Synthesis, spectroscopic characterization, and structural studies of organogermanium tri- and monothiocarbonates. Crystal structures of Me2Ge[S2CSEt]2, Ph3Ge[SCO2Me], Ph3Ge[SCO2(i-Pr)], and Ph2Ge[SCO2Me]2

1998 ◽  
Vol 76 (3) ◽  
pp. 319-334 ◽  
Author(s):  
John E Drake ◽  
Jincai Yang
Keyword(s):  
Mass Spectrometry ◽  
Nmr Spectroscopy ◽  
Crystal Structures ◽  
Sodium Salt ◽  
Variable Temperature ◽  
Spectroscopic Characterization ◽  
Structural Studies ◽  
Cell Parameters ◽  
Derivatives Of ◽  
C Nmr

Two series of S-alkyl trithiocarbonate derivatives of imethylgermane, Me2Ge[S2CSR]2, and halodiphenylgermane, Ph2GeX[S2CSR], where R = Me, i-Pr, n-Pr, n-Bu and X = Cl, Br, and three series of O-alkyl monothiocarbonate derivatives of triphenylgermane, Ph3Ge[SCO2R], diphenylgermane, Ph2Ge[SCO2R], and trimethylgermane, me3Ge[SCO2R], where R = Me, i-Pr, and n-Pr, have been prepared in 73-92% yields by the reaction of the potassium or sodium salt of the appropriate tri- or monothiocarbonic acid with dichlorodimethyl-, chlorotriphenyl-, dichlorodiphenyl-, and chlorotrimethylgermane. The compounds were principally characterized by infrared, Raman, and 1H and 13C NMR spectroscopy, including some variable temperature studies, as well as by mass spectrometry. Me2Ge[S2CSEt]2, 1: P21/m (No. 11) with cell parameters a = 6.647(4) Å, b = 7.423(2) Å, c = 16.290(4) Å, β = 91.07(3)°, V = 803.6(4) Å3, Z = 2, R = 0.0484,Rw = 0.0485. Ph3Ge[SCO2Me],13: P1bar (No. 2) with cell parameters a = 9.970(4) Å, b = 10.660(3) Å, c = 9.853(2) Å, α = 101.78(2)°, β = 109.98(2)°, γ = 89.76(3)°, V = 961.0(5) Å3, Z = 2, R = 0.0534, Rw = 0.0451. Ph3Ge[SCO2(i-Pr)], 14: P 1bar (No. 2) with cell parameters a = 14.386(7) Å, b = 18.598(6) Å, c = 9.223(3) Å, α = 102.85(3)°, β = 94.58(3)°, γ = 108.13(3)°, V = 2256(1) Å3, Z = 2, R = 0.0545, Rw = 0.0552. Ph2Ge[SCO2Me]2, 16: Cc, (No. 9) with cell parameters a = 11.790(4) Å, b = 13.696(5) Å, c = 23.232(6) Å, β = 92.26(3)°, V = 3748(2) Å3, Z = 8, R = 0.0563, Rw = 0.0512. The immediate environment about Ge is that of tetrahedral but the orientations of the thiocarbonate groups display interesting features.Key words: structure, germanium, phenyl, methyl, thiocarbonates.

9-Silyl(-Germyl,-Stannyl) Substituted Derivatives of 1-(9-Fluorenyl)- germatranes. Synthesis, Characterisation, and Crystal Structures

1998 ◽  
Vol 53 (11) ◽  
pp. 1247-1254 ◽  
Author(s):  
Galina S. Zaitseva ◽  
Sergey S. Karlov ◽  
Bettina A. Siggelkow ◽  
Evgeni V. Avtomonov ◽  
Andrei V. Churakov ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Nmr Spectroscopy ◽  
Crystal Structures ◽  
Elemental Analyses ◽  
Derivatives Of ◽  
C Nmr

9-Trimethylsilyl- and 9-trimethylgermyl substituted derivatives of 1-(9-fluorenyl)germatranes C13H8(R)Ge(OCH2CH2)3N (1 - 3) (1: R = H; 2: R = Me3Si; 3: R = Me3Ge) were prepared by the reaction of 9-tribromogermyl derivatives of fluorene C13H8(R)GeBr3 (4 - 6) with N(CH2CH2OSnAlk3)3 (7: Alk = Et; 8: Alk = Bu). 1-(9-Trimethylstannyl- 9-fluorenyl)germatrane (14) was synthesised by the reaction o f the germatrane (1) with Me3SnNMe2 . Formulas and structures were established by elemental analyses, (1H, 13C) NMR spectroscopy and mass spectrometry; crystal structures of 2 and 14 are reported.

A study of a variety of O,O-alkylene dithiophosphate derivatives of triphenyl-and diphenylgermane. Crystal structures of and

1995 ◽  
Vol 73 (7) ◽  
pp. 915-928 ◽  
Author(s):  
John E. Drake ◽  
Anil G. Mislankar ◽  
Raju Ratnani ◽  
Jincai Yang
Keyword(s):  
Mass Spectrometry ◽  
Nmr Spectroscopy ◽  
Crystal Structures ◽  
Distorted Tetrahedron ◽  
Space Group ◽  
X Ray ◽  
Cell Parameters ◽  
X Ray Crystallography ◽  
Derivatives Of

The O,O-alkylene dithiophosphate derivatives of triphenyl- and diphenylgermane, [Formula: see text] [Formula: see text] [Formula: see text] [Formula: see text] [Formula: see text] and [Formula: see text] have been prepared and characterized by infrared, Raman, and 1H, 13C, and 31P NMR spectroscopy, mass spectrometry, and, in three cases, X-ray crystallography. [Formula: see text] 1, crystallizes as monoclinic in the space group P21/a (No. 14) with the cell parameters a = 12.868(5) Å, b = 11.354(4) Å, c = 17.207(4) Å, β = 95.42(2)°, V = 2502(1) Å3, Z = 4, R = 0.0640, and Rw = 0.0585. [Formula: see text] 2, crystallizes as orthorhombic in the space group Pbca (No. 61) with the cell parameters a = 23.007(4) Å, b = 16.840(4) Å, c = 12.068(3) Å, V = 4657(3) Å3, Z = 8, R = 0.0502, and Rw = 0.0329. [Formula: see text] 3, crystallizes as monoclinic in the space group C2/c (No. 15) with the cell parameters a = 35.48(2) Å, b = 9.275(5) Å, c = 20.78(1) Å, β = 120.93(3)° V = 5866(5) Å3, Z = 8, R = 0.0674, and Rw = 0.0562. As with their methylgermanium analogues, the environment about germanium is essentially that of a distorted tetrahedron, with the terminal sulfur atoms oriented towards germanium rather than away from it, in contrast with analogous noncyclic dithiophosphatogermanes. The substituents on the atoms in both the five- and six-membered rings maintain their nonequivalence in solution, in contrast with tin analogues. Keywords: structure, germanium, diphenyl, triphenyl, cyclic dithiophosphates

Synthesis, spectroscopic characterization and structural studies of organotin monothiocarbonates. Crystal structures of Ph3Sn[SCO2Me] and Ph3Sn[SCO2(i-Pr)]

2000 ◽  
Vol 78 (9) ◽  
pp. 1214-1221 ◽  
Author(s):  
John E Drake ◽  
Jincai Yang
Keyword(s):  
Intramolecular Interaction ◽  
Spectroscopic Characterization ◽  
Triclinic Space Group ◽  
Cell Parameters ◽  
X Ray Crystallography ◽  
H Nmr ◽  
Trigonal Bipyramidal ◽  
Considerable Distortion ◽  
Derivatives Of ◽  
C Nmr

O-alkyl monothiocarbonate (monoxanthate) derivatives of tin were obtained by the reaction of a sodium salt of the monothiocarbonic acid with an organotin chloride to give Ph3Sn[SCO2R], Ph2Sn[SCO2R]2, and Me3Sn[SCO2R], where R = Me and i-Pr. The compounds have been characterized by infrared, Raman, 1H NMR, and 13C NMR spectroscopy, as well as mass spectrometry, and in two cases by X-ray crystallography. Ph3Sn[SCO2Me] (1) and Ph3Sn[SCO2(i-Pr)] (2), crystallize in the triclinic space group P[Formula: see text] (no. 2) with cell parameters a = 10.218(4), b = 10.568(6), c = 9.366(7) Å, α = 106.73(5), β = 96.99(5), γ = 85.55(4)°, V = 960(1) Å3, and Z = 2 for 1; and a = 14.793(2), b = 17.856(3), c = 9.813(3) Å, α = 103.86(5), β = 98.36(5), γ = 106.85(4)°, V = 2343(1) Å3, and Z = 2 for 2. The latter has two molecules in the asymmetric unit. The immediate environment about tin in both 1 and 2 is that of the expected distorted tetrahedron. However, the orientation of the monothiocarbonate group is such that there is an Sn-O intramolecular interaction of 3.040(8) for 1 and 3.05(2) Å on average for 2. Thus, the considerable distortion is consistent with a tendency to form a five-coordinate, trigonal bipyramidal species with one of the O-Sn-C angles approaching 180o (153.4(4) for 1 and an average of 157.1(6) for 2). Estimations of the Pauling partial bond orders suggest this weak Sn-O interaction is slightly stronger than the corresponding Ge-O interaction in the analogous germanium derivative, Ph3Ge[SCO2Me].Key words: structure, tin, methyl, phenyl, isopropyl, monothiocarbonates.

Synthesis and characterization of dimethyl- and dimethoxyphenylbis(N,N-dialkyldithiocarbamato)tellurium(IV) and chlorodimethyl- and chlorodimethoxyphenyl-(N,N-dialkyldithiocarbamato)tellurium(IV). Crystal structures of Me2Te[S2CNMe2]2 and (p-MeOC6H4)2Te[S2CNMe2]2

1993 ◽  
Vol 71 (1) ◽  
pp. 42-50 ◽  
Author(s):  
Jane H. E. Bailey ◽  
John E. Drake
Keyword(s):  
Nmr Spectroscopy ◽  
Crystal Structures ◽  
Variable Temperature ◽  
Reductive Elimination ◽  
Synthesis And Characterization ◽  
Space Group ◽  
Cell Parameters

The compounds Me2Te[S2CNR2]2, Me2TeCl[S2CNR2], (p-MeOC6H4)2Te[S2CNR2]2, and (p-MeOC6H4)2TeCl[S2CNR2], where R = Me, Et, have been prepared and characterised primarily by vibrational and NMR spectroscopy. Variable temperature NMR spectroscopy and qualitative time studies indicate that in solution the dimethoxyphenyltellurium derivatives undergo the reductive-elimination noted for analogous phenyl derivatives but the reductive-elimination does not occur with the dimethyl tellurium derivatives. The crystal structures of Me2Te[S2CNMe2]2, 1, and (p-MeOC6H4)2-Te[S2CNMe2]2, 5, were completed. The cell parameters for 1, which crystallizes as monoclinic in space group P21/n, are a = 13.550(2), b = 13.034(2), c = 17.854(2) Å, β = 106.61(1)°, V = 3021.6(7) Å3, Z = 8, R = 0.0368, and Rw = 0.0402 and for 5, which crystallizes as monoclinic in space group C2/c, are a = 35.36(1), b = 11.063(3), c = 12.778(3) Å, β = 96.16(3)°, V = 4963(3) Å3, Z = 8, R = 0.0627, and Rw = 0.0646.

Synthesis, spectroscopic and structural studies of O-methyl and O-isopropyl monothiocarbonate (monoxanthate) derivatives of dimethyl-and diphenyltellurium(IV). Crystal structures of Me2Te[SCO2(i-Pr)]2, Ph2Te[SCO2(i-Pr)]2, Me2TeCl[SCO2Me], and Me2TeBr[SCO2(i-Pr)]

1996 ◽  
Vol 74 (11) ◽  
pp. 1968-1982 ◽  
Author(s):  
John E. Drake ◽  
Robert J. Drake ◽  
Layla N. Khasrou ◽  
Anil G. Mislankar ◽  
Raju Ratnani ◽  
...  
Keyword(s):  
Nmr Spectroscopy ◽  
Key Words ◽  
Lone Pair ◽  
Supramolecular Interactions ◽  
Equatorial Position ◽  
Structural Studies ◽  
Cell Parameters ◽  
Distorted Trigonal Bipyramid ◽  
Derivatives Of ◽  
Oxygen Atoms

Monothiocarbonate derivatives of diorganotellurium(IV), R2Te[SCO2R′]2, and R2TeX[SCO2R′], where R = Me, Ph; R′ = Me, i-Pr; X = Cl, Br, and I, have been prepared and characterized by vibrational and 1H, 13C, and 125Te NMR spectroscopy. Me2Te[SCO2(i-Pr)]2 (2): P21/n (No. 14) with cell parameters a = 6.942(6) Å, b = 25.599(3) Å, c = 9.404(6) Å, β = 94.48(6)°, V = 1666(1) Å3, Z = 4, R = 0.0648, Rw = 0.0624; Ph2Te[SCO2(i-Pr)]2 (4): P21/n (No. 14) with a = 12.360(4) Å, b = 12.277(3) Å, c = 15.066(3) Å, β = 102.82(2)°, V = 2229.1(9) Å3, Z = 4, R = 0.0368, Rw = 0.0312; Me2TeCl[SCO2Me] (5); P21/c (No. 14) with a = 5.193(2) Å, b = 18.118(4) Å, c = 9.613(5) Å, β = 91.31(6)°, V = 904.2(6) Å3, Z = 4, R = 0.0396, Rw = 0.0361; and Me2TeBr[SCO2(i-Pr)] (8): P21/n (No. 14) with a = 11.701(2) Å, b = 6.250(2) Å, c = 16.152(2) Å, β = 98.43(1)°, V = 1168.4(4) Å3, Z = 4, R = 0.0369, Rw = 0.0325. In all molecules, the immediate environment about tellurium is that of the saw-horse structure in which the lone pair is assumed to be stereochemically active and occupying an equatorial position in a distorted trigonal bipyramid. In 2 and 5, the terminal oxygen atoms are oriented toward tellurium, whereas in 4, one O(i-Pr) group is oriented toward tellurium, as it is in 8. In the latter cases, the terminal oxygen atoms act as weak bridges to form a pseudo dimeric species in 4 and a pseudo polymer in 8. Supramolecular interactions in 2 and 5 lead to a sulfur-bridged dimer in the former and a chlorine-bridged polymer in the latter. Key words: structure, tellurium, dimethyl, diphenyl, monothiocarbonates.

The mechanism of formation of 2,7-dimethyl-2,6-octadiene in the synthesis of 3-methylene-7-methyl-1,6-octadiene

1983 ◽  
Vol 48 (7) ◽  
pp. 1864-1866
Author(s):  
Jan Bartoň ◽  
Ivan Kmínek
Keyword(s):  
Mass Spectrometry ◽  
Nmr Spectroscopy ◽  
Alkali Metal ◽  
Chromatographic Analysis ◽  
Solid Phase ◽  
Reaction Pathway ◽  
Mechanism Of Formation ◽  
Gas Chromatographic Analysis ◽  
C Nmr ◽  
Visual Observations

2,7-Dimethyl-2,6-octadiene is formed in the catalytic solution for the dimerization of 2-methyl-1,3-butadiene to β-myrcene (3-methylene-7-methyl-1,6-octadiene), as revealed by mass spectrometry and 13C NMR spectroscopy. Visual observations together with the results of gas chromatographic analysis of the catalytic solution suggest that the formation of 2,7-dimethyl-2,6-octadiene is associated with the transition of the alkali metal (sodium) from the solid phase into the solution. A reaction pathway is suggested accounting for the formation of 2,7-dimethyl-2,6-octadiene in the system.

A New Dimeric Derivative of Ethoxyquin from Its Reaction with Alkylperoxy Radicals

1993 ◽  
Vol 58 (8) ◽  
pp. 1914-1918 ◽  
Author(s):  
Jaroslav Kříž ◽  
Luděk Taimr
Keyword(s):  
Mass Spectrometry ◽  
Nmr Spectroscopy ◽  
Peroxy Radicals ◽  
Methyl Group ◽  
Alkylperoxy Radicals ◽  
C Nmr

The structure of a new compound formed in the reaction of ethoxyquin with alkylperoxy radicals was resolved by 1H and 13C NMR spectroscopy (including COSY, NOESY, HHC RCT and SSLR INEPT techniques) and confirmed by mass spectrometry. The structure suggest participation of 4-methyl group of ethoxyquin in the deactivation of peroxy radicals. A mechanism of this reaction is proposed.

Structural studies of digitoxin and related cardenolides by two-dimensional NMR

1990 ◽  
Vol 68 (2) ◽  
pp. 272-277 ◽  
Author(s):  
Torbjörn Drakenberg ◽  
Peter Brodelius ◽  
Deane D. McIntyre ◽  
Hans J Vogel
Keyword(s):  
Nmr Spectroscopy ◽  
Nmr Spectra ◽  
Chair Conformation ◽  
Coupling Constants ◽  
Two Dimensional ◽  
Structural Studies ◽  
Solution Conformation ◽  
Phase Sensitive ◽  
Multiple Relay ◽  
C Nmr

The 1H and 13C NMR spectra of the cardenolides digitoxigenin, digoxigenin, digitoxin, and mono- and bis-digitoxigenin digitoxosides have been completely assigned by two-dimensional NMR spectroscopy. The techniques used include phase-sensitive COSY, multiple relay COSY, and carbon–proton correlation (HETCOR and HMQC) spectra. Various aspects of the solution conformation of the steroid moiety of digitoxin and digoxigenin could be determined from coupling constants and NOE difference experiments and they are indicative of an all-chair conformation. The carbohydrate rings in digitoxin and the mono- and bis-digitoxigenin digitoxosides are also in the chair conformation. Keywords: cardenolides, digitoxigenin, digitoxin, 2-dimensional NMR, conformational analysis.

Synthesis and crystal structures of three novel benzimidazole/benzoindolizine hybrids

2016 ◽  
Vol 71 (3) ◽  
pp. 231-239 ◽  
Author(s):  
Roumaissa Belguedj ◽  
Sofiane Bouacida ◽  
Hocine Merazig ◽  
Ali Belfaitah ◽  
Aissa Chibani ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Nmr Spectroscopy ◽  
Crystal Structures ◽  
Dipolar Cycloaddition ◽  
Dimethyl Acetylenedicarboxylate ◽  
X Ray ◽  
X Ray Crystallography ◽  
Dimethyl Maleate

AbstractThree benzoindolizine derivatives, 1, 2, and 3, were obtained via 1,3-dipolar cycloaddition. The reaction of 1-(2′-benzimidazolylmethyl)isoquinolinium ylides with dimethyl acetylenedicarboxylate gave a mixture of pyrrolo[2,1-a]isoquinoline-1,2-dicarboxylate (1) and 1,10b-dihydropyrrolo[2,1-a]isoquinoline-1,2-dicarboxylate (2) derivatives containing a benzimidazole moiety. The reaction of this isoquinolinium N-ylide with dimethyl maleate gave an unexpected 2,3-dihydropyrrolo[2,1-a]isoquinoline-1,2-dicarboxylate (3). The structures of all reported compounds have been examined by X-ray crystallography, mass spectrometry, and NMR spectroscopy.

Sign in / Sign up

Export Citation Format

Share Document