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Although a superficial circumflex iliac artery perforator (SCIP) flap has recently been widely used owing to its various advantages, reports on its use in the pediatric population are limited. A case of a supermicrosurgical reconstruction of a soft tissue defect of the ankle associated with the congenital deficiency of the tibia using a free sensate SCIP flap in a 1-year-old child has been presented. The correction of the valgus deformity of the ankle resulted in a soft tissue defect, which required flap coverage. The lateral cutaneous branch of the intercostal nerve of the flap was coapted with the deep peroneal nerve for sensory recovery. Postoperative course was uneventful and the flap completely survived. The patient was able to ambulate independently at 7 months after surgery. To the best of our knowledge, this is the youngest case of a SCIP flap transfer in literature. This case showed that young age is not a contraindication for SCIP flap transfer. It is believed that the SCIP flap procedure may be a useful option for free flap reconstruction in children.

Nipple adenoma is an uncommon proliferative process of the breast and predominantly occurs in women aged 40-50. Its incidence is extremely low in men, and it has not been reported in a boy. Although nipple adenoma is rare and benign, being familiar with it is important because it clinically resembles Paget disease and histologically adenocarcinoma. We report a case of nipple adenoma in a boy.

A styrene-based monomer having a five-membered cyclic dithiocarbonate structure, 4-vinylbenzyl 1,3-oxathiolane-2-thione-5-ylmethyl ether (VBTE), was synthesized from 4-vinylbenzyl glycidyl ether (VBGE) and carbon disulfide in the presence of lithium bromide in 86% yield. Radical polymerization of VBTE in dimethyl sulfoxide by 2,2′-azobisisobutyronitrile was carried out at 60 °C to afford the corresponding the polymer, polyVBTE, in 64% yield. PolyVBTE with number-averaged molecular weight higher than 31,000 was obtained. The glass transition temperature (Tg) and 5 wt % decomposition temperature (Td5) of the polyVBTE were evaluated to be 66 and 264 °C under nitrogen atmosphere by differential scanning calorimetry and thermal gravimetry analysis, respectively. It was confirmed that a polymer consisting of the same VBTE repeating unit could also be obtained via polymer reaction, that is, a lithium bromide-catalyzed addition of carbon disulfide to a polyVBGE prepared from a radical polymerization of VBGE. Copolymerization of VBTE and styrene with various compositions efficiently gave copolymers of VBTE and styrene. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

The structures of a lipoprotein carrier, LolA, and a lipoprotein receptor, LolB, are similar except for an extra C-terminal loop containing a 3(10) helix and beta-strand 12 in LolA. Lipoprotein release was significantly reduced when beta-12 was deleted. Deletion of the 3(10) helix also inhibited the lipoprotein release. Furthermore, lipoproteins were non-specifically localized to membranes when LolA lacked the 3(10) helix. Thus, the membrane localization of lipoproteins with the LolA derivative lacking the 3(10) helix was independent of LolB whereas LolB was essential for the outer membrane localization of lipoproteins with the wild-type LolA.

Various 2-(2′-hydroxy-4′-methyl-1′-cyclohexylidene) carboxylic acid lactones were synthesised in good yield from carboxylic acids and 4-methylcyclohexanone. For example, mintlactone (VI) and isomintlactone (VII) were prepared from 2-(1′- hydroxy-4′-methylcyclohexan-1′-yl) propanoic acid (III) which was obtained by reaction of propanoic acid (I) with 4-methylcyclohexanone (II) using lithium naphthalenide in the presence of diethylamine. Compound (VI) could be separated from compound (VII) by silica gel column chromatography. Several new 2-(2′- hydroxy-4′-methyl-1′-cyclohexylidene) carboxylic acid lactones which may be used as perfumery materials, were obtained in good yield by this method.

Various 1, 4-diketones were prepared from carboxylic acids via two steps : Grignard reaction with vinylmagnesium chloride and oxidation with Jones reagent catalysed by mercuric propionate. For example, 2, 5-undecanedione was prepared from heptanoic acid via 1-undecen-5-one.

Several, 2,4-dialkyl-2-cycloalkenyl-γ-butyrolactones were synthesised from 2-(cycloalken-1′-yl) carboxylic acids and epoxides using lithium naphthalenide in the presence of diethylamine. From 2-(cyclohexen-1′-yl)propanoic acid and propylene oxide, 4-hydroxy-2-(cyclohexen-1′-yl)-2-methylpentanoic acid was obtained. The latter easily cyclised to give 2-(cyclohexen-1′-yl)-2,4-dimethyl-γ-butyrolactone. Similarly, 2,4-dialkyl-2-(cycloalken-1′-yl)-μ-butyrolactones were prepared from other 3,4-unsaturated carboxylic acids and epoxides. These lactones may be used as perfumery materials.

One mole of propionic acid (I) reacts with 2 mol of 1,2-butylene oxide (II) in the presence of lithium naphthalenide to give 4-hydroxy-2-(2′-hydroxybutyl)-2-methylhexanoic acid (V), which can be easily converted into 2-(2′-hydroxybutyl)-2-methyl-4-ethyl-γ-butyrolactone (VII). Similarly, 2,4-dialkyl- and 2,4,4-trialkyl-2-hydroxyalkyl-γ-butyrolactones were prepared from other carboxylic acids having two hydrogens at 2-position and various epoxides.

3-Hydroxy acids were synthesised in good yield from ketones and carboxylic acids using lithium naphthalenide in the presence of diethylamine. From cyclohexanone and propionic acid, 2-(1′-hydroxycyclohexan-1′-yl) propionic acid (I) was obtained in 98.3% yield. 3-Hydroxy acids were treated with various acidic materials to give 3,4-unsaturated carboxylic acids and γ-butyrolactones. From the reaction of (I) with p-toluenesulphonic acid or potassium bisulphate, 2-(cyclohexen-1′-yl) propionic acid (II) (a 3,4-unsaturated acid) was obtained (yield 98%), and with 97% sulphuric acid 2-(1′-hydroxycyclohexan-1′-yl) propionic acid lactone (III) was formed (93% yield). Several new γ-butyrolactones were obtained in good yield by this method.

The reaction of isoprene with phenol, catalysed by nickelocene and phenylmagnesium bromide, yields 2,2-dimethylchroman, 2-(3′-methyl-2′-buten-1′-yl)phenol, 4-(3′-methyl-2′-buten-1′-yl)phenol, 2,2-dimethyl-8-(3′-methyl-2′-buten-1′-yl)chroman and 2,2-dimethyl-6-(3′-methyl-2′-buten-1′-yl)chroman. Reactions with other phenols were examined.

The oligomerisation of isoprene catalysed by nickel naphthenate and isoprene magnesium was studied under various conditions. The use of various phosphites as donors gives cyclic dimers containing dimethyloctadiene (about 90%); in particular 1,1,1-trishydroxymethylpropane phosphite gives trimethylcyclo-dodecatriene selectively. The use of triphenylphosphine gives a linear isoprene trimer containing farnessene.

5-Cyclohexadecenone is prepared from cyclododecanone via four new steps: chlorination, Grignard reaction with vinylmagnesium chloride and rearrangement with aluminium isopropoxide, revinylation with vinylmagnesium chloride and oxy-Cope rearrangement.

New cyclohexenyl alkenyl ketones are prepared by the reaction of various methyl cyclohexenyl carboxylates and vinylmagnesium chloride; for example, 1-(4′-methyl-3′-cyclohexene-1′-yl)-1-oxo-4-pentene is obtained from methyl 4-methyl-3-cyclohexene-1-carboxylate and vinylmagnesium chloride.

The reaction of vinylmagnesium chloride with an aromatic carboxylic acid gives a vinyl ketone. From benzoic acid, 5-oxo-5-phenyl-1-pentene is obtained. Similarly, from aliphatic carboxylic acid, a mixture of vinyl ketone and divinyl carbinol is obtained. From pentanoic acid, a mixture of butyl divinyl carbinol and 5-oxo-1-nonene is obtained.

It was found that lithium naphthalenide can be prepared from metallic lithium cuttings and naphthalene in non-ethereal solvents, such as benzene–N,N,N′,N′-tetramethylethylenediamine (TMEDA) or benzene-N,N,N′,N′-tetramethyldiaminopropane (TMDAP), under ultrasonic irradiation. Secondary amines reacted with conjugated olefins, such as isoprene or myrcene, using lithium naphthalenide in such non-ethereal solvents to give allylic amines. The yields of products were higher than in the reaction using lithium naphthalenide in tetrahydrofuran. From diethylamine (I) and isoprene (II), a mixture of N,N-diethyl-3-methyl-2-butenylamine (IV) and N,N-diethyl-2-methyl-2-butenylamine (V) (IV:V = 79:21) was obtained in 77% yield, and from diethylamine (I) and myrcene (III), N,N-diethylgeranylamine (VI) and N,N-diethylnerylamine (VII) (VI:VII = 88:12) were produced in 72% yield. These terpenic amines, VI and VII, are used as starting compounds for the preparation of perfumery materials.

Various 2-alkyl-3-methyl-2-cyclopentenones were prepared via 2-alkyl-4-penten-2-ols serving as common intermediates from carboxylic acids or methylketones. For example, dihydrojasmone was prepared from heptanoic acid as follows: Grignard reaction of heptanoic acid (I) with allylmagnesium chloride gave 1-decen-4-one (II) and re-Grignard reaction of (II) with methylmagnesium iodide produced 4-methyl-1-decen-4-ol (IV). 4-Methyl-1,4-decanediol (V) was obtained by hydroboration of (IV). Oxidation of (V) with chromium trioxide gave 4-hexyl-4-methyl-4-butanolide (VI). Dihydrojasmone may be prepared by dehydration of (VI) with polyphosphoric acid. Several new 2-alkyl-3-methyl-2-cylopentenones were obtained by this method.

5-Methyl-2-isopropyl-4-hexenoic acid, dihydrolavandulic acid (III), was synthesised in 65% yield from 3-methylbutanoic acid and isoprene with sodium naphthalenide in the presence of N,N,N′,N′-tetramethylethylenediamine. Reduction of III with lithium aluminum hydride gave 5-methyl-2-isopropyl-4-hexen-l-ol, dihydrolavandulol (IV) (85% yield). Oxidation of IV with pyridinium chlorochromate gave 5-methyl-2-isopropyl-4-hexenal, dihydrolavandulyl aldehyde (V) (81 % yield).

Various 2,3-dialkyl parasorbic acids were prepared from carboxylic acids. For example, 2-methyl-5-pentyI parasorbic acid was prepared from hexanoic acid and propanoic acid as follows: Grignard reaction of hexanoic acid (I) with allylmagnesium chloride gave l-nonen-4-one (II) and the reaction of (II) with propanoic acid (III) with lithium naphthalenide in the presence of diethylamine produced 3-allyl-3-hydroxy-2-methyloctanoic acid (IV). From the reaction of (IV) with 97% (v/v) sulphuric acid, 2-methyl-3-pentyl parasorbic acid was formed. Several 2,3-dialkyl parasorbic acids were obtained by this method. These products may be used as perfumery materials.

Various oxo-dimethylallyl compounds were prepared from intermediates which are obtained by the reaction of allylic Grignard reagents with carboxylic acid derivatives. For example, the reaction of prenylmagnesium chloride with ethyl hexanoate gave 3,3–dimethyl-4–prenyl-1-nonen-4–ol (1) in 92% yield. The thermolysis of 1 at the temperature of 693 K gave 2–methyl-2–decen-5–one (2) in 81% yield. Furthermore, 3,3–dimethyl-1-alken-4–ones (E) were prepared by the methylation of 1-alken-4-ones (C), which are obtained by the reaction of allylmagnesium chloride with carboxylic acids (A).

3,4-Unsaturated acids were condensed with paraformaldehyde in boiling acetic acid containing a small amount of aluminium chloride to afford 2,3-unsaturated-δ-lactones. For example, from 2-(cyclohexen-1′-yl)caprylic acid (I) and paraformaldehyde, 2′-hydroxymethyl-2-cyclohexylidenecaprylic acid lactone (II) was obtained in up to 93% yield. Several 2,3-unsaturated-δ-valerolactones were obtained in good yield by this new method. These lactones may be used as perfumery materials.

A number of derivatives of thiocarboxylic acid were prepared from the reaction of 3-mercaptopropionic acid and alkyl halides, and screened for anti-rust properties in water-soluble metalworking fluids. Aqueous metalworking fluids containing octylthiopropionic acid or hexylthioacetic acid showed excellent anti-rust properties for water-soluble metalworking fluids.

Photochemical δ-hydrogen abstraction from acyclic and semicyclic monothioimides have been studied. Photolysis of acyclic monothioimides possessing a benzylic hydrogen atom at the δ-position gave γ-lactams, via a 1,5-diradical intermediate, accompanied by thioamides were generated by γ-hydrogen abstraction. Irradiation of the five-membered semicyclic monothioimide, N-(3-phenylpropionyl)pyrrolidine-2-thione, yielded 5-mercapto-4-phenyl-1-azabicyclo[3.3.0]octan-2-one. For N-(3-phenylbutyryl)pyrrolidine-2-thione, disproportionation, involving 1,6-hydrogen migration, was the main path. Photolysis of the six-membered semicyclic monothioimide, N-(3-phenylbutyryl)piperidine-2-thione, gave an unsaturated thiol, via a 1,4-hydrogen shift of a 1,5diradical intermediate, accompanied by cyclisation product and piperidine-2-thione.

Photolysis of N-(α, β-unsaturated carbonyl)thioamides gave thietane-fused β-lactams in good yields, whereas some of the thioimides formed thiones viaβ-hydrogen abstraction of the thiocarbonyl group. Substituents at the α-position to the carbonyl carbon lead to a preference for [2 + 2 ]cyclisation over β-hydrogen abstraction. From a sensitisation experiment this reaction was shown to proceed via an nπ* triplet excited state.

Irradiation of N,N-dibenzyl-α,β-unsaturated thioamides leads to cyclisation involving γ-hydrogen abstraction by the aikene unit via a zwitterionic intermediate.

Photolysis of chiral crystals of an achiral N-isopropyl-N-tiglylbenzoylformamide in the solid state proceeded [2+2] cycloaddition to give a chiral oxetane, 5,7-dimethyl-3-isopropyl-1-phenyl-6-oxa-3-azabicyclo[3.1.1] heptane-2,4-dione, in high chemical end optical yields

α-Trifluoromethylated carboxylic acids have been obtained with high optical purity by enzymatic hydrolysis. Further, the synthesis of optically active α-trifluoromethylated ketones by the thermolysis of diallyl alcohols, produced from the reaction of Grignard reagent and optically pure α-trifluoromethylated carboxylic acid ethyl esters, is described.

Enantioselective hydrosilylation of carbon–nitrogen double bonds of nitrones with diphenylsilane using Ru2Cl4-[(S)-(–)-p-tolbinap]2(NEt3)[p-tolbinap = 2,2′-bis(di-p-tolyphosphino)-1,1′-binaphthyl] catalyst at 0°C gives the corresponding optically active N,N-disubstituted hydroxylamines; up to 91% enantiomeric excess (e.e.) is achieved.

A practical synthetic route to a series of (R)- or (S)-(1-trifluoromethyl)alkyl 4-hydroxybenzoateshas been developed. These materials were prepared by the reaction of p-hydroxybenzoic acid with (R)- or (S)-1-(trifluoromethyl)alkanols in the presence of p-toluenesulfonic acid under reflux conditions. Further reaction with the acid chloride of4′-alkoxybiphenyl-4-carboxylic acid gave the desired liquid crystals.

N,N-Disubstituted and cyclic hydroxylamines can be converted into the corresponding imines efficiently upon treatment with anhydrous titanium trichloride in THF at room temperature. Similar treatment of N-allylhydroxylamines with anhydrous titanium trichloride gives 1-azadienes, which are versatile synthetic intermediates for aza-Diels–Alder reactions. On the other hand, the same hydroxylamines can be converted into the corresponding secondary amines upon treatment with aqueous titanium trichloride in methanol. It is noteworthy that optically active hydroxylamines, which have chirality at the α-position to nitrogen, can be converted into optically active secondary amines without loss of chirality. Dihydro-2(1H)-quinolinones can be prepared upon treatment of 1-hydroxy-3,4-dihydro-2(1H)-quinolinones with aqueous titanium trichloride. The substrates of N,N-disubstituted and cyclic hydroxylamines can be prepared readily upon treatment of nitrones with nucleophiles. Since nitrones can be prepared by metal-cata...

Reformatsky reactions of trifluoroacetaldehyde with lower bromoesters gave their corresponding adducts. The reaction of trifluoroacetaldehyde with methyl 2-(bromomethyl)acrylate gave γ-trifluoromethyl-α-methylene-γ-butyrolactone.

Irradiation of 3-cyano-2-alkoxypyridines gave dehydrogenated dimers, 1,8-dialkoxy-6,9-dicyanopyrido-[3,2-c]azocines, and heterophotodimers, 3,12-dicyano-4,8-dialkoxy-5,9-diazatetracyclo[4.3.3.0 2,7 -0 3,10 ]- dodeca-4,8,11-trienes, in the presence of different pyridines

The reactions of 2-(trifluoromethyl)propenoic acid ( I ) with unsaturated Grignard reagentshave been examined. Vinylmagnesium bromide with I gave 2-difluoromethylene-4-pentenoicacid ( II ) and analogous acids were obtained from propenyl and butenyl magnesiumhalides. The iodolactonization of II gave 2-difluoromethylene-4-iodomethyl-γ-lactone ( III ).2-Monofluoromethylene-4-penten-1-ol ( IV ) was obtained by the reduction of II with lithiumaluminium hydride.

The photochemistry of cyclic N-(α,β-unsaturated carbonyl)-thionocarbamates and -dithiocarbamates has been studied. Photolysis of a benzene solution of 3-(methacryloyl)thiazolidine-2-thione gave 4-methyl-2,9-dithia-6-azatricyclo[4.3.0.01.4]nonan-5-one (a tricyclic-β-lactam)(30%) and 2-(3′-methyl-2′-oxothietan-3′-yl)-2-thiazoline (a β-thiolactone)(30%). Irradiation of 3-(2′-methylbut-2-enoyl)thiazolidine-2-thione, 3-(methacryloyl)oxazolidine-2-thione, and 3-(2′-methylbut-2-enoyl)oxazolidine-2-thione gave the corresponding β-lactams (33–67%), whereas that of the six-membered compounds, 3-(methacryloyl)- and 3-(2′-methylbut-2-enoyl)tetrahydro-1,3-oxazine-2-thione, led to β-thiolactones (33–66%). The ring transformation of this new ring system (thietane-fused penams and oxapenams) to β-thiolactones was confirmed by the fact that, on pyrolysis, the β-lactams gave the corresponding β-thiolactones in quantitative yield.

A series of trans- and cis-γ-lactones with high optical purity have been prepared from the lactonization of (S)-(−)-2-(trifluoromethyl)-4-pentenoic acid (>94% ee) under acidic conditions. These materials have been transformed into new types of dopant for ferroelectric liquid crystals possessing a trifluoromethyl group.

The photochemistry of O-allyl and O-but-3-enyl thiocarbamates has been studied. Photolysis of benzene solutions of O-allyl N-phenylthiocarbamates gave S-allyl N-phenylthiocarbamates. The 1,3-allyl migration from the oxygen to the sulfur involves a concerted process. The same type of 1,3-migration took place in the conversion of O-benzyl N-phenylthiocarbamate into S-benzyl N-phenylthiocarbamate. Irradiation of O-but-3-enylthiocarbamates produced iminooxolanes via aminothietane intermediates. In the case of O-but-3-enyl N-benzoyl-N-phenylthiocarbamates, 3-(benzoylsulfanylmethyl)-2-phenyliminooxolanes were obtained via a ring opening of the aminothietanes involving a 1,5-benzoyl shift.

The reaction of trifluoromethyltrimethylsilane with a variety of terpenoid carbonyl compounds and other carbonyl compounds used in perfumery gave the corresponding trifluoromethylated derivatives. Pentafluoroethylated compounds were similarly obtained from the reaction of pentafluoroethyltrimethylsilane with various substrates. (−)-2-Trifluoro-1-furyl ethanol has been obtained with high optical purity by enzymatic hydrolysis of 2-trifluoro-1-furyl ethyl acetate.

Photochemical reactions of various N-(α,β-unsaturated carbonyl)benzoylformamides both in solution and in a solid state were investigated. Under homogeneous conditions, all acyclic imides underwent photochemical 2 + 2 cycloaddition that resulted in the production of bicyclic oxetanes. N-Isopropyl- and N-benzyl-N-tigloylbenzoylformamides crystallized in a chiral space group, and the photolysis in the solid state yielded corresponding optically-active oxetanes. N-Tigloylbenzoylformanilide underwent cis−trans isomerization to yield a photostationary state (cis/trans = 1.3). Solid state oxetane formation of N-benzyl- and N-(o-tolyl)- and N-(2,6-xylyl)-N-tigloylbenzoylformamides progressed via the crystal-to-crystal pathway which was followed by X-ray powder diffraction. N-Benzyl-N-methacryloylbenzoylformamide crystallized in a chiral space group, and the solid state reaction led to an optically active β-lactam via topochemically-controlled hydrogen abstraction by the alkenyl carbon atom. Photolysis of N-isopro...

Photochemical reactions of S-aryl 2-benzoylbenzothioates 1 in solution media have been investigated. These thioesters undergo photoinduced cyclization to 3-aryl-3-arylthioisobenzofuranones 2 in yields of 14–46% upon direct irradiation. The photocyclization reaction is accompanied by a subsequent homolytic cleavage reaction of the isobenzofuranone leading to the dihydroisobenzofuranone dimer, (±)- and meso-3,3′-dioxo-1,1′-diphenyl-1,1′,3,3′-tetrahydro-1,1′-bi(isobenzofuranyl) 5. The formation of the dihydroisobenzofuranone 2 can be explained by a stepwise mechanism involving (i) intramolecular cyclization to a zwitterionic intermediate and (ii) subsequent aryl migration. Furthermore, sensitization and quenching studies reveal that the photochemical process occurs from the singlet excited states of the thioesters 1.

Photochemical reaction of asymmetrically substituted N-benzyl-N-isopropyl-α,β-unsaturated thioamides both in solution and in the solid state was investigated. All thioamides exist in an equilibrium between two rotamers owing to the rotation of the C(S)–N bond. The free energy of activation for the bond rotation was estimated by temperature-dependent 1H NMR spectroscopy. The free energy of activation lies in a range 18.4–19.5 kcal mol–1. Irradiation in benzene solution proceeded to give hydrogen abstraction by alkenyl carbon from both benzyl and isopropyl groups, leading to β-thiolactam and 1,3,5-dithiazinane products, respectively. Hydrogen abstraction from only the isopropyl group took place in the solid-state photolysis, giving an isomeric β-thiolactam product.

Solid-state photoreactions of S-(o-tolyl), S-phenyl, and S-(m-tolyl) 2-benzoylbenzothioates, which formed chiral crystals by spontaneous resolution, underwent an unprecedented intramolecular cyclization involving phenyl migration to afford optically active corresponding 3-phenyl-3-(arylthio)phthalide in good chemo- and enantioselectivities. Stereochemical assignment and substituent probe experiment of this photoreaction sequence led to a reliable conclusion that this reaction was rationalized on the basis of the aryl migration rather than the well-recognized radicalic mechanism. Furthermore, the chirality preservation in the crystals was demonstrated by means of the bisignated CD spectra, which allowed assignment of the origin of the specific CD band and the helicity of the chiral molecules.

The photochemical reaction of the bis-aromatic system pyridine–furan was investigated. Irradiation of a benzene solution containing 3-cyano-2-methoxypyridines 1 (0.02 M) and furan (0.2 M) resulted in the formation of a 1∶1 adduct, 11-cyano-10-methoxy-8-methyl-4-oxa-9-azapentacyclo[5.4.0.02,6.03,11.05,8]undec-9-ene and 10-cyano-9-methoxy-7-methyl-5-oxa-8-azatricyclo[5.4.0.02,6]undeca-3,8,10-triene in 30 and 16% yield, accompanied by the transpositional pyridine, 5-cyano-2-methoxy-6-methylpyridine, and the pyridine dimer, in 2 and 44% yield, respectively, when the reaction conversion reached 48% yield. The cage and the face-to-face structures were established by X-ray structural analyses. The cage adduct was stable under neutral conditions; however, it easily converted to a face-to-face structure in acidic conditions. On the other hand, though the face-to-face structure was stable at rt, the starting pyridine 1 and furan were easily regenerated quantitatively by heating (>100 °C) or irradiation (>290 nm). The 4 + 4 adduct of pyridine with furan was detected by 1H NMR spectroscopy, and subsequently transformed to a cage structure on irradiation.