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1.
Trimethylsilyl and Trimethylstannyl Esters of the Trithiophosphonic Acids; Preparation, Protolysis, and Further Reactions The organotrithiophosphonic acid bis(trimethylsilyl) esters RP(S)(SSiMe3)2, R = Ph ( 1a ), R = t-Bu ( 1b ) and R = Me ( 1c ) are formed in high yield from the organo-bis(trimethylsilyl)-phosphanes RP(SiMe3)2 by the addition of three sulfur atoms (3/8 S8) in toluene solution. 1b has also been prepared by reacting disodium tert-butyltrithiophosphonate, Na2t-BuP(S)S2 ( 2 ) with SiMe3Cl. Analogous reactions can be used for the preparation of the stannyl esters RP(S)(SSnMe3)2, R = t-Bu ( 5a ) and R = Me ( 5b ). More favorable, however, these compounds are synthesized from the corresponding silyl esters 1b, c and SnMe3Cl or, as has been shown in the case of 5a , by reacting dithiophosphonic acid anhydrides (RP(S)S)2 with (SnMe3)2S. Low temperature solvolysis of the silyl esters 1b, c with water or methanol results in the free organotrithiophosphonic acids RP(S)(SH)2, R = t-Bu ( 6a ) and R = Me ( 6b ), which can be isolated as white solids at —30°C. Contrary to the sodium salt 2 and the stannyl esters 5a, b , the acids 6a, b , and, to a smaller extent, the silyl esters 1a—c are thermally not stable towards decomposition into the thioanhydrides (RP(S)S)2. The silyl and stannyl esters 1a—c and 5a, b , respectively, are capable of cleaving the ether linkage of tetrahydrofuran, which in the case of 1b leads to the quantitative formation of t-BuP(S)[S(CH2)4OSiMe3]2 ( 9 ). 1b, c and 5a, b react with Cl2 and Br2 forming the 3,6-diorgano-3,6-dithio-1,2,4,5,3,6-tetrathiadiphosphorinanes (RP(S)S2)2, R = t-Bu ( 7a ) and R = Me ( 7b ). 相似文献
2.
Contributions to the Chemistry of Phosphorus. 152. Functionalized Cyclotriphosphanes of the Type (t-BuP)2PX (X = K, SiMe3, SnMe3, Cl, Br, PCl2, P(t-Bu)Cl, P(t-Bu)I) Functionalized cyclotriphosphanes of the type (t-BuP)2PX with electropositive or electronegative substituents X have been prepared on various synthetic routes: KP(t-BuP)2 ( 1 ) can be obtained in 50–55 per cent purity by reacting (t-BuP)4 or (t-BuP)3 with potassium. Reaction of 1 with Me3SiCl or Me3SnCl leads to the cyclotriphosphanes (t-BuP)2PSiMe3 ( 2 ) and (t-BuP)2PSnMe3 ( 3 ), respectively; the cyclocondensation of Cl(t-Bu)P? P(t-Bu)Cl with P(SnMe3)3, however, is more convenient for the preparation of 3 . In a similar way the halogenated compounds (t-BuP)2PCl ( 4 ) and (t-BuP)2PBr ( 5 ) can be obtained from Me3Sn(t-Bu)P? P(t-Bu)SnMe3 ( 6 ) and PX3 (X = Cl, Br). The phosphino-substituted cyclotriphosphanes (t-BuP)2P? PCl2 ( 7 ), (t-BuP)2P? P(t-Bu)Cl ( 8 ), and (t-BuP)2P? P(t-Bu)I ( 9 ) are accessible by the reaction of 3 with PCl3 and t-BuPX2 (X = Cl, I), respectively. 2–9 could be obtained free from phosphorus-containing by-products and were 31P-NMR spectroscopically characterized as compounds with a cyclic P3 skeleton. 相似文献
3.
Contributions to the Chemistry of Phosphorus. 160. About the Ring Cleavage of the Phosphorus Three-Membered Heterocycles (t-BuP)2CMe2 and (t-BuP)2N(i-Pr) with Potassium or K-Naphthalenide The reaction of (t-BuP)2CMe2 with potassium or K-naphthalenide in tetrahydrofuran or 1,2-dimethoxyethane mainly leads to the symmetric phosphide K(t-Bu)P? ;CMe2? ;P(t-Bu)K ( 1 ) via P? ;P-bond cleavage. Above —78°C 1 decomposes into the monophosphides KHP(t-Bu) ( 3 ) and KP(t-Bu)(i-Pr) ( 4 ). In the case of (t-BuP)2N(i-Pr) under analogous conditions essentially the P? ;N-bond is split up yielding the phosphide K(t-Bu)P? ;P(t-Bu)? ;NH(i-Pr) ( 5 ), which is stable at room temperature. Contrary to (t-BuP)2BN(i-Pr)2 cyclic phosphides are not formed. The different reactive behavior in the metalation of phosphorus three-membered heterocycles of the type (PR1)2ER (E = hetero atom) is discussed. 相似文献
4.
Contributions to the Chemistry of Phosphorus. 123. Synthesis and Properties of the Diphosphagermiranes (t-BuP)2GePh2 and (t-BuP)2GeEt2 The first three-membered P2Ge heterocycles, 1,2-di-tert-butyl-3, 3-diphenyl-1, 2, 3-diphosphagermirane, (t-BuP)2GePh2 (1) , and 1, 2-di-tert-butyl-3, 3-diethyl-1, 2, 3-diphosphagermirane, (t-BuP)2GeEt2 (2) , were synthesized by [2+1] cyclocondensation reactions of K(t-Bu)P—P(t-Bu)K with diphenylgermanium dichloride and diethylgermanium dichloride, respectively. The four-, five-, and six-membered cyclogermaphosphanes (t-BuP)2(GePh2)2 (3) , (t-BuP)3GeR2 ( 6 R = Ph; 7 R = Et), (t-BuP)4GePh2 (5) and (t-BuP)4(GePh2)2 (4) as well as (t-BuP)4 are formed as by-products. The diphosphagermiranes 1 and 2 could be isolated in 93 and 100% purity, respectively, and were unambiguously characterized as compounds with a cyclic P2Ge skeleton. The 31P-NMR parameters of the cyclogermaphosphanes 3—7 are reported. 相似文献
5.
Contributions to the Chemistry of Phosphorus. 101 Synthesis and Properties of Diphosphaboriranes (t-BuP)2BNR2 and (t-BuP)2BNR1R2 The reaction of K(t-Bu)P? P(t-Bu)K with diorganylaminodichloroboranes under suitable conditions leads to the new 1,2-di-tert-butyl-3-diorganylamino-1,2,3-diphosphaboriranes (-1,2-diphospha-3-boracyclopropanes) (t-BuP)2BNR2 ( 2 , 7 ) and (t-BuP)2BNR1R2 ( 3 — 6 ), respectively. The P2B three-membered heterocycles 2 — 5 can be isolated in good yields. They are relatively stable against dimerization to the corresponding phosphorus boron six-membered ring compounds with opposite boron atoms. The rate of dimerization depends on steric and electronic influences of the substituents at the three-membered ring. All NMR spectroscopic results are only consistent with a structure in which the B and N atoms show planar coordination and are connected by a partial double bond. 相似文献
6.
Contributions to the Chemistry of Phosphorus. 129. Synthesis and Properties of the Phospha-germa-cyclobutanes (t-BuP)2(GePh2)2 and (t-BuP)3GePh2 The phospha-germa-cyclobutanes 1,2-di-tert-butyl-3,3,4,4-tetraphenyl-1,2-diphospha-3,4-digerma-cyclob utane, (t-BuP)2(GePh2)2 ( 1 ), and 1,2,3-tri-tert-butyl-4,4-diphenyl-1,2,3-tri-phospha-4-germa-cyclobutan e, (t-BuP)3GePh2 ( 2 ), are obtained as main-products of the cyclocondensation of K(t-Bu)P? P(t-Bu)K with Ph2GeCl2 under certain reaction conditions. 1 and 2 could be isolated in the pure state and were clearly characterized as the first four-membered P2Ge2 and P3Ge heterocycles, respectively. 相似文献
7.
Contributions to the Chemistry of Phosphorus. 128. Synthesis of the Diphosphastanna-cyclopropane (t-BuP)2Sn(t-Bu)2 The first three-membered P2Sn heterocycle, 1,2,3,3-tetra-tert-butyl-1,2,3-diphosphastanna-cyclopropane (1,2,3,3-tetra-tert-butyl-1,2,3-diphosphastannirane) ( 1 ), has been synthesized by [2+1] cyclocondensation of K(t-Bu)P—P(t-Bu)K with (t-Bu)2SnCl2. 1 is stable at room temperature. Besides, (t-BuP)2[Sn(t-Bu)2]2 ( 2 ), (t-BuP)4Sn(t-Bu)2 ( 3 ), and (t-BuP)4 are formed. In the reaction with Et2SnCl2, the six-membered ring compound [(t-BuP)2SnEt2]2 ( 4 ) is the main-product; the four- and five-membered cyclostannaphosphanes (t-BuP)3SnEt2 ( 5 ) and (t-BuP)3(SnEt2)2 ( 6 ) are also formed. 1 could be isolated in the pure state and has been unambiguously characterized as a three-membered heterocycle with a P2Sn skeleton. The 31P-NMR parameters of the other new cyclostannaphosphanes 2–6 are reported. 相似文献
8.
Contributions to the Chemistry of Phosphorus. 144. Synthesis and Properties of the Hexaphospha-3-germaspiro[2.4]heptane (t-BuP)2Ge(t-BuP)4 The cyclocondensation of K(t-Bu)P? P(t-Bu)K with germanium tetrachloride in the molar ratio of 2:1 yields the novel spirocyclic compound 1,2,4,5,6,7-hexa-tert-butyl-1,2,4,5,6,7-hexaphospha-3-germaspiro[2.4]heptane, (t-BuP)2Ge(t-BuP)4 ( 1 ). Besides considerable amounts of (t-BuP)4 are formed and occasionally some (t-BuP)3 can be found. 1 could be isolated in the pure state and has been NMR-spectroscopically characterized as a spirocyclic compound with a P2GeP4 skeleton. 相似文献
9.
Contributions to the Chemistry of Phosphorus. 159. On the Reaction of the Diphosphaborirane (t-BuP)2BN(i-Pr)2 with Potassium or Potassium Naphthalenide The reaction of (t-BuP)2BN(i-Pr)2 with potassium or K-naphthalenide in tetrahydrofuran leads to K(t-Bu)P? ;BN(i-Pr)2? P(t-Bu)K ( 1 ) via P? ;P bond cleavage of the three-membered ring skeleton. Above ? 78°C 1 changes into the asymmetric compound K(t-Bu)P? ;P(t-Bu)? BHN(i-Pr)2 ( 2 ). In dimethoxyethane additionally the monometallated diphosphaborirane K(t-Bu)P2BN(i-Pr)2 ( 3 ) is formed. 1 and 3 , which could be isolated free from other phosphorus containing compounds, as well as the corresponding silylphosphanes Me3Si(t-Bu)P? ;BN(i-Pr)2? ;P(t-Bu)SiMe 3 ( 4 ) and Me3Si(t-Bu)P2BN(i-Pr)2 ( 5 ) were characterized by NMR spectroscopy. Protolysis of 3 or 5 leads to a decomposition of the three-membered ring skeleton with formation of H(t-Bu)P? ;PH2. 相似文献
10.
Contributions to the Chemistry of Phosphorus. 106. Synthesis and Properties of the Diphosphacyclopropane (t-BuP)2CHMe The new 1,2-di-tert-butyl-3-methyl-1,2-diphosphacyclopropane (1,2-di-tert-butyl-3-methyl-diphosphirane), (t-BuP)2CHMe ( 1 ), is obtained by reacting K(t-Bu)P? P(t-Bu)K with 1,1-dichloroethane under suitable conditions. 1 can be isolated by high vacuum distillation and is stable for months when stored under inert gas at room temperature. Particularly, no dimerization to the corresponding 1,2,4,5-tetraphosphacyclohexane takes place. The NMR parameters indicate an increase of the exocyclic bond angles compared to (t-BuP)2CH2. The signs of all CP coupling constants have been determined by spin tickling experiments. The 2J(CCP)-coupling of the methyl group at the ring carbon depends strongly on the dihedral angle. 相似文献
11.
Contributions to the Chemistry of Phosphorus. 224. On the Thermolysis of 1,2-Di-tert-butyldiphosphane, 1,2,3-Tri-tert-butyltriphosphane, and Tetra-tert-butylcyclotetraphosphane On disproportionation of 1,2-di-tert-butyldiphosphane, H(t-Bu)P? P(t-Bu)H (1) , 1,2,3-tri-tert-butyltriphosphane, H2(t-BuP)3 (2) , is formed which reacts further at temperatures above 100°C to give 1-(tert-butylphosphino)-2,3,4-tri-tert-butylcyclotetraphosphan, P5(t-Bu)4H (4) . Compound 4 reacts with 1 or 2 with lengthening of the P-sidechain to furnish the corresponding 1-(1,2-di-tert-butyldiphosphino)-2,3,4-tri-tert-butylcyclotetraphosphane, P6(t-Bu)5H (5) . At temperatures above 170°C, 5 disproportionates into the tetra-tert-butylcyclotetraphosphane, (t-BuP)4 (3) which is stable up to about 200°C, and the bicyclo[3.1.0]hexaphosphane P6(t-Bu)4 from which the polycyclophosphanes P9(t-Bu)3 and P8(t-Bu)6 arise during the further course of the thermolysis. These products are finally converted through even more phosphorus-rich and more highly condensed t-butylcyclophosphanes into elemental phosphorus. In each reaction step, varying amounts of the monophosphane derivatives t-BuPH2, (t-Bu)2PH, and (t-Bu)3P are formed. The proposed course of the reaction is further substantiated by the pyrolysis products of pure 2 and 3 . 相似文献
12.
Contributions to the Chemistry of Phosphorus. 138. P5(t-Bu)4H — the First Derivative of iso-P5H5 The thermolysis of 1,2-di-tert-butyldiphosphane, H(t-Bu)P? P(t-Bu)H, yields under suitable conditions the compound P5(t-Bu)4H ( 1 ) as the main product. Besides, the tert-butylphosphanes t-BuPH2, P6(t-Bu)5H ( 2 ), H2(t-BuP)3, and (t-BuP)4 are formed. 1 has been isolated in the pure state and structurally characterized as 1-(tert-butylphosphino)-2,3,4-tri-tert-butyl-cyclotetraphosphane. Hence, compound 1 is a derivative of iso-P5H5 with a branched phosphorus skeleton built up by a four-membered ring and a phosphorus side chain. 相似文献
13.
Flash vacuum pyrolysis (FVP) of tert-butylthiosulfinic acid S-tert-butylester, t-BuS(O)St-Bu, at a temperature of 500 °C and a pressure of 0.07 hPa leads to the formation of tert-butylthiosulfoxylic acid, t-BuSSOH ( 1 ), and 2-methylpropene as byproduct. 1 has been identified in the gas phase by its IR absorption bands at ν(OH) = 3598 cm–1, δ(SOH) = 1149 cm–1 and ν(SO) = 718 cm–1. At higher temperatures (700 °C) the elimination of a second mole of 2-methylpropene and the shift of ν(SO) to higher wavenumbers (750 cm–1) indicate the formation of 1-oxatrisulfane, HSSOH. Different sulfenic acids RSOH (R = Me, i-Pr, t-Bu) were synthesized by FVP in order to study the influence of the substituent R on the vibrational wavenumbers ν(OH), ν(SO) and δ(SOH) observed in the gas phase. The strongest effect results for δ(SOH) leading to a decrease by 6 wavenumbers if the methyl group is substituted by a tert-butyl group. The assignment of the experimental wavenumbers has been supported by theoretical values obtained from ab initio calculations at the MP2(fc)/6-311G** level. Furthermore, the theoretical studies show that of all compounds RS2OR′ (R = R′ = H, Me; R = Me (H), R′ = H (Me)) the unbranched chain isomers RSSOR′ are energetically favored over the branched chain isomers. Relaxed potential energy surface scans at the MP2(fc)/6-311G** level have been carried out to study the rotational isomers of the branched molecules RS(Y)XR′ (R = R′ = H, Me; R = Me (H), R′ = H (Me); X = O (S), Y = S (O)). Of the three conformations (+)syn-clinal, (–)syn-clinal, and anti-periplanar resulting from molecular model considerations only the two latter ones correspond to local minima on the calculated potential curve. The (–)syn-clinal conformation is slightly favored for all other constitutional isomers except for HS(O)SH and MeS(O)SH, which prefer the anti-periplanar conformation. 相似文献
14.
Organoarsino-Substituted Sulphur Diimides: Crystal Structure Analyses of 3, 7-Di-t-butyl-3H, 7H-1λ4, 5λ4, 2, 4, 6, 8, 3, 7-dithiatetrazadiarsocine and Bis (diphenylarsino)sulphur Diimide Reaction of the salt K2SN2 with organoarsenic chlorides leads to sulphur diimides containing organoarsino substituents at both ends. Single crystal X-ray structure analyses were carried out for two typical compounds, i.e. the cyclic eight-membered 3, 7-di-t-butyl-3H, 7H-1λ4, 5λ4, 2, 4, 6, 8, 3, 7-dithiatetrazadiarsocine ( 1a , prepared from K2SN2 and (t-Bu)AsCl2 (1:1)) and the open-chain bis(diphenylarsino)sulphur diimide ( 2a , prepared from K2SN2 and Ph2AsCl (1:2)). In both compounds the sulphur diimide groups are coplanar with their directly bound arsenic atoms. This coplanarity principle leads, in the case of 1a , to about conformation (mm2(C2v) symmetry) of the eight-membered heterocycle; the t-butyl substituents occupy quasi equatorial positions. Small deviations from mm2 symmetry and torsions around the S?N bonds up to 12° can be explained as a consequence of the transnnular repulsion of the lone pairs at the arsenic atoms (As …As distance 3.683(1) Å). In the case of the open-chain S(N? AsPh2)2 ( 2a , 2(C2) symmetry), a cis, cis configuration was found at the S?N double bonds which indicates As…As interaction. The As…As distance (3.379(1) Å) is shorter than in 1a and parallells a reduced interaction of the lone pairs at the As atoms. The S?N bond lenghts (1.517(5) Å in 1 a and 1.521(3) Å in 2a ) are characteristic of sulphur diimides withoug significant π-interaction with the substituents and correspond to SIV?N double bonds. 相似文献
15.
Beiträge zur Chemie des Phosphors. 142. P6(t-Bu)5H – das erste Cyclotetraphosphan mit P2-Seitenkette
Contributions to the Chemistry of Phosphorus. 142. P6(t-Bu)5H – the First Cyclotetraphosphane with a P2 Side Chain The thermolysis of 1, 2-di-tert-butyldiphosphane, H(t-Bu)P? P(t-Bu)H, leads to formation of the hitherto unknown hexaphosphane P6(t-Bu)5H ( 1 ). In the first instance the iso-P5H5 derivative P5(t-Bu)4H [3] is formed, which reacts further with H2(t-BuP)2 or H2(t-BuP)3 yielding 1 . Compound 1 has been isolated in the pure state and structurally characterized as 1-(1,2-di-tert-butyldiphosphino)-2, 3, 4-tri-tert-butyl-cyclotetraphosphane, i. e. as a four-membered ring compound with a P2 side chain. Due to the chirality of the P atoms in the side chain, 1 exists as a mixture of two configurational isomers, the threo-and the erythro-form. 相似文献
16.
P. A. Kikilo B. I. Khairutdinov Yu. G. Shtyrlin V. V. Klochkov E. N. Klimovitskii 《Russian Journal of Organic Chemistry》2005,41(7):1089-1092
3-Substituted 1H,5H-naphtho[1,8-ef][1,3]dithiocines (R = H, Me, Ph, t-Bu) were oxidized with m-chloroperoxybenzoic acid to the corresponding 2-oxides having trans configuration (R ≠ H). According to the 1H and 13C NMR data (including NOESY experiments), the disubstituted compounds at room temperature exist in a boat conformation with equatorial orientation of the substituent on C3 and oxygen atom on S2. The compound with no substituent on C3 gives rise to a mixture of boat conformers with axial and equatorial sulfoxide oxygen atoms at a ratio of 83:17.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 7, 2005, pp. 1109–1112.Original Russian Text Copyright © 2005 by Kikilo, Khairutdinov, Shtyrlin, Klochkov, Klimovitskii. 相似文献
17.
Contributions tot he Chemistry of Phosphorus. 148. Synthesis and Properties of the 1,2-Diphospha-3,4-diboretane (t-BuP)2(BNMe2)2 The first 1, 2-diphospha-3,4-diboretane (1,2-diphospha-3, 4-diboracyclobutane) (t-BuP)2(BNMe2)(1) was prepared by [2+2] cyclocondensation of K(t-Bu)P? P(t-Bu)K with Cl(Me2N)B? B(NMe2)Cl. 1 could be isolated in the pure state and was NMR spectroscopically characterized as a compound with a planar P2 B2 ring skeleton. 相似文献
18.
Contributions to the Chemistry of Phosphorus. 104. Synthesis and Properties of 1,3-Dihalogen-1,2,3-tri-tert-butyltriphosphanes (t-BuP)3X2, X = Cl, Br, I The halogenating ring-cleavage of tri-tert-butyl-cyclotriphosphane, (t-BuP)3, by iodine, bromine or phosphorus(V)bromide as well as phosphorus(V)chloride leads to the first 1,3-dihalogen-1,2,3-triorganyltriphosphanes (t-BuP)3I2 ( 1 ), (t-BuP)3Br2 ( 2 ), and (t-BuP)3Cl2 ( 3 ). The 1,2-dihalogen-1,2-di-tert-butyldiphosphanes (t-BuP)2I2 ( 4 ), (t-BuP)2Br2 ( 6 ), and (t-BuP)2Cl2 ( 9 ) as well as the dihalogen-tert-butylphosphanes t-BuPI2 ( 5 ), t-BuPBr2 ( 7 ), and t-BuPCl2 ( 10 ) are formed as by-products. Moreover, the reaction of (t-BuP)3 with PBr5 leads to 1-bromo-2,3,4-tri-tert-butyl-cyclo-tetraphosphane, (t-BuP)3(PBr) ( 8 ). The compounds 1 and 3 could be isolated in a pure state and were characterized in all details. 3 is a reMarkably stable open-chain triphosphane. 相似文献
19.
Contributions to the Chemistry of Phosphorus. 134. On the Triphosphanes H(t-BuP)3H' Li(t-BuP)3Li, and Me3Si(t-BuP)3SiMe3 The reaction of 1,3-diiodo-1,2,3-tri-tert-butyltriphosphane, I(t-BuP)3I, with lithium aluminium hydride leads to 1,2,3-tri-tert-butyltriphosphane, H(t-BuP)3H ( 1 ). 1 reacts with n-butyllithium to 1,3-dilithium-1,2,3-tri-tert-butyltriphosphide, Li(t-BuP)3Li ( 2 ), which reacts further with trimethylchlorosilane yielding 1,3-bis(trimethylsilyl)-1,2,3-tri-tert-butyltriphosphane, Me3Si(t-BuP)3SiMe3 ( 3 ). The triphosphanes 1, 2 and 3 could be isolated in a pure state. In solution 1 forms the threo, threo and the threo,erythro configurated diastereomers 1a and 1b in a ratio of about 2:1. 3 predominantly exists in form of the threo,erythro configurated diastereomer 3b by steric reasons. 相似文献
20.
Kikilo P. A. Khairutdinov B. I. Shaikhutdinov R. A. Shtyrlin Yu. G. Klochkov V. V. Klimovitskii E. N. 《Russian Journal of General Chemistry》2001,71(6):960-964
The oxidation of 3-R-1,5-dihydro-2,4-benzothiepines with m-chloroperbenzoic acid occurs in a highly diastereoselective fashion. The resulting trans-sulfoxides at -60°C in CDCl3 exist as an equilibrium mixture of the chair and boat forms with the substituents in the equatorial position. The fraction of the boat conformation increases in the series R = Ph, Me, t-Bu. 相似文献