Reaction of t-butyl lithium with (±)-3-methoxy-N-chloromorphinan

Preparation of (±)-3-methoxy-16-t-butylmorphinan ( 4 ) by reaction of t-butyl lithium with (±)-3-methoxy-N-chloromorphinan ( 1 ) is described. The structure of 4 was confirmed by X-ray crystallography.     

The synthesis of 1-(2-dialkylaminoethyl)-5 (and 6)-methoxy-2-methyl (and H)-benzimidazoles

The syntheses of twenty 1-(2-dialkylaminoethyl)-5 (and 6)-methoxy-2-methyl (and H)-benzimidazoles in which the dialkylamino groups are dimethylamino, diethylamino, pyrrolidino, piperidino and morpholino, are presented. These compounds failed to show any significant biological activity.     

(2S)-(+)-2-溴-1-(6'-甲氧基-2'-萘基)丙-1-酮的不对称合成

以(2R,3R)-酒石酸二甲酯为手性辅助剂,6-甲氧基-2-丙酰基萘经缩酮化、溴化铜不对称溴化、水解等反应合成了(2S)-2-溴-1-(6'-甲氧基-2'-萘基)丙-1-酮。总收率94%。     

The synthesis of some 1-(β-diethylaminoethyl)-2-(p-ethoxybenzyl)-5-substituted benzimidazoles

The syntheses of several 5-substituted benzimidazoles structurally related to the highly active analgesic 1-(β-diethylaminoethyl)-2-(p-ethoxybenzyl)-5-nitrobenzimidazole are presented.     

The reaction of N-cyanoamines with 1-(t-butyl)-3,3-diphenylaziridinone: A general method for the synthesis of 1-alkyl-, 1-aralkyl- and 1-aryl-5,5-diphenylhydantoins and -glycocyamidines

N-Cyanomanines react with aziridinone1 to yield the amides2. Base catalysed ring closure of the latter furnished the glycocyamidines3. Acid catalysed de-t-butylation, and deimination combined with de-t-butylation of the compounds3 leads to 1-substituted 5,5-diphenylglycocyamidines (4) and -hydantoins (5), respectively. Part of the hydantoins5 were also directly obtained by hydrochloric acid treatment of amides2. Selective de-t-butylation in position 3 of the glycocyamidine3 (R = t-Bu) was brought about by heating with methanolic NH₃ in the presence of NH₄I. Reaction of1 with the un substituted N-cyanoamine furnished carbodiimide7 which was cyclized to the glycocyamidine8. The mass spectra of some glycocyamidines4 and hydantoins5, as well as of compounds7 and8 are discussed.     

The synthesis of 5- and 6-acyl-2(1H)-pyrimidinones

The synthesis of 5-acyl-2(1H)-pyrimidinones is described. In addition, one example of the hitherto unknown 6-acyl-2(1H)-pyrimidinones has been prepared.     

One-pot synthesis of 2-（1-acyloxypentyl） benzoic acids

A one-pot synthesis of 2-（1-acyloxypcntyl） benzoic acids by trapping the carboxylatc/alkoxide dianion with acylating reagents following Grignard addition with n-BuMgBr to 2-formylbcnzoic acid was described. Compared with routine synthetic method, this novel procedure has the advantage of convenient operation and higher yields.     

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.     

The synthesis of 1-substituted-2-(β-dimethylaminoethyl)benzimidazoles

2-(β-Dimethylaminoethyl)benzimidazoles have been prepared by the reduction of the corresponding 2-benzimidazole-N,N-dimethylacetamides. Condensation of ethyl cyanoacetate with N-benzyl or phenyl-o-phenylenediamines led to N-cyanoacetyl-N'-substituted-o-phenylenediamines, the structure of which were assigned from u.v. and n.m.r. data. An improved synthesis of benzimidazole - 2 - acetic acid derivatives, from substituted ethyl acetimidates and o-phenylenediamines, is described. Dimerisation of 1-phenyl-benzimidazole occurs in the presence of phenyllithium.     

The crystal and molecular structure of 3,5-Di-(t-butyl)-1-phenylphosphoryl-4-aza-2,5-cyclohexadiene

The crystal and molecular structure of the title compound (C₁₈H₂₆NOP) has been determined by a single crystal, x-ray diffraction study using Cu-Kα. radiation. The compound was found to crystallize in the orthorhombic space group Pnma with unit cell constants a = 12.686 ± .001 Å, b = 14.776 ± .001 Å, and c = 9.540 ± .001 Å. The structure was solved by the heavy atom method and refined by block-diagonal least-squares to a final R = 0.09₉ for the 696 statistically significant reflections. The compound exhibits orientational disorder in the crystalline state. Nevertheless, the planarity of this ring; the lengthening of the diene carbon-carbon bond to 1.41 Å the resultant shortening of both the carbon-nitrogen bond (1.43 Å) and the carbon-phosphorus bond (1.74 Å), and the CNC bond angle of 121° all strongly support the assumption of delocalization of the diene π-electrons within the heterocyclic ring system.     

The synthesis of 1H-pyrazol-4-ols from 2-(2-alkylidenehydrazino)acetic acids

A new general method for synthesizing 1H-pyrazol-4-ols by cyclizing2-(2-alkylidenehydrazino) acetic acids with acetic anhydride in pyridine is reported.     

2-[4-取代苯基-2-氧-3-酰氨基-1-吖丁啶基]-2-苯基乙酸类化合物的合成

用叠氮钠和D-苯基甘氨酸为原料合成了2-[4-取代苯基-2-氧-3-酰氨基-1-吖啶基]-2-苯基乙酸类化合物. 在叠氮乙酰氯和亚胺化合物在三乙胺存在下在-78℃时进行环缩合反应, 可导致立体专一性合成顺-甲基-2-(4-取代苯基-2-酮-3-叠氮-1-吖啶基)-2-苯基乙酸, 催化氢化或硫化氢可减少叠氮基和得到氨基β-内酰胺后者被酰化生成α-酰氨基-β-内酰胺, 在温和碱性条件下选择性地氢化酯基既不会影响β-内酰胺环, 又不全影响酰胺侧链. 合成了二十个标题化合物, 其中九个被表明对β-内酰胺酶有抑制活性.     

AuCl(3)-catalyzed synthesis of highly substituted furans from 2-(1-alkynyl)-2-alken-1-ones

Highly substituted furans have been synthesized by the reaction of 2-(1-alkynyl)-2-alken-1-ones and various nucleophiles under very mild reaction conditions in good to excellent yields. Gold and some other transition metals are efficient catalysts for this reaction.     

“一锅串联法”合成2-[(E)-2-2-氯-1-甲基-3-吲哚基)乙烯基]喹啉-3-羧酸(英文)

设计了以2-(溴甲基)喹啉-3-甲酸乙酯(4)与2-氯-1-甲基-3-吲哚醛(5)为起始化合物,通过简便有效的"一锅法"反应,首次将吲哚环引入2-苯乙烯基喹啉骨架模型,从而得到一新颖结构的双杂环化合物,即(E)-2-(2-(2-氯-1-甲基-1H-3-吲哚基)乙烯基)喹啉-3-羧酸(3),其结构通过波谱数据和元素分析得以证实。     

The synthesis and spectra of new (E)-(trans) and (Z)-(cis)-1-alkyl-2-aryl (alkyl) - 3 -aroylaziridines

The synthetic scope of the reaction of primary amines with α,β-dibromochalones to form aroylaziridines is explored and found to require at least one hydrogen on the α-carbon of the amine. Fourteen new epimeric l-alkyl-2-aryl(alkyl)-3-aroylaziridines are synthesized accordingly. Next, representative aroylaziridines are investigated by infra-red spectroscopy in solvents of ambient polarity to assess the relative populations of the gauche and cisoid conformers present in the (Z)-(cis) series.     

Stereoselective synthesis of 3-(1-Hydroxyethyl)-2-azetidinonesfrom 3-hydroxybutyrates

Addition of dianions of 3-hydroxybutyrates to benzylideneaniline results in direct formation of $\text{trans}$$\text{S*}$-3-(l-hydroxyethyl)-1,4-diphenyl-2-azetidinone with 95% diastereoselectivity. Inversion of the configuration at Cα, gives the desired $\text{trans}$$\text{R*}$-2-azetidinone in high yield.     

An alternative synthesis of 2-(N-arylhydrazono)-1-benzothiophen-3-ones

In the presence of triethylamine, 2-mercaptobenzoic acid readily adds onto acylhydrazonoyl chlorides (1a-c) (precursors of the reactive nitrile imine 1,3-dipolar species) to afford good yields of the corresponding 2-[(2-oxo-1-arylhydrazonopropan-1-yl)mercapto]benzoic acids (2a-c). The latter acyclic adducts, in THF in the presence of 1,1'-carbonyldiimidazole, undergo intramolecular cyclization involving the activated carboxy and the enol functionality to deliver the respective 2-(N-arylhydrazono)-3-oxobenzothiophenes (3a-c). In the solid state, the latter compounds adopt the (Z)-geometry around the C=N double bond as evidenced by single crystal X-ray structure determination for 3b.     

A palladium-catalyzed synthesis of isatins (1H-Indole-2,3-diones) from 1-(2-haloethynyl)-2-nitrobenzenes

An inherently regiospecific synthesis of isatins (1H-indole-2,3-diones) starting from 1-halo-2-nitrobenzenes is described. The isatins are formed by an intramolecular palladium-catalyzed annulation of 2-(2-haloethynyl)-1-nitrobenzenes via the formation of 2-haloisatogens.