JPS6072858A - Production of methylene dithiocyanate - Google Patents
Production of methylene dithiocyanateInfo
- Publication number
- JPS6072858A JPS6072858A JP17938083A JP17938083A JPS6072858A JP S6072858 A JPS6072858 A JP S6072858A JP 17938083 A JP17938083 A JP 17938083A JP 17938083 A JP17938083 A JP 17938083A JP S6072858 A JPS6072858 A JP S6072858A
- Authority
- JP
- Japan
- Prior art keywords
- methylene
- reaction
- solvent
- alkali metal
- iodide
- 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
- JWZXKXIUSSIAMR-UHFFFAOYSA-N methylene bis(thiocyanate) Chemical compound N#CSCSC#N JWZXKXIUSSIAMR-UHFFFAOYSA-N 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000002904 solvent Substances 0.000 claims abstract description 20
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 8
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 6
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 2
- VNEBWJSWMVTSHK-UHFFFAOYSA-L disodium;3-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=CC2=C1 VNEBWJSWMVTSHK-UHFFFAOYSA-L 0.000 claims 1
- PDMYFWLNGXIKEP-UHFFFAOYSA-K gold(3+);trithiocyanate Chemical compound [Au+3].[S-]C#N.[S-]C#N.[S-]C#N PDMYFWLNGXIKEP-UHFFFAOYSA-K 0.000 claims 1
- -1 alkali metal thiocyanate Chemical class 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 13
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002244 precipitate Substances 0.000 abstract description 6
- 238000009835 boiling Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 abstract 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 abstract 2
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 150000003863 ammonium salts Chemical class 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 abstract 1
- 238000011010 flushing procedure Methods 0.000 abstract 1
- 235000019256 formaldehyde Nutrition 0.000 abstract 1
- 230000000855 fungicidal effect Effects 0.000 abstract 1
- 239000000417 fungicide Substances 0.000 abstract 1
- 238000009434 installation Methods 0.000 abstract 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- 230000008018 melting Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 3
- 229940116357 potassium thiocyanate Drugs 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 description 2
- 150000008045 alkali metal halides Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 238000004040 coloring Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はメチレンジチオシアナートの製造方法に関する
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing methylene dithiocyanate.
メチレンジチオシアナートは殺菌剤、スライム防除剤な
どとして有用であシ、製紙工業、あるいは工業用水の管
理などに使用されている。Methylene dithiocyanate is useful as a disinfectant, slime control agent, etc., and is used in the paper industry and industrial water management.
従来、メチレンジチオシアナートの製造方法としては多
くの方法が知られている。例えば１）、ジメチルスルホ
キシド、またはジメチルホルムアミドの極性溶媒中で、
沃化カリあるいは臭化カリの存在下で塩化メチレンとチ
オシアン酸アルカリ金属塩とを反応させる方法（特公昭
４２−４２４９号公報、特公昭４２−４４５２号公報参
照）。Conventionally, many methods are known for producing methylene dithiocyanate. For example 1), in a polar solvent of dimethyl sulfoxide or dimethyl formamide,
A method in which methylene chloride and an alkali metal thiocyanate are reacted in the presence of potassium iodide or potassium bromide (see Japanese Patent Publication No. 42-4249 and Japanese Patent Publication No. 42-4452).
２）、メタノール、エタノール、アセトンの極性有機溶
媒中で、臭化メチレンとチオシアン酸アルカリ金属塩と
を反応温度７５〜１１０℃で加圧下に反応させる方法（
特公昭４５−１９８８７号公報参照）。2) A method in which methylene bromide and an alkali metal thiocyanate are reacted under pressure at a reaction temperature of 75 to 110°C in a polar organic solvent such as methanol, ethanol, or acetone (
(See Japanese Patent Publication No. 45-19887).
３）、水溶媒中で、臭化メチレンとチオシアン酸アルカ
リ金属塩またはチオシアン酸アンモニウム塩とを、９５
〜１３０℃で加圧下に反応させる方法（特開昭５１−１
９７２５号公報参照）、などが知られている。3) In an aqueous solvent, methylene bromide and an alkali metal thiocyanate salt or an ammonium thiocyanate salt were combined at 95%
A method of reacting under pressure at ~130°C (Unexamined Japanese Patent Publication No. 51-1
9725), etc. are known.
しかし、これらの方法はいずれも高品質で、しかも好収
率でメチレンジチオシアナートを得ることはできない。However, none of these methods makes it possible to obtain methylene dithiocyanate with high quality and good yield.
例えば白色針状結晶で融点１０２〜１０３℃のものを得
る場合は、その収率は最高６７％であり、また、収率が
９５％の場合は、その品質が悪くなる等の欠点がある。For example, when obtaining white needle-like crystals with a melting point of 102 to 103°C, the yield is at most 67%, and when the yield is 95%, there are drawbacks such as poor quality.
更に前記欠点のほか前記１）の方法では、ジメチルスル
ホキシド、ジメチルホルムアミドの溶剤は高価であるば
かシでなく、沃化力ＩＪ ｔたは臭化カリの存在下で反
応させる必要があり、原価が高くなる等の欠点がある。Furthermore, in addition to the above drawbacks, in the method 1), the solvents dimethyl sulfoxide and dimethyl formamide are expensive, and the reaction must be carried out in the presence of iodizing power or potassium bromide, resulting in low cost. There are disadvantages such as being expensive.
前記２）の方法では、メタノール、アセトンの低沸点の
溶媒を使用するため、加圧下で反応させることを要し、
設備費も高くなると共に操業も面倒となるばかりでなく
、溶剤の蒸発等の公害を起こす原因となる等の欠点を有
する。In method 2), since low boiling point solvents such as methanol and acetone are used, the reaction must be carried out under pressure.
This method not only increases equipment costs and is troublesome to operate, but also has drawbacks such as causing pollution such as evaporation of the solvent.
前記５）の方法も加圧下で反応を行うことが必要で設備
費も高く、操業も面倒である等の欠点を有する。The method 5) also has drawbacks such as requiring the reaction to be carried out under pressure, requiring high equipment costs, and being troublesome to operate.
本発明は従来の方法における欠点を解消すべくなされた
もので、その第１の目的は高品位のメチレンジチオシア
ナートを高収率で得る方法を提供するにある。また他の
目的は高圧釜を必要とせず、操業も容易で、公害を起す
原因もなく安価にメチレンジチオシアナートを製造する
方法を提供するにある。The present invention was made to overcome the drawbacks of conventional methods, and its first objective is to provide a method for obtaining high-grade methylene dithiocyanate in high yield. Another object of the present invention is to provide a method for producing methylene dithiocyanate at low cost, which does not require a high-pressure cooker, is easy to operate, and causes no pollution.
本発明者らは、前記目的を達成すべく鋭意研究の結果、
臭化メチレンまたは沃化メチレンとチオシアン酸アルカ
リ金属塩またはチオシアン酸アンモニウム塩とを反応さ
せるに際し、一般式ｌ０−（ＣＨ２０Ｈ２０）ｎ−Ｈ（
ただし、ｎは１〜３を表わす）で示される多価アルコー
ルを溶媒として使用すると、融点１０３℃以上の白色ま
だは僅かに黄味を帯びたメチレンジチオシアナートを収
率９５％以上で得られることを究明し得た。この知見に
基いて本発明を完成した。As a result of intensive research to achieve the above object, the present inventors have found that
When reacting methylene bromide or methylene iodide with an alkali metal thiocyanate or ammonium thiocyanate, the general formula 10-(CH20H20)n-H(
However, when a polyhydric alcohol represented by (n represents 1 to 3) is used as a solvent, white, yet slightly yellowish methylene dithiocyanate with a melting point of 103°C or higher can be obtained in a yield of 95% or higher. I was able to find out. The present invention was completed based on this knowledge.
本発明の要旨は一般式ＨＯ−（ＯＨ２０Ｈ２０）ｒｌ−
Ｈ（ただし、ｎは１〜３を表わす）で示される多価アル
コールの溶媒中で、臭化メチレンまたは沃化メチレンと
チオシアン酸アルカリ金属塩またはチオシアン酸アンモ
ニウム塩とを反応させることを特徴とするメチレンジチ
オシアナートの製造方法にある。The gist of the present invention is the general formula HO-(OH20H20)rl-
It is characterized by reacting methylene bromide or methylene iodide with an alkali metal thiocyanate or an ammonium thiocyanate in a polyhydric alcohol solvent represented by H (where n represents 1 to 3). In the method for producing methylene dithiocyanate.
本発明で溶媒として使用する前記一般式で示さレル多価
アルコールハ、エチレングリコール、ジｘ−ｆ−レンク
リコールマタ［）リエチレングリコールである。これら
の多価アルコールはいずれも沸点、引火点は高く、無臭
で安価であシ、しかも取扱いも安全で公害を起すことが
ない。まだ、沸点も高いので圧力釜からなる反応容器を
必要とせず設備費も安くてすむこと、更にまた、これら
の溶媒は、メチレンジチオシアナート、及び副生物のハ
ロゲン化アルカリ金属塩またはハロゲン化アンモニウム
塩には貧溶媒であるため、溶媒中で析出し易く、目的物
の精製も容易である等の優れた作用効果を奏し得られる
。The polyhydric alcohol represented by the above general formula used as a solvent in the present invention is ethylene glycol, dixf-lene glycol, or diethylene glycol. All of these polyhydric alcohols have high boiling points and flash points, are odorless, inexpensive, safe to handle, and do not cause pollution. Furthermore, since these solvents have a high boiling point, there is no need for a reaction vessel consisting of a pressure cooker, and the equipment cost is low.Furthermore, these solvents can be used in combination with methylene dithiocyanate and the by-product alkali metal halide or ammonium halide. Since the salt is a poor solvent, it is easy to precipitate in the solvent, and it can provide excellent effects such as easy purification of the target product.
多価アルコールの溶媒の使用量は、チオシアン酸アルカ
リ金属塩まだはチオシアン酸アンモニウム塩に対し、０
．５〜３倍であるととが好ましい。The amount of polyhydric alcohol solvent used is 0 for alkali metal thiocyanate and ammonium thiocyanate.
．． It is preferably 5 to 3 times.
これより少ないと反応生成物の取出しが困１１になり、
これより多いとメチレンジチオシアナートの溶存量が増
して収率が低で、する。If the amount is less than this, it will be difficult to remove the reaction product,
If the amount is more than this, the dissolved amount of methylene dithiocyanate will increase and the yield will be low.
原料臭化メチレンまたは沃化メチレンと２倍モルのチオ
シアン酸アルカリ金属塩またはチオシアン酸アンモニウ
ム塩とを使用し、反応温度は５０〜１００℃、好ましく
は６０〜８０℃である。これより低い温度では反応の進
行がおそく、これより（５）
高い温度では得られるメチレンジチオシアナートの着色
やチオシアンの生成が起る。反応時間は反応温度にもよ
るが、約６時間でよい。The raw materials methylene bromide or methylene iodide and twice the molar amount of alkali metal thiocyanate or ammonium thiocyanate are used, and the reaction temperature is 50 to 100°C, preferably 60 to 80°C. At a temperature lower than this, the reaction progresses slowly, and at a temperature higher than this (5), coloring of the resulting methylene dithiocyanate and formation of thiocyanate occur. The reaction time may be about 6 hours, although it depends on the reaction temperature.
この反応は常圧下でよい。しかし加圧下に反応させても
差支えない。This reaction may be carried out under normal pressure. However, the reaction may be carried out under pressure.
反応によってメチレンジチオシアナートとハロゲン化ア
ルカリ金属塩またはハロゲン化アンモニウム塩の混合物
が得られる。反応終了後、この反応混合物を冷却ｒ過し
て沈殿物をとり、これを水洗してハロゲン化塩を除き、
メチレンジチオシアナートを得る。The reaction yields a mixture of methylene dithiocyanate and an alkali metal halide or ammonium halide salt. After the reaction is completed, the reaction mixture is cooled and filtered to remove the precipitate, which is washed with water to remove the halide salt.
Methylene dithiocyanate is obtained.
このようにして、融点１０４℃以上の白色または僅かに
黄味を帯び九メチレンジチオシアナートが得られる。In this way, a white or slightly yellowish 9-methylene dithiocyanate having a melting point of 104° C. or higher is obtained.
水溶液中にはハロゲン化アルカリ塩またはハロゲン化ア
ンモニウム塩が溶解しているので、常法により臭素また
は沃素を回収することができる。Since the alkali halide salt or ammonium halide salt is dissolved in the aqueous solution, bromine or iodine can be recovered by a conventional method.
また反応後、沢過された溶媒は、これに新しい溶媒を補
給して、次回の反応の溶媒として繰返して使用すること
ができる。Further, after the reaction, the filtered solvent can be replenished with new solvent and used repeatedly as a solvent for the next reaction.
（６）
実施例１゜
エチレングリコール１６０ｖにチオシアン酸ナトリウム
８１４（１モル）を溶解し、攪拌下で６５℃に保ち、こ
れに沃化メチレン１３４ ｆ （０，５モル）を３０分
間かかつて滴下した。このままの状態で５〜６時間攪拌
を続けた後室温まで冷却した。濾過して反応混合物を分
離し、該反応混合物に水１ノを入れ、沈殿物を濾過した
。更に沃化ナトリウムを除くため、十分水洗して乾燥し
てメチレンジチオシアナート６４１を得た。その収率は
９８．５％であった。(6) Example 1 Sodium thiocyanate 814 (1 mol) was dissolved in 160 v of ethylene glycol, kept at 65°C under stirring, and methylene iodide 134 f (0.5 mol) was added dropwise for 30 minutes or once. did. Stirring was continued for 5 to 6 hours in this state and then cooled to room temperature. The reaction mixture was separated by filtration, one portion of water was added to the reaction mixture, and the precipitate was filtered. Furthermore, in order to remove sodium iodide, the mixture was thoroughly washed with water and dried to obtain methylene dithiocyanate 641. The yield was 98.5%.
得られ九メチレンジチオシアナートは白色の融点１０５
〜１０６℃のものであった。The resulting nine methylene dithiocyanate is white with a melting point of 105
The temperature was ~106°C.
実施例２〜４゜
チオシアン酸カリウム９７ｔ（１モル）を次表に示す溶
媒９７ｆに溶解し、攪拌下に６５〜７５℃に保ち、臭化
メチレン８７ ｆ （０，５モル）を３０分間かかつて
滴下した。滴下終了後５時間半攪拌を続けた後、室温ま
で冷却し、濾過して沈殿物を得た。沈殿物に水５００
ｆｔ／を加え、沈殿物をｒ過分離し、十分水洗乾燥した
。得られたメチレンジチオシアナートの性状と収率は次
の表に示すものであった。Examples 2 to 4 97t (1 mol) of potassium thiocyanate was dissolved in 97f of the solvent shown in the following table, kept at 65-75°C with stirring, and 87f (0.5 mol) of methylene bromide was added for 30 minutes. Once dripped. After the dropwise addition was completed, stirring was continued for 5.5 hours, then cooled to room temperature and filtered to obtain a precipitate. 500ml water for sediment
ft/ was added, and the precipitate was separated by filtration, thoroughly washed with water and dried. The properties and yield of the obtained methylene dithiocyanate are shown in the following table.
実施例５゜
チオシアン酸カリウム１４５．５１ （１，５モル）を
エチレングリコール２６〇−中に溶解し、攪拌下に６５
〜７５℃に保ち臭化メｆ しｙ １３０．５ ｆ （０
，７５モル）を、３０分間かけて滴下した。滴下終了後
５時間半攪拌を続けた後、室温まで冷却し濾過した。得
られた沈殿物を水中に投じ臭化カリウムを溶解した後濾
過乾燥した。白色結晶、融点１０５〜１０６℃のメチレ
ンジチオシアナートを収率９８％で得られた。Example 5 145.51 (1.5 mol) of potassium thiocyanate were dissolved in 260 - of ethylene glycol and 65.51 (1.5 mol) of potassium thiocyanate was dissolved under stirring.
Keep bromide at ~75°C 130.5 f (0
, 75 mol) was added dropwise over 30 minutes. After the dropwise addition was completed, stirring was continued for 5 and a half hours, and then the mixture was cooled to room temperature and filtered. The obtained precipitate was poured into water to dissolve potassium bromide, and then filtered and dried. White crystals of methylene dithiocyanate having a melting point of 105-106°C were obtained in a yield of 98%.
反応後、ｆ液として回収した溶媒に新しいエチレングリ
コールを補給して２６０−とじ、これを同様な方法で２
〜６回繰返し使用したが、いずれも前記と同様な結果が
得られた。臭化カリ水溶液からの臭素回収率は９５％以
上であった。After the reaction, fresh ethylene glycol was added to the solvent recovered as f-liquid, and 260-mm was added.
It was used repeatedly ~6 times, and the same results as above were obtained in each case. The bromine recovery rate from the potassium bromide aqueous solution was 95% or more.
以上のように、本発明の方法によると、反応溶媒として
多価アルコールを使用することにより、融点１０４〜１
０６℃の白色のメチレンジチオシアナートを９５〜９９
％の好収率で得られ、しかも沸点も高いため従来法にお
けるような圧力下で反応させることを必要としないため
設備も簡単で操業も容易であり、また公害を起すことな
く、生成物の分離も極めて容易である等の優れた作用効
果を奏し得られる。As described above, according to the method of the present invention, by using a polyhydric alcohol as a reaction solvent, the melting point is 104 to 1.
06℃ white methylene dithiocyanate 95-99
%, and the boiling point is high, so there is no need to react under pressure as in conventional methods, so the equipment is simple and operation is easy, and the product can be easily processed without causing pollution. Excellent effects such as extremely easy separation can be achieved.
（９）(9)
Claims (1)
ｎは１〜３を表わす）で示される多価アルコールの溶媒
中で、臭化メチレンまたは沃化メチレンとチオシアン酸
アルカリ金Ｒ塩またはチオシアン酸アンモニウム塩とを
反応させることを特徴とするメチレンジチオシアナート
の製造方法。t General formula HO-(OH20H20), 7H (however,
methylene dithiocyanate, characterized in that methylene bromide or methylene iodide is reacted with an alkali gold thiocyanate R salt or an ammonium thiocyanate salt in a polyhydric alcohol solvent represented by n represents 1 to 3. Method of manufacturing nato.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17938083A JPS6072858A (en) | 1983-09-29 | 1983-09-29 | Production of methylene dithiocyanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17938083A JPS6072858A (en) | 1983-09-29 | 1983-09-29 | Production of methylene dithiocyanate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6072858A true JPS6072858A (en) | 1985-04-24 |
Family
ID=16064841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17938083A Pending JPS6072858A (en) | 1983-09-29 | 1983-09-29 | Production of methylene dithiocyanate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6072858A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4993320A (en) * | 1973-01-12 | 1974-09-05 |
-
1983
- 1983-09-29 JP JP17938083A patent/JPS6072858A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4993320A (en) * | 1973-01-12 | 1974-09-05 |
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