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Propanal → Isocyanate

HRID 482636
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 482636
[CH:1](=[O:4])CC.O.NN.C=CC=C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH2:31]([CH:33]1CC=CCCC=[CH:38][CH2:37][CH:36](CC)[N:35]=[N:34]1)[CH3:32].[H][H]>C(O)(C)(C)C.[Rh].[Ni].C/C(/[O-])=C/C(C)=O.C/C(/[O-])=C/C(C)=O.[Ni+2]>[CH3:32][CH2:31]/[CH:33]=[N:34]/[N:35]=[CH:36]/[CH2:37][CH3:38].[N-:34]=[C:1]=[O:4]
KomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

12

Edukt 6

HCID 527PropanalHCID 78451,3-ButadieneHCID 11776TriphenylphosphineHCID 24654Hydrazine hydrate (1:1)HCID 566066523,12-Diethyl-1,2-diaza-1,5,9-cyclododecatrieneHCID 178418361HCID 178418361, Verbindung

Produkt 2

HCID 105034
Isocyanate
Ausbeute 90 %
HCID 9576785Propanal, propylidenehydrazone

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 935NickelKatalysatorHCID 23948RhodiumKatalysatorHCID 9834912Nickel(II) acetylacetonateKatalysatorHCID 6386tert-ButanolLösungsmittel

Versuchsvorschrift

Propionaldazine is synthesized by the reaction of propionaldehyde with hydrazine hydrate by operating as in Example 1. The cyclooligomerization reaction is then carried out according to the conditions described in Example 1, by causing the azine to react with the butadiene in a ratio of 1/3 in the presence of nickel prepared by the reduction of nickel acetylacetonate (1 at.g. of Ni for 20 moles of azine) and of triphenylphosphine. In 100 ml of tert. butanol, 12.15 g of 3,12-diethyl-1,2-diaza-1,5,9-cyclododecatriene are hydrogenated in 300-ml autoclave, in the presence of 1.3 g of rhodium catalyst deposited at 5% on alumina. The reaction is allowed to proceed for 30 minutes at 45° C. under 130 bars of hydrogen, then for 111/2 hours at 185° C. under 150 bars. The diamine (8.71 g) is phosgenated, in the form of the chlorhydrate, as in Example 1 in order to lead to 9.6 g (yield 90%) of crude isocyanate. The distillation of the latter leads to 1,10-diethyldecane-1,10-diisocyanate, a colorless liquid having a content of 2 NCO groups per mole and the following N.M.R. characteristics of the 13C atom (chemical shifts in relation to CDCl3 at 77 ppm): ##STR12##

Aufarbeitung

  1. customThe cyclooligomerization reaction
  2. custom2 hours
  3. customat 185° C.

Quellen und Nachweise

ORD-Eintrag
ord-739f379b20384130b8e43d179b0604c7
Quelldatensatz
uspto-grants-1986_03
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US04574059

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