JPH03240782A - Production of 2,3-dicyan-1,4-dithia-anthraquinone - Google Patents
Production of 2,3-dicyan-1,4-dithia-anthraquinoneInfo
- Publication number
- JPH03240782A JPH03240782A JP2032520A JP3252090A JPH03240782A JP H03240782 A JPH03240782 A JP H03240782A JP 2032520 A JP2032520 A JP 2032520A JP 3252090 A JP3252090 A JP 3252090A JP H03240782 A JPH03240782 A JP H03240782A
- Authority
- JP
- Japan
- Prior art keywords
- water
- surfactant
- dimercaptomaleonitrile
- alkali metal
- salt
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- PYZSVQVRHDXQSL-UHFFFAOYSA-N dithianon Chemical compound S1C(C#N)=C(C#N)SC2=C1C(=O)C1=CC=CC=C1C2=O PYZSVQVRHDXQSL-UHFFFAOYSA-N 0.000 title claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004094 surface-active agent Substances 0.000 claims abstract description 14
- -1 alkali metal salt Chemical class 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- SVPKNMBRVBMTLB-UHFFFAOYSA-N 2,3-dichloronaphthalene-1,4-dione Chemical compound C1=CC=C2C(=O)C(Cl)=C(Cl)C(=O)C2=C1 SVPKNMBRVBMTLB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 239000012046 mixed solvent Substances 0.000 claims abstract description 8
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 7
- 150000004714 phosphonium salts Chemical class 0.000 claims abstract description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 3
- DMDOIBWPFWJPQJ-ARJAWSKDSA-N (z)-2,3-bis(sulfanyl)but-2-enedinitrile Chemical compound N#CC(/S)=C(/S)C#N DMDOIBWPFWJPQJ-ARJAWSKDSA-N 0.000 claims abstract 6
- 238000000034 method Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- 239000011575 calcium Substances 0.000 abstract description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 239000003242 anti bacterial agent Substances 0.000 abstract 1
- 238000003898 horticulture Methods 0.000 abstract 1
- KIAJWKWOKTWTIZ-UHFFFAOYSA-N 1,4-dioxonaphthalene-2,3-dicarbonitrile Chemical compound C1=CC=C2C(=O)C(C#N)=C(C#N)C(=O)C2=C1 KIAJWKWOKTWTIZ-UHFFFAOYSA-N 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 238000010813 internal standard method Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 1
- OOCMUZJPDXYRFD-UHFFFAOYSA-L calcium;2-dodecylbenzenesulfonate Chemical compound [Ca+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O OOCMUZJPDXYRFD-UHFFFAOYSA-L 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 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
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 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
- Agricultural Chemicals And Associated Chemicals (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyrane Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は２．３−ジクロロ−１，４−ナフトキノン（以
下にこれをＤＣＮＱと略称する）とジメチルカプトマレ
オニトリルのアルカリ金属塩（以下にこれをＤＤＭと略
称する）から農園芸用殺菌剤と有用な２．３−ジシアノ
−１，４−ジチア−９，１０−アンスラキノン（以下、
ＤＤＡＱと略す）を製造する新規な製法に関するもので
あり、高純度のＤＤＡＱを収率良く、しかも工業的に有
利で安価に製造する方法を提供するものである。Detailed Description of the Invention [Industrial Application Field] The present invention provides an alkali metal salt of 2,3-dichloro-1,4-naphthoquinone (hereinafter abbreviated as DCNQ) and dimethylcaptomaleonitrile (hereinafter abbreviated as DCNQ). This is abbreviated as DDM) to 2,3-dicyano-1,4-dithia-9,10-anthraquinone (hereinafter referred to as DDM), which is useful as an agricultural and horticultural fungicide.
The present invention relates to a new manufacturing method for producing DDAQ (abbreviated as DDAQ), and provides a method for producing high-purity DDAQ in good yield, industrially advantageous, and at low cost.
ＤＣＮＱとＤＤＭとを反応させてＤＤＡＱを合成する方
法としては以下の方法か知られている。The following method is known as a method of reacting DCNQ and DDM to synthesize DDAQ.
■アルコール、又はアセトンを溶媒として用いる方法（
ＵＳＰ−２９７６２９６，ＤＥ−１０６０６５５、特開
昭５Ｏ−１３５０８７）
■界面活性剤の存在下水中で反応させる方法（特開昭５
７−６４６９０）
〔発明か解決しようとする課題〕
ＤＤＭは水溶性であり有機溶媒に溶けにくいのに対して
ＤＣＮＱは水に難溶性てかつ有機溶媒にも溶けにくく、
その上ＤＤＭか高温では不安定であることもあって反応
そのものかきわめてコントロールしにくく、工業的に効
率よ＜ ＤＤＡＱを製造することは困難であった。■Method using alcohol or acetone as a solvent (
USP-2976296, DE-1060655, JP-A No. 5 O-135087) ■ Method of reacting in water in the presence of a surfactant (JP-A No. 5 O-135087)
7-64690) [Problem to be solved by the invention] DDM is water-soluble and hardly soluble in organic solvents, whereas DCNQ is poorly soluble in water and hardly soluble in organic solvents.
Furthermore, since DDM is unstable at high temperatures, the reaction itself is extremely difficult to control, making it difficult to produce DDAQ industrially and efficiently.
上述の、アルコール又はアセトンを溶媒として用いる方
法は、得られるＤＤＡＱの純度・収率か低く、例えば実
施例に従って追試することによって得られたＤＤＡＱの
純度は高速液体クロマトグラフィー（以下ＨＰＬＣと略
す）を用い内標法によって求めると７８％程度であり収
率も８０％以下であった。The above-mentioned method using alcohol or acetone as a solvent has a low purity and yield of DDAQ. The yield was determined to be about 78% using the internal standard method, and the yield was also below 80%.
また界面活性剤の存在下、水溶液中で反応させる方法は
反応温度か高いことと、激しくかきまぜる必要かあり、
かつ水量か多いことか必要なため生産性（単位液量当り
の得量）か低く工業的に不利であり、得られるＤＤＡＱ
の純度も追試してみると８０％程度のものでしかなかっ
た。In addition, the method of reacting in an aqueous solution in the presence of a surfactant requires a high reaction temperature and requires vigorous stirring.
In addition, since a large amount of water is required, the productivity (yield per unit liquid amount) is low, which is disadvantageous industrially, and the resulting DDAQ is low.
When I retested the purity, it was only about 80%.
本発明者は、ＤＤＡＱの製法に関して工業的に有利な方
法を提供すべく検討したところ、相間移動触媒（以下Ｐ
ＴＣと略す）及び又は界面活性剤の存在下、水と有機溶
媒の混合溶媒中に於いてＤＤＭとＤＣＮＱを反応させる
ことによって高収率で純度の高いＤＤＡＱを製造できる
ことを見だしたものである。The present inventor conducted studies to provide an industrially advantageous method for producing DDAQ, and found that a phase transfer catalyst (hereinafter referred to as P
It was discovered that DDAQ with high yield and high purity can be produced by reacting DDM and DCNQ in a mixed solvent of water and an organic solvent in the presence of TC) and/or a surfactant. .
さらに酢酸、塩酸等の酸を添加して反応液のｐｌを３〜
７にコントロールすることにより副生物の生成か抑制で
きること、また分散剤として界面活性剤を加えることに
よって分散化（微粒化）できることかわかり、スムース
な攪拌によって反応のコントロールと生産性の向上が達
成でき、さらに純度と収率の向上に結びついたものであ
る。Furthermore, add acids such as acetic acid and hydrochloric acid to reduce the pl of the reaction solution to 3~
It was found that the generation of by-products can be suppressed by controlling the temperature at , further leading to improved purity and yield.
また水と有機溶媒の混合溶媒中に於いてＤＤＭとＤＣＮ
Ｑを反応させる際に、界面活性剤のみを添加し、かつ酸
を加えて反応液のｐＨを３〜７にコントロールすること
によっても純度の高いＤ［）ＡＱが収率よく製造てきる
ことを見い出し本発明を完成してものである。Furthermore, in a mixed solvent of water and an organic solvent, DDM and DCN
It has been shown that when reacting Q, highly pure D[)AQ can be produced in good yield by adding only a surfactant and controlling the pH of the reaction solution to 3 to 7 by adding an acid. Heading Completes the Invention.
本発明における反応式は次のように表わせる。The reaction formula in the present invention can be expressed as follows.
（ＯＤＭ ） （ＤＣＮＱ ） （ＤＯＡＱ）
（ここではＭはアルカリ金属塩を示す。）本発明におい
て、ＰＴＣとは、例えばトリオクチルメチルアンモニウ
ムクロライド、テトラブチルアンモニウムブロマイド、
トリブチルベンジルアンモニウムクロライド、オクチル
トリエチルアンモニウムブロマイド等の４級アンモニウ
ム塩や、テトラフェニルホスホニウムブロマイド、テト
ラブチルホスホニウムクロライド、トリオクチルエチル
ホスホニウムブロマイド等のホスオニウム塩が有効に使
用され、その使用量はＤＣＮＱに対して好ましくは０．
０１〜５重量％である〇
本発明において使用する界面活性剤としては、例えばア
ルキル芳香族スルホン酸カルシウム、高級アルコール硫
酸エステルソーダなどのアニオン系活性剤、ポリオキシ
エチレンまたは高級オレフィンエーテルなどのノニオン
系活性剤、またはセチルトリメチルアンモニウムクロラ
イド、ポリオキシエチレンアルキルアミンなどのカチオ
ン系活性剤、あるいは、これらを任意に混合した活性剤
か使用できるが、得に分散化力、乳化力のすぐれたもの
が好適である。(ODM) (DCNQ) (DOAQ)
(Here, M represents an alkali metal salt.) In the present invention, PTC includes, for example, trioctylmethylammonium chloride, tetrabutylammonium bromide,
Quaternary ammonium salts such as tributylbenzylammonium chloride and octyltriethylammonium bromide, and phosphonium salts such as tetraphenylphosphonium bromide, tetrabutylphosphonium chloride and trioctylethylphosphonium bromide are effectively used, and the amount used is relative to DCNQ. Preferably 0.
The surfactant used in the present invention is, for example, an anionic surfactant such as calcium alkyl aromatic sulfonate, higher alcohol sulfate ester soda, or a nonionic surfactant such as polyoxyethylene or higher olefin ether. An activator, a cationic activator such as cetyltrimethylammonium chloride or polyoxyethylene alkylamine, or an arbitrary mixture of these activators can be used, but those with excellent dispersing power and emulsifying power are particularly preferred. It is.
その使用量はＤＣＮＱに対して好ましくは０．０１〜５
重量％である。The amount used is preferably 0.01 to 5 for DCNQ.
Weight%.
有機溶媒としては、例えばトルエン、キシレン、クロル
ベンセン、クロロホルム、ジクロルメタン、ジクロルエ
タン（芳香族又は脂肪族の炭化水素）等、水と混ざらな
い溶媒か好適であるか、アテセトン、メチルエチルテト
ン、ジオキサン、低級アルコールＤＭＦ （ケトン、
エステル、エーテル、アルコール、アシド系溶媒）等水
と混合する溶媒であっても使用できる。その使用量はＤ
ＣＮＱに対して好ましくは１００〜２，０００ ｍ１１
モルてあり、ＤＣＮＱを懸濁させた状態で使用できる。Suitable organic solvents include water-immiscible solvents such as toluene, xylene, chlorobenzene, chloroform, dichloromethane, dichloroethane (aromatic or aliphatic hydrocarbons), acetone, methylethyltetone, dioxane, lower Alcohol DMF (ketone,
Even solvents that mix with water, such as esters, ethers, alcohols, and acidic solvents, can be used. The amount used is D
Preferably 100-2,000 m11 for CNQ
DCNQ can be used in a suspended state.
反応液のｐＨを３〜７に保持するのに使用する酸として
は、酢酸、プロピオン酸、シュウ酸、マロン酸等のカル
ボン酸や、塩酸、リン酸、スルホン酸、なとの有機、無
機の酸か使用できる。Acids used to maintain the pH of the reaction solution at 3 to 7 include carboxylic acids such as acetic acid, propionic acid, oxalic acid, and malonic acid, as well as organic and inorganic acids such as hydrochloric acid, phosphoric acid, sulfonic acid, and so on. Can be used with acid.
反応液のｐＨか高いと、反応液か粘稠となり攪拌不良と
なり、また副生物か生成し純度・収率か低下する。加え
る酸の量は、ＤＤＭに対して通常は１０〜５０％モル（
ＤＣＮＱに対して通常は２０〜６０％モル）であり、初
めに加えておいても、ＤＤＭを滴下中に同時に滴下して
もよく、好適にはｐＨを４〜６に保持するのか好ましい
。ＤＤＭは例えばｃｈｅｍｉｓｃｈｅＢｅｒｉｃｈｔｅ
８８巻（１９５５年）１９５７項またはドイツ特許第
１１５８０５６号（１９６３年）明細書に記載された方
法で合成することかでき、固体の状態でも水溶液の状態
でも使用てきる。If the pH of the reaction solution is high, the reaction solution will become viscous, resulting in poor stirring, and by-products will be produced, reducing purity and yield. The amount of acid added is usually 10 to 50% molar (based on DDM).
It is usually 20 to 60% mole based on DCNQ), and may be added at the beginning or added dropwise at the same time as DDM is added, preferably by keeping the pH at 4 to 6. DDM is for example chemistry
It can be synthesized by the method described in Vol. 88 (1955), Section 1957 or German Patent No. 1158056 (1963), and can be used in either a solid state or an aqueous solution state.
またＤＤＭは熱により分解しやすいから、ＤＣＮＱの懸
濁液にＤＤＭ水溶液を滴下する間−５〜４０°Ｃに保ち
、昇温する前にも反応混合物を同温度にて３０分〜２時
間保つことか好ましい。また酸化されやすいからＮ２雰
囲気下で反応させたほうか好ましい。In addition, since DDM is easily decomposed by heat, the temperature is kept at -5 to 40°C while dropping the DDM aqueous solution to the DCNQ suspension, and the reaction mixture is kept at the same temperature for 30 minutes to 2 hours before raising the temperature. That's preferable. Furthermore, since it is easily oxidized, it is preferable to carry out the reaction under an N2 atmosphere.
水の量は特に規定しないか、ＤＤＭに対して好ましくは
１００〜２．０００ｙｄ１モルである。The amount of water is not particularly specified, or is preferably 100 to 2.000 yd1 mol based on DDM.
ＤＤＭとＤＣＮＱとの使用割合は、そのモル比をγとす
ればγ＝０．９５〜１．２、好ましくは、１．０〜１．
０５である。The molar ratio of DDM and DCNQ is γ = 0.95 to 1.2, preferably 1.0 to 1.
It is 05.
本発明は一般に次のように実施する。即ち、所定量のＤ
ＣＮＱを有機溶媒に懸濁した溶液にＰＴＣ又は界面活性
剤あるいはＰＴＣと界面活性剤の両方を加え、ついで酢
酸等の酸を加えてよく攪拌しながら好ましくは０〜２０
°Ｃにて所定量のＤＤＭ水溶液を滴下する。The invention generally operates as follows. That is, a predetermined amount of D
PTC or a surfactant or both PTC and a surfactant are added to a solution of CNQ suspended in an organic solvent, and then an acid such as acetic acid is added to the solution, preferably from 0 to 20% while stirring well.
A predetermined amount of DDM aqueous solution is added dropwise at °C.
滴下後間温度にて３０分〜２時間攪拌し、ついて好まし
くは３０〜５０°Ｃにて３０分〜３時間反応させる。After the dropwise addition, the mixture is stirred at the same temperature for 30 minutes to 2 hours, and then reacted preferably at 30 to 50°C for 30 minutes to 3 hours.
滴下中途々にｐｌか上昇するが、必要ならば酸を加えて
ｐＨか７を越えないように調整する。反応液は黒褐色を
呈し、析出している結晶をろ別し、水洗ついてメタノー
ル等で洗浄したのち、減圧下乾燥することにより、高純
度のＤＤＡＱか褐色〜灰色結晶として得られる。During the dropwise addition, the PL will rise, but if necessary, add acid to adjust the pH so that it does not exceed 7. The reaction solution exhibits a dark brown color, and precipitated crystals are filtered, washed with water and methanol, and then dried under reduced pressure to obtain highly pure DDAQ as brown to gray crystals.
なお、本反応はＮ２雰囲気下で行うのが好ましい。Note that this reaction is preferably carried out under an N2 atmosphere.
本発明の方法により、農園芸用殺菌剤として有用なジチ
アノン（ＤＤＡＱ）が、純度良く、工業的に有利な方法
で得られる。By the method of the present invention, dithianone (DDAQ) useful as an agricultural and horticultural fungicide can be obtained in a highly pure and industrially advantageous manner.
以下に実施例および参考例をあげて本発明をさらに詳し
く説明するか、本発明はこの実施例に限定されるもので
はない。The present invention will be explained in more detail with reference to Examples and Reference Examples below, but the present invention is not limited to these Examples.
（実施例１）
ＤＣＮＱ （純度９９％）２０．４ｇをキシレン５〇−
中に懸濁させ、ＰＴＣとしてトリオクチルメチルアンモ
ニウムクロライド（ＴＯＭＡＣと略す）０．５ｇ、酸と
して酢酸２．５ｍＪ及び界面活性剤としてドデシルベン
ゼンスルホン酸カルシウム（７０％ＭｅｏＨ溶液）１．
０ｇを加えた後、各攪拌下０〜５°ＣにてＤＤＭの１２
重量％水溶液１４０ｇを３０分かけて滴下した。滴下す
るにつれて徐々に反応液のｐｌか上昇し、６．３まで達
するかその後次第に低下して、滴下終了後１時間はどで
５．０になった。その後３０°Ｃにて２時間、攪拌し反
応を完結させた。反応終了時のｐＨは４．６であった。(Example 1) 20.4 g of DCNQ (99% purity) was mixed with 50-
0.5 g of trioctylmethylammonium chloride (abbreviated as TOMAC) as PTC, 2.5 mJ of acetic acid as acid, and calcium dodecylbenzenesulfonate (70% MeoH solution) as surfactant.
12 of DDM at 0-5 °C under each stirring after adding 0 g.
140 g of a wt % aqueous solution was added dropwise over 30 minutes. As the dropwise addition was continued, the PL of the reaction solution gradually increased, reaching 6.3, and then gradually decreasing to 5.0 one hour after the completion of the dropwise addition. Thereafter, the mixture was stirred at 30°C for 2 hours to complete the reaction. The pH at the end of the reaction was 4.6.
反応液をろ別し、得られた固形物を常温の水１００−１
ついてＭｅｏＨ２００−にて洗滌したのち、５０℃にて
３時間減圧乾燥することにより灰褐色結晶２５゜１ｇ
（粗収率９５．２％）を得た。ＨＰＬＣ（内標法）によ
り純度を測定したところ純度９５．６％であった。The reaction solution was filtered, and the obtained solid was mixed with room temperature water 100-1
After washing with MeoH200-, drying under reduced pressure at 50°C for 3 hours yielded 25°1 g of gray brown crystals.
(crude yield 95.2%). Purity was measured by HPLC (internal standard method) and found to be 95.6%.
（ＤＣＮＱからの収率９１％）また得られたＤＤＡＱ中
に含まれるＤＣＮＱは０．１重量％であった。(Yield from DCNQ: 91%) Also, DCNQ contained in the obtained DDAQ was 0.1% by weight.
（実施例２）
実施例１において有機溶媒の種類と量、ＰＴＣの種類と
量、界面活性剤の種類の量、酸の種類と量を第１表のよ
うに変えて、あとは実施例１と同様に操作ＤＤＡＱを得
た。結果は第１表に示すよってあった。(Example 2) In Example 1, the type and amount of organic solvent, the type and amount of PTC, the type and amount of surfactant, and the type and amount of acid were changed as shown in Table 1, and the rest was as in Example 1. Operation DDAQ was obtained in the same manner as . The results were as shown in Table 1.
（参考例） 実施例１と同様に操作した参考例を表１に示す。(Reference example) Table 1 shows a reference example that was operated in the same manner as in Example 1.
Claims (6)
ルカプトマレオニトリルのアルカリ金属塩とを水と有機
溶媒の混合溶媒中において反応せしめるに際して、相間
移動触媒及び／又は界面活性剤を添加することを特徴と
する２，３−ジシアン−１，４−ジチア−アントラキノ
ンの製法。(1) Adding a phase transfer catalyst and/or a surfactant when reacting 2,3-dichloro-1,4-naphthoquinone and an alkali metal salt of dimercaptomaleonitrile in a mixed solvent of water and an organic solvent. A method for producing 2,3-dicyan-1,4-dithia-anthraquinone, characterized by the following.
ルカプトマレオニトリルのアルカリ金属塩とを水と有機
触媒の混合溶媒中において反応せしめるに際して、相間
移動触媒を添加する特許請求の範囲第（１）項の製法。(2) A phase transfer catalyst is added when reacting 2,3-dichloro-1,4-naphthoquinone and an alkali metal salt of dimercaptomaleonitrile in a mixed solvent of water and an organic catalyst. 1) Manufacturing method.
ルカプトマレオニトリルのアルカリ金属塩とを水と有機
溶媒の混合溶媒中において反応させるに際して、界面活
性剤を添加する特許請求の範囲第（１）項の方法。(3) Claim No. 2, wherein a surfactant is added when reacting 2,3-dichloro-1,4-naphthoquinone and an alkali metal salt of dimercaptomaleonitrile in a mixed solvent of water and an organic solvent. 1) Method.
ルカプトマレオニトリルのアルカリ金属塩とを水と有機
溶媒の混合溶媒中に於いて反応させるに際して、相間移
動触媒及び界面活性剤を添加する特許請求の範囲第（１
）項の方法。(4) Adding a phase transfer catalyst and a surfactant when reacting 2,3-dichloro-1,4-naphthoquinone and an alkali metal salt of dimercaptomaleonitrile in a mixed solvent of water and an organic solvent. Claim No. 1
) method.
ることを特徴とする特許請求の範囲第（１）項、第（２
）項、第（３）項記載の方法。(5) The pH of the reaction solution is maintained in the range of 3 to 7 by adding an acid.
), the method described in paragraph (3).
ム塩又は３級アミンの塩である特許請求の範囲第（１）
項、第（４）項記載の方法。(6) Claim No. 1, wherein the phase transfer catalyst is a quaternary ammonium salt, a phosphonium salt, or a tertiary amine salt.
The method described in paragraph (4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2032520A JPH03240782A (en) | 1990-02-15 | 1990-02-15 | Production of 2,3-dicyan-1,4-dithia-anthraquinone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2032520A JPH03240782A (en) | 1990-02-15 | 1990-02-15 | Production of 2,3-dicyan-1,4-dithia-anthraquinone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03240782A true JPH03240782A (en) | 1991-10-28 |
Family
ID=12361239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2032520A Pending JPH03240782A (en) | 1990-02-15 | 1990-02-15 | Production of 2,3-dicyan-1,4-dithia-anthraquinone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03240782A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112500391A (en) * | 2020-12-14 | 2021-03-16 | 江西禾益化工股份有限公司 | Device and method for producing dithianon through continuous kettle type reaction |
-
1990
- 1990-02-15 JP JP2032520A patent/JPH03240782A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112500391A (en) * | 2020-12-14 | 2021-03-16 | 江西禾益化工股份有限公司 | Device and method for producing dithianon through continuous kettle type reaction |
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