Triethylamine → Bis(2-chloroethyl)-4-isocyanatophenylamine

HRID 716832ノート

反応式

HRID 716832 の反応式
[Cl:1][CH2:2][CH2:3][N:4]([CH2:12][CH2:13][Cl:14])[C:5]1[CH:10]=[CH:9][C:8]([NH2:11])=[CH:7][CH:6]=1.C(N(CC)CC)C.Cl[C:23](Cl)([O:25]C(=O)OC(Cl)(Cl)Cl)Cl>C(Cl)(Cl)Cl>[Cl:1][CH2:2][CH2:3][N:4]([C:5]1[CH:10]=[CH:9][C:8]([N:11]=[C:23]=[O:25])=[CH:7][CH:6]=1)[CH2:12][CH2:13][Cl:14]

参加物

5

反応物 3

HCID 8471TriethylamineHCID 74946N1,N1-Bis(2-chloroethyl)-1,4-benzenediamine2 回HCID 94429Triphosgene

生成物 1

HCID 10777647Bis(2-chloroethyl)-4-isocyanatophenylamine

試薬・触媒・溶媒 1

HCID 6212Chloroform溶媒2 回

実験手順

The known compound phenylisocyanate N-mustard 19 can be prepared by following the literature procedure35,36 with modification (Scheme 3). The commercially available 4-fluoronitrobenzene (15) is reacted with diethanolamine under refluxing to give 4-[N,N-bis(2-hydroxyethyl)amino]nitrobenzene (16), which is then converted to 4-[N,N-bis(2-chloroethyl)amino]nitrobenzene (17) by treating with thionyl chloride. Catalytic hydrogenation (10% Pd/C, H2) of compound 17 in ethyl acetate affords N,N-bis(2-chloroethyl)benzene-1,4-diamine (18), which is immediately treated with HCl in ethyl acetate to yield hydrochloride salt of 18. The hydrochloride salt 18 is suspended in CHCl3 and cooled in an ice-bath. To the suspension is added triethylamine and stirred in Argon atmosphere for 5 to 10 min. and then is added dropwise triphosgene solution in CHCl3 and continuously stirred for 20 min. The reaction mixture is evaporated under reduced pressure and the residue is the triturated with THF, filtered and the filtrate containing phenylisocyanate 19, which is used directly for the next reaction without purification. Compound 18 and 19 can be used for the synthesis of the newly invented compounds.

後処理

  1. temperaturecooled in an ice-bath
  2. stirringcontinuously stirred for 20 min
  3. customThe reaction mixture is evaporated under reduced pressure
  4. customtriturated with THF
  5. filtrationfiltered
  6. additionthe filtrate containing phenylisocyanate 19, which
  7. customis used directly for the next reaction without purification

出典と根拠

ORDレコード
ord-072b544c1a6549e3802009a12d6abf02
出典データセット
uspto-grants-2015_11
特許番号
US09193687B2

反応ノート

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