6α-取代的(1S, 7aS)-(+)-1-叔丁氧基-7a-甲基-2, 3, 5, 6, 7, 7a-六氢茚-5- 酮的合成

用化学动力学控制的方法在化合物3的5-C上C=O与6-C发生烯醇化生成锂盐,然后可在6-C位分别引入甲基、烯丙基、苄基、溴以及羟基取代基。产物6、7、8、9a和11经鉴定,除9α外其他都是α和β构型的混合物,其中以α-构型取代物为主。     

Synthesis of 1, 5- and 1, 7-dichloro-9H-thioxanthen-9-ones

1, 5-Dichloro-9H-thioxanthen-9-one ( 2 ) was prepared by cyclization of 2-chloro-6-[(2-chlorophenyl)thio]-benzoic acid ( 10 ) obtained from 2-chloro-6-iodobenzoic acid ( 9 ) and 2-chlorobenzenethiol. Similarly, 1, 7-di-chloro-9H-thioxanthen-9-one ( 6 ) was prepared from 9 via 2-chloro-6-[(4-chlorophenyl)thio]benzoic acid ( 11 ). Compound 6 was also obtained by condensation of 2-chloro-6-mercaptobenzoic acid ( 12 ) with chlorobenzene in the presence of sulfuric acid.     

Molecular structure of 1-methyl-5, 7-diphenyl-1, 3-diazaadamantan-6-one iodide

Journal of Structural Chemistry -     

一锅法合成新型7-苯基-1,4,5,6,7,8-六氢喹啉酮衍生物

以5-苯基-1,3-环己二酮,醛,乙酰乙酸乙酯(或乙酰丙酮)和乙酸铵为原料,在无水乙醇中经一锅反应合成了14个新型的7-苯基-1,4,5,6,7,8-六氢喹啉酮衍生物,总收率85%~95%,其结构经¹H NMR, ¹³C NMR, IR和HR-MS表征。采用X-ray单晶衍射研究了2-甲基-4,7-二苯基-5-氧代-1,4,5,6,7,8-六氢喹啉顺反异构体(5a和5a′)的晶体结构。结果表明：5a空间群为C2/c, a=9.458 35(19) ,b=19.789 0(4) ,c=11.040 9(2) , α=90°, β=105.614(2)°, γ=90°,V=1 990.28(7) ³, Z=4, μ=0.673 mm^-1, F(000)=824; 5a′空间群为C2/c, a=9.770 2(5) , b=19.981 0(10) , c=10.430 1(4) , α=90°, β=98.361(5)°, γ=90°, V=2 014.51(17) ³, Z=4, μ=0.665 mm^-1, F(000)=824。     

7,7-二甲基-2-对溴苯基-4-苯基-5-氧代-1,4,5,6,7,8-六氢化-6H-喹啉的合成及晶体结构

标题化合物C23H22BrNO是由1-(4-溴苯基)-3-苯基-2-丙烯-1-酮与5,5-二甲基-1, 3-环己二酮在N, N-二甲基甲酰胺(DMF)中在NH4OAc催化下反应而得。结构通过单晶X-射线衍射分析确定,其晶体属于单斜晶系,空间群C2/C, a = 19.678(4),b = 13.571(2),c = 17.311(3) 牛琤 = 118.74(1),Mr = 408.33, V = 4055(1) ?,Dc = 1.338 g/cm3, Z = 8, m (MoKa) = 2.038 mm-1, F(000) = 1680, R = 0.0539,wR = 0.1369。X-衍射分析表明,六元环C(10)C(13)C(16)C(17)采用半椅式构象:原子C(10),C(11),C(12),C(16)和C(17)在同一个平面内,而原子C(13)远离平面为0.3282 牛闷矫嬗?个苯环的夹角分别为41.09, 81.97,2个苯环的夹角为75.87。另外在晶体结构中,存在1个分子间氢键。     

Studies on Selena-Macrocyclic Amides Synthesis and Structural Characterization of 7-Phenyl-5, 9-dioxo-1-selena-4, 7, 10-triazacyclododecane and 6-(4-Nitrobenzyl )-5, 9-dioxo-1, 4, 7, 10-selenatriazacyclododecane

lmTR0DUCTI0NSincetheseleniumcoronandswereachivevedin1989tli,thesynthesisandcoor-dinationchemistrystudyofthismacrocycliccomPOundshavereceivedwideattentionowingtotheirstrongcomplexingabilitiestowardssoft.transiti0nandheavymetals.InourprevibuspaPer,wereP0rtedthecrystalstructureoftw0selenacrownethers(2'3)andaPd(1)complexwith10'selenabenzo-15-crown-5t4i.Duetothedifficultyofthepreparationsofselenium-nitr0genmixeddonorc0n-..tainingmacrocycles,thestudyontheseligandsisconsiderablyscarce.Thesynthes…     

Structure of 5, 11-dithia-1, 3, 7, 9-tetraazatricyclo[7.3.0.03, 7]dodecane in the crystal

Russian Chemical Bulletin - The multicomponent condensation of hydrazine with formadehyde and H2S at 20 °C affords 5, 11-dithia-1, 3, 7, 9-tetraazatricyclo[7.3.0.03, 7]dodecane. The structure...     

Synthesis of 5, 7-dimethylthieno-, 3, 1-dimethylthionaphtheno-, and 6, 4-dimethylthienothienopyridines

New heterocyclic compounds with a condensed thiophene ring are synthesized.     

Synthesis of 5, 7-dimethylthieno-, 3, 1-dimethylthionaphtheno-, and 6, 4-dimethylthienothienopyridines

New heterocyclic compounds with a condensed thiophene ring are synthesized.     

松毛虫性信息素(5Z,7E)-十二碳二烯醇的立体选择性合成

从简单原料乙炔出发,通过炔对丙烯醛的加成反应得到7-溴代-(4Z,6E)-庚二烯醛,再经乙二醇保护、Pd催化偶联、水解、Wittig反应和还原等步骤,立体选择性地得到松毛虫性信息素(5Z,7E)-十二碳二烯醇,其结构通过IR,NMR和MS等技术得到确认.     

Crystal structure,dissociation and zwitterion formation in 2,6-diaryl-1(3)-oxo-3(1)-hydroxy-5(7)-imino-7(5)-amino-1 H,5H-(3-H,7H)-pyrazolo[1,2-a]pyrazoles

Single crystal X-ray analysis and quaternization of 2,6-diphenyl-1(3)-oxo-3(1)-hydroxy-5(7)-imino-7(5)-1H,-5H[3H,7H)-pyrazolo[1,2-a]pyrazole is described. The dissociation constants are determined and compared with those of 4-phenyl-1,2-dimethyl-3(5)-oxo-5(3)-hydroxypyrazole and 4-phenyl-3,5-diaminopyrazole. The quaternization of the latter compound is also described. The influence of electron donating substituents at the cationic moiety on the electronic spectra of such paraionic systems is discussed. The title products exist in the solid state as zwitterions and probably as covalent species in solution.     

Solvent Extraction Studies of Two Isomeric 5, 7, 7, 12, 12, 14-Hexamethy-1, 4, 8, 11-Tetraazacyclotetradecanes

The distribution ratios of two isomeric 5, 7, 7, 12, 12, 14-hexamethyl-1, 4, 8, 11-tetraazacyclotetradecane, tet c and tet d, in several solvent systems at 25.0°C as functions of hydrogen ion concentration were determined. The protonation constants and the distribution constants of these macrocyclic ligands and their protonated species were obtained from the variations of the distribution ratios in the range of 6<–log [H⁺]<14.     

Über 1, 5-Diphenyl-2, 3, 6, 7-tetrahydro-1H, 5H-pyrazolo[1, 2-a]pyrazole(2, 6-Diphenyl-1, 5-diazabicyclo[3, 3, 0]octane)

The synthesis of a 1, 5-diphenyl perhydro-pyrazolo-[1, 2-a] pyrazole (IV) (m. p. = 170–171°) by LiAlH₄-reduction of its 3, 7-dioxo derivative Va, one of the stereoisomers of V, is described. Va was obtained in small yield by the reaction of cinnamic acid with its hydrazide or with hydrazine. It proved to be identical with the compound obtained previously by interaction of cinnamic acid hydrazide with iodine which in the literature erroneously had been described as N, N′-dicinnamoyl hydrazine. This hydrazine now was obtained by bis-acylation of hydrazine with cinnamoyl chloride. In Va the extremely low NMR. absorption of the tertiary protons at ρ = 4,6 ppm is probably due to the spatial grouping with the proton situated in the deshielding region of the carbonyl group. Previously, another tertiary proton with a very low NMR. absorption at ρ = 4,85 ppm has been observed in the «bisimide M», the main criss-cross addition product of one mole benzaldazine and two moles of N-(n-butyl)-maleinimide. A stereostructure for bisimide M is now proposed, which is a hybrid between those of the bisimides L and H.     

(+)-(1S,7aS)-1-羟基-7a-甲基-茚满-4-烯-5-酮的合成及其烷基化反应研究

以2-甲基-2-(3-丁酮)环戊烷-1,3-二酮为原料,经环合和还原反应合成了手性(+)-(1S,7aS)-1-羟基-7a-甲基-茚满-4-烯-5-酮(3);3在其羟基未进行保护情况下与不同芳香侧链进行α,β-不饱和酮的α-位烷基化反应,制备了5个3的衍生物,其结构经1H NMR确证。     

N-Alkylated 4, 5, 6, 7-tetrafluoroindoles

The electrochemical reduction of 2-nitro-1-pentafluorophenylalkanols in the presence of carbonyl compounds has given hydrochlorides of secondary amino alcohols which, in the form of the free bases, have been converted by heating in dimethylformamide into N-substituted derivatives of 4, 5, 6, 7-tetrafluoroindole and its homologs.