Preparation,characterization and properties of β-chitin and N-acetylated β-chitin

Free amino groups in β-chitin from squid pen were acetylated to obtain N-acetylated β-chitin. After careful control of degree of acetylation, thermal and mechanical properties of β-chitin and N-acetylated β-chitin were compared. The structural differences of β-chitin and N-acetylated β-chitin were characterized by Fourier transform infrared (FTIR) and wide-angle x-ray diffraction (WAXD) analysis. The results indicated that the crystallinity of N-acetylated β-chitin was higher than that of β-chitin and N-acetylated β-chitin exhibited characteristics similar to α-chitin. Equilibrium water content (EWC) of β-chitin reached to about 50% and this hydrophilic nature was assumed to be caused by a relatively weak hydrogen bonding force of β-chitin with parallel main chains. On the other hand, EWC of N-acetylated β-chitin was 40% due to the introduction of ordered structure. β-chitin and N-acetylated β-chitin have the tensile strength of 0.4 and 0.7 Mpa in the swollen state, respectively. Viscoelastic properties and thermal relaxation behaviors were investigated by dynamic mechanical thermal analysis (DMTA). DMTA spectra of these samples showed that α-transition peaks of β-chitin and N-acetylated β-chitin were observed at 170 and 190°C, respectively. These relaxation peak maxima were assigned to be their glass transition temperature. In addition, a second relaxation peak of β-chitin resulting from acetamide groups was found at 112°C and a broad relaxation peak of N-acetylated β-chitin at around 81–100°C. As a result of thermogravimetric analysis, 10% weight loss temperatures of β-chitin and N-acetylated β-chitin were 270 and 285°C, respectively. © 1996 John Wiley & Sons, Inc.     

Acetyl- and O-alkyl- derivatives of β-mangostin from Garcinia mangostana and their anti-inflammatory activities

Pure β-mangostin (1) was isolated from the stem bark of Garcinia mangostana L. One monoacetate (2) and five O-alkylated β-mangostin derivatives (3–7) were synthesised from β-mangostin. The structures of these compounds were elucidated and determined using spectroscopic techniques such as 1D NMR and MS. The cytotoxicities and anti-inflammatory activities of these five compounds against RAW cell 264.7 were tested. The structural-activity relationship studies indicated that β-mangostin showed a significant activity against the LPS-induced RAW cell 264.7, while the acetyl- as well as the O-alkyl- β-mangostin derivatives did not give good activity. Naturally occurring β-mangostin demonstrated comparatively better anti-inflammatory activity than its synthetic counterparts.     

Carotenoids of Rhizobia. I. New Carotenoids from Rhizobium lupini

The main pigments of Rhizobium lupini were 2,3,2′,3′-di-trans-tetrahydroxy-β,β-caroten-4-one and 2,3,2′,3′-di-trans-tetrahydroxy-β,β-carotene. As minor components 7,8,7′,8′-tetrahydro-ψ, ψ-carotene (ζ-carotene), β, β-carotene (β-carotene), and tentatively, a 2,3,2′(or 3′)-trihydroxy-β, β-caroten-4-one and a 2,3,2′(or 3′)-trihydroxy-β, β-carotene were identified.     

β-Peptides: Synthesis by Arndt-Eistert homologation with concomitant peptide coupling. Structure determination by NMR and CD spectroscopy and by X-ray crystallography. Helical secondary structure of a β-hexapeptide in solution and its stability towards pepsin

The β-hexapeptide (H-β-HVal-β-HAla-β-HLeu)₂-OH ( 2 ) was prepared from the component L -β-amino acids by conventional peptide synthesis, including fragment coupling. A cyclo-β-tri- and a cyclo-β-hexapeptide were also prepared. The β-amino acids were obtained from α-amino acids by Arndt-Eistert homologation. All reactions leading to the β-peptides occur smoothly and in high yields. The β-peptides were characterized by their CD and NMR spectra (COSY, ROESY, TOCSY, and NOE-restricted modelling), and by an X-ray crystal-structure analysis. β-Sheet-type structures (in the solid state) and a compact, left-handed or (M) 3₁ helix of 5-Å pitch (in solution) were discovered. Comparison with the analogous secondary structures of α-peptides shows fundamental differences, the most surprising one at this point being the greater stability of β-peptide helices. There are structural relationships of β-peptides with oligomers of β-hydroxyalkanoic acids, and dissimilarities between the two classes of compounds are a demonstration of the power of H-bonding. The β-hexapeptide 2 is stable to cleavage by pepsin at pH 2 in H₂O for at least 60 h at 37°, while the corresponding α-peptide H-(Val-Ala-Leu)₂-OH is cleaved instantaneously under these conditions. The implication of the described results are discussed.     

Solid phase microextraction and gas chromatography mass spectrometry analysis of Zingiber officinale and Curcuma longa

SPME analysis of Zingiber officinale Roscoe and Curcuma longa L. were performed by using a DVB/CARB/PDMS fiber. The SPME analysis of Zingiber officinale showed that the main components found were camphene (7.27%), geranial (8.37%), α-zingiberene (14.50%), α-farnesene (9.14%), β-bisabolene (6.52%), and β-sesquiphellandrene (9.92%). The SPME analysis of Curcuma longa showed that main components were p-cymene (12.96%) and ar-turmerone (12.08%). Other components were β-phellandrene (7.86%), terpinolene (6.97%), ar-curcumene (8.53%), α-zingiberene (8.46%), and β-sesquiphellandrene (7.37%).     

Convenient Synthesis and Purification of N-Trifluoroacetylated Neuraminic Acid Tetraol: A Key Precursor for the Synthesis of New Sialyl Donors Containing Labile O-Acyl Protecting Groups

A convenient synthesis and separation of α- and β-anomers of methyl (phenyl 3,5-dideoxy-2-thio-5-trifluoroacetamido-D-glycero-D-galacto-nonulopyranosid)onate (6a and 6b) on a multigram scale was developed. Both α- and β-isomers of 6 were obtained as crystals suitable for safe storage. The β-isomer forms a crystalline solvate with methanol. Fully O-trichloroacetylated and O-trifluoroacetylated N-trifluoroacetyl thiosialosides were synthesized in an efficient manner from the β-tetraol 6b.     

Mycelia-associated β-xylosidase in pellets ofAspergillus sps.

A screening of 10 strains ofAspergillus for pellet formation and mycelia-associated β-xylosidase activity was performed in media containing glucose and glucose supplemented with methyl β-d-xylopyranoside. The aim was to produce an immobilized enzyme preparation. Three strains with high mycelia-associated β-xylosidase activity were investigated for enzyme leakage and enzyme stability:A. terreus QM 1991,A. phoenicis ATCC 13157, andA. phoenicis QM 329. The pellets ofA. phoenicis QM 329 had the highest β-xylosidase activity (280 IU/g dry wt mycelia) after 333 h of incubation. From measurements of both cell-bound enzyme activity and the activity in solution, it could be concluded that forAspergillus phoenicis QM 329 and ATCC 13157 the decrease in β-xylosidase activity bound to the pellets was owing to enzyme leakage. ForAspergillus terreus QM 1991, the decrease of pellet-bound β-xylosidase activity was the result of both leakage and enzyme deactivation at 50°C. β-Xylosidase in pellets ofA. phoenicis QM329 hydrolyzes xylobiose andp-nitrophenyl β-d-xylopyranoside with the same rate of conversion.

     

Synthese von (R)-β, β-Carotin-2-ol und (2R, 2′R)-β, β-Carotin-2,2′-diol

Synthesis of (R)-β, β-Caroten-2-ol and (2R, 2′R)-β, β-Carotene-2,2′-diol Starting from geraniol, the two carotenoids (R)-β, β-caroten-2-ol ( 1 ) and (2R, 2′R)-β, β-carotene-2,2′-diol ( 3 ) were synthesized. The optically active cyclic building block was obtained by an acid-catalysed cyclisation of the epoxide (R)- 4 . The enantiomeric excess of the product was > 95 %.     

Behaviour of the Primary Nitro Group Under Denitration Conditions

ABSTRACT

Treatment of per-O-acetylated or acetalated glycosylnitromethanes derived from the common hexoses and pentoses with tributyltin hydride and a catalytic amount of a radical initiator [1,1′-azobis(cyclohexanecarbonitrile)] in refluxing benzene easily afforded the corresponding glycosylmethanal oximes in 84-97% yields. Per-O-acetylated C-β-glycopyranosylmethanal oximes were employed for synthesis of versatile C-β-glycopyranosyl cyanides of the β-D-gluco, β-D-manno, β-D-galacto, β-D-xylo, and β-L-rhamno configurations.     

Photochemical reactions of β-aminovinyl aryl thioketones

Irradiation of β-aminovinyl aryl thioketones ( 1a-b ) afforded β-aminovinyl aryl ketones ( 2a-b ). 2H-Thiopyran derivatives ( 4a-b ) were obtained when β-aminovinyl phenyl thioketone ( 1a ) was irradiated with methyl acrylate and acrylonitrile. 4H-Thiopyran derivatives ( 6,8 ) were also obtained thermally in the reaction of β-aminovinyl phenyl thioketone ( 1a ) and methyl propiolate and maleic anhydride.     

Volatile constituents of Amomum maximum Roxb and Amomum microcarpum C. F. Liang & D. Fang: two Zingiberaceae grown in Vietnam

The chemical composition of essential oils obtained from the hydrodistillation of different parts of Amomum maximum Roxb and Amomum muricarpum C. F. Liang & D. Fang (Zingiberaceae) grown in Vietnam are reported. The analysis was performed by means of gas chromatography–flame ionisation detectoorand gas chromatography coupled with mass spectrometry. The major compounds identified in the oils of A. maximum were β-pinene (20.4–40.8%), α-pinene (6.8–15.0%), β-elemene (2.5–12.8%) and β-caryophyllene (2.3–10.3%). Moreover, β-phellandrene (11.6%) was present in the root oil. The main compound identified in all the oil samples of A. muricarpum was α-pinene (24.1–54.7%) and β-pinene (9.2–25.9%). In addition, limonene (7.4%) and δ-3-carene (9.4%) were present in the leaves and stem oils, respectively. However, while β-phellandrene (8.3%) could be seen prominent in the root oil, the fruits contained significant amount of zingiberene (6.3%). The largest amount of τ-muurolol (13.0%) was found in the flower oil.     

On the Effect of the Aglycon Structure of Three Aryl β-D-Galactosides on the Yield and the Regioselectivity of the Transglycolytic Synthesis of N-Acetyllactosamine

ABSTRACT

We examined the effect as donors of three aryl β-D-galactosides (i.e. p-nitrophenyl β-D-galactopyranoside, o-nitrophenyl β-D-galactopyranoside and phenyl β-D-galacto-pyranoside) on the regioselectivity and the yield of the synthesis of N-acetyllactosamine obtained from the transglycosylation reaction catalyzed by a crude preparation of β-D-galactosidase from Bacillus circulans at 25 °C, 37 °C and 55 °C, respectively. Using p-nitrophenyl β-D-galactopyranoside the reaction results were fully regiospecific at all the temperatures considered: the maximum molar yield (74%) was obtained at an incubation temperature of 55 °C. Using o-nitrophenyl β-D-galactopyranoside as the donor the reaction was still highly regioselective and the maximum molar yield (50%) was achieved at an incubation temperature also of 55 °C. Using phenyl β-D-galactopyranoside transglycolytic products appear only at an incubation temperature of 55 °C but at very low molar yield (about 14%) and lower regioselectivity.     

Reactivity characteristics of squid β-chitin as compared with those of shrimp chitin: High potentials of squid chitin as a starting material for facile chemical modifications

Chemical reactivity of β-chitin isolated from squid pens has been examined in various reactions to elucidate the possibility of facile modifications in simple manners leading to the preparation of derivatives with well-defined structures. β-Chitin swelled in common solvents such as methanol and pyridine unlike the ordinary α-chitin and exhibited much higher reactivity than β-chitin. Free amino groups present in β-chitin were easily and selectively acetylated with acetic anhydride in methanol to give chitin with a uniform structure, poly(N-acetyl-D-glucosamine). When acetylation reaction was carried out in pyridine, O-acetylation proceeded smoothly besides N-acetylation. In the presence of 4-dimethylaminopyridine as the catalyst, even full acetylation was achieved under mild conditions. Tosylation was also quite efficient in pyridine without side reactions such as N-deacetylation which is unavoidable in the tosylation of α-chitin. β-Chitin also enabled direct tritylation in pyridine in the presence of 4-dimethylaminopyridine. All these reactions were quite sluggish with β-chitin, and no reactions or only very low extents of substitution were observed, indicating the high potential of β-chitin as a versatile starting material for facile modification reactions. © 1994 John Wiley & Sons, Inc.     

Preparation of N-Fmoc-Protected β2- and β3-Amino Acids and their use as building blocks for the solid-phase synthesis of β-peptides

N-Fmoc-Protected (Fmoc = (9H-fluoren-9-ylmethoxy)carbonyl) β-amino acids are required for an efficient synthesis of β-oligopeptides on solid support. Enantiomerically pure Fmoc-β³-amino acids β³: side chain and NH₂ at C(3)(= C(β)) were prepared from Fmoc-protected (S)- and (R)-α-amino acids with aliphatic, aromatic, and functionalized side chains, using the standard or an optimized Arndt-Eistert reaction sequence. Fmoc-β²- Amino acids (β² side chain at C(2), NH₂ at C(3)(= C(β))) configuration bearing the side chain of Ala, Val, Leu, and Phe were synthesized via the Evans' chiral auxiliary methodology. The target β³-heptapeptides 5–8 , a β³- pentadecapeptide 9 and a β²-heptapeptide 10 were synthesized on a manual solid-phase synthesis apparatus using conventional solid-phase peptide synthesis procedures (Scheme 3). In the case of β³-peptides, two methods were used to anchor the first β-amino acid: esterification of the ortho-chlorotrityl chloride resin with the first Fmoc-β-amino acid 2 (Method I, Scheme 2) or acylation of the 4-(benzyloxy)benzyl alcohol resin (Wang resin) with the ketene intermediates from the Wolff rearrangement of amino-acid-derived diazo ketone 1 (Method II, Scheme 2). The former technique provided better results, as exemplified by the synthesis of the heptapeptides 5 and 6 (Table 2). The intermediate from the Wolff rearrangement of diazo ketones 1 was also used for sequential peptide-bond formation on solid support (synthesis of the tetrapeptides 11 and 12 ). The CD spectra of the β²- and β³-peptides 5 , 9 , and 10 show the typical pattern previously assigned to an (M) 3₁ helical secondary structure (Fig.). The most intense CD absorption was observed with the pentadecapeptide 9 (strong broad negative Cotton effect at ca. 213 nm); compared to the analogous heptapeptide 5 , this corresponds to a 2.5 fold increase in the molar ellipticity per residue!     

α-Alkylierung von β-Hydroxycarbonsäuren über 1,3-Dioxan-4-on-Enolate

Highly Diastereoselective α-Alkylation of β-Hydroxycarboxylic Acids Through Lithium Enolates of 1,3-Dioxan-4-ones From serine, β-hydroxyisobutyric acid (‘Roche’ acid) and β-hydroxybutyric acid, the dioxanones 1–6 were prepared. The generation of the enolates of type I with LDA at ?75° and alkylation gave products with trans-configuration whereas protonation of the 5-methyl-substituted enolate allowed access to the cis-configurated β-hydroxybutyric-acid derivative 12 . Hydrolysis gave the free β-hydroxy acids of ‘syn’-and ‘anti’-configuration. Alkylation of the 6-unsubstituted dioxanones 1 and 3 yielded predominantly products resulting from attack in the cis-position of the t-Bu group. The ‘reactive’ conformation of the enolates involved is tentatively derived from the product configuration. The selectivity of the alkylation is also discussed in terms of the results of an ab-initio calculation on the enolates M–P.     

Photochemical reactivity of α,β-unsaturated δ-lactams: Synthesis of seco-steroids. Photochemical reactions. XIII [1]

The UV. irradiation of 17 β-hydroxy-2-aza-4-androsten-3-one (1) , N-methyl-17 β-hydroxy-2-aza-4-androsten-3-one (3) , 17 β-hydroxy-4-aza-5 β-androst-1-en-3-one (2) and N-methyl-17 β-hydroxy-4-aza-5 β-androst-1-en-3-one (4) , gives rise to 1,10-seco (from 1 and 3 ) and 5, 10-seco (from 2 and 4 ) steroids.     

Synthesis of New N-Sulfonyl Monocyclic β-Lactams and the Investigation of Their Antibacterial Activities

New monocyclic β-lactams 4–6 were synthesized by a ketene-imine [2+2] cycloaddition reaction. The prepared monocyclic β-lactams 4–6 were cleaved by ceric ammonium nitrate (CAN) to give NH-β-lactams 7–9. The NH-β-lactams were converted to N-sulfonyl β-lactams 10–21 by treatment with four different sulfonyl chlorides in the presence of Et₃N and 4-N,N-dimethylaminopyridine (DMAP). Some of these monocyclic β-lactams were active against Staphylococcus aureus, Bacillus subtilis, Escherichia coli, and Pseudomonas aeruginosa.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Preparation and characterization of phenyl carbamate derivative β-cyclodextrin bonded phase for chiral HPLC

A partially substituted β-cyclodextrin chiral stationary phase was prepared by the reaction of phenyl isocyanate. The enantiomers of a series of O,O-diethyl(p-methylbenzenesulfonamido)-aryl(or alkyl)-methylphosphonates were studied on the prepared phenyl carbamate derivative β-cyclodextrin bonded phase and a commercial (S)-(+)-1–(1-naphthyl) ethylcarbamate derivative β-cyclodextrin bonded phase on normal phase chromatographic condition. Results show that the prepared phenyl carbamate derivative β-cyclodextrin bonded phase has better enantiomeric selectivity to the series of compounds. A chiral recognition mechanism was suggested for the separation of these novel organic phosphorus enantiomers.     

Die Cope-Umlagerung als Prinzip einer repetierbaren Ringerweiterung

The Cope Rearrangement, a Reaction for Repeatable Ring Expansions Starting with the unsaturated β-ketoesters of type I, a vinyl group is introduced into the β-position by 1,4-addition of vinyl magnesium chloride to give II (Scheme 3). Treatment of the β-ketoester II with phenyl vinyl sulfoxide in the presence of sodium hydride yields the sulfoxides III, which on thermolysis lead to the α, β-divinyl ketoesters of type IV via elimination of sulfinic acid (Scheme 3). The Cope-System IV undergoes rearrangement to V, which is again an unsaturated β-ketoester. The latter is suitable for a further ring expansion sequence. These reaction steps were carried out with the nine-, twelve- and fifteen-membered ketoesters 32, 33 and 34 , as well as with the open-chain compound 35 (Table 1). With the cyclohexane derivative 31 , ring expansion could not be achieved with the described sequence.     

Bifunctionalized allenes. Part XXI. Electrophilic cyclization and addition reactions of 3-(α- or β-hydroxyalkyl)-allenylphosphonates and allenyl phosphine oxides

Abstract

The present paper discusses the electrophilic cyclization and addition reactions of 3-(α- or β-hydroxyalkyl)-allenylphosphonates and phosphine oxides. Treatment of 3-(α- or β-hydroxy-alkyl)-allenylphosphonates with electrophiles takes place with 5-endo-trig cyclization and gives 2-methoxy-2,5-dihydro-1,2-oxaphosphole 2-oxides as a result of the neighboring phosphonate group participation in the electrophilic cyclization. On the other hand, 3-(α- or β-hydroxyalkyl)-alk-(1E)-en-1-yl phosphine oxides were prepared by chemo-, regio-, and stereoselective electrophilic addition to the C²-C³-double bond in the 3-(α- or β-hydroxyalkyl)-alka-1,2-dienyl phosphine oxides and subsequent attack of the external nucleophile (halide anion). The paper proposes a possible mechanism that involves electrophilic cyclization and addition reactions of the phosphorylated (α- or β-hydroxyalkyl)allenes.