Ring-forming reaction via regioselective intramolecular insertion by (phenylthio) carbene into α c-h bond of alkoxides

ω-(Phenylthio)-ω-chloroalkyl acetates were allowed to react with MeLi (3.2 equiv) to give 2-(phenylthio) cycloalkanols which were produced by the regioselective intramolecular insertion by (phenylthio) carbenes.     

Synthesis of amine, halide, and pyridinium terminated 2-alkyl-p-tert-butylcalix[4]arenes

The synthesis of calix[4]arenes with functional groups tethered to a single methylene bridge has been explored. Mono-lithiated calix[4]arenes react with 1,ω-bromochloroalkanes to give 2-(ω-chloroalkyl)-calix[4]arenes, which function as key intermediates in the synthesis of a variety of tether-functionalized calix[4]arenes. Subsequent reactivity of these chloroalkyl species has allowed for successful synthesis of 2-(ω-iodoalkyl)-calix[4]arenes, 2-(ω-pyridiniumalkyl)-calix[4]arenes, and 2-(ω-aminoalkyl)-calix[4]arenes. This latter group of amine-terminated calix[4]arenes are especially significant as they may serve as useful entries to a wide range of subsequent chemistry, including metal coordination or attachment to a solid support. Both alkyl and aryl amines have been incorporated at the end of the tether, and a 2,6-diisopropylaniline derivative has been analyzed by X-ray diffraction.     

Synthesis of 3-oxooxa- and 3-oxoazacycloalk-4-enes by ring-closing metathesis. Application to the synthesis of an inhibitor of cathepsin K

3-Oxooxa- and 3-oxoazacycloalk-4-enes were obtained with good yield from 1-(ω-alkenyloxy)- and 1-(ω-alkenylamino)-but-3-en-2-ones by using a ring-closing metathesis. This methodology has been used to synthesize an inhibitor of cathepsin K.     

α,ω-Bis(4-substituted-3-quinolinylthio)alkanes from reactions of thioquinanthrene with alkoxides

The reaction of thioquinanthrene 1 with sodium alkoxides and α,ω-dihaloalkanes leads to the formation of α,ω-bis[4-(4-methoxy-3-quinolinylthio)-3-quinolinylthio]alkanes 4 . The yield depends on the nature of α,ω-dihalo-alkanes. The effect of α,ω-dihaloalkanes of the following types: XCH₂X (X = Cl,Br,I), X(CH₂)₂X (X = Cl,Br,I), Br(CH₂)₃Br and Br(CH₂)₆Br were studied. The preparation of 4-alkoxy-3′-(ω-bromoalkylthio)-3,4′-diquinolinyl sulfide 3 and their transformation to α,ω-bis(4-alkoxy-3-quinolinylthio)alkanes 6 were studied as well.     

Investigation of the direction of enolization of some furyl-substituted β-diketones

It was found that ω-benzoyl-2-acetyl-, ω-benzoyl-2-acetyl-5-bromo-, ω-(2-thenoyl-2-acetyl-, and ω-(5-bromo-2-thenoyl)-2-acetyl-bromofurans are enolized at the carbonyl group in the α position relative to the furyl grouping.     

Preparation and thermal degradation of α,ω-alkylene bis[5-(1,2,3,4-thiatriazolyl)] sulfides

Syntheses of some extremely shock sensitive α,ω-alkylene bis[ 5-(1,2,3,4-thiatriazolyl)] sulfides via reaction of sodium 1,2,3,4-thiatriazoline thionate (1) and α,ω-dihaloalkanes are described. Dichloromaleic imide reacted analogously with 1 to give 3,4-bis(5-(1,2,3,4-thiatriazolyl)thio)maleic imide. The compounds decompose thermally in solution with formation of α,ω-alkylene bis(thio-cyanates), nitrogen and sulfur. The infrared spectra are discussed.     

一水甲酸锂晶体三阶非线性光学性质理论研究

用含时藕合微扰Hartrre一Fork（CPHF）方法，有限场MP2理方法以及有向气 体方法，首次分别在分子和晶体水平上计算了一水甲酸锂晶体三次谐波极化率，表 明超分子γ(一3ω；ω,ω,ω)数值与超分子链长有线性关系；晶体x（一3ω;ω, ω,ω）计算值主要受到电子相关影响，其次受到基组和局域场影响，在非共振 条件下，频率色散的影响甚小'最后，估算了一水甲酸锂的三次谐波系数．     

四波混频过程中差频与和频的竞争研究

Tunable intense Vacuum Ultraviolet (VUV) laser was generated by two-photon resonant four wave difference frequency mixing (ω-=2ωUV-ωT) in Xenon. In the experiment some resonance attenuations of the VUV were observed at certain difference frequencies. These attenuations occur when the sum frequencies ω+=2ωUV+ωT coincide with excited ns (n=10,11) and nd (n=8~13) states. The third order linear susceptibility χ(3)（2ωUV+ωT;ωUV,ωUV+ωT） is reasonably increased by the double resonance enhancement, so the conversion efficiency of sum frequency mixing can be very high and the power of the pump laser is decreased and thus the difference frequency output is attenuated.     

New ω-chloroalkyl-substituted isatins and isoindigo

Russian Journal of Organic Chemistry - New 1-(ω-chloroalkyl)isatins were synthesized by alkylation of isatin with α-bromo-ω-chloroalkanes. The reaction of 1-(3-chloropropyl)isatin...     

Ring chain transformations. XIV. 3-(ω-Aminoalkyl)-1,2,4-triazoles by reaction of isothiosemicarbazides with lactam acetals or lactim ethers

Isothiosemicarbazide hydrohalides 1 react with lactam acetals 2 or lactim ethers 3 by the formation of lactamisothiosemicarbazones 4 or ring transformed 3-(ω-aminoalkyl)-1,2,4-triazoles 6 . The latter can independently by synthesized by alkylation of lactamthiosemicarbazones 9 . Condensation of primary 3-(ω-aminoalkyl)-1,2,4-triazoles 6 with lactim ethers 7 can lead to 3-lactamiminoalkyl-1,2,4-triazoles 8 .     

Synthesis and ‘click’ cycloaddition reactions of tetramethoxy- and tetrapropoxy-2-(ω-azidoalkyl)calix[4]arenes

2-(ω-Chloroalkyl)tetramethoxycalix[4]arenes are converted to 2-(ω-azidoalkyl)tetramethoxy- and cone-2-(ω-azidoalkyl)tetrapropoxycalix[4]arenes, the former by substitution and the latter by demethylation to 2-(ω-chloroalkyl)tetrahydroxycalix[4]arenes, which are O-propylated before substitution of azide for chloride. The azide-terminated calixarenes undergo Cu(I)-catalyzed 1,3-cycloaddition to terminal alkynes to give 1,4-disubstituted 1,2,3-triazoles, demonstrating the potential to couple calixarenes from a tether at the 2-position (methylene bridge) to substrates that bear a terminal alkyne group. The cone conformation of cone-2-(4-chlorobutyl)tetrapropoxycalix[4]arene has been confirmed by X-ray diffraction.     

Synthesis of phthalonitriles containing ω-alkenyl, ω-(alkylsulfanyl)alkyl, and ω-(alkylsulfonyl)alkyl substituents and phthalocyanine derivatives based thereon

Alkylation of phthalonitrile radical anion sodium salt with terminal alkenyl bromides (4-bromobut-1-ene, 5-bromopent-1-ene, and 6-bromohex-1-ene) gave the corresponding 4-alkenylphthalonitriles which reacted with alkanethiols (BuSH and n-C₁₀H₂₁SH) to produce 4-(ω-alkylsulfanylalkyl)phthalonitriles. Oxidation of the latter with hydrogen peroxide afforded 4-(ω-alkylsulfonylalkyl)phthtalonitriles. 4-Alkenyl- and 4-(ω-alkylsulfonylalkyl)phthalonitriles were brought into condensation with zinc(II) acetate to obtain the corresponding zinc phthalocyanines.     

Functional polymers and sequential copolymers by phase transfer catalysis. XXVIII. Synthesis and characterization of alternating block copolymers and polyformals of polyisobutylene and aromatic polyether sulfone

Alternating—i.e., -(A-B)_n- type—block copolymers of polyisobutylene (PIB) and aromatic polyether sulfone (PSU) have been prepared by phase transfer catalyzed Williamson polyetherification of α,ω-di(phenol)PIB with α,ω-di(chloroallyl)- or -(bromobenzyl)PSU. Block copolymers of the two prepolymers were also synthesized by the phase transfer catalyzed polyetherification of methylene chloride with α,ω-di(phenol)PIB and α,ω-di(phenol)PSU (bisphenol-A-terminated PSU). This method leads to -[(A)_x-(B)_y]_n- block copolymers with formal linkages between segments. At sufficiently high segment lengths, both types of block copolymers exhibit two distinct T_gs, indicating phase separation into rubbery PIB and glassy PSU domains.     

Macrolactones built from the bis-3,4(indol-1-yl)maleimide scaffold

15, 16, and 17-Membered lactones based on the bis-3,4(indol-1-yl)maleimide framework were obtained using intramolecular esterification reaction starting from 3-(1-ω-carboxyalkyl-2,3-dihydroindol-1-yl)-4-(1-ω-hydroxyalkyl-2,3-dihydroindol-1-yl)-maleimides. 3,4-Dibromo-maleimide, ω-(2,3-dihydroindol-3-yl)alkanoic acids, and ω-(2,3-dihydroindol-3-yl)alkanoles were used as starting compounds. Substitution of Br for the substituted indolines followed by the intramolecular cyclization of O-silylated hydroxyl acids derivatives led to macrolactones that incorporated 4-(dihydroindol-1-yl)-3-(indol-1-yl)maleimide moieties. Indoline nuclei in these compounds were dehydrogenated by DDQ in refluxing toluene to give 15, 16 or 17-membered lactones 3-[(ω-3-carboxyalkylindol-1-yl)-4-(ω-hydroxyalkylindol-1-yl)maleimides. Quantum chemical calculations showed that the formation of macrolactones of smaller size (13-membered) corresponds to the higher Gibbs energy ΔG^# and correlates with the absence of the target reaction product.     

一些含氟单体的合成及其聚合反应的初步研究

合成了含氟单体3-氧杂全氟戊烷-1,5-二磺酰溴(3),N-烯丙基-2-(ω-碘-n-全氟烷氧基)-1,1,2,2-四氟乙磺酰胺(16～18).初步研究了含氟单体3与非共轭二烯的聚合反应、连二亚硫酸钠引发的含氟单体16～18的聚合反应以及α,ω-全氟烷基二碘代烷22,23与非共轭端二烯的聚合反应,得到了相应的含氟聚合物或寡聚物.     

Synthesis of polymer networks containing degradable polyacetal segments

Four different routes for the production of polyacetal containing networks are described : (1) free radical copolymerization of α,ω-(meth)acrylate terminated polyacetals, (2) hydrosilylation reactions of α,ω-allyl terminated poly- (1,3-dioxolane) with a multifunctional silane, (3) modification of α,ω-hydroxy terminated poly(1,3-dioxepane) through reaction with 3-isocyanatopropyl-triethoxysilane and subsequent cross-linking under influence of H₂O and (4) cross-linking of multifunctional hydroxy-terminated polyacetals by reaction with a diisocyanate.     

High-frequency asymptote for the velocity auto-correlation function spectrum of argon-like systems

The work is devoted to the analysis of high-frequency behavior of the velocity auto-correlation function spectrum ?(V)(ω) for argon-like systems. The theoretical predictions are compared with results of computer simulations of ?(V)(ω). It is shown that (1) ?(V)(ω) takes the exponential behavior ?(V)(ω)?ω(q(n)) (ω→∞)exp(-(ωτ(a)(n))(p(n))), where p(n), q(n), and τ(a)(n) are the definite functions of the steepness exponent n for the power repulsive part of interparticle potential; (2) there is full agreement between theoretical predictions and the values of p(n), q(n), and τ(a)(n) obtained in computer simulations. Weighty arguments about the universal character of the exponential frequency decay exp(-(ωτ(a)(n))(p(n))) for spectra of different correlation functions are given. The experimental spectrum of the depolarized light scattering in argon for high frequencies is analyzed. It is shown that the steepness exponent n for the power repulsive potential takes the value: n ≈ 24 that is essentially different from n = 12 characteristic for the Lennard-Jones potential.     

Preparation of ω-tetrahydropyran-2-ylsulfanylalkylmagnesium chlorides: Useful reagents for the synthesis of 1-(ω-mercaptoalkyl)-1,2-dihydrobuckminsterfullerenes (C60)

ω-Tetrahydropyran-2-ylsulfanylalkylmagnesium chlorides are prepared as Grignard reagents containing protected mercaptoalkyl chains, which are useful for the direct introduction of ω-mercaptoalkyl chains to electrophiles. In order to prove the usefulness of these reagents, they were reacted with buckminsterfullerene (C₆₀) to give 1-(ω-mercaptoalkyl)-1,2-dihydrobuck minsterfullerenes after the deprotection of THP group with TFA.     

Synthesis of organosiloxanes with reactive groups at silicon atoms

The heterofunctional condensation of (dihydroxy)organodisiloxanes and -trisiloxanes with vinyl(hydro)organodichlorosilanes was studied with the purpose of preparing a,ω-dichloroorganosiloxanes with reactive Si-H and Si-CH=CH₂ groups. During the isolation, 1,9-dichloro-1,9-dihydropentamethyloctasiloxane disproportionates with the elimination of (dichloro)methylsilane to form heptamethylcyclotetrasiloxane. A series of cyclotetra-, cyclohexa-, and cyclooctasiloxanes with Si-H and Si-CH=CH₂ groups was obtained by the condensation of a,ω-dihydroxyorganosiloxanes with a,ω-(dichloro)divinyl(dihydro)organosiloxanes.     

Preparation of 1-[ω-(1,4,5,6-Tetrahydropyrimidin-2-Yl)Alkyl]Thymines

One-stage preparation of 1-[ω-(1,4,5,6-tetrahydropyrimidin-2-yl)alkyl]-thymines from 1-(ω-cyanoalkyl)thymines and a 1:1-mixture of 1,3-diaminopropane and ethanol saturated with hydrogen sulfide is described. 1-(2-Cyanoethyl)-thymine gave a facile reversal of the Michael reaction to thymine under the conditions used. The reaction of 1,3-bis(3-cyanobenzyl)thymine with the above reagent produced 1,3-bis[3-(1,4,5,6-tetrahydropyrimidin-2-yl)benzyl]thymine.