US010669248B2

(12 ) United States Patent ( 10 ) Patent No.: US 10,669,248 B2 Thomas et al. (45 ) Date of Patent : Jun . 2 , 2020

(54 ) METHODS TO CHEMICALLY MODIFY 10,195,159 B2 2/2019 Whittle et al. CANNABINOIDS 10,238,705 B2 3/2019 Speier 2004/0147767 Al 7/2004 Whittle et al. 2005/0042172 A1 2/2005 Whittle ( 71) Applicant: Natural Extraction Systems, LLC , 2009/0054711 A1 2/2009 Lawrence et al. Boulder , CO (US ) 2012/0157719 Al 6/2012 Teles et al . 2016/0038437 A1 2/2016 Whittle et al. (72 ) Inventors : C. Russell Thomas, Boulder , CO (US ) ; 2018/0078874 A1 3/2018 Thomas Matthew M.DePalo , Broomfield , CO 2018/0296617 Al 10/2018 Rivas (US ) 2019/0151171 Al 5/2019 Johnson et al. ( 73) Assignee : Natural Extraction Systems, LLC , FOREIGN PATENT DOCUMENTS Boulder, CO (US ) CA 2472561 A1 * 8/2002 C07D 311/80 EP 3453397 A1 3/2019 ( * ) Notice: Subject to any disclaimer , the term of this JP 4849578 B1 1/2012 patent is extended or adjusted under 35 WO WO - 2002 /089945 A2 11/2002 WO WO - 2015 /049585 A2 4/2015 U.S.C. 154 (b ) by 0 days . WO WO - 2016153347 Al * 9/2016 C07C 37/004 WO WO - 2016 / 161420 Al 10/2016 ( 21) Appl. No.: 16 /271,782 WO WO - 2017 / 192527 A1 11/2017 WO WO - 2018009514 Al * 1/2018 BO1D 3/10 ( 22 ) Filed : Feb. 9 , 2019 WO WO - 2018 / 102711 A1 6/2018 (65 ) Prior Publication Data OTHER PUBLICATIONS US 2020/0048214 A1 Feb. 13 , 2020 U.S. Appl . No. 16 / 271,783 , Thomas . U.S. Appl. No. 16 /271,820 , Thomas. Related U.S. Application Data International Search Report and Written Opinion for International (60 ) Provisional application No.62 /717,235 , filed on Aug. Application No. PCT/ US2019 /045992 dated Oct. 18 , 2019 . 10 , 2018, provisional application No. 62/ 803,408 , International Search Report and Written Opinion for International filed on Feb. 8 , 2019 . Application No. PCT /US2019 / 045950 dated Nov. 15 , 2019 . Kanter et al. , “ Quantitative determination of detla9 -tetrahydrocan nabinol and delta9 - tretrahydro - cannabinolic acid in marihuana by (51 ) Int. Ci. high - pressure liquid chromatography, ” J Chromatogr 171: 504-508 CO7D 311/78 ( 2006.01 ) ( 1979 ). C07C 29/80 (2006.01 ) Veress et al. , “ Determination of cannabinoid acids by high C07C 67/08 (2006.01 ) performance liquid chromatography of their neutral derivatives BOID 5/00 ( 2006.01 ) formed by thermal decarboxylation : I. Study of the decarboxylation (52 ) U.S. CI. process in open reactors ,” J Chromatogr, 520 :339-347 ( 1990 ). CPC CO7D 311/78 (2013.01 ) ; C07C 29/80 ( 2013.01) ; C07C 67/08 (2013.01 ) ; B01D 5/006 * cited by examiner (2013.01 ) (58 ) Field of Classification Search Primary Examiner Noble E Jarrell CPC CO7D 311/78 ; C07C 29/80 ; BO1D 5/006 ( 74 ) Attorney, Agent, or Firm - Douglas G. Metcalf See application file for complete search history. (57 ) ABSTRACT (56 ) References Cited Various aspects of this disclosure relate to methods to lower the activation energy of the cannabinoid decarboxylation U.S. PATENT DOCUMENTS reaction by performing the decarboxylation reaction in the 4,396,487 A 8/1983 Strumskis gas phase . 9,987,567 B1 * 6/2018 Ko C07C 37/004 10,159,908 B2 12/2018 Thomas 15 Claims, 4 Drawing Sheets U.S. Patent Jun . 2 , 2020 Sheet 1 of 4 US 10,669,248 B2

Fig. 1 OH a H j. H " i H b d H? ?. ? ZoCOV H g HO locom OH b Coa H H jo--- M2 H io SH Ia H 8t H H g h ?? U.S. Patent Jun . 2 , 2020 Sheet 2 of 4 US 10,669,248 B2

Fig. 2

a h

ON U.S. Patent Jun . 2 , 2020 Sheet 3 of 4 US 10,669,248 B2

Fig . 3 Representative Cannabinoid Concentrations in USDA Organic IndustrialHemp 12 %

10 %

8 % 6 % 4 %

2 %

0 % THCA THC CBDA CBD CBN CBG

Fig . 4 Representative Cannabinoid Concentrations in Concentrate Produced from Liquid Distillate 70 % 60 % 50 % 40 % 30 % 20 % 10 % 0 % THCA THC CBDA CBD CBN CBG U.S. Patent Jun . 2 , 2020 Sheet 4 of 4 US 10,669,248 B2 Fig . 5 Representative Terpene , Terpene Alcohol, and Terpenoid Concentrations in Concentrate Produced from Liquid Distillate 3.96 %

Sl 2.33 % 1.2 %

poods

0.6 %

Humulene Guaiol(-) Linalool AlphaTerpineol- Myrcene Eucalyptol Limonene Nerolidol Alpha-Terpinene Borneol -Isopulegol Beta-Caryophyllene BisabololAlpha-() OxideCaryophyllene US 10,669,248 B2 1 2 METHODS TO CHEMICALLY MODIFY show a predicted, single - step , cyclic chemical reaction cata CANNABINOIDS lyzed by a first THCA molecule that results in the decar boxylation of a second THCA molecule . PRIORITY CLAIM FIG . 3 is a bar graph depicting the THCA , THC , CBDA , 5 CBD , CBN , and CBG concentrations found in a typical This patent application claims priority to U.S. Provisional sample of USDA organic industrial hemp. Patent Application No.62 /717,235 , filed Aug. 10 , 2018 , and FIG . 4 is a bar graph depicting the THCA , THC , CBDA , U.S. Provisional Patent Application No. 62/ 803,408 , filed CBD , CBN , and CBG concentrations found in four different Feb. 8 , 2019, each of which is incorporated by reference in concentrate products produced according to methods dis its entirety . 10 closed in this patent document. FIG . 5 is a bar graph depicting terpene , terpene alcohol , BACKGROUND and terpenoid concentrations found in two different concen trate products produced according to methods disclosed in Industrial hemp and other forms of cannabis contain a this patent document. variety of different cannabinoids , which predominantly each 15 contain a carboxyl group . These cannabinoid carboxylic DETAILED DESCRIPTION acids bind the human cannabinoid receptors with relatively low affinity . The production of therapeutic pharmaceuticals The present disclosure describes methods to rapidly and psychoactive drugs from cannabis therefore generally decarboxylate cannabinoids without generating appreciable utilizes a decarboxylation step, which typically involves 20 quantities of undesirable side products . Various methods prolonged heating . This heating also generally introduces comprise ( 1 ) rapidly vaporizing and decarboxylating a can other chemical modifications that are typically undesirable . nabinoid , and then ( 2 ) contacting the vaporized , decarboxy Marijuana produces tetrahydrocannabinolic acid lated cannabinoid with a heat sink to condense the decar (“ THCA " ), for example , which lacks robust pharmacologi boxylated cannabinoid . cal effects . THCA is converted into the psychoactive mol- 25 Cannabinoids are typically decarboxylated by heating . ecule tetrahydrocannabinol ( “ THC ” ) by decarboxylation , Traditional hydrocarbon -based extraction methods typically which occurs when marijuana is smoked . THC is commer extract cannabinoid carboxylic acids from cannabis prior to cially produced from THCA by heating the THCA for decarboxylation . The extracted cannabinoid carboxylic several hours . Prolonged heating nevertheless results in acids are typically then converted into activated decarboxy undesirable side products . THCA can be oxidized , for 30 lated cannabinoids by heating in a vacuum oven for several example , into cannabinolic acid (“ CBNA ” ), which decom hours. The inventors modelled possible reaction mecha poses into cannabinol (“ CBN ” ). CBNA lacks well- known nisms for the decarboxylation and determined that cannabi pharmacological properties, and CBN causes drowsiness. noid carboxylic acids can self - catalyze the reaction . Industrial hemp similarly produces cannabidiolic acid According to the self -catalyzed reaction mechanism , (“ CBDA ” ) , which lacks robust pharmacological effects . 35 decarboxylation can proceed in a single - step, cyclic reaction CBDA is converted into the pharmaceutical cannabidiol depicted in FIG . 1 , which shows a first 2,4 -dihydroxy - 3 (“ CBD ” ) by decarboxylation . CBD is commercially pro [( 1R ,OR ) -6 - isopropenyl- 3 -methylcyclohex - 2- en - 1 - yl ) -6 duced from CBDA by heating the CBDA for several hours . pentylbenzoic acid (“ CBDA ” ) molecule ( FIG . 1 , top ) cata Prolonged heating nevertheless results in undesirable side lyzing the decarboxylation of a second CBDA molecule products including CBN . 40 ( FIG . 1 , bottom ). Immediately prior to the reaction , the first The industrial production of decarboxylated cannabinoids and second CBDA molecules form two intermolecular also degrades and vaporizes other molecules found in can hydrogen bonds denoted by two long dotted lines in FIG . 1. nabis including terpenes , terpene alcohols , terpenoids, and The hydrogen bond depicted by the top -most dotted line is flavonoids, which often impart favorable characteristics to between an electron pair of the carbonyl oxygen of the first products containing cannabinoids including favorable flavor 45 CBDA molecule (FIG . 1 , “ a ” ) and the hydroxyl proton of the and aroma. second CBDA molecule (FIG . 1 , “ b ” ) . The hydrogen bond Improved methods to decarboxylate cannabinoids are depicted by the bottom -most dotted is between the pi desirable . electron cloud of the second CBDA molecule ( FIG . 1 , “ g ” ) and the carboxylic acid proton of the first CBDA molecule SUMMARY 50 (FIG . 1 , “ h ” ) . An intramolecular hydrogen bond also forms between an electron pair of the hydroxyl oxygen of the Various aspects of this patent document relate to the rapid , second CBDA molecule (FIG . 1 , “ c ” ) and the carboxylic stoichiometric decarboxylation of cannabinoid carboxylic acid proton of the second CBDA molecule (FIG . 1 , " d " ) . acids ( for example, CBDA or THCA ) in the gas phase The predicted , single - step , cyclic reaction shown in FIG . followed by the condensation of a decarboxylated cannabi- 55 1 proceeds by converting the three hydrogen bonds into noid product ( for example , CBD or THC ) . covalent bonds , breaking four single bonds, converting two single bonds into double bonds, and converting a double BRIEF DESCRIPTION OF THE DRAWINGS bond into a single bond . The hydrogen bond between an electron pair of the carbonyl oxygen of the first CBDA FIG . 1 depicts the skeletal formula of two CBDA mol- 60 molecule (FIG . 1 , “ a ” ) and the hydroxyl proton of the second ecules before a first CBDA molecule catalyzes the decar CBDA molecule (FIG . 1, “ b ” ) becomes a covalent bond , boxylation of a second CBDA molecule to regenerate the which converts the double bond between the carbonyl first CBDA molecule and to produce CBD and carbon oxygen (FIG . 1, “ a ” ) and the carbonyl carbon ( FIG . 1, “ J” ) dioxide from the second CBDA molecule . of the first CBDA molecule into a single bond . The hydroxyl FIG . 2 is a ball and stick model of two THCA molecules , 65 of the second CBDA molecule reforms by converting the which depicts two intermolecular hydrogen bonds between hydrogen bond between an electron pair of the hydroxyl the two THCA molecules and electron pair arrow pushing to oxygen of the second CBDA molecule (FIG . 1, “ c ” ) and the US 10,669,248 B2 3 4 carboxylic acid proton of the second CBDA molecule ( FIG . molecule (FIG . 2 , “ a” ) and the hydroxyl proton of the second 1 , " d ” ) into a covalent bond . The extra electron pair of the THCA molecule (FIG . 2 , “ b ” ) becomes a covalent bond , deprotonated carboxylate oxygen of the second CBDA which converts the double bond between the carbonyl molecule (FIG . 1 , “ e ” ) converts the single bond of the oxygen ( FIG . 2 , “ a ” ) and carbonyl carbon of the first THCA deprotonated carboxylate into a double bond , and the elec- 5 molecule into a single bond . The hydroxyl of the second tron pair of the carbon - carbon single bond at the 1 - position THCA molecule reforms by converting the hydrogen bond of the second CBDA molecule (FIG . 1 , “ I ') enters the pi between an electron pair of the hydroxyl oxygen of the electron cloud of the aromatic ring of the second CBDA second THCA molecule (FIG . 2 , “ c ” ) and the carboxylic molecule (FIG . 1 , “ g '' ) to release the deprotonated carboxy acid proton of the second THCA molecule (FIG . 2 , “ d ” ) into late from the second CBDA molecule as a carbon dioxide 10 a covalent bond . The extra electron pair of the deprotonated molecule . The hydrogen bond between the pi electron cloud carboxylate oxygen of the second THCA molecule (FIG . 2 , of the second CBDA molecule (FIG . 1 , " g ” ) and the car “ e ” ) converts the single bond of the deprotonated carboxy boxylic acid proton of the first CBDA molecule (FIG . 1 , “ h ” ) late into a double bond , and the electron pair of the carbon becomes a covalent bond to replace the deprotonated car carbon single bond at the 2 -position of the 6H -benzo [ c ] boxylate at the 1 - position of the second CBDA molecule 15 chromene of the second THCA molecule (FIG . 2 , “ 1 ” ) enters ( which left the second CBDA molecule as a carbon dioxide the pi electron cloud of the aromatic ring of the second molecule ) with the proton . The extra electron pair of the THCA molecule (FIG . 2 , “ g ” ) to release the deprotonated deprotonated oxygen of the first CBDA molecule (FIG . 1 , carboxylate from the second THCA molecule as a carbon “ 4” ) converts the single bond between the deprotonated dioxide molecule . The hydrogen bond between the pi elec oxygen (FIG . 1 , “ i” ) and the carbonyl carbon (FIG . 1 , “ J” ) 20 tron cloud of the second THCA molecule (FIG . 2 , “ g ” ) and into a double bond to reform the carboxylic acid of the first the carboxylic acid proton of the first THCA molecule (FIG . CBDA molecule . 2 , “ h ” ) becomes a covalent bond to replace the deprotonated The reaction mechanism described above is represented carboxylate at the 2 -position of the 6H -benzo [ c ]chromene of by arrows in FIG . 1 , which depict electron pair pushing . the second THCA molecule (which left the second THCA Specific atoms are annotated by the lowercase letters “ a ” -“ e ” 25 molecule as a carbon dioxide molecule ) with the proton . The and “ h ” -“ j” in FIG . 1 as described above. The bond that extra electron pair of the deprotonated oxygen of the first breaks to decarboxylate the second CBDA molecule and THCA molecule ( FIG . 2 , " i" ) converts the single bond release a carbon dioxide molecule is annotated by the between the deprotonated oxygen and carbonyl carbon into lowercase letter “ f” in FIG . 1 as described above . The pi a double bond to reform the carboxylic acid of the first electron cloud of the aromatic ring of the second CBDA 30 THCA molecule . molecule is annotated by the lowercase letter “ g ” in FIG . 1 The reaction mechanism described above is represented as described above . by arrows in FIG . 2 , which depict electron pair pushing . The proposed reaction mechanism described above was Atoms that form hydrogen bonds that become covalent modeled in three dimensions to determine whether the bonds are shown with white fill in FIG . 2. Covalent bonds sterics of the actual CBDA and THCA molecules are com- 35 that break are shown with white fill in FIG . 2. Three patible with the proposed reaction mechanism . The inven hydrogen bonds that become covalent bonds are shown with tors determined that two CBDA or THCA molecules can dotted lines in FIG . 2. Specific atoms are annotated by the form near -perfect hydrogen bond lengths and geometries lowercase letters “ a ” -“ ,” “ h ” , and “ i” in FIG . 2 as described without steric clashes or significant entropic penalty pro above . The bond that breaks to decarboxylate the second vided that a first CBDA or THCA molecule can interact with 40 THCA molecule and release a carbon dioxide molecule is a second CBDA or THCA molecule at an approximate annotated by the lowercase letter “ f” in FIG . 2 as described orthogonal orientation . above . The pi electron cloud of the aromatic ring of the FIG . 2 shows a first (6R , 10aR )-1 -hydroxy -6,6,9 -trim second THCA molecule is annotated by the lowercase letter ethyl- 3 - pentyl- 6a , 7,8,10a- tetrahydro -6H -benzo [ c ] “ g ” in FIG . 2 as described above . chromene - 2 - carboxylic acid (“ THCA ” ) molecule (FIG . 2 , 45 The reaction mechanisms set forth above are descriptive top ) catalyzing the decarboxylation of a second THCA approximations that conform with classical theories of molecule (FIG . 2 , bottom ). Immediately prior to the reac organic chemistry . Other scientific theories such as quantum tion , the first and second THCA molecules form two inter mechanical theory might describe the same chemical reac molecular hydrogen bonds denoted by two long dotted lines tion differently and in a manner that contradicts the reaction in FIG . 2. The hydrogen bond depicted by the left- most 50 mechanism set forth above . The precise description of the dotted line is between an electron pair of the carbonyl decarboxylation reaction mechanism is irrelevant to this oxygen of the first THCA molecule ( FIG . 2 , “ a ” ) and the patent document and any claim that matures from the hydroxyl proton of the second THCA molecule (FIG . 2 , disclosure of this patent document. Two insights obtained “ b ” ). The hydrogen bond depicted by the right- most dotted from this reaction mechanism are relevant: (1 ) a molecule is between the pi electron cloud of the second THCA 55 having a functional group that is both a Bronsted acid and a molecule (FIG . 2 , “ g ” ) and the carboxylic acid proton of the Bronsted base ( such as a carboxylic acid ) can catalyze the first THCA molecule (FIG . 2, “ h ” ) . An intramolecular decarboxylation of a cannabinoid , and ( 2) the accessible hydrogen bond also forms between an electron pair of the orientations between a cannabinoid and a catalyst affect the hydroxyl oxygen of the second THCA molecule (FIG . 2 , decarboxylation reaction rate . “ c” ) and the carboxylic acid proton of the second THCA 60 An implication of the insights set forth above is that the molecule (FIG . 2 , “ d ” ) . activation energy of the cannabinoid decarboxylation reac The predicted , single - step , cyclic reaction shown in FIG . tion can be lowered by increasing the probability that a 2 proceeds by converting the three hydrogen bonds into catalyst will contact a cannabinoid at an appropriate geom covalent bonds , breaking four single bonds, converting two etry to form two intermolecular hydrogen bonds between the single bonds into double bonds, and converting a double 65 catalyst and the cannabinoid . During self -catalysis in the bond into a single bond . The hydrogen bond between an liquid phase , cannabinoids preferably form roughly -parallel electron pair of the carbonyl oxygen of the first THCA pi- stacking interactions that inhibit the formation of inter US 10,669,248 B2 5 6 molecular hydrogen bonds having geometries capable of the surprisingly more efficient than prior art methods and allow cyclic decarboxylation reaction described above . Traditional simultaneous purification and decarboxylation . Other decarboxylation by heating cannabinoids partially disrupts advantages are disclosed in this patent document. the pi- stacking interactions and introduces entropy, which The inventors identified parameters that result in marked each increase the probability that intermolecular hydrogen 5 improvements over prior art methods: ( 1 ) the cannabinoids bonds will form that have an appropriate geometry and should be present in a composition having a high surface connectivity for the decarboxylation reaction . One inventive area -to - volume ratio , ( 2 ) the cannabinoids should be present aspect of this patent document is the discovery that the in the composition at a relatively high concentration , and ( 3 ) activation energy can be lowered by introducing entropy cannabinoid vapor should be condensed immediately after into the system by performing the decarboxylation reaction 10 vaporization . High surface area and high relative cannabi in a gas phase . noid concentration ensures that the energy used to vaporize Smoking and vaporizing marijuana are both known to and decarboxylate a cannabinoid carboxylic acid favors decarboxylate cannabinoids , but smoking and vaporizing vaporization and decarboxylation relative to the heating and marijuanayields. Smoking are not degrades known ato substantial result in nearportion- stoichiometric of cannabi- 15 vaporization of other molecules. Rapid condensation of noids by combustion , thermal oxidation , pyrolysis, and cannabinoid vapor minimizes contact between cannabinoid isomerization . Vaporization minimizes combustion , but vapor and other heated molecules . vaporization nevertheless results in oxidation , pyrolysis , and Vaporizing a cannabinoid carboxylic acid does not nec isomerization . essarily result in decarboxylation , and vaporization often Laboratory analyses suggest that commercially - available 20 results in undesirable pyrolysis . When the above parameters personal vaporizers are capable of variable decarboxylation are optimized , cannabinoid carboxylic acids can be both efficiencies ranging from about 80 % efficiency to near decarboxylated and vaporized at temperatures near or below complete decarboxylation when operated under laboratory their boiling points to allow simultaneous decarboxylation conditions, but personal vaporizers generate substantial and purification and minimize undesirable pyrolysis . amounts of undesirable side products such as cannabinol. 25 The inventors contemplate that reducing the duration of Consumers compensate for variable efficiency, oxidation , time that heated cannabinoids spend in contact with other pyrolysis , and isomerization by simply titrating their dose . heated molecules reduces the rate of undesirable oxidation , The laboratory analyses of consumer products that generate pyrolysis , and isomerization of the cannabinoids. Surpris a vapor are informative , but these products are less relevant ingly , reducing the duration of time that heated cannabinoids to commercial strategies to produce high -value liquid can- 30 spend in contact with other heated molecules and reducing nabinoids . the duration of time that cannabinoids are exposed to Attempts to decarboxylate cannabinoids by vaporization heat nevertheless permits rapid and efficient decarboxy in industrial processes have met with limited success . The lation and allows near- stoichiometric decarboxylation while prior art discloses methods to decarboxylate cannabinoids minimizing oxidation , pyrolysis , and isomerization . from plantmaterial by vaporization at a temperature of 1450 35 The conceptual framework described above allows for the C. ( 293 ° F. ) for about 30 minutes , which resulted in a minimization of the time and energy required to decarboxy purported 95 % decarboxylation efficiency (PCT Patent late cannabinoids by minimizing the activation energy of the Application Publication No. WO 02/089945 A2 ). Actual decarboxylation reaction . The conceptual framework simi yields relative to the amounts of cannabinoids in the starting larly allows for the optimization of the power required to materials were not reported . The prior art methods were also 40 decarboxylate cannabinoids . incapable of recovering high yields of decarboxylated can This patent document discloses for the first time that a nabinoids without converting a substantial portion of the cannabinoid can catalyze the decarboxylation of another cannabinoids into undesirable degradation products such as cannabinoid . This patent document discloses for the first cannabinol (PCT Patent Application Publication No. WO time that the activation energy of the cannabinoid decar 02/089945 A2 at pages 41-43 ). The recovered cannabinoids 45 boxylation reaction can be minimized relative to prior art included 6.2-14.1 % cannabinol. Formulations comprising methods , and thus, the energy added during a decarboxy cannabinol at concentrations of 1 % or greater as a percent lation reaction can be minimized relative to prior art meth age of total cannabinoids are typically useful only as sleep ods . This patent document discloses for the first time that the aids, and concentrations of 5 % or greater cause extreme power driving the cannabinoid decarboxylation reaction can drowsiness. No known method allows for the purification of 50 be optimized , and thus, the rate of a decarboxylation reac pharmacologically -relevant cannabinoids from cannabinol tion can be maximized relative to prior art methods. in a commercially -viable process, and thus, the prior art Various aspects of the disclosure relate to a method to methods have limited commercial utility . chemically modify a cannabinoid molecule . In some The inventors previously developed systems to extract embodiments , a chemicalmodification is a decarboxylation cannabinoids by vaporization ( for example , PCT Patent 55 of a cannabinoid carboxylic acid . In some specific embodi Application Publication No. WO 2015/049585 A2 and WO ments, a chemical modification is the conversion of canna 2018/102711 A1 ). Vaporization generally requires high tem bidiolic acid or cannabidiolate into cannabidiol. In some peratures , which favor both undesirable pyrolysis and decar specific embodiments , a chemical modification is the con boxylation ( i.e. , desirable pyrolysis ) . The inventors previ version of cannabidivarin carboxylic acid (“ CBDVA ” ) or the ously disclosed methods that minimize or eliminate 60 conjugate base of CBDVA into cannabidivarin ( " CBDV ” ) . pyrolysis, which minimizes or eliminates decarboxylation In some specific embodiments , a chemical modification is by definition ( for example , PCT Patent Application Publi the conversion of tetrahydrocannabinolic acid or tetrahydro cation No. WO 2015/049585 A2 and WO 2018/102711 A1) . cannabinolate into tetrahydrocannabinol. In some specific The inventors have now identified methods that decouple embodiments , a chemical modification is the conversion of decarboxylation from other undesirable chemical reactions 65 tetrahydrocannabivarin carboxylic acid (“ THCVA ” ) or tet during vaporization , which are generally applicable to all rahydrocannabivarin carboxylate into tetrahydrocannabi known methods of vaporization . These methods are also varin (“ THCV ” ). In some specific embodiments , a chemical US 10,669,248 B2 7 8 modification is the conversion of perrottetinenic acid or the nabidiorcolic acid (“ CBDOA ” ) , cannabichromenic acid conjugate base of perrottetinenic acid into perrottetinene. (“ CBCA ” ), cannabichromevarinic acid (“ CBCVA” ), can In some embodiments , a method comprises providing a nabigerolic acid ( “ CBGA ” ) , cannabigerovarinic acid (“ CB composition comprising cannabinoids , in which the can GVA " ), cannabicyclolic acid (“ CBLA " ) , cannabielsoic acid nabinoids comprise a native cannabinoid molecule , the 5 (“ CBEA” ), perrottetinenic acid , carboxylates of any of the native cannabinoid molecule comprises a carboxyl group , preceding molecules , naturally -occurring ethers of any of and the native cannabinoid molecule is in a liquid phase or the preceding molecules , and stereoisomers of any one of the a solid phase in the composition . preceding molecules. In some embodiments , a method comprises contacting a In some embodiments , a cannabinoid molecule , modified composition with sufficient energy to convert a native can- 10 cannabinoid molecule , or condensed cannabinoid molecule nabinoid molecule of the composition into ( i) a carbon is selected from one or more of THC , THCV, tetrahydro dioxide molecule and ( ii ) a modified cannabinoid molecule cannabiorcol (“ THCO " ) , CBD , CBDV, cannabidiorcol, in a gas phase. (“ CBDO ” ) , cannabichromene (“ CBC ” ), cannabichrom In some embodiments , a method comprises contacting a evarin (“ CBCV ), cannabigerol (" CBG ” ), cannabigerovarin modified cannabinoid molecule with a heat sink to condense 15 (“ CBGV” ), cannabicyclol (“ CBL” ) , cannabielsoin (“ CBE ” ) , the modified cannabinoid molecule into a condensed can perrottetinene , naturally occurring ethers of any of the pre nabinoid molecule in a liquid distillate . ceding molecules , and stereoisomers of any of the preceding In some embodiments , a method comprises collecting a molecules . liquid distillate . In some specific embodiments , a cannabinoid molecule , In some embodiments , a composition comprises a plant 20 native cannabinoid molecule , or condensed cannabinoid material . In some very specific embodiments , a composition molecule is CBDA . In some very specific embodiments , a comprises a plantmaterial , and the plant material comprises native cannabinoid molecule is CBDA . a native cannabinoid molecule . In some specific embodi In some specific embodiments , a cannabinoid molecule , ments, a composition comprises a ground plant material. In native cannabinoid molecule , or condensed cannabinoid some embodiments , a composition has a surface - area - to- 25 molecule is CBDVA , which is also known as 2,4 - dihydroxy volume ratio greater than 1000 per meter. 3 -[ ( 1R ,6R ) -6 - isopropenyl- 3 -methylcyclohex - 2 -en - 1- yl )-6 In some embodiments , a plant material is a species of the propylbenzoic acid . In some very specific embodiments , a genus Cannabis . In some specific embodiments , a plant native cannabinoid molecule is CBDVA . material is Cannabis sativa . In some specific embodiments , In some specific embodiments , a cannabinoid molecule , a plant material is Cannabis indica . In some specific 30 native cannabinoid molecule , or condensed cannabinoid embodiments , a plant material is Cannabis ruderalis . In molecule is THCA . In some very specific embodiments , a some very specific embodiments , a plant material is Can native cannabinoid molecule is THCA . nabis sativa forma indica. In some specific embodiments , a In some specific embodi a cannabinoid molecule , plant material lacks THC and potential THC at a combined native cannabinoid molecule , or condensed cannabinoid concentration by weight exceeding 0.3 % . The term “ poten- 35 molecule is THCVA , which is also known as ( 6aR , 10aR ) tial THC ” refers to THCA multiplied by 314.47 ( the molecu 1 -hydroxy -6,6,9 -trimethyl - 3 - propyl- 6a, 7,8,10a -tetrahydro lar weight of THC ) and divided by 358.48 ( the molecular 6H -benzo [ c ]chromene - 2 -carboxylic acid . In some very spe weight of THCA ). A plant material that lacks THC and cific embodiments , a native cannabinoid molecule is contains 0.33 % THCA , for example , contains THC and THCVA . potential THCA at a combined concentration by weight of 40 In some specific embodiments , a cannabinoid molecule , 0.29 % . native cannabinoid molecule , or condensed cannabinoid In some embodiments , a composition comprises an molecule is perrottetinenic acid , which is also known as extracted oil from the genus Cannabis . In some specific (6a , 10aR ) -1 -hydroxy -6,6,9 - trimethyl -3- ( 2 -phenylethyl ) embodiments , a composition comprises an extracted oil 6,7,8,10a - tetrahydro -6H -benzo [ c ] chromene - 2 -carboxylic from industrial hemp . 45 acid . In some very specific embodiments , a native cannabi In some embodiments , a composition comprises mari noid molecule is perrottetinenic acid . juana or a composition is derived from marijuana . In some specific embodiments , a modified cannabinoid In some embodiments , a composition is a liquid such as molecule , or condensed cannabinoid molecule is CBD , an oil. In someembodiments , a composition is an aerosol . In which is also known as 2 - [ ( 1R ,6R ) -6 - isopropenyl- 3 -meth some specific embodiments , a composition comprises a 50 ylcyclohex -2 - en - 1 -yl ] -5 -pentylbenzene - 1,3- diol. In some suspension of solid particles in a gas. In some specific very specific embodiments , a modified cannabinoid mol embodiments , a composition comprises a suspension of ecule is CBD . In some very specific embodiments , a con liquid droplets in a gas. In some specific embodiments , a densed cannabinoid molecule is CBD . composition comprises a powder . In some specific embodi In some specific embodiments , a modified cannabinoid ments , a composition comprises crystals . In some specific 55 molecule , or condensed cannabinoid molecule is CBDV, embodiments , a composition comprises wax . which is also known as 2 - [( 1R ,6R ) -6 - isopropenyl- 3- meth In some embodiments , a composition is suspended in a ylcyclohex - 2 -en - 1- yl] -5 - propylbenzene - 1,3 -diol . In some gas phase . very specific embodiments , a modified cannabinoid mol In some embodiments , a method comprises grinding plant ecule is CBDV. In some very specific embodiments , a material . In some embodiments , a method comprises sepa- 60 condensed cannabinoid molecule is CBDV. rating particles of industrial hemp, marijuana , or other plant In some specific embodiments , a modified cannabinoid material by size such as by using a screen , mesh , or particle molecule , or condensed cannabinoid molecule is THC , classifier . which is also known as (6aR , 10aR ) -6,6,9 - trimethyl - 3 -pen In some embodiments , a cannabinoid molecule , native tyl- 6a , 7,8,10a - tetrahydro -6H -benzo [c ] chromen - 1 -ol . In cannabinoid molecule , or condensed cannabinoid molecule 65 some very specific embodiments , a modified cannabinoid is selected from one or more of THCA , THCVA , tetrahy molecule is THC . In some very specific embodiments, a drocannabiorcolic acid (“ THCOA ” ) , CBDA , CBDVA , can condensed cannabinoid molecule is THC . US 10,669,248 B2 9 10 In some specific embodiments, a modified cannabinoid CBDA , CBDVA , THCA , THCVA , and CBGA at a concen molecule, or condensed cannabinoid molecule is THCV, tration by weight of 1 % to 10 % , 5 % to 15 % , 10 % to 20 % , which is also known as (6aR , 10aR ) -6,6,9 -trimethyl - 3 -pro 15 % to 25 % , 20 % to 30 % , or 25 % to 35 % . In some very pyl- 6a ,7,8,10a - tetrahydro -6H -benzo [ c ] chromen - 1 -ol . In specific embodiments , a composition comprises CBDA at a some very specific embodiments , a modified cannabinoid 5 concentration of at least 5 % by weight. In some very specific molecule is THCV . In some very specific embodiments , a embodiments , a composition comprises CBDA at a concen condensed cannabinoid molecule is THCV . tration by weight of 1 % to 10 % , 5 % to 15 % , 10 % to 20 % , In some specific embodiments , a modified cannabinoid 15 % to 25 % , 20 % to 30 % , or 25 % to 35 % . In some very molecule , or condensed cannabinoid molecule is per specific embodiments , a composition comprises CBDVA at rottetinene, which is also known as (6aS , 10aR ) -6,6,9 - trim- 10 a concentration of at least 0.1 % by weight. In some very ethyl- 3- ( 2 -phenylethyl ) -6a ,7,8,10a -tetrahydro -6H -benzo [c ] specific embodiments , a composition comprises CBDVA at chromen - 1 -ol . In some very specific embodiments , a a concentration by weight of 0.1 % to 10 % , 5 % to 15 % , 10 % modified cannabinoid molecule is perrottetinene . In some to 20 % , 15 % to 25 % , 20 % to 30 % , or 25 % to 35 % . In some very specific embodiments , a condensed cannabinoid mol very specific embodiments , a composition comprises THCA ecule is perrottetinene. 15 at a concentration of at least 20 % by weight. In some very In some specific embodiments , a native cannabinoid specific embodiments , a composition comprises THCA at a molecule is THCA , a modified cannabinoid molecule is concentration by weight of 10 % to 20 % , 15 % to 25 % , 20 % THC , and a condensed cannabinoid molecule is THC . to 30 % , or 25 % to 35 % . In some very specific embodiments , In some specific embodiments , a native cannabinoid a composition comprises THCVA at a concentration of at molecule is THCVA , a modified cannabinoid molecule is 20 least 1 % by weight. In some very specific embodiments , a THCV, and a condensed cannabinoid molecule is THCV . composition comprises THCVA at a concentration by weight In some specific embodiments, a native cannabinoid of 0.1 % to 10 % , 5 % to 15 % , 10 % to 20 % , 15 % to 25 % , 20 % molecule is THCOA , a modified cannabinoid molecule is to 30 % , or 25 % to 35 % . THCO , and a condensed cannabinoid molecule is THCO . In some embodiments , a method comprises suspending a In some specific embodiments , a native cannabinoid 25 particle of a composition comprising cannabinoids in a gas molecule is CBDA , a modified cannabinoid molecule is phase , in which the particle comprises a native cannabinoid CBD , and a condensed cannabinoid molecule is CBD . molecule . In some specific embodiments , a composition In some specific embodiments , a native cannabinoid comprising a native cannabinoid molecule is contacted with molecule is CBDVA , a modified cannabinoid molecule is sufficient energy to convert the native cannabinoid molecule CBDV, and a condensed cannabinoid molecule is CBDV. 30 into (i ) a carbon dioxide molecule and ( ii ) a modified In some specific embodiments , a native cannabinoid cannabinoid molecule in a gas phase while a particle of the molecule is CBDOA , a modified cannabinoid molecule is composition comprising the native cannabinoid molecule is DO , and a condensed cannabinoid molecule is CBDO . suspended in the gas phase . In some specific embodiments , a native cannabinoid In some embodiments , a method comprises suspending a molecule is CBCA , a modified cannabinoid molecule is 35 plurality of particles of a composition comprising cannabi CBC , and a condensed cannabinoid molecule is CBC . noids in a gas phase , in which the plurality of particles In some specific embodiments , a native cannabinoid comprises a native cannabinoid molecule . In some specific molecule is CBCVA , a modified cannabinoid molecule is embodiments , a composition comprising a native cannabi CBCV , and a condensed cannabinoid molecule is CBCV . noid molecule is contacted with sufficient energy to convert In some specific embodiments , a native cannabinoid 40 the native cannabinoid molecule into ( i) a carbon dioxide molecule is CBGA , a modified cannabinoid molecule is molecule and ( ii ) a modified cannabinoid molecule in a gas CBG , and a condensed cannabinoid molecule is CBG . phase while a plurality of particles of the composition In some specific embodiments , a native cannabinoid comprising the native cannabinoid molecule is suspended in molecule is CBGVA , a modified cannabinoid molecule is the gas phase . CBGV , and a condensed cannabinoid molecule is CBGV. 45 In some embodiments , a method comprises suspending a In some specific embodiments , a native cannabinoid droplet of a composition comprising cannabinoids in a gas molecule is CBLA , a modified cannabinoid molecule is phase , in which the droplet comprises a native cannabinoid CBL , and a condensed cannabinoid molecule is CBL . molecule . In some specific embodiments , a composition In some specific embodiments , a native cannabinoid comprising a native cannabinoid molecule is contacted with molecule is CBEA , a modified cannabinoid molecule is 50 sufficient energy to convert the native cannabinoid molecule CBE , and a condensed cannabinoid molecule is CBE . into (i ) a carbon dioxide molecule and ( ii ) a modified In some specific embodiments , a native cannabinoid cannabinoid molecule in a gas phase while a droplet of the molecule is perrottetinenic acid , a modified cannabinoid composition comprising the native cannabinoid molecule is molecule is perrottetinene, and a condensed cannabinoid suspended in the gas phase . molecule is perrottetinene . 55 In some embodiments , a method comprises suspending a In some embodiments , a composition comprises a plural plurality of droplets of a composition comprising cannabi ity of cannabinoids, and at least 95 % of the cannabinoids of noids in a gas phase , in which the plurality of droplets the plurality of cannabinoids comprises a carboxyl group . comprises a native cannabinoid molecule . In some specific In some embodiments , a composition comprises a native embodiments , a composition comprising a native cannabi cannabinoid molecule at a concentration of at least 5 % by 60 noid molecule is contacted with sufficient energy to convert weight. In some embodiments , a composition comprises a the native cannabinoid molecule into ( i ) a carbon dioxide native cannabinoid molecule at a concentration by weight of molecule and ( ii ) a modified cannabinoid molecule in a gas 1 % to 10 % , 5 % to 15 % , 10 % to 20 % , 15 % to 25 % , 20 % to phase while a plurality of droplets of the composition 30 % , or 25 % to 35 % . In some specific embodiments , a comprising the native cannabinoid molecule is suspended in composition comprises CBDA , CBDVA , THCA , THCVA , 65 the gas phase . and CBGA at a concentration of at least 5 % by weight. In In some embodiments , a gas phase comprises water vapor some specific embodiments , a composition comprises at a concentration of at least 5 % by volume. In some US 10,669,248 B2 11 12 embodiments , a gas phase comprises ethanol vapor at a probability that a first native cannabinoid molecule will concentration of at least 5 % by volume. In some embodi interact with either a second native cannabinoid molecule or ments , a gas phase comprises molecular nitrogen , ethanol other catalyst with an appropriate orientation to catalyze the vapor, water vapor, carbon dioxide , noble gases, cannabi decarboxylation of the first native cannabinoid molecule . noids , terpenes , terpene alcohols , and terpenoids at a total 5 In some embodiments , a method comprises directing a concentration of at least 90 % by volume. In some specific composition along a path having a length of at least 4 meters embodiments , a gas phase comprises molecular nitrogen , at a rate of at least 2 meters per second . Directing a ethanol vapor, water vapor, carbon dioxide, noble gases , composition along a path of a specific length at a specific cannabinoids, terpenes, terpene alcohols , and terpenoids at a rate can control the amount of energy that contacts the total concentration of at least 95 % by volume. 10 composition . In some embodiments , contacting a composition with In some embodiments , a path comprises one or more sufficient energy to convert a native cannabinoid molecule surfaces , and a method comprises heating the one or more into (i ) a carbon dioxide molecule and ( ii ) a modified surfaces to a temperature of 190 ° C. to 250 ° C. cannabinoid molecule in a gas phase comprises contacting In some embodiments , a composition comprises a non the composition with less than 100 kilojoules (“ kJ” ) of 15 volatile molecule , and a method comprises separating a energy per gram of the composition . In some specific modified cannabinoid molecule in a gas phase from a embodiments , contacting a composition with sufficient non -volatile molecule . In some specific embodiments , sepa energy to convert a native cannabinoid molecule into (i ) a rating a modified cannabinoid molecule in a gas phase from carbon dioxide molecule and ( ii ) a modified cannabinoid a non -volatile molecule is performed after converting a molecule in a gas phase comprises contacting the composi- 20 native cannabinoid molecule into (i ) a carbon dioxide mol tion with 2 kJ to 50 kJ per gram of the composition . ecule and ( ii ) the modified cannabinoid molecule in the gas In some embodiments , contacting a composition with phase . In some specific embodiments , separating a modified sufficient energy to convert a native cannabinoid molecule cannabinoid molecule in a gas phase from a non - volatile into ( i ) a carbon dioxide molecule and ( ii ) a modified molecule is performed prior to contacting the modified cannabinoid molecule in a gas phase comprises contacting 25 cannabinoid molecule with a heat sink . In some very specific the composition with energy at a rate of less than 100 embodiments , a method comprises separating a modified kilowatts (“ kW ” ) of power per gram of the composition for cannabinoid molecule in a gas phase from a non - volatile a duration of less than 60 seconds . In some specific embodi molecule by directing the gas phase through a cyclone . In ments , contacting a composition with sufficient energy to some very specific embodiments , a method comprises sepa convert a native cannabinoid molecule into (i ) a carbon 30 rating a modified cannabinoid molecule in a gas phase from dioxide molecule and ( ii ) a modified cannabinoid molecule a non -volatile molecule by directing the gas phase through in a gas phase comprises contacting the composition with 1 a filter such as an air filter. In some specific embodiments , kW to 100 kW of power per gram of the composition for 200 a method comprises collecting a non - volatile molecule . milliseconds to 20 seconds . Non -volatile molecules optionally include one or more of In some embodiments , a method comprises irradiating a 35 chlorophyll, cellulose , nucleic acids, proteins , carbohy composition , convectively heating a composition , or con drates , sugars , glycerol, triglyceride, phospholipid , glycerol, ductively heating a composition , in which contacting a fatty acids, salts , ions , ash , glass , sand , rock , metal, and composition with sufficient energy comprises one or more of certain microwave -absorbing agents . irradiating the composition , convectively heating the com In some embodiments , a method converts less than 2 % of position , or conductively heating the composition . Suitable 40 a cannabinoid molecule of a composition into cannabinol methods of irradiating a composition are described , for (which is also known as 6,6,9 - trimethyl- 3 -pentyl - benzo [c ] example , in PCT Patent Application Publication No. WO chromen - 1 - ol) by mole . In some very specific embodiments , 2018/102711 A1, which is incorporated by reference in its a method comprises producing a liquid distillate comprising entirety . Suitable methods of convectively heating a com a condensed cannabinoid molecule and cannabinol at a position are described , for example , in PCT Patent Appli- 45 molar ratio greater than 100 : 1 . cation Publication No. WO 2015/049585 A2 , which is In some specific embodiments , a composition comprises incorporated by reference in its entirety . Suitable methods of CBDA , and a method converts less than 2 % of the CBDA conductively heating a composition are described , for of the composition into cannabinol by mole . In some very example , in PCT Patent Application Publication No. WO specific embodiments , a method comprises producing a 2016/161420 A1 and WO 2017/192527 A1, each of which 50 liquid distillate comprising CBD and cannabinol at a molar is incorporated by reference in its entirety . ratio greater than 100 : 1 . In some specific embodiments , a In some embodiments , a method comprises contacting a composition comprises THCA , and a method converts less composition with a heated gas. In some specific embodi than 2 % of the THCA of the composition into cannabinolby ments , a method comprises contacting a composition with a mole . In some very specific embodiments , a method com heated gas having a temperature of 190 ° C. to 250 ° C. In 55 prises producing a liquid distillate comprising THC and some embodiments , a method comprises contacting a com cannabinol at a molar ratio greater than 100 : 1 . position with a heated surface . In some specific embodi In some embodiments , a method converts less than 0.2 % ments , a method comprises contacting a composition with a of a cannabinoid molecule of a composition into 6,6,9 heated surface having a temperature of 190 ° C. to 250 ° C. trimethyl- 3 - pentyl- 6a , 7,10,10a- tetrahydro -6H -benzo [ c ] In some embodiments , a method comprises directing a 60 chromen - 1 -ol (“ A8 - THC ” or “ delta -8 -tetrahydrocannabi composition comprising cannabinoids along a path having a nol” ) by mole . In some very specific embodiments , a method length of at least 4 meters , in which the composition is comprises producing a liquid distillate comprising a con contacted with sufficient energy to convert a native cannabi densed cannabinoid molecule and A8 - THC at a molar ratio noid molecule of the composition into (i ) a carbon dioxide greater than 300 : 1 . molecule and (ii ) a modified cannabinoid molecule in a gas 65 In some specific embodiments , a composition comprises phase while the composition is being directed along the path CBDA , and a method converts less than 0.2 % of the CBDA or heated path . Increasing the length of a path increases the of the composition into A8 - THC by mole . In some very US 10,669,248 B2 13 14 specific embodiments , a method comprises producing a convert a native cannabinoid molecule into ( i) a carbon liquid distillate comprising CBD and A8 - THC at a molar dioxide molecule and ( ii ) the modified cannabinoid mol ratio greater than 300 :1 . In some specific embodiments , a ecule in a gas phase. composition comprises THCA , and a method converts less In some specific embodiments , a method comprises pro than 0.2 % of the THCA of the composition into 48 - THC by 5 ducing a liquid distillate comprising cannabinol at a con mole . In some very specific embodiments , a method com centration less than 0.8 % by weight. In some very specific prises producing a liquid distillate comprising THC and embodiments , a method comprises producing a liquid dis A8 - THC at a molar ratio greater than 300 : 1 . In some specific embodiments , a method converts less tillate comprising one or both of CBD and THC at a than 2 % of a native cannabinoid molecule of a composition 10 combinedcannabinol concentrationat a concentration greater less than than 6 0.8% %by by weight weight and. into cannabinol by mole . In some very specific embodi In some very specific embodiments , a method comprises ments , a composition comprises a native cannabinoid mol producing a liquid distillate comprising cannabinoids, and ecule , the native cannabinoid molecule is CBDA , and a less than 2 % of the cannabinoids of the liquid distillate methodby mole .converts In some lessvery than specific 2 % ofembodiments the CBDA , into a composition cannabinol 15 comprise a carboxyl group. In some very specific embodi comprises a native cannabinoid molecule , the native can ments , a method comprises converting at least 95 % of a nabinoid molecule is THCA , and a method converts less native cannabinoid molecule of a composition into a con than 2 % of the THCA into cannabinol by mole . densed cannabinoid molecule in a liquid distillate by mole . In some specific embodiments , a method converts less In some embodiments , a method comprises producing a than 0.2 % of a native cannabinoid molecule into A8 - THC by 20 liquid distillate comprising condensed cannabinoid mol mole . In some very specific embodiments , a composition ecules selected from one , two , three , four, or each of CBD , comprises a native cannabinoid molecule , the native can CBDV , THC , THCV , and CBG . In some specific embodi nabinoid molecule is CBDA , and a method converts less ments, a method comprises producing a liquid distillate than 0.2 % of the CBDA into A8 - THC by mole . In some very comprising condensed cannabinoid molecules in which at specific embodiments , a composition comprises a native 25 least 95 % of the condensed cannabinoid molecules of the cannabinoid molecule , the native cannabinoid molecule is liquid distillate are CBD , CBDV, THC , THCV , and CBG by THCA , and a method converts less than 0.2 % of the THCA weight. into A8- THC by mole . In some embodiments , a method comprises producing a In some embodiments , a heat sink has a surface area liquid distillate comprising ethanol. In some specific greater than 10 % of the surface area of a composition 30 embodiments , a method comprises producing a liquid dis comprising cannabinoids. A heat sink having a relatively tillate comprising ethanol at a concentration of at least 50 % large surface area allows for rapid condensation . In some by weight. Ethanol reduces the viscosity of a liquid distil specific embodis ts , a heat sink is a colloid comprising a ate , which improves the flow of a liquid distillate in an gas -phase dispersion medium . In some very specific automated system . embodiments , a heat sink is an aerosol or a foam . In some 35 In some embodiments , a liquid distillate comprises a very specific embodiments , a heat sink is a spray . Colloids non - cannabinoid molecule and a condensed cannabinoid such as aerosols and foams generally have large surface molecule , and a method comprises separating the non areas, and colloids are therefore suitable heat sinks. cannabinoid molecule from the condensed cannabinoid mol In some embodiments , a heat sink comprises a volatile ecule to produce a product . In some embodiments , a liquid liquid . Heat sinks comprising a volatile liquid are particu- 40 distillate comprises a non - cannabinoid molecule and a con larly useful because the vaporization of a volatile liquid can densed cannabinoid molecule , and a method comprises absorb a large amount of energy. In some specific embodi separating the non - cannabinoid molecule from the con ments , a heat sink comprises a volatile liquid , and the densed cannabinoid molecule to produce a product compris volatile liquid comprises one or both of ethanol and water . ing the condensed cannabinoid molecule at a concentration In some very specific embodiments , a heat sink comprises a 45 of at least 55 % by weight. In some embodiments , a liquid volatile liquid , and the volatile liquid comprises ethanol and distillate comprises a non - cannabinoid molecule and a con water at a combined concentration by weight of at least 90 % . densed cannabinoid molecule , and a method comprises In some embodiments , contacting a modified cannabinoid separating the non -cannabinoid molecule from the con molecule with a heat sink comprises passive cooling such as densed cannabinoid molecule to produce a product compris by exposing the modified cannabinoid molecule or a con- 50 ing the condensed cannabinoid molecule at a concentration tainer comprising the modified cannabinoid molecule to of 55 % to 80 % by weight. In some embodiments , a liquid ambient temperature . In some specific embodiments , expos distillate comprises a non -cannabinoid molecule and a con ing a modified cannabinoid molecule or a container com densed cannabinoid molecule , and a method comprises prising the modified cannabinoid molecule to ambient tem separating the non -cannabinoid molecule from the con perature comprises cooling in an autoclave . In some specific 55 densed cannabinoid molecule to produce a product compris embodiments , exposing a modified cannabinoid molecule to ing the condensed cannabinoid molecule at a concentration ambient temperature comprises directing the modified can of 75 % to 99.9 % by weight. nabinoid molecule through a fluid -cooled condenser. In some embodiments , a liquid distillate comprises a In some embodiments , a method comprises contacting a non - cannabinoid molecule and CBD , and a method com modified cannabinoid molecule with a heat sink less than 60 prises separating the non - cannabinoid molecule from the 240 seconds after contacting a composition with sufficient CBD to produce a product comprising the CBD at a con energy to convert a native cannabinoid molecule into ( i ) a centration of at least 55 % by weight . In some embodiments , carbon dioxide molecule and ( ii ) the modified cannabinoid a liquid distillate comprises a non - cannabinoid molecule and molecule in a gas phase. In some embodiments , a method CBD , and a method comprises separating the non -cannabi comprises condensing a modified cannabinoid molecule into 65 noid molecule from the CBD to produce a product compris a condensed cannabinoid molecule less than 240 seconds ing the CBD at a concentration of 55 % to 80 % or 75 % to after contacting a composition with sufficient energy to 99.9 % by weight. US 10,669,248 B2 15 16 In some embodiments , a liquid distillate comprises a molecule lacks a carboxyl group ; (ii ) providing a hydro non - cannabinoid molecule and CBDV, and a method com philic molecule, in which the hydrophilic molecule com prises separating the non - cannabinoid molecule from the prises two ionizable functional groups, the two ionizable CBDV to produce a product comprising the CBDV at a functional groups comprise a carboxyl group , and the car concentration of at least 0.7 % by weight. In some embodi- 5 boxyl group comprises a second carbon atom ; and ( iii ) ments , a liquid distillate comprises a non - cannabinoid mol forming a carboxylate ester between the cannabinoid mol ecule and CBDV , and a method comprises separating the ecule and the hydrophilic molecule , in which the first carbon non - cannabinoid molecule from the CBDV to produce a atom forms a covalent bond with an oxygen atom in the product comprising the CBDV at a concentration of 0.1 % to carboxylate ester , and the oxygen atom forms a covalent 10 % by weight. 10 bond with the second carbon atom in the carboxylate ester . In some embodiments , a liquid distillate comprises a In some specific embodiments , a hydrophilic molecule is non - cannabinoid molecule and THC , and a method com selected from citric acid , fumaric acid , malic acid , maleic prises separating the non -cannabinoid molecule from the acid , aconitic acid , gluconic acid , malonic acid , succinic THC to produce a product comprising the THC at a con acid , glutaric acid , adipic acid , azelaic acid , tartaric acid , a centration of at least 55 % by weight. In some embodiments , 15 deprotonated form of any one of the preceding molecules , or a liquid distillate comprises a non -cannabinoid molecule and a stereoisomer of any one of the preceding molecules . In THC , and a method comprises separating the non - cannabi some specific embodiments , a hydrophilic molecule is noid molecule from the THC to produce a product compris selected from aspartic acid , glutamic acid , lysine , arginine, ing the THC at a concentration of 55 % to 80 % or 75 % to histidine , serine, threonine, asparagine , glutamine , glycine, a 99.9 % by weight. 20 protonated or deprotonated form of any one of the preceding In some embodiments , a liquid distillate comprises a molecules , or a stereoisomer of any one of the preceding non - cannabinoid molecule and THCV , and a method com molecules . prises separating the non -cannabinoid molecule from the In some specific embodim a cannabinoid molecule of THCV to produce a product comprising the THCV at a a cannabinoid ester is selected from CBD , CBDV, CBDO , concentration of at least 0.7 % by weight. In some embodi- 25 CBG , CBGV , CBL , CBE , THC , THCV , THCO , and per ments , a liquid distillate comprises a non -cannabinoid mol rottetinene , a naturally -occurring ether of any one of CBD , ecule and THCV, and a method comprises separating the CBDV , CBDO , CBG , and CBGV, and a stereoisomer of any non -cannabinoid molecule from the THCV to produce a one of the preceding molecules . product comprising the THCV at a concentration of 0.1 % to Various combinations of the features disclosed in this 10 % by weight. 30 patent document will be evident to those of ordinary skill , Various aspects of the disclosure relate to a carboxylate and these combinations are expressly contemplated by the ester of a cannabinoid molecule and a hydrophilic molecule , inventors . This patent document discloses each linguistic which is also referred as a cannabinoid ester in this patent and grammatical combination of different features disclosed document. anywhere in the patent document as though any specific In some embodiments , a method comprises converting a 35 combination were disclosed in the same sentence. The cannabinoid molecule into a carboxylate ester of the can language and grammar of this patent document is intention nabinoid molecule and a hydrophilic molecule . In some ally selected to explicitly clarify the combinations contem specific embodiments , a method comprises converting a plated by the inventors such that , for example , embodiments cannabinoid molecule that lacks a carboxyl group into a related to methods of producing a cannabinoid ester are carboxylate ester of the cannabinoid molecule and a hydro- 40 combinable with methods of decarboxylating a cannabinoid philic molecule . In some very specific embodiments , a molecule . method comprises converting a condensed cannabinoid mol The words " comprising ," " comprises, " and " comprise " ecule as described in this patent document into a carboxylate refer to open - ended sets . For example , a composition com ester of the condensed cannabinoid molecule and a hydro prising water can also comprise ethanol. philic molecule . 45 The phrases “ consisting of, " " consists of, ” and “ consist In some embodiments , a cannabinoid molecule such as a of” refer to closed sets . For example , a composition con condensed cannabinoid molecule has a solubility in water of sisting of water cannot also comprise ethanol. less than 100 mg per liter, 50 mg per liter , 25 mg per liter , The following examples provide a framework to imple 10 mg per liter , 5 mg per liter , 2 mg per liter , or 1 mg per ment certain aspects of the disclosure in commercially liter , and a cannabinoid ester of the cannabinoid molecule 50 viable processes, and these examples do not limit the scope and a hydrophilic molecule has a solubility in water of of this patent document or any claim that matures from the greater than 100 mg per liter , 50 mg per liter, 25 mg per liter, disclosure of this patent document. 10 mg per liter , 5 mg per liter , 2 mg per liter , or 1 mg per liter, respectively . EXEMPLIFICATION In some specific embodiments , a condensed cannabinoid 55 molecule comprises a hydroxyl group , and the hydroxyl Example 1 group comprises an oxygen atom . In some specific embodi ments , a hydrophilic molecule comprises a carboxyl group , Decarboxylation and Distillation of Cannabinoids and the carboxyl group comprises a carbon atom . In some from Organic Industrial Hemp specific embodiments, an oxygen atom of a hydroxyl group 60 of a cannabinoid molecule forms an ester bond with a carbon Example 1 is prophetic and representative of actualmeth atom of a carboxyl group of a hydrophilic molecule in a ods. The method of PCT Patent Application Publication No. cannabinoid ester . WO 2016/161420 Al is performed using organic industrial In some embodiments , a method comprises (i ) providing hemp . The water content of the hemp is less than 10 % by a cannabinoid molecule , in which the cannabinoid molecule 65 weight. The cannabinoid content of the hemp is about comprises a hydroxyl group , the hydroxyl group is cova 11-12 % by weight and consists of about 11 % CBDA , 0.1 % lently bound to a first carbon atom , and the cannabinoid CBD , 0.3 % THCA , and 0 % THC by weight ( see , for US 10,669,248 B2 17 18 example , FIG . 3 ) . The hemp is ground and sifted to provide were determined by an accredited , third - party cannabis a particulate having an average diameter less than 2 mm and testing laboratory . Actual cannabinoid concentrations by a surface- area - to - volume ratio greater than 3000 per meter . weight of concentrated products produced from liquid dis The hemp is suspended in heated gas to vaporize the tillates are shown in FIG . 4 and Table 1. In each instance , cannabinoids . The heated gas is produced by resistive heat- 5 greater than 99.5 % of the cannabinoids of the concentrated ing at 10-20 kW . The oxygen content of the heated gas is products were decarboxylated . significantly below the ~ 20 % oxygen content of air by volume. Oxygen is reduced relative to air by blanketing the TABLE 1 distillation machine in an inert gas and by evaporating water Actual Concentrations of Cannabinoids in Four Concentrated Products from the hemp. The heated gas and suspended hemp are 10 Produced from Liquid Distillate Following Decarboxylation and directed through heated tubes having a length of 5 to 50 Distillation of the Cannabinoids from Organic Industrial Hemp meters at a rate of 5 to 20 meters per second . A known mass of hemp is directed through the heated tubes at a known rate 1 2 3 4 . such that the hemp is exposed to less than 100 kJ of energy CBD 66.5 % 65.2 % 68.1 % 67.6 % per gram of the hemp . The heated tubes reverse direction in 15 CBDA 0.0 % 0.6 % 0.0 % 0.3 % THC 2.7 % 2.6 % 3.2 % 2.6 % Cartesian space several times to increase the number of THCA 0.0 % 0.0 % 0.0 % 0.0 % collisions between particles and gas -phase molecules . Can CBN 0.4 % 0.3 % 0.4 % 0.0 % nabinoid vapor is mechanically separated from suspended CBG 0.96 % 0.76 % 1.27 % 1.62 % non - volatile molecules of the hemp using a cyclone and filters . Cannabinoid vapor is condensed approximately 1 to 20 5 seconds after vaporization . A liquid distillate is collected Example 3 by rinsing the condensed cannabinoids from the surfaces of the heat sink with ethanol. Greater than 90 % of the can Co -distillation of Cannabinoids, Terpenes, Terpene nabinoids of the hemp are recovered as cannabinoids of the Alcohols , and Terpenoids from Organic Industrial liquid distillate by mole . Greater than 95 % of the cannabi- 25 Hemp noids of the liquid distillate are decarboxylated . A rotary evaporator is used to remove ethanol and water from the Themethod of Example 1 was performed on two different liquid distillate to produce a uniform product comprising at batches of organic hemp to produce two liquid distillates , least 10 % by weight cannabinoids. which were then processed to produce two concentrated 30 products . Terpene , terpene alcohol, and terpenoid concen Example 2 trations of the two concentrated products were determined by an accredited , third -party cannabis testing laboratory . Products Produced by Decarboxylation and Actual terpene , erpene alcohol, and terpenoid concentra Distillation of Cannabinoids from Organic tions by weight are shown in FIG . 5 and Table 2. Approxi Industrial Hemp 35 mately 8.7 % of a first concentrated product consisted of terpenes , terpene alcohols , and terpenoids by weight , and Themethod of Example 1 was performed on four different approximately 5.0 % of a second concentrated product con batches of organic hemp, and cannabinoid concentrations of sisted of terpenes, terpene alcohols , and terpenoids by concentrated products produced from the liquid distillates weight. TABLE 2 Actual Concentrations of Terpene , Terpene Alcohols , and Terpenoids in Two Concentrated Products Produced from Liquid Distillates Following Co - distillation of Terpene, Terpene Alcohols , and Terpenoids with Cannabinoids from Organic Industrial Hemp Concentration by Weight (parts per million ) Boiling Molecule 2 Point Molecule Type Beta- Caryophyllene 39,574 23,348 263° F. Terpene Humulene 11,485 72,40 224 ° F. Terpene ( - )- Guaiol 10,351 6,390 273 ° F. Terpene Alcohol ( - )- Alpha - Bisabolol 9,840 4,653 307° F. Terpene Alcohol Linalool 5,400 2,222 199 ° F. Terpene Alcohol Alpha - Terpineol 2,998 2,032 420 ° F. Terpene Alcohol Caryophyllene Oxide 1,765 1,291 536 ° F. Terpenoid Myrcene 1,070 176 167 ° F. Terpene Eucalyptol 1,058 ND * 177 ° F. Terpenoid Limonene 718 197 176 ° F. Terpene Nerolidol 532 547 252 ° F. Terpene Alcohol Alpha - Terpinene 414 340 174 ° F. Terpene Borneol 310 218 213 ° F. Terpene Alcohol ( - ) - Isopulegol 206 170 413 ° F. Terpene Alcohol Delta - 3 - Carene ND * 356 338 ° F. Terpene Para - Cymene ND * 205 351 ° F. Terpene Oxidation Product Terpinolene ND * 185 369 ° F. Terpene *ND indicates that a given terpene , terpene alcohol, terpenoid, or terpene oxidation product was not detected at a concentration above the detection limit for the terpene US 10,669,248 B2 19 20 Example 4 contacting the composition with sufficient energy to con vert the native cannabinoid molecule into (i ) a carbon Decarboxylation and Distillation of Cannabinoids dioxide molecule and ( ii ) a modified cannabinoid mol from Organic Cannabis ecule in a gas phase ; 5 contacting the modified cannabinoid molecule with a heat Example 4 is prophetic and representative of actualmeth sink to condense the modified cannabinoid molecule ods. The method of PCT Patent Application Publication No. into a condensed cannabinoid molecule in a liquid WO 2016/161420 A1 is performed using organic cannabis . distillate ; and The water content of the cannabis is less than 10 % by collecting the liquid distillate , in which the liquid distil 10 late comprises the condensed cannabinoid molecule weight. The cannabinoid content of the cannabis is about and cannabinol at a molar ratio greater than 100 : 1 . 20-30 % by weight . The cannabis is ground and sifted to 3. A method to chemically modify a cannabinoid mol provide a particulate having an average diameter less than 2 ecule , comprising: mm and a surface -area - to - volume ratio greater than 3000 per providing a composition comprising cannabinoids, in meter. The cannabis is suspended in heated gas to vaporize 15 which the cannabinoids comprise a native cannabinoid the cannabinoids. The heated gas is produced by resistive molecule , the native cannabinoid molecule comprises a heating at 10-20 kW . The oxygen content of the heated gas carboxyl group , and the native cannabinoid molecule is is significantly below the ~ 20 % oxygen content of air by in a liquid phase or a solid phase ; volume. Oxygen is reduced relative to air by blanketing the contacting the composition with sufficient energy to con distillation machine in an inert gas and by evaporating water 20 vert the native cannabinoid molecule into ( i) a carbon from the cannabis . The heated gas and suspended cannabis dioxide molecule and (ii ) a modified cannabinoid mol are directed through heated tubes having a length of 5 to 50 ecule in a gas phase ; meters at a rate of 5 to 20 meters per second . A known mass contacting the modified cannabinoid molecule with a heat of cannabis is directed through the heated tubes at a known sink to condense the modified cannabinoid molecule rate such that the cannabis is exposed to less than 100 kJ of 25 into a condensed cannabinoid molecule in a liquid energy per gram of the cannabis . The heated tubes reverse distillate ; direction in Cartesian space several times to increase the collecting the liquid distillate , in which the liquid distil number of collisions between particles and gas -phase mol late comprises ethanol; and ecules . Cannabinoid vapor is mechanically separated from evaporating the ethanol to produce a product from the suspended non -volatile molecules of the cannabis using a 30 liquid distillate , in which the product comprises the cyclone and filters . Cannabinoid vapor is condensed condensed cannabinoid molecule at a concentration of approximately 1 to 5 seconds after vaporization . A liquid at least 55 % by weight. distillate is collected by rinsing the condensed cannabinoids 4. A method to chemically modify a cannabinoid mol from the surfaces of the heat sink with ethanol . Greater than ecule , comprising : 90 % of the cannabinoids of the cannabis are recovered as 35 providing a composition comprising cannabinoids, in cannabinoids of the liquid distillate by mole . Greater than which the cannabinoids comprise a native cannabinoid 95 % of the cannabinoids of the liquid distillate are decar molecule , the native cannabinoid molecule comprises a boxylated . A rotary evaporator is used to remove ethanol and carboxyl group , and the native cannabinoid molecule is water from the liquid distillate to produce a uniform product in a liquid phase or a solid phase ; comprising at least 10 % by weight cannabinoids. 40 contacting the composition with 2 kilojoules to 50 kilo joules of energy per gram of the composition thereby What is claimed is : converting the native cannabinoid molecule into ( i) a 1. A method to chemically modify a cannabinoid mol carbon dioxide molecule and ( ii ) a modified cannabi ecule , comprising: noid molecule in a gas phase ; providing a composition comprising cannabinoids, in 45 contacting the modified cannabinoid molecule with a heat which the cannabinoids comprise a native cannabinoid sink to condense the modified cannabinoid molecule molecule , the native cannabinoid molecule comprises a into a condensed cannabinoid molecule in a liquid carboxyl group , and the native cannabinoid molecule is distillate ; and in a liquid phase or a solid phase; collecting the liquid distillate . contacting the composition with sufficient energy to con- 50 5. A method to chemically modify a cannabinoid mol vert the native cannabinoid molecule into (i ) a carbon ecule , comprising : dioxide molecule and ( ii ) a modified cannabinoid mol providing a composition comprising cannabinoids, in ecule in a gas phase ; which the cannabinoids comprise a native cannabinoid contacting the modified cannabinoid molecule with a heat molecule , the native cannabinoid molecule comprises a sink to condense the modified cannabinoid molecule 55 carboxyl group , and the native cannabinoid molecule is into a condensed cannabinoid molecule in a liquid in a liquid phase or a solid phase ; distillate , in which at least 95 % of the native cannabi contacting the composition with sufficient energy to con noid molecule is converted into the condensed cannabi vert the native cannabinoid molecule into ( i) a carbon noid molecule per mole ; and dioxide molecule and ( ii ) a modified cannabinoid mol collecting the liquid distillate. 60 ecule in a gas phase ; 2. A method to chemically modify a cannabinoid mol contacting the modified cannabinoid molecule with a heat ecule , comprising : sink to condense the modified cannabinoid molecule providing a composition comprising cannabinoids, in into a condensed cannabinoid molecule in a liquid which the cannabinoids comprise a native cannabinoid distillate ; and molecule , the native cannabinoid molecule comprises a 65 collecting the liquid distillate , carboxyl group , and the native cannabinoid molecule is in which contacting the composition with sufficient in a liquid phase or a solid phase ; energy to convert the native cannabinoid molecule into US 10,669,248 B2 21 22 ( i) the carbon dioxide molecule and (ii ) the modified molecule , the native cannabinoid molecule comprises a cannabinoid molecule in the gas phase comprises con carboxyl group , and the native cannabinoid molecule is tacting the composition with energy at a rate of less in a liquid phase or a solid phase ; than 100 kilowatts of power per gram of the composi contacting the composition with sufficient energy to con tion for a duration of less than 60 seconds. 5 vert the native cannabinoid molecule into (i ) a carbon 6. A method to chemically modify a cannabinoid mol dioxide molecule and ( ii ) a modified cannabinoid mol ecule , comprising : ecule in a gas phase; providing a composition comprising cannabinoids and directing the composition along a heated path having a cellulose , in which the cannabinoids comprise a native cannabinoid molecule , the native cannabinoid mol- 10 length of at least 4 meters , in which the composition is ecule comprises a carboxyl group , and the native can contacted with the sufficient energy in the heated path ; nabinoid molecule is in a liquid phase or a solid phase ; contacting themodified cannabinoid molecule with a heat contacting the composition with sufficient energy to con sink to condense the modified cannabinoid molecule vert the native cannabinoid molecule into (i ) a carbon into a condensed cannabinoid molecule in a liquid dioxide molecule and ( ii ) a modified cannabinoid mol- 15 distillate ; and ecule in a gas phase ; collecting the liquid distillate . separating the modified cannabinoid molecule in the gas 10. The method of claim 9 , comprising directing the phase from the cellulose ; composition comprising cannabinoids along a heated path at collecting the cellulose ; a rate of at least 2 meters per second . contacting the modified cannabinoid molecule with a heat 20 11. A method to chemically modify a cannabinoid mol sink to condense the modified cannabinoid molecule ecule , comprising : into a condensed cannabinoid molecule in a liquid providing a composition comprising cannabinoids , in distillate ; and which the cannabinoids comprise a native cannabinoid collecting the liquid distillate. molecule , the native cannabinoid molecule comprises a 7. A method to chemically modify a cannabinoid mol- 25 carboxyl group , and the native cannabinoid molecule is ecule , comprising: in a liquid phase or a solid phase ; providing a composition comprising cannabinoids, in contacting the composition with sufficient energy to con which the cannabinoids comprise a native cannabinoid vert the native cannabinoid molecule into ( i) a carbon molecule , the native cannabinoid molecule comprises a dioxide molecule and ( ii ) a modified cannabinoid mol carboxyl group , and the native cannabinoid molecule is 30 ecule in a gas phase ; in a liquid phase or a solid phase ; contacting the modified cannabinoid molecule with a heat suspending a particle or a droplet of the composition sink to condense the modified cannabinoid molecule comprising cannabinoids in a gas phase , in which the into a condensed cannabinoid molecule in a liquid particle or droplet comprises the native cannabinoid distillate ; and molecule ; 35 collecting the liquid distillate , contacting the composition with sufficient energy to con in which both contacting the composition with the suffi vert the native cannabinoid molecule into ( i) a carbon cient energy and condensing the modified cannabinoid dioxide molecule and (ii ) a modified cannabinoid mol molecule into the condensed cannabinoid molecule are ecule in a gas phase ; performed in less than 60 seconds. contacting the modified cannabinoid molecule with a heat 40 12. A method to chemically modify a cannabinoid mol sink to condense the modified cannabinoid molecule ecule , comprising: into a condensed cannabinoid molecule in a liquid providing a composition comprising cannabinoids, in distillate ; and which the composition has a surface - area -to - volume collecting the liquid distillate . ratio greater than 1000 per meter; the cannabinoids 8. A method to chemically modify a cannabinoid mol- 45 comprise a native cannabinoid molecule ; the native ecule , comprising: cannabinoid molecule comprises a carboxyl group ; and providing a composition comprising cannabinoids, in the native cannabinoid molecule is in a liquid phase or which the cannabinoids comprise a native cannabinoid a solid phase ; molecule , the native cannabinoid molecule comprises a contacting the composition with sufficient energy to con carboxyl group , and the native cannabinoid molecule is 50 vert the native cannabinoid molecule into ( i) a carbon in a liquid phase or a solid phase ; dioxide molecule and ( ii ) a modified cannabinoid mol coating a heated surface with the composition at a sur ecule in a gas phase ; face -area -to - volume ratio of the composition that is contacting the modified cannabinoid molecule with a heat greater than 500 per meter ; sink to condense the modified cannabinoid molecule contacting the composition with sufficient energy to con- 55 into a condensed cannabinoid molecule in a liquid vert the native cannabinoid molecule into ( i ) a carbon distillate ; and dioxide molecule and ( ii ) a modified cannabinoid mol collecting the liquid distillate . ecule in a gas phase ; 13. A method to chemically modify a cannabinoid mol contacting the modified cannabinoid molecule with a heat ecule , comprising: sink to condense the modified cannabinoid molecule 60 providing a composition comprising cannabinoids, in into a condensed cannabinoid molecule in a liquid which the cannabinoids comprise a native cannabinoid distillate ; and molecule ; the native cannabinoid molecule is canna collecting the liquid distillate. bidiolic acid or tetrahydrocannabinolic acid ; the com 9. A method to chemically modify a cannabinoid mol position comprises the native cannabinoid molecule at ecule , comprising : 65 a concentration of at least 5 % by weight; the native providing a composition comprising cannabinoids, in cannabinoid molecule is in a liquid phase or a solid which the cannabinoids comprise a native cannabinoid phase ; US 10,669,248 B2 23 24 contacting the composition with sufficient energy to con contacting the composition with sufficient energy to con vert the native cannabinoid molecule into ( i ) a carbon vert the cannabidiolic acid into ( i) a carbon dioxide dioxidemolecule and ( ii ) a modified cannabinoid mol molecule and ( ii ) gas phase cannabidiol; ecule in a gas phase ; contacting the gas phase cannabidiol with a heat sink to contacting the modified cannabinoid molecule with a heat 5 condense the gas phase cannabidiol into liquid phase sink to condense the modified cannabinoid molecule cannabidiol of a liquid distillate , in which at least 95 % into a condensed cannabinoid molecule in a liquid of the cannabidiolic acid is converted into the liquid distillate , in which at least 95 % of the native cannabi phase cannabidiol per mole ; and noid molecule is converted into the condensed cannabi collecting the liquid distillate . noid molecule per mole ; and 10 15. The method of claim 14 , comprising : collecting the liquid distillate . contacting the composition with 2 kilojoules to 50 kilo 14. A method to chemically -modify a cannabinoid mol joules of energy per gram of the composition to convert ecule , comprising: the cannabidiolic acid into (i ) the carbon dioxide mol providing a composition comprising cannabinoids , in ecule and ( ii ) the gas phase cannabidiol; and which the composition has a surface- area -to -volume 15 contacting the gas phase cannabidiol with the heat sink ratio greater than 1000 per meter , the cannabinoids less than 240 seconds after contacting the composition comprise cannabidiolic acid at a concentration of at with the 2 kilojoules to 50 kilojoules of energy per least 5 % by weight , and the cannabidiolic acid is in a gram of the composition . liquid phase or a solid phase ;