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1.
In this article, it is reported that the isomerization/chlorination reactions of nitrogen heterocyclic O,O-dialkyl thiophosphoramidates 5 with equivalent amounts of phosphorus oxychloride give nitrogen heterocyclic S-alkyl thiophosphorochloridates 6 and O-alkyl phosphorodichloridates 3. After removal of the by-products 3 under reduced pressure, the crude products 6 are directly reacted with various nucleophiles, NuH, in the presence of triethylamine to give nitrogen heterocyclic S-alkyl thiophosphoramidic acid derivatives 7. Thus, a new convenient method has been provided for the synthesis of the title compounds. © 1996 John Wiley & Sons, Inc. 相似文献
2.
E. S. Batyeva 《Russian Chemical Bulletin》1993,42(10):1627-1633
This review summarizes the data on the synthesis of various phosphorus-and-sulfurcontaining organic compounds based on the
reactions of elemental phosphorus and sulfur and their derivatives (various types of esters of trivalent phosphorus thioacids)
with a variety of organic compounds.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1706–1711, October, 1993. 相似文献
3.
4.
O. I. Kolodiazhnyi 《Russian Journal of General Chemistry》2017,87(3):425-441
The data on stereoselective reactions of achiral compounds of trivalent phosphorus with chiral nucleophiles (derivatives of secondary alcohols, amines, and amino acids) are analyzed and discussed. In certain cases, these reactions enable preparation of optically active aminophosphines and phosphinites, precursors in the synthesis of chiral organophosphorus compounds and phosphine ligands. The reactions are suitable for elucidation of mechanism and stereochemistry of nucleophilic substitution at trivalent phosphorus atom. 相似文献
5.
Cummins CC 《Angewandte Chemie (International ed. in English)》2006,45(6):862-870
Anionic terminal one-atom nitride, phosphide, and carbide complexes are excellent starting materials for the synthesis of ligands containing low-coordinate phosphorus centers in the protecting coordination sphere of the metal complex. Salt-elimination reactions with chlorophosphanes lead to phosphaisocyanide, iminophosphinimide, and diorganophosphanylphosphinidene complexes in which the unusual phosphorus ligands are stabilized by coordination. X-ray structure analyses and density-functional calculations illuminate the bonding in these compounds. 相似文献
6.
Tris(oxalato)phosphorus acid and its lithium salt 总被引:1,自引:0,他引:1
Wietelmann U Bonrath W Netscher T Nöth H Panitz JC Wohlfahrt-Mehrens M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(10):2451-2458
The conversion of three equivalents of anhydrous oxalic acid with phosphorus pentachloride yields tris(oxalato)phosphorus acid 1, which crystallizes from diethyl ether solutions as protonated diethyl ether complex [(Et2O)2H](+)[P(C2O3)3)]-. The superacidic compound can be used as catalyst for Friedel-Crafts-type reactions. Upon neutralization with lithium hydride, the lithium salt Li[P(C2O3)3] 2 is obtained, which is highly soluble in aprotic solvents and which exhibits a wide voltage window. Thus, the lithium compound is a promising candidate as electrolyte for high performance non-aqueous batteries. 相似文献
7.
G. G. Furin 《Chemistry of Heterocyclic Compounds》2006,42(3):285-319
Methods for the construction of heterocyclic systems containing polyfluoroalkyl substituents from derivatives of ethylene
and acetylene are discussed. It is shown that various compounds with polyfluoroalkyl groups can be used as building blocks:
α,β-unsaturated carbonyl compounds, their synthetic organosilicon equivalents (silyl-substituted alcohols, silyl ethers of
enols), and also sulfones, nitriles, polyfluoroalkenes (in reactions at the double bond), acetylenecarboxylic acids, their
esters, and polyfluoroalkynes.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 323–360, March, 2006. 相似文献
8.
The activation of phosphorus remains a popular and competitive area of research driven by the dual goals of finding ways to avoid the environmentally questionable P-Cl compounds applied in many industrial processes and the target of catalytic functionalization of P(4). In recent years the activation, degradation, fragmentation, and functionalization of white phosphorus by compounds with heavier main group elements have become a fertile area of research. The isolation of various carbenes and functionalized silylenes has prompted chemists to investigate their reactions with white phosphorus. The most intriguing fact in these reactions is the subtle change in the substituents may afford strikingly different compounds. For example, from the reaction of P(4) with PhC(NtBu)(2)SiCl a cyclic Si(2)P(2) derivative is obtained, whereas the analogous reaction with PhC(NtBu)(2)SiN(SiMe(3))(2) resulted in an acyclic Si(2)P(4) framework. Similar phenomena have also been observed in the carbene mediated P(4) activation. Apart from these, a new entry point into phosphorus chemistry is the gentle activation of P(4) by an alkyne analogue of tin. In this feature article we have covered the activation of phosphorus by compounds with low valent group 14 elements with special concern to the recent developments in this topic. 相似文献
9.
《Tetrahedron letters》1988,29(15):1827-1828
Cumyl hydroperoxide causes oxidative desulphurisation at pentacovalent phosphorus with retention of configuration in the presenceof various manganese (iii) and iron (ii) mesotetraphenylporphyrins provided imidazole is present, the yields of oxidised phosphorus compounds being influenced by the rate of destruction of the hydroperoxide by parasitic side reactions. 相似文献
10.
Sergey P. Ivonin Andrew A. Tolmachev Alexandra A. Chaikovskaya Tamara N. Kudraya Andrew A. Anischenko Eduard B. Rusanov Alexander N. Chernega Alexandr M. Pinchuk 《Heteroatom Chemistry》2001,12(7):658-664
The reaction of phosphorus tribromide with phenylhydrazones of heterocyclic aldehydes leads to formation of a new phosphorus‐containing heterocyclic system—heterocondensed 1,2,3‐diazaphosphorines. Properties of the phosphorus‐containing heterocyclic compounds that have been synthesized are described. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:658–664, 2001 相似文献
11.
This review is devoted to the stereochemistry of nucleophilic substitution reactions at phosphorus. The study of the reactions of phosphoryl group transfer is important for biological and molecular chemistry. The stereochemistry and mechanisms of SN1(P) monomolecular and SN2(P) bimolecular nucleophilic substitution reactions of organophosphorus compounds are discussed. It has been shown that hydrolysis of many natural phosphates proceeds according to the monomolecular SN1(P) mechanism via the formation of metaphosphate intermediate (PO3?). SN2(P) nucleophilic substitution at chiral trivalent or pentavalent phosphorus compounds proceeds via the formation of penta-coordinated transition state or pentacoordinate intermediate. 相似文献
12.
A study of the substoichiometric extraction of phosphorus is described. Phosphorus was extracted in the form of ternary compounds
such as ammonium phosphomolybdate, 8-hydroxyquinolinium phosphomolybdate, tetraphenylarsonium phosphomolybdate and tri-n-octylamine
phosphomolybdate. Consequently, phosphorus was extracted substoichiometrically by the addition of a substoichiometric amount
of molybdenum for all four phosphomolybdate compounds. On the other hand, phosphorus could be separated substoichiometrically
with a substoichiometric amount of tetraphenylarsonium chloride or tri-n-octylamine. Stoichiometric ratios of these ternary
compounds obtained substoichiometrically were 1∶12∶3 for phosphorus, molybdenum and organic reagent. Applicability of these
compounds to phosphorus determination was also discussed. 相似文献
13.
Oscar Mendoza 《Journal of organometallic chemistry》2006,691(6):1110-1116
Calcium and magnesium atoms were cocondensed with aromatic heterocycles containing five- and six-membered rings in the presence of THF at 77 K. In the case of calcium the cocondensation with five-membered heterocyclic compounds resulted in C-H bond activations and led to the corresponding aryl calcium compounds, while magnesium did not show comparable reactions. When six-membered heterocyclic compounds, e.g., pyridine and 4-methylpyridine (4-picoline) were cocondensed with calcium, magnesium and lithium atoms, all reactions led to the formation of non-metallated aromatic products and the formation of metal hydride. DFT calculations at the B3LYP/6-31G** level of theory were carried out in order to interpret the pathways of the cocondensation reactions using calcium atoms and identify the possible intermediates involved. In all reactions π- and σ-complexes between calcium atoms and the heterocyclic aromatic reactant were found as stable intermediates on the energy hypersurface. 相似文献
14.
Yoshinori Tominaga Satoshi Takada Shinya Kohra Yasumitsu Shigemitsu 《Journal of heterocyclic chemistry》2001,38(5):1143-1151
3‐[(Trimethylsilylmethylamino)(methylthio)]methylene‐2‐coumaranone ( 4a ) and 1‐methyloxindole ( 4b ), readily prepared by reactions of the corresponding bis(methylthio)methylene heterocyclic compounds ( 2a, b ), with (trimethylsilylmethyl)amine (3), were found to be synthetic equivalents of heterocyclic alkylidene‐azomethine ylides. Reactions of 4a, b with reactive heterodipolarophiles such as aldehydes and ketones and reactive alkenes in the presence of cesium fluoride gave the 1,3‐dipolar cycloadducts, 3‐(2‐oxazoli‐dinylidene)‐oxindole and ‐coumaran‐2‐one derivatives ( 8a‐j, 9a‐h ), as well as pyrrolylidenecoumaran‐2‐one and oxindole derivatives ( 12‐15,17,18 ), via the 1,3‐elimination of (methylthio)trimethylsilane. 相似文献
15.
Conclusions Energies of formation of complexes of hydrogen fluoride with compounds of tetracoordinated phosphorus, charge transfers in complexing, and other characteristics of these reactions calculated by CNDO/2 methods agree well with the measured values.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 496–502, March, 1979. 相似文献
16.
三配位磷化物与烷氧基苯硫醚反应合成了一系列含磷五元环的五配位化合物。在不同温度下,测定了这些化合物的19FNMR。化合物(7)与三氟乙氧基苯硫醚反应生成化合物(19)以及(20)和(21);化合物(11)与六氟异丙氧基苯硫醚反应生成化合物(18)和(21),并对这些反应机理进行了讨论。 相似文献
17.
Xi‐Jia Liu Chao Zheng Yi‐Han Yang Shicheng Jin Shu‐Li You 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(31):10603-10609
Described herein is an asymmetric allylic aromatization (AAAr) strategy that employs readily accessible equivalents of benzylic nucleophiles in iridium‐catalyzed allylic substitution reactions with the concomitant formation of aromatic rings by aromatization. The optimized reaction conditions involving a catalyst derived from a commercially available iridium precursor and the Carreira ligand are compatible with equivalents of benzylic nucleophiles derived from 4‐ or 5‐methyloxazoles, 5‐methylthiazoles, 4‐ or 5‐methylfurans, 2‐ or 3‐methylbenzofurans, 3‐methylbenzothiophene, 3‐methylindole, 1‐methylnaphthalene, and methylbenzene. This strategy provides straightforward accesses to valuable heterocyclic aromatic compounds, bearing a homobenzylic stereogenic center, in an enantiopure form and would be difficult to access otherwise. The versatility of the reaction was showcased by the further elaboration of the products into useful building blocks and a drug analogue. 相似文献
18.
The literature on the electrophilic heterocyclization of unsaturated sulfur and phosphorus compounds has been reviewed. The factors influencing the reactivity of unsaturated compounds in such reactions are discussed, and data on the stereo-chemistry of the addition are presented.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 291–302, March, 1986. 相似文献
19.
The reactions of Schiff bases with phosphorus trichloride in the medium of acetone containing pyridine are facile and compounds of the types RC(PCl2)NR′ and [RC(PCl2)N]2C6H4 have been prepared. 相似文献
20.
Reza Heydari Malek Taher Maghsoodlou Sayyed Mostafa Habibi-khorassani Nourallah Hazeri Farahnaz Barahuie Mohsen Rostamizadeh 《Arabian Journal of Chemistry》2010,3(4):229-232
Stable crystalline phosphorus ylides and 1,4-diionic organophosphorus compounds were obtained in good to excellent yields from the 1:1:1 addition reaction between triphenylphosphine, dialkyl acetylenedicarboxylates and β-dicarbonyl or heterocyclic compounds, such as diethyl malonate, acetyl acetone, 1,3-diphenyl propane-1,3-dione, 1,3-dimethylbarbituric acid, meldrum’s acid, 2-benzoxazolinone, benzotirazole, and 2-thiazoline-2-thiol in the presence of sodium dodecyl sulfate as a surfactant in water. Green synthesis, mild conditions, decreasing timescale of reaction, low cost, and easy workup are the main advantages of this method. 相似文献