1-肼基-2,3-二氮杂萘盐酸盐的合成新方法

研究了l-肼基-2,3-二氮杂萘盐酸盐的合成新方法.以相对廉价易得的邻苯二甲酸酐为起始原料,依次通过还原、溴代、环合、取代、酸化等反应步骤得到目标产物1-肼基-2,3-二氮杂萘盐酸盐.研究表明该方法具有原料便宜易得、收率高、产物易分离纯化、后处理操作简单、总成本低等优点.     

Synthesis of 1,2-dihydroxyindolizidines from 1-(2-pyridyl)-2-propen-1-ol

1-(2-Pyridyl)-2-propen-1-ol, obtained by vinylation of commercially available picolinaldehyde, resulted a good starting material for the synthesis of the indolizidine skeleton. In particular, a simple process involving bromination, reduction, and nucleophilic substitution (via elimination and addition) allowed an easy conversion of the starting material into (±)-lentiginosine in ~27% overall yield.     

A convenient approach towards the 1-aminomethyl-1-fluorocycloalkane scaffold

A three-step synthesis towards 1-aminomethyl-1-fluorocycloalkanes was developed starting from methylenecycloalkanes. Methylenecyclobutane, methylenecyclopentane and methylenecyclohexane were first bromofluorinated to provide the corresponding Markovnikov products, 1-bromomethyl-1-fluorocycloalkanes, which were then converted towards the title compound via azide substitution and hydrogenation. The bromofluorination of methylenecyclopropane, however, led to both the Markovnikov and the anti-Markovnikov product.     

Synthesis of 1-alkynyl-2-dialkylaminocyclopropanes and 1-alkynyl-2-diazolylcyclopropanes by reactions of 1-alkynyl-1-chlorocyclopropanes with amines and their lithium derivatives

Reactions of 1-alkynyl-1-chlorocyclopropanes with lithium dialkylamides gave previously unknown 1-alkynyl-2-dialkylaminocyclopropanes. 1-(Alk-1-ynyl)-2-diazolylcyclopropanes were obtained by reactions of 1-alkynyl-1-chlorocyclopropanes with diazoles in the presence of KOH in DMSO at 100 °C. These reactions passed through the formation of conjugated alky-nylcyclopropenes and reversible addition of amide anions to them. The regioselectivity and stereoselectivity of these transformations depend on the substituents in the starting chlorocyclopropanes and amines.     

Synthesis of (1R)-1-(4-Bromophenyl)-2,2,2-trifluoroethan-1-amine Hydrochloride through Diastereoselective Trifluoromethylation of a Chiral Sulfinimine

An efficient three-step synthesis of (1R)-1-(4-bromophenyl)-2,2,2-trifluoroethan-1-amine hydrochloride ( 1 ) starting from inexpensive and readily available starting materials was developed. The sequence features a highly diastereoselective trifluoromethylation of a chiral sulfinimine using the Rupert–Prakash reagent TMSCF₃ in combination with K₃PO₄ as an initiator. The diastereomeric purity of the resulting sulfinamide was further improved by direct precipitation of the desired diastereomer from the reaction mixture upon addition of water. The chiral auxiliary was then removed under acidic conditions, resulting in the isolation of chiral benzylamine 1 as its hydrochloride salt in 71 % overall yield and excellent purity (LC/MS: >99 % a/a; e.r.=99 : 1).     

Stereocontrolled entry to 1-oxapenams and 1-oxacephems from carbohydrates

N-Benzyl-2-carboxy-2-deoxypento and hexopyranosylaminolactams readily available via addition of trichloroacetyl isocyanate to substituted glycals, were transformed into enantiomerically pure N-benzyl-4-alkoxy-3-hydroxymethylazetidinones-2. The transformation involved the glycolic cleavage which was followed by sodium borohydride reduction. The above compounds can serve as starting materials for the synthesis of 1-oxapenams and 1-oxacephems.     

Synthesis of Isoquinoline-1, 3-Dicarboxylic Acid

Chiropticalluminescencemeasurementslhavebeenusedforstudyingchiralitydependentmolecularexcited-statedynamic,forstlldyingexcited-stateracemizationkineticsassociatedwithintermolecularchiralrecognitionprocessesinsolution2.Intheseprocesses,therearetwomolecularspecies,lanthanidecomplexes(luminophore)andresolvedtransitioncomplexes(AorA,quencher).Manykindsoftransitionmetalcomplexeshavebeenusedasquencherstoinvestigateinfluenceoftheintermolecularchiralrecognition.However,theluminophoreswereonlyconfined…     

A method for the regioselective synthesis of 1-alkyl-1H-indazoles

A method for the regioselective synthesis of 3-unsubstituted 1-alkyl-1H-indazoles, starting with 2-halobenzonitriles and N-alkylhydrazines, is described. The two-step reaction pathway proceeds through the intermediacy of 1-alkyl-3-amino-1H-indazoles followed by reductive deamination.     

Synthesis of 1-substituted-6-methyluracils

A series of 6-methyl-1H-pyrimidin-2,4-diones bearing different substituents in the 1-position of the uracil ring were prepared starting from substituted ureas and diketene.     

Synthesis of 5-Cinnamoyl-3,4-dihydropyrimidine-2(1H)-ones

Two different approaches to the synthesis of 1-unsubstituted 5-cinnamoyl-3,4-dihydropyrimidine-2(1H)-ones have been developed. The first includes N(1)-protection of the starting 5-acetyl-3,4-dihydropyrimidine-2(1H)-one, further Claisen–Schmidt reaction, and cleavage of the protecting group. The second approach consists of one-pot condensation of urea, aldehyde, and cinnamoylacetone as dicarbonyl component. The 5-cinnamoylderivative synthesis starting from 5-acetyl-1,3-dialkyl-3,4-dihydropyrimidine-2(1H)-ones is also shown.     

Synthesis of 1,2-Diamino-1-phenylpropane Diastereoisomers from u-N-Trifluoroacetyl-2-amino-1-phenylpropan-1-ol

A new simple procedure for the synthesis of diastereomeric 1,2-diamino-1-phenylpropanes starting from u-N-trifluoroacetyl-2-amino-1-phenylpropan-1-ol (N-trifluoroacetylnorephedrine) is described. The trifluoroacetyl protecting group was particularly suitable for the protection of the amino group in order to reduce side reactions.     

Stereoselective synthesis of N-benzyl conduramine F-1, N-benzyl ent-conduramine E-1, dihydroconduramine F-1 and ent-dihydroconduramine E-1

A short and stereoselective synthesis of conduramine F-1 and ent-conduramine E-1 derivatives have been achieved starting from d-mannitol using nucleophilic vinylation on imine. A concise sequence of vinylation at both ends of d-mannitol and followed by RCM allowed us to prepare target compound.     

Synthesis of novel 1-alkyl or 1-aryl-2-(4-substituted-1-piperazinyl)-1-H-benzothieno[2,3-d]imidazoles

The synthesis of novel 1-alkyl or 1-aryl-2-(4-substituted-1-piperazinyl)-1-H-benzothieno[2,3-d]imidazoles 7e-x starting from 2-nitro-3-bromobenzo[b]thiophene is described. These compounds were prepared as potential H₁-antihistaminic agents.     

Synthesis of a 1α-amino-1-deoxy analogue of forskolin

1α-Amino-1,6,9-trideoxy forskolin was synthesized starting from drimenal and an isoprenoid C₅ unit. A tricyclic labdane with the entire forskolin skeleton was available in only four steps. Barton's nitrite photolysis was applied to functionalize C-1.     

Dispersed fluorescence spectroscopy of the CBr2A1B1-X1A1 transition

Dispersed fluorescence spectra following the excitation of the CBr2A1B1-X1A1 2 and 2 bands at visible wavelengths were acquired in a discharge supersonic free jet expansion using an intensified charge-coupled device (ICCD) detector. The dispersed fluorescence spectra show signal-to-noise ratios of up to 60 and extend out to a maximum red shift frequency of 6000 cm(-1). Complete and detailed vibrational structure of the ground singlet state (X1A1) was observed. Vibrational parameters including fundamental frequencies, anharmonicities, and coupling constants were determined for the CBr2 X1A1 state. Additional vibrational structure starting at approximately 3650 cm(-1) was observed and this indicates the singlet-triplet energy gap to be >10 kcal mol(-1).     

Synthesis of 7-Amino-1-nitro-2-heptanone Derivatives

Abstract

New N-substituted 7-amino-1-nitro-2-heptanone derivatives have been obtained starting from readily accessible 2-(nitromethylidene)hexahydro-1H-azepine. These compounds have been further used as starting materials for the synthesis of some heterocycles with 5-aminopentyl fragment.     

Oxy-cope rearrangements of bicyclo[3.2.0]heptenones. Synthesis of bicyclo[4.2.1]non-1(4)-en-6-ones and bicyclo[5.2. 1]dec-1(10)-en-5-ones

6-exo-Methylbicyclo[3.2.0]hepten-7-ones and their 2-alkylidene analogues are readily prepared from dialkyl squarates. These compounds undergo facial oxy-Cope ring expansions upon treatment with vinyllithium; the former leads to bicyclo[4.2. 1]non-1(4)-en-6-ones and the latter to the first examples of bicyclo[5.2.1]dec-1(10)-en-5-ones, compounds having exceptionally strained bridgehead double bonds. The transformations are controlled by the 6-exo-methyl group in the starting material along with the substituent at position-1 (bridgehead) which force attack of the lithium reagent from the concave face of the starting material, thus allowing the cyclopentenyl or alkylidene groups to participate in the sigmatropic event.     

Synthesis of 1, 3, 5-trisubstituted-4,5-dihydro-1H-pyrazole catalyzed by vitamin B1 and its fluorescence properties

Research on Chemical Intermediates - An efficient synthesis of 1,3,5-trisubstituted-1H-pyrazoles was developed via cyclocondensation in 78–92% yields starting from α,β-unsaturated...     

间叔丁基苯乙醚的合成研究

通过两条路线合成了生产新型农药乙螨唑的关键中间体间叔丁基苯乙醚。其一以叔丁基苯为原料,通过溴代、硝化、还原(脱卤素)、重氮化和乙醚化反应得到目标化合物;另一采用对氨基叔丁基苯为原料,通过乙酰化、溴代、脱乙酰化、重氮化去氨基和乙醚化反应得到目标化合物。两条路线的总收率都较高,分别为45%和63%。所得产品中未检测到异构体对叔丁基苯乙醚,质量好,纯度高。其中路线一原料便宜,操作简单,更适合进一步工业化放大生产。合成路线中的有机中间体和目标化合物的化学结构通过MS和NMR进行确证。     

The diels-alder reactions of furans 1: the reactions of furans with α-chloroacryonitrile

The intermolecular Diels-Alder reactions of several furans with α-chloroacrylonitrile occurs at atmospheric pressure. The role of temperature in affecting starting material: product ratio is examined from a preparative viewpoint.