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Handbook of Solvents - George Wypych - ChemTech - Ventech!

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13.3 Effects <strong>of</strong> organic solvents on phase-transfer catalysis 817<br />

(E) Oxidation by dimethyl polyethylene glycol and oxidant<br />

Dimethyl polyethylene glycol solubilizes potassium permanganate in benzene or dichloromethane<br />

and can thus be used as a phase-transfer agent for permanganate oxidation.<br />

The reaction is highly dependent on the organic solvent. If benzene is used as solvent,<br />

dimethyl polyethylene glycol does not efficiently extract KMnO 4 from an aqueous solution,<br />

but it solubilizes the solid reagent when CH 2Cl 2 is used as the solvent, KMnO 4 may be transferred<br />

from either aqueous solution or from the solid phase. The effect <strong>of</strong> organic solvent on<br />

the distribution <strong>of</strong> products is given in Table 13.3.14. 58<br />

Table 13.3.14. Oxidation <strong>of</strong> cyclododecene<br />

Solvent system<br />

Oxidation<br />

ratio a<br />

Phase transfer<br />

agent<br />

Products (%)<br />

Benzene+17% acetic acid 3.3 Polyether b 1,2-Cyclododecanedione (16), dodecanedioic<br />

acid (59), cyclododecane (23)<br />

Benzene+17% acetic acid 3.3 Crown ether c 1,2-Cyclododecanedione (22), dodecanedioic<br />

acid (56), cyclododecane (12)<br />

Benzene+17% acetic acid 3.3 Adogen 464<br />

Dichloromethane+17%<br />

acetic acid<br />

Dichloromethane+17%<br />

acetic acid<br />

Dichloromethane+17%<br />

acetic acid<br />

Dichloromethane+17%<br />

acetic acid<br />

Dichloromethane+17%<br />

acetic acid<br />

Dichloromethane+17%<br />

acetic acid<br />

Dichloromethane+10%<br />

acetic acid<br />

Dichloromethane/water<br />

+10% acetic acid<br />

Dichloromethane/aqueous<br />

NaOH<br />

3.3 Polyether<br />

3.3 Crown ether<br />

3.3 Adogen 464<br />

2.2 Adogen<br />

1.6 Agogen 464<br />

2.2 Adogen 464<br />

2.2 Adogen 464<br />

2.2 Polyether<br />

1.0<br />

Benzyl triethyl<br />

ammonium chloride<br />

1,2-Cyclododecanedione (8), dodecanedioic<br />

acid (58), cyclododecane (9)<br />

1,2-Cyclododecanedione (8), dodecanedioic<br />

acid (77), cyclododecane (1)<br />

1,2-Cyclododecanedione (7), dodecanedioic<br />

acid (83), cyclododecene<br />

1,2-Cyclododecanedione (7), dodecanedioic<br />

acid (83), cyclododecene (2)<br />

1,2-Cyclododecanedione (18), dodecanedioic<br />

acid (63), 2-hydroxycyclododecanone (6)<br />

1,2-Cyclododecanedione (14), dodecanedioic<br />

acid (40), 2-hydroxycyclododecanone (6),<br />

cyclododecene (23)<br />

1,2-Cyclododecanedione (19), dodecanedioic<br />

acid (27), 2-hydroxycyclododecone (7),<br />

cyclododecene (23)<br />

1,2-Cyclododecanedione (69), dodecanedioic<br />

acid (13), 2-hydroxycyclododecane (3),<br />

cyclododecene (9)<br />

1,2-Cyclododecanedione (16), dodecanedioic<br />

acid (82)<br />

1,2-Cyclododecanediol (50)<br />

Data obtained from Lee and Chang; 58 a number <strong>of</strong> moles <strong>of</strong> potassium permanganate per mole <strong>of</strong> alkene,<br />

b dimethylpolyethylene glycol, c dicyclohexano-18-crown-6 ether

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