6,14-Endoethenotetrahydrooripavine: parent molecule from which all Bentley's are made

[Nagelfar]

Does anybody know the proper IUPACesque name by which the structure in this thread's title can be constructed to exacting qualifications in a program like Marvin Beans (chemicalize.org)?

For instance, etorphine, when you click the floppy disk image for "export" (on chemicalize.org after loading 'etorphine') and under structure find "name" in the drop menu, it gives:

(1R,2R,6S,14R,15R,19R)-19-[(2R)-2-hydroxypentan-2-yl]-15-methoxy-3-methyl-13-oxa-3-azahexacyclo[13.2.2.1²,⁸.0¹,⁶.0⁶,¹⁴.0⁷,¹²]icosa-7(12),8,10,16-tetraen-11-ol

What would be the equivalent for 6,14-Endoethenotetrahydrooripavine, so that Marvin Beans may draw it? It's been a long time coming and I'd like to add this compound to WP; since it is the beginning structure from which all Orvinols/Thevinols/Bentley-Compounds are derived. I think this one has been a long enough time coming....

Thank any and all for any and all assistance.

 

[sekio]

(4R,7S,7aR,12bR)-7-methoxy-3-methyl-2,3,4,4a,7,7a-hexahydro-1H-4al5-4a,7-ethano-4,12-methanobenzofuro[3,2-e]isoquinolin-9-ol

parent molecule from which all Bentley's are made

It's not: most bentley compounds are made from thebaine. It's the central nucleus of bentley compounds, but not the precursor.

 

[Nagelfar]

(4R,7S,7aR,12bR)-7-methoxy-3-methyl-2,3,4,4a,7,7a-hexahydro-1H-4al5-4a,7-ethano-4,12-methanobenzofuro[3,2-e]isoquinolin-9-ol

It's not: most bentley compounds are made from thebaine. It's the central nucleus of bentley compounds, but not the precursor.

Thanks sek, but it doesn't seem to be written properly to be pasted into the name=import section of chemicalize.org, it gives a failure message as thus:

Molecule import failed:Response is not OK from /webservices2/rest-v0/util/calculate/molExport
HTTP ERROR:
Status code:400
Status text:Bad Request

What gives? What need be changed so I can copy and paste it in there to work right?

 

[sekio]

I'll find you an INCHI key later.

 

[Nagelfar]

I'll find you an INCHI key later.

K, thank you sek.

 

[sekio]

http://pubchem.ncbi.nlm.nih.gov/substance/238982770#section=Top
InChI=1S/C20H23NO3/c1-21-10-9-20-15-12-3-4-13(22)16(15)24-17(20)19(23-2)7-5-18(20,6-8-19)14(21)11-12/h3-5,7,14,17,22H,6,8-11H2,1-2H3/t14-,17+,18?,19-,20+/m1/s1

 

[Nagelfar]

http://pubchem.ncbi.nlm.nih.gov/substance/238982770#section=Top
InChI=1S/C20H23NO3/c1-21-10-9-20-15-12-3-4-13(22)16(15)24-17(20)19(23-2)7-5-18(20,6-8-19)14(21)11-12/h3-5,7,14,17,22H,6,8-11H2,1-2H3/t14-,17+,18?,19-,20+/m1/s1

It still says, from the InChi import template:

Molecule import failed:Response is not OK from /webservices2/rest-v0/util/calculate/molExport
HTTP ERROR:
Status code:500
Status text:Internal Server Error

It exports morphine's *name* as:

(1S,5R,13R,14S,17R)-4-methyl-12-oxa-4-azapentacyclo[9.6.1.0¹,¹³.0⁵,¹⁷.0⁷,¹⁸]octadeca-7,9,11(18),15-tetraene-10,14-diol

and exports morphine's *SMARTS* as:

[#6]-[#7]-1-[#6]-[#6][C@@]23[#6@H]-4-[#8]-[#6]-5=[#6]2-[#6](-[#6]-[#6@@H]-1-[#6@@H]3-[#6]=[#6]-[#6@@H]-4-[#8])=[#6]-[#6]=[#6]-5-[#8]

But it even *exports* morphine's InChi & InChiKey as that above error. Can someone just draw me the molecule I am requesting, please?

 

[sekio]

 

[Nagelfar]

Directly from PubChem, eh? Works for now I suppose.

I did it, it was a long time coming:

https://en.wikipedia.org/wiki/6,14-Endoethenotetrahydrooripavine

Thanks for the assist, sek

 

[adder]

Are you sure you got the C and F rings right? Acrolein adds to the C ring from "the top" and the double bond is present in oripavine's original C ring. The stereochemistry at C5 is wrong too.

BTW, it's a very common problem with PubChem, I noticed, that the stereochemistry is wrong for many compounds. For morphinan derivatives it's basically everywhere.

 

[Nagelfar]

Spoiler: large image unresized

Hey adder, there are wedge bonds in this new re-uploaded *.svg that show stereochemistry, could you give it the once over for me? I feel responsible, having made the page, for immediately forthcoming copyerrors. ;-p

 

[adder]

The first from the left is the product (orvinone) of Diels-Alder reaction of oripavine with methylvinylketone, Bentley compounds like etorphine or buprenorphine are then made from this intermediate in one or more steps depending on the target product. So if you want a structure of a compound that may be considered a backbone, it's the one on the right.

 

[Hammilton]

Those programs very commonly cannot properly interpret even perfectly done SMILES or other format names for complex structures. Just the way it is until they're reprogrammed

 

[clubcard]

Adders pictures are spot on. The compound on the left is legal (AFAIK) and x60 morphine. If anyone wondered, the methoxy and the hydroxy of Bentley compounds interact. Remove the methoxy and potency drops by a couple of orders of magnitude. Anyone interested in this field should know that Bentley almost killed himself & his team when a glass rod was used to stir the tea for 11s (bad practice) and it was lucky someone happened to look in. It was mentioned in the Nelson Eddy lectures.

I think people would do better to make 14-methoxymorphone - that's STILL too strong to be safe. I think anything over x10 M is going to kill a lot of people.

 

[serotonin2A]

The compound on the left is NOT legal, at least in the US. The controlled substance act states that all opiates in opium are controlled, as well as their derivatives. The compound on the left can be derived from thebaine or morphine.

 

[blowpipe]

The compound on the left is NOT legal, at least in the US. The controlled substance act states that all opiates in opium are controlled, as well as their derivatives. The compound on the left can be derived from thebaine or morphine.

Not a US law specialist, but "as well as their derivatives"? That's pretty broad isn't it, what are the limitations? In theory, you can "derive" pretty much anything in a finite number of steps. If I just burn the thebaine from opium and produce carbon dioxide, does that make the latter illegal?

 

[sekio]

AFAICT, anything with a similar effect to sch. 1 or 2 narcotics is quite liable to get on a ban list.

 

[serotonin2A]

Not a US law specialist, but "as well as their derivatives"? That's pretty broad isn't it, what are the limitations? In theory, you can "derive" pretty much anything in a finite number of steps. If I just burn the thebaine from opium and produce carbon dioxide, does that make the latter illegal?

It is a broad interpretation but it has appeared in the Federal Register many times. Technically it would have to be litigated by a court but courts generally grant federal agencies wide latitude to interpret statutory language.

In your example, how would they prove the CO2 was derived from thebaine? Apomorphine, which is derived from morphine, is a much better example. Apomorphine was listed as a schedule II morphine derivative until 1976 when it was explicitly removed from control.

http://www.ncbi.nlm.nih.gov/pubmed/23949903

 

[Nagelfar]

Adders pictures are spot on.
...
I think people would do better to make 14-methoxymorphone

"Adder's pictures are spot-on", or "Adder, pictures (already there) are spot on?" ;p

Is there another name by which 14-methoxymorphone goes by in the literature? A google-search didn't really turn out anything for me.

 

[sekio]

I would suspect you'd really want 14-methoxydihydromorphinone. I recall that shit like 14-OH-morphine and 14-OH-morphinone are way weaker than the dihydro versions.