Elucidation of biochemical formation of C1/C2-(bromo-/chloro)-hydrocarbons

Summary To elucidate possible biochemical pathways of the formation of halogenated C₁/C₂-hydrocarbons we investigated the product pattern of the reaction of chloroperoxidase (CPO) with natural substances including the haloform reaction as a second step. The analysis of the reaction products was performed by HRGC-ECD. We report here first results. As substrates we used acetic acid and acetone while KBr and NaCl served as halogen sources. The system acetic acid/KBr/CPO formed tribromomethane as the main product, with dibromochloromethane (CHBr₂Cl) and 1,1,2,2-tetrachloroethane as by-products. Incubation with acetone resulted in the formation of CHBr₃ as the main product, with CHBr₂Cl, CH₂Br-CH₂Br, CHCl₂-CHCl₂, CHCl₂-CCl₃ and trichloroethene as side products, while the reaction of acetone with NaCl and CPO yielded chloroform as a main product.Results partly presented at the ANAKON '91 in Baden-Baden, April 22–24, 1991     

Molecular and Crystal Structure of 1- ( 2- chloro) - Benzoyl - 3- (4- methylphenyl ) Thiourea

1　INTRODUCTIONBenzoylphenyltioureas having a generalformula( ) were reported to have in secticidalactivity〔1〕,which isclosely related to theirstructures,particularly tothedi hedralangle between the- CONH- plane and phenylring〔2〕.Surprisingly there islittle reported in the literature,only three related structures stored in CSD〔3〕 until1 998.In thispaper,we reportthe crystalstructure ofthe title compound.R CONHCSNHR2　EXPERIMENTAL2 .1　Synthesis　　The synthesisofthetitl…     

Novel nucleophilic substitution of alkyl bromo-2(1H)-pyridones

Nucleophilic substitution of certain alkyl bromo-2(1H)-pyridones gave some unexpected products where the alkyl group is substituted and the ring bromine is replaced by hydrogen. The expected ring substituted product is also formed, but only as the minor product in most cases. Many reactions are cited with various nucleophiles, and a plausible mechanism is also presented.     

Reaction of 9-hydroxy(chloro,bromo)-4-azafluorene to bis[9-chloro(bromo-4-aza-fluoren-9-yl]

4-Aza-fluoren-9-ol and 9-chloro(bromo)-4-azafluorenes are converted in high yields upon refluxing with thionyl chloride to form bis[9-chloro(bromo)-4-azafluoren-9-yl]. At about 20C, azafluorenol and thionyl chloride form 9-chloro-4-azafluorene. Mechanisms are proposed for these reactions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 72–74, January, 1990.     

An efficient synthesis of 2-bromo(chloro)-3-selenyl(sulfenyl)indoles via tandem reactions of 2-(gem-dibromo(chloro)vinyl)anilines with diselenides(disulfides)

A novel and efficient synthesis of 2-bromo(chloro)-3-selenyl(sulfenyl)indoles through tandem reactions of 2-(gem-dibromo(chloro)vinyl)-N-methylsulfonylanilines with diselenides and disulfides in the presence of t-BuOLi and I(2) (10 mol%) in DMSO was developed. The reactions generated the desired products in good yields with high regio-selectivity under transition-metal-free conditions in one-pot.     

1,2-Bis-[(5-methyl/chloro/nitro)-2-1H-benzimidazolyl]-1,2-ethanediols and their PdCl2 complexes

1,2-Bis-[(5-methyl)-2-1H-benzimidazolyl]- (L ¹), 1,2-bis-[(5-chloro)-2-1H-benzimidazolyl]- (L ²), 1,2-bis-[(5-nitro)-2-1H-benzimidazolyl]-1,2-ethanediol (L ³) and their PdCl₂ complexes were synthesized and characterized by elemental analysis, molar conductivity, i.r. and ¹H-n.m.r. spectra. The benzene ring substituents lead to a decrease in melting point. The methyl group reduces the solubility and the acidity of L ¹ and Pd(L ¹)Cl₂, whereas the Cl and NO₂ groups increase the solubility and the acidity of L ², L ³, Pd(L ²)Cl₂ and Pd(L ³)Cl₂. In Pd(L ¹)Cl₂ and Pd(L ²)Cl₂ complexes, the ligands act as a bidentate through two nitrogen atoms. In Pd(L ³)Cl₂, ligand coordination occurs through one OH group oxygen atom and one of the benzimidazole nitrogen atoms.     

Synthese et reactivite du bromo-2 (F-ethyl-2 ethyl thio)-1,3 propane

In this paper we have reported the synthesis and reactivity of 2-bromo 1,3-di (2-F-ethyl ethyl thio) propane. New compounds, especially those resulting from removal of bromine in alcoholic or basic media, are unambigously identified by mass spectrometry. Mechanisms requiring a thiiranium are discussed. For the first time such a F-alkyl substituted intermediate is involved.     

Reaction of N-trimethylsilyl derivatives of amides and lactams with chloro(chloromethyl)dimethylstannane: Crystal and molecular structure of 1-(chlorodimethylstannylmethyl)-2-piperidone

A general scheme of reactions between chloro(chloromethyl)dimethylstannane and N-trimethylsilylamides and -lactams was established by NMR and IR techniques. The reactions proceed via transmetallation followed by transformation of the N-stannylated intermediate (1) into (N-Sn)-coordinated O-stannylmethyl (2) and (O-Sn)-coordinated N-stannylmethyl (3) derivatives. In the cases of 2-piperidone and 2-hexahydroazepinone these products were isolated as individual compounds (2b,c and 3b,c). X-ray diffraction study of 1-(chlorodimethylstannylmethyl)-2-piperidone (3b) confirmed (3 + 2)-coordination state of the tin atom and axial positions of oxygen and halogen atoms. The experimental and quantum-chemically calculated structural parameters are discussed in comparison with those of related trigonal bipyramidal (TBP) silicon, germanium and tin derivatives. Calculation at the MP2/LanL2DZ/D95 level reveals that the stability of the (O-M)chelates increases in the following order: (O-Si) < (O-Ge) < (O-Sn).     

The mass spectrum of 1-(2-thienyl) hexane-1-13C

The mass spectrum of 1-(2-thienyl) hexane-1-¹³C is reported. The principal fragmentation routes ofthe parent ion are delineated. Beta cleavage of the alkyl chain predominates, and the label retention indicates that the alpha carbon atom remains with the charged ring moiety. A substantial part of the m/e 97 ion undergoes a ring expansion to a six membered ring. A small amount of alpha cleavage of the alkyl chain occurs with the expected loss of the label. Further fragmentation of the ions from initial alpha or beta cleavage produces similar fragment ions. It is noted that many of the neutral particles lost in the formation of the fragment ions are typical of those encountered in the alkylbenzenes or other aromatic ion systems.     

Total synthesis of (-)-CP2-disorazole C1

The total synthesis of a bis-cyclopropane analog of the antimitotic natural product (-)-disorazole C(1) was accomplished in 23 steps and 1.1% overall yield. A vinyl cyclopropane cross-metathesis reaction generated a key (E)-alkene segment of the target molecule. IC(50) determinations of (-)-CP(2)-disorazole C(1) in human colon cancer cell lines indicated low nanomolar cytotoxic properties. Accordingly, this synthetic bioisostere represents the first biologically active disorazole analog not containing a conjugated diene or polyene substructure element.     

新试剂4,4′-二(2-氯-4-硝基苯基重氮氨基)联苯与汞的显色反应

报道了新三氮烯试剂4,4′_二 (2_氯_4_硝基苯基重氮氨基 )联苯 (CNDADP)与汞的显色反应 ;在非离子表面活性剂TritonX_100存在下 ,于 pH7.8的KH2PO4-NaOH缓冲介质中 ,该试剂与汞生成摩尔比1∶1的橙红色配合物 ;其最大吸收波长在500nm处 ,表观摩尔吸光系数为1.03×105 L·mol-1·cm -1;汞量在0～720μg/L范围内遵守比尔定律 ;方法应用于废水中微量汞的测定 ,结果令人满意。     

Thio-analogues of 2-(1H-Heteroarylidene)-1H-indene-1,3(2H)-diones,synthesis and formation of metal complexes

2-(1H-Heteroarylidene)-1H-indene-1,3(2H)-diones were converted into anils and dianils and then into monothio- and dithio-derivatives by treatment with hydrogen sulphide. The 2-pyridinyl monothioderivate was converted into S-alkyl ethers. In contrast with the dione1 the thio-derivatives readily formed isolable complexes with transition metals. Spectroscopic and magnetic data are reported.

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Thio-Analoge von 2-(1H-Heteroaryliden)-1H-inden-1,3(2H)-dionen. Synthese und Bildung von Metallkomplexen

Zusammenfassung 2-(1H-Heteroaryliden)-1H-inden-1,3(2 H)-dione wurden in Anile und Dianile und durch anschließende Behandlung mit Schwefelwasserstoff in die entsprechenden Mono- und Di-thio-derivate umgewandelt. Aus den 2-Pyridinyl-monothio-derivaten wurdenS-Alkyl-ether erhalten. Im Gegensatz zum Dion1 bildeten die Thioderivate glatt isolierbare Komplexe mit Übergangsmetallen. Spektroskopische und magnetische Daten werden mitgeteilt.

     

Palladium(II)-assisted conversion of a 2-alkenyl sulfone into a 3-acetoxy(or chloro)-1-alkenyl sulfone

2-alkenyl p-tolyl sulfone was converted into the corresponding 3-acetoxy-1-alkenyl p-tolyl sulfone via a π-allyl palladium complex which underwent regiospecific attack of a nucleophile, acetate ion, and the reaction conditions for predominant formation of 3-chloro-1-alkenyl p-tolyl sulfone are also described.     

Synthesis and properties of 1-(2-bromoethyl)-, 1-(2-alkoxyethyl)- and 1-(2-dialkylaminoethyl)2-alkylpyrroles

The reaction of 3-chloropropenyl alkyl ketones or 2,3-dichloropropyl alkyl ketones with 2-substituted ethylamine derivatives leads to the formation of the hitherto unknown 1-(2-R-ethyl)-2-alkylpyrroles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1047–1049, August, 1990.     

S-烃基-1-烃基-3-[4-(5-取代苯并咪唑-2-巯基)苯基]异硫脲的合成及生物活性

以 5 甲氧基 (或氯 ) 2 巯基苯并咪唑 ( 1)为原料 ,经缩合和还原得到 5 甲氧基 (或氯 ) 2 ( 4 氨基苯硫基 )苯并咪唑 ( 3 ) ,再与异硫氰酸烃基酯反应得到取代硫脲 4,最后与卤代烃反应得到 12个新的S 烃基 1 烃基 3 [4 ( 5 甲氧基 (或氯 )苯并咪唑 2 巯基 )苯基 ]异硫脲化合物 5 .其结构经IR ,1 HNMR ,MS及元素分析确证 .初步的药理试验表明 ,12个目标化合物的iNOS抑制活性均强于阳性对照药氨基胍