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Propanal → Isocyanate

HRID 482636
ノート
印刷プレビュー

反応式

HRID 482636 の反応式
[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]
参加物実験手順後処理出典と根拠反応ノート

参加物

12

反応物 6

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

生成物 2

HCID 105034Isocyanate
収率 90%
HCID 9576785Propanal, propylidenehydrazone

試薬・触媒・溶媒 4

HCID 935Nickel触媒HCID 23948Rhodium触媒HCID 9834912Nickel(II) acetylacetonate触媒HCID 6386tert-Butanol溶媒

実験手順

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##

後処理

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

出典と根拠

ORDレコード
ord-739f379b20384130b8e43d179b0604c7
出典データセット
uspto-grants-1986_03
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US04574059

反応ノート

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