NICOTINE .......FRIEND FOR ORGANIC SPECTROSCOPY

NICOTINE
(-)-NICOTINE is classified as super toxic. Probable oral lethal dose in humans is less than 5 mg/kg or a taste (less than 7 drops) for a 70 kg (150 lbs.) person. It may be assumed that ingestion of 40-60 mg of nicotine is lethal to humans. There is fundamental difference between acute toxicity from use of nicotine as insecticide or from ingestion, and chronic toxicity that may be caused by prolonged exposure to small doses as occurs in smoking. Maternal smoking during pregnancy is associated with increased risk of spontaneous abortion, low birth weight and still-birth. Nicotine was found as a co-carcinogen in animals.

An alkaloid produced from tobacco. Colorless, oily liquid, combustible, highly toxic. When heated to decomposition (-)-NICOTINE(54-11-5) emits very toxic fumes of carbon monoxide and oxides of nitrogen [Lewis, 3rd ed., 1993, p. 919].

Properties of Nicotine  

Formula	C10H14N2
Molecular Weight	162,234 g.mol-1
Melting point	-7,9 ° C
Boiling point	247 ° C
Rotatory index (S)	aD = -168    at 20° C
Density	d=1,010
Refractive index	n=1,530
Comments	Pale yellow to dark brown liquid with a slight, fishy odor when warm.     Insecticide.

1D 1H(+/-) Nicotine





2D [1H,1H]-TOCSY(+/-) Nicotine



1D 13C(+/-) Nicotine



1D DEPT90(+/-) Nicotine




1D DEPT135(+/-) Nicotine






2D [1H,13C]-HSQC(+/-) Nicotine

IR analysis

On this spectrum, we can notice several peaks, which characterise the different chemical functions of nicotine: 

·    Around 3400 cm^-1, we can see the large peak of water (it deals with a liquid film).
·    Between 2970 and 2780 cm^-1 : C-H stretching.
·    The peak at 1677 cm^-1 : aromatic C=N double bond stretching.
·    The peak at 1691 cm^-1 : aromatic C=C double bond stretching.
·    The peaks at 717 cm^-1 and 904 cm^-1 correspond to the out of plane bending of the C-H bond of the monosubstituted pyridinic cycle.

Mass spectrum analysis

We can notice the molecular peak at 162 m/z. However, the biggest peak is at 84 m/z. It corresponds to the fragmentation of nicotine. It deals with the pyrrolidine cycle, which has this molecular weight. During the electronic bombardment, the nicotine was split between the two cycles. 

¹H-RMN analysis in CDCl₃ (400MHz)

Assignment	Chemical shift (ppm)
A	8,543
B	8,487
C	7,711
D	7,255
E	3,237
F	3,087
G	2,307
J	2,200
K	2,160
L	1,958
M	1,820
N	1,725
Done with C-H   COSY

¹³C-RMN analysis in CDCl₃

Assignment	Chemical shift (ppm)	Integration
1	149,45	750
2	148,51	783
3	138,80	517
4	134,86	917
5	123,54	894
6	68,83	1000
7	56,96	844
8	40,32	783
9	35,23	833
10	22,60	839

L-Nicotine

CAS:54-11-5

Nicotine biosynthesis

ANETHOLE

Anethole (Synonym Anise camphor, Monasirup)

1-Methoxy-4-(1-propenyl)-benzene
Formula:	C10H12O
CAS#:	104-46-1
MW:	148.2

1-methoxy-4-propenylbenzene
4-propenylanisole
1-methoxy-4-[(E)-prop-1-enyl]benzene
1-methoxy-4-[(E)-prop-1-enyl]benzol
1-méthoxy-4-[(E)-prop-1-enyl]benzène
1-メトキシ-4-[(E)-プロプ-1-エニル]ベンゼン

Melting Point: 23 ºC
Boiling Point: 234-237 ºC

Density: 0.9875 g/mL
Refractive Index: 1.5610

It has a monohydric phenolic ether function.

Occurrence It is the chief constituent of anise (anise fruit, aniseed) i.e., the dried ripe fruits of Pimpinella anisum Linn' (Family: Umbelliferae); star anise (star anise fruit, Chinese anise i.e., the dried ripe fruits of Illicium verum Hoop (Family: Magnoliaceae); and fennel (fennel fruits finnocchio), i.e., the dried ripe fruits of Foeniculum vulgare Mill (Family: Apiaceae). It is also found in Ocimum basilicum L. (Family: Lamiaceae)-Sweet Basil, Garden Basil; Pinus elliottii Engelm. (Family: Abiataceae)-Slash Pine; Sassafras albidum (Nutt.) Nees (Family: Lauraceae)-sassafras; and Syzygium aromaticum (L.) Merr & Perry (Family: Myrtaceae)-cloves, clavos.

Isolation It may be isolated from the volatile oils by first subjecting the oil to fractionation and then cooling the corresponding fraction to a very low temperature and recrystallization. However, it may also be obtained directly from the anethole-rich oils, such as: oil of anise, oil of fennel by simply chilling it to – 30°C in a deep freezer. Commercially, anethole may be synthesized in its purest form from anisole as shown below:

Anisole on reacting with propionaldehyde in the presence of HCl and H₃PO₄ yields an intermediate anisole-p-(1-chloropropane) which finally with pyridine yields anethole.

Characteristic Features It exists in two isomeric forms namely: trans-and cis-isomer, having physical parameters as stated below:

It is a white crystalline substance with an intense sweet odour. It possesses a characteristic taste similar to anise fruit. It is practically soluble in most organic solvents but insoluble in water.

Formation of ‘Photoanethole’ (or p, p′-dimethoxystilbene) Anethole on exposure to air (oxygen), light or heat undergoes structural modifications to yield photoanethole which is a viscid yellow coloured mass having a disagreeable taste and odour with a poor solubility in solvents. Perhaps the conversion of anethole to photoanethole lakes place via the formation of anisaldehyde as given below:

Identification

1. Anethole undergoes oxidation with K₂Cr₂O₇ in two steps; first step-yields anisaldehyde (paramethoxy benzaldehyde), and second step-gives rise to para-methoxy benzoic acid (mp 184°C) as depicted below:

2. It gets condensed with maleic anhydride to yield a condensation product having mp 310°C as shown below:

3. It gives rise to the formation of nitroso derivative having mp 126°C.

Uses

1. It is used as a flavouring agent in perfumery particularly for soap and dentifrices.

2. It is also employed as a pharmaceutical and (flavour).

3. It finds its application as an imbedding material in microscopy.

4. It is employed as a flavouring agent in alcholic, non-aleoholic beverages and confectionaries.

5. It is used as a sensitizer in bleaching colours in colour photography.

Anethole, C10H12O, a major constituent of the oil of anise, has the 1H NMR spectrum shown.


1H NMR




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13C NMR

OXYGEN ATTACHED CARBON IS UPFIELD AT 158.7

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MS


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IR




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http://www.google.com/patents/EP0203386B1

• Example 2. Anethole, (4-Propenylanisol), is extracted from Fennel, or Foeniculum Vulgare Mill. 1 kg of grated Fennel is extracted with 3 l of 95% ethanol at room temperature for 24 hrs. Ethanol is recovered by distillation under reduced pressure from the ethanol extract and a residue containing crude anethole is dissolved in 1 l of distilled water. This aqueous soluton is distilled under reduced pressure whereby Fennel oil is distilled over with steam. Crude Fennel oil is separated from water and extracted with an equal volume of diethyl ether. The ether extract is distilled under reduced pressure thereby recovering the diethyl ether and a residue of Fennel oil respectively. Yield of this crude Fennel oil is about 5.5%.
• [0015]
  The resulting Fennel oil is fractionated with reflux on an oil bath. The fraction collected at a distilling temperature from 229-237°C is Anethol.
  

  overall yield:

  3.3%
  Anethole has the following chemical structure:
  

  

  Anethole has a light yellow color.

  specific gravity:

  at 25/25°C 0.983 - 0.987

  refractive index at 25°:

  1.588 - 1.561

  REFERENCES

  Seeman, J.I., Grassian, V.H., and Bernstein, E.R. 1988. J. Am. Chem. Soc. 110:8542-8543.

  Lange, G., and Schultze, W. 1992. Org. Mass Spectrom. 27:481-488.

  Vella, A.J. 1992. Org. Mass Spectrom. 27:145-150.

  Baxendale, I.R., Lee, A.-L., and Ley, S.V. 2002. A polymer-supported iridium catalyst for the stereoselective isomerisation of double bonds. Syn. Lett. 3:516-518.

  Polkanov, M.A., Shapiro, I.O., Chernoplekova, V.A., and Shatenshtein, A.I. 1988. J. Org. Chem. USSR (Engl. Transl.). 24:1123-1127. The Journal of Organic Chemistry, 50, p. 1797, 1985 DOI: 10.1021/jo00211a002 Tetrahedron, 24, p. 2183, 1968

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