Hydrazine hydrate (1:1) → 4-Hydroxymethyl benzophenone hydrazone

HRID 40450Notes

Reaction equation

HRID 40450 reaction equation
[Br:1][CH2:2][C:3]1[CH:16]=[CH:15][C:6]([C:7]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)=[O:8])=[CH:5][CH:4]=1.[OH:17][CH2:18][C:19]1[CH:32]=[CH:31][C:22]([C:23]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=O)=[CH:21][CH:20]=1.O.[NH2:34][NH2:35]>C(O)C>[Br:1][CH2:2][C:3]1[CH:16]=[CH:15][C:6]([C:7]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)=[O:8])=[CH:5][CH:4]=1.[OH:17][CH2:18][C:19]1[CH:32]=[CH:31][C:22]([C:23](=[N:34][NH2:35])[C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=[CH:21][CH:20]=1

Participants

6

Reactant 3

HCID 24654Hydrazine hydrate (1:1)HCID 1229514-(Bromomethyl)benzophenoneHCID 13149642(4-(Hydroxymethyl)phenyl)(phenyl)methanone2×

Product 2

HCID 1229514-(Bromomethyl)benzophenoneHCID 722408194-Hydroxymethyl benzophenone hydrazoneYield 98%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

4-Bromomethyl benzophenone (2) was prepared as described in Reference Example 1. 4-Bromomethyl benzophenone (2) was converted into 4-Hydroxylmethyl benzophenone (3) as described in Reference Example 2. To solution of 3 (2.5 g, 12 mmol) in ethanol (20 ml) was added hydrazine hydrate (2.9 g 59 mmol). The mixture was heated to reflux for 24 h. then concentrated in vacuo. The residue was portioned between DCM and water and the organic layer collected and concentrated to yield 4 (2.6 g, 98%) a mixture of cis and trans isomers and as a yellow semi solid; δH (CDCl3) 2.84, 3.09 (2×bs, 1H, OH), 4.51, 4.61 (2×s, 2H, CH2OH), 5.32 (bs, 2H, NNH2), 7.13-7.17 (m, 4H, 3-, 3′-, 5-, 5′-H), 7.30-7.43 (m, 5H, 2-, 2′-, 4′-, 6-, 6′-H) ppm; δC (CDCl3) 64.4, 64.6 (2×CH2OH), 126.4, 126.6, 127.7, 128.0, 128.1, 128.6, 128.8, 128.9, 129.3 (Ar—C), 131.8, 132.7 (2×1′-C), 137.5, 138.2 (2×1-C), 141.0, 141.8 (2×4′-C), 149.2 (C═N) ppm; νmax (thin film) 3384, 2870, 1583, 1444, 1412, 1015 cm−1; found (ES) 227.1180, C14H15N2O requires 227.1179.

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux for 24 h.
  3. concentrationthen concentrated in vacuo
  4. customthe organic layer collected
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-44a0190a43174d7aaa6b5622451cb43c
Source dataset
uspto-grants-2013_09
Patent number
US08530212B2

Reaction notes

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