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Ethyl chloroformate → Tris(8-ethoxycarbonyl-2,2,6,6-tetramethylbenzo[1,2-d:4,5-d']-bis(1,3)dioxole-4-yl)methane

HRID 1450033
Notes
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Reaction equation

HRID 1450033 reaction equation
[CH3:1][C:2]1([CH3:49])[O:6][C:5]2[C:7]([CH:16]([C:33]3[C:43]4[O:44][C:45]([CH3:48])([CH3:47])[O:46][C:42]=4[CH:41]=[C:35]4[O:36][C:37]([CH3:40])([CH3:39])[O:38][C:34]=34)[C:17]3[C:27]4[O:28][C:29]([CH3:32])([CH3:31])[O:30][C:26]=4[CH:25]=[C:19]4[O:20][C:21]([CH3:24])([CH3:23])[O:22][C:18]=34)=[C:8]3[O:12][C:11]([CH3:14])([CH3:13])[O:10][C:9]3=[CH:15][C:4]=2[O:3]1.[Li]CC[CH2:53][CH3:54].[CH2:55]([O:57][C:58](Cl)=[O:59])[CH3:56]>C1COCC1>[CH2:55]([O:57][C:58]([C:41]1[C:35]2[O:36][C:37]([CH3:40])([CH3:39])[O:38][C:34]=2[C:33]([CH:16]([C:17]2[C:18]3[O:22][C:21]([CH3:23])([CH3:24])[O:20][C:19]=3[C:25]([C:11]([O:12][CH2:53][CH3:54])=[O:10])=[C:26]3[O:30][C:29]([CH3:31])([CH3:32])[O:28][C:27]=23)[C:7]2[C:5]3[O:6][C:2]([CH3:49])([CH3:1])[O:3][C:4]=3[C:15]([C:2]([O:3][CH2:4][CH3:5])=[O:6])=[C:9]3[O:10][C:11]([CH3:13])([CH3:14])[O:12][C:8]=23)=[C:43]2[C:42]=1[O:46][C:45]([CH3:48])([CH3:47])[O:44]2)=[O:59])[CH3:56]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 3

HCID 10928Ethyl chloroformateHCID 67729115Tris(2,2,6,6-tetramethyl-benzo[1,2-d:4,5-d']bis(1,3)-dioxole-4-yl)methaneHCID 178418339Butyllithium

Product 1

HCID 18943071Tris(8-ethoxycarbonyl-2,2,6,6-tetramethylbenzo[1,2-d:4,5-d']-bis(1,3)dioxole-4-yl)methaneYield 45.9%

Reagents, catalysts & solvents 1

HCID 8028
Tetrahydrofuran
Solvent
2×

Conditions

Temperature
-60 °C

Procedure

Tris(2,2,6,6-tetramethylbenzo[1,2-d:4,5-d']-bis(1,3)dioxole-4-yl)methane (1.35 g, 2.0 mmol (Example 17)) was dissolved in dry THF (400 mL) under N2, and the temp was lowered to -40° C. and n-BuLi (4.86 mL, 12.2 mmol) was added and the temperature was allowed to rise gradually to 0° C. The mixture was cooled to -60° C., and a solution of ethylchloroformate (4.0, 36.7 mmol) in THF (50 mL) was added. The reaction mixture was left overnight and worked up as described under Example 20 above. The chromatography gave (0.41 g, 24%) of tris(8-ethoxycarbonyl-2,2,6,6-tetramethylbenzo[1,2-d:4,5-d']-bis(1,3)dioxole-4-yl)methane.

Workup

  1. customwas lowered to -40° C.
  2. customto rise gradually to 0° C

Sources & evidence

ORD record
ord-be38ea3e18514244bceb92572c0a3ef8
Source dataset
uspto-grants-1997_02
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US05599522

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes