有机电致发光材料芴衍生物的合成

芴衍生物被认为是很有开发前景和实用价值的一类发光材料,它具有较为优异的综合性能,如良好的发光效率,较好的热稳定性等。本研究工作采用条件温和、产率较高的合成路线,对芴为单体进行官能团修饰,制备了9,9-二甲基芴、9,9-二甲基-2-硝基芴、9,9-二甲基-2-氨基芴、N-（4-联苯基）-9,9-二甲基-2-氨基芴。并对影响反应的重要因素进行了考察和讨论。     

3-Amino-furo[2.3-b]pyridine

3-Amino-furo[2,3-b]pyridines The reaction of the 3-cyano-2-pyridones 1 with α-halogen carbonyl compounds yields 2-alkoxy-pyridines 2 which can be cyclized in the presence of sodium ethoxide to form 3-amino-furo[2,3-b]pyridines 3 . From 4,6-dimethyl-3-cyano-2-pyridone, mixtures of N- and O-alkylated compounds are obtained which by cyclization in addition to 3-amino-furopyridines 6 yield indolizinones 7 . From 3 , pyridofuro-pyrimidines 9 can be synthesized.     

N-Alkylation During the Removal of a Carbamate-Type Protecting Group

Acidolysis of 2-(p-biphenylyl)isopropyl N-(5-nitro-2-pyridyloxy)carbamate (IV) resulted in loss of carbon dioxide and formation of N-2-(p-biphenylyl)isopropyl-O-(5-nitro-2-pyridyl) hydroxylamine (V). The mechanism of this unusual reaction is discussed.     

Anionic synthesis of aromatic carboxyl functionalized polymers. Chain-end functionalization of poly(styryl)lithium with 4,5-dihydro-4,4-dimethyl-2-[4-(1-phenylethenyl)phenyl] oxazole

The novel syntheses of 4-(4,5-dihydro-4,4-dimethyl-2-oxazolyl)benzophenone, 1-[4-(4,5-dihydro-4,4-dimethyl-2-oxazolyl)phenyl]-1-phenylethanol and 4,5-dihydro-4,4-dimethyl-2-[4-(1-phenylethenyl)phenyl]oxazole ( 1 ) are described. ω-Oxazolyl polystyrene ( 2 ) was synthesized in quantitative yields by the reaction of poly(styryl)lithium with stoichiometric amounts of 4,5-dihydro-4,4-dimethyl-2-[4-(1-phenylethenyl)phenyl]oxazole ( 1 ) in toluene/tetrahydrofuran (4 : 1 v/v) at −78°C. Deblocking of the oxazoline protecting group by acid hydrolysis followed by saponification quantitatively provides the corresponding aromatic carboxyl chain-end functionalized polystyrene ( 3 ). The functionalization agent and functionalized polymers were characterized by HPLC, thin layer chromatography, size exclusion chromatography, vapor phase osmometry, spectroscopy (¹H NMR, ¹³C NMR and FTIR), potentiometry and elemental analysis.     

Antifertility agents: 5. Synthesis of 2,2-dimethyl-3,4-diphenyl-5,6-benzochromenes and 1,1-dimethyl-2,3-diphenylphenalenes

3-phenyl-4-(p-(beta-pyrrolidinoethoxy)- HCl, HC1, 2,2-dimethyl-3-phenyl-4(p-(beta-pyrrolidinoethoxy) -phenyl)-5,6-benzochromene-HCl, 1,1-dimethyl-2,3-diphenyl-4-(beta-pyrrolidinoethoxy) -phenalene, and 1,1-dimethyl-2-phenyl-3-(p-(beta-pyrrolidinoethoxy) -phenyl)-4-beta-pyrrolidinoethoxy phenalene were synthesized from 5,6-benzocoumarins. When tested in rats at 10 mc/kg orally for 5 days for antiimplantation activity, they were ineffective.     

大果木姜子茎挥发油化学成分分析及在卷烟中的应用

为研究大果木姜子茎挥发油成分及其对卷烟吸食品质的影响,采用水蒸气蒸馏法,从大果木姜子茎中提取挥发油,对主要化学成分进行GC-MS分析,并进行了卷烟加香试验。从挥发油中共鉴定出20个化合物,主要包括芳樟醇、D-苧烯、柠醛、（Z）-柠檬醛、6-甲基-5-庚烯-2-酮、（1S）-6,6-二甲基-2-亚甲基二环[3.1.1]庚烷、（-）-4-萜品醇、氧化芳樟醇、（＋）-α-松醇、1R-α-蒎烯等。评吸结果表明,大果木姜子茎挥发油对卷烟的香气质、香气量、余味、甜润感指标有一定改善作用。研究实,大果木姜子茎挥发油含有多种香味成分,在卷烟加香中具有一定的应用潜力。     

AM/DAAM二元共聚物的合成与表征

用一种氧化还原体系的引发剂,采用水溶液聚合法合成了丙烯酰胺-N-(1,1-二甲基-3-氧代丁基)丙烯酰胺(AM/DAAM)二元共聚物。实验中分别考察了原料中单体配比、反应时间、引发剂用量对共聚物的特性粘数的影响;同时采用定量的方法考察了共聚物的溶解性能。结果表明,当DAAM在共聚物中的摩尔百分含量为33.64%时,聚合物的特性粘数比相同条件下合成的聚丙烯酰胺提高9.9倍;当共聚物中DAAM的含量为15%时,共聚物的溶解速率是相同条件下合成的聚丙烯酰胺的4倍。通过对各种组成共聚物在不同盐溶液中的特性粘数的测定,结果显示该共聚物具有良好的耐盐性能。另外,采用红外光谱、核磁共振氢谱对共聚物进行了定性和定量的表征。     

Water-soluble copolymers,XXIII. Copolymers of acrylamide with N-(1,1-dimethyl-3-oxobutyl)-N-(n-propyl)acrylamide: Synthesis and characterization

The copolymerization of acrylamide (AM) with N-(1,1-dimethyl-3-oxobutyl)-N-(n-propyl)acrylamide (PDAAM) has been studied in the range from 5 to 20% PDAAM in the feed. The copolymer compositions have been determined from elemental analysis and ¹³C-NMR. Reactivity ratio studies have been performed and the value of r₁ r₂ determined to be 2.20. The molecular weights of the copolymers were found to decrease with increasing PDAAM content in the feed. The copolymer microstructures were predicted from the experimentally determined reactivity ratios. These model structures are utilized for assessment of structure/dilute solution property relationships reported in a subsequent paper in this series.     

Semiochemicals of the Scarabaeinae. VII: Identification and synthesis of EAD-active constituents of abdominal sex attracting secretion of the male dung beetle,Kheper subaeneus

Using gas chromatography with flame ionization detection (FID) and electroantennographic detection (EAD) in parallel, butanoic acid, skatole, and (E)-2,6-dimethyl-6-octen-2-ol were identified as constituents of the abdominal sex-attracting secretion of the male dung beetle, Kheper subaeneus, which reproducibly elicited EAD responses in male and female antennae. This is the first report of the occurrence of (E)-2,6-dimethyl-6-octen-2-ol as a natural product, for which the name (E)-subaeneol is proposed. In some experiments, a few other constituents of the secretion also gave reproducible responses in specific male and female antennae but did not elicit responses when the analyses were repeated with other antennae. The major volatile constituent of the secretion, identified as (S)-(+)-2,6-dimethyl-5-heptenoic acid, is one of these EAD-active compounds. Both this compound and (E)-2,6-dimethyl-6-octen-2-ol were synthesized from authentic starting materials for comparison with the natural products.     

Water-soluble copolymers,XXIV. Copolymers of acrylamide with N-(1,1-dimethyl-3-oxobutyl)-N-(n-propyl)acrylamide: Solution properties

Solution properties of copolymers of acrylamide (AM) with N-(1,1-dimethyl-3-oxobutyl)-N-(n-propyl)acrylamide (PDAAM) of known molecular weight have been studied as a function of composition, added electrolytes, and polymer concentration. Arrhenius-type studies have been performed by viscometry and NMR to assess the effects of temperature. Phase separation studies have also been performed using turbidimetry. The solution properties of the AM-PDAAM copolymers are dictated by the presence of intramolecular hydrophobic interactions. These interactions may result in decreased hydrodynamic dimensions relative to polyacrylamide of similar molecular weight.     

Silyl Modification of Biologically Active Compounds. 14. Organosilicon Lipid-like Derivatives of Hydroxyethyl Tetrahydro(iso)quinoline and Thiazole with Antitumour,Antibacterial and Antifungal Properties

Silicon - A series of novel lipid-like O- and N-(3-trimethylsilyl)propyl derivatives of N-(2-hydroxyethyl)-1,2,3,4-tetrahydroquinoline, -tetrahydroisoquinoline and...     

Base induced [1,2]- and [3,2]-rearrangements of N-(2-Thenyl)-N-benzyldimethylammonium ion

The title compound 4 underwent Sommelet and Stevens rearrangements induced by a number of bases. Ionization of the thenyl methylene group of 4 to the corresponding ylid 10 was the prevalent process, yielding subsequently N-[2-(2′-thienyl)-2-phenethyl]dimethylamine 12 and N-[α-(o-tolyl)-2-thenyl]-dimethylamine 13 . The strong trend of the 2-thenyl ylids to produce large relative amounts of the Sommelet amine was confirmed. Minor products are N-[2-(2′-thienyl)-1-phenethyl]dimethylamine 15 and N-[α-phenyl-2-(3-methylthienyl)]dimethylamine 16 derived from the benzyl ylid 11 .     

三唑酮原药中主要杂质的GC-MS定性研究

通过气相色谱-质谱联用(GC-MS)的方法对三唑酮原药中的杂质进行了定性研究。从质谱图推断出杂质的可能结构，合成出了杂质标样。由保留时间及质谱图确认了三唑酮原药中的三个主要杂质为Ⅰ：1-(4-溴苯氧基)-3，3-二甲基-1-(1H-1，2，4-三氮唑-1-烷基)-2-丁酮；Ⅱ：1-(2，4-二氯苯氧基)-3，3-二甲基-1-(1H-1，2，4-三氮唑-1-烷基)-2-丁酮；Ⅲ：1，1-二(4-氯苯氧基)-3，3-二甲基-2-丁酮。     

Reaction of ethyl N-(6-ethoxycarbonyl-2-methylthiothieno[2,3-d]-pyrimidin-5-yl) formimidate with alkyl- and arylhydrazines: Formation of modified thieno[2,3-d]pyrimidines and thieno[2,3-d:4,5-d]dipyrimidin-4-ones

The reaction of ethyl N-(6-ethoxycarbonyl-2-methyl-thiothieno[2,3-d]pyrimidin-5-yl)formimidate ( 1 ) with methyl-hydrazine, N,N′-dimethyl- and N,N′-diphenylhydrazines separately in refluxing ethanol resulted in hydrolysis of formimidate group to give ethyl 5-amino-2-methylthiothieno[2,3-d] pyrimidine-6-carboxylate ( 2 ). The reaction on 1 with methyl-hydrazine without solvent afforded ethyl 5-amino-2-(1-methyl-hydrazino)thieno[2,3-d]pyrimidine-6-carboxylate ( 3 ), which underwent hydrazone formation with p-nitrobenzaldehyde to give 4 . Treatment of 1 with N,N-dimethylhydrazine afforded a mixture of 3-dimethylamino-7-methylthiothieno[2,3-d:4,5-d']dipyrimidin-4(3H)-one ( 5 ) and 2 . Displacement of methylthio group in 5 with morpholine, piperidine and 4-methylpiperazine gave the corresponding 7-substituted derivatives 6a-c . The reaction of 1 with para-substituted phenylhydrazines resulted in the formation of 3-(p-substituted phenylamino)7-methylthiothieno[2,3-d:4,5-d']dipyrimidin-4 (3H)ones ( 7a-c ).     

4,5-二甲基-3-腈基呋喃Schiff碱的合成与表征

以自制的4,5-二甲基-3-腈基-2-氨基呋喃与取代芳醛为主要原料,以乙醇为溶剂、醋酸为催化剂,通过回流反应合成了新型4,5-二甲基-3-腈基呋喃Schiff碱化合物。目标化合物通过IR、1HNMR、MS进行了表征。     

Pyryliumverbindungen. 37. Arylbenzene aus 2,4,6-Triaryl-pyryliumsalzen und Carbonsäureanhydriden

Pyrylium Compounds. 37. Arylbenzenes from 2,4,6-Triarylpyrylium Salts and Carboxylic Acid Anhydrides Refluxing 2,4,6-triarylpyrylium salts 1 with excess carboxylic acid anhydrides (RCH₂CO)₂O ( 2a : R = H, 2b : R = Me) in the presence of condensing agents like sodium or potassium acetate, sodium carbonate or methoxide, triethylamine or pyridine results in 1,3,5-triarylbenzenes 3 (R = H, Me). Under similar conditions, phenylacetic acid anhydride ( 2c ), generated in situ from sodium phenylacetate and excess 2a or 2b , yields 1,2,3,5-tetraarylbenzenes 3 (R = Ph). Thus, the reaction 1 + 2 → 3 represents a new and simple method for replacing the pyrylium heteroatom =O^⊕– by the =CR– moiety (R = H, Me, Ph). The structure of the arylbenzenes 3 was proved by spectroscopic methods, by comparison with literature data or by independent synthesis. As by-products 2-acyloxy-benzophenones 10 are formed. Reaction of 3,5-dimethyl-2,4,6-triphenyl-pyrylium perchlorate ( 11 ) with acetic acid anhydride/sodium acetate (or sodium phenylacetate) takes another course leading to 2-acetoxy-3,5-dimethyl-4,6-diphenyl-benzophenone ( 15 ), whereas treatment of 11 with propionic acid anhydride/sodium acetate follows the reaction scheme 1 + 2 → 3 giving 1,3,5-trimethyl-2,4,6-triphenylbenzene ( 16 ). The mechanisms of the different pyrylium ring transformations are discussed.     

Synthese von Heterocyclen durch C-C-Knüpfung. II. Katalytische Cyclisierung von N-Alkyl-N-allyl-acrylamiden und N.N-Diallyl-carbonsäureamiden

Synthesis of Heterocycles by C C-Bond Formation. II. Catalytic Cyclization of N-Alkyl-N-allyl-acrylamides and N,N-Diallyl Carbonic Acid Amides N-Alkyl-N-allyl-acrylamides 2 cyclize in the presence of PdCl₂ to 1-alkyl-3,4-dimethyl-3-pyrrolin-2-ones 4 and 1-alkyl-4-methyl-3-methylene-pyrrolidin-2-ones 5 . Compounds 4 predominate in the mixture. With RhCl₃, ring closure gives comparable amounts of lactams 4 and 7 (1-alkyl-3,4-dimethyl-3-pyrrolin-2-ones) besides some product of allyl elimination. N. N-Diallyl carboxylic amides 3 form cyclic enamides (1-acyl-3,4-dimethyl-2-pyrrolines, 9 ) on the action of PdCl₂ besides the products 10 of allyl elimination. RhCl₃ effects cyclization of 3 to form 1-acyl-3-methyl-4-methylene-pyrrolidines 11 besides some 9 . The acid amide groups of compounds 9 and 11 are shown by n.m.r. spectroscopy to exist as rotamers.     

Identification of minor cyclic fatty acids in fractionated tall oil

The structure of several minor cyclic fatty acids present in Finnish tall oil fatty acids are elucidated by gas chromatography-mass spectrometry. The origin and mechanism of formation of these cyclic fatty acids are discussed. The cyclic fatty acids identified in tall oil fatty acids are: 4-(5-pentyl-3a,4,7,7a-tetrahydro-4-indanyl)butanoic acid,ω-(o-alkylphenyl)alkanoic acid, 2,6-dimethyl-9-(3-isopropylphenyl)-6-nonenoic acid, 4-(5-pentyl-4-indanyl)butanoic acid, and 4-(2-hexyl-1,2,4a,5,6,7,8,8a-octahydro-1-naphthyl)butanoic acid. In addition, three different branched or cyclic unsaturated C₁₉ fatty acids are reported to be present in tall oil.     

3-硝基-N-乙基咔唑单溴代产物合成

研究了在不同的溶剂和后处理方式下3种3-硝基-N-乙基咔唑的单溴化方法(1)冰醋酸－水稀释法;(2)冰醋酸-蒸馏法;(3)1,2-二氯乙烷-蒸馏法。比较了3种方法各自的优缺点,认为(3)法是较佳的工业化路线。按此工艺路线,在最佳工艺条件即3-硝基-N-乙基咔唑与溴的摩尔比为1∶1、反应时间为3h、反应温度为15℃、溶剂的量为2.5ml/mmol下,收率达到96.0%。     

3-硝基-N-乙基咔唑单溴代产物合成工艺的研究

研究了在不同的溶剂和后处理方式下３种３－硝基－Ｎ－乙基咔唑的单溴化方法：（１）冰醋酸－水稀释法；（２）冰醋酸一蒸馏法；（３）１，２－二氯乙烷一蒸馏法。比较了３种方法各自的优缺点，认为（３）法是较佳的工业化路线。按此工艺路线，在最佳工艺条件即３．硝基．Ｎ－乙基咔唑与溴的摩尔比为１：１、反应时间为３ｈ反应温度为１５℃、溶剂的量为２．５ｍｌ／ｍｍｏｌ下，收率达到９６．０％。