Carbon Dioxide → 2,2'-Dicyanato-3,3'-dimethoxy-5,5'-dimethyl-1,1'-biphenyl

HRID 531399

Reaction equation

HRID 531399 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[C:7]([CH3:9])[CH:6]=[C:5]([C:10]2[C:11]([OH:19])=[C:12]([O:17][CH3:18])[CH:13]=[C:14]([CH3:16])[CH:15]=2)[C:4]=1[OH:20].[N:21]#[C:22]Br.C(=O)=O.C[CH2:28][N:29](CC)CC>CCOCC.CC(C)=O.C1COCC1>[O:19]([C:11]1[C:12]([O:17][CH3:18])=[CH:13][C:14]([CH3:16])=[CH:15][C:10]=1[C:5]1[CH:6]=[C:7]([CH3:9])[CH:8]=[C:3]([O:2][CH3:1])[C:4]=1[O:20][C:22]#[N:21])[C:28]#[N:29]

Participants

8

Reactant 4

HCID 280Carbon DioxideHCID 8471TriethylamineHCID 10476Cyanogen BromideHCID 166971Dimethoxy di-p-cresol

Product 1

HCID 1213608052,2'-Dicyanato-3,3'-dimethoxy-5,5'-dimethyl-1,1'-biphenylYield 94%

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-40 °C

Procedure

A THF (30 mL) solution containing 1 (0.971 g, 3.5 mmol) and CNBr (1.032 g, 9.8 mmol) was placed in a dry ice and acetone bath at −40° C. Et3N (0.738 g, 7.30 mmol) was added and the solution was allowed to stir at −40° C. for 2 h under N2. The solution was diluted with ether (˜150 mL) and washed with water (2×200 mL), brine (50 mL), and then dried over MgSO4. Removal of the solvent under reduced pressure afforded 2 as an off-white powder (1.06 g, 94%). Further purification can be achieved by recrystallization from acetonitrile (0.96 g, 85%). 1H NMR (CDCl3) δ 6.91 (d, J=2 Hz, 2 H), 6.72 (d, J=2 Hz, 2H), 4.00 (s, 3H) 2.41 (s, 3H); 13C NMR (CDCl3) δ 150.1, 138.9, 137.8, 127.2, 123.1, 114.5, 110.2, 56.7, 21.7. Anal. Calcd for C18H16O4N2: C, 66.86; H, 4.97. Found: C, 65.77; H 5.09.

Workup

  1. washwashed with water (2×200 mL), brine (50 mL)
  2. dry with materialdried over MgSO4
  3. customRemoval of the solvent under reduced pressure

Sources & evidence

ORD record
ord-14abb20ed44e46268e1c81d21bcd94a9
Source dataset
uspto-grants-2016_05
Patent number
US09353219B1

Linked notes

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