1H-NMR spectroscopy

Yet another complication in 1H NMR spectroscopy arises when a signal is split by two or more nonequivalent kinds of protons, as is the case with trans-cinnamaldehyde, isolated from oil of cinnamon (Figure 13.19). Although the n + l rule predicts splitting caused by equivalent protons, splittings caused by nonequivalent protons are more complex. 

The synthesis of 1 -benzothiepin 1 -oxide (23) can be achieved via complex formation with tricarbonyl iron, and quantitative oxidation of the coordination compound 22 with 3-chloroperoxy-benzoic acid. Subsequent irradiation at — 50 C provides 23, which crystallized as yellow needles after low-temperature (-40 C) chromatography, and was characterized by 1H NMR spectroscopy at — 30 C23 before loosing sulfur within one hour at 13°C to give naphthalene. 

Compound 6 crystallizes from cyclohexane as colorless needles which have no definite melting point there is a change of color to yellow at 128-134 C and the compound then melts sharply at 187-189 r C. When the colorless form is kept for a long time or recrystallized from pyridine or dimethyl sulfoxide it is changed into the yellow modification of mp 187-189 C recrystallization from cyclohexane reverses the process. It has been suggested that the yellow stable form has structure 6A and that the colorless metastable compound is the tautomer 2-methyl-l//-pyrido[2,3-6][l, 4]diazepin-4(5//)-one (6B). There is evidence from 1H NMR spectroscopy that the isomeric pyridodiazepin-2-one, yellow crystals, mp 195—197 " C, exists as an inseparable mixture of the tautomers 4-methyl-l//-pyrido[2,3-6][l,4]diazepin-2(3//)-one (7 A) and 4-methyl-l H-pyrido[2,3-6][l, 4Jdiazepin-2(5//)-one (7B) in the ratio 1 3. 

The synthesis and purification of cumyl alcohol (CumOH), p-dicumyl methyl ether (DCE)) and 2-chloro-2,4,4-trimethylpentane (TMPC1), and the sources and purification of methyl chloride (MeCl), methylcyclohexane (MCHx), isobutylene have been described [9, 10]. P-Pinene (P-PIN), (Aldrich), was chromatographed over alumina (activity I, Fisher), and freshly distilled over CaH2 under nitrogen according to 1H-NMR spectroscopy and GC analysis the purity was >99%. 2,6-Di-/er/-butylpyridine (DtBP), (Aldrich), anhydrous A,A-dimethylacetamid (DMA), (Aldrich), ethylaluminum dichloride (EtAlCl2), 1.0 M solution in hexanes (Aldrich), and methanol (Fisher) were used as received. 

Magnesium-hydroxyl interactions have been used in the same way with a p-hydroquinone unit attached at the meso position of a magnesium porphyrin (103). Again, the evidence for oligomerization comes from 1H NMR spectroscopy, and the results can equally be interpreted as dimerization rather than polymerization. 

The synthesis of /ac-L3, L = PT = 2, mercaptopyridine-1-oxide (230), 3Me-PT, and 4Me-PT, and their characterization by UV-vis, IR, 1H NMR spectroscopy, has been reported.400 The ligand FlS-CH2-CH(OH)-CF[2-OH, HL, binds to Ir111 in a bidentate manner, coordinating through the S atom and the primary alcohol O atom to form IrL3.401... 

The molecular conformation of trans- [(tBu)2PPh]2Ir(CO)Cl has been investigated by 31P 1H NMR spectroscopy and reveals four diastereoisomers two major conformations in which the phenyl groups are mutually anti and orientated on the same side or opposite sides of the coordination plane, and two minor isomers in which the two phenyl groups are syn to the CO ligand.557... 

Englert, G. and Vecci, M. 1980. Trans/cis isomerization of astaxanthin diacetate/isolation by HPLC and identification by 1H-NMR spectroscopy of three mono-civ- and six di-civ-isomers. Helv. Chim. Acta 63 1711-1717. 

The complex OsH(OH)(CO)(P Pr3)2 also reacts with methyl acrylate, methyl vinyl ketone, and allyl alcohol.91 Reaction with methyl acrylate leads to OsH(OH) (COXrf-CH2=CHC02MeXP Pr3)2 containing the olefin trans to the hydride ligand. In solution, this complex releases the olefin to generate the starting complex. The thermodynamic magnitudes involved in the equilibrium have been determined in toluene-t/a by 31P 1H NMR spectroscopy. The values reported are AH° = 17.0 0.5 kcal-mor1 and AS° = 54.0 1.2 cal-K 1-mol 1. In the presence of the methyl vinyl ketone complex OsH(OH)(CO)(P Pr3)2 affords 0sH CHCHC(0) Me (CO)(P Pr3)2 and water, whereas in the presence of allyl alcohol the loss of... 

In order to more accurately identify the contaminant, and to determine if the fuel delivery system module filter was the source, both materials were analyzed using 1H NMR spectroscopy Samples were dissolved in a 60 40 mixture of deuterated chloroform/triflouroethanol. It should be noted that the amount of contaminant available for analysis was quite small, so for this sample, the NMR spectral acquisition time was set to 1 h in order to record a spectrum of adequate signal-to-noise ratio. 

Fox et al.101-103 have studied the structure of Ni(II) complexes being derivatives of frans-l,2-diaminocyclohexane, using 1H NMR spectroscopy. Chemical shift differences (A<5) between di-Schiff base and its nickel (II) complexes observed for aromatic protons were attributed to the ring currents [40]. 

Reactivity ratios for 1-hexene (M ) with 5-methyl-1,4-hexadiene CM2) copolymerization at 30 c in hexane solvent using a Et2AlCl/6-TiCl3 AA catalyst system (Al/Ti atomic ratio s 1.5) were determined. The compositions of copolymers were measured by 300 MHz 1H-NMR spectroscopy. The reactivity ratios, calculated by the Tidwell-Mortimer method, were 1.1 + 0.2 for each of the two monomers. 

Evidence was shown for migration of an alkyl group in carbonyl insertion, and deinsertion steps between the methyl carbonyl rhodium complex [ r/Vi/ -Indenyl-l -(CH2)3PPh2 Rh(CO)-Me](BF4) and the acetyl rhodium complex [ r/5 r/l-(Indenyl-l -(Cl I2)3PPh2) RhI(COMe)] by crystallography as well as by 1H NMR spectroscopy.28... 

Two equiv. of 6,6-di(cyclopropyl)fulvene react at 60 °C over a period of a week with Ca[N(SiMe3)2]2-(THF)2 bis in THF to yield the metallocene 170. The heteroleptic amido complex 171 is detected as an intermediate with 111 and 13C 1H NMR spectroscopy. A 1 1 reaction of the calcium amide and 170 also produces 171 in solution, an equilibrium involving these three derivatives exists (Equation (30)). The calcocene 170 crystallizes at — 20 °C from THF as colorless cuboids. The metal center is surrounded by the four ligands in a distorted tetrahedral manner, and the cyclopentadienyl group and the propylidene fragment are coplanar with each other.393... 

Gotoh, Y., Tsukada, M., and Minoura, N. (1993) Chemical modification of silk fibroin with cyanuric chloride-activated polyethylene glycol Analysis of reaction site by 1H-NMR spectroscopy and conformation of the conjugates. Bioconjugate Cbem. 4, 554-559. 

In our hands, this gave as principal product on reaction with pyridine the complex [PtCl2(py) CHD=C(Me)CDMe2 ] and not the product shown in equation (3). This reaction is complicated by a side reaction apparently involving 8-elimination from one of the methyl substituents, but an analysis similar to that described above by H, 13C 1H and 2H 1H NMR spectroscopy showed that the major product was formed by the a-elimination pathway (15). 

Nuclear magnetic resonance spectroscopy for /V-acyloxy-/V-alkoxyamides 13C NMR spectroscopy, 56-58 15N NMR spectroscopy, 58-59 dynamic 1H NMR spectroscopy, 59 Nucleophilic substitution (SN2) reactions, /V-acyloxy-/V-alkoxyamidcs, 70-90 alcoholysis reactions, 89-90 with aromatic amines, HERON reactions, 70-74... 

---