HomeMCPWorkbenchSkills
HomeWorkbenchNotificationsMe
llms.txt · MCP GuidePrivacy Policy · Terms of Service · Supportv1.8.0
  1. Home
  2. /Reaction

Chlorotrimethylsilane → 6-[4-(N-acetyl-4-hydroxy-L-prolylamino)phenyl]-1,2-dihydro-2-oxonicotinic acid

HRID 1106188
Notes
Print preview

Reaction equation

HRID 1106188 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[NH:9][C:10](=[O:17])[C:11](=[CH:15][CH:16]=2)[C:12]([OH:14])=[O:13])=[CH:4][CH:3]=1.C(N(CC)CC)C.Cl[Si](C)(C)C.[C:30]([N:33]1[CH2:40][CH:39]([OH:41])[CH2:38][C@H:34]1[C:35](O)=[O:36])(=[O:32])[CH3:31].CN1CCOCC1.ClC(OC)=O.O=C1N=CC=CC1C(O)=O>ClCCl.C(O)(=O)C.C(O)(C)C>[C:30]([N:33]1[CH2:40][CH:39]([OH:41])[CH2:38][C@H:34]1[C:35]([NH:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[NH:9][C:10](=[O:17])[C:11](=[CH:15][CH:16]=2)[C:12]([OH:14])=[O:13])=[CH:6][CH:7]=1)=[O:36])(=[O:32])[CH3:31]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

11

Reactant 7

HCID 6397ChlorotrimethylsilaneHCID 6586Methyl chloroformateHCID 79724-MethylmorpholineHCID 8471TriethylamineHCID 2729005(2S)-1-acetyl-4-hydroxypyrrolidine-2-carboxylic acidHCID 129189566-(4-Aminophenyl)-1,2-dihydro-2-oxonicotinic acid
HCID 21995586
2-Oxo-2,3-dihydropyridine-3-carboxylic acid

Product 1

HCID 130021066-[4-(N-acetyl-4-hydroxy-L-prolylamino)phenyl]-1,2-dihydro-2-oxonicotinic acidYield 75.1%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 3776IsopropanolSolventHCID 6344DichloromethaneSolvent2×

Procedure

A suspension of 40.0 g (0.173 mol) of 6-(4-aminophenyl)-1,2-dihydro-2-oxonicotinic acid, 72.1 ml (0.517 mol) of triethylamine, and 2800 ml of dichloromethane is stirred at room temperature and 67.8 ml (0.52 mol) of chlorotrimethylsilane is added. The mixture is stirred at room temperature until the solid is almost completely dissolved. A suspension of 63 g (0.362 mol) of N-acetyl-4-hydroxy-L-proline in 650 ml of dichloromethane is cooled to -10° to -15° and 41 ml (0.363 mol) of N-methylmorpholine is added followed by 28.3 ml (0.363 mol) of methyl chloroformate. The reaction is stirred at -15° to -10° for 25 minutes. The reaction temperature is then lowered below -20° and the oxonicotinic acid solution is added in aliquots keeping the temperature below -5°. When the addition is complete, the reaction is stirred in an ice bath overnight, allowing the bath to come to room temperature. The reaction is treated with 30 ml of isopropanol and 30 ml of glacial acetic acid and the resulting mixture is stirred for 10 min at room temperature. The reaction is concentrated and filtered to give 50.1 g of 6-[4-(N-acetyl-4-hydroxy-L-prolylamino)phenyl]-1,2-dihydro-2-oxonicotinic acid [α]D23 -60.5° (cl, pH 7).

Workup

  1. stirringThe mixture is stirred at room temperature until the solid
  2. dissolutionis almost completely dissolved
  3. temperatureis cooled to -10° to -15°
  4. stirringThe reaction is stirred at -15° to -10° for 25 minutes
  5. customis then lowered below -20°
  6. customthe temperature below -5°
  7. additionWhen the addition
  8. stirringthe reaction is stirred in an ice bath overnight
  9. customto come to room temperature
  10. stirringthe resulting mixture is stirred for 10 min at room temperature
  11. concentrationThe reaction is concentrated
  12. filtrationfiltered

Sources & evidence

ORD record
ord-ca44d51db4264ddfa29a3de089b921f8
Source dataset
uspto-grants-1982_01
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US04311698

Reaction notes

Loading…

On this pageParticipantsProcedureWorkupSources & evidenceReaction notes