CIM单元镍脂肪酸及其甲酯氢化催化剂的研制

在CIM - 6油脂氢化催化剂及其相关技术的基础上 ,研制成功CIM - 7脂肪酸氢化催化剂和CIM - 8脂肪酸甲酯氢化催化剂。又在相同条件下对十八碳烯酸加氢 ,同Pricat 9932 - 6(UnichemaInternational)、KE -FS40 (Sud -ChemicAg .)、G - 5 3 - 1(U .C .I.)催化剂对比 ,考察了CIM - 7的催化性能 ;当温度、压力、搅拌、时间相同 ,改变催化剂质量分数对不同酸值的棕榈油甲酯加氢 ,同SD - 2 5 0 (吉野Co .)催化剂对比 ,考察了CIM - 8的催化性能。结果表明 :(1)产品硬脂酸的碘值 (gI2 10 0g)分别为 0 76 (CIM - 7)、0 85 (Pricat9932 - 6 )、1.0 4(KE -FS40 )、1.2 8(G -5 3- 1) ,即催化活性和抗酸性CIM - 7>Pricat 9932 - 6 >KE -FS40 >G - 5 3 - 1。 (2 )当原料酸值为 1 1mgKOH g、w(催化剂 ) =0 2 0 %时 ,产品氢化棕榈油甲酯碘值 (gI2 10 0g)为 1 12 (CIM -8) ,2 4 0 7(SN - 2 5 0 ) ;当原料酸值为 0 0 3mgKOH g,w(催化剂 ) =0 0 76 %时 ,产品碘值为 1 90(CIM 8) ,12 18(SN - 2 5 0 ) ,即催化活性和抗酸性CIM - 8>>SN - 2 5 0。 3 产物中w(镍 ) =38 5×10 - 6 (CIM - 7) ,41 2× 10 - 6 (Pricat 9932 - 6 ) ,48 7× 10 - 6 (KE -SF40 ) ,5 7 4× 10 - 6 (G - 5 3- 1) ;1 18× 10 - 6 (CIM 8) ,1 83× 1     

Stability,structure, and antioxidant activity of astaxanthin crystal from Haematococcus pluvialis

Crystallized anthaxanthin was prepared through the cleaning crystallization method and the stabilities during thermal, lighting, and pH treatment, and antioxidant activities in vitro were evaluated. The structural characterizations of astaxanthin crystal were verified by ¹H, ¹³C NMR, and XRD analysis. The stability data showed that the astaxanthin crystal was more sensitive to heat, light, and pH compared to oleoresin. The sucrose had no outstanding influence on the astaxanthin crystal, while the stability of astaxanthin oleoresin slightly increased with the increase of sugar concentration. The XRD and nuclear magnetic resonance spectra elucidated that the astaxanthin crystal was all trans structure. The astaxanthin crystal showed the dominant 1,1′-diphenyl-2-picrylhydrazyl (IC₅₀ 18.65 μmol L⁻¹), 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt˙⁺(21.1 μmol L⁻¹), •OH (IC₅₀ 49.46 μmol L⁻¹) and ferric reducing antioxidant power (IC₅₀ 81.60 μmol L⁻¹) activities. The investigated results would be helpful for improving the development of astaxanthin crystal in food products.     

The Cyclization of Cis- and Trans- Methoxybenzaldoximes to Methoxy-3,1,4-Benzoxadiazepines and Methoxy-Quinazoline-3-Oxides Respectively

Cis and trans forms of 2-amino-3(4, 5, and 6)-methoxybenzaldoximes were separated chromatographically and distinguished by their spectra. The trans-isomers, with triethyl orthoformate, gave 5(6, 7, or 8)-methoxyquinazoline-3-oxide whereas appropriate cis-isomers gave 7- or 9-methoxy-3,1,4-benzoxadiazepine. The structures of the bicyclic products were confirmed by their mass spectra.     

Dienoligomerisierung. XVI. Nickelkomplexkatalysierte Codimerisierung von isomeren Octatrienen mit Ethen

Dienoligomerization. XVI. Catalytic Codimerization of Isomeric Octatrienes with Ethene by Nickel Complexes The isomeric octatrienes (n-octa-1,3c,t,7-triene 1 , n-octa-1,3c,6t-triene 2 and 3-methylhepta-1,4t,6-triene 3 ), which are easily obtained in high yields by transition metal catalysed dimerization of butadiene, react with ethene 4 in the presence of the cationic tetrakis-(triethylphosphite)-nickelhydride complex 5 to the dodimers 3-methylnona-1,4c,t,8-triene 6 , 4-vinylocta-2c, 7-diene 7 , 3-methyl nona-1,4c,t,7t-triene 8 , 4-vinylocta-2c,6t-diene 9 , 3,6-dimethylocta-1,4c,t,7-triene 10 and 3-methyl-4-vinylhepta-1,5c-diene 11 . The concentration-time dependence and a possible reaction mechanism of the codimerization are discussed and the structure data of the reaction products are reported.     

Anti- and Prooxidant Properties of Carotenoids

Carotenoids can be effective singlet oxygen quenchers and inhibit free-radical induced lipid peroxidation. A remarkable property of β-carotene ( 1a ) is the change from an antioxidant to a prooxidant depending on oxygen pressure and concentration. In the present study a considerable number of carotenoids ( 1a , 2c , 2d , 2e , 3a , 4a , 5a , 6a , 7a , 8a , 8h , 8i , 8j , 9f , 10a , 11a , 12g ) was investigated using two independent approaches: 1. Comparison of their effects on inhibition of the free-radical oxidation of methyl linoleate, and 2. The direct study of the effect of oxygen partial pressure upon their rates of oxidation. It is shown that some carotenoids ( 7a , 8a ) are even more effective than the well-known compounds β-carotene ( 1a ) and astaxanthin ( 5a ) and are powerful antioxidants without any prooxidative property. Different carotenoids display different behaviour depending on chain length and end groups. The influence of these functional groups on the antioxidative reactivity is discussed.     

联氢化嘧啶衍生物的合成及其构象研究

报道了一种合成联氢化嘧啶衍生物１￣５、四氮杂全氢芴衍生物６和７的新方法。讨论了化合物１￣５的稳定构象,提出了化合物５和７的顺反异构体的酸催化下的转变机理。     

Bacterial production of poly-3-hydroxyalkanoates containing arylalkyl substituent groups

6-Phenylhexanoic acid (6PHxA), 7-phenylheptanoic acid (7PHpA), 9-phenylnonanoic acid (9PNA), 11-phenylundecanoic acid (11PUA), 9-p-tolylnonanoic acid (9TNA) and 9-p-styrylnonanoic acid (9SNA) were prepared and evaluated as substrates for cell growth and polyester production by Pseudomonas oleovorans and Pseudomonas putida. P. putida was more effective than P. oleovorans for producing polyesters from these aromatic substrates. Poly-3-hydroxyalkanoates, PHAs, were obtained from 6PHxA, 7PHpA, 9PNA and 11PUA. The PHAs produced from all of these substrates contained mostly 3-hydroxy-5-phenylvalerate (H5PV) and 3-hydroxy-6-phenylhexanoate (H6PHx) units. Polymer yields ranging from 3 to 47% of cell dry weight were obtained with molecular weights ranging from 156 000 to 37 000 and polydispersities from 2.3 to 2.9. Cofeeding of most of these substrates with nonanoic acid produced mixtures of two different PHAs with different glass transitions, one in the region of −8 to 12°C for the PHA with arylalkyl substituent groups, and one in the region of −14 to −35°C for the PHA from nonanoic acid. The PHA from 9TNA also had a crystalline melting transition.     

Synthesis of pyrazolo[4′,3′:5,6]pyrazino[2,3-c]pyrazoles and pyrazolo[4′,3′:5,6]pyrazino[2,3-d]pyrimidines and their application to polyester fibres

4-Nitroso-1-phenyl-3-methyl-5-aminopyrazole ( 1 ) was condensed with ethylcyanoacetate ( 2 ), malononitrile ( 4a ) and 2-cyanomethylbenzimidazole ( 4b ) to yield 6-hydroxy-5-cyano, 6-amino-5-cyano and 6-amino-5-(benzimidazol-2-yl)-3-methylpyrazolo [3,4-b]pyrazines 3, 5a and 5b , respectively. 5-Cyano-6-chloro derivative 6 obtained from 3 was converted to 3-aminopyrazolo[4′,3′:5,6]pyrazino[2,3-c]pyrazoles 8a and 8b by the treatment with hydrazin hydrate ( 7a ) and phenylhydrazine ( 7b ), respectively. Compound 5a was treated with formamide ( 9a ), urea ( 9b ) and thiourea ( 9c ) to give 4-aminopyrazolo[4′,3′:5,6]pyrazino[2′3′-d]pyrimidines 10a–10c. With refluxing acetic anhydride compounds 8a, 8b and 10a gave corresponding acetamido derivatives 8c, 8d and 10d. Compound 5a was treated with ethylorthoformate ( 11 ), acetic anhydride ( 12 ) or benzoylchloride ( 13 ) to give fused benzimidazopyrazolo[4′,3′:5,6]pyrazino[2′,3′-d]pyrimidines, viz., benzimidazol[1,2-c]pyrazolo[4,3-g]pteridines ( 14a–14c ). Some of the compounds 8, 10 and 14 were applied to polyester as disperse dyes and their fastness properties were studied.     

Cyclocondensation of 4-Benzyl-1-hydrazinophthalazine

1-Hydrazino-4-benzylphthalazine 1 underwent closure and/or condensation reaction with formic acid, acetic acid, acetic anhydride, trifluoroacetic anhydride, ortho esteres, aldehydes, urea or carbon disulphide to afford the N-formyl 3a , N-acyl 3b , and the appropriate 3-substituted-6-benzyl-s-triazolo [3,4-a] phthalazines 4a , c , 7 , 8 . Alkylation of the obtained s-triazolo[3,4-a]-phthalazine-3-thione 7 and s-triazolo [3,4-a] phthalazin-3-one 8 with N-substituted chloroacetamides gave the thioether 9 and N-substitution products 10 , respectively. Likewise, applying Mannich conditions of the previously mentioned intermediates 7 and 8 yielded the N-Mannich bases ( 11 and 12 ). The new products were characterized by their elemental and spectral data.     

Total synthesis of angucyclines. 9. An Alternative Biomimetic-Type Synthesis of 8-Deoxytetrangomycin

Base-catalyzed cyclization of the naphthoquinone 5 afforded the 1,2-dihydroanthraquinone 6a . The bisalkylation products 9 and 10 were obtained by Stille-type chain elongation of the corresponding triflate 6b with the stannanes 7 or 8 . The dihydroanthraquinone 9 is a potential precursor for the SS-228 Y-type angucyclinones, where as the diketone 10 can be converted to 8-deoxytetrangomycin ( 11 ).     

天然虾青素的提取纯化及其应用

本文对从虾加工废弃物中提取虾青素(Astaxanthin)的常用方法进行了评述。碱提法对环境污染严重,虾青素易被氧化成为虾红素(Astacene);油溶法提取效率高,但提取物不易与高沸点的油分离;低沸点有机溶剂如二氯甲烷等是提取虾青素的有效溶剂,可借助蒸馏技术将溶剂循环利用;超临界萃取法可避免虾青素的降解,可得到高品质的产品,但生产成本高。同时,综述了虾青素在食品、保健品、医药和着色剂等领域中的应用。     

六苄基六氮杂异伍兹烷氧化产物的亚硝化

采用硝酸（65％）／亚硝酸钠体系对六苄基六氮杂异伍兹烷氧化物－乙酰基三苯甲酰基二苄基六氮杂异伍兹烷（3）、二乙酰基二苯甲酰基二苄基六氮杂异伍兹烷（4）和三乙酰基一苯甲酰基二苄基六氮杂异伍兹烷（5）进行亚硝解，成功脱去了上述三种化合物上剩余的两个苄基，将苄基转换为亚硝基，得到了一乙酰基三苯甲酰基二亚硝基六氮杂异伍兹烷（6）、二乙酰基二苯甲基二亚硝基六氮杂异伍兹烷（7）和三乙基酰基一苯甲酰基二亚硝基六氮杂异伍兹烷（8）。     

Synthesis and X-ray structure analysis of 2-[cyano(aryl)-methylene]-imidazolidines, -hexahydropyrimidines,and -hexahydro-1H-1,3-diazepines

2-[Cyano(aryl)methylene]-imidazolidines ( 7 ), -hexahydropyrimidines ( 8 ) and -hexahydro-1 H -1,3-diazepines ( 9 ) were synthesized by the reaction of (dimethylthiomethylene)-phenylacetonitriles ( 6 ) with ethylenediamine, 1,3-diaminopropane and 1,4-diaminobutane, respectively. These molecules were designed to study the tautomeric equilibrium between the ketene aminal form and the amidine form by changing the substituent on the para position of the phenyl group. But all the products obtained were the ketene aminals. Because the phenyl group was twisted over 30° from the plane containing the two nitrogen atoms and the double bond as shown by the crystal structure of 7a, 8a and 9a , the substituents had no effect on the equilibrium.     

Silver‐Mediated Oxidative Fluorotrifluoromethylation of Unactivated Alkenes

An efficient regioselective fluorotrifluoromethylation of unactivated alkenes has been developed. The reaction of alkenes with (trifluoromethyl)trimethylsilane (TMSCF₃) and Selectfluor in the presence of silver trifluoromethanesulfonate (AgOTf), cesium fluoride (CsF), and iodobenzene diacetate [PhI(OAc)₂] in N,N‐dimethylformamide (DMF) at −20 °C gave the corresponding fluorotrifluoromethylated products in moderate to good yields. The silver salt turns out to be crucial for this transformation.

     

Oxidation reactions of acetylenic fatty esters with selenium dioxide/tert-butyl hydroperoxide

Reaction of methyl undec-10-ynoate (1) with selenium dioxide/tert-butyl hydroperoxide (TBHP) in aqueous dioxane gave methyl 9-oxo-undec-10-ynoate (2, 9%) and 9-hydroxy-undec-10-ynoate (3, 60%), while methyl octadec-9-ynoate (4) yielded mixtures of positional isomers of mono-keto (viz. methyl 8-oxo- and 11-oxo-octadec-9-ynoate, 5, 5%), hydroxy-keto (viz. methyl 8-hydroxy-11-oxo-and 11-hydroxy-8-oxo-octadec-9-ynoate, 6, 10%), and dihydroxy (viz. methyl 8,11-dihydroxy-octadec-9-ynoate, 7, 24%) derivatives. Similar treatment of a conjugated diacetylenic fatty ester (methyl octadeca-6,8-diynoate, 8) furnished a mixture of methyl 5-oxo-and 10-oxo-octadeca-6,8-diynoate (9, 12%) and a complex mixture of very polar products. Reaction of methyl octadec-11E-en-9-ynoate (methyl santalbate) (10) with selenium dioxide/TBHP in aqueous dioxane gave exclusively a mixture of regiospecific products, viz. methyl 8-oxo-octadec-11(E) Z-en-9-ynoate (11, 6%) and methyl 8-hydroxy-octadec-11 E-en-9-ynoate (12, 70%). The structures of the various products were determined by a combination of spectroscopic and mass spectral analyses.     

Phosphonitrilic chloride: 30. Synthesis of chelating polymers from cyclophosphazene derivatives and studies of their electrical conductivity and thermal properties

Chelating polymers containing copper, nickel and cobalt have been formed by reaction of the cyclophosphazene derivatives P₃N₃(NCSNHC₆H₅)₆ or P₃N₃(NCSNHNHC₆H₅)₆ and the corresponding metal ions. The polymers prepared are amorphous solids and insoluble in most organic solvents. The electrical conductivity of the products range from 8.8 × 10⁹ to 1.8 × 10¹⁴ θ-cm. The products are more stable than the corresponding ligand compounds.     

Titanium dioxide-mediated photocatalysed degradation of few selected organic pollutants in aqueous suspensions

The photocatalytic degradation of maleic hydrazide (1), propham (2), tebuthiuron (3), propachlor (4), chlortoluron (5), thiram (6), phenoxyacetic acid (7), 2,4,5-trichlorophenoxy acetic acid (8), 4-chlorophenoxy acetic acid (9), uracil (10), 5-bromouracil (11) and bromothymol blue (12) have been investigated in aqueous suspensions of titanium dioxide (TiO₂) under a variety of conditions. The degradation was studied by monitoring the change in substrate concentration employing UV spectroscopic analysis technique and depletion in total organic carbon (TOC) content as a function of irradiation time. The degradation kinetics of the compounds were investigated under different conditions, such as types of TiO₂, pH, catalyst concentration, substrate concentration, temperature and in the presence of different electron acceptors, such as hydrogen peroxide (H₂O₂), potassium persulphate (K₂S₂O₈), ammonium persulphate (NH₄)₂S₂O₈ and potassium bromate (KBrO₃) besides molecular oxygen. TiO₂ Degussa P25 was found to be more efficient photocatalyst for the degradation of the model compounds as compared with other photocatalysts. The degradation products were analysed using GC/MS analysis technique and probable pathways for the formation of different products have been proposed.     

3‐Methyl‐4‐oxa‐5‐azahomoadamantane as an Organocatalyst for the Aerobic Oxidation of Primary Amines to Oximes in Water

A simple and efficient catalytic system for the aerobic oxidation of primary amines into corresponding oximes has been developed, with 3‐methyl‐4‐oxa‐5‐azahomoadamantane as catalyst, acetaldoxime as co‐catalyst and water as solvent. This process, which uses oxygen (O₂) as an economic and green oxidant and water as a green solvent, tolerates a wide range of substrates, affording the target oximes in moderate to excellent yields. It was found that high selectivity was achieved when 3‐methyl‐4‐oxa‐5‐azahomoadamantane was used, and E‐type oximes were the only detected products. A possible mechanism for this catalytic process is proposed.

     

Zur Telomerisierung von Isopren mit Palladium-Komplexen bei niedriger Temperatur

On the Telomerization of Isoprene at Low Temperature The telomerization of isoprene was carried out by means of a catalyst system of Pd(acac)₂/PPh₃ and complexes of the type Pd(acac)₂ · L (L = PPh₃; py; NHEt₂) at 298 K. The reaction in methanol gave 8-methoxy-2, 7-dimethyl-octa-1, 6-diene (3a) , 8-methoxy-3, 7-dimethyl-octa-1, 6-diene (4a) and oligomer products. 2, 7-Dimethyl-octa-1,3, 7-triene (1) , 8-i-propoxy-2, 7-dimethyl-octa-1, 6-diene (3b) and oligomer products were obtained in i-PrOH. During the reaction a formation phase of the catalyst was observed.     

2,5—二甲基—3,4—二乙酰基呋喃及其衍生物的合成

以ＫＩ－ＮａＩ为间接电解质，丙酮为溶剂，用间接电氧化的方法将乙酰丙酮（３）、乙酰乙酸乙酯（４）进行偶联反应，高产率地得到偶联产物四羰基化合物（５－６），进而在酸性介质中经Ｐａａｌ－Ｋｎｏｒｒ环化，合成了２，５－二甲基－３，４－二乙酰基呋喃（７）和２，５－二甲基－３，４－二乙氧羰基呋喃（８）。（７）再经ＮａＢＨ４还原得２，５－二甲基－３，４－二（１－羟基乙基）呋喃（９）。