Forty-Five Year Old Method Provides Insight Into the Accurate Declaration of Phyto-Cannabinoid Biosynthesis Pathway

Forty-Five Year Old Method Provides Insight Into the Accurate Declaration of Phyto-Cannabinoid Biosynthesis Pathway

This document presents the genuine thought process experienced by the author, an inventor and experimental phyto-cannabinoid chemistry detective. These preliminary findings are not the refined finished product which will include exact chemical formulas for the proper expression of the specific reactions. Theorem and findings first, formulas second.

Here is the problem, consider the solvents and reactant compounds which were used to extract and isolate acid fractions. CBNA exists, we cannot be sure that it is a chemical compound formed by naturally occurring bio-synthetic processes. Unless it is identified directly from the analysis of cannabis flower or trichome samples which are normally extracted and analyzed using chemically altering and/either destructive methods.

Note: In the English language there are cases for the word "or" to be used as an inclusive statement, in other cases exclusive. Hence the use of the more exact statement "and/either." Less confusion and ambiguity within legal documents.

The following is a link to the publication which contains the chemically altering and inaccurate methods in question. Understand that in 1975 methods and available analysis technologies were very different than those of today.
https://www.researchgate.net/publication/281181609_Isolation_of_two_new_cannabinoid_acids_from_Cannabis_sativa_L_of_Czechoslovak_origin

If CBNA exists in naturally occurring processes, then I will agree that it should be declared as an intermediate form of phyto-cannabinoid between those of THC and CBN. Most documents published since 2016 are now stating the phyto-cannabinoid biosynthesis pathway as such, THCA -> CBNA -> CBN. The following will present the proposed correction and reasoning which leads to the logically sound version.

Am I making assumptions or deducing from available knowledge and experience? Every effort is made to remain in the realm of the latter, till having the quantifiable confirmations of modern NMR spectroscopy analysis.

For THC to produce a subsequent acid form of phyto-cannabinoid would require a synthase or reactant. Even THC concentrates of the highest purity always degrade from yellow to red. The process is identified as an oxidation. The suggestion of CBNA being the intermediate between THC and CBN requires the acceptance of two subsequent reductions of molecular structure. This would defy the processes and reaction order known as REDOX reactions, reduction then oxidation. Such an exception requires the introduction of a synthase or reactant, neither are present in high purity THC concentrate.

It would seem more logical that CBN exposed to a reactant/s would then create it's acid form CBNA.

Note: The unconventional separators "-" are included to help differentiate between the numeral "0" and the letter "O" within declaration of molecular formulas.

The biosynthetic pathway reaction order as cited in recent publications:
THCA (C22-H30-O4, 358.47 g/mol)
THC (C21-H30-O2, 314.45 g/mol)
CBNA (C22-H26-O4, 354.44 g/mol)
CBN (C21-H26-O2, 310.43 g/mol)

..or

The proposed correction:
THCA (C22-H30-O4, 358.47 g/mol)
THC (C21-H30-O2, 314.45 g/mol)
CBN (C21-H26-O2, 310.43 g/mol)
CBNA (C22-H26-O4, 354.44 g/mol)

I prefer the latter, though analysis and logic will confirm.

Chemistry detective for patients.

Eureka!! ..now the pieces will fit together neatly.

The method used to extract and isolate the acid forms of phyto-cannabinoids, a mild acidification of solution (5% sulfuric acid) with added reactants to subsequently neutralize the solution are very likely suspects for causing the addition of one carbon atom and two oxygen. This would account for the increased molecular weight of CBNA if we consider the reaction to take place after the formation of CBN.

Considering the phyto-cannabinoid biosynthesis pathway including further details.

Note: The unconventional separators "-" are included to help differentiate between the numeral "0" and the letter "O" within declaration of molecular formulas.

THCA (C22-H30-O4, 358.47 g/mol)

THCA undergoes a REDUCTION in molecular structure which is commonly known as decarboxylation. During this reduction, the missing portion of the molecule creates a compound called carboxylic acid (COOH). This product of reduction itself experiences a reduction to form a CO2 molecule which leaves a remainder of one hydrogen atom. The remaining hydrogen atom is then free to return to the source molecule completing the formation of THC by raising the intermediate hydrogen count of H29 back to H30. The molecular formula for the reduction product of THCA which is known as THC can then be declared as (C21-H30-O2, 314.45 g/mol).

THC (C21-H30-O2, 314.45 g/mol)

The OXIDATION reaction of the reactants THC and O2 requires that four hydrogen atoms be removed from the molecular structure of THC. The products of this oxidative reaction are two water molecules (H2O + H2O) and one molecule of cannabinol, CBN (C21-H26-O2, 310.43 g/mol).

During the oxidation reaction it can also be said that THC is dehydrogenated by the loss of four hydrogen atoms which form two water molecules. This dehydrogenation of hydrocarbon oil can account for the observed change in chemical property, the solubility in water of cannabinol (CBN). Whereas THC and it's precursor THCA are water insoluble.

CBN (C21-H26-O2, 310.43 g/mol)

Considering the change in chemical formula between CBN and CBNA, the addition of one carbon atom and two oxygen is notable. The method of extraction and isolation of CBNA provide us with the reactants and the electro-chemical environment within the solution which make the reaction possible. The acidification of the solution by the addition of sulfuric acid (H2SO4) creates the electro-chemical condition. Sodium carbonate used to neutralize the acid solution add Na2CO3 to the reaction. The reactants sodium carbonate and sulfuric acid yield the products sodium sulfide (Na2S), carbon dioxide (CO2), water (H2O) and oxygen (O2). The sulfuric acid reacts with cannabinol (CBN) allowing for the addition of CO2 available in the solution to the molecular structure which then forms CBNA. Given the complexity of a hydrocarbon compound such as cannabinol, this reaction will require more than preliminary consideration. The specifics of the reaction between the reactants cannabinol (CBN) and sulfuric acid (H2SO4), determine the exact atoms which are taken from the molecular structure of cannabinol that allow for the addition of CO2 and relocation of one hydrogen atom which form the COOH structure in the cannabinolic acid molecule (CBNA).

CBNA (C22-H26-O4, 354.44 g/mol)

CBNA can be REDUCED (decarboxylated), the reaction will produce the exact molecular structure and composition of cannabinol (C21-H26-O2). The reduction will subtract COOH from CBNA's chemical formula. Carboxylic acid (COOH) will reduce to the products CO2 and H (hydrogen). The free hydrogen atom is then free to add itself back to the molecular structure from which it originated, to yield the product cannabinol (C21-H26-O2). This begs the question, can cannabinol (CBN) be the product of an organic reaction and a synthetic process?

The synthesis of CBNA from CBN is redundant considering the cannabinolic acid will be reduced (decarboxylated) back to cannabinol from which it was produced. A false positive, resulting from the reactants which were used during the extraction and isolation process Na2O3 and H2SO4. If anything, a method for producing CBNA from CBN has been accidentaly discovered, it's application has yet to be fathomed though I expect this will be useful in the future. For more details and confirmation we will need to reproduce the method, identifying the products of this reaction using more modern analysis technology which is now available (1975 is a long time ago).

The Second Half of This Document Presents the Earlier Aspects Which Have Led to the Proposed Corrections Presented Above

The following link leads to the previous publication which considers the many aspects that have led to the answers above. It is not a professional finished publication free of personal thought, initial shock and emotion experienced during the discovery of discrepancies. Though some readers do enjoy the honesty of the true story, hence the inclusion.

https://steemit.com/cannabis/@deanpiecka/method-for-correction-and-re-establishment-of-phyto-cannabinoid-biosynthesis-pathways