Ammonia → 3-Amino-5,6,7,8-tetrahydroquinoxaline-2-carbonitrile

HRID 1199639Notes

Reaction equation

HRID 1199639 reaction equation
CC1C=CC(S(ON=[C:13]([C:16]#[N:17])[C:14]#[N:15])(=O)=O)=CC=1.[N:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.N1(C2CCCCC=2)CCC[CH2:25]1.[NH3:35]>CO.O.C(O)C.O1CCCC1>[NH2:35][C:16]1[C:13]([C:14]#[N:15])=[N:18][C:23]2[CH2:22][CH2:21][CH2:20][CH2:19][C:25]=2[N:17]=1

Participants

9

Reactant 4

HCID 222AmmoniaHCID 1049PyridineHCID 707681-Pyrrolidino-1-cyclohexeneHCID 88722((((4-Methylphenyl)sulphonyl)oxy)imino)malononitrile

Product 1

HCID 123650113-Amino-5,6,7,8-tetrahydroquinoxaline-2-carbonitrileYield 20%

Reagents, catalysts & solvents 4

HCID 702EthanolSolventHCID 887MethanolSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To a mixture of 33 g (0.1324 mol) of (O-p-tosylisonitroso)-malononitrile, 300 ml of tetrahydrofuran, and 11 ml (0.136 mol) of pyridine at -35° C. is added portionwise a mixture of 20 g (0.1322 mol) of 1-(pyrrolidino)-1-cyclohexene and 300 ml of tetrahydrofuran. After 2 hrs., the reaction mixture is allowed to warm to 0° C. for 30 min. To the reaction mixture at 0° C. is added 300 ml of a saturated solution of ammonia in methanol. The reaction mixture is stirred at ambient temperature overnight, then diluted with water, and extracted with methylene chloride. The combined extracts are dried (Na2SO4), and concentrated in vacuo to give an oily solid. Trituration with ethanol furnishes 4.7 g (20%) of title compound. Recrystallization from ethanol provides an analytical sample: m.p. 200°-202° C.; IR (KBr) 3400, 3340, 3200, 2240, 1665, and 1580 cm-1 ; NMR (DMSO-d6) δ 6.90 (br-s, 2H), exchangeable), 2.85-2.55 (m, 4H), and 1.90-1.55 (m, 4H).

Workup

  1. additionis added portionwise
  2. extractionextracted with methylene chloride
  3. dry with materialThe combined extracts are dried (Na2SO4)
  4. concentrationconcentrated in vacuo
  5. customto give an oily solid

Sources & evidence

ORD record
ord-8734152115e842288e876f4579b85ed0
Source dataset
uspto-grants-1990_02
Patent number
US04902685

Reaction notes

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