Reaction #69056

Reaction equation

DIPEA

thiomorpholine

ethyl acetate

CC-12

1-(4-methylbenzamido)-2-(chloroacetamido)-anthraquinone

→

1-(4-methylbenzamido)-2-[2-(1,4-thiazinan-4-yl)acetylamino]-anthraquinone

Yield 51.0%

Solvents

EtOH

n-hexane

tetrahydrofuran

Conditions

Workup

1. 1
   TemperatureThis mixture was heated
2. 2
   Temperatureunder reflux for 16 hours
3. 3
   OtherAfter the completion of the reaction
4. 4
   Filtrationthe mixture was filtered
5. 5
   Concentrationthe filtrate was concentrated by reduced pressure concentrator (such as Vacuum Evaporator)
6. 6
   ExtractionThe residue was extracted with ethyl acetate for several times
7. 7
   OtherThe extract was dried on magnesium sulfate
8. 8
   Concentrationconcentrated under reduced pressure
9. 9
   WashThe crude product was washed with ethyl acetate/hexane
10. 10
    OtherFinally, the crude product was recrystallized in hot ethanol
11. 11
    Otherto obtain a kelly green compound CC-42

Procedure

Compound CC-12 (0.86 g, 2 mmole) was dissolved in anhydrous tetrahydrofuran (30 ml), and to the solution was added successively with DIPEA (1 ml, 6 mmole) and thiomorpholine (0.80 ml, 8 mmole) under stirring for 5 to 10 minutes. This mixture was heated under reflux for 16 hours. After the completion of the reaction, the mixture was filtered, and the filtrate was concentrated by reduced pressure concentrator (such as Vacuum Evaporator). The residue was extracted with ethyl acetate for several times. The extract was dried on magnesium sulfate, and concentrated under reduced pressure. The crude product was washed with ethyl acetate/hexane. Finally, the crude product was recrystallized in hot ethanol to obtain a kelly green compound CC-42. Mol. Wt.: 499.5808 (C28H25N3O4S); Rf: 0.43 (ethyl acetate:n-hexane=1:2); Yield: 51%; Mp.: 210-211° C. (EtOH); HRMS (EI) m/z: calcd [M]+, 499.1566 (C28H25N3O4S+). Found, 499.1570. 1H-NMR (300 MHz, DMSO-d6) δ (ppm): 2:39 (br, 4H, —CH2—), 2.45 (s, 3H, —CH3), 3.15 (s, 2H, —CH2N—), 3.23 (br, 4H, —CH2—), 7.45 (d, J=8.1 Hz, 2H, Ar—H), 7.88-7.91 (m, 2H, Ar—H), 8.07-8.19 (m, 4H, Ar—H), 8.27 (d, J=8.4 Hz, 1H, Ar—H), 8.73 (d, J=8.4 Hz, 1H, Ar—H), 10.00 (s, 1H, Ar—NH—), 10.61 (s, 1H, Ar—NH—); 13C-NMR (75 MHz, DMSO-d6) δ (ppm): 20.89, 26.48, 53.13, 54.62, 61.92, 65.54, 127.72, 126.30, 126.40, 126.92, 127.69, 127.92, 127.98, 129.22, 129.43, 130.53, 132.30, 134.12, 134.41, 134.45, 140.21, 142.61, 166.27 (NCO), 168.89, 169.15 (NCO), 181.42 (CO), 183.84 (CO).

Source