Hydrochloric Acid → HCID 178501374、化合物

HRID 65595ノート

反応式

HRID 65595 の反応式
Cl.N(OCCC(C)C)=O.[NH:10]1[C:14](=[O:15])[CH2:13][CH2:12][C@H:11]1[C:16]([NH:18][C@H:19]([C:26]([NH:28][C@H:29]([C:40]([N:42]=[N+]=[N-])=[O:41])[CH2:30][C:31]1[C:39]2[C:34](=[CH:35][CH:36]=[CH:37][CH:38]=2)[NH:33][CH:32]=1)=[O:27])[CH2:20][C:21]1[N:25]=[CH:24][NH:23][CH:22]=1)=[O:17].Cl.[CH3:46][O:47][C:48](=[O:65])[C@H:49]([CH2:57][C:58]1[CH:63]=[CH:62][C:61]([OH:64])=[CH:60][CH:59]=1)[NH:50][C:51](=[O:56])[C@H:52]([CH2:54][OH:55])N>O1CCCC1.C(N(CC)CC)C.CS(C)=O.CN(C)C=O>[CH3:46][O:47][C:48](=[O:65])[C@H:49]([CH2:57][C:58]1[CH:63]=[CH:62][C:61]([OH:64])=[CH:60][CH:59]=1)[NH:50][C:51](=[O:56])[C@H:52]([CH2:54][OH:55])[NH:42][C:40](=[O:41])[C@H:29]([CH2:30][C:31]1[C:39]2[C:34](=[CH:35][CH:36]=[CH:37][CH:38]=2)[NH:33][CH:32]=1)[NH:28][C:26](=[O:27])[C@H:19]([CH2:20][C:21]1[N:25]=[CH:24][NH:23][CH:22]=1)[NH:18][C:16](=[O:17])[C@@H:11]1[CH2:12][CH2:13][C:14](=[O:15])[NH:10]1

参加物

9

反応物 4

HCID 313Hydrochloric AcidHCID 8053Isoamyl NitriteHCID 70166468HCID 70166468、化合物HCID 178514637HCID 178514637、化合物

生成物 1

HCID 178501374HCID 178501374、化合物

試薬・触媒・溶媒 4

HCID 679Dimethyl Sulfoxide溶媒HCID 6228Dimethylformamide溶媒HCID 8028Tetrahydrofuran溶媒HCID 8471Triethylamine溶媒

反応条件

温度
-20 °C

実験手順

To a solution of 932 mg. of L-pyroglutamyl-L-histidyl-L-tryptophanyl hydrazide (prepared as described in (b) above) in a mixture of 8.4 ml. of dry N,N-dimethylformamide and 7.0 ml. of dimethyl sulfoxide, cooled to -12° C., is added dropwise 5.16 ml. of 2.325 N hydrogen chloride in tetrahydrofuran. The mixture is cooled to -20° C., 0.4 ml. of isoamyl nitrite is added, and the resulting mixture is stirred at -20° C. for 30 minutes. The mixture, which contains L-pyroglutamyl-L-histidyl-L-tryptophanyl azide, is cooled to -25° C., and to it are added first 1.96 ml. of triethylamine and then 636 mg. of L-seryl-L-tyrosine methyl ester hydrochloride (prepared as described in (c) above). The reaction mixture is stirred at -20° C. for 30 minutes and at 0° C. for 30 minutes and is stored in a refrigerator at -5° C. for 48 hours. It is then filtered and the filtrate is evaporated under reduced pressure. The residue is triturated with tetrahydrofuran, the mixture is stored in the refrigerator for 26 hours, and the solvent is decanted to give a residue of L-pyroglutamyl-L-histidyl-L-tryptophanyl-L-seryl-L-tyrosine methyl ester, which is dissolved in 20 ml. of methanol. To the solution is added 1 ml. of 99% hydrazine hydrate, and the mixture is stirred at room temperature overnight to give solid L-pyroglutamyl-L-histidyl-L-tryptophanyl-L-seryl-L-tyrosyl hydrazide, which is isolated by filtration and dried under reduced pressure; m.p. 215°-217° C., following crystallization from water; [α]D25 -17° (1.01% in N,N-dimethylformamide).

後処理

  1. additionis added dropwise 5.16 ml
  2. temperatureis cooled to -25° C.
  3. additionto it are added first 1.96 ml
  4. stirringThe reaction mixture is stirred at -20° C. for 30 minutes and at 0° C. for 30 minutes
  5. waitis stored in a refrigerator at -5° C. for 48 hours
  6. filtrationIt is then filtered
  7. customthe filtrate is evaporated under reduced pressure
  8. customThe residue is triturated with tetrahydrofuran
  9. waitthe mixture is stored in the refrigerator for 26 hours
  10. customthe solvent is decanted

出典と根拠

ORDレコード
ord-11c3a27739e64a668bc59bf50f183ad7
出典データセット
uspto-grants-1978_12
特許番号
US04128540

反応ノート

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