Methanamine, N-methoxy-, hydrochloride (1:1) → HCID 59380605, compound

HRID 2261424Notes

Reaction equation

HRID 2261424 reaction equation
Cl.[CH3:2][NH:3][O:4][CH3:5].[CH3:6][C:7]1([CH3:20])[C@@H:9]2[CH2:10][C:11]3[C:15]([C@H:8]12)=[C:14]([CH3:16])[S:13][C:12]=3[C:17](O)=[O:18].C(N(C(C)C)CC)(C)C.CCN=C=NCCCN(C)C.Cl>C(Cl)Cl.C(#N)C>[CH3:5][O:4][N:3]([CH3:2])[C:17]([C:12]1[S:13][C:14]([CH3:16])=[C:15]2[C:11]=1[CH2:10][C@H:9]1[C:7]([CH3:20])([CH3:6])[C@H:8]12)=[O:18]

Participants

7

Reactant 4

HCID 81138Methanamine, N-methoxy-, hydrochloride (1:1)HCID 81531DiisopropylethylamineHCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochlorideHCID 57892448(1aS,5aR)-1,1,2-trimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalene-4-carboxylic acid

Product 1

HCID 59380605HCID 59380605, compoundYield 55.8%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent2×

Procedure

A mixture of N,O-dimehtylhydroxylamine hydrochloride (158 mg, 1.62 mmol) and (1aS,5aR)-1,1,2-trimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalene-4-carboxylic acid (300 mg, 1.35 mmol) in DCM (30 mL) and acetonitrile (10 mL) is treated with diisopropylethylamine (209 mg, 1.62 mmol). To the resulting clear solution EDC.HCl (311 mg, 1.62 mmol) is added and the mixture is stirred at rt for 18 h before it is diluted with DCM (50 mL) and washed with 1 N aq. HCl (2×50 mL) and 1 N aq. NaOH (50 mL). The organic layer is dried over Na2SO4 and evaporated. The crude product is purified by prep. HPLC (Phenomenex AQUA 30×75 mm, gradient of 20-95% acetonitril in water containing 0.5% formic acid) to furnish (1aS,5aR)-1,1,2-trimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalene-4-carboxylic acid methoxy-methyl-amide (200 mg) as a pale yellow solid. LC-MS: tR=1.02 min, [M+1]+=266.04. 1H NMR (CDCl3): δ 3.75 (s, 3H), 3.29 (s, 3H), 3.12-3.01 (m, 1H), 2.93 (d, J=19.0 Hz, 1H), 2.38 (s, 3H), 1.90-1.82 (m, 2H), 1.12 (s, 3H), 0.71 (s, 3H).

Workup

  1. washwashed with 1 N aq. HCl (2×50 mL) and 1 N aq. NaOH (50 mL)
  2. dry with materialThe organic layer is dried over Na2SO4
  3. customevaporated
  4. customThe crude product is purified by prep

Sources & evidence

ORD record
ord-5da37b2b7a6a4e3887cfb3d54e258172
Source dataset
uspto-grants-2010_12
Patent number
US07846964B2

Reaction notes

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