾過し、その濾液を分液ロートに移し、分相する
未反応の多硫化ナトリウムを含む水、メタノール層を分
離して油層１３９．０ｇを得た。この油層をガスクロマ
トグラフで分析すると、ジシクロヘキシルジスルフィド
の含有率７６．２％でクロルシクロヘキサンからの収率
は７５％であった。 （実施例２）４８％水酸化ナトリウム水溶液の仕込量を
４２．０ｇ（０．５０モル）とした以外は実施例１と同
様の操作を行って、油層１３２．５ｇを得た。この油層
をガスクロマトグラフで分析するとジシクロヘキシルジ
スルフィドの含有率は８５．０％で、クロルシクロヘキ
サンからの収率は８０％であった。 （実施例３）４８％水酸化ナトリウム水溶液の仕込量を
６３．０ｇ（０．７６モル）とした以外は実施例１〜２
と同様の操作を行って、油層１３３．０ｇを得た。この
油層をガスクロマトグラフで分析するとジシクロヘキシ
ルジスルフィドの含有率は８４．８％でクロルシクロヘ
キサンからの収率は８０％であった。 （実施例４）４８％水酸化ナトリウム水溶液の代わり
に、８５％水酸化カリウム水溶液の仕込量を３２．９ｇ
（０．５０モル）とした以外は、実施例１〜３と同様の
操作を行なって、油層１３１．９ｇを得た。この油層を
ガスクロマトグラフで分析するとジシクロヘキシルジス
ルフィドの含有率は８３．５％で、クロルシクロヘキサ
ンからの収率は７８％であった。 （実施例５）メタノールの仕込量を４６．３ｇ（１．４
５モル）とした以外は実施例２と同様の操作を行って、
油層１４３．７ｇを得た。この油層をガスクロマトグラ
フで分析するとジシクロヘキシルジスルフィドの含有率
は７４．８％でクロルシクロヘキサンからの収率は７６
％であった。 （実施例６）温度計、攪拌機を備えた５００ｍｌ容の加
圧容器を用いる以外は実施例４と同様の仕込みを行い、
締切り、撹拌下、加熱して液温を６０〜６５℃に維持し
ながら３０分間反応した。次いで、加圧ポンプを用いて
純度９７．５％のクロルシクロへキサンを実施例５と同
一量添加した。さらに、加熱を続け、液温が１００℃に
到達したら同温度を維持しながら５時間反応を続けた。
この間の圧力は最大１．８ｋｇ／ｃｍ2 Ｇであった。以
後、実施例４と同様の操作を行って油層１３５．１ｇを
得た。この油層をガスクロマトグラフで分析するとジシ
クロヘキシルジスルフィドの含有率は８２．７％でクロ
ルシクロヘキサンからの収率は７９％であった。 （比較例１）４８％水酸化ナトリウムの仕込みをやめた
以外は実施例１〜３と同様の操作を行って油層１３８．
７ｇを得た。この油層をガスクロマトグラフで分析する
とジシクロヘキシルジスルフィドの含有率は７３．２％
でクロルシクロヘキサンからの収率は７２％であった。 （比較例２）４８％水酸化ナトリウムの仕込みをやめた
以外は実施例４と同様の操作を行って油層１４１．２ｇ
を得た。この油層をガスクロマトグラフで分析するとジ
シクロヘキシルジスルフィドの含有率は６７．２％でク
ロルシクロへキサンからの収率は６７％であった。 （比較例３）メタノールの使用量を１９３ｇ（６．０モ
ル）とした以外は実施例２と同様の操作を行って油層１
３４．０ｇを得た。この油層をガスクロマトグラフで分
析するとジシクロヘキシルジスルフィドの含有率は８
５．５％でクロルシクロヘキサンからの収率は８１％で
あった。 （比較例４）４８％水酸化ナトリウムの仕込みをやめた
以外は実施例５と同様の操作を行って油層１４７．１ｇ
を得た。この油層をガスクロマトグラフで分析するとジ
シクロヘキシルジスルフィドの含有率は５２．９％でク
ロルシクロヘキサンからの収率は５５％であった。(Example 1) 65.6 g (2.1 mol) of methanol and 107. sodium sulfide were placed in a 500 ml four-necked flask equipped with a back-flow condenser, a thermometer, a dropping funnel, and a stirrer.
0 g (0.82 mol as 60% content), sulfur 19.0
g (0.59 mol), 48% sodium hydroxide aqueous solution 2
Charge 0.0 g (0.24 mol) and heat to a liquid temperature of 6
The mixture was stirred for 30 minutes while maintaining 0 to 65 ° C. Then
The solution was heated to reflux, and 150.0 g (1.23 mol) of chlorocyclohexane having a purity of 97.5% was added little by little from a dropping funnel. After the addition was completed, the reaction was continued for 15 hours while maintaining the reflux state. After the liquid temperature was set to 50 ° C. or lower, the precipitated sodium chloride was filtered using a small centrifuge, the filtrate was transferred to a separating funnel, and the water containing the unreacted sodium polysulfide and the methanol layer were separated. Separation gave 139.0 g of an oil layer. When this oil layer was analyzed by gas chromatography, the dicyclohexyldisulfide content was 76.2% and the yield from chlorocyclohexane was 75%. (Example 2) The same operation as in Example 1 was carried out except that the amount of the 48% aqueous sodium hydroxide solution charged was 42.0 g (0.50 mol) to obtain 132.5 g of an oil layer. When this oil layer was analyzed by gas chromatography, the dicyclohexyl disulfide content was 85.0%, and the yield from chlorocyclohexane was 80%. (Example 3) Examples 1 and 2 except that the amount of 48% sodium hydroxide aqueous solution charged was 63.0 g (0.76 mol).
The same operation as above was performed to obtain 133.0 g of an oil layer. When this oil layer was analyzed by gas chromatography, the content of dicyclohexyl disulfide was 84.8% and the yield from chlorocyclohexane was 80%. (Example 4) Instead of the 48% sodium hydroxide aqueous solution, an amount of the 85% potassium hydroxide aqueous solution charged was 32.9 g.
The same operation as in Examples 1 to 3 was carried out except that (0.50 mol) was obtained to obtain 131.9 g of an oil layer. When this oil layer was analyzed by gas chromatography, the dicyclohexyl disulfide content was 83.5%, and the yield from chlorocyclohexane was 78%. (Example 5) The charged amount of methanol was 46.3 g (1.4
(5 mol), except that the same operation as in Example 2 was performed,
143.7 g of an oil layer was obtained. When this oil layer was analyzed by gas chromatography, the dicyclohexyl disulfide content was 74.8% and the yield from chlorocyclohexane was 76.
%Met. (Example 6) The same preparation as in Example 4 was carried out except that a 500 ml pressure vessel equipped with a thermometer and a stirrer was used.
The reaction was carried out for 30 minutes while maintaining the liquid temperature at 60 to 65 ° C by heating under a deadline and stirring. Then, using a pressure pump, 97.5% pure chlorocyclohexane was added in the same amount as in Example 5. Further, heating was continued, and when the liquid temperature reached 100 ° C., the reaction was continued for 5 hours while maintaining the same temperature.
The maximum pressure during this period was 1.8 kg / cm 2 G. Thereafter, the same operation as in Example 4 was carried out to obtain 135.1 g of an oil layer. When this oil layer was analyzed by gas chromatography, the dicyclohexyl disulfide content was 82.7%, and the yield from chlorocyclohexane was 79%. (Comparative Example 1) The same procedure as in Examples 1 to 3 was carried out except that the charging of 48% sodium hydroxide was stopped.
7 g were obtained. When this oil layer is analyzed by gas chromatography, the content of dicyclohexyl disulfide is 73.2%.
The yield from chlorocyclohexane was 72%. (Comparative Example 2) An oil layer of 141.2 g was prepared in the same manner as in Example 4 except that the addition of 48% sodium hydroxide was stopped.
I got When this oil layer was analyzed by gas chromatography, the content of dicyclohexyldisulfide was 67.2%, and the yield from chlorocyclohexane was 67%. (Comparative Example 3) Oil layer 1 was prepared in the same manner as in Example 2 except that the amount of methanol used was 193 g (6.0 mol).
34.0 g was obtained. When this oil layer is analyzed by gas chromatography, the content of dicyclohexyl disulfide is 8
At 5.5%, the yield from chlorocyclohexane was 81%. (Comparative Example 4) An oil layer of 147.1 g was prepared in the same manner as in Example 5, except that the addition of 48% sodium hydroxide was stopped.
I got When this oil layer was analyzed by gas chromatography, the dicyclohexyl disulfide content was 52.9% and the yield from chlorocyclohexane was 55%.
【００２３】実施例１〜６の結果、および比較例１〜４
の結果を、それぞれ第１表および第２表にまとめて示
す。Results of Examples 1 to 6 and Comparative Examples 1 to 4
The results are shown in Tables 1 and 2 respectively.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【表２】 [Table 2]
【００２６】[0026]
【発明の効果】本発明の製造方法は、安価でかつ汎用的
である薬品を共存下反応させることにより、大幅な溶媒
使用量の低減や製造する時間の短縮を可能とするもので
あり、本発明により、品質、収率に支障をきたすことな
く工業的規模でジシクロヘキシルジスルフィドを効率
的、経済的に製造することが可能となった。EFFECT OF THE INVENTION The production method of the present invention makes it possible to significantly reduce the amount of solvent used and the production time by reacting inexpensive and general-purpose chemicals in the coexistence. The invention makes it possible to efficiently and economically produce dicyclohexyldisulfide on an industrial scale without affecting the quality and yield.
Claims (9)
アルカリ金属硫化物またはそれを含む混合物と反応させ
るに際し、アルカリ金属水酸化物を共存させ反応せしめ
ることを特徴とするジスルフィド類の製造方法。1. A monochloro-substituted compound in the presence of a solvent,
A process for producing disulfides, which comprises reacting with an alkali metal hydroxide in the reaction with an alkali metal sulfide or a mixture containing the same.
チウム、水酸化ナトリウムおよび水酸化カリウムから選
ばれたひとつであることを特徴とする請求項１記載のジ
スルフィド類の製造方法。2. The method for producing disulfides according to claim 1, wherein the alkali metal hydroxide is one selected from lithium hydroxide, sodium hydroxide and potassium hydroxide.
トリウムであることを特徴とする請求項１記載のジスル
フィド類の製造方法。3. The method for producing disulfides according to claim 1, wherein the alkali metal hydroxide is sodium hydroxide.
リ金属水酸化物を含む水溶液であることを特徴とする請
求項１、２または３記載のジスルフィド類の製造方法。4. The method for producing disulfides according to claim 1, 2 or 3, wherein the alkali metal hydroxide is an aqueous solution containing the alkali metal hydroxide.
ル置換化合物１モルに対して０．１〜０．６モルの範囲
で共存させることを特徴とする請求項１、２、３または
４記載のジスルフィド類の製造方法。5. The method according to claim 1, wherein the alkali metal hydroxide is allowed to coexist in the range of 0.1 to 0.6 mol per mol of the monochloro-substituted compound. Method for producing disulfides.
力を常圧〜１．９ｋｇ／ｃｍ2 Ｇの範囲として反応せし
めることを特徴とする請求項１記載のジスルフィド類の
製造方法。6. The process for producing disulfides according to claim 1, wherein the reaction is carried out at a temperature of the internal liquid of 72 to 110 ° C. and a pressure of atmospheric pressure to 1.9 kg / cm 2 G.
ルコールであることを特徴とする請求項１記載のジスル
フィド類の製造方法。7. The method for producing disulfides according to claim 1, wherein the solvent used is an aliphatic alcohol having 1 to 3 carbon atoms.
ルに対して０．８〜３．０モルの範囲で用いる請求項７
記載のジスルフィド類の製造方法。8. The solvent is used in the range of 0.8 to 3.0 mol per mol of the monochloro-substituted compound.
A method for producing the disulfides described.
ロヘキサンであることを特徴とする請求項１〜８記載の
ジスルフィド類の製造方法。9. The method for producing disulfides according to claim 1, wherein the monochloro-substituted compound is chlorocyclohexane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19617295A JP3787791B2 (en) | 1995-07-07 | 1995-07-07 | A method for producing dicyclohexyl disulfide. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19617295A JP3787791B2 (en) | 1995-07-07 | 1995-07-07 | A method for producing dicyclohexyl disulfide. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0920751A true JPH0920751A (en) | 1997-01-21 |
| JP3787791B2 JP3787791B2 (en) | 2006-06-21 |
Family
ID=16353404
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19617295A Expired - Lifetime JP3787791B2 (en) | 1995-07-07 | 1995-07-07 | A method for producing dicyclohexyl disulfide. |
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| Country | Link |
|---|---|
| JP (1) | JP3787791B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007326786A (en) * | 2006-06-06 | 2007-12-20 | Nippon Soda Co Ltd | Method for producing disulfide compound |
| JP2007326850A (en) * | 2006-05-09 | 2007-12-20 | Toray Fine Chemicals Co Ltd | Method for producing dicyclohexyl disulfide |
| CN102993069A (en) * | 2011-09-19 | 2013-03-27 | 河南省汤阴县永新助剂厂 | Automatic salt separation technique and device in dicyclohexyl disulfide reaction |
| CN115417798A (en) * | 2022-08-15 | 2022-12-02 | 山东戴瑞克新材料有限公司 | Continuous liquid separation process for dicyclohexyl disulfide |
-
1995
- 1995-07-07 JP JP19617295A patent/JP3787791B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007326850A (en) * | 2006-05-09 | 2007-12-20 | Toray Fine Chemicals Co Ltd | Method for producing dicyclohexyl disulfide |
| JP2007326786A (en) * | 2006-06-06 | 2007-12-20 | Nippon Soda Co Ltd | Method for producing disulfide compound |
| CN102993069A (en) * | 2011-09-19 | 2013-03-27 | 河南省汤阴县永新助剂厂 | Automatic salt separation technique and device in dicyclohexyl disulfide reaction |
| CN115417798A (en) * | 2022-08-15 | 2022-12-02 | 山东戴瑞克新材料有限公司 | Continuous liquid separation process for dicyclohexyl disulfide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3787791B2 (en) | 2006-06-21 |
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