JPS6333358A - Production of dithiocarbamate - Google Patents
Production of dithiocarbamateInfo
- Publication number
- JPS6333358A JPS6333358A JP61176675A JP17667586A JPS6333358A JP S6333358 A JPS6333358 A JP S6333358A JP 61176675 A JP61176675 A JP 61176675A JP 17667586 A JP17667586 A JP 17667586A JP S6333358 A JPS6333358 A JP S6333358A
- Authority
- JP
- Japan
- Prior art keywords
- amine
- reaction
- solvent
- dbu
- carbon disulfide
- 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
- 239000012990 dithiocarbamate Substances 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 title claims description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- 150000001350 alkyl halides Chemical class 0.000 claims abstract description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 21
- 239000002904 solvent Substances 0.000 abstract description 18
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 4
- 150000001348 alkyl chlorides Chemical class 0.000 abstract description 3
- 150000002894 organic compounds Chemical class 0.000 abstract description 3
- 150000003335 secondary amines Chemical class 0.000 abstract description 3
- SCZNXLWKYFICFV-UHFFFAOYSA-N 1,2,3,4,5,7,8,9-octahydropyrido[1,2-b]diazepine Chemical compound C1CCCNN2CCCC=C21 SCZNXLWKYFICFV-UHFFFAOYSA-N 0.000 abstract 3
- 150000004659 dithiocarbamates Chemical class 0.000 description 11
- -1 aliphatic amines Chemical class 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001347 alkyl bromides Chemical class 0.000 description 2
- 150000001351 alkyl iodides Chemical class 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 1
- WLVCBAMXYMWGLJ-UHFFFAOYSA-N 3-(chloromethyl)heptane Chemical compound CCCCC(CC)CCl WLVCBAMXYMWGLJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 description 1
- PAMIQIKDUOTOBW-UHFFFAOYSA-N N-methylcyclohexylamine Natural products CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- AGVKXDPPPSLISR-UHFFFAOYSA-N n-ethylcyclohexanamine Chemical compound CCNC1CCCCC1 AGVKXDPPPSLISR-UHFFFAOYSA-N 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 239000008096 xylene Substances 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〕
本発明はジチオカルバメートの新規な製造方法に関する
ものである。さらに詳しくいえば、本発明は、農薬、医
薬品、その他化成品の原料などとして有用なジチオカル
バメートを、アミン、二硫化炭素およびハロゲン化アル
キルを原料に用いて工業的に有利に製造する方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel method for producing dithiocarbamates. More specifically, the present invention relates to an industrially advantageous method for producing dithiocarbamates, which are useful as raw materials for agricultural chemicals, pharmaceuticals, and other chemical products, using amines, carbon disulfide, and alkyl halides as raw materials. It is.
従来、ジチオカルバメートは農薬、医薬品、その他化成
品の原料などとして重要な化合物であることが知られて
いる。It has been known that dithiocarbamates are important compounds as raw materials for agricultural chemicals, pharmaceuticals, and other chemical products.
このジチオカルバメートは、通常水酸化ナトリウム、水
酸化カリウム、炭酸ナトリウム、炭酸カリウムなどのア
ルカリの存在下、第一級アミンまたは第二級アミンに二
硫化炭素を反応させ、次いでこれにを機ハロゲン化物を
加えて反応させることにより製造されている。しかしな
がら、この方法においては、ジチオカルバメートの収率
は比較的高いものの、前記のアルカリを溶解させて反応
を行う必要があるため、反応溶媒としてメタノールやエ
タノールなどのアルコールを多量に使用しなければなら
ず、その結果製造装置が大規模となり、また、溶剤回収
などの付帯設備を多数必要とするなど、設備費が高（つ
（のを免れない上に、エネルギーコストも高（つき、工
業的には必ずしも有利な方法とはいえない。This dithiocarbamate is produced by reacting a primary or secondary amine with carbon disulfide, usually in the presence of an alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, or potassium carbonate, and then reacting this with a halide. It is produced by adding and reacting. However, in this method, although the yield of dithiocarbamate is relatively high, it is necessary to dissolve the alkali mentioned above to carry out the reaction, so a large amount of alcohol such as methanol or ethanol must be used as a reaction solvent. As a result, the manufacturing equipment becomes large-scale, and a large number of ancillary equipment such as solvent recovery are required, resulting in high equipment costs and high energy costs. is not necessarily an advantageous method.
本発明は、このような従来のジチオカルバメートの製造
方法における欠点を改良し、溶媒の不在下もしくは少量
の溶媒の存在下、温和な条件で反応がスムースに進行し
て収率よくジチオカルバメートが得られるような工業的
に有利なジチオカルバメートの製造方法の提供を目的と
するものである。The present invention improves the drawbacks of the conventional method for producing dithiocarbamates, and enables the reaction to proceed smoothly under mild conditions in the absence of a solvent or in the presence of a small amount of solvent, resulting in a high yield of dithiocarbamates. The purpose of the present invention is to provide an industrially advantageous method for producing dithiocarbamates.
本発明者らは前記目的を達成するために鋭意研究を重ね
た結果、超塩基性有機化合物である１゜８−ジアザビシ
クロ（５，４，０〕ウンデ−７−センを用い、アミンに
二硫化炭素およびハロゲン化アルキルを反応させること
により、その目的を達成しうろことを見い出し、この知
見に基づいて本発明を完成するに至った。As a result of extensive research to achieve the above object, the present inventors used 1°8-diazabicyclo(5,4,0]unde-7-cene, an ultrabasic organic compound, to add disulfide to amines. The inventors discovered that the object could be achieved by reacting carbon and alkyl halide, and based on this knowledge, they completed the present invention.
すなわち、本発明は、１．８−ジアザビシクロ〔５，４
，０〕ウンデ−７−センの存在下、アミンに当量の二硫
化炭素およびハロゲン化アルキルを反応させることを特
徴とするジチオカルバメートの製造方法を提供するもの
である。That is, the present invention provides 1,8-diazabicyclo[5,4
.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明方法に原料として用いるアミンとしては、脂肪族
アミン、脂環式アミン、芳香族アミン、複素環式アミン
のいずれも使用することができ、例えばモノまたはジメ
チルアミン、モノまたはジエチルアミン、モノまたはジ
−ｎ−プロピルアミン、モノまたはジー１ｓｏ−プロピ
ルアミン、モノまたはジ−ｎ−ブチルアミン、モノまた
はジー５ｅＣ−ブチルアミンなどの脂肪族アミン、シク
ロヘキシルアミン、Ｎ−メチルシクロヘキシルアミン、
Ｎ−エチルシクロヘキシルアミン、ジシクロヘキシルア
ミンなどの脂環式アミン、アニリン、°トルイジン、Ｎ
−メチルアニリン、Ｎ−エチルアニリン、ジフェニルア
ミン、ベンジルアミンなどの芳香族アミン、ピペリジン
、各種とベコリン、ピペラジン、モルホリンなどの複素
環式アミンが挙げられる。As the amine used as a raw material in the method of the present invention, any of aliphatic amines, alicyclic amines, aromatic amines, and heterocyclic amines can be used, such as mono- or dimethylamine, mono- or diethylamine, mono- or di-ethylamine, -n-propylamine, mono- or di-1so-propylamine, mono- or di-n-butylamine, mono- or di-5eC-butylamine, aliphatic amines, cyclohexylamine, N-methylcyclohexylamine,
Cycloaliphatic amines such as N-ethylcyclohexylamine and dicyclohexylamine, aniline, °toluidine, N
- Aromatic amines such as methylaniline, N-ethylaniline, diphenylamine, and benzylamine, piperidine, various types, and heterocyclic amines such as becolin, piperazine, and morpholine.
これらの中で、好ましくは第二級アミンが用いられる。Among these, secondary amines are preferably used.
一方、ハロゲン化アルキルとしては、塩化アルキル、臭
化アルキル、ヨウ化アルキルが好ましく、例えばメチル
クロライド、エチルクロライド、ｎ−プロピルクロライ
ド、１ｓｏ−プロピルクロライド、ｎ−ブチルクロライ
ド、１ｓｏ−ブチルクロライド、５ｅｃ−ブチルクロラ
イド、ｎ−へキシルクロライド、２−エチルへキシルク
ロライドなどの塩化アルキルおよびこれらに対応する各
種ブロマイドやヨーダイトなどの臭化アルキルやヨウ化
アルキルが挙げられる。On the other hand, the alkyl halide is preferably alkyl chloride, alkyl bromide, or alkyl iodide, such as methyl chloride, ethyl chloride, n-propyl chloride, 1so-propyl chloride, n-butyl chloride, 1so-butyl chloride, 5ec- Examples include alkyl chlorides such as butyl chloride, n-hexyl chloride, and 2-ethylhexyl chloride, and alkyl bromides and alkyl iodides such as various bromides and iodites corresponding thereto.
本発明方法においては、１．８−ジアザビシクロ（５’
、 ４．０〕ウンデ−７−セン（以下、ＤＢＵと略称
する）が用いられる。この化合物は、式で示される構造
の強力な塩基性を有する超塩基性物質であって、極めて
優れた触媒能力をもち、はとんどの溶剤に溶解するとい
う性質を有している。In the method of the present invention, 1,8-diazabicyclo (5'
, 4.0] unde-7-cene (hereinafter abbreviated as DBU) is used. This compound is an ultra-basic substance with a structure represented by the formula and has extremely basic properties, has extremely excellent catalytic ability, and has the property of being soluble in most solvents.
次に、本発明の好適な実施態様の１例について説明する
と、まず、アミン１モルあたり好ましくは０．５〜５０
モル、より好ましくは１〜５モルのＤＢｔＪの存在下、
アミンに、これと当量の二硫化炭素を反応させる。ここ
で当量というのは厳密な意味での当量ではな（、実質的
に当量であることを意味し、多少の増減は問題としない
。この際、反応は溶媒の不存在下行ってもよいし、必要
ならば少量の溶媒の存在下行ってもよい。溶媒としては
、例えばベンゼン、トルエン、キシレン、エチルベンゼ
ンなどの芳香族炭化水素、ｎ−ヘキサンなどの脂肪族炭
化水素、シクロヘキサンなどの脂環式炭化水素などを用
いることができる。Next, to explain one example of a preferred embodiment of the present invention, first, preferably 0.5 to 50
In the presence of mol, more preferably 1 to 5 mol of DBtJ,
The amine is reacted with an equivalent amount of carbon disulfide. Equivalent here does not mean equivalent in the strict sense (it means substantially equivalent, and slight increase or decrease does not matter. In this case, the reaction may be carried out in the absence of a solvent. If necessary, it may be carried out in the presence of a small amount of a solvent. Examples of solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, aliphatic hydrocarbons such as n-hexane, and alicyclic hydrocarbons such as cyclohexane. Hydrocarbons and the like can be used.
反応温度は通常−５０〜８０℃、好ましくは０〜５０℃
の範囲で選ばれ、また反応圧力については特に制限はな
く、常圧下で反応を行ってもよいし、あるいは加圧下で
反応を行ってもよいが、加圧下で行う場合には、圧力は
１００ ｋｇ／ｃＩａ−Ｇ以下、好ましく ５０ ｋｇ
／ｃｊ −Ｇ以下が望ましい、さらに、反応時間は反応
温度などによって左右されるが、通常は５分〜５時間、
好ましくは０．１〜２時間程度である。The reaction temperature is usually -50 to 80°C, preferably 0 to 50°C.
The reaction pressure is not particularly limited, and the reaction may be carried out under normal pressure or under increased pressure, but when carried out under increased pressure, the pressure is 100 kg/cIa-G or less, preferably 50 kg
/cj -G or less is desirable.Furthermore, the reaction time depends on the reaction temperature, etc., but is usually 5 minutes to 5 hours,
Preferably it is about 0.1 to 2 hours.
なお、ＤＢＵはこの反応には加えずに、次の反応工程で
加えてもよい。Note that DBU may be added in the next reaction step without being added to this reaction.
次いで、この反応液に、該アミンに対して実質的に当量
のハロゲン化アルキルを添加して反応を行う。この際、
必要ならば、溶媒を少量添加して反応を行ってもよいが
、前記反応で溶媒を使用した場合には、同一溶媒を用い
ることが好ましい。Next, a substantially equivalent amount of alkyl halide to the amine is added to this reaction solution to carry out the reaction. On this occasion,
If necessary, the reaction may be carried out by adding a small amount of a solvent, but if a solvent is used in the reaction, it is preferable to use the same solvent.
この反応温度は、通常−５０〜１５０℃、好ましくは０
〜１００℃の範囲で選ばれ、また反応圧力については特
に制限はなく、常圧下で反応を行ってもよいし、加圧下
で反応を行ってもよいが、加圧下で行う場合には、圧力
はｌｏｏｋｇ／ｃ＋Ｊ−Ｇ以下、好ましくは５０ ｋｇ
／ａＪ −Ｇ以下が望ましい。This reaction temperature is usually -50 to 150°C, preferably 0.
The reaction pressure is selected within the range of ~100°C, and there is no particular restriction on the reaction pressure.The reaction may be performed under normal pressure or under increased pressure. is lookkg/c+J-G or less, preferably 50 kg
/aJ -G or less is desirable.
さらに反応時間は、前記ＤＢＵの使用量および反応温度
などによって左右されるが、通常は０．５〜２４時間、
好ましくは１〜５時間程度である。Furthermore, the reaction time depends on the amount of DBU used and the reaction temperature, but is usually 0.5 to 24 hours.
Preferably it is about 1 to 5 hours.
なお、全反応を通じて、窒素やアルゴンなどの不活性ガ
ス雰囲気下で反応を行うことが好ましいが、もちろんこ
れに制限されるものではない。In addition, it is preferable to carry out the reaction under an inert gas atmosphere such as nitrogen or argon throughout the entire reaction, but of course the reaction is not limited thereto.
このようにして、生成した反応液中のジチオカルバメー
トは通常用いられている方法により回収することができ
る。例えば反応液をベンゼンなどの溶剤で抽出し、十分
に洗浄したのち、溶剤を留去することにより、目的のジ
チオカルバメートが得られる。The dithiocarbamate in the reaction solution thus produced can be recovered by a commonly used method. For example, the desired dithiocarbamate can be obtained by extracting the reaction solution with a solvent such as benzene, washing thoroughly, and then distilling off the solvent.
本発明方法によると、このように、溶媒の不在下もしく
は少量の溶媒の存在下、温和な反応条件で、ジチオカル
バメートを収率よく工業的有利に製造することができる
。According to the method of the present invention, dithiocarbamates can be industrially produced in good yield under mild reaction conditions in the absence of a solvent or in the presence of a small amount of a solvent.
次に実施例により本発明をさらに詳細に説明するが、本
発明はこれらの例によってなんら限定されるものではな
い。EXAMPLES Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way.
実施例１〜４
フラスコに、表示のアミンおよびＤＢＵを表示量採り、
ベンゼンｌＱｍｊ！を加え、アルゴン雰囲気下、水冷下
で攪拌しながら、これに二硫化炭素表示量を滴下し、２
５℃で０．５時間反応を行った。Examples 1 to 4 The indicated amounts of amine and DBU were placed in a flask,
Benzene lQmj! was added, and while stirring under water cooling under an argon atmosphere, the indicated amount of carbon disulfide was added dropwise to it, and 2
The reaction was carried out at 5°C for 0.5 hour.
次いでブチルブロマイド表示量とベンゼン５ｍｌを、こ
の反応液に加えて、２５℃で２時間反応を行った。Next, the indicated amount of butyl bromide and 5 ml of benzene were added to this reaction solution, and the reaction was carried out at 25° C. for 2 hours.
次に、反応終了液をベンゼン５０ｍｌで３回抽出し、こ
の抽出層を２Ｎ−ＨＣ１７５ｍｊ！で１回、水５０ｍ１
で２回、さらに飽和食塩水５０ｍ１で１回洗浄したのち
、無水硫酸ナトリウムで乾燥後、減圧下でベンゼンを留
去し、ジチオカルバメートを得た。Next, the reaction completed liquid was extracted three times with 50 ml of benzene, and this extracted layer was extracted with 2N-HC175 mj! 50ml of water once
After washing twice with 50 ml of saturated saline and once with 50 ml of saturated saline, the mixture was dried over anhydrous sodium sulfate, and benzene was distilled off under reduced pressure to obtain dithiocarbamate.
その結果を次表に示す。The results are shown in the table below.
（以下余白）
〔発明の効果〕
本発明のジチオカルバメートの製造方法は、超塩基性有
機化合物のＤＢＵを用い、アミンに二硫化炭素とハロゲ
ン化アルキルを反応させる方法であって、溶媒の不存在
下もしくは少量の溶媒の存在下、極めて温和な反応条件
で収率よく、ジチオカルバメートが得られるなど、工業
的価値の高い方法であり、また得られたジチオカルバメ
ートは農薬、医薬品、その低化成品の原料として極めて
有用である。(The following is a blank space) [Effects of the Invention] The method for producing dithiocarbamates of the present invention is a method in which an ultrabasic organic compound DBU is used to react an amine with carbon disulfide and an alkyl halide, and in the absence of a solvent. This method has high industrial value, as dithiocarbamates can be obtained in good yield under extremely mild reaction conditions in the presence of a small amount of solvent, and the dithiocarbamates obtained can be used as agricultural chemicals, pharmaceuticals, and their low-chemical products. It is extremely useful as a raw material.
Claims (1)
−センの存在下、アミンに当量の二硫化炭素およびハロ
ゲン化アルキルを反応させることを特徴とするジチオカ
ルバメートの製造方法。[Claims] 1,1,8-diazabicyclo[5,4,0]under-7
- A method for producing a dithiocarbamate, which comprises reacting an amine with an equivalent amount of carbon disulfide and an alkyl halide in the presence of sen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61176675A JPS6333358A (en) | 1986-07-29 | 1986-07-29 | Production of dithiocarbamate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61176675A JPS6333358A (en) | 1986-07-29 | 1986-07-29 | Production of dithiocarbamate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6333358A true JPS6333358A (en) | 1988-02-13 |
Family
ID=16017756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61176675A Pending JPS6333358A (en) | 1986-07-29 | 1986-07-29 | Production of dithiocarbamate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6333358A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992013835A1 (en) * | 1991-01-30 | 1992-08-20 | Ihara Chemical Industry Co., Ltd. | Salt of dithiocarbamic acid, production thereof, and production of isothiocyanate from said salt |
| CN103191689A (en) * | 2013-04-26 | 2013-07-10 | 青岛中科荣达新材料有限公司 | Production device of potassium dimethyldithiocarbamate and preparation method thereof |
-
1986
- 1986-07-29 JP JP61176675A patent/JPS6333358A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992013835A1 (en) * | 1991-01-30 | 1992-08-20 | Ihara Chemical Industry Co., Ltd. | Salt of dithiocarbamic acid, production thereof, and production of isothiocyanate from said salt |
| US5274166A (en) * | 1991-01-30 | 1993-12-28 | Ihara Chemical Industry Co., Ltd. | Dithiocarbamic acid salt, process for production thereof, and process for production of isothiocyanate using said dithiocarbamic acid salt |
| CN103191689A (en) * | 2013-04-26 | 2013-07-10 | 青岛中科荣达新材料有限公司 | Production device of potassium dimethyldithiocarbamate and preparation method thereof |
| CN103191689B (en) * | 2013-04-26 | 2015-12-09 | 青岛中科荣达新材料有限公司 | The process units of the U.S. potassium of a kind of liquid good fortune and production method thereof |
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