Methyl (methylsulfinyl)methyl sulfide → Methyl 6-aminomethyl-10-methyl-phenothiazine-4-acetate hydrochloride

HRID 2395115Notes

Reaction equation

HRID 2395115 reaction equation
C(OC(OCC)C1C=CC=C2C=1SC1C(C=O)=CC=CC=1N2C)C.CSCS(C)=O.[ClH:31].C([N+](C)(C)C)C1C=CC=CC=1.C(C1C=CC=C2C=1SC1C(CC(OC)=O)=CC=CC=1N2C)=O.C([O-])(=O)C.[Na+].Cl.NO.[N:73](=[CH:75][C:76]1[CH:89]=[CH:88][CH:87]=[C:86]2[C:77]=1[S:78][C:79]1[C:80]([CH2:91][C:92]([O:94][CH3:95])=[O:93])=[CH:81][CH:82]=[CH:83][C:84]=1[N:85]2[CH3:90])O>O1CCCC1.CO.Cl.[Pd].O>[ClH:31].[NH2:73][CH2:75][C:76]1[CH:89]=[CH:88][CH:87]=[C:86]2[C:77]=1[S:78][C:79]1[C:80]([CH2:91][C:92]([O:94][CH3:95])=[O:93])=[CH:81][CH:82]=[CH:83][C:84]=1[N:85]2[CH3:90]

Participants

13

Reactant 7

HCID 99129Methyl (methylsulfinyl)methyl sulfideHCID 443297Hydroxyamine hydrochlorideHCID 517045Sodium AcetateHCID 561166Benzyltrimethylammonium hydrochlorideHCID 189724746-Diethoxymethyl-10-methylphenothiazine-4-carbaldehydeHCID 54246440Methyl 6-formyl-10-methyl-phenothiazine-4-acetateHCID 86753153Methyl 6-[(hydroximino)methyl]-10-methyl-phenothiazine-4-acetate

Product 1

HCID 67645243Methyl 6-aminomethyl-10-methyl-phenothiazine-4-acetate hydrochloride

Reagents, catalysts & solvents 5

HCID 23938PalladiumCatalystHCID 313Hydrochloric AcidSolventHCID 887MethanolSolvent3×HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 500 mg (1.46 mmol) of 6-diethoxymethyl-10-methyl-phenothiazine-4-carbaldehyde in 5 ml of tetrahydrofuran can be converted analogously to that described in Example 1.1.1.d with 0.22 g (1.75 mmol) of methyl (methylthiomethyl) sulphoxide, 0.14 ml of TRITON B (benzyltrimethylammonium hydrochloride) solution (35% in methanol) and hydrolysis into methyl 6-formyl-10-methyl-phenothiazine-4-acetate. This compound can be converted analogously to that described in Example 1.1.1.e in methanol, water and tetrahydrofuran using sodium acetate and hydroxylamine hydrochloride into methyl 6-[(hydroximino)methyl]-10-methyl-phenothiazine-4-acetate. This compound can be hydrogenated over palladium/charcoal in methanol and methanolic hydrochloric acid (20%) analogously to that described in Example 1.1.1.f, whereby there is obtained methyl 6-aminomethyl-10-methyl-phenothiazine-4-acetate hydrochloride which can be converted analogously to that described in Example 1.1.2 in dioxan and 1N sodium hydroxide solution using di-tert-butyl dicarbonate into methyl 6-[(1-tert-butylformamido)methyl]-10-methyl-phenothiazine-4-acetate. The product obtained can be hydrolyzed with 1N potassium hydroxide solution in methanol analogously to that described in Example 1.1.3 to give (6-tert-butoxycarbonyl-aminomethyl-10-methyl-phenothiazin-4-yl)-acetic acid prepared according to Example 2.1.1.g.

Sources & evidence

ORD record
ord-e4f48d2ed23846fa85f75a69d5cd20cf
Source dataset
uspto-grants-1998_09
Patent number
US05811389

Reaction notes

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