AZIRINE

One of the simplest heterocyclic compound or azacyclo propene. It could have structure 1 or II
H 1 3 N 2 3 1 N 2 1-Azirine

2-Azirine

Azirine found natmaly as a part of some compound such as III and IV Which are used as an antibiotic and could be synthesis.
COOH Me H H N H COOMe Disidiaziridine

Azirinomycin

Which are used as an antibiotic and could be synthesis.

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Reactions:1. Methanol reacted by addition with 1- azririne to give 2- Methoxy azirine in presence of sodmethoxide as a catalyst.
H - + Me-OH N OMe R R N R

2.

3,3 dimethyl -2- phynyl -1- azirine react with sulphonic acid.
O3SH Me Me H Ph N O4SH4C6Me Me Me

N Ph

+
H3C

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3.

Reaction with acetic acid and acetic anhydride.

AC N R Me AC2O ACOH R OAC

n

NHAC R-CH-CO-Me

N Me

4.

Reaction with Grignard reagent.

H N Ph Ph

EtMgBr

Et Ph
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H Ph
3

Synthesis:1.From thermal analysis of Ethanyl azide which can be prepared from alkenes.
Br2 R-CH-CH2-Br Br - + N-N=N R-CH-CH2-Br N3
4

R-CH=CH2

NaN3

: N: N R-C-=CH2

NoOH -HBr R-C=CH2 -N2

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Oxirane
Oxirane or ethylene oxide (1) it was first obtain by wartz in 1859. in 1931 P taent was taken out on direct oxidation of ethylene to okirane by oxygen. Oxiranes found naturally in a plant, animal and insect. Orapetene (2) was oxirane separated from natural source. In general orxirane ring found as a part of structure of many compound specially prostalandine.

O
MeO O O

Some oxirane drevative use as an antibiotic and its effective in treatment of malignant toummer.

- It is colourless liquide misible with water

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Chemical properties:1. When oxirane heated its rearranged to aldehyde.

O O CH3-C H

2. Ring opening:The most important reaction of oxirane is the ring opening became its very important in organic synthesis.

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3. Nucleophillic reagent:-

It react with oxirane such as ammonia to give mono ethanolamine in excess of oxirane it give diethanol amine and triethanol amine.
a.. NH3
O

+ NH3-CH2-CH2-O

NH2-CH2-CH2-OH ethanolamine

NH(CH2CH2OH)2

N(CH2CH2OH)3 triethano lamine

b - With Grignard reagent it give alcohol

CH3CH2MgBr :

CH3CH2CH2CH2OMgBr

+ H

CH3CH2CH2CH2OH
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c with halogen in presence of ph3p or lix give B- halo alcohol

Ph3P I

+
O

I2

+ Ph3PI ICH2CH2O

H2O

ICH2CH2OH

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1.Reduction
Oxirane reduce to alcohol
O H2 / Pd

CH2CH2OH

O R

Sod,borohyd give mix true

RCH2CH2OH OH

RCH-CH3
OH LiALH4 O H3C LiALH4 ALCL3 H2 / Ni CH2-CH2-CH3 OH
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CH3-CH Sec-alcohol CH3 pri-alcohol

2. Electrophillic reactions:H R R1 O R2 R3 + H R R1 O R2 R3 OH + RR1-C-CR2R3 or RR1-C-CR2R3 OH OH O H3C Hcl CH3-C-CH2-CL major

CH3-CH-CH2OH CL

3. Polymarisation:+ H O H + O
n

OH O CH2-CH2 + O
O

polymer

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Synthesis:1. From B- Halo alcohol by elimination of hydrogen halide by base

OH O O CL

+
CL CL

2. Darzen reaction:halo ester with carbonyl compound in presence of sod. Ethoxide.

CL-CH2-COOEt O C R1 R2

NaOEt

CL-CH-COOEt O

EtOH

CH-COOEt CL

R1

C-CH-COOEt R2 CL

R1 R2

O COOEt

CL
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Thirane
It is known also as ethylene sulphide its highly strain ring less stable than oxirane. Substituted thirane more stable than un-substituted one. It is colourless liquid in sulible in water but dissolve in organic solvent, boil at 55Co

Chemical reactions:1. it react with ammonia to give drevative of B- aminothiol

S RNH2

+
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RNH-CH2-CH2-SH

12

2. Nucleophilic reagent always attack carbon atom but in thirane it attack carbon atom but in thirane it attack the sulphur atom leading to alkene formation.
S Me Me Bu SBuLi Me Me
n

Li

BuSLi

3. It react with sodium periodate to give thirane okide.

O S NaIO4 S CH2=CH2 S=O

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4. Reduction
Me-CH(SH)CH3 LiALH4 Me S HCL Me-CH(SH)CH2-CL major

+
Me-CHCl-CH2SH

This became the proton added to sulphur and carbonium ion formed.

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Synthesis:
-1CH2 CH2 SH OH 200 C Na2CO3 -H2O S

1. From chlorothiol cyclised by sod. Bicarbonate

CL OH HCL SH SH
n

SH

SH

2. From okirane when treated with pot. Thiocyanate.

NaNCS O S O C N
n

O C S

N
n

SH

NCO

O CN S

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Heterocyclic analogues of cyclobutane

Four membered ring are not highly strained as the corresponding three-membered rings. But are more difficult to prepare by the direct cyclisation of straight chain intermediate. The most important of four membered ring are Azetidine, oxetane and thietane.

O NH

Oxetanes:Synthesis
By cyclo addition of two double bond.
CH2 C O
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CH2 O

ZnCL2 10 C O O

Reaction
They are susceptible to acid catalyzed ring-opening reaction (like three membered ring analogues.
trace O

C2H5OH

H2SO4

C2H5-O-CH2CH2CH2OH

It react with nucleophilic reagent but are less reactive than the analogues three membered ring compounds.
- + C6H5CH2SNa H2O 100 / 6 hr C6H5CH2SCH2CH2CH2OH 3-benzyl thiopropane

Sod.salt of benzylthioalcohol

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Azetidine
Synthesis:Similar to oxetanes preparation
O Ph C C Ph CHPh N Ph Ph Ph N O

(Ph)3

C=C=O

.. Ph-HC=N-Ph

(ph)-C=C-O PH-HC=N-Ph +

Ph Ph Ph
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O N
18

Thietanes
Syntesis:By ring closure similar to azetidine

CL-CH2-CH2-CH2-CL

Na2S

C2H5OH S

1,3- dichloropropane

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