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Sodium Chloride → 2-(2,2-Difluoro-6-methoxybenzo[d][1,3]dioxol-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

HRID 1746055
Notes
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Reaction equation

HRID 1746055 reaction equation
[F:1][C:2]1([F:14])[O:6][C:5]2[CH:7]=[C:8]([O:12][CH3:13])[C:9](I)=[CH:10][C:4]=2[O:3]1.[Cl-].[Li+].C([Mg+])(C)C.[Cl-].C(O[B:26]1[O:30][C:29]([CH3:32])([CH3:31])[C:28]([CH3:34])([CH3:33])[O:27]1)(C)C.[NH4+].[Cl-].[Na+].[Cl-]>O1CCCC1.C(OCC)(=O)C>[F:1][C:2]1([F:14])[O:6][C:5]2[CH:7]=[C:8]([O:12][CH3:13])[C:9]([B:26]3[O:30][C:29]([CH3:32])([CH3:31])[C:28]([CH3:34])([CH3:33])[O:27]3)=[CH:10][C:4]=2[O:3]1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

8

Reactant 5

HCID 5234Sodium ChlorideHCID 25517Ammonium ChlorideHCID 50177412-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 904149712,2-Difluoro-5-iodo-6-methoxybenzo[d][1,3]dioxoleHCID 178461732HCID 178461732, compound

Product 1

HCID 90413372
2-(2,2-Difluoro-6-methoxybenzo[d][1,3]dioxol-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
2.5 °C

Procedure

2,2-Difluoro-5-iodo-6-methoxybenzo[d][1,3]dioxole (1.6 g, 5.0 mmol) was dissolved in dry tetrahydrofuran (15 mL), cooled to 0-5° C. and treated in portions with isopropylmagnesium lithium chloride (1.3 M; 4.1 mL, 5.3 mmol). After 50 min, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.0 g, 5.4 mmol) was added and stirring was continued for 40 min at 15-20° C. The mixture was treated with saturated NH4Cl (10 mL) and then mixed with saturated NaCl (10 mL) and ethyl acetate (20 mL). The organic phase was washed with saturated NaCl (10 mL), dried (Na2SO4) and evaporated to give title compound as a thick oil which was used without further purification (1.4 g, 89%): 1H NMR (400 MHz, CDCl3) δ 7.35 (s, 1H), 6.65 (s, 1H), 3.81 (s, 3H), 1.34 (s, 12H); 19F NMR (376 MHz, CDCl3) δ −50.17 (s); EIMS m/z 314.

Workup

  1. waitwas continued for 40 min at 15-20° C
  2. washThe organic phase was washed with saturated NaCl (10 mL)
  3. dry with materialdried (Na2SO4)
  4. customevaporated

Sources & evidence

ORD record
ord-874d5c44b6ca438b95ba84a71dbf649b
Source dataset
uspto-grants-2015_10
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US09149038B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes