JPS645592B2 - - Google Patents
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- Publication number
- JPS645592B2 JPS645592B2 JP15807681A JP15807681A JPS645592B2 JP S645592 B2 JPS645592 B2 JP S645592B2 JP 15807681 A JP15807681 A JP 15807681A JP 15807681 A JP15807681 A JP 15807681A JP S645592 B2 JPS645592 B2 JP S645592B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- mixture
- carbon atoms
- formula
- added
- 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.)
- Expired
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- KDBUUJSOUXNTOE-UHFFFAOYSA-N 2-bromopropanediamide Chemical compound NC(=O)C(Br)C(N)=O KDBUUJSOUXNTOE-UHFFFAOYSA-N 0.000 claims description 16
- -1 cyanoformate ester Chemical class 0.000 claims description 16
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 15
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 15
- 239000001119 stannous chloride Substances 0.000 claims description 15
- 235000011150 stannous chloride Nutrition 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- TUZVMPXGFZSNBG-UHFFFAOYSA-N 3-aminopyrrole-2,5-dione Chemical compound NC1=CC(=O)NC1=O TUZVMPXGFZSNBG-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 33
- 239000000203 mixture Substances 0.000 description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 239000013078 crystal Substances 0.000 description 18
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 15
- 239000012044 organic layer Substances 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- MSMGXWFHBSCQFB-UHFFFAOYSA-N ethyl cyanoformate Chemical compound CCOC(=O)C#N MSMGXWFHBSCQFB-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- QTQZTRTXGIDTMP-UHFFFAOYSA-N 2-bromo-N,N'-dimethylpropanediamide Chemical compound CNC(C(C(=O)NC)Br)=O QTQZTRTXGIDTMP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- HJMZMZRCABDKKV-UHFFFAOYSA-M cyanoformate Chemical compound [O-]C(=O)C#N HJMZMZRCABDKKV-UHFFFAOYSA-M 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- XHXOLHROLSADIX-UHFFFAOYSA-N n,n'-dibenzyl-2-bromopropanediamide Chemical compound C=1C=CC=CC=1CNC(=O)C(Br)C(=O)NCC1=CC=CC=C1 XHXOLHROLSADIX-UHFFFAOYSA-N 0.000 description 2
- YYAQOJILQOVUSK-UHFFFAOYSA-N n,n'-diphenylpropanediamide Chemical compound C=1C=CC=CC=1NC(=O)CC(=O)NC1=CC=CC=C1 YYAQOJILQOVUSK-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- ODOJAEHIIFIICL-UHFFFAOYSA-N 2-bromo-N,N'-diethylpropanediamide Chemical compound C(C)NC(C(C(=O)NCC)Br)=O ODOJAEHIIFIICL-UHFFFAOYSA-N 0.000 description 1
- SAHJOSKPGKTZTC-UHFFFAOYSA-N 5h-pyrrolo[3,4-d]pyrimidine Chemical compound C1=NC=C2CN=CC2=N1 SAHJOSKPGKTZTC-UHFFFAOYSA-N 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 1
- 241000221785 Erysiphales Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IDRIISKVLZHPDP-UHFFFAOYSA-N butyl cyanoformate Chemical compound CCCCOC(=O)C#N IDRIISKVLZHPDP-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- OBWFJXLKRAFEDI-UHFFFAOYSA-N methyl cyanoformate Chemical compound COC(=O)C#N OBWFJXLKRAFEDI-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- KEWOIBUJAMSMSU-UHFFFAOYSA-N propyl cyanoformate Chemical compound CCCOC(=O)C#N KEWOIBUJAMSMSU-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pyrrole Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
この発明は、新規化合物であるアミノマレイミ
ド類の製造法である。さらに詳しくは、この発明
は、
式 N≡C−COOR1 〔〕
(式中、R1は炭素数1〜4のアルキル基を示
す。)で表わされるシアノギ酸エステルと、
式
〔式中、R2は水素原子、炭素数1〜4のアルキ
ル基、炭素数2〜4のアルケニル基、炭素数5〜
7のシクロアルキル基、炭素数7〜10のアラルキ
ル基、または
This invention is a method for producing aminomaleimides, which are new compounds. More specifically, the present invention provides a cyanoformic acid ester represented by the formula N≡C-COOR 1 [] (wherein R 1 represents an alkyl group having 1 to 4 carbon atoms); [In the formula, R 2 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkenyl group having 5 to 4 carbon atoms.
7 cycloalkyl group, C7-10 aralkyl group, or
【式】(R3は炭素数1〜
4のアルキル基、炭素数1〜4のアルコキシ基、
またはハロゲン原子を示し、nは0、1、2また
は3である。)で表わされる基を示す。〕で表わさ
れるブロモマロンアミド類とを、塩化第一スズの
存在下に反応させ、ついで得られる反応生成物を
水または酸性水溶液で処理することを特徴とする
式
(式中、R2は前記と同じ意味を有する。)で表わ
されるアミノマレイミド類の製造法である。
式〔〕で表わされるアミノマレイミド類は、
新規化合物であり、医薬、農薬さらにはこれらの
中間体として有用である。特に、イネ白葉枯病お
よびキユウリうどん粉病に対する農園芸用殺菌剤
として有用である。
式〔〕で表わされるシアノギ酸エステルの具
体例としては、シアノギ酸メチル、シアノギ酸エ
チル、シアノギ酸プロピル、シアノギ酸ブチルな
どが挙げられる。
式〔〕で表わされるブロモマロンアミド類の
具体例としては、ブロモマロンアミド、N,
N′−ジメチルブロモマロンアミド、N,N′−ジ
エチルブロモマロンアミド、N,N′−ジプロピ
ルブロモマロンアミド、N,N′−ジブチルブロ
モマロンアミド、N,N′−ジアリルブロモマロ
ンアミド、N,N′−ジシクロヘキシルブロモマ
ロンアミド、N,N′−ジベンジルブロモマロン
アミド、ブロモマロンアニリド、ブロモマロント
ルイド、ブロモマロンクロロアニリド、ブロモマ
ロンジクロロアニリド、ブロモマロンジアニシド
などが挙げられる。
この発明の方法におけるシアノギ酸エステル、
ブロモマロンアミド類、および塩化第一スズとの
反応は、溶媒を用いて行なうことが好ましい。溶
媒としては、この発明の方法における反応の不活
性なものであればどのようなものでもよく、たと
えばベンゼン、トルエン、クロロベンゼン、ジク
ロロベンゼンなどの芳香族炭化水素、塩化メチレ
ン、クロロホルム、四塩化炭素、塩化エチレンな
どのハロゲン化炭化水素、ジエチルエーテル、ジ
ブチルエーテル、テトラヒドロフランなどのエー
テル類が挙げられる。ただし、前記芳香族炭化水
素およびハロゲン化炭化水素を溶媒として使用し
た場合に反応が遅くなることがあり、このような
場合には、前記エーテル類を共存させて反応を行
なうか、これを溶媒として用いて反応を行なうこ
とが好ましい。なお、溶媒は反応に先立ち十分に
脱水しておくのが望ましい。
シアノギ酸エステルの使用量は、ブロモマロン
アミド類の使用量に対して等モル量以上であるこ
とが好ましい。ブロモマロンアミド類の使用量に
対して等モル量より少ないシアノギ酸エステルの
使用は、副生成物が生ずる原因となるので好まし
くない。
塩化第一スズの使用量は、ブロモマロンアミド
類の使用量と等モル量であるが、これに限ること
はなく、前記の量よりも過剰モル量用いてもさし
つかえない。
シアノギ酸エステル、ブロモマロンアミド類お
よび塩化第一スズの反応は、実質的に無水の条件
下で、シアノギ酸エステルとブロモマロンアミド
類と塩化第一スズとを所定温度および所定時間接
触させることができれば、いかなる方法でもよ
い。また、前記三者の混合はいかなる順序で行な
つてもよい。
シアノギ酸エステルとブロモマロンアミド類と
塩化第一スズとの反応の温度は、余り高い温度で
反応を行なうと最終の目的生成物の収率が低下す
るので、一般には−10〜100℃の範囲の温度であ
るのが好ましい。
反応時間は、使用する原料の種類、反応温度な
どによつて種々異なるが、一般には0.5〜50時間
である。
目的生成物であるアミノマレイミド類は、反応
後に得られる反応生成物を水または酸性水溶液で
処理することによつて、単離することができる。
水の使用量は、使用したブロモマロンアミド1
ミリモル当り0.2〜5mlである。
酸性水溶液としては、たとえば塩酸、硫酸など
の鉱酸や、パラトルエンスルホン酸のような有機
酸の希薄水溶液が挙げられる。酸性水溶液の使用
量は、通常、使用したブロモマロンアミド1ミリ
モル当り、1ミリグラム当量の酸を含む水溶液
0.2〜5mlである。
水または酸性水溶液で反応生成物を処理する温
度は、通常0〜30℃であり、また処理時間は、通
常1時間で十分である。
処理方法としては、たとえば、前記反応に溶媒
としてベンゼンのような水と混和しない溶媒を用
いたときは、反応生成物を含む反応液に直接水ま
たは酸性水溶液を添加し、前記温度で前記時間撹
拌混合するだけでよく、また前記反応に溶媒とし
てテトラヒドロフランのような水と混和する溶媒
を用いたときは、反応生成物を含む反応液から蒸
留などにより溶媒を除去した残渣に直接、あるい
は水と混和しない溶媒を加えたのち、水または酸
性水溶液を添加し、前記温度で前記時間撹拌混合
するだけでよい。
前記処理によつて、この発明の目的生成物であ
るアミノマレイミド類を含む処理液が得られる。
アミノマレイミド類が不溶物として存在する場
合、処理液を過することによつてアミノマレイ
ミド類を単離することができる。アミノマレイミ
ド類が前記有機溶媒中に溶解して存在する場合に
は、処理液を水層と有機層とに分離し、得られる
有機層から公知の単離方法によつてアミノマレイ
ミド類を単離することができる。
この発明によつて得られるアミノマレイミドと
しては、3−アミノ−4−カルバモイルマレイミ
ド、3−アミノ−1−メチル−4−(メチルカル
バモイル)マレイミド、3−アミノ−1−エチル
−4−(エチルカルバモイル)マレイミド、3−
アミノ−1−プロピル−4−(プロピルカルバモ
イル)マレイミド、3−アミノ−1−ブチル−4
−(ブチルカルバモイル)マレイミド、1−アリ
ル−3−(アリルカルバモイル)−4−アミノマレ
イミド、3−アミノ−1−シクロヘキシル−4−
(シクロヘキシルカルバモイル)マレイミド、3
−アミノ−1−ベンジル−4−(ベンジルカルバ
モイル)マレイミド、3−アミノ−1−フエニル
−4−(フエニルカルバモイル)マレイミド、3
−アミノ−1−トリル−4−(トリルカルバモイ
ル)マレイミド、3−アミノ−1−クロロフエニ
ル−4−(クロロフエニルカルバモイル)マレイ
ミド、3−アミノ−1−ジクロロフエニル−4−
(ジクロロフエニルカルバモイル)マレイミド、
3−アミノ−1−アニシル−4−(アニシルカル
バモイル)マレイミドなどが挙げられる。
つぎに実施例を示す。実施例において、アミノ
マレイミドの収率は、使用したブロモマロンアミ
ド基準の収率である。
実施例 1
塩化第一スズ2.28gとシアノギ酸エチル1.98g
とをテトラヒドロフラン50mlに加えて得た溶液を
撹拌しながら、これに室温でブロモマロンアミド
1.81gを加え、混合すると、混合物は黄色を呈
し、混合物の温度は25℃から34.5℃まで上昇し
た。混合物を室温で撹拌しながら16時間反応を行
なつた。
反応後、反応混合物を減圧下に濃縮して得た残
渣に水20mlを加えて過し、3−アミノ−4−カ
ルバモイルマレイミドの結晶1.45g(収率:94
%)を得た。これを水で再結晶して、分解点300
℃の微黄色針状結晶を得た。その元素分析値をつ
ぎに示す。
C H N
分析値 38.43 3.30 27.20
計算値 38.72 3.25 27.10
(C5H5N3O3として)
実施例 2
シアノギ酸エチル1.98gを塩化メチレン50mlに
溶解して得た溶液を室温で撹拌しながら、これに
室温で塩化第一スズ2.28gを加え、ついでブロモ
マロンアミド1.81gを加え、混合した。混合物を
加熱して、還流下に9時間反応を行なつたが、混
合物のガスクロマトグラフイー分析よりシアノギ
酸エチルはほとんど消費されていなかつた。混合
物にテトラヒドロフラン10mlを加え、再び混合物
を加熱して、還流下に7時間反応を行なつた。
反応後、得られた反応生成物に、室温で2規定
塩酸5mlと水20mlを加え、室温で1時間の撹拌に
よつて得られた反応混合物を過して、微黄色結
晶1.66gを得た。これを水200mlで再結晶して、
3−アミノ−4−カルバモイルマレイミドの微黄
色微針状結晶1.11g(収率:72%)を得た。
実施例 3
減圧下、100℃で乾燥した塩化第一スズ2.28g
に塩化エチレン25mlを加えて得た懸濁液を撹拌し
ながら、これに室温でシアノギ酸エチル0.99gを
塩化エチレン25mlに溶解した溶液を滴下し、つい
でブロモマロンアニリド3.33gを加え、混合する
と、混合物は黄色を呈し、混合物の温度は25℃か
ら35.5℃まで上昇した。混合物を室温で撹拌しな
がら、1日反応を行なつた。
反応後、反応混合物を寒剤(氷−食塩)で冷却
しながら、これに水30mlを加え、寒剤冷却下に1
時間の撹拌によつて得られた混合物を過して、
マロンアニリドの結晶0.60gを得た。液を水層
と有機層とに分液し、有機層を減圧下に濃縮して
得た残渣にエタノール10mlを加え、過して、3
−アミノ−1−フエニル−4−(フエニルカルバ
モイル)マレイミドの結晶1.05g(収率:34%)
を得た。これを塩化エチレンで再結晶して、融点
210〜211℃の黄色結晶を得た。その元素分析値を
つぎに示す。
C H N
分析値 66.76 4.45 13.44
計算値 66.44 4.26 13.67
(C17H13N3O3として)
実施例 4
シアノギ酸エチル1.98gを塩化メチレン50mlに
溶解して得た溶液を室温で撹拌しながら、これに
室温で塩化第一スズ2.28gを加え、ついでブロモ
マロンアニリド3.33gを加え、混合すると、混合
物は黄橙色を呈し、混合物の温度は26.5℃から
33.5℃まで上昇した。混合物を室温で撹拌しなが
ら、1日間反応を行なつた。
反応後、混合物に室温で水20mlを加え、室温で
30分間の撹拌によつて得られた反応混合物を過
して、マロンアニリドの結晶0.74gを得た。液
を水層と有機層とに分液し、有機層を無水硫酸ナ
トリウムで乾燥した後、減圧下に濃縮して、3−
アミノ−1−フエニル−4−(フエニルカルバモ
イル)マレイミドの粗結晶2.39g(収率:78%)
を得た。これをエタノール280mlで再結晶して、
3−アミノ−1−フエニル−4−(フエニルカル
バモイル)マレイミドの純粋な黄色針状結晶1.28
g(収率:42%)を得た。
実施例 5
塩化第一スズ2.28gとシアノギ酸エチル1.98g
とをテトラヒドロフラン50mlに加えて得た溶液を
撹拌しながら、これに室温でN,N′−ジメチル
ブロモマロンアミド2.09gを加え、混合すると、
混合物は黄色を呈し、混合物の温度は26℃から
36.5℃まで上昇した。混合物を加熱して、還流下
に1.5時間反応を行なつた。
反応後、反応混合物を減圧下に濃縮して得た残
渣に塩化エチレン50mlと水30mlを加えて過し、
3−アミノ−1−メチル−4−(メチルカルバモ
イル)マレイミドの結晶0.81g(収率:44%)を
得た。これをメタノールで再結晶して、融点276
〜277℃の黄色針状結晶を得た。その元素分析値
をつぎに示す。
C H N
分析値 45.92 5.01 23.10
計算値 45.90 4.95 22.94
(C7H9N3O3として)
実施例 6
塩化第一スズ2.28gとシアノギ酸エチル1.98g
とをテトラヒドロフラン50mlに加えて得た溶液を
撹拌しながら、これに室温でN,N′−ジベンジ
ルブロモマロンアミド3.61gを加え、混合する
と、混合物は黄色を呈し、混合物の温度は27℃か
ら37℃まで上昇した。混合物を室温で撹拌しなが
ら21時間反応を行なつた。
反応後、反応混合物を減圧下に濃縮して得た残
渣に塩化メチレン50mlと水30mlを加え、有機層と
水層とに分液した。有機層を無水硫酸ナトリウム
で乾燥した後、減圧下に濃縮した。残渣にエタノ
ール20mlを加えて過し、3−アミノ−1−ベン
ジル−4−(ベンジルカルバモイル)マレイミド
の結晶2.66g(収率:79%)を得た。これをベン
ゼンで再結晶して、融点129〜129.5℃の黄色塊状
結晶を得た。その元素分析値をつぎに示す。
C H N
分析値 68.27 5.05 12.56
計算値 68.05 5.10 12.53
(C19H17N3O3として)
実施例 7
塩化第一スズ2.28gとシアノギ酸エチル1.98g
とをテトラヒドロフラン50mlに加えて得た溶液を
撹拌しながら、これに室温でN,N′−ジアリル
ブロモマロンアミド2.39gを加え、混合すると、
混合物は黄色を呈し、混合物の温度は28℃から35
℃まで上昇した。混合物を室温で撹拌しながら1
日反応を行なつた。
反応後、反応混合物を減圧下に濃縮して得た残
渣にベンゼン50mlと水20mlを加え、有機層と水層
とに分液した。有機層を無水硫酸ナトリウムで乾
燥した後、減圧下に濃縮した。残渣の結晶を熱イ
ソプロピルエーテル130mlで抽出して得た溶液を、
減圧下に濃縮して、1−アリル−3−(アリルカ
ルバモイル)−4−アミノマレイミドの結晶1.13
g(収率:53%)を得た。これをイソプロピルエ
ーテルで再結晶して、融点94〜95℃の黄色針状結
晶を得た。その元素分析値をつぎに示す。
C H N
分析値 56.33 5.62 18.02
計算値 56.16 5.57 17.86
(C11H13N3O3として)
実施例 8
塩化第一スズ2.28gとシアノギ酸エチル1.98g
を含むテトラヒドロフラン50mlに、室温でN,
N′−ジシクロヘキシルブロモマロンアミド3.45g
を加え、混合すると、混合物は黄色を呈し、混合
物の温度は27℃から35℃まで上昇した。混合物を
室温で撹拌しながら、1日反応させた。
反応後、反応混合物を減圧下に濃縮した。残渣
にベンゼン50mlと水30mlを加え、有機層と水層と
に分液した。有機層を無水硫酸ナトリウムで乾燥
したのち、減圧下に濃縮した。残渣を、シリカゲ
ル(ワコーゲルC−200、70g)を詰めたカラム
(直径25mm)に通し、ベンゼンと酢酸エチルとの
容量比9:1の混合溶媒で溶離した。溶媒350ml
で溶出して得た溶液を、減圧下に濃縮して、3−
アミノ−1−シクロヘキシル−4−(シクロヘキ
シルカルバモイル)マレイミドの黄色カルメラ
2.72g(収率:85%)を得た。
この物質は、ピリジン存在下にクロロギ酸トリ
クロロメチルエステルと反応させて、3,6−ジ
シクロヘキシル−2−ヒドロキシ−3,4,6,
7−テトラヒドロ−4,5,7−トリオキソ−
5H−ピロロ〔3,4−d〕ピリミジンに変換す
ることによつて確認した。
上記反応で得た3−アミノ−1−シクロヘキシ
ル−4−(シクロヘキシルカルバモイル)マレイ
ミドの黄色カルメラ2.72gに、室温でピリジン
3.37gを含む塩化エチレン70mlを加えたのち、寒
剤(氷−食塩)冷却下、クロロギ酸トリクロロメ
チルエステル2.27gを含む塩化エチレン20mlを滴
下した。滴下後、混合物を室温で撹拌しながら、
1日反応させた。
反応後、得られた反応生成混合物に、室温で水
50mlを加えて過し、3,6−ジシクロヘキシル
−2−ヒドロキシ−3,4,6,7−テトラヒド
ロ−4,5,7−トリオキソ−5H−ピロロ〔3,
4−d〕ピリミジンの結晶1.35gを得た。液を
水層と有機層とに分液し、有機層を無水硫酸ナト
リウムで乾燥した後、減圧下に濃縮した。残渣を
ジオキサンで再結晶して、3,6−ジシクロヘキ
シル−2−ヒドロキシ−3,4,6,7−テトラ
ヒドロ−4,5,7−トリオキソ−5H−ピロロ
〔3,4−d〕ピリミジンとジオキサンとのモル
比2:1の付加物0.51g(分解点290℃)を得た。
その元素分析値をつぎに示す。
C H N
分析値 61.84 7.22 11.19
計算値 61.68 6.99 10.79
(C18H23N3O4・1/2C4H8O2として)[Formula] (R 3 is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms,
or represents a halogen atom, and n is 0, 1, 2 or 3. ) represents a group. ] is reacted with a bromomalonamide represented by the formula in the presence of stannous chloride, and then the resulting reaction product is treated with water or an acidic aqueous solution. (In the formula, R 2 has the same meaning as above.) This is a method for producing aminomaleimides represented by the formula. Aminomaleimides represented by the formula [] are
It is a new compound and is useful as a medicine, agrochemical, and an intermediate thereof. It is particularly useful as an agricultural and horticultural fungicide against rice blight and cucumber powdery mildew. Specific examples of the cyanoformate represented by the formula [] include methyl cyanoformate, ethyl cyanoformate, propyl cyanoformate, butyl cyanoformate, and the like. Specific examples of bromomalonamides represented by formula [] include bromomalonamide, N,
N'-dimethylbromomalonamide, N,N'-diethylbromomalonamide, N,N'-dipropylbromomalonamide, N,N'-dibutylbromomalonamide, N,N'-diallylbromomalonamide, N , N'-dicyclohexylbromomalonamide, N,N'-dibenzylbromomalonamide, bromomalonanilide, bromomalon toluide, bromomalon chloroanilide, bromomalon dichloroanilide, bromomalon dianiside, and the like. Cyanoformic acid ester in the method of this invention,
The reaction with bromomalonamides and stannous chloride is preferably carried out using a solvent. Any solvent may be used as long as it is inert to the reaction in the method of the present invention, such as aromatic hydrocarbons such as benzene, toluene, chlorobenzene, and dichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, Examples include halogenated hydrocarbons such as ethylene chloride, and ethers such as diethyl ether, dibutyl ether, and tetrahydrofuran. However, when the above-mentioned aromatic hydrocarbons and halogenated hydrocarbons are used as a solvent, the reaction may become slow. In such cases, the reaction may be carried out in the presence of the above-mentioned ethers, or when this is used as a solvent. It is preferable to carry out the reaction using Note that it is desirable that the solvent be sufficiently dehydrated prior to the reaction. The amount of cyanoformate used is preferably equal to or more than the amount of bromomalonamide used. It is not preferable to use less than an equimolar amount of cyanoformic acid ester with respect to the amount of bromomalonamide used, since this may cause formation of by-products. The amount of stannous chloride used is equimolar to the amount of bromomalonamides used, but is not limited to this, and may be used in an excess molar amount than the above amount. The reaction of the cyanoformic acid ester, the bromomalonamides, and the stannous chloride can be carried out by bringing the cyanoformic acid ester, the bromomalonamide, and the stannous chloride into contact with each other at a predetermined temperature and for a predetermined time under substantially anhydrous conditions. Any method is fine if possible. Further, the above three components may be mixed in any order. The temperature for the reaction of cyanoformic acid ester, bromomalonamide, and stannous chloride is generally in the range of -10 to 100°C, since the yield of the final target product will decrease if the reaction is carried out at too high a temperature. Preferably, the temperature is . The reaction time varies depending on the type of raw materials used, reaction temperature, etc., but is generally 0.5 to 50 hours. The desired product, aminomaleimide, can be isolated by treating the reaction product obtained after the reaction with water or an acidic aqueous solution. The amount of water used is 1 bromomalonamide used.
0.2 to 5 ml per mmol. Examples of the acidic aqueous solution include dilute aqueous solutions of mineral acids such as hydrochloric acid and sulfuric acid, and organic acids such as para-toluenesulfonic acid. The amount of acidic aqueous solution used is usually an aqueous solution containing 1 milligram equivalent of acid per 1 millimol of bromomalonamide used.
The amount is 0.2 to 5 ml. The temperature at which the reaction product is treated with water or an acidic aqueous solution is usually 0 to 30°C, and the treatment time is usually 1 hour. As a treatment method, for example, when a water-immiscible solvent such as benzene is used as a solvent in the above reaction, water or an acidic aqueous solution is directly added to the reaction solution containing the reaction product, and the mixture is stirred at the above temperature for the above period of time. When a water-miscible solvent such as tetrahydrofuran is used as a solvent in the above reaction, the solvent may be removed directly from the reaction solution containing the reaction product by distillation, etc., or mixed with water. It is sufficient to simply add water or an acidic aqueous solution and stir and mix at the above temperature for the above period of time. Through the above treatment, a treatment solution containing aminomaleimides, which are the target products of the present invention, is obtained.
When the aminomaleimide is present as an insoluble substance, the aminomaleimide can be isolated by passing the treated solution. When the aminomaleimides are dissolved in the organic solvent, the treated liquid is separated into an aqueous layer and an organic layer, and the aminomaleimides are isolated from the resulting organic layer by a known isolation method. can do. The aminomaleimide obtained by this invention includes 3-amino-4-carbamoylmaleimide, 3-amino-1-methyl-4-(methylcarbamoyl)maleimide, 3-amino-1-ethyl-4-(ethylcarbamoyl) ) Maleimide, 3-
Amino-1-propyl-4-(propylcarbamoyl)maleimide, 3-amino-1-butyl-4
-(Butylcarbamoyl)maleimide, 1-allyl-3-(allylcarbamoyl)-4-aminomaleimide, 3-amino-1-cyclohexyl-4-
(cyclohexylcarbamoyl)maleimide, 3
-Amino-1-benzyl-4-(benzylcarbamoyl)maleimide, 3-amino-1-phenyl-4-(phenylcarbamoyl)maleimide, 3
-Amino-1-tolyl-4-(tolylcarbamoyl)maleimide, 3-amino-1-chlorophenyl-4-(chlorophenylcarbamoyl)maleimide, 3-amino-1-dichlorophenyl-4-
(dichlorophenylcarbamoyl)maleimide,
Examples include 3-amino-1-anisyl-4-(anisylcarbamoyl)maleimide. Next, examples will be shown. In the Examples, the yield of aminomaleimide is the yield based on the bromomalonamide used. Example 1 2.28 g of stannous chloride and 1.98 g of ethyl cyanoformate
Add bromomalonamide to 50 ml of tetrahydrofuran at room temperature while stirring the solution obtained.
When 1.81 g was added and mixed, the mixture turned yellow and the temperature of the mixture rose from 25°C to 34.5°C. The reaction was carried out for 16 hours while stirring the mixture at room temperature. After the reaction, the reaction mixture was concentrated under reduced pressure, and 20 ml of water was added to the resulting residue, which was filtered to give 1.45 g of crystals of 3-amino-4-carbamoylmaleimide (yield: 94
%) was obtained. Recrystallize this with water to reach a decomposition point of 300.
Pale yellow needle-shaped crystals at ℃ were obtained. The elemental analysis values are shown below. C H N Analytical value 38.43 3.30 27.20 Calculated value 38.72 3.25 27.10 (as C 5 H 5 N 3 O 3 ) Example 2 A solution obtained by dissolving 1.98 g of ethyl cyanoformate in 50 ml of methylene chloride was stirred at room temperature. To this, 2.28 g of stannous chloride was added at room temperature, and then 1.81 g of bromomalonamide was added and mixed. The mixture was heated and reacted under reflux for 9 hours, but gas chromatography analysis of the mixture showed that ethyl cyanoformate was hardly consumed. 10 ml of tetrahydrofuran was added to the mixture, and the mixture was heated again to carry out the reaction under reflux for 7 hours. After the reaction, 5 ml of 2N hydrochloric acid and 20 ml of water were added to the obtained reaction product at room temperature, and the reaction mixture was filtered by stirring at room temperature for 1 hour to obtain 1.66 g of pale yellow crystals. . Recrystallize this with 200ml of water,
1.11 g (yield: 72%) of pale yellow fine needle crystals of 3-amino-4-carbamoylmaleimide were obtained. Example 3 2.28 g of stannous chloride dried at 100°C under reduced pressure
While stirring the suspension obtained by adding 25 ml of ethylene chloride to the suspension, a solution of 0.99 g of ethyl cyanoformate dissolved in 25 ml of ethylene chloride was added dropwise at room temperature, and then 3.33 g of bromomalonanilide was added and mixed. The mixture took on a yellow color and the temperature of the mixture increased from 25°C to 35.5°C. The reaction was carried out for one day while stirring the mixture at room temperature. After the reaction, 30 ml of water was added to the reaction mixture while cooling it with a cryogen (ice-salt), and the mixture was cooled with a cryogen (ice-salt) for 1 hour.
Filter the mixture obtained by stirring for an hour.
0.60 g of malonanilide crystals were obtained. The liquid was separated into an aqueous layer and an organic layer, and the organic layer was concentrated under reduced pressure. To the resulting residue, 10 ml of ethanol was added, filtered, and
-Amino-1-phenyl-4-(phenylcarbamoyl)maleimide crystals 1.05g (yield: 34%)
I got it. This was recrystallized with ethylene chloride to obtain a melting point of
Yellow crystals were obtained at 210-211°C. The elemental analysis values are shown below. C H N Analytical value 66.76 4.45 13.44 Calculated value 66.44 4.26 13.67 (as C 17 H 13 N 3 O 3 ) Example 4 A solution obtained by dissolving 1.98 g of ethyl cyanoformate in 50 ml of methylene chloride was stirred at room temperature. To this, 2.28 g of stannous chloride was added at room temperature, and then 3.33 g of bromomalonanilide was added and mixed.
The temperature rose to 33.5℃. The reaction was carried out for 1 day while stirring the mixture at room temperature. After the reaction, add 20ml of water to the mixture at room temperature.
The reaction mixture obtained by stirring for 30 minutes was filtered to obtain 0.74 g of malonanilide crystals. The liquid was separated into an aqueous layer and an organic layer, and the organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and 3-
2.39 g of crude crystals of amino-1-phenyl-4-(phenylcarbamoyl)maleimide (yield: 78%)
I got it. This was recrystallized with 280ml of ethanol,
Pure yellow needle crystals of 3-amino-1-phenyl-4-(phenylcarbamoyl)maleimide 1.28
g (yield: 42%) was obtained. Example 5 2.28 g of stannous chloride and 1.98 g of ethyl cyanoformate
was added to 50 ml of tetrahydrofuran. While stirring, 2.09 g of N,N'-dimethylbromomalonamide was added at room temperature and mixed.
The mixture has a yellow color and the temperature of the mixture is from 26℃
The temperature rose to 36.5℃. The mixture was heated and the reaction was carried out under reflux for 1.5 hours. After the reaction, the reaction mixture was concentrated under reduced pressure and the resulting residue was filtered by adding 50 ml of ethylene chloride and 30 ml of water.
0.81 g (yield: 44%) of crystals of 3-amino-1-methyl-4-(methylcarbamoyl)maleimide was obtained. This was recrystallized from methanol and had a melting point of 276.
Yellow needle-shaped crystals at ~277°C were obtained. The elemental analysis values are shown below. C H N Analytical value 45.92 5.01 23.10 Calculated value 45.90 4.95 22.94 (as C 7 H 9 N 3 O 3 ) Example 6 2.28 g of stannous chloride and 1.98 g of ethyl cyanoformate
was added to 50 ml of tetrahydrofuran, and 3.61 g of N,N'-dibenzylbromomalonamide was added at room temperature while stirring, and the mixture turned yellow and the temperature of the mixture increased from 27°C. The temperature rose to 37℃. The reaction was carried out for 21 hours while stirring the mixture at room temperature. After the reaction, the reaction mixture was concentrated under reduced pressure, and to the resulting residue were added 50 ml of methylene chloride and 30 ml of water, and the layers were separated into an organic layer and an aqueous layer. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. 20 ml of ethanol was added to the residue and filtered to obtain 2.66 g (yield: 79%) of crystals of 3-amino-1-benzyl-4-(benzylcarbamoyl)maleimide. This was recrystallized from benzene to obtain yellow bulk crystals with a melting point of 129-129.5°C. The elemental analysis values are shown below. C H N Analytical value 68.27 5.05 12.56 Calculated value 68.05 5.10 12.53 (as C 19 H 17 N 3 O 3 ) Example 7 2.28 g of stannous chloride and 1.98 g of ethyl cyanoformate
was added to 50 ml of tetrahydrofuran. While stirring, 2.39 g of N,N'-diallylbromomalonamide was added at room temperature and mixed.
The mixture takes on a yellow color and the temperature of the mixture ranges from 28℃ to 35℃.
The temperature rose to ℃. 1 while stirring the mixture at room temperature.
A day reaction was carried out. After the reaction, the reaction mixture was concentrated under reduced pressure, and to the resulting residue were added 50 ml of benzene and 20 ml of water, and the layers were separated into an organic layer and an aqueous layer. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The solution obtained by extracting the residual crystals with 130 ml of hot isopropyl ether,
Concentrate under reduced pressure to give 1.13 crystals of 1-allyl-3-(allylcarbamoyl)-4-aminomaleimide.
g (yield: 53%) was obtained. This was recrystallized from isopropyl ether to obtain yellow needle crystals with a melting point of 94-95°C. The elemental analysis values are shown below. C H N Analytical value 56.33 5.62 18.02 Calculated value 56.16 5.57 17.86 (as C 11 H 13 N 3 O 3 ) Example 8 2.28 g of stannous chloride and 1.98 g of ethyl cyanoformate
To 50 ml of tetrahydrofuran containing N,
N'-dicyclohexylbromomalonamide 3.45g
was added and mixed, the mixture took on a yellow color and the temperature of the mixture rose from 27°C to 35°C. The mixture was allowed to react for one day with stirring at room temperature. After the reaction, the reaction mixture was concentrated under reduced pressure. 50 ml of benzene and 30 ml of water were added to the residue, and the layers were separated into an organic layer and an aqueous layer. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue was passed through a column (diameter 25 mm) packed with silica gel (Wako Gel C-200, 70 g) and eluted with a mixed solvent of benzene and ethyl acetate in a volume ratio of 9:1. 350ml solvent
The solution obtained by elution was concentrated under reduced pressure to obtain 3-
Amino-1-cyclohexyl-4-(cyclohexylcarbamoyl)maleimide yellow carmela
2.72g (yield: 85%) was obtained. This material was prepared by reacting with chloroformic acid trichloromethyl ester in the presence of pyridine to obtain 3,6-dicyclohexyl-2-hydroxy-3,4,6,
7-tetrahydro-4,5,7-trioxo-
This was confirmed by conversion to 5H-pyrrolo[3,4-d]pyrimidine. Add pyridine to 2.72 g of yellow carmela of 3-amino-1-cyclohexyl-4-(cyclohexylcarbamoyl)maleimide obtained in the above reaction at room temperature.
After adding 70 ml of ethylene chloride containing 3.37 g, 20 ml of ethylene chloride containing 2.27 g of chloroformic acid trichloromethyl ester was added dropwise under cooling with a cryogen (ice-salt). After the addition, the mixture was stirred at room temperature while
It was allowed to react for one day. After the reaction, the resulting reaction product mixture was added with water at room temperature.
Add 50 ml of 3,6-dicyclohexyl-2-hydroxy-3,4,6,7-tetrahydro-4,5,7-trioxo-5H-pyrrolo[3,
4-d] 1.35 g of pyrimidine crystals were obtained. The liquid was separated into an aqueous layer and an organic layer, and the organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue was recrystallized from dioxane to give 3,6-dicyclohexyl-2-hydroxy-3,4,6,7-tetrahydro-4,5,7-trioxo-5H-pyrrolo[3,4-d]pyrimidine and dioxane. 0.51 g of adduct (decomposition point: 290°C) with a molar ratio of 2:1 was obtained.
The elemental analysis values are shown below. C H N Analysis value 61.84 7.22 11.19 Calculated value 61.68 6.99 10.79 (as C 18 H 23 N 3 O 4・1/2C 4 H 8 O 2 )
Claims (1)
す。)で表わされるシアノギ酸エステルと、 式 〔式中、R2は水素原子、炭素数1〜4のアルキ
ル基、炭素数2〜4のアルケニル基、炭素数5〜
7のシクロアルキル基、炭素数7〜10のアラルキ
ル基、または【式】(R3は炭素数1〜 4のアルキル基、炭素数1〜4のアルコキシ基、
またはハロゲン原子を示し、nは0、1、2また
は3である。)で表わされる基を示す。〕で表わさ
れるブロモマロンアミド類とを、塩化第一スズの
存在下に反応させ、ついで得られる反応生成物を
水または酸性水溶液で処理することを特徴とする 式 (式中、R2は前記と同じ意味を有する。)で表わ
されるアミノマレイミド類の製造法。[Scope of Claims] 1 A cyanoformate ester represented by the formula N≡C-COOR 1 [] (wherein R 1 represents an alkyl group having 1 to 4 carbon atoms); [In the formula, R 2 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkenyl group having 5 to 4 carbon atoms.
7 cycloalkyl group, aralkyl group having 7 to 10 carbon atoms, or [Formula] (R 3 is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms,
or represents a halogen atom, and n is 0, 1, 2 or 3. ) represents a group. ] is reacted with a bromomalonamide represented by the formula in the presence of stannous chloride, and then the resulting reaction product is treated with water or an acidic aqueous solution. (In the formula, R 2 has the same meaning as above.) A method for producing an aminomaleimide represented by the formula:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15807681A JPS5859967A (en) | 1981-10-06 | 1981-10-06 | Production of aminomaleimide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15807681A JPS5859967A (en) | 1981-10-06 | 1981-10-06 | Production of aminomaleimide |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5859967A JPS5859967A (en) | 1983-04-09 |
JPS645592B2 true JPS645592B2 (en) | 1989-01-31 |
Family
ID=15663765
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP15807681A Granted JPS5859967A (en) | 1981-10-06 | 1981-10-06 | Production of aminomaleimide |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5859967A (en) |
-
1981
- 1981-10-06 JP JP15807681A patent/JPS5859967A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS5859967A (en) | 1983-04-09 |
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