Cyclisierungen mit 1-Nitro-2-anilino-äthylenen

Cyclizations with 1-nitro-2-anilino-ethylenes The reaction of 1-nitro-2-anilino-2-methylthio-ethylenes 1 with oxalyl chloride yields the substituted 4-nitropyrrol-2,3-diones 4 , and with chlorocarbonyl-sulfenylchloride the 5-nitro-thiazolones 6 . The methylthio group from 6 can be exchanged by amines. From 1-nitro-2,2-bis(anilino)ethylenes 2 – available from 1-nitro-2,2-bis(methylthio)-ethylene and anilines – and the same reagents, the substituted 2-nitromethylene-imidazolidine-4,5-diones 5 and the thiazolo[4,5-d]thiazoledione 9 result. The condensation of 1-nitro-2-anilino-2-hydrazino-ethylene 3 with derivatives of carboxylic acids yields 2-nitromethyl-s-triazole 12 , with diacetyl the substituted 3-nitromethylene-as-triazine 13 .     

Tautomerism and Reactions of 1H-1,2,4-Triazole-5-thiones with Hydrazonoyl Halides

The acid dissociation constants (K_a) of a series of 3,4-diaryl-1H-1,2,4-triazole-5-thiones ( 1 ) were determined and were found to correlated linearly with Hammett substituent constants; log K_a = 1.06 σ_x − 11.01. Such a result indicates that 1 exists essentially in one tautomeric form namely the thione form. Reactions of 1 with hydrazonoyl chlorides 2 gave the thiohydrazides 5 . Similiar reaction of 3-phenyl-1H(4H)- 1,2,4-triazole-5-thione 1g with 2a gave the thiohydrazide 5h which was converted into 1,3,5-triphenyl-1,2,4-triazolo[3,4-c]-1,2,4-triazole ( 9 ). The latter was also prepared from 3-phenyl-5-methylthio-4H-1,2,4-triazole ( 6 ) and 2a . The mechanism of the reaction of 1 with 2 is discussed.     

5,7-二甲基-N-芳基-1,2,4-三唑[1,5-a]嘧啶-2-磺酰胺的合成

以5-氨基-3-巯基-1,2,4-三唑为原料,经氧氯化后分别与6个芳胺反应,得到5氨基-N-芳基1,2,4-三唑-3-磺酰胺,继而和乙酰丙酮于乙酸中环合,制得6个取代的1,2,4-三唑[1,5-a]嘧啶-2-磺酰胺衍生物,同时讨论了胺解反应和环合反应的影响因素。所有目标产物的结构均经IR和1HNMR谱验证。     

Studies on 1,2,4-triazine derivatives. III. The Behaviour of some Derivatives of 1,2,4-Triazine toward diazomethane,amines, ethyl monobromoacetate and tetra-O-acetyl-α-D-glucopyranosyl bromide

The reaction of diazomethane with 6-phenyl-3-thioxo-5-oxo-2,3,4,5-tetrahydro-1,2,4-triazine 2a , and with 6-phenyl-3-methylmercapto-5-oxo-4,5-dihydro-1,2-triazine 3a effected N-methylation to 2b and 3b , respectively. Compound 3a and 3-methyl-mercapto-5, 6-diphenyl-1,2,4,-triazine 4a react with amines to give 3-N-substituted-amino-triazines 5a–h and 6a–h , respectively. 3-Mercapto-5,6-diphenyl-1,2,4-triazine 4b underwent S-alkylation with ethyl monobromoacetate and with tetra-O-acetyl-α-D-glucopyraosyl bromide.     

用小药量至爆时间试验研究炸药爆发分解反应动力学

用小药量至爆试验测定了10种炸药:单质炸药3-硝基-1,2,4-三唑-5-酮(NTO)及其铵盐(ANTO)、铅盐(PbNTO)、钾盐(KNTO)、乙二胺盐(ENTO)、混合炸药JO-6、JOB-9003、JP-1、JD-1、JH-16在不同温度下的爆发延滞期(t_(ind)).依据谢苗诺夫方程lnt_(ind,i)=(E_σ)/(RT_i),-lnA_,由lnt_(ind,i)对1/T_i的关系,用最小二乘法计算了爆发分解反应的表观活化能(E_α)、指前因子(A_σ)和1 000 s时的热爆炸临界温度(T_b).用非线性等转化率积分法所得的表观活化能(E_σ)校验了由lnt_(ind,i)~1/T_i关系得到的E_σ值.借助热力学关系式,计算了爆发分解反应的活化反应热力学参量[活化自由能(ΔG~≠),活化焓(ΔH~≠)和活化熵(ΔS~≠].结果表明:(1) 以T_b和ΔG~≠作判据,知5种单质炸药和5种混合炸药的对热抵抗能力次序分别为:NTO＞ENTO＞ANTO＞KNTO＞PbNTO和JP-1＞JD-1＞JO-6＞JOB-9003＞JH-16;(2) E_α=E_α的事实佐证不同温度下爆发分解反应延滞期内分解深度相等,由此所得A_σ值可信,谢苗诺夫方程推导过程中A_σG(α)的假设合理.     

Umsetzung von 1-(2-Benzoxazolon-3-yl)-2-propanonen mit Hydrazinhydrat

Reaction of 1-(2-Benzoxazolon-3-yl)-2-propanones with Hydrazinhydrate . The reaction of 1-(2-benzoxazolon-3-yl)-2-propanones 1a–g with hydrazinhydrate is studied. It is shown that according to the reactional conditions are obtained hydrazones 2a–b , azines 4a–b and 6-Methyl-4-(2-hydroxyphenyl)-2,3,4,5-tetrahydro-1,2,4-triazine-3-ones 6a–g . The structure of the products is discussed on the base of i.r. and n.m.r.-spectras.     

Structure and Tautomerism of ANTA (aminonitrotriazole)

Energy and dipole moment calculations show 3-nitro-5- amino-1,2,4-triazole is the most stable tautomer of ANTA either in the gas phase and polar solvents, in agreement with X-ray findings. Our calculations predict that the 5-nitro-3-amino-1,2,4-triazole tautomer is more sensitive to shock or impact. Some discrepancies between semiempirical (AMI and PM3) calculations and ab initio (up to 6-31G*//6-31G) are studied.     

Darstellung und Reaktionen von 2-Arylamino-3-nitrochinolinen

Synthesis and Reactions of 2-Arylamino-3-nitroquinolines Condensation of 1-nitro-2,2-bis(methylthio)ethylene with esters of anthranilic acid yields 2-arylamino-3-nitro-4-quinolones. 2 . Analogously, from 1-nitro-2-anilino-2-methylthioethylene and o-aminoketones, 2-anilino-3-nitroquinolines 4 are obtained which can be reduced to 2-anilino-3-amino-quinolines 7 . The latter undergo cyclizations by usual methods to yield substituted triazolo-, imidazolo-, diazepino- and pyrazino-quinolines 9–12 . Reaction of ethyl-2-aminothiophene-3-carboxylates with 1-nitro-2-anilino-2-methylthio-ethylene affords 2-anilino-3-nitrothieno[2,3-b]-4-pyridones 5 .     

The Chemistry of Cyclic Hydrazides. IX. The Synthesis and Alkylation of 1,2-Disubstituted-Perhydropyridazine-3,6-Diones

The synthesis of 1,2-disubstituted perhydropyridazine-3,6-diones in high yield is described. The reaction of succinic anhydride and 1,2-dialkylhydrazines leads to N,N′-dialkyl-3-carboxypropionhydrazides which are converted to 1,2-dialkylperhydropyridazine-3,6-diones in refluxing xylene or polyphosphoric acid. The reaction of 1,2-diarylhydrazines with 3-carbomethoxypropionyl chloride and hydrolysis of the resulting N,N′-diaryl-3-carbomethoxypropionhydrazides yields N,N′-diaryl-3-carboxypropionhydrazides. Cyclization of these acid-hydrazides in thionyl chloride at low temperature affords the corresponding 1, 2-diarylperhydropyridazine-3,6-diones. The alkylation of 1,2-dipropyl-perhydropyridazine-3,6-dione in various base-solvent systems with methyl and isopropyl iodide is reported.     

2种ω-1H-1,2,4-三氮唑基-2,4-二氯苯乙酮肟羧酸酯的合成及生物活性

以 2 ,4 二氯苯乙酮为原料 ,经溴化得ω 溴 2 ,4 二氯苯乙酮 ,该化合物在以三乙胺做缚酸剂 ,温度 0℃的条件下与 1H 1,2 ,4 三氮唑反应 5h ,所得产物ω 1H 1,2 ,4 三氮唑基 2 ,4 二氯苯乙酮与盐酸羟胺在添加吡啶 ,加热回流条件下反应 4 5h ,得到的酮肟分别与乙酰氯、苯甲酰氯在以三乙胺做缚酸剂 ,常温条件下反应 12h ,合成了目标产物ω 1H 1,2 ,4 三氮唑基 2 ,4 二氯苯乙酮肟乙酸酯与ω 1H 1,2 ,4 三氮唑基 2 ,4 二氯苯乙酮肟苯甲酸酯两种肟羧酸酯 ,总收率分别为 32 4 %与 34 8%,化合物的结构经元素分析、气质联用及核磁共振所证实。对目标产物进行了初步的杀菌、杀虫与除草活性测定 ,结果表明 ,ω 1H 1,2 ,4 三氮唑基 2 ,4 二氯苯乙酮肟苯甲酸酯对粘虫 (Mythimnaseparata)具有杀虫活性。     

球形红细菌降解2,4-二硝基甲苯的途径及酶学性质

采用气相色谱-质谱联用仪(GC-MS)分析了球形红细菌降解2,4-二硝基甲苯(2,4-DNT)的中间代谢产物,分析了可能的降解途径,讨论了培养基中2,4-DNT的初始质量浓度、溶液pH值及反应温度对3种酶的酶比活力影响。结果表明,当2,4-DNT的初始质量浓度为40 mg/L时,培养72h后,可以检测到5种物质:2,4-二硝基甲苯、4-氨基-2硝基甲苯、2-氨基-4硝基甲苯、4-硝基-1,2-二(三甲基硅烷)苯、1,2,4-三(三甲基硅烷)苯,其可能的降解途径为2,4-DNT首先还原为4-氨基-2-硝基甲苯和2-氨基4-硝基甲苯,再进一步转化为4-硝基-1,2-羟基苯,然后氧化为1,2,4-三羟基苯,之后开环生成β-酮己二酸,最终降解为小分子物质。硝基还原酶、邻苯二酚2,3-双加氧酶和邻苯二酚1,2-双加氧酶的酶比活力最适宜温度分别为35、30、35℃,最适宜pH值分别为7.0、8.0、7.0,最适宜培养基初始2,4-DNT质量浓度均为40mg/L。     

The behaviour of some derivatives of 1,2,4-triazine toward organomagnesium halides

6-Phenyl-3,5-dioxo-2,3,4,5-tetrahydro-1,2,4-triazine 1 , 3-oxo-5,6-diphenyl-2,3-dihydro-1,2,4-triazine 3 , 3,5,6-triphenyl-1,2,4-triazine 4 , and 3-chloro-5,6-diphenyl-1,2,4-triazine 8 , react with phenylmagnesium bromide. The reactions involved are represented by scheme A. Compound 3 reacts with o- and/or p-methoxyphenylmagnesium bromide to give compounds believed to have structures like 10 and 11 respectively. Compound 1 reacts with methylmagnesium bromide and with benzylmagnesium chloride to give products believed to have structures like 12 a , b .     

吡蚜酮合成工艺改进研究

4,5-二氢-4-乙酰胺基-6-甲基-1,2,4-三嗪-3-(2H)-酮在浓硫酸催化剂作用下与氯化氢反应,脱乙酰基得到吡蚜酮关键中间体2,3,4,5-四氢-3-氧-4-氨基-6-甲基-1,2,4-三嗪,再与烟醛缩合得到吡蚜酮原药,总收率大于97.0%,比文献报导提高了7.7%,产品含量大于96.0%。     

Separation of NTO Related 1,2,4-Triazole-3-One Derivatives by a high performance liquid chromatography and capillary electrophoresis

This report describes a direct, rapid and sensitive method for separating and quantifying 5-nitro-1,2,4-triazole-3-one 1 (NTO) and 5-amino-1,2,4-triazole-3-one 2 . Analyses were performed on water and on soil containing compounds 1 and/or 2 , using reversed phase HPLC columns. A mixture of compounds 1 , 2 , Urazole 3 and 1,2,4-triazole-3-one 4 was well separated by HPLC on a Hypercarb column packed with porous graphitic carbon, or by capillary electrophoresis. Both methods could be used to detect such compounds in the environment and monitor their biological and chemical degradation.     

1-[2-(2,4-二氯苯基)-4-烃氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑类化合物的合成及杀菌活性研究

2,4-二氯苯乙酮经溴化得ω-溴-2,4-二氯苯乙酮,该化合物与丙三醇在对甲基苯磺酸催化下脱水,得2-(2,4-二氯苯基)-2-溴甲基-4-羟甲基-1,3-二氧戊环,该中间体与苯甲酰氯在常温下反应,合成了2-(2,4-二氯苯基)-2-溴甲基-4-苯甲酰氧基甲基-1,3-二氧戊环,然后与三氮唑钠盐在130℃反应36 h,之后在碱性条件下水解,获得1-[2-(2,4-二氯苯基)-4-羟甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑,再以吡啶为缚酸剂继续与甲磺酰氯反应,合成了1-[2-(2,4-二氯苯基)-4-甲磺酰氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑,最后在碱性条件下,与12个不同结构的酚缩合成标题化合物1-[2-(2,4-二氯苯基)-4-烃氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑。标题化合物的结构用GC-MS、FTIR进行了表证。生物活性实验结果表明,12个标题化合物对水稻稻瘟病菌的抑菌率均在88.0%以上,其中,1-[2-(2,4-二氯苯基)-4-间甲基苯氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑达100%。1-[2-(2,4-二氯苯基)-4-苯氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑和1-[2-(2,4-二氯苯基)-4-对硝基苯氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑对油菜菌核病菌的抑菌率分别为100%和97.8%;1-[2-(2,4-二氯苯基)-4-间甲基苯氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑对小麦赤霉病菌的抑制活性为91.2%。     

Cycloadditions-Eliminierungsreaktionen mit 4-Aryl-5-arylimino-1,2,4-dithiazolidin-3-onen (Senföloxiden)

Cycloaddition Elimination Reactions of 4-Aryl-5-arylimino-1,2,4-dithiazolidin-3-ones (Mustard Oil Oxides) 4-Aryl-5-arylimino-1,2,4-dithiazolidin-3-ones ( 1 ) react with isocyanates, isothiocyanates, and cyanic acid esters by exchange of the COS-part from 1 affording thiadiazole and dithiazole derivatives 4 , 5 , 6 or 12 . The reaction products are able to give further exchange reactions. Ring opening of 2-substituted 4-aryl-5-arylimino-1,2,4-thiadiazolin-3-ones ( 4 ) and -3-thiones ( 6 ) yields thio- and dithiobiurets ( 7 , 8 ) with aryl substituent in 3-position. Oxidation of dithiobiurets, generated from 6 , affords dithiazolidines 9 , which are Dimroth-isomers of 6 .     

两种新型2-偕二硝甲基-5-硝基四唑含能离子盐的合成、表征及性能预估

以氨基-1,2,4-三唑和2-偕二硝甲基-5-硝基四唑(HDNMNT)为原料,通过中和反应合成出两种新型含能离子盐——2-偕二硝甲基-5-硝基四唑3-氨基-1,2,4-三唑盐(3-ATDNMNT)和2-偕二硝甲基-5-硝基四唑4-氨基-1,2,4-三唑盐(4-ATDNMNT),收率分别为95.4%和96.7%;利用FT-IR、1 H NMR、13C NMR、15 N NMR及元素分析等方法对其结构进行表征;采用量子化学方法计算了3-ATDNMNT和4-ATDNMNT的爆轰性能;在标准状态下(膨胀比为70∶1),利用最小自由能原理,分别计算了两种离子盐在丁羟复合推进剂中的能量性能。结果表明,3-ATDNMNT的爆速和爆压分别为8.587km/s和33.58GPa,4-ATDNMNT的爆速和爆压分别为8.693km/s和34.31GPa。以3-ATDNMNT部分取代丁羟复合推进剂中的AP后,丁羟复合推进剂的理论比冲可达2 635.7N·s/kg。以4-ATDNMNT部分取代丁羟复合推进剂中的AP后,当HTPB、Al、AP及4-ATDNMNT各组分质量分数分别为10%、5%、15%及70%时,获得该丁羟复合推进剂的最高理论比冲为2 677.2N·s/kg。     

Z-2′-[1-(1,2,4-三唑)基]-O-(α-甲基对卤苄基)-2,4-二氯苯乙酮肟硝酸盐的合成

以 2 ,4 二氯氯代苯乙酮、1,2 ,4 三唑和羟胺为原料 ,合成了Z 2′ [1 (1,2 ,4 三唑 )基 ] 2 ,4 二氯苯乙酮肟 (Ⅰ ) ,以对氯 (对溴 )苯乙酮合成对氯 (对溴 ) α 氯乙苯 (ⅡA 和ⅡB) ,Ⅰ分别与ⅡA和ⅡB 反应生成Z 2′ [1 (1,2 ,4 三唑 )基 ] O (α 甲基对卤苄基 ) 2 ,4 二氯苯乙酮肟硝酸盐两个化合物 ,产率为 6 2 .5 %和 5 8.8% ,化合物结构经元素分析、IR和1HNMR确定。     

除草剂氟酮磺隆中间体5-甲氧基-4-甲基-2,4-二氢-1,2,4-三唑-3-酮的合成

5-甲氧基-4-甲基-1,2,4-三唑-3-酮是氟酮磺隆的关键中间体。以硫氰酸钾和氯甲酸甲酯为起始原料,经三步反应得到目的产物。(1)以甲基异丁酮为溶剂,硫氰酸钠和氯甲酸甲酯、甲醇反应制得1,3-二甲基硫代亚胺二羟酸酯;(2)以上产物与水合肼环化制得5-甲氧基-2,4-二氢-3H-1,2,4-三唑-3-酮;(3)经硫酸二甲酯甲基化制得目的产物5-甲氧基-4-甲基-2,4-二氢-3H-1,2,4-三唑-3-酮(MMT)。分别考察了催化剂对1,3-二甲基硫代亚胺二羟酸酯,缚酸剂对5-甲氧基-2,4-二氢-3H-1,2,4-三唑-3-酮和pH值对5-甲氧基-4-甲基2,4-二氢-3H-1,2,4-三唑-3-酮收率的影响。产物总收率55.61%。     

Die Nitril-Carboxamid-Umlagerung

The Nitrile Carboxamide Rearrangement By reaction of cyclohexanone-2-carboxamide ( 4 ) with cyan amide 1-cyano-cyclohex-1-en-2-yl-urea ( 6 ) is formed via nitrile carboxamide rearrangement. Whilst compound 6 with 1,2-diaminobenzene hydrochloride forms 11-amino-1 H-2,3,4,5-tetrahydrodibenzo[b,e][1,4]diazepin hydrochloride ( 8 and 8a ), compound 6 and 1,2-diaminobenzene form hexahydro-benzimidazo[1,2-c]-quinazolin-6-one ( 12 ). Compound 8 with sodium hydroxide yields 11-amino-1 H-2,3,4,11a-tetrahydrodibenzo[b,e]-[1,4]diazepin ( 9 ). Compound 6 reacts with cyclohexylamine to form N-(1-cyanocyclohex-1-en-2-yl)-N′-cyclohexyl urea ( 10 ). Compound 10 with 1,4- or 1,2-diaminobenzene hydrochloride yields compound 7 and 8 . In alkaline solution 10 cyclises to 4-amino-3-cyclohexyl-2,3,5,6,7,8-hexahydroquinazolin-2-one ( 11 ). Compound 4 and malonitrile form either 3-amino-4-cyano-1,2,5,6,7,8-hexahydro-isoquinol-1-one ( 13 ) or 1-amino-4-cyano-2,3,5,6,7,8-hexahydro-isoquinol-3-one ( 14 ). Compound 13 and alkaline formaldehyde react to cyanooctahydroisoquinoline-[2,3-c] [1,3,5]oxdiazin-6-one ( 17 ). 2-Cyanoethyl-cyclohexan-one-2-carboxamide ( 22 ), prepared by Michael-reaction from 4 and acrylonitrile, forms via nitrile carboxamide rearrangement 10-cyano-1,2,3,4,5,6,7,10-octahydroquinolin-2-one ( 24 ) and 2-(1′-cyano-cyclohexyl-2′-one)-propionic acid ( 25 ). Nucleophilic attack of the NH₂-group at the cyanogroup of compound 22 forms 5-(spirocyclohexan-2′-one)-hexahydropyridin-2,6-dione ( 27 ).