Triethylamine → Ethyl 2-(tert-butoxycarbonylamino)-2-(hydroxymethyl)hex-5-enoate

HRID 579512노트

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HRID 579512 반응식
[C:1]([O:5][C:6]([NH:8][C:9]([C:17]([O:19][CH2:20][CH3:21])=[O:18])([CH2:13][CH2:14][CH:15]=[CH2:16])[C:10](O)=[O:11])=[O:7])([CH3:4])([CH3:3])[CH3:2].C(N(CC)CC)C.ClC(OCC)=O.[BH4-].[Na+]>C1COCC1.O>[C:1]([O:5][C:6]([NH:8][C:9]([CH2:10][OH:11])([CH2:13][CH2:14][CH:15]=[CH2:16])[C:17]([O:19][CH2:20][CH3:21])=[O:18])=[O:7])([CH3:2])([CH3:4])[CH3:3]

참가 물질

7

반응물 4

HCID 8471TriethylamineHCID 10928Ethyl chloroformateHCID 4311764Sodium borohydrideHCID 715799912-(Tert-butoxycarbonylamino)-2-(ethoxycarbonyl)hex-5-enoic acid

생성물 1

HCID 71579992Ethyl 2-(tert-butoxycarbonylamino)-2-(hydroxymethyl)hex-5-enoate수율 78.3%

시약·촉매·용매 2

HCID 962Water용매HCID 8028Tetrahydrofuran용매

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온도
-40 °C

실험 절차

A solution of the 2-(tert-butoxycarbonylamino)-2-(ethoxycarbonyl)hex-5-enoic acid (7.5 g, 24.9 mmol) and triethylamine (3.01 g, 29.9 mmol, 4.15 mL) in THF (10 mL) was cooled to −40° C. and treated with ethyl chloroformate (2.97 g, 27.4 mmol, 2.65 mL). After stirring for 30 minutes, the precipitate (triethylamine hydrochloride) was removed by filtration and the filtrate was collected and cooled to −40° C. A solution of sodiumborohydride (950 mg, 24.9 mmol) in water (10 mL) was added and the resulting solution was stirred for 30 minutes. After quenching the reaction mixture with 3 N hydrochloric acid (5 mL), the mixture was diluted with ethyl acetate (150 mL), washed with water (1×50 mL) and extracted with ethyl acetate (1×150 mL). The combined organic layers were concentrated, dried over MgSO4, filtered and purified using a combiflash system (80 g silica gel column, eluting with 10-50% ethyl acetate in heptanes) to give ethyl 2-(tert-butoxycarbonylamino)-2-(hydroxymethyl)hex-5-enoate (5.6 g, 78%). 1H NMR (CDCl3) δ 5.71-5.62 (m, 1H), 5.52 (bs, 1H), 4.96-4.87 (m, 2H), 4.20-4.12 (m, 2H) 4.07-4.03 (m, 2H), 3.73 (d, J=12.0 Hz, 1H), 2.22-1.62 (m, 4H), 1.37 (m, 9H), 1.22 (t, J=7.2 Hz, 3H).

후처리

  1. customthe precipitate (triethylamine hydrochloride) was removed by filtration
  2. customthe filtrate was collected
  3. stirringthe resulting solution was stirred for 30 minutes
  4. customAfter quenching the reaction mixture with 3 N hydrochloric acid (5 mL)
  5. additionthe mixture was diluted with ethyl acetate (150 mL)
  6. washwashed with water (1×50 mL)
  7. extractionextracted with ethyl acetate (1×150 mL)
  8. concentrationThe combined organic layers were concentrated
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. custompurified
  12. washa combiflash system (80 g silica gel column, eluting with 10-50% ethyl acetate in heptanes)

출처 및 근거

ORD 기록
ord-0439863d044c48dd858132146fde6697
출처 데이터셋
uspto-grants-2015_05
특허 번호
US09040703B2

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