Diethyl Ether → Cumyl dithiobenzoate

HRID 1760375

Reaction equation

HRID 1760375 reaction equation
[C:1]1([Mg]Br)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:9](=S)=S.[C:12]([SH:20])(=[S:19])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.C(O[CH2:24][CH3:25])C>O1CCCC1>[C:12]([S:20][C:24]([C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1)([CH3:25])[CH3:9])(=[S:19])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 6348Carbon DisulfideHCID 67141Benzenecarbodithioic acidHCID 178418255HCID 178418255, compound

Product 1

HCID 11065602Cumyl dithiobenzoate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

100 ml of a 3 M phenylmagnesium bromide solution in diethyl ether were added to 35 g of carbon disulfide in 150 ml of tetrahydrofuran (THF), while maintaining the temperature below 40° C. After one hour, the reaction was terminated by adding 50 ml of water. Ether and THF were removed by a rotary evaporator, after which the mixture obtained was transferred into a 500 ml separating funnel by adding 150 ml of water. 50 ml of heptane and 40 g of α-methylstyrene were added thereto, Concentrated aqueous hydrochloric acid was then added in portions, shaking vigorously each time. The addition of hydrochloric acid was continued until the aqueous layer was virtually colorless. The pH of the aqueous phase fell to a value of less than 7. The organic phase became deep violet, and this color is characteristic of the dithioester. The violet organic phase was separated from the aqueous phase. Volatile materials were removed from the mixture using a rotary evaporator. 93.5 g of a violet oil which contained dithiobenzoic acid were obtained. Dithiobenzoic acid contained in the oil was removed by extraction with 2% sodium hydroxide solution, after which 85 g of cumyl dithiobenzoate were obtained and may be used without further purification in RAFT polymerizations.

Workup

  1. temperaturewhile maintaining the temperature below 40° C
  2. customthe reaction was terminated
  3. additionby adding 50 ml of water
  4. customEther and THF were removed by a rotary evaporator
  5. customafter which the mixture obtained
  6. customseparating funnel
  7. additionby adding 150 ml of water
  8. addition50 ml of heptane and 40 g of α-methylstyrene were added
  9. additionConcentrated aqueous hydrochloric acid was then added in portions
  10. additionThe addition of hydrochloric acid
  11. customThe violet organic phase was separated from the aqueous phase
  12. customVolatile materials were removed from the mixture
  13. customa rotary evaporator
  14. customwere obtained
  15. customwas removed by extraction with 2% sodium hydroxide solution

Sources & evidence

ORD record
ord-b62bc54dfdd14292bec6793079cf4346
Source dataset
uspto-grants-2005_01
Patent number
US06841695B2

Linked notes

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