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41.
The structure of 1-hydroxy-1,2,3-benzotriazolium diphenyl phosphate (HOBt/DPP) has been investigated by X-ray analysis. The compound crystallizes in the monoclinic space group P21/n with Z = 4 and the following lattice parameters: a = 11.711(2), b = 12.727(2) and c = 12.794(3) Å, β = 105.12(2)°, V = 1840.9(6) Å3. The structure was solved by direct methods and refined on F2 to R values of wR2 = 0.084 and R1 = 0.034 for 1985 observed reflections. HOBt/DPP has an ionic structure with very short OHO and NHO hydrogen bonds linking the different ions. Owing to these hydrogen bonds, infinite screw-shaped chains which are twisted parallel to the y-axis are formed. 相似文献
42.
The complex, bis[N‐6‐aminopyridyl‐N‐(1S)‐(+)‐10‐camphorsulfonylamino]palladium, Pd[(S)‐APCS]2, 1 , was prepared by reaction of 2‐[(1S)‐(+)‐10‐camphorsulfonamino]‐6‐aminopyridine with PdCl2 in THF. Complex 1 has been characterized by spectroscopic methods and its structure has been determined by X‐ray crystallography. Crystal data: space group C2, a= 16.082 (2), b = 17.104 (2), c = 13.051 (2)Å, β = 99.95 (1)°, V = 3535.9 (8) Å3, Z = 2 with final residuals R1 = 0.0491 and wR2 = 0.0944. Two independent molecules, (S,S)‐Pd[(S)‐APCS]2, 1a , and (R,R)‐Pd[(S)‐APCS]2, 1b , were found in each asymmetric unit, which exchange to each other via a series of nitrogen inversion and C‐C bond rotation. The inversion energy (ΔGc1≠) and the energy barrier (δGc2≠) were 11.5 ± 0.1 Kcal mol?1 at 246 K and 9.8 ± 0.1 Kcal mol?1 at 199 K, respectively, calculated by dynamic NMR data. 相似文献
43.
Ouro-Sama Adetchessi 《Tetrahedron》2005,61(18):4453-4460
2-Substituted-4a-hydroxy-9H-cycloalkyl[1,2-e]oxazolo[3,2-a]pyrimidin-9-ones 2a-c were synthesized by an one-step cyclocondensation from the 5-substituted-2-amino-2-oxazolines 1a-c with ethyl 2-oxocyclohexanecarboxylate in ethanol at room temperature, and easily dehydrated to provide 2-substituted-9H-cycloalkyl[1,2-e]oxazolo[3,2-a]pyrimidin-9-ones 3. In refluxing xylene, the reaction conducted with various ethyl 2-oxocycloalkanecarboxylates led to the two isomeric 2-substituted-8/9H-cycloalkyl[1,2-e]oxazolo[3,2-a]pyrimidin-8/9-ones 3 and 2-substituted-5H-cycloalkyl[1,2-d]oxazolo[3,2-a]pyrimidin-5-ones 4. The structure of some compounds was unambiguously established using X-ray crystallography. According to results from the DSC analysis of compound 2a, formation of the thermodynamically stable pyrimidinones 4 could be related to an intramolecular rearrangement of kinetically controlled pyrimidinones 3. 相似文献
44.
Two trans stereoisomers of 3‐methylcyclopentadecanol (=muscol), (1R,3R)‐ 2 and (1S,3S)‐ 2 , were efficiently synthesized from (3RS)‐3‐methylcyclopentadecanone (=muscone; (3RS)‐ 1 ) by a highly stereoselective reduction (Scheme). L‐Selectride® (=lithium tri(sec‐butyl)borohydride) was used, followed by the enantiomer resolution by lipase QLG (Alcaligenes sp.). The cis stereoisomers of muscol, (1S,3R)‐ 2 and (1R,3S)‐ 2 , were obtained by the Mitsunobu inversion of (1R,3R)‐ 2 and (1S,3S)‐ 2 , respectively (Scheme). The absolute configuration of (1R,3R)‐ 2 was determined by X‐ray crystal‐structure analysis of its 3‐nitrophthalic acid monoester, 2‐[(1R,3R)‐3‐methylcyclopentadecyl hydrogen benzene‐1,2‐dicarboxylate ((1R,3R)‐ 3b ), and by oxidation of (1R,3R)‐ 2 to (3R)‐muscone. 相似文献
45.
Several reactions of the α,β‐unsaturated thioamide 8 with diazo compounds 1a – 1d were investigated. The reactions with CH2N2 ( 1a ), diazocyclohexane ( 1b ), and phenyldiazomethane ( 1c ) proceeded via a 1,3‐dipolar cycloaddition of the diazo dipole at the C?C bond to give the corresponding 4,5‐dihydro‐1H‐pyrazole‐3‐carbothioamides 12a – 12c , i.e., the regioisomer which arose from the bond formation between the N‐terminus of the diazo compound and the C(α)‐atom of 8 . In the reaction of 1a with 8 , the initially formed cycloadduct, the 4,5‐dihydro‐3H‐pyrazole‐3‐carbothioamide 11a , was obtained after a short reaction time. In the case of 1c , two tautomers 12c and 12c ′ were formed, which, by derivatization with 2‐chlorobenzoyl chloride 14 , led to the crystalline products 15 and 15 ′. Their structures were established by X‐ray crystallography. From the reaction of 8 and ethyl diazoacetate ( 1d ), the opposite regioisomer 13 was formed. The monosubstituted thioamide 16 reacted with 1a to give the unstable 4,5‐dihydro‐1H‐pyrazole‐3‐carbothioamide 17 . 相似文献
46.
47.
Prof. Dr. Steven Stevenson Amanda J. Rothgeb Katelyn R. Tepper Prof. Dr. James Duchamp Prof. Dr. Harry C. Dorn Xian B. Powers Mrittika Roy Prof. Dr. Marilyn M. Olmstead Prof. Dr. Alan L. Balch 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(54):12545-12551
Purified samples of Ho3N@C2(22010)-C78 and Tb3N@C2(22010)-C78 have been isolated by two distinct processes from the rich array of fullerenes and endohedral fullerenes present in carbon soot from graphite rods doped with Ho2O3 or Tb4O7. Crystallographic analysis of the endohedral fullerenes as cocrystals with Ni(OEP) (in which OEP is the dianion of octaethylporphyrin) shows that both molecules contain the chiral C2(22010)-C78 cage. This cage does not obey the isolated pentagon rule (IPR) but has two sites where two pentagons share a common C−C bond. These pentalene units bind two of the metal ions, whereas the third metal resides near a hexagon of the cage. Inside the cages, the Ho3N or Tb3N unit is planar. Ho3N@C2(22010)-C78 and Tb3N@C2(22010)-C78 use the same cage previously found for Gd3N@C2(22010)-C78 rather than the IPR-obeying cage found in Sc3N@D3h-C78. 相似文献
48.
49.
《Journal of Coordination Chemistry》2012,65(17):1891-1904
The triethylammonium dicarboxylatotriorganostannates, [(C2H5)3NH][R3Sn(3,5-pdc)]?·?mH2O (3,5-pdc?=?3,5-pyridinedicarboxylate) (m?=?1, R?=?Me 1; m?=?0, R?=?Ph 2, PhCH2 3, n-Bu 4), [(C2H5)3NH][R3Sn(5-nip)] (5-nip?=?5-nitroisophthalate) (R?=?Me 5, Ph 6, PhCH2 7, n-Bu 8) have been prepared from triethylamine, 3,5-pyridinedicarboxylic acid, 5-nitroisophthalic acid and triorganotin chloride. Complexes 1–8 have been characterized by elemental, IR, 1H, 13C and 119Sn NMR analyses. Complexes 1, 2, 5 and 6 are also determined by single crystal X-ray diffraction. For 1, 2, 5 and 6, each carboxylate moiety is involved in coordination to a tin center via only one O atom showing that the Sn atoms are five-coordinate and exist in trigonal bipyramidal geometries. Moreover, for 2, 5 and 6, the nitrogen atoms of ammonium are hydrogen bonded to the pendant carboxyl oxygen. In 1, adjacent polymeric chains and triethylammonium are linked by hydrogen bonds through the co-crystallized water molecule, thus a 2D network is formed. 相似文献
50.