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1.
Marcos A. P. Martins Emerson A. Guarda Clarissa P. Frizzo Mara R. B. Marzari Dayse N. Moreira Nilo Zanatta Helio G. Bonacorso 《Monatshefte für Chemie / Chemical Monthly》2008,139(11):1321-1327
A series of twenty halomethylated β-enaminones [RC(O)CH=C(R
1)NR
3
R
4, where R = CF3,CCl3, CHCl2; R
1 = H, Me, Ph; R
3 = H, Me, Bu, Et; R
4 = Me, Et, Bu, allyl, tert-amyl, CH2CH2OH, Bn, Ph] were synthesized using the ionic liquid [bmim]BF4 at room temperature. It is demonstrated that this ionic liquid is a reaction medium suitable for the amination of β-alkoxyvinyl
halomethyl ketones. The advantages of this method are the absence of solvents, short reaction times, and good yields.
Correspondence: Marcos A. P. Martins, Núcleo de Química de Heterociclos – NUQUIMHE, Universidade Federal de Santa Maria, Santa
Maria, RS, Brazil. 相似文献
2.
Dayse N. Moreira Clarissa P. Frizzo Kelvis Longhi Nilo Zanatta Helio G. Bonacorso Marcos A. P. Martins 《Monatshefte für Chemie / Chemical Monthly》2008,139(9):1049-1054
The synthesis of eleven 1-cyanoacetyl-5-hydroxy-5-halomethyl-4,5-dihydro-1H-pyrazoles from the reaction of 4-alkoxy-3-alken-2-ones f(R
3C(O)C(R
2) = C(R
1)OR, where R
3 = CF3, CCl3, CHCl2, CO2
Et; R
2/R
1 = H/H, H/Me, H/Et, -(CH2)4-, Me/H, H/Pr, and R = Me, Et) with cyanoacetohydrazide is reported. The reaction was carried out in the ionic liquid ([bmim][BF4]) and molecular solvents. The results showed that when the ionic liquid was used as reaction medium, the reaction time was
drastically decreased and the yield was improved.
Correspondence: Marcos A. P. Martins, Núcleo de Química de Heterociclos – NUQUIMHE, Universidade Federal de Santa Maria, Santa
Maria, RS, Brazil. 相似文献
3.
Upon reacting SeCl4 with Me3Si–F–Al(ORF)3, the selenonium salt SeMeCl2[al‐f‐al] ( 1 ) {[al‐f‐al]– = [F[Al(OC(CF3)3)3]2]–} was obtained and characterized by NMR, IR, and Raman spectroscopy as well as single crystal XRD experiments. Despite the [SeX3]+ (X = F, Cl, Br, I) and [SeR3]+ salts (R = aliphatic organic residue) being well known and thoroughly studied, the mixed cations are scarce. The only previous example of a salt with the [SeMeCl2]+ cation is SeMeCl2[SbCl6], which was never structurally characterized and is unstable in solution over hours. Only 1H‐NMR studies and IR spectra of this compound are known. The unexpected use of Me3Si–F–Al(ORF)3 as a methylating agent was investigated via DFT calculations and NMR experiments of the reaction solution. The reaction of SeCl3[al‐f‐al] with Me3Si‐Cl at room temperature in CH2Cl2 proved to yield the same product with Me3Si–Cl acting as a methylating agent. 相似文献
4.
Alexander Kolomeitsev Michaela Görg Uwe Dieckbreder Enno Lork Gerd-Volker Röschenthaler 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4):597-600
Abstract The System CF3I/Me3P is re-investigated and Me2PCF3, Me4P+γ, (CF3)2PMe3, Me3PI2, [Me3(CF3)P]+γ are found as products. Using CF3Br/P(NEt2)3 the phosphines R1 2PCF3 and R1P(CF3)2 (e.g. R1 = Me, iPr, NEt2) can be obtained which are precursors either for phosphoranes (e.g. 1,2λ5σ5-oxaphosphetanes) or phosphonium salts (e.g. [R1 2(Me)PCF3]+X? or [R1(Me)P(CF3)2X?]. The latter are deprotonated to furnish methylene phosphoranes R1 2(CH2=)PCF3 or R1(CH2=)P(CF3)2, reactive synthons. From CF3Br/P(NEt2)3/P(OPh)3 the phosphine P(CF3)3 is available, which turned out to be a potent electrophile. Amido phospites ROP(NEt2)2 and halides R2X (R2=CCl2CF3, X=Cl; R2=CF=CFCF3, X=F; R2=C6F5, X=Br, I; R2=C(CF3)3, X=Br; R2=SCF3, X=CF3) undergo an ARBUZOV reaction. 相似文献
5.
Silicon‐ and Tin‐Containing Open‐Chain and Eight‐Membered‐Ring Compounds as Bicentric Lewis Acids toward Anions 下载免费PDF全文
Dr. Anicet Siakam Wendji Dr. Christina Dietz Dr. Silke Kühn Michael Lutter Dr. Dieter Schollmeyer Dr. Wolf Hiller Prof. Dr. Klaus Jurkschat 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(1):404-416
Herein, we report the syntheses of silicon‐ and tin‐containing open‐chain and eight‐membered‐ring compounds Me2Si(CH2SnMe2X)2 ( 2 , X=Me; 3 , X=Cl; 4 , X=F), CH2(SnMe2CH2I)2 ( 7 ), CH2(SnMe2CH2Cl)2 ( 8 ), cyclo‐Me2Sn(CH2SnMe2CH2)2SiMe2 ( 6 ), cyclo‐(Me2SnCH2)4 ( 9 ), cyclo‐Me(2?n)XnSn(CH2SiMe2CH2)2SnXnMe(2?n) ( 5 , n=0; 10 , n = 1, X= Cl; 11 , n=1, X= F; 12 , n=2, X= Cl), and the chloride and fluoride complexes NEt4[cyclo‐ Me(Cl)Sn(CH2SiMe2CH2)2Sn(Cl)Me?F] ( 13 ), PPh4[cyclo‐Me(Cl)Sn(CH2SiMe2CH2)2Sn(Cl)Me?Cl] ( 14 ), NEt4[cyclo‐Me(F)Sn(CH2SiMe2CH2)2Sn(F)Me?F] ( 15 ), [NEt4]2[cyclo‐Cl2Sn(CH2SiMe2CH2)2SnCl2?2 Cl] ( 16 ), M[Me2Si(CH2Sn(Cl)Me2)2?Cl] ( 17 a , M=PPh4; 17 b , M=NEt4), NEt4[Me2Si(CH2Sn(Cl)Me2)2?F] ( 18 ), NEt4[Me2Si(CH2Sn(F)Me2)2?F] ( 19 ), and PPh4[Me2Si(CH2Sn(Cl)Me2)2?Br] ( 20 ). The compounds were characterised by electrospray mass‐spectrometric, IR and 1H, 13C, 19F, 29Si, and 119Sn NMR spectroscopic analysis, and, except for 15 and 18 , single‐crystal X‐ray diffraction studies. 相似文献
6.
The perfluoropinacolyl qroup (=PFP) stabilises halogenophosphoranes of the type e.g. X1=X2=X3=F,Cl,Br or X1=X2=Cl,Br, X3=F , covalent species which are able to react with Li2PFP to form spirocyclic systems [1]. Precursors of compounds are the phosphites (X=F,Cl,Br). The aminophosphite with X=NH2 shows interesting behaviour towards hexafluoroacetone forming a spiro system containg a four and a five membered ring. Phosphites with X=NR1R2 add readily chlorine to give stable chlorophosphoranes. Products of the ammonolysis of the trifluorophosphoranes (X1=X2=X3=F) were the aminophosphoranes (H2N)nPF3?n(PFP) (n=1,2,3) in good yields. Dynamic processes of the latter compounds were discussed on the bases of low temperatur 19F n.m.r. spectroscopy. 相似文献
7.
I. P. Beletskaya A. Z. Voskoboinikov A. K. Shestakova I. N. Parshina 《Russian Chemical Bulletin》1993,42(3):543-547
The ligand-exchange equilibria in cyclopentadienyl and metal carbonyl complexes of lanthanum have been qualitatively studied by139La NMR spectroscopy: 2X1X2X3La X1X2
2 La + X1X3, La, where X1=X2=Cp, X3=I; X1=X2 = 1, 3-(Me3Si)2C5H3, X3=Cl; X1=Ru(CO)2Cp; X2=Cp, X3=I. Similar equilibria are typical of the coordination chemistry of light lanthanides.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 578–581, March, 1993. 相似文献
8.
A Dimeric Gallium Hydrazide as an Active Lewis Pair – Complexation and Activation of Me2GaH and Various Heterocumulenes 下载免费PDF全文
Werner Uhl Matthias Willeke Alexander Hepp Damian Pleschka Marcus Layh 《无机化学与普通化学杂志》2017,643(5):387-397
Treatment of the dimeric gallium hydrazide [Me2Ga‐N(2‐Ad)‐NC5H10]2 ( 5 ) with Me2GaH resulted in the formation of an adduct 6 by Ga–N bond cleavage and coordination of the metal hydride via a Ga–N and a 3c–2e Ga–H–Ga bond. This reaction reflects the typical behavior of frustrated Lewis pairs. Reactions with heterocumulenes R–N=C=X (R = Ph, CMe3, Dipp, X = O; R = Ph, X = S) or X=C=X (X = O, S) resulted in the formation of the cyclic Ga–N insertion products Me2Ga–N(R)C(O)N(2‐Ad)‐NC5H10 ( 7a – c ), Me2GaS2C‐N(2‐Ad)‐NC5H10 ( 8 ) or Me2GaX2C‐N(2‐Ad)‐NC5H10 [X = O ( 9 ); S ( 10 )] in moderate to good yields. Three different structural motifs were observed in the solid state: Five‐membered GaNCN2 heterocycles with exocyclic C=O bonds for compounds 7a – c , four‐membered GaSCN or GaSCS heterocycles for compounds 8 and 9 (chelating coordination of the Ga atoms by SCN and CS2 ligands) and an eight‐membered (GaOCO)2 heterocycle for the dimeric CO2 insertion product 10 . Treatment of 5 with PhCN or Ph2CO resulted in a completely different reaction and afforded a dimeric Ga imide 11a or an alcoholate 11b . These reactions may start by retro‐hydrogallation with the formation of H10C5N–N=C(C9H14) and Me2GaH and proceed by addition of the metal hydride to the polar multiple bonds of the nitrile or ketone. 相似文献
9.
Synthesis and Structure of Pentaalkylchlorohexastibane Sb6R5Cl [R = (Me3Si)2CH] The reaction of RSbCl2 [R = (Me3Si)2CH] with Na‐K alloy in tetrahydrofuran gives besides the known rings SbnRn (n = 3, 4), (Me3Si)2CH2 and the pentaalkylchlorohexastibane Sb6R5Cl ( 1 ). 1 was characterized by spectroscopic methods (MS, 1H‐, 13C‐NMR, X‐ray diffraction). The structure of 1 consists of a folded four membered antimony ring in the all‐trans configuration with three alkyl groups and one Sb(R)—Sb(R)Cl fragment as substituents. 相似文献
10.
(N,N,N′,N′ -tetramethylethylendiamine) di(tert-butyl)aluminium Cations — Molecular Structure of [(Me3C)2Al(TMEDA)]⊕[(Me3C)2AlBr2]? Dimeric di(tert-butyl)aluminium halides (Me3C)2AlX (X = Cl, Br) react with N,N,N′,N′ -tetramethylethylendiamine (TMEDA) to give three compounds: the salt-like [(Me3C)2Al(TMEDA)]⊕[(Me3C)2AlX2]? 1 , characterized by crystal structure determination, and [(Me3C)2Al(TMEDA)]⊕X? 3 both with chelating amine, and the more covalent, pentane soluble (Me3C)2AlX(TMEDA) 2 with TMEDA bound by only one nitrogen atom. The reaction resembles the symmetrical and unsymmetrical cleavage of diborane(6). 3 (X = Cl) is also formed by treatment of 1 with boiling n-hexane in the presence of TMEDA over a period of 24 hours, while for X = Br the more covalent 2 is the main product under similar conditions. In solution 2 decomposes slowly yielding different products in dependency of the solvent: in benzene 3 and in n-pentane 1 are formed. 相似文献
11.
Sonja Pavlik Roland Schmid Karl Kirchner Kurt Mereiter 《Monatshefte für Chemie / Chemical Monthly》2004,35(2):1349-1357
The reaction of RuTp(COD)Cl (1) with PPh2Pri and terminal alkynes HCCR (R=C6H5, C4H3S, C6H4OMe, Fc, C6H4–Fc, C6H9) affords the neutral vinylidene complexes RuTp(PPh2Pri) (Cl)(=C=CHR) (2a–2f) in high yields. These complexes do not react with MeOH to give methoxy carbene complexes of the type RuTp(PPh2Pri)(Cl)(=C(OMe)CH2R), but react with oxygen to yield the CO complex RuTp(PPh2R)(Cl)(CO) (3). The structures of 2b, 2f, and 3 have been determined by X-ray crystallography. 相似文献
12.
Summary. The reaction of RuTp(COD)Cl (1) with PPh2Pri and terminal alkynes HCCR (R=C6H5, C4H3S, C6H4OMe, Fc, C6H4–Fc, C6H9) affords the neutral vinylidene complexes RuTp(PPh2Pri) (Cl)(=C=CHR) (2a–2f) in high yields. These complexes do not react with MeOH to give methoxy carbene complexes of the type RuTp(PPh2Pri)(Cl)(=C(OMe)CH2R), but react with oxygen to yield the CO complex RuTp(PPh2R)(Cl)(CO) (3). The structures of 2b, 2f, and 3 have been determined by X-ray crystallography. 相似文献
13.
Four novel bridged‐amidines H2L {1,4‐R1[C(=NR2)(NHR2)]2 [R1=C6H4, R2=2,6‐iPr2C6H3 (H2L1); R1=C6H4, R2=2,6‐Me2C6H3 (H2L2); R1=C6H10, R2=2,6‐iPr2C6H3 (H2L3); R1=C6H10, R2=2,6‐Me2C6H3 (H2L4)]} were synthesized in 65%–78% isolated yields by the condensation reaction of dicarboxylic acid with four equimolar amounts of amines in the presence of PPSE at 180°C. Alkane elimination reaction of Ln(CH2SiMe3)3(THF)2 (Ln=Y, Lu) with 0.5 equiv. of amidine in THF at room temperature afforded the corresponding bimetallic rare earth alkyl complexes (THF)(Me3SiCH2)2LnL1Ln(CH2SiMe3)2(THF) [Ln=Y ( 1 ), Lu ( 2 )], (THF)(Me3SiCH2)2LnL2Ln‐ (CH2SiMe3)2(THF) [Ln=Y ( 3 ), Lu ( 4 )], (THF)(Me3SiCH2)2YL3Y(CH2SiMe3)2(THF) ( 5 ), (THF)(Me3SiCH2)2YL4‐ Y(CH2SiMe3)2(THF) ( 6 ) in 72% –80% isolated yields. These neutral complexes showed activity towards L‐lactide polymerization in toluene at 70°C to give high molecular weight (M>104) and narrow molecular weight distribution (Mw/Mn≦1.40) polymers 相似文献
14.
Abinet E Martin D Standfuss S Kulinna H Spaniol TP Okuda J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(52):15014-15026
The preparation and characterization of a series of neutral rare‐earth metal complexes [Ln(Me3TACD)(η3‐C3H5)2] (Ln=Y, La, Ce, Pr, Nd, Sm) supported by the 1,4,7‐trimethyl‐1,4,7,10‐tetraazacyclododecane anion (Me3TACD?) are reported. Upon treatment of the neutral allyl complexes [Ln(Me3TACD)(η3‐C3H5)2] with Brønsted acids, monocationic allyl complexes [Ln(Me3TACD)(η3‐C3H5)(thf)2][B(C6X5)4] (Ln=La, Ce, Nd, X=H, F) were isolated and characterized. Hydrogenolysis gave the hydride complexes [Ln(Me3TACD)H2]n (Ln=Y, n=3; La, n=4; Sm). X‐ray crystallography showed the lanthanum hydride to be tetranuclear. Reactivity studies of [Ln(Me3TACD)R2]n (R=η3‐C3H5, n=0; R=H, n=3,4) towards furan derivatives includes hydrosilylation and deoxygenation under ring‐opening conditions. 相似文献
15.
Diaryl‐substituted triazenides Ar(Ar′)N3HgX [Ar/Ar′ = Dmp/Mph, X = Cl ( 2a ), Br ( 3a ), I ( 4a ); Ar/Ar′ = Dmp/Tph, X = Cl ( 2b ), I ( 4b ) with Mph = 2‐MesC6H4, Mes = 2,4,6‐Me3C6H2, Tph = 2′,4′,6′‐triisopropylbiphenyl‐2‐yl and Dmp = 2,6‐Mes2C6H3] were synthesized by salt‐metathesis reactions in ethyl ether from the readily available starting materials Ar(Ar′)N3Li and HgX2. These compounds may be used for redox‐transmetallation reactions with rare‐earth or alkaline earth metals. Thus, reaction of 4b or 2b with magnesium or ytterbium in tetrahydrofuran afforded the triazenides Dmp(Tph)N3MX(thf) ( 5b : M = Mg, X = I; 6b : M = Yb, X = Cl) in good yield. All new compounds were characterized by melting point, 1H and 13C NMR spectroscopy and for selected species by IR spectroscopy or mass spectrometry. In addition, the solid‐state structures of triazenides 2a , 2b , 3a , 4b , 5b and 6b were investigated by single‐crystal X‐ray diffraction. 相似文献
16.
Dennis A. Buschmann Dr. H. Martin Dietrich Dr. David Schneider Dr. Verena M. Birkelbach Dr. Christoph Stuhl Prof. Dr. Karl W. Törnroos Dr. Cäcilia Maichle-Mössmer Prof. Dr. Reiner Anwander 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(47):10834-10840
Tetramethylaluminato/halogenido(X) ligand exchange reactions in half-sandwich complexes [CpRLa(AlMe4)2] are feasible in non-coordinating solvents and provide access to large coordination clusters of the type [CpRLaX2]x. Incomplete exchange reactions generate the hexalanthanum clusters [CpR6La6X8(AlMe4)4] (CpR=Cp*=C5Me5, X=I; CpR=Cp′=C5H4SiMe3, X=Br, I). Treatment of [Cp*La(AlMe4)2] with two equivalents Me3SiI gave the nonalanthanum cluster [Cp*LaI2]9, while the exhaustive reaction of [Cp′La(AlMe4)2] with the halogenido transfer reagents Me3GeX and Me3SiX (X=I, Br, Cl) produced a series of monocyclopentadienyl rare-earth-metal clusters with distinct nuclearity. Depending on the halogenido ion size the homometallic clusters [Cp′LaCl2]10 and [Cp′LaX2]12 (X=Br, I) could be isolated, whereas different crystallization techniques led to the aggregation of clusters of distinct structural motifs, including the desilylated cyclopentadienyl-bridged cluster [(μ-Cp)2Cp′8La8I14] and the heteroaluminato derivative [Cp′10La10Br18(AlBr2Me2)2]. The use of the Cp′ ancillary ligand facilitates cluster characterization by means of NMR spectroscopy. 相似文献
17.
Comparative analysis of the oxidizing and complexing properties of the DMSO–HX (X = Cl, Br, I) and DMSO–HX–ketone (X = Br, I; the ketone is acetone, acetylacetone, or acetophenone) systems toward silver was performed. The reaction products are AgX (X = Cl, Br, I), [Me3S+]Ag
n
X–
m
(n= 1, 2; m= 2, 3; X = Br, I) and [Me2S+CH2COR]AgX–
2(R = Me, Ph; X = Br, I). The composition of the obtained complexes depends on both the DMSO : HX ratio and the nature of HX, as well as on the methods used to isolate solid products from the solution. It was noted that the formation of the [Me2S+CH2COMe]AgBr–
2complex in the Ag0–DMSO–HBr–acetylacetone system occurs with cleavage of the acetylacetone C–C bond and follows a specific reaction course. The optimum conditions for production of the silver compounds in the title systems are determined. 相似文献
18.
Soon‐Sik Kwon Tae‐Sung Kim Hong Choi Sung‐Tae Shin Jeong‐Kyu Park 《Liquid crystals》2013,40(9):1005-1014
Six banana‐shaped compounds with a central core based on a 4,6‐dichloro‐1,3‐phenylene group were synthesized by varying the terminal chains (R = OC10H21 or OC11H21) and the lateral substituents (X = H, F or Cl). Their mesophases were characterized by a combination of differential scanning calorimetry, polarizing optical microscopy, triangular wave method, and X‐ray diffractometry. Mesomorphic properties of the banana‐shaped mesogens with an olefinic group (R = OC11H21) as a terminal chain are sensitive to lateral halogen substituents as much as those of the analogues with a saturated group (R = OC10H21). The compounds with X = F showed an antiferroelectric switchable smectic phase, which has been designated a B2 phase. The compounds without a lateral halogen substituent only formed a nematic phase, while the compounds with X = Cl did not exhibit a mesophase in the melt. 相似文献
19.
《无机化学与普通化学杂志》2018,644(3):142-148
Three diacylthioureas 1,4‐C6H4[C(O)NHC(S)NHAr]2 (Ar = 2,6‐iPr2C6H3) ( L1 , 1 ), 1,3‐C6H4[C(O)NHC(S)NHAr]2 ( L2 , 2 ), and 1,3‐C6H4[C(O)NHC(S)NHAr′]2 (Ar′ = 2,6‐Me2C6H3) ( L3 , 3 ) were synthesized and characterized. The CuI complexes from the reactions of bipodal ligands Ln with CuX (X = Cl, Br, I) were structurally investigated by single‐crystal X‐ray diffraction methods. Treatment of L1 with CuX gave the metallamacrocyclic complexes ( L1 CuX)2 [X = Cl ( 4 ), Br ( 5 ), I ( 6 )] with the ligand to metal in a ratio of 2:2, where both sulfur and halide anions function as terminal substituents. In contrast, when L2 or L3 was reacted with CuBr, the two Ln ligands coordinate to four copper atoms each in a bridging and terminal fashion to yield [ Ln (CuBr)2]2 [n = 2 ( 7 ), 3 ( 8 )]. The obtained S4Cu4Br4 core contains all four bromide anions in bridging positions. The reaction of L3 with CuX (X = Cl, I) gave the 3:3 trinuclear complexes ( L3 CuX)3 [X = Cl ( 9 ) I ( 10 )], interconnected by halide bridges. The obtained diacylthioureas ( 1 – 3 ) and their CuI complexes ( 4 – 10 ) were also characterized by elemental analysis, FT‐IR, 1H and 13C NMR spectroscopy. 相似文献
20.
Elisabeth Öhler Mahmoud El-Badawi Erich Zbiral 《Monatshefte für Chemie / Chemical Monthly》1985,116(1):77-86
Zusammenfassung -Substituierte -Acylvinylphosphonate3 mitE-Konfiguration [R
2CO-CH=C(R
1)-P(O)(OR)2], werden in guten Ausbeuten durchWittig-Reaktion von Acylphosphonsäureestern1 [R
1CO-P(O)(OR)2,R
1=Alkyl oder Aryl] mit (2-Oxoalkyliden)triphenylphosphoranen2 [R
2CO-CH=PPh
3,R
2=Alkyl, O-Alkyl oder CH2
X (X=Br, OMe, CO2
Et)] erhalten.
A convenient route to -substituted dialkyl (E)-3-oxo-1-alkenylphosphonates
-Substituted dialkyl (E)--acylvinylphosphonates [R 2CO-CH=C(R 1)-P(O)(OR)2,3], are easily obtained in good yields byWittig-reaction of dialkyl acylphosphonates1 [R 1CO-P(O)(OR)2,R 1=alkyl or aryl) with 2-oxoalkylidene triphenylphosphoranes2 [R 2CO-CH=PPh 3,R 2=alkyl, O-alkyl and CH2 X (X=Br, OMe, CO2 Et)].相似文献