Reaction of 2-chloroethyl isothiocyanate with N-phenylethyleneimine and ethylene sulfide

The reaction of 2-chloroethyl isothiocyante with N-phenylethyleneimine in the presence of triethylamine gives 2-(2-chloroethyl)imino-3-phenyl-1,3-thiazolidine. A mixture (12) of 2-(2-chloroethyl)imino-3-phenyl-l,3-thiazolidine and 7-phenyl-2,3,5,6-tetrahydroimidazo-[2,1-b]thiazolinium chloride is obtained in the absence of a catalyst. The reaction of 2-chloroethyl isothiocyanate with ethylene sulfide in the presence of triethylamine gives 2,3,5,6-tetrahydrothiazolo[2,3-b]thiazolinium chloride, while the reaction with tetraethyl-ammonium bromide gives 2-ethyleneiminium-l,3-dithiolane chloride.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1651–1653, December, 1971.     

Synthesis of enantiomerically enriched oxazolinyl[1,2]oxazetidines

The first stereoselective synthesis of oxazolinyl[1,2]oxazetidines based on the reaction of lithiated 2-(1-chloroethyl)-2-oxazolines with nitrones is described. Highly enantioenriched oxazolinyl[1,2]oxazetidines have also been prepared starting from a 1:1 diastereomeric mixture of optically active 2-(1-chloroethyl)-2-oxazolines.     

High-Temperature Synthesis of Thiophene from Bis(2-chloroethyl) Sulfide

Gas-phase reaction of bis(2-chloroethyl) sulfide (Yperite) with acetylene at 550–700°C leads to formation of thiophene in 45% yield, the conversion of the initial sulfide being complete. The yield of thiophene reaches 63–68% in the thermolysis of a mixture of acetylene, bis(2-chloroethyl) sulfide, and lower organic disulfides.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 6, 2005, pp. 910–912.Original Russian Text Copyright © 2005 by Voronkov, Levanova, Sukhomazova, Russavskaya, Deryagina, Korchevin.     

Reaction of bis(2-chloroethyl)-2-nitroethynylphosphonate with diazoacetic ester

Reactions of 1,3-dipolar cycloaddition of bis(2-chloroethyl)-2-nitroethenylphosphonate to methyl and ethyl diazoacetates proceed with the formation of a mixture of regioisomers of phosphorylated nitropyrazoline carboxylates that under the reaction conditions undergo isomeric transformations and denitration and afford a mixture of Δ¹- and Δ²-pyrazoline- and pyrazolecarboxylates. Structures of the synthesized substances are studied by the methods of IR and ¹H, ³¹P NMR spectroscopy and partially by X-ray structural analysis.     

Nonlinear optically active polymeric coordination networks based on metal m-pyridylphosphonates

A family of polymeric coordination networks based on meta-pyridylphosphonate bridging ligands has been synthesized and characterized by single-crystal X-ray crystallography. Compounds [M(2)(L-Et)(4)(mu-H(2)O)] (M = Mn, 1; Co, 2; Ni, 3; L-Et = ethyl-4-[2-(3-pyridyl)ethenyl]phenylphosphonate) were obtained by hydro(solvo)thermal reactions between diethyl-4-[2-(3-pyridyl)ethenyl]phenylphosphonate (L-Et(2)) and corresponding metal salts, while [Cd(L-H)(2)], 4 (L-H is monoprotonated 4-[2-(3-pyridyl)ethenyl]phenylphosphonate), was obtained by a hydro(solvo)thermal reaction between (L-H(2)).HBr and Cd(CF(3)SO(3))(2).6H(2)O. Compounds 1-3 are isostructural and crystallize in noncentrosymmetric space group Fdd2, and they adopt a complicated 3D framework structure composed of [M(2)(L-Et)(4)(mu-H(2)O)] building units, while compound 4 adopts a centrosymmetric 3D network structure resulted from linking 1D sinusoidal cadmium phosphate chains with L-H bridging ligands. Consistent with their polar structures, compounds 1-3 exhibit powder second harmonic generation signals larger than that of potassium dihydrogen phosphate.     

Synthesis of diazahexathia-24-crown-8 derivatives and structures of Ag+ complexes

Diazahexathia-24-crown-8 (2) has been isolated from the reaction mixture during the preparation of monoazatrithia-12-crown-4 (1). When N-Boc protected bis(2-chloroethyl)amine was employed as a starting material, N-Boc protected monoazatrithia-12-crown-4 (3) and N-Boc protected diazahexathia-24-crown-4 (4) were separated easily. Double-armed diazahexathia-24-crown-8 having two 3',5'-dichlorobenzyl groups (5a) or two 2-phenylethyl groups (5b) were also prepared using reductive amination. The stoichiometry and detailed structures of the Ag+ complexes with and were investigated by 1H NMR titration experiments and X-ray crystallography.     

Vilsmeier-Haack reaction of 1-cyclopropyl-2-arylethanones

A convenient and efficient method to synthesize 3-(2-chloroethyl)-5-aryl-4H-pyran-4-ones 2 and 2-chloro-3-(2-chloroethyl)-1-naphthaldehydes 3 in moderate to good yields was developed via the Vilsmeier-Haack reaction of readily available 1-cyclopropyl-2-arylethanones 1 at different temperature. This reaction proceeds via sequential enolization, ring opening, haloformylation, and intramolecular nucleophilic cyclization or Friedel-Crafts alkylation reactions to produce 2 or 3.     

正丁胺对苯膦酸铜的插层反应研究

分别采用溶液搅拌和超声的方法,研究了有机正丁胺分子对苯膦酸铜的插层反应.对插层复合物进行了红外光谱(IR)、X射线粉末衍射(XRD)和热重分析等测试及结构分析.结果表明,有机正丁胺的插入使得苯膦酸铜的层间距增大.     

Derivatives of 2-sulfonamido-4,5-dimethoxyphenylacetic acid and of 2-carboxamido(2-chloroethyl)methylbenzenesulfonamides

Series of variously sustituted amides of 2-sulfonamido-4,5-dimethoxyphenylacetic acid have been prepared. The reaction of diethylamine, piperidine, morpholine and bis(2-chloroethyl)amine with carbo-methoxymethyl-3,4-dimethoxybenzenesulfonyl chloride produced the corresponding sulfonamido derivatives. Acid hydrolysis of the latter and action of thionyl chloride gave the chlorocarboxymethyl-benzenesulfonamides. The acid chlorides of the sulfonamides were transformed to the 2-carboxamido-bis(2-chloroethyl)methylbenzenesulfonamides with bis(2-chloroethyl)amine. These agents were tested in L-1210 and P-388 leukemias and were found not to possess antitumor activity in these two transplantable tumor lines.     

Novel photocurable monomers: The synthesis of difunctional vinyl ethers with a phosphonate group and difunctional 1‐propenyl ethers with a phosphonate group and their photoinitiated cationic polymerization

Phosphorus‐containing vinyl ether monomers and 1‐propenyl ether monomers were prepared by the regioselective addition reaction of glycidyl vinyl ether (GVE) or 1‐propenyl glycidyl ether with diaryl phosphonates with quaternary onium salts as catalysts. The reaction of GVE with bis(4‐chlorophenyl) phenylphosphonate gave bis[1‐(4‐chlorophenoxy methyl)‐2‐(vinyloxy)ethyl]phenylphosphonate in a 68% yield. The structures of the resulting phosphorus‐containing vinyl ether monomers and 1‐propenyl ether monomers were confirmed by IR and ¹H NMR spectra and elemental analysis. Photoinitiated cationic polymerizations of the resulting phosphorus‐containing vinyl ether monomers and 1‐propenyl ether monomers were investigated with photoacid generators. The polymerization of vinyl ether groups and 1‐propenyl ether groups of the obtained monomers proceeded very smoothly with a sulfonium‐type cationic photoinitiator, bis[4‐(diphenylsulfonio)phenyl]sulfide‐bis(hexafluorophosphate), upon UV irradiation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3105–3115, 2005     

Phosphonation of arenes with dialkyl phosphites catalyzed by Mn(II)/Co(II)/O2 redox couple

[reaction: see text]. Arylphosphonates were first synthesized through a catalytic phosphonation of various arenes with dialkyl phosphites under the influence of an Mn(OAc)2/Co(OAc)2/O2 redox couple. For instance, the reaction of benzene with diethyl phosphite in the presence of Mn(OAc)2 (5 mol %) and Co(OAc)2 (1 mol %) under a mixed gas of O2 (0.5 atm) and N2 (0.5 atm) at 45 degrees C led to diethyl phenylphosphonate in 81% selectivity at 62% conversion. This is the first successful phosphonation of benzene with dialkyl phosphites through a catalytic radical process.     

Layered calcium phenylphosphonate: Synthesis and properties

Calcium phenylphosphonate, Ca(HO₃PPh)₂, was synthesized by the reaction of calcium nitrate and phenylphosphonic acid. A thorough investigation was performed to study the effect of reaction parameters on the synthesis and growth of crystalline product in a high yield. The compound was structurally characterized by single-crystal X-ray diffraction technique. It consists of a layered structure with inorganic framework of CaO₈ polyhedra from which phenyl groups are pointing out. The inorganic framework is also stabilized by the OH⋯O hydrogen bonds. Results from thermal analysis by thermogravimetry and thermodiffractometry revealed that calcium phenylphosphonate is stable up to 300°C. The compound undergoes consequent thermal decomposition and phase transitions above 300°C temperatures until it converts to δ-Ca(PO₃)₂ at 620°C.     

Enzymatic removal of carboxyl protecting groups. III. Fast removal of allyl and chloroethyl esters by Bacillus subtilis esterase (BS2)

An esterase from Bacillus subtilis (BS2) allows the fast and selective removal of allyl, 2-chloroethyl, and 2,2,2-chloroethyl esters under mild conditions in high yields. In addition, BS2 easily hydrolyzes phenacyl esters, while the hydrolysis of sterically hindered diphenylmethyl esters is slow, requiring longer reaction time and higher enzyme/substrate ratio.     

Incorporation of phosphorus oxyacids into layered double hydroxides

Four phosphonate anions (methyl-, ethyl-, phenyl- and benzylphosphonate) were successfully incorporated into [Cu₂Cr(OH)₆]Cl·yH₂O. It was found that two phases exist for the phenylphosphonate intercalate; one in which the anions are arranged perpendicular to the layers, and one with a tilted orientation. Systematic variation of the reaction conditions allowed the former to be isolated with phase purity, but not the latter. The solid-state ³¹P NMR data suggest that proton transfer may occur between host and guest. Some neutral guest is incorporated in the case of phenylphosphonate and benzylphosphonate, presumably owing to relatively poor solvation of these guests. Heat treatments only resulted in the formation of a covalent bond between host and guest in the case of the methylphosphonate intercalate. The intercalation of the related and redox-active phenylphosphinate into a range of LDHs is also reported. Time-resolved in situ diffraction techniques were used to both monitor and quantify the intercalation of phenylphosphonate into [Cu₂Cr(OH)₆]Cl·yH₂O and phenylphosphinate into the hexagonal form of [LiAl₂(OH)₆]Cl·yH₂O. Kinetic and mechanistic parameters have been determined from the diffraction data.     

New derivatives of N-nitrosamines

Two new derivatives are proposed for determination of nitrosamines by GLC. One is formed by reaction with di(2-chloroethyl) phosphochloridate and the other by reaction with m-trifluorotoluene sulphonyl chloride.     

Infrared spectrum of the 2-chloroethyl radical in solid para-hydrogen

The addition reaction of chlorine with ethylene (C(2)H(4)) is expected to proceed via a free radical intermediate, the 2-chloroethyl radical, however, this intermediate has not been previously observed spectroscopically. Irradiation at 365 nm of a co-deposited mixture of Cl(2), C(2)H(4), and p-H(2) at 3.2 K produces a series of new lines in the infrared spectrum. A strong line at 664.0 cm(-1) and weaker lines at 562.1, 1069.9, 1228.0, 3041.1 and 3129.3 cm(-1) are concluded to be due to a single carrier based on their behavior upon subsequent annealing to 4.5 K and secondary irradiation at 254 and 214 nm. The positions and intensities of these lines agree with the MP2/aug-cc-pVDZ predicted vibrational spectrum of the 2-chloroethyl (˙CH(2)CH(2)Cl) radical. In order to confirm this assignment, isotopic experiments were performed with C(2)D(4) and t-C(2)H(2)D(2) and the corresponding infrared bands due to the deuterium isotopomers of this radical (˙CD(2)CD(2)Cl and ˙C(2)H(2)D(2)Cl) have been observed. A final set of experiments were performed following irradiation of the Cl(2)/C(2)H(4)/p-H(2) mixture at 365 nm, in which the matrix was irradiated with filtered infrared light from a globar source, which has been shown to induce reactions between isolated Cl atoms and matrix H(2) to produce HCl and H atoms. In these experiments, the major products observed were HCl, the ethyl radical (˙C(2)H(5)) and ethyl chloride (C(2)H(5)Cl) and the possible mechanisms for the formation of these species are discussed.     

Surface-relief-grating formation behavior of two hyperbranched azo polymers

In this work,surface-relief-grating formation behavior was studied by using two hyperbranched azo polymers.The hyperbranched polymers containing pseudo-stilbene type azo chromophores throughout the hyperbranched structure were synthesized by step-growth polycondensation of AB₂ type monomers.The AB₂ monomer,4-（4’-（bis（2-chloroethyl）amino）-phenylazo） benzoic acid（BAA）,was prepared through azo-coupling reaction between N,N’-bis（2-chloroethyl）aniline and 4- aminobenzenic acid.The another AB₂ monomer,4-（4’-（bis（2-chloroethyl）amino）phenylazo）-3-nitro-benzoic acid（BANA）, was prepared through azo-coupling reaction between N,N-bis（2-chloroethyl）aniline and 3-nitro-4-aminobenzcnic acid.The hyperbranched polymers（PBAA and PBANA） were prepared through nucleophilic substitution reaction of BAA and BANA, respectively.The polymers synthesized were characterized by using spectroscopic methods and thermal analysis.The photoinduced dichroism and photo-induced surface-relief-grating（SRG） formation of the hyperbranched polymers were investigated upon irradiation with Ar⁺ laser at 488 nm.PBAA shows typical photoinduced dichroism SRG formation behavior.On the contrary,PBANA does not show the photoresponsive properties.The results indicate that the nitro at the ortho position of azo group of PBANA shows the effect of inhibiting the photoinduced variations.The effect can be attributed to the blockage of the trans-cis isomerization of the azobenzene moieties by the steric hindrance.     

Reactions of o-aminonitriles with isocyanates. 1. A two-step synthesis of 2,6-dihydroimidazo[1,2-c]quinazolin-5-(3H)one

The reaction of anthranilonitrile with 2-chloroethyl isocyanate yields 2-[3-(2-chloroethyl)ureido]benzo-nitrile ( 6 ) which, upon heating, or treatment with base, undergoes a double cyclization to form 2,6-dihydroimidazo[1,2-c]quinazolin-5-(3H) one ( 8 ) in excellent yield. When heated with hydrochloric acid, 6 is converted initially into 2-(2-chloroethylamino)-4H-[3,1]benzoxazin-4-one ( 18 ) and further into 3-(2-chloroethyl)-2,4-(1H,3H)quinazolinedione ( 15 ). The acid-catalyzed reaction of 2,3-dihydro-5H-oxazolo[2,3-b]quinazolin-5-one ( 14 ) with nucleophilic reagents yields 3-substituted 2,4-(1H,3H)quinazolinediones.     

Investigation of the mobility of methylene group hydrogen atoms in some derivatives of 2-iminothiazolidin-4-one

A study is made of the reaction of 2-arylamino- and 3-aryl-2-arylimino derivatives of thiazolidin-4-one with p-[N, N-di(2-chloroethyl)amino]benzaldehyde and p-nitroso-N, N-di(2-chloroethyl) aniline. It is shown that replacement of hydrogen at the endocyclic nitrogen atom of 2-iminothiazolidine-4-one raises mobility of hydrogen atoms in the methylene group in the order phenyl > p-tolyl > > benzyl. The results obtained are confirmed by IR spectroscopy.     

Preparation of 1-amino-4-methylpiperazine

The selectivity of the formation of N-di(2-chloroethyl)methylamine in reactions with various chlorinating agents has been investigated and the optimum chlorinating agent has been found. 1-Amino-4-methylpiperazine has been obtained for the first time by the cyclization of N-di(2-chloroethyl)methylamine with aqueous hydrazine. A possible mechanism has been proposed for the cyclization reaction.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1794–1797, December, 2004.