반응 #2463133

반응 방정식

sodium hydroxide

phenyl phosphine

diethylamine

n-BuLi

diphenyl-phosphinic acid 1-{2-[1-(diphenyl-phosphinoyloxy)-ethyl]-phenyl}-ethyl ester

→

1,3-Dimethyl-2-phenyl-2,3-dihydro-1H-isophosphindole

용매

THF

TBME

THF

water

반응 조건

후처리

1. 1
   workup.ADDITIONwas added drop wise under efficient stirring
2. 2
   workup.ADDITIONimmediately afterwards was added
3. 3
   기타wise over two minutes
4. 4
   workup.ADDITIONWhen the addition
5. 5
   workup.STIRRINGThe mixture was stirred for 10 minutes, by which time two clear layers
6. 6
   기타had formed
7. 7
   기타The aqueous layer was removed via syringe
8. 8
   건조the organic layer was dried (Na2SO4)
9. 9
   기타Removal of the solvent in vacuum
10. 10
    workup.WAITleft the product as colourless oil

실험 절차

Under an atmosphere of nitrogen a Schlenk flask was charged with diethylamine (0.584 g, 8 mmol), to which a solution of n-BuLi (2.5 ml 1.6 N-solution in hexanes, 4 mmol) was added drop wise under efficient stirring. To the slightly hazy solution was then added phenyl phosphine (0.110 g, 1 mmol) which led to the formation of a yellow solution. This mixture was diluted with THF (2 ml), and immediately afterwards was added under efficient stirring a solution of diphenyl-phosphinic acid 1-{2-[1-(diphenyl-phosphinoyloxy)-ethyl]-phenyl}-ethyl ester (0.567 g, 1 mmol) in THF (made up to 2 ml total volume) drop wise over two minutes into the Schlenk flask. When the addition was complete, the mixture was stirred for another ten minutes. To the mixture was then added water (3 ml), sodium hydroxide (1 ml 40% solution in water), and TBME (15 ml). The mixture was stirred for 10 minutes, by which time two clear layers had formed. The aqueous layer was removed via syringe, and the organic layer was dried (Na2SO4). Removal of the solvent in vacuum left the product as colourless oil. 1H/13C-NMR (CDCl3, 300 MHz, HSQC/HMBC, indices A/B relate to syn/anti to P-lone pair) δ/δ 1.21 (dd, J=7.3 Hz, J=11.2 Hz)/14.45 (s) (B-CH3); 1.62 (dd, J=7.7 Hz, J=18.6 Hz)/21.73 (d, J=29.9 Hz) (A-CH3); 3.59 (dq, J=16.6 Hz)/40.04 (d, J=8.5 Hz) (A CHMe); 3.77 (dq, J=2.3 Hz)/35.57 (d, J=13.5 Hz) (B CHMe); 7.17 (m)/125.27 (d, J=1.1 Hz) (A Ar ortho-CH); 7.26 (m)/126.88, 7.26/127.22 (2 Ar meta-CH); 7.36 (m)/125.60 (d, J=1.3 Hz) (B Ar ortho-CH); 7.21 (m)/128.15 (d, J=7.2 Hz) (Ph meta-CH); 7.27 (m)/129.26 (d, J=1.0 Hz) (Ph para-Ch); 7.27 (m)/133.81 (d, J=19.8 Hz) (Ph ortho-CH); 135.90 (d, J=22.1 Hz) (Ph ipso-C); 145.09 (d, J=3.8 Hz) (B Ar ipso-C); 149.04 (d, J=2.3 Hz) (A Ar ipso-C). 31P-NMR δ 22.14.

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