Triethylamine → Thiomorpholinecarboxylic acid ethyl ester

HRID 23210Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 23210
[C:1]([N:8]1[CH2:13][CH2:12][S:11][CH2:10][CH:9]1C(O)=O)([O:3][C:4](C)(C)[CH3:5])=[O:2].Cl.C(OC(=O)[C@H](CS)N)C.C(N(CC)CC)C.BrC(Br)C>C1COCC1>[CH2:4]([O:3][C:1]([N:8]1[CH2:9][CH2:10][S:11][CH2:12][CH2:13]1)=[O:2])[CH3:5]

Komponenten

6

Edukt 4

HCID 8471TriethylamineHCID 112011,1-DibromoethaneHCID 2723617Ethyl cysteinate hydrochlorideHCID 27568314-(tert-Butoxycarbonyl)thiomorpholine-3-carboxylic acid

Produkt 1

HCID 53680559Thiomorpholinecarboxylic acid ethyl esterAusbeute 87 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

4-Boc-thiomorpholine-3-carboxylic acid can also be substituted for the compound of formula (XXIV) in Reaction Scheme 7 and can be prepared in the following manner: To THF was added cysteine ethyl ester hydrochloride (1.15 g, 6.18 mmol), triethylamine (4.17 mL, 30 mmol) and dibromoethane (2.51 mL, 6.2 mmol). After stirring for 1 hour and refluxing for 16 hours, the solids were removed by filtration. The solvent was removed in vacuo and the residue was chromatographed on silica to give thiomorpholinecarboxylic acid ethyl ester (0.94 g, 87%). The ester (15.3 g, 95 mmol) was dissolved in dioxane/water (1/1) and di-t-butyldicarbonate (24 g, 110 mmol) and LiOH were added. After stirring for 3 hours, the solvent was removed in vacuo and the pH was adjusted to 3 with KHSO3 and extracted with ethyl acetate. The organic layer was separated, washed with brine, dried (MgSO4), and the solvent was removed in vacuo to give 17.4 g (78%) 4-Boc-thiomorpholine-3-carboxylic acid: 1H NMR (CDCl3) δ 1.45 (m, 9), 2.45 (m, 1), 2.71 (m, 1). 2.93 (m, 1), 3.10 (m. 1), 3.29 (m, 1), 4.11 (m, 1), 4.19 (m, 1), 5.20 (m, 1).

Aufarbeitung

  1. customcan be prepared in the following manner
  2. temperaturerefluxing for 16 hours
  3. customthe solids were removed by filtration
  4. customThe solvent was removed in vacuo
  5. customthe residue was chromatographed on silica

Quellen und Nachweise

ORD-Eintrag
ord-a4039b47d4a5467a87ff25fb54707f59
Quelldatensatz
uspto-grants-2005_02
Patentnummer
US06849739B2

Notizen zur Reaktion

Wird geladen…