Thiophene → HCID 68972577, compound

HRID 854219Notes

Reaction equation

HRID 854219 reaction equation
[CH3:1][Si:2]1([CH3:12])[CH2:11]OC2C(=CSC=2)O[CH2:3]1.[CH3:13][O:14][C:15]([C:17]1[S:18][C:19]([C:24]([O:26][CH3:27])=[O:25])=[C:20]([OH:23])[C:21]=1[OH:22])=[O:16].S1C=CC=C1.OC([SiH](C)C)O.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCOC(/N=N/C(OCC)=O)=O>C1COCC1.O>[CH3:27][O:26][C:24]([C:19]1[S:18][C:17]([C:15]([O:14][CH3:13])=[O:16])=[C:21]2[C:20]=1[O:23][CH2:3][Si:2]([CH3:12])([CH3:11])[CH2:1][O:22]2)=[O:25]

Participants

9

Reactant 6

HCID 8030ThiopheneHCID 11776TriphenylphosphineHCID 350052Dimethyl 3,4-dihydroxythiophene-2,5-dicarboxylateHCID 5462977Diethyl azodicarboxylateHCID 69023724HCID 69023724, compoundHCID 123424012HCID 123424012, compound

Product 1

HCID 68972577HCID 68972577, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

A synthesis for 6,6-dimethy-6,7-dihydro-5H-4,8-dioxa-2-thia-6-sila-azulene, a silicon-containing EC monomer generally related to 3,4-alkylenedioxythiophene, is shown in FIG. 7. First, 3,4-Dihydroxy-thiophene-2,5-dicarboxylic acid dimethyl ester, the thiophene derivative labeled A7 in FIG. 7 (hereinafter referred to as compound A7) is synthesized from commercially available chemicals according to prior art techniques (see K. Zong, L. Madrigal, L. B. Groenendaal, R. Reynolds, Chem. Comm., 2498, 2002). Note that the same initial step is employed in the synthesis of FIG. 5. Then, a solution of compound A5, dihydroxylmethyldimethylsilane (labeled B7 in FIG. 7), PPh3 (labeled C7 in FIG. 7), and DEAD (labeled D7 in FIG. 7) is refluxed in THF for about 15-24 hours (preferably under an inert atmosphere). A small amount of water is then added to quench the reaction. The reaction mixture is evaporated to dryness. The resulting material is loaded into a silica gel column and eluded by hexane and dichloromethane (2:1, 1:1, volume ratio) to yield 6,6-Dimethyl-6,7-dihydro-5H-4,8-dioxa-2-thia-6-sila-azulene-1,3-dicarboxylic acid dimethyl ester, the silicon-containing thiophene derivative labeled E7 in FIG. 7 (hereinafter referred to as compound E7).

Workup

  1. additiona silicon-containing EC monomer
  2. customis synthesized from commercially available chemicals
  3. customis employed in the synthesis of FIG. 5
  4. customto quench
  5. customthe reaction
  6. customThe reaction mixture is evaporated to dryness

Sources & evidence

ORD record
ord-c6cde93695e14c72b3e17e04cc54ce63
Source dataset
uspto-grants-2007_08
Patent number
US07256923B2

Reaction notes

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