Crystal structure of methyl iV,0-diacetyl-a-L-acosaminide, C11H19NO5

ζ. Kristallogr. NCS 213 (1998) 795-796

795

© by R. Oldenbourg Verlag, München

Crystal structure of methyl iV,0-diacetyl-a-L-acosaminide, C11H19NO5

S. Henkel, A. Menzel and V. Jäger

Universität Stuttgart. Institut für Organische Chemie, Pfaffenwaldring 55. D-70569 Stuttgart, Germany Received April 15, 1998, CSD-No. 409292

Source of material: The title compound is a derivative of L-aco- samine, which forms part of highly active cancerostatics such as epirubicin (see ref. 1 ), and which has repeatedly been synthesized before (see refs. 2-3). In a new synthesis the title compound (see refs. 4-6) was prepared by Henry reaction (see refs. 4-8) of a lactaldehyde derivative with nitropropanal dimethylacetal (see refs. 9) followed by cyclization to the methyl glycoside. This was reduced and acetylated to get the title compound, (mp 432 K;

- 1 9 1 , c = 0.54,MeOH).

The molecules are stacked in four columns, in each one with identical orientation, linked by an intermolecular hydrogen bridge of the amido group (N7) to the oxygen atom (08) of the N-acetyl group. The molecules adopt a 4C conformation with the 1-methoxy group oriented axially and all other ring substituents placed equa- tonally.

Table 3. Final atomic coordinates and displacement parameters (in Â^)

CiiHi9N05,orthorhombic,/^l2i2i (No. 19), α =5.021(1) À,

¿=12.857(2) Â, с =20.978(4) Â, V=1354.2Â^ Z=4, R(F) =0.052, Rv^F^) =0.124.

Table 1. Parameters used for the X-ray data collection

Ciystal: colorless block, size 0.3 χ 0.5 χ 0.7 mm Wavelength: Mo Ka radiation (0.71073 Â)

μ: 0.95 cm"'

Diffractometer: NicoletPS

Scan mode: Wyckoff

Tmeasur^n,: 293 К

2 в т « : 51.96°

N(AW)^«,: 1482

Criterion for ¡0. /ο>2σ(/ο)

^(рагатУгфтГ· 155

Programs: SHELXS-86, SHELXL-93

Table 2. Final atomic coordinates and displacement parameters (in Â^)

Atom Site ^X У ^{г í/iso}

H(l) 4a ^{0.8835(8) 1.1028(3) 0.5713(2) 0.065}

H{2A) 4a 0.5855(8) 1.2039(3) 0.5143(2) 0.078 H(2B) 4a 0.3419(8) 1.1520(3) 0.5486(2) 0.078 H(3) 4a 0.403(1) 1.3113(3) 0.5937(2) 0.087 H(5) 4a 0.8193(9) 1.1587(3) 0.6883(2) 0.077 H(51A) 4a ^{0.550(1) 1.1592(4) 0.7797(2) 0.144}

H(51B) 4a 0.648(1) 1.0454(4) 0.7668(2) 0.144 H(51C) 4a 0.357(1) 1.0780(4) 0.7484(2) 0.144 H(6) 4a 0.4438(8) 1.0144(3) 0.6375(2) 0.067

H(7) 4a 0.5036 0.9600 0.5243 0.075

H(9A) 4a 0.591(1) 0.8588(4) 0.4498(2) 0.141 H(9B) 4a 0.854(1) 0.7988(4) 0.4662(2) 0.141 H(9C) 4a 0.849(1) 0.8785(4) 0.4097(2) 0.141 H(llA) 4a 0.986(2) 1.4220(3) 0.6375(3) 0.167 H ( l l B ) 4a ^{0.762(2) 1.3825(3) 0.6837(3) 0.167}

H(llC) 4a 0.686(2) 1.4466(3) 0.6227(3) 0.167 H(14A) 4a 1.099(1) 0.8458(4) 0.7025(3) 0.166 H(14B) 4a 1.027(1) 0.7564(4) 0.6548(3) 0.166 H(14C) 4a 0.884(1) 0.7628(4) 0.7212(3) 0.166

Atom Site X У ζ Un U22 ί/33 Un t/l3 ί/23

C d ) 4a ^{0.6965(8) 1.0810(3)} 0.5711(2) 0.040(2) 0.063(2) 0.060(2) -0.005(2) 0.004(2) -0.010(2) C(2) 4a 0.5245(8) 1.1747(3) 0.5544(2) 0.051(2) 0.080(3) 0.064(2) -0.003(2) -0.002(2) 0.005(2) C(3) 4a 0.533(1) 1.2574(3) 0.6048(2) 0.073(3) 0.069(2) 0.074(3) 0.019(2) 0.007(3) 0.009(2) 0 ( 4 ) 4a ^{0.4660(6) 1.2168(2)} 0.6655(1) 0.079(2) 0.076(2) 0.071(2) 0.017(2) 0.022(2) 0.002(2) C(5) 4a 0.6356(9) 1.1334(3) 0.6853(2) 0.068(2) 0.067(2) 0.057(2) 0.000(2) 0.004(2) 0.002(2) C(51) 4a 0.539(1) 1.1010(4) 0.7511(2) 0.133(5) 0.092(3) 0.063(2) 0.008(4) 0.018(3) 0.003(2) C(6) 4a 0.6230(8) 1.0447(3) 0.6378(2) 0.045(2) 0.063(2) 0.059(2) -0.003(2) 0.002(2) -0.004(2) N(7) 4a 0.6633(6) 1.0000(3) 0.5241(2) 0.040(2) 0.079(2) 0.070(2) -0.007(2) -0.001(2) -0.017(2)

796

Table 3. (Continued)

Atom Site X У ζ t/ll ί/22 ί/зз 1/12 U\ì Uli

C(8) 4a 0.8600(8) 0.9489(3) 0.4963(2) 0.050(2) 0.081(3) 0.065(2) 0.000(2) -0.001(2) -0.013(2) СЧ8) 4a 1.0961(6) 0.9704(3) 0.5066(2) 0.041(2) 0.138(3) 0.130(3) -0.001(2) 0.006(2) -0.054(3) C(9) 4c 0.781(1) 0.8636(4) 0.4515(2) 0.083(3) 0.102(3) 0.097(3) 0.006(3) -0.002(3) -0.038(3) O(I0) 4a 0.7870(7) 1.3017(2) 0.6042(1) 0.087(2) 0.061(2) 0.081(2) -0.007(2) 0.012(2) -0.005(2) C ( l l ) 4a 0.807(2) 1.3959(3) 0.6399(3) 0.149(6) 0.071(3) 0.115(4) -41.011(4) 0.008(4) -0.017(3) 0(12) 4a 0.8137(6) 0.9684(2) 0.6597(1) 0.058(2) 0.058(2) 0.077(2) -0.001(2) -0.006(2) -0.000(1) C(13) 4a 0.750(1) 0.8681(4) 0.6588(3) 0.066(3) 0.068(3) 0.105(4) -0.002(3) 0.012(3) 0.006(3) 0(13) 4a 0.5481(9) 0.8363(3) 0.6352(2) 0.099(3) 0.085(2) 0.180(4) -0.024(2) -0.022(3) 0.003(3) C(14) 4a 0.958(1) 0.8026(4) 0.6867(3) 0.094(4) 0.082(3) 0.155(5) 0.020(3) 0.004(4) 0.019(4)

Acknowledgments. We are grateful to the Fonds der Chemischen Industrie for fínancial support and to Dr. Wolfgang Frey for help with the preparation of the files.

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