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

HRID 716832노트

반응식

HRID 716832 반응식
[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]

참가 물질

5

반응물 3

HCID 8471TriethylamineHCID 74946N1,N1-Bis(2-chloroethyl)-1,4-benzenediamine2회HCID 94429Triphosgene

생성물 1

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

시약·촉매·용매 1

HCID 6212Chloroform용매2회

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-072b544c1a6549e3802009a12d6abf02
출처 데이터셋
uspto-grants-2015_11
특허 번호
US09193687B2

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