STEREOSPECIFIC ELIMINATION OF DEUTERIUM AS A METHOD FOR DETERMINING THE STEREOCHEMISTRY OF A NUMBER OF METABOLITES OF THE TETRAHYDROCANNABINOLS
STEREOSPECIFIC ELIMINATION OF DEUTERIUM AS A METHOD FOR DETERMINING THE STEREOCHEMISTRY OF A NUMBER OF METABOLITES OF THE TETRAHYDROCANNABINOLS
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DOI：
10.1002/bms.1200070107
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发表时间：
1980-01-01
期刊：
影响因子：
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通讯作者：
HARVEY, DJ
中科院分区：
文献类型：
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作者：
HARVEY, DJ
研究了[2H]-Δ-1-四氢大麻酚(Δ-1-THc)、Δ6-THc和Δ7-THc代谢物中3-H原子的立体特异性消除，作为一种测定萜环上羟基或酸性取代代谢物立体化学的可能方法。HCOOTMS的消除被发现涉及三种大麻素的代谢物六氢大麻酚-7-OIC酸的轴向3-氢，而不是赤道异构体。在5α-羟基-Δ、6-α-羟基-Δ和1-α，2-β-Δ-1-Thc的TMS衍生物中，也观察到了类似的立体特异性消除。1-α，7-和1-β，7-二羟基-HHC的TMSOH的损失都涉及3-氢，但异构体可以被区分为它们的烷烃-硼酸酯衍生物；只有1-α，7-二羟基-HHC的衍生物通过立体定向去除3-氢而失去了硼酸环。不能用这种方法测定1，6-二羟基-HHC的四个异构体的立体化学，因为所有四个化合物的[M-TMSOH]+·离子都失去了3-氢，可能是1，6-键断裂的结果。
The stereospecific elimination of the 3‐deuterium atom from metabolites of [2H]‐analogues of Δ1‐tetrahydrocannabinol (Δ1‐THC), Δ6‐THC and Δ7‐THC has been investigated as a possible method for determining the stereochemistry of metabolites substituted with hydroxy or acid groups in the terpene ring. Elimination of HCOOTMS was found to involve the 3‐hydrogen of the axial but not the equatorial isomer of hexahydrocannabinol‐7‐oic acid, a metabolite of all three cannabinoids. Similar stereospecific eliminations were observed during the loss of TMSOH from the TMS derivatives of 5α‐hydroxy‐Δ6‐THC, 6α‐hydroxy‐Δ1‐THC and 1α,2β‐dihydroxy‐Δ1‐THC. Loss of TMSOH from 1α,7‐ and 1β,7‐dihydroxy‐HHC involved the 3‐hydrogen in both cases but the isomers could be distinguished as their alkane‐boronate derivatives; only the derivative of 1α,7‐dihydroxy‐HHC lost the boronate ring with stereospecific removal of the 3‐hydrogen. The stereochemistry of the four isomers of 1,6‐dihydroxy‐HHC could not be determined in this way as the [M‐TMSOH]+˙ions from all four compounds had lost the 3‐hydrogen, presumably as the result of 1,6‐bond cleavage.