JPH09202765A - Production of 2,3-diaminoacrylonitrile derivative - Google Patents
Production of 2,3-diaminoacrylonitrile derivativeInfo
- Publication number
- JPH09202765A JPH09202765A JP3127696A JP3127696A JPH09202765A JP H09202765 A JPH09202765 A JP H09202765A JP 3127696 A JP3127696 A JP 3127696A JP 3127696 A JP3127696 A JP 3127696A JP H09202765 A JPH09202765 A JP H09202765A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen cyanide
- base
- solvent
- water
- group
- 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
- XIFVSHJDIVUZJB-UHFFFAOYSA-N 2,3-diaminoprop-2-enenitrile Chemical class NC=C(N)C#N XIFVSHJDIVUZJB-UHFFFAOYSA-N 0.000 title abstract description 6
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 239000003021 water soluble solvent Substances 0.000 claims abstract description 4
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims abstract 3
- 239000000126 substance Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 24
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 9
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 4
- -1 sulfide compound Chemical class 0.000 abstract description 4
- 239000008096 xylene Substances 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 4
- 150000003568 thioethers Chemical class 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 125000004454 (C1-C6) alkoxycarbonyl group Chemical group 0.000 description 2
- ICHQGWRWEHDLFX-UHFFFAOYSA-N 2,3-diamino-3-phenylsulfanylprop-2-enenitrile Chemical compound N#CC(N)=C(N)SC1=CC=CC=C1 ICHQGWRWEHDLFX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 description 1
- ZIXXRXGPBFMPFD-UHFFFAOYSA-N 1-chloro-4-[(4-chlorophenyl)disulfanyl]benzene Chemical compound C1=CC(Cl)=CC=C1SSC1=CC=C(Cl)C=C1 ZIXXRXGPBFMPFD-UHFFFAOYSA-N 0.000 description 1
- KVRWQSNKNNXGKH-UHFFFAOYSA-N 2,3-diamino-3-(4-chlorophenyl)sulfanylprop-2-enenitrile Chemical compound N#CC(N)=C(N)SC1=CC=C(Cl)C=C1 KVRWQSNKNNXGKH-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- RUIAMTBZKXVQHW-UHFFFAOYSA-N C(C1=CC=CC=C1)S(=O)(=O)O.NC(C#N)=C(SC1=CC=CC=C1)N Chemical compound C(C1=CC=CC=C1)S(=O)(=O)O.NC(C#N)=C(SC1=CC=CC=C1)N RUIAMTBZKXVQHW-UHFFFAOYSA-N 0.000 description 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、医薬、農薬等の中
間体として有用な、一般式［Ｉ］TECHNICAL FIELD The present invention relates to a compound of the general formula [I] which is useful as an intermediate for medicines, agricultural chemicals and the like.
【０００２】[0002]
【化２】 Embedded image
【０００３】（式中Ｒはアリール基、アルキル基、アラ
ルキル基、またはアルケニル基を示す。）で表される
２，３−ジアミノアクリロニトリル誘導体（以下ＤＡＡ
Ｎと言う）の製造方法に関する。(Wherein R represents an aryl group, an alkyl group, an aralkyl group, or an alkenyl group) and a 2,3-diaminoacrylonitrile derivative (hereinafter referred to as DAA).
(Referred to as N).
【０００４】[0004]
【従来の技術】従来一般式［Ｉ］で表されるＤＡＡＮは
シアン化水素と一般式ＲＳＳＲで表されるジスルフィド
類とをアセトニトリル等の極性溶媒中で反応し、ｐ−ト
ルエンスルホン酸塩等の塩として単離していた。2. Description of the Related Art Conventionally, DAAN represented by the general formula [I] is obtained by reacting hydrogen cyanide with disulfides represented by the general formula RSSR in a polar solvent such as acetonitrile to obtain a salt such as p-toluenesulfonate. It was isolated.
【０００５】[0005]
【発明が解決しようとする課題】ＤＡＡＮは極性溶媒に
溶解しやすく、ｐ−トルエンスルホン酸塩としても回収
率が低く、収率の向上が望まれていた。また、溶媒への
溶解度を調節する為に混合溶媒とする為に溶媒の回収が
複雑化し、効率の良い製造方法ではなかった。しかも、
得られた結晶はｐ−トルエンスルホン酸塩等の塩の形で
ある為に、次の反応に供する為にその塩を取り除く必要
が有る場合が多く、操作が繁雑になるという問題点を有
していた。DISCLOSURE OF THE INVENTION DAAN is easily dissolved in a polar solvent, and the recovery rate of p-toluenesulfonate is low, and improvement of the yield has been desired. Further, since the mixed solvent is used to adjust the solubility in the solvent, the recovery of the solvent is complicated, and the production method is not efficient. Moreover,
Since the obtained crystals are in the form of a salt such as p-toluenesulfonate, it is often necessary to remove the salt for use in the next reaction, which causes a problem that the operation becomes complicated. Was there.
【０００６】[0006]
【課題を解決するための手段】本発明は、シアン化水素
と一般式ＲＳＳＲ又はＲＳＨで表される化合物とを難水
溶性の溶媒中、塩基の存在下反応させた後、水を添加し
てＤＡＡＮを析出させる事を特徴とする製造方法であ
る。According to the present invention, hydrogen cyanide and a compound represented by the general formula RSSR or RSH are reacted in a poorly water-soluble solvent in the presence of a base, and then water is added to give DAAN. This is a manufacturing method characterized by precipitation.
【０００７】[0007]
【発明の実施の形態】本発明は、難水溶性の溶媒に、シ
アン化水素と一般式ＲＳＳＲ又はＲＳＨで表される化合
物（以下スルフィド類という）と塩基とを加え、然るべ
き熟成の後水を添加してＤＡＡＮを析出させ、結晶を分
離する事によって行なわれる。Ｒで表される置換基とし
てはハロゲン原子、Ｃ1-6 アルコキシカルボニル基、カ
ルボキシ基、Ｃ1-6 アルキルチオ基、ヒドロキシル基、
メルカプト基、シクロアルキル基又は複素環基等で置換
されていてもＣ1-12アルキル基、ハロゲン原子、Ｃ1-6
アルキル基、ヒドロキシル基、メルカプト基、Ｃ1-6 ア
ルコキシカルボニル基、またはカルボキシル基等で置換
されていてもよいフェニル基等のアリール基もしくは同
様の置換基で置換されていてもよいベンジル基等のアラ
ルキル基またはハロゲン原子等で置換されていてもよい
Ｃ2-6 のアルケニル基が挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, hydrogen cyanide, a compound represented by the general formula RSSR or RSH (hereinafter referred to as sulfides), and a base are added to a poorly water-soluble solvent, and water is added after appropriate aging. By precipitating DAAN and separating the crystals. The substituent represented by R is a halogen atom, a C 1-6 alkoxycarbonyl group, a carboxy group, a C 1-6 alkylthio group, a hydroxyl group,
C 1-12 alkyl group, halogen atom, C 1-6 , even if substituted with a mercapto group, cycloalkyl group or heterocyclic group
An alkyl group, a hydroxyl group, a mercapto group, a C 1-6 alkoxycarbonyl group, or an aryl group such as a phenyl group which may be substituted with a carboxyl group, or a benzyl group which may be substituted with a similar substituent group, etc. Examples thereof include an aralkyl group or a C 2-6 alkenyl group which may be substituted with a halogen atom or the like.
【０００８】反応溶媒は、トルエンやキシレンといった
炭化水素類、酢酸エチルや酢酸ブチルといったエステル
類、ジクロロメタンやクロロホルム等のハロゲン化炭化
水素類が使用できる。塩基としては、トリメチルアミ
ン、ジメチルエチルアミン、トリエチルアミン、ピリジ
ンあるいは、１，８−ジアザビシクロ［５．４．０］−
７−ウンデセン（ＤＢＵ）等の塩基が使用できる。反応
における塩基の量は、使用するスルフィド類に対して１
モルから３モル当量の範囲で、好ましくは２〜３モル当
量の範囲が適している。反応温度は０〜５０℃、好まし
くは１０〜２０℃の範囲が適している。As the reaction solvent, hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, and halogenated hydrocarbons such as dichloromethane and chloroform can be used. As the base, trimethylamine, dimethylethylamine, triethylamine, pyridine or 1,8-diazabicyclo [5.4.0]-
A base such as 7-undecene (DBU) can be used. The amount of base in the reaction is 1 with respect to the sulfides used.
A range of 3 to 3 molar equivalents, preferably a range of 2 to 3 molar equivalents, is suitable. The reaction temperature is suitably in the range of 0 to 50 ° C, preferably 10 to 20 ° C.
【０００９】スルフィド類を完全に消費し、ＤＡＡＮに
するにはシアン化水素はスルフィド類に対し３モル当量
必要となる。反応を円滑に進める為には３モル当量以上
が必要で、３〜６モル当量の範囲が適している。熟成に
要する時間は、温度により大きく異なるが、１０分〜２
時間で反応温度２０℃においては好ましくは１時間〜２
時間の範囲が適している。熟成の後、水を加えてＤＡＡ
Ｎの結晶を析出させる。ここでの水の量は溶媒により異
なるが、溶媒に対し０．５倍〜２倍の範囲で使用する。
尚、水の温度は０〜２５℃の範囲が適している。To completely consume the sulfides and form DAAN, hydrogen cyanide is required in an amount of 3 molar equivalents with respect to the sulfides. In order to proceed the reaction smoothly, 3 molar equivalents or more are necessary, and the range of 3 to 6 molar equivalents is suitable. The time required for aging varies greatly depending on the temperature, but is 10 minutes to 2 minutes.
When the reaction temperature is 20 ° C., it is preferably 1 hour to 2 hours.
Time range is suitable. After aging, add water and DAA
Precipitate N crystals. Although the amount of water here varies depending on the solvent, it is used in a range of 0.5 times to 2 times that of the solvent.
The temperature of water is preferably in the range of 0 to 25 ° C.
【００１０】[0010]
【実施例】次に実施例を挙げて本発明をさらに詳細に説
明する。反応の進行は高速液体クロマトグラフィー（Ｈ
ＰＬＣ）や薄層クロマトグラフィー（ＴＬＣ）により確
認した。また生成物については、ＮＭＲ、ＩＲ、ＨＰＬ
Ｃにより確認した。Next, the present invention will be described in more detail with reference to examples. The progress of the reaction was determined by high performance liquid chromatography (H
PLC) and thin layer chromatography (TLC). For the product, NMR, IR, HPL
C.
【００１１】実施例１ ジフェニルジスルフィド２４ｇ（０．１１ｍｏｌ）、キ
シレン１２５ｍｌ、トリエチルアミン２２．３ｇ（０．
２２ｍｏｌ）をフラスコに仕込み、攪拌下約１０℃に冷
却した。これにシアン化水素２５．５ｍｌ（０．６６ｍ
ｏｌ）を一時に加えた。温度を２０℃に保ちつつ１時間
攪拌した。その後、５℃に冷却した水を１２０ｍｌ一時
に加え、析出した結晶を濾過して乾燥し、２，３−ジア
ミノ−３−（フェニルチオ）アクリロニトリル１６．２
ｇを得た。分解点６６〜６８℃。Example 1 24 g (0.11 mol) of diphenyl disulfide, 125 ml of xylene, 22.3 g of triethylamine (0.
(22 mol) was charged into a flask and cooled to about 10 ° C. with stirring. 25.5 ml of hydrogen cyanide (0.66 m
ol) was added at one time. The mixture was stirred for 1 hour while maintaining the temperature at 20 ° C. Then, 120 ml of water cooled to 5 ° C. was added at once, and the precipitated crystals were filtered and dried to give 2,3-diamino-3- (phenylthio) acrylonitrile 16.2.
g was obtained. Decomposition point 66-68 ° C.
【００１２】実施例２ ｐ−クロロフェニルジスルフィド３．５ｇ（１２．３ｍ
ｍｏｌ）、キシレン１８．５ｍｌ、トリエチルアミン
２．５ｇ（２５ｍｍｏｌ）をフラスコに仕込み、攪拌下
１０℃に冷却した。これにシアン化水素２．９ｍｌ（７
４ｍｍｏｌ）を一時に加えた。温度を２０℃に保ちつつ
１時間２０分攪拌した。その後５℃の冷水１８ｍｌを一
時に加え、析出した物質を濾過乾燥して１．５ｇの粗
２，３−ジアミノ−３−（ｐ−クロロフェニルチオ）ア
クリロニトリルを得、これをアセトニトリルに溶解し、
ｐ−トルエンスルホン酸を加え、析出した結晶を濾過乾
燥して分解点を測定したところ１５３〜１５４℃であっ
た。Example 2 3.5 g (12.3 m) of p-chlorophenyl disulfide
mol), xylene 18.5 ml, and triethylamine 2.5 g (25 mmol) were charged into a flask and cooled to 10 ° C. with stirring. Add 2.9 ml of hydrogen cyanide (7
4 mmol) was added at one time. The mixture was stirred for 1 hour and 20 minutes while maintaining the temperature at 20 ° C. Then, 18 ml of cold water at 5 ° C. was added at once, and the precipitated substance was filtered and dried to obtain 1.5 g of crude 2,3-diamino-3- (p-chlorophenylthio) acrylonitrile, which was dissolved in acetonitrile,
p-Toluenesulfonic acid was added, and the precipitated crystals were filtered and dried, and the decomposition point was measured to be 153 to 154 ° C.
【００１３】実施例３ ジフェニルジスルフィド２４ｇ（０．１１ｍｏｌ）、ト
ルエン１２５ｍｌ、トリエチルアミン２２．３ｇ（０．
２２ｍｏｌ）をフラスコに仕込み、攪拌下約１０℃に冷
却した。これにシアン化水素２５．５ｍｌ（０．６６ｍ
ｏｌ）を一時に加えた。温度を２０℃に保ちつつ１時間
攪拌した。その後、５℃に冷却した水を１２０ｍｌ一時
に加え、析出した結晶を濾過して乾燥し、２，３−ジア
ミノ−３−（フェニルチオ）アクリロニトリル１５．１
ｇを得た。分解点６６〜６８℃。Example 3 24 g (0.11 mol) of diphenyl disulfide, 125 ml of toluene, 22.3 g of triethylamine (0.
(22 mol) was charged into a flask and cooled to about 10 ° C. with stirring. 25.5 ml of hydrogen cyanide (0.66 m
ol) was added at one time. The mixture was stirred for 1 hour while maintaining the temperature at 20 ° C. Then, 120 ml of water cooled to 5 ° C. was added at once, and the precipitated crystals were filtered and dried to give 2,3-diamino-3- (phenylthio) acrylonitrile 15.1.
g was obtained. Decomposition point 66-68 ° C.
【００１４】実施例４ ジフェニルジスルフィド２４ｇ（０．１１ｍｏｌ）、酢
酸エチル１２５ｍｌ、トリエチルアミン２２．３ｇ
（０．２２ｍｏｌ）をフラスコに仕込み、攪拌下約１０
℃に冷却した。これにシアン化水素２５．５ｍｌ（０．
６６ｍｏｌ）を一時に加えた。温度を２０℃に保ちつつ
１時間攪拌した。その後、５℃に冷却した水を１２０ｍ
ｌ一時に加え、析出した結晶を濾過して乾燥し、２，３
−ジアミノ−３−（フェニルチオ）アクリロニトリル１
４．５ｇを得た。分解点６６〜６８℃。Example 4 24 g (0.11 mol) of diphenyl disulfide, 125 ml of ethyl acetate, 22.3 g of triethylamine
(0.22 mol) was charged in a flask and stirred for about 10 minutes.
Cooled to ° C. 25.5 ml of hydrogen cyanide (0.
66 mol) was added at one time. The mixture was stirred for 1 hour while maintaining the temperature at 20 ° C. After that, 120m of water cooled to 5 ° C
1 time, the precipitated crystals were filtered and dried,
-Diamino-3- (phenylthio) acrylonitrile 1
4.5 g were obtained. Decomposition point 66-68 ° C.
【００１５】比較例１ ジフェニルジスルフィド２ｇ、アセトニトリル５０ｍ
ｌ、トリエチルアミン６ｇをフラスコに仕込み、攪拌下
約１０℃に冷却した。これにシアン化水素２０ｍｌを一
時に加えた。温度を２０℃に保ちつつ１時間攪拌した。
その後、反応液を減圧下に保ち、トリエチルアミンおよ
びアセトニトリルの一部を留去した後、ｐ−トルエンス
ルホン酸を３ｇ添加した。析出した結晶を濾取し、ｎ−
ヘキサンで洗浄した後真空乾燥し、１．２ｇの２，３−
ジアミノ−３−（フェニルチオ）アクリロニトリルのｐ
−トルエンスルホン酸塩を得た。Comparative Example 1 Diphenyl disulfide 2 g, acetonitrile 50 m
1 and 6 g of triethylamine were placed in a flask and cooled to about 10 ° C. with stirring. To this, 20 ml of hydrogen cyanide was added at once. The mixture was stirred for 1 hour while maintaining the temperature at 20 ° C.
Then, the reaction liquid was kept under reduced pressure, and after triethylamine and a part of acetonitrile were distilled off, 3 g of p-toluenesulfonic acid was added. The precipitated crystals were collected by filtration and n-
After washing with hexane and vacuum drying, 1.2 g of 2,3-
P of diamino-3- (phenylthio) acrylonitrile
-Toluenesulfonate was obtained.
【００１６】[0016]
【発明の効果】本発明の製造方法は、従来行われてい
た、塩基の除去、ｐ−トルエンスルホン酸の添加反応等
の繁雑な工程が省略できかつ、これらの工程で分解等に
より損失していた部分を少なくでき、高収率、短時間で
工業的に有利に２，３−ジアミノアクリロニトリル誘導
体を得る事が出来る。EFFECTS OF THE INVENTION In the production method of the present invention, complicated steps such as removal of base and addition reaction of p-toluenesulfonic acid, which have been conventionally performed, can be omitted, and loss occurs due to decomposition or the like in these steps. It is possible to obtain a 2,3-diaminoacrylonitrile derivative industrially advantageously in a high yield and in a short time by reducing the number of parts.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 黒石 義徳 岡山県倉敷市児島塩生字新浜2767−12 日 本曹達株式会社水島工場内 (72)発明者 田元 義浩 岡山県倉敷市児島塩生字新浜2767−12 日 本曹達株式会社水島工場内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yoshinori Kuroishi 2767-12 Niihama Shiojima Kojima, Kurashiki-shi, Okayama Nihon Soda Co., Ltd. Mizushima Plant (72) Yoshihiro Tamoto 2767 Niihama Shiojima Kojima, Kurashiki-shi, Okayama Prefecture −12 Nihon Soda Co., Ltd., Mizushima Plant
Claims (1)
Ｈ（式中Ｒはアリール基、アルキル基、アラルキル基ま
たはアルケニル基を示す。）で表される化合物とを、難
水溶性の溶媒中、塩基の存在下反応させた後水を添加し
て目的物を析出させる事を特徴とする、一般式［Ｉ］ 【化１】 （式中、Ｒは前記と同じ意味を示す。）で表される２，
３−ジアミノアクリロニトリル誘導体の製造方法。1. Hydrogen cyanide and the general formula RSSR or RS
A compound represented by H (in the formula, R represents an aryl group, an alkyl group, an aralkyl group or an alkenyl group) is reacted in a poorly water-soluble solvent in the presence of a base, and water is then added. [I] embedded image characterized by depositing a substance (In the formula, R has the same meaning as described above.) 2,
Process for producing 3-diaminoacrylonitrile derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03127696A JP3845848B2 (en) | 1996-01-25 | 1996-01-25 | Method for producing 2,3-diaminoacrylonitrile derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03127696A JP3845848B2 (en) | 1996-01-25 | 1996-01-25 | Method for producing 2,3-diaminoacrylonitrile derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09202765A true JPH09202765A (en) | 1997-08-05 |
| JP3845848B2 JP3845848B2 (en) | 2006-11-15 |
Family
ID=12326810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03127696A Expired - Lifetime JP3845848B2 (en) | 1996-01-25 | 1996-01-25 | Method for producing 2,3-diaminoacrylonitrile derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3845848B2 (en) |
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| US8664392B2 (en) | 2004-12-23 | 2014-03-04 | Medibeacon, LLC | Pyrazine derivatives for bioconjugation |
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-
1996
- 1996-01-25 JP JP03127696A patent/JP3845848B2/en not_active Expired - Lifetime
Cited By (11)
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|---|---|---|---|---|
| US8664392B2 (en) | 2004-12-23 | 2014-03-04 | Medibeacon, LLC | Pyrazine derivatives for bioconjugation |
| US8778309B2 (en) | 2004-12-23 | 2014-07-15 | Medibeacon Llc | Fluorescent pyrazine derivatives and methods of using the same in assessing renal function |
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| US9376399B2 (en) | 2004-12-23 | 2016-06-28 | Medibeacon Llc | Fluorescent pyrazine derivatives and methods of using the same in assessing renal function |
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| US8115000B2 (en) | 2006-06-22 | 2012-02-14 | Mallinckrodt Llc | Pyrazine derivatives and uses thereof in renal monitoring |
| US9216963B2 (en) | 2006-06-22 | 2015-12-22 | Medibeacon Inc. | Pyrazine derivatives with extended conjugation and methods of using the same in optical applications |
| US10370362B2 (en) | 2006-06-22 | 2019-08-06 | Medibeacon Inc. | Pyrazine derivatives with extended conjugation and methods of using the same in optical applications |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3845848B2 (en) | 2006-11-15 |
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