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1.
Antiradical and antiand prooxidant activities of the newly obtained triphenylantimony(V) catecholate complexes derived from gallic acid esters of the general formulas (RO(O)C–Cat)SbPh3 (R = Me (1), C8H17 (2), C12H25 (3)) and (MeO(O)C–(OH?NEt3)Cat)SbPh3 (4) were studied. The comparative study involving gallic acid esters of the general formula RO(O)C–GallH3 (R = Me (5), C8H17 (6), C12H25 (7)) was performed in order to evaluate the effect of organic ligands on the properties of the antimony(V) compounds. The values of EC50, the number of converted molecules of stable radical (nDPPH), as well as the relative content of oleic acid hydroperoxides confirm the antiradical and antioxidant activity of triphenylantimony(V) complexes in reactions with diphenylpicrylhydrazyl radicals and in the antioxidation of oleic acid. The influence of more active compounds 1 and 4 and ester 5 on lipid peroxidation of the rat liver homogenate of male Wistar line was determined. The membraneprotective properties were evaluated for induced hemolysis of erred blood cells as an example, and catalase activity of erythrocyte hemolysate was studied. 相似文献
2.
The gas chromatographic analysis of alkyldiazoacetates N 2CHCO 2R (R = CH 3 ? C 4H 9), ??-aliphatic diazoketones RCOCHN 2 (R = C 3H 7, C 5H 11, and C 9H 19), and aryl-substituted diazoketones Ph (CH 2) n COCHN 2 ( n = 0?C2) is shown to be possible when their retention temperatures are below the boiling points of compounds of this series at atmospheric pressure without decomposition (about 140°C). At higher temperatures occurs partial or complete decomposition of ??-diazoketones in chromatographic columns to form ketenes. Among the impurities in the reaction mixtures at the diazotization of corresponding alkyl glycinates were identified for the first time the nitrate esters of glycolic acid O 2NOCH 2CO 2R, as well as the dimeric products. All diazocarbonyl compounds and the impurities were characterized by mass spectra. For the first time their gas chromatographic retention indices were determined. 相似文献
3.
Summary Dichloromethyleneamide dialkyl phosphates (AlkO) 2P(O)N=CCl 2 (alkyl: C 2H 5,C 3H 7, i-C 3H 7, C 4H 9, i-C 4H 9) were obtained by reaction between chlorine and the corresponding isothiocyanatophosphate esters. The dichlorides obtained reacted vigorously with amines, alcohols, and alcoholates.Translated from Izvestiya Akademii Nauk SSR, Seriya Khimicheskaya, No. 5, pp. 932–933, May, 1964 相似文献
4.
Preparation and Chemical Properties of N-Trifluoromethylthiophosphaneimines In n-hexane (CF 3S) 3N and (C 6H 5) 3As react to CF 3SN?As(C 6H 5) 3 and CF 3SSCF 3. With (RO) 3P (CF 3S) 3N forms CF 3SSCF 3 and CF 3SN?P(OR) 3 (R = C 6H 5, CH 3, C 2H 5). While CF 3SNP-(OC 6H 5) 3 is stable up to 100°C the other Phosphaneimines rearange to (R′O) 2P(O)N(R′)SCF 3 (R′ = CH 3, C 2H 5). Hydrolysis leads to ROH and (RO) 2P(O)N(H)SCF 3. Only for R = C 6H 5 in addition (C 6H 5O) 2P(O)NH 2 is formed. Physical data and nmr spectra of the newly prepared substances are presented. 相似文献
5.
On Chalcogenolates. 137. Alkyl Esters of Isothiocyanoformic, Isothiocyanomonothioformic and Isothiocyanodithioformic Acids The esters RO? CO? NCS, where R = CH 3, C 2H 5, as well as RS? CO? NCS and RS? CS? NCS with R = C 2H 5, nC 3H 7 have been prepared by three different methods. The reaction between the corresponding chloro compound and KSCN in the presence of the phase transfer catalyst 18-crown-6 gives the highest yields. The electron absorption, infrared, nuclear magnetic resonance, and mass spectra of these compounds are reported. 相似文献
6.
Experimental data obtained from the study of the behaviour of monoalkyl phosphates ROP(O)(OH)O ? or monoalkyl phosphonates C 6H 5P(O)(OR)O ? in aquo-alcoholic (H 2O + R′OH) solutions suggest: (1) in the case of monoalkyl phosphonates the exchange of R and R′ must proceed by a direct alcoholysis; (2) in the case of monoalkyl phosphates, where the scission of the ester at about pH 4,5 proceeds via the intermediate formation of metaphosphate ion PO 3?, R′OPO 3H ? can also be formed by the addition of R′OH to PO 3? (competitive to the addition of water) besides direct alcoholysis of ROPO 3H ?. 相似文献
7.
On Chalcogenolates. 139. Studies on Dialkyl Esters of Chalcogenocarbonic Acids. 2. O,Se- and S, Se-Dialkyl Monothiomonoselenocarbonates The hitherto unknown esters RSe? CS? OR′, where R = C 2H 5, nC 3H 7 and R′ = C 2H 5, nC 3H 7, are formed by reaction of NaSeR with Cl? CS? OR′ and of RSe? CS? Cl with HOR′. At the first time, the esters RSe? CO? SR′ with R = R′ = C 2H 5, nC 3H 7 have been prepared by reaction between NaSeR and Cl? CO? SR′. The compounds have been characterized by means of diverse spectroscopic methods. 相似文献
8.
Tris-chloromethyl-phosphine oxide, (ClCH 2)3 P?O(I), is obtained by chlorination of (HOCH 2)3P?O with PCl 5 or (C 6H 5)3PCl 2, and also by oxidation of (CICH 2)3P?O and (ClCh 2)2(CH 3)P?O. High yields of tris-(dialkyloxyphosphonly-methyl)-phosphine oxides, [RO 2(O)PCH 2]2P?O (II) (R?CH 3, C 2H 5, iso-C 3H 7, n-C 4H 9, 2- ethyl-hexyl), tris (alkyloxyphosphinyl-methyl)-phosphine oxides, [R 2(O)PCH 2]3P?O(R = C 6H 5, CH 3) are obtained by heating tris-chloromethyl-phosphine oxides, [(RO) (R′) (O)PCH 2]3P?O (R = C 4H 9, R′? C 6H 5) and tris-(oxophosphoranyl-phosphine oxides with phosphites, phosphonites and phosphinites, respectively, at 170–180°C for several hours. Compounds II possess an extraordinarily high absorption capacity. Thus a warm. 2% solution of II (R = C 2H 5) in benzene solidifies completely on cooling so that no benzene can be poured off. Tris-dihydroxyphosphonyl-methyl)-phosphine oxide, [(HO) 2(O)PCH 2]3P?O, obtained by hydrolysis of II (R ? C 2H 5) with refluxing conc. HCl or by thermal decomposition of II (R ? iso-C 3H 7) at 190°, titrates in aqueous solution as a hexabasic acid with breaks at pH = 4,4 (three equivalents) and pH = 10,7 (three equivalents). It forms crystalline salts with amines, alkali and alkaline earth metals, and is an excellent chelating agent. The 1H- and 31?P-NMR. spectra of all the compounds prepared are discussed. 相似文献
9.
On chalcogenolates. 138. Studies on Dialkyl Esters of Chalcogenocarbonic A cids. 1. O, Se-Dialkyl Monoselenocarbonates The esters RSe? CO? OR′ with R = R′ = C 2H 5 as well as with R = nC 3H 7 and R′ = CH 3, C 2H 5 have been prepared by reaction of sodium alkane selenolates with alkyl esters of chloroformic acid. The compounds have been characterized by means of electron absorption, infrared, nuclear magnetic resonance ( 1H, 13C, and 77Se), and mass spectra. 相似文献
10.
Bis-chloromethyl-alkyl-and - aryl-phosphine oxides, (CICH 2)2P(O)R, which are obtained by reaction of (CICH 2)2P(O)Cl with GRIGNARD reagents, undergo a MICHAELIS -ARBUSOV reaction when heated for several hours with trivalent phosphorus esters (phosphites, phosphonites, or phosphinites) at 170–180°C. The reaction affords bis-(dialkyloxyphosphonyl-methyl)-, bis (alkyloxyphosphinyl-methyl)-, and bis-(oxophosphoranyl-methyl)-, -alkyl- or -aryl-phosphine oxides, R(O)P[CH 2P(O)R′R″] 2 R = CH 3, C 2H 5, n-C 8H 17, n-C 12H 25, C 6H 5; R′ and R″ = C 2H 5O, C 4H 9O, C 6H 5, CH 3 in good yields. Conversion of the compounds containing alkyloxy groups to the free acids is achieved by refluxing with conc. HCl. Bis-(dihydroxyphosphonyl-methyl)-dodecylphosphine oxide, n-C 12H 25(O)P[CH 2P(O) (OH) 2]2, obtained by hydrolysis of the all-ethyl ester, titrates in aqueous solution as a tetrabasic acid with breaks at pH = 4 (two equivalents), pH = 6,9 (one equivalent) and pH = 9,6 (one equivalent). This acid, its disodium salt (m. p. 405–410°) and its tetrasodium salt (m.p. > 460°) are surface active and are excellent chelating agents. The 1H- and 31P-NMR. spectra of all the compounds prepared are discussed. 相似文献
11.
Eight diorganotin(IV)-oxo-carboxylates {[R 2Sn(O(O)CR′)] 2O} 2?·?Y (R′?=?C 4H 3N 2Y? = H 2OR?=? nBu 1, Y?=?0 R?=?Me 2, Y?=?0 R?=?C 6H 5 3, Y?=?0 R?=?C 6H 5CH 2 4; R′?=?CH 2SC 4H 3N 2-2,6Y?=?0 R?=? nBu 5, Y?=?CH 2Cl 2R?=?Me 6, Y?=?0 R?=?C 6H 5 7, Y?=?0 R?= C 6H 5CH 2 8) have been prepared in 1?:?1 molar ratios by reactions of diorganotin(IV) oxide with 2-pyrazinecarboxylic acid or (2-pyrimidylthio)acetic acid, respectively. All the complexes are characterized by elemental analysis, IR, 1H NMR and 13C NMR spectra. Except for 2, 4 and 7, the complexes are also characterized by X-ray crystallography diffraction analyses, which reveal that the complexes adopt the familiar dicarboxylato tetraorganodistannoxane structural mode. Among them, the evident difference is that weak intramolecular interactions between Sn and N atoms are recognized in complexes 1 and 3. However, for complex 5 two different coordination modes are found in the same lattice. 相似文献
12.
在水和乙醇溶剂中, 通过Cu(II), Fe(III)和Fe(II)与2,2-联咪唑协同作用, 构筑了四种新的超分子配合物[Cu(H 2biim)(gly)(H 2O)]Cl•H 2O ( 1), [Cu(H 2biim)(C 3H 2O 4)(H 2O)]•1.5H 2O ( 2), [Fe 2( μ-O)(H 2biim) 4(H 2O) 2](NO 3) 4•C 2H 5OH ( 3)和[Fe(H 2biim) 3]SO 4 ( 4) (H 2biim=2,2-联咪唑; gly -=甘氨酸根; C 3H 2O=丙二酸根). 并通过元素分析, 红外光谱和X射线单晶衍射对其组成、结构和谱学性质进行研究. H 2biim配体, 丙二酸根和甘氨酸根三种配体都采用了双齿螯合方式与金属离子配位. 配合物 1~ 4中, 通过H 2biim配体的N—H键与阴离子、水分子和溶剂分子形成多种氢键, 如R(7), R(9)和R(4)等, 以及H 2biim配体之间的π-π堆积, 阳离子不对称单元构筑了多维结构的超分子配合物. 相似文献
13.
In this study, three middle range α-olefin monomers including 1-hexene, 1-octene, and 1-decene were oligomerized using conventional AlCl 3/H 2O catalytic system. Molecular weight and microstructure of the oligomers were analyzed by GPC and 1HNMR, respectively. By 1HNMR spectra, both internal (C HR=C HR′ and C HR=CR′R′′) and external (C H2=CR′R′′) olefins containing di and tri-substituted C=C bonds were detected. After successful oligomerization, synthesized polyα-olefins underwent hydrogenation process using Pd(0)-Hal catalyst to yield synthetic oils of PHex, POct, and PDec, respectively and then completion of the hydrogenation was confirmed by 1HNMR spectroscopy. The microstructure of the synthesized oligomers was rationalized using the ratio under the peak of C H?+?C H2/C H3 hydrogens (S1/S2) in 1HNMR spectra and the degree of oligomerization obtained from M n. According to the results, the best match between theoretical and real S1/S2 is obtained when considering double bond isomerization in the synthesized PAOs. By knowing PAO molecular weight, a relationship between monomer type and S1/S2 in the PAO homopolymers was detected. Our suggested methodology can be generalized to the unknown PAO homopolymers to unravel their monomer type by simple 1HNMR and GPC analyses. 相似文献
14.
Preparation and Oxidative Derivatisation of Phosphonothionic Esters The kind of the amine used influences decisively course and rate of the reaction of trialkyl phosphites, (RO) 3P (R = Me, Et, Ph) with H 2S in the presence of different amines (Et 3N, Et 2NH, Et 2NPh, pyridine). Phosphonothionic esters, (RO) 2P(S)H (R = Me, Et, Bu), are obtained in over 80% yield by using pyridine as base and an alkali alcoholate as catalyst. The oxidative derivatisation of phosphonothionic esters by means of CCI 4 and protic (4-nitrophenol, 2,4,5-trichlorophenol, ammonia, piperidine, phenylhydrazine) or anionic nucleophiles (F ?, NCS ?, NCO ?, CN ?, N 3?) (Atherton-Todd reaction) yields thiophosphoric acid derivatives (RO) 2P(S)Nuc (R = Me, Et, Bu: Nuc = 4-nitrophenoxy, PhNHNH; R = Me, Et: Nuc = 2,4,5-trichlorophenoxy, F, NCS, N 3; R = Me: NH 2, C 5H 10N; R = Et: Nuc = CI, CN) and in some cases the dealkylated products (RO)P(Nuc)SO ? (R = Me; Nuc = CI, F, NCS, CN). The phosphazenes (EtO) 2P(S)? N = PPh 3 and (MeO) 2P(S)? N ? P(OEt) 3, up to now unknown in literature, were obtained by treating thiophosphoryl azides with PPh 3 or P(OEt) 3, resp. 相似文献
15.
Zusammenfassung Es wird über die Synthese der bisher unbekannten Trithiopyrophosphonate (C 6H 5)(RO)P(S)–S–P(S)(RO)(C 6H 5) aus der entsprechenden thiophosphonigen Säure mit Morpholinosulfenylchlorid berichtet. In Anwesenheit von Triäthylamin bilden sich die bisher nicht beschriebenen S-Morpholino-dithiophosphonate, die dem angenommenen Reaktionsmechanismus nach mit Chlorwasserstoff und thiophosphoniger Säure die Trithiopyrophosphonate liefern. Als Vertreter der Schwefelchloride der Thiophosphonsäuren, die sich bei der Umsetzung von S-Morpholino-dithiophosphonate mit HCl bilden, konnte (C 6H 5)(C 2H 5O)P(S)–SCl isoliert werden.
A new synthetic route to trithiophosphonates; Reaction mechanism The synthesis of the unknown trithiopyrophosphonates, (C6H5)(RO)P(S)–S–P(S)(RO)(C6H5), which are formed by the interaction between the corresponding thiophosphonic acid and morpholinosulfenyl chloride, is reported.In the presence of triethylamine the reaction leads to the S-morpholinodithiophosphonates which, corresponding to the assumed reaction mechanism, gives, with hydrogen chloride and thiophosphonic acid the trithiopyrophosphonates.Among the sulfenylchlorides of the thiophosphonic acids which arise by the interaction of S-morpholinodithiophosphonates with hydrogen chloride, only (C6H5)(C2H5O)P(S)–SCl could be isolated. 相似文献
16.
Abstract In this work, the reactions of diphenylphosphinic chloride, (C 6H 5) 2P(O)Cl, 1, with the sodium salts of sterically hindered phenol derivatives ( 2a- 2j) were investigated. Novel alkyl-substituted aryl diphenyl phosphinate esters (C 6H 5) 2P(O)OAr ( 3- 12) were obtained from these reactions. Satisfactory analytical and spectroscopic results were obtained for all the new compounds. GRAPHICAL ABSTRACT 相似文献
17.
4′‐Ferrocenyl‐1,1′‐biphenyl‐4‐yl 4‐alkoxybenzoates Fc–(C 6H 4) 2–OC(O)–C 6H 4–O–C n H 2n+1 ( n = 8, 10, 12) ( 3a– c), representing a new class of ferrocene‐containing thermotropic mesogens with nematogenic properties, were prepared. Two approaches were used for the construction of these mesogens: (i) reaction of 4′‐ferrocenyl‐1,1′‐biphenyl‐4‐ol with 4‐alkoxybenzoylchlorides, and (ii) crosscoupling of tris(4‐ferrocenylphenyl)boroxine with the corresponding halobenzenes. Crosscoupling was also applied for the synthesis of terphenyl‐containing mesogens Fc–(C 6H 4) 3–OC(O)–C 6H 4–O–C n H 2n+1 ( n = 10, 12) ( 6a,b) and ( RC 5H 4)Fe‐[C 5H 4–(C 6H 4) 3–OC(O)–C 6H 4–O–C 10H 21] ( 11a, R = Et; 11b, R = n?Bu). The latter compounds also form nematic phases. Mesogens 6a,b form mesophases with wider temperature ranges than their biphenyl‐containing counterparts 3b,c. The most pronounced mesomorphism was displayed by compounds 11a and 11b, which have mesophases in the ranges 141–253°C and 120–238°C, respectively. The purity of compounds was established by 1H NMR spectra and elemental analysis. Mesophases were identified by polarizing optical microscopy and differential scanning calorimetry. 相似文献
18.
Abstract The reaction of (μ 3-S)RuCo 2(CO) 9 with functionally substituted cyclopentadienyl tricarbonyl metal anions M(CO) 3(C 5H 4C(O)R) (M = Mo, W; R = OEt, CH 2CH 2COOMe) in THF under reflux gave new chiral skeleton clusters (μ 3-S)RuCoM(CO) 8(C 5H 4C(O)R) [M = Mo, R = OEt ( 1); M = W, R = OEt ( 2); M = Mo, R = CH 2CH 2COOMe ( 3); M = W, R = CH 2CH 2COOMe ( 4)]. These complexes were characterized by elemental analysis, IR and 1H NMR spectra. The molecular structure of compound ( 1) was determined by single-crystal X-ray diffraction methods. 相似文献
19.
The intermolecular radical functionalization of arenes with aryl and alkyl H‐phosphinate esters, as well as diphenylphosphine oxide and H‐phosphonate diesters, is described. The novel catalytic Mn II/excess Mn IV system is a convenient and inexpensive solution to directly convert C sp2?H into C?P bonds. The reaction can be employed to functionalize P‐stereogenic H‐phosphinates since it is stereospecific. With monosubstituted aromatics, the selectivity for para‐substitution increases in the order (RO) 2P(O)H<R 1P(O)(OR)H<Ph 2P(O)H, a trend that may be explained by steric effects. 相似文献
20.
N‐sulfinylacylamides R‐C(=O)‐N=S=O react with (CF 3) 2BNMe 2 ( 1 ) to form, by [2+4] cycloaddition, six‐membered rings cyclo‐(CF 3) 2B‐NMe 2‐S(=O)‐N=C(R)‐O for R = Me ( 2 ), t‐Bu ( 3 ), C 6H 5 ( 4 ), and p‐CH 3C 6H 4 ( 5 ) while N‐sulfinylcarbamic acid esters R‐O‐C(=O)‐N=S=O react with 1 to yield mixtures of six‐membered ( cyclo‐(CF 3) 2B‐NMe 2‐S(=O)‐N=C(OR)‐O) and four‐membered rings ( cyclo‐(CF 3) 2B‐NMe 2‐S(=O)‐N(C=O)OR) for R = Me ( 6 and 9 ), Et ( 7 and 10 ), and C 6H 5 ( 8 and 11 ). The structure of 5 has been determined by X‐ray diffraction. 相似文献
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