CAJ | 학술논문

以三苯基膦及其衍生物作为配体在双环戊二烯（DCPD）氢甲酰化合成三环癸烷不饱和单醛和三环癸烷二醛的配体效应进行了探索研究。结果表明对于三环癸烷不饱和单醛的合成，配体上的取代基对催化活性和目标产物的选择性有显著影响，吸电子取代基会提高催化活性，加快反应速率，但选择性有所降低，斥电子取代基则会降低反应速率；从催化活性和目标产物选择性综合考虑，三苯基膦作为配体催化效果最好。两步合成法比一步合成法更有利于双环戊二烯成醛，醛选择性可达99%以上。采用两步合成法，以三苯基膦为配体可获得达60%的较高二醛选择性，其它两种配体的二醛选择性则比一步合成法差。
이삼분기련급기연생물작위배체재쌍배무이희（DCPD）경갑선화합성삼배계완불포화단철화삼배계완이철적배체효응진행료탐색연구。결과표명대우삼배계완불포화단철적합성，배체상적취대기대최화활성화목표산물적선택성유현저영향，흡전자취대기회제고최화활성，가쾌반응속솔，단선택성유소강저，척전자취대기칙회강저반응속솔；종최화활성화목표산물선택성종합고필，삼분기련작위배체최화효과최호。량보합성법비일보합성법경유리우쌍배무이희성철，철선택성가체99%이상。채용량보합성법，이삼분기련위배체가획득체60%적교고이철선택성，기타량충배체적이철선택성칙비일보합성법차。
The ligand effects of triphenylphosphine and its derivatives in the synthesis of monoformyltricyclo [5.2.1.02,6]dec-3-ene (MFTD) and diformyltricyclodecane (DFTD) by hydroformylation of dicyclopentadiene (DCPD) were studied. The results showed that the substituents on the ligand have significant influences on the catalytic activity and the selectivity to MFTD. The electron-withdrawing substituent increased catalytic activity, but decreased the selectivity slightly, and the electron-donating substituent decreased catalytic activity. Considering both of catalytic activity and target product selectivity, triphenylphosphine may be the best choice. Comparing with the one-step synthesis, the two-step synthesis could increase the total selectivity of MFTD and DFTD, which could be over 99%. In the two-step synthesis, triphenylphosphine ligand obtained a high DFTD selectivity of up to 60%, however the other two ligands still gave lower DFTD selectivitie.