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Postoperative chylothorax in infants prolongs hospital stay and possibly causes developmental delay because of its conservative treatment including inanition. Several medical and surgical treatments may be applied, but none constitute the absolute solution. Treatment with lipiodol during lymphangiography for postoperative chylothorax has been reported to be highly effective and less invasive in adults. On the other hand, few cases have been reported in infants. We demonstrate successful blockage of chyle leakage with lipiodol injection through the inguinal lymph node in a 2-year-old infant. The patient had undergone on-pump coarctectomy and chylothorax developed soon after surgery. Several medical treatments were partially effective, but the chest tube could not be removed because sequential aspiration was required to maintain a normal respiratory status. With the patient under general anesthesia, lipiodol injection combined with indocyanine green (ICG) lymphography was performed. Lymphography combined with ICG significantly contributed not only to intraoperative detection of the inguinal lymph nodes but also to postoperative early detection of lymphedema caused by this procedure. This procedure required a simple maneuver and is probably applicable to other cases of traumatic chylothorax, such as after surgeries on the esophagus, trachea, or other components of the posterior mediastinum.

Lymphatic malformation (LM), also known as lymphangioma, is a rare condition that can occur anywhere in the body in adults and children. LM, especially micro-cystic type, consists of multiple clustering skin/subcutaneous cysts that may involve deeper functional tissue. Although LM is generally benign, it may cause serious location-dependent problems. Periorbital LM, for example, often causes facial disfigurement and visual impairment. Especially, micro-cystic type of lymphatic malformation (mLM), is a challenging condition to treat. Currently available therapies for mLM have limited effectiveness and carry a high risk of complications. Thus, it is necessary to develop a novel treatment for mLM that is less invasive and highly effective. There has been a question of the exact location and direction of lymphatic flow into, within, and out of LM. There were some reports investigating the intra-cystic flow of LM; however, only a few focused on the afferent and efferent lymphatic flow of LM. With our detailed study using lymphography, we were able to determine the lymphatic flow pattern in periorbital LM, which was large enough to perform lymphatic venous anastomosis (LVA). LVA is a surgically-placed bypass between afferent collecting lymphatic vessels and veins, which in our study resulted in decreasing both the influx and the total volume of lymph in the LM. To our knowledge, this is the first study of Indocyanine green (ICG) lymphography on mLM, and LVA for its treatment. Here we present our case of periorbital mLM with LVA and discuss its less invasive surgical strategy.

Background: Lymphatic malformation is a congenital lymphatic disorder. Although a few lymphangiographic and lymphoscintigraphic studies of lymphatic malformation exist, its lymphatic flow has not been fully assessed, and a classification system has not yet been established. However, indocyanine green lymphography has been developed to safely provide a fine assessment of lymph flow in the treatment of lymphedema. In addition, indocyanine green lymphography has been shown to be helpful in detecting the lymphatic malformation inflow for the treatment of refractory microcystic type lymphatic malformation using the venous anastomosis technique. Therefore, the authors aimed to reveal the in vivo lymph flow around the lymphatic malformation using indocyanine green lymphography, and to design a classification system according to the observed patterns. Methods: Indocyanine green lymphography was performed in 20 sequential pediatric patients with lymphatic malformation (aged 11 months to 10 years). Most of the cases were intractable, with microcystic or mixed-type lymphatic malformation. Results: All patients successfully completed lymphography with clear observations. The flow patterns were classified into four types: type 1 had a strong detectable inflow; type 2 had multiple small observable inflows; type 3 had a superficial lymph flow over the lesion; and type 4 had a flow around the lymphatic malformation, without any connections to the lesion. Conclusion: The proposed classification system may aid in the further development of surgical treatments for lymphatic malformation.

The process development of ethyl-(R)-3-amino-2,5-dioxopyrrolidine-3-carboxylate (2), the chiral intermediate for the manufacture of AS-3201 (1), is described. A practical and scalable Shibasaki asymmetric amination that generates the chiral quaternary center was developed and demonstrated on kilogram scale. A safe, convenient, and large-scale hydrogenation of the hydrazine intermediate was also developed.

We suggest a novel method that uses artificial blood cells (hemoglobin vesicles, Hb-Vs) as photosensitizers in dye laser treatment (at 595-nm wavelength) for port-wine stains (i.e., capillary malformations presenting as red birthmarks) based on the results of animal experiments. As compared with human red blood cells, Hb-Vs have the same absorbance of 595 nm wavelength light and produce the same level of heat following dye laser irradiation. Small sized Hb-Vs (250 nm) distribute in the plasma phase in blood and tend to flow in the marginal zone of microvessels. Intravenous injections of Hb-Vs caused the dilatation of microvessels, and dye laser treatment with Hb-Vs destroyed the vessel wall effectively. Following the intravenous injection of Hb-Vs, the microvessels contained more Hb that absorbed laser photons and produced heat. This extra Hb tended to flow near the endothelial cells, which were the target of the laser treatment. These attributes of Hb-Vs will potentially contribute to enhancing the efficacy of dye laser treatment for port-wine stains. Hemoglobin is a type of porphyrin. Thus, our proposed treatment may have aspects of photodynamic therapy using porphyrin that leads to a cytotoxicity effect by active oxygen.

Background:. Less-invasive surgeries, such as lymphaticovenular anastomosis (LVA), are the widely accepted intervention for lymphedema. This study aimed to assess the outcomes of flow-oriented LVA modification on lymphatic malformation (LM). Methods:. We included 19 patients diagnosed with LM mixed type or microcystic type, who came to our clinic from June 2015 to December 2017. Under general anesthesia, all patients were administered an indocyanine green lymphography injection subcutaneously. In the case of a strong inflow, the patient underwent afferent lymph vessel of LM to venous anastomosis (LMVA). Otherwise, the side wall of LMVA was performed to the cysts. Outcomes were classified into the following groups based on the size changes: treatment effect (TE) 4 = >80% reduction rate; TE 3 = 50%–80% reduction rate; TE 2 = 20%–50% reduction rate; and TE 1 = 0%–20% reduction rate. Results:. All cases underwent surgery, with no case having an increased size. The results were as follows: TE 4 = 4 (21%) patients; TE 3 = 6 (32%) patients; TE 2 = 5 (26%) patients; and TE 1 = 4 (21%) patients. No case required study termination due to disease progression. Minor complication occurred in 3 cases. One vesicle increased at the labial mucosa and one wound dehiscence that epithelized within 1 month. Conclusion:. LMVA could be a novel, minimally invasive lymph flow-oriented surgical method for intractable LM.

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 crystal structure and the dynamic feature of molecular structure in solution for 1,8-dibenzoyl-2,7-dimethoxynaph-thalene are revealed by X-ray crystallographic analysis and VT-NMR measurements. In crystal, the molecule of the title compound is located on a twofold rotation axis. The two benzoyl groups are situated in an opposite direction. The dihedral angle between the mean planes of the phenyl ring and the naphthalene ring system is 80.25(6). The benzene ring and carbonyl moiety in each benzoyl group are almost coplanar. The molecular packing is stabilized by weak C–H…O hydrogen bonds and aπ-πstacking interaction between the benzene rings [centroid-centroid and interplanar distances of 3.6383(10) and 3.294 , respectively]. In solution, the temperature-dependent rotation behavior of the C–C bond between the benzene ring and the ketonic carbonyl group has been observed by1H VT-NMR measurements. Furthermore, comparison of the C–C bond rotation behavior between the benzene ring and the carbonyl group with 1-ben-zoyl-2,7-dimethoxynaphthalene has clarified that the C–C bond between the ketonic carbonyl group and the naphthalene ring rotates slower than the 1,8-dibenzoylated homologue.

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.

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.

This review article describes preparations and properties of various types of water-soluble cutting fluids additives derived from various materials. It is concerned with synthetic additives classified according to their functional groups: carboxylic acids, esters, dibasic acids, ethers, amides, substituted fatty acids and others for iron materials. Testing methods for water-soluble cutting fluids are described on ways for laboratory and practical tests for factory.

Several types of achiral N,N-dibenzyl-α,β-unsaturated thioamides were subjected to X-ray crystallographic analysis, and it was revealed that methylcrotonthioamide and 1-cyclohexenecarbothioamide provided chiral crystals. The absolute configuration determined by anomalous scattering method corresponded to the cotton effect in the solid-state CD spectra. The solid-state photoreaction gave optically active β-thiolactams. On the other hand, E–Z isomerization takes place in the photoreaction of a tiglylthioamide derivative. Stereochemical assignment before and after the reaction was rationalized by the hydrogen abstraction by alkenyl carbon followed by cyclization via a zwitterionic intermediate.

Examination was made of the preparation and properties of new types of water-based cutting fluids additives derived from various materials. Attention was directed to synthetic additives classified according to their functional groups : carboxylic acids, esters, dibasic acids, ethers, amides, substituted fatty acids and others. Methods for examining water-soluble cutting fluids additives for laboratory and practical use are described in detail.

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.

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 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...

α-Trifluoromethyl amines (IV) were prepared in three steps: preparation of α-trifluoromethyl ketones (I), their conversion tobenzyloximes (II), and reduction of the oximes (II) with lithium aluminium hydride and sodium methoxide. For example, α-trifluoromethyltridecylamine was obtained from the reduction of trifluoromethyl dodecyl ketone benzyl oxime.

Various adducts were prepared by reactions of amino acids with acid chlorides, and examined for antirust and other characteristic properties. Aqueous solutions of N-acyl leucine and N-acylglutamic acid salts with triethanolamine showed antirust and antiwear properties forward water-based cutting fluids to be quite satisfactory.

Esters were prepared by the reaction of acid chloride with copolymer of propylene oxide and ethylene oxide (CPO) for anti-rust and other properties in water-based cutting fluids. Aqueous emulsions of triethanolamine and oleic acid ester of CPO showed very high anti-rust properties for water-based cutting fluids.

A number of adducts were prepared from the reaction of adamantanecarbonyl chloride (I)with aminoalcohols or aminoacids, and screened for anti-rust properties and antimicrobial activity in spent fluids of water-based cutting fluids. Aqueous solutions of N-(l-adamantanecarbonyl)-O-(1-adamantanecarbonyl) mono-ethanolamine (III) showed good antirust and antimicrobial properties for water-based cutting fluids

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.

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...

Irradiation of N-[(R)-1-phenylethyl]-N-tigloythiobenzamide in benzene solution resulted in both [2+2] thietane and thioketone formation reactions (via β-hydrogen abstraction by the thiocarbonyl sulfur). Diastereoselectivity in the thietane formation was not observed, in that four β-lactams were obtained in similar yields. In contrast to the solution photochemistry, irradiation of the crystals provided remarkably high diastereoselectivities. At 15 o C, de of the syn-β-lactams was 61% and the ratio of syn/anti was to 8.7 (chemical yield: 78%). The solid-state photoreaction proceeded even at -78 o C, with higher diastereoselectivity. At low conversion (9%) only syn isomers (de=93%) were obtained, and 71% de was observed even at 90 % conversion. An X-ray crystal structure of the monothioimide indicates that the crystal is orthorhombic, of space group P2 1 2 1 2 1 , and the distances between the sulfur atom and the alkenyl carbon, and from the thiocarbonyl carbon to the alkenyl carbon, are 4.29 and 3.00 A, respectively. The twist angle τ of the C(=O)-N bond is 40.8° and that of the C(=S)-N bond is 19.9°. On the other hand, the sulfur atom and abstractable hydrogen atom are in close proximity, and the value for d is 2.40 A, for θ is 127.3°, for Δ is 67.9°, and for ω is 6.2°. From these values, it is apparent that this reactant is well-positioned for hydrogen transfer in the crystalline state

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.

Photochemical reactions of thioamides and thioimides are reviewed. Topics included are (1) photochemical [2+2] cycloaddition reactions of thioamides and thioimides with alkenes, (2) photochemical hydrogen abstraction of thioamides and thioimides by the thiocarbonyl sulfur atom.

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.

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.

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.

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

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.

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.