Acetic Acid → (1S,2R,19R,22R,34S,37R,40R,52S)-2,64-bis[[(2R,3S,4R,5S,6S)-3-acetamido-4,5-dihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy]-22-amino-5,15-dichloro-26,31,44,49-tetrahydroxy-21,35,38,54,56,59-hexaoxo-47-[(2R,3S,4R,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-7,13,28-trioxa-20,36,39,53,55,58-hexazaundecacyclo[38.14.2.23,6.214,17.219,34.18,12.123,27.129,33.141,45.010,37.046,51]hexahexaconta-3,5,8,10,12(64),14,16,23(61),24,26,29(60),30,32,41(57),42,44,46(51),47,49,62,65-henicosaene-52-carboxylic acid

HRID 1249285Notes

Reaction equation

HRID 1249285 reaction equation
CCCCCCCC[CH2:9][C:10]([NH:12][C@H:13]1[C@H:18]([O:19][C:20]2[C:25]3[O:26][C:27]4[CH:32]=[CH:31][C:30]([C@@H:33]([O:113][C@@H:114]5[O:119][C@H:118]([CH2:120][OH:121])[C@@H:117]([OH:122])[C@H:116]([OH:123])[C@H:115]5[NH:124][C:125]([CH3:127])=[O:126])[C@@H:34]5[NH:54][C:52](=[O:53])[C@H:51]([NH:55][C:56]([C@@H:58]6[NH:59][C:60]([C@H:62]7[NH:93][C:91](=[O:92])[C@@H:81]([CH2:82][C:83]8[CH:89]=[CH:88][C:86]([O:87][C:21]=2[CH:22]=[C:23]6[CH:24]=3)=[C:85]([Cl:90])[CH:84]=8)[NH:80][C:78](=[O:79])[C@H:77]([NH2:94])[C:75]2=[CH:76][C:71](=[C:72]([OH:95])[CH:73]=[CH:74]2)[O:70][C:65]2=[CH:66][C:67]([OH:69])=[CH:68][C:63]7=[CH:64]2)=[O:61])=[O:57])[C:49]2=[CH:50][C:45](=[C:46]([OH:96])[CH:47]=[CH:48]2)[C:44]2[C:39](=[CH:40][C:41]([OH:109])=[CH:42][C:43]=2[O:97][C@H:98]2[O:103][C@H:102]([CH2:104][OH:105])[C@@H:101]([OH:106])[C@H:100]([OH:107])[C@@H:99]2[OH:108])[C@H:38]([C:110]([OH:112])=[O:111])[NH:37][C:35]5=[O:36])=[CH:29][C:28]=4[Cl:128])[O:17][C@H:16]([CH2:129][OH:130])[C@@H:15]([OH:131])[C@@H:14]1[OH:132])=[O:11].C(O)(=O)C.Cl>C(OCC)C>[CH3:9][C:10]([NH:12][C@@H:13]1[C@H:18]([O:19][C:20]2[C:25]3[O:26][C:27]4[CH:32]=[CH:31][C:30]([C@@H:33]([O:113][C@@H:114]5[O:119][C@@H:118]([CH2:120][OH:121])[C@@H:117]([OH:122])[C@H:116]([OH:123])[C@@H:115]5[NH:124][C:125]([CH3:127])=[O:126])[C@@H:34]5[NH:54][C:52](=[O:53])[C@H:51]([NH:55][C:56]([C@@H:58]6[NH:59][C:60]([C@H:62]7[NH:93][C:91](=[O:92])[C@@H:81]([CH2:82][C:83]8[CH:89]=[CH:88][C:86]([O:87][C:21]=2[CH:22]=[C:23]6[CH:24]=3)=[C:85]([Cl:90])[CH:84]=8)[NH:80][C:78](=[O:79])[C@H:77]([NH2:94])[C:75]2[CH:74]=[CH:73][C:72]([OH:95])=[C:71]([CH:76]=2)[O:70][C:65]2=[CH:64][C:63]7=[CH:68][C:67]([OH:69])=[CH:66]2)=[O:61])=[O:57])[C:49]2[CH:48]=[CH:47][C:46]([OH:96])=[C:45]([CH:50]=2)[C:44]2[C:43]([O:97][C@H:98]3[O:103][C@H:102]([CH2:104][OH:105])[C@@H:101]([OH:106])[C@@H:100]([OH:107])[C@@H:99]3[OH:108])=[CH:42][C:41]([OH:109])=[CH:40][C:39]=2[C@@H:38]([C:110]([OH:112])=[O:111])[NH:37][C:35]5=[O:36])=[CH:29][C:28]=4[Cl:128])[O:17][C@@H:16]([CH2:129][OH:130])[C@@H:15]([OH:131])[C@@H:14]1[OH:132])=[O:11]

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 313Hydrochloric AcidHCID 1613192361036-62-2

Product 1

HCID 73348316(1S,2R,19R,22R,34S,37R,40R,52S)-2,64-bis[[(2R,3S,4R,5S,6S)-3-acetamido-4,5-dihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy]-22-amino-5,15-dichloro-26,31,44,49-tetrahydroxy-21,35,38,54,56,59-hexaoxo-47-[(2R,3S,4R,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-7,13,28-trioxa-20,36,39,53,55,58-hexazaundecacyclo[38.14.2.23,6.214,17.219,34.18,12.123,27.129,33.141,45.010,37.046,51]hexahexaconta-3,5,8,10,12(64),14,16,23(61),24,26,29(60),30,32,41(57),42,44,46(51),47,49,62,65-henicosaene-52-carboxylic acid

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
80 °C

Procedure

2.65 g of teicoplanin complex (i.e. the antibiotic complex containing teichomycin factors A1, A2 and A3, as obtained by fermentation of strain ATCC 31121 according to U.S. Pat. No. 4,239,751), is dissolved with stirring into 180 ml of acetic acid. To this solution 20 ml of 37% (w/v) HCl are added and the mixture is heated at 80° C. for one hour (the reaction time has been determined according to previous experiments where the reaction was followed by HPLC). After cooling to room temperature, the reaction mixture is poured into 1 liter of ice-cooled ethyl ether. The obtained precipitate is collected by filtration, washed with ethyl ether and then dissolved in 60 ml of a mixture of methanol and 0.1 N HCl 3:2 (v/v). To the resulting solution, 600 ml of a mixture of water/ethyl acetate/n-butanol 4:5:1 (v/v/v) are added and the pH is adjusted to 8.5 by adding 1 N NaOH. The organic layer is then discarded and the aqueous phase chromatographed through a column prepared with 270 g of silanized silica gel as described in the last part of Example 4. Yield 750 g of substantially pure deglucoteicoplanin.

Workup

  1. customas obtained by fermentation of strain ATCC 31121 according to U.S
  2. dissolution4,239,751), is dissolved
  3. temperatureAfter cooling to room temperature
  4. filtrationThe obtained precipitate is collected by filtration
  5. washwashed with ethyl ether
  6. dissolutiondissolved in 60 ml of a mixture of methanol and 0.1 N HCl 3:2 (v/v)
  7. additionTo the resulting solution, 600 ml of a mixture of water/ethyl acetate/n-butanol 4:5:1 (v/v/v) are added
  8. additionby adding 1 N NaOH
  9. customthe aqueous phase chromatographed through a column
  10. customprepared with 270 g of silanized silica gel

Sources & evidence

ORD record
ord-b2b728b4d42b4570a073e72c42b0b8ec
Source dataset
uspto-grants-1986_12
Patent number
US04629781

Reaction notes

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