2-Pyridyl pyrrolidines

The carbonylation of the sp3 C-H bond adjacent to a nitrogen atom is also possible by means of chelation-assisted C-H bond activation.121 The carbonylation reaction of A-(2-pyridyl)pyrrolidine occurs at the a-position of the pyrrolidine ring by using [RhCl(cod)]2 as a catalyst and 2-propanol as a solvent. Cyclic amines exhibit a high reactivity (up to 84%) (Equation (93)), while acyclic amines show relatively low reactivity (18%). The use of Ru3(CO)i2 as a catalyst does not result in a carbonylation reaction, but instead the addition of the sp3 C-H bond across the olefin bond to give an alkylation product, as mentioned before (Section 10.05.4). 

L-Proline (S)-3-(2-Pyridyl)pyrrolidine (5)-3-(2-Pyridyl)piperidine (S)-3-(2-Pyridyl)tetrazole... 

Scheme 7 Ru3(CO)i2-catalysed a-aUcylation of iV-(2-pyridyl)pyrrolidine with alkenes...

Methyl-2-(3-pyridyl)pyrrolidine, nl 9 Methyl pyruvate, m3 5 5 Methyl stearate, m346... 

We now consider 7V-methyl-2-(3-pyridyl)pyrrolidine (7), also known as the alkaloid nicotine. Parallelling our discussion of coniine, we find in Kharasch and Domalski the nearly century-old enthalpy of formation for the liquid of 39 kJmol-1. Is this value plausible With (liquid, tert/R, R1, R2) necessary to transform a tertiary amine into the corresponding hydrocarbon24, we would conclude that the enthalpy of formation of liquid l-methyl-2-(3-pyridyl)cyclopentane (8, R = 3-Py) is ca —50 kJmol-1. To estimate the last datum in another way, we assume that equation 10 is essentially thermoneutral. 

I-Methyl-2-(3-Pyridyl) Pyrrolidine 3-( 1 -Methyl-2-Pyrrolidyl) Pyridine Nicotine... 

Nicotinoids. Nicotine from tobacco was one of the earliest insecticides and was recommended for use in 1763 as a tea for the destruction of aphids (1,20). Nicotine [54-11 -3], L-l-methyl-2-(3 -pyridyl)pyrrolidine (1) (bp 247°C, d 1.009), is found in the leaves of Nicotiana tobacum and N. rustica (Solanaceae) in amounts ranging from 2 to 14%, and also is found in Duboisia hopwoodii and in Aesclepias syriaca. It occurs as the principal alkaloid along with small amounts of 12 other alkaloids of which nomicotine [494-97-3], 2-(3,-pyridyl)pyrrolidine (2) (bp 270°C, d 1.07 g/mL), and anabasine [494-52-0], l-2-(3 -pyridyl)piperidiae (3) (bp 281°C, d 1.048), are of insecticidal importance (see Alkaloids). Nomicotine occurs as both the D and L forms, the former in D. hopn oodii and the latter commonly predominating in Nicotiana. Anabasine is the chief alkaloid of Anabasis aphylla, where it occurs from 1—2% in the shoots and is found to ca 1% in Nicotianaglauca. 

SYNS NICOTINE, I -NITROSO-l -DEMETHYL- 1 -NITROSO-l -DEMETHYLNICOTINE l-NITROSO-2-(3-PYRIDYL)PYRROLIDINE 3-(l-NITROSO-2-PYRRO-UDINYL)PYRIDINE PYRIDINE, 3-(l-NITROSO-2-PYRROLIDINYL)-, (S)-... 

METHYL PYRIDYL KETONE see ABIOOO METHYL-3-PYRIDYL KETONE see ABIOOO METHYL-P-PYRIDYL KETONE see ABIOOO l-METHYL-2-(3-PYRIDYL)PYRROLIDINE see NDNOOO... 

Nicotine. 3-tl-Methyl-2-pyrrolidinyl)pyridine 1 -methyl -2-(3 -pyridyl)pyrrolidine -pyridy] -a -N-methyl -pyrrolidine C1 HltNt mol wt 162.23. C 74.03%, H 8,70% N 17,27% From the dried leaves of Nieotiami tabacum and N. rustica where it occurs to the extent of 2 to 8%, combined with citric and malic acids. Commercial nico -tine is entirely a byproduct o the tobecco industry. Extraction procedure Gattermann, Wieland, Laboratory Methods of Organic Chemistry (New York, 24th ed-, 1937) Schwyzer,... 

OTHER names r(S)-3-(i-methyl-2-pyr-rolidinyDpyridine l-methyl-2-(3-pyridyl)-pyrrolidine... 

SYNONYMS black leaf, l-methyl-2-(3-pyridyl)pyrrolidine, 3-( I-methyl-2-... 

Nicotine, l-methyl-2 (3-pyridyl) pyrrolidine, is found in tobacco derived from Nicotiana tabacum and other plants of the Solanaceae, including the Australian pituri (Duboisia hopwoodii), whose properties were exploited by the indigenous Australians of the central desert... 

Subgenus (according to Goodspeed 1954, not mono-phyletic, see text) Section Species Pyridyl-pyrrolidines Pyridyl- piperidines ... 

Cl7H22Br2N2, (3S,5R)-2,2-Dimethy1-5-pheny1-3-(4-pyridyl)pyrrolidine dihydrobromide, 46B, 215... 

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