Illicit Production of Cocaine Casale JF, Klein RFX
Forensic Forensic Science Review 5, 95-10 !199"#
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$%stract The predominant methods currently used for illicit production of cocaine are described. For illicit natural cocaine (i.e., from coca leaf), this includes production of coca paste from coca leaf via both the solvent and acid extraction techniues, purification of coca paste to cocaine base, and conversion of cocaine base to cocaine hydrochloride. hydrochloride. For illicit synthetic cocaine (i.e., synthesi!ed from precursor chemicals), the classic five"step synthetic route used in all clandestine laboratories sei!ed to date is summari!ed. The ori#ins of the most common al$aloidal impurities and processin#%synthetic by"products typically identified in illicit natural, illicit synthetic, and pharmaceutical cocaine are discussed. Forensic differentiation of exhibits arisin# from the various production methods are addressed both in terms of overall product purity and the presence%absence of these impurities and byproducts. byproducts.
&a%le of Contents &. Table of 'ontents . ntroduction &. *ro+in# and Harvestin# of 'oca Leaf . llicit 'ocaine roduction &. llicit -atural 'ocaine &. 'oca aste . 'o$e ase /. 'ocaine Hydrochloride . llicit 0ynthetic 'ocaine /. Licit (harmaceutical) 'ocaine roduction 1. Forensic 2ifferentiation of Licit 3ersus 3ersus llicit 'ocaine &. llicit -atural 'ocaine . llicit 0ynthetic 'ocaine /. harmaceutical 'ocaine &. References
Introduction
Throu#hout the &456s and into the &446s, cocaine ( 0tructure 1) has been the most +idely used 7hard7 dru# of abuse in the 8nited 0tates 91. :lthou#h :lthou#h recent dru# abuse monitors have su##ested that illicit cocaine usa#e in the 8nited 0tates is declinin# 9/, +orld+ide use is still rapidly increasin# due to expandin# e xpandin# mar$ets in ;urope, 0outh :merica, and the Far ;ast 9<,99. ecause of the disastrous socioeconomic conseuences associated +ith the +idespread abuse of cocaine, the 8nited -ations, the 8nited 0tates, and other developed nations continue to commit extensive resources to research and combat this problem. : si#nificant percenta#e of this effort is directed to+ard interdiction of cocaine production and smu##lin#. 0uch efforts reuire detailed $no+led#e of typical production techniues and the analytical profiles of the final products. Ho+ever, open scientific research into cocaine production has been severely restricted due to the inherently sensitive nature of the topic. First, cocaine is under strict +orld+ide le#al controls, and reuires special permits to possess and%or +or$ +ith. 0econdly, althou#h an extensive amount of research has already been commissioned and completed, the results are often either proprietary or sealed under varyin# levels of #overnment classification. :s a result, there is a critical lac$ of current, accurate information in the open scientific literature concernin# both licit and illicit cocaine processin#. This information #ap has resulted in extensive duplication of already researched topics and%or misdirection of many research initiatives. n order to partially address these issues, the authors report detailed descriptions of the most common illicit (i.e., natural and synthetic) cocaine production techniues in current use. :lthou#h certain aspects of illicit cocaine processin# have been previously summari!ed (e.#.,&,<=,9), to the authors> $no+led#e this is the first comprehensive, in"depth study of this topic. n addition, the authors briefly discuss analytical profiles for cocaine produced via these techniues +hich allo+ for forensic differentiation of sei!ed cocaine exhibits.
I' (rowin) and *arvestin) of Coca +eaf (")"'ocaine (cocaine) is a naturally occurrin# al$aloid found in certain varieties of plants of the #enus ;rythroxylum. There are over 66 distinct species of ;rythroxylum, of +hich only t+o, ;rythroxylum coca and ;rythroxylum novo#ranatense, contain si#nificant amounts of cocaine. n 0outh :merica, t+o varieties +ithin each of these t+o species are cultivated? these are ;rythroxylum coca var. coca (;'3'), ;rythroxylum coca var. ipadu (;M), ;rythroxylum novo#ranatense var. novo#ranatense (;-3-), and ;rythroxylum novo#ranatense var. truxillense (;-3T)=,<1,<<. 'oca cultivation is distributed throu#hout the central and northern :ndean Rid#e, +ith approximately 96@ in eru, /6@ in olivia and the remainder (in approximate order of importance) scattered throu#hout 'olumbia, ;cuador, 3en 3ene!uela, e!uela, ra!il, & :r#entina, and anama .
;ach of the cultivated varieties of ;rythroxylum has a distinct total al$aloidal profile and a#ricultural ran#e. Af the four, ;'3' is the most common cultivar and the source from +hich most cocaine, both licit and illicit, is derived <1. Therefore, its cultivation and harvest are described in detail in the follo+in# section. ;'3' contains cocaine (ran#e 6./ to &.<@, avera#e 6.5@ relative to dry leaf +ei#ht) as the principle al$aloid, +ith approximately &6 to &<@ cis" and trans"cinnamoylcocaine and to /@ truxillines relative to cocaine 1=,<9. ;'3', +hich is botanically classified as a shrub, is readily cultivated in +idely varied climates and soil conditions. ts primary a#ricultural ran#e is throu#hout the montane tropical forests alon# the eastern slopes of the :ndes, principally from <66 to &,<66 m altitude <<. t can live up to <6 years and can #ro+ to a hei#ht of up to / m, but cultivated plants are commonly pruned to from & to m for ease of harvest. :fter < to &6 years, the plants are usually uprooted or cut bac$ to near #round level, reportedly due to decreasin# cocaine content in the rene+ed leaf #ro+th. The hi#hest cocaine contents are #enerally found in fresh leaves harvested from plants #ro+n at hi#her, cooler altitudes. n some areas, the plants are commonly interplanted +ith other crops (corn, yucca, etc.) or in 7fallo+7 fields (i.e., mixed +ith indi#enous #rasses and +eeds). n addition, various a#ricultural enhancements, e.#., fertili!ers, pesticides, herbicides, irri#ation, etc., are sporadically used. The overall effect of such efforts on leaf yield, harvest interval, or cocaine content are currently un$no+n. Leaf harvestin# is usually not a periodic, 7set"piece7 operation similar to traditional farmin# techniues? rather, it is a continuous, on#oin# operation usually extendin# over the entire year " thus providin# the farmer +ith a continuous source of income and a hed#e a#ainst mar$et fluctuations, +hich can be severe. ndividual plots (i.e., a specific small field or several ro+s in a lar#e field) are harvested on an avera#e of four times a year. The leaves are comprehensively stripped from the plants by hand. Harvested leaves are usually immediately sun dried on an open"air patio until dry enou#h to be readily bro$en up bet+een the fin#ers. This normally ta$es & to days, dependin# on the prevailin# +eather conditions. f the leaf is destined for a nearby illicit laboratory, the dryin# sta#e is sometimes s$ipped. The leaves are freuently ra$ed and turned to aid the dryin# process, and care is ta$en to #et them undercover immediately if the +eather turns threatenin#. The leaves +ill ferment (rot) very uic$ly if they are not dried immediately, especially if they #et rain"soa$ed durin# the dryin# process<1. 8pon sun dryin#, the fresh leaf loses from t+o"thirds to three"uarters of its +ei#ht due to evaporation of +ater &/? this reduced +ei#ht aids eventual transportation. The immediately dried leaf is reasonably stable +ith respect to cocaine content and decomposition if $ept dry and cool
the cinnamoylcocaines relative to cocaine (approximately @ <9) and probably a correspondin#ly ne#li#ible percenta#e of the truxillines 1&. ;-3- is primarily seen in 'olombia, and is much more tolerant of diverse ecolo#ical conditions versus the other cultivars<1. ts cocaine content is comparable to ;'3' (avera#e ca. 6.5@ <9)? ho+ever, it also contains a much hi#her percenta#e of the cinnamoylcocaines and truxillines (each typically 16 to 96@ relative to cocaine 1=,<<,<9). ;-3T is primarily seen in the arid north+est areas of eru <1, and is uite similar to ;-3- in al$aloid content 1&,1=,<<,<9. t also has a relatively hi#h percenta#e of flavonoids versus the other three cultivars, and " althou#h currently supplanted by ;'3' " it +as cultivated for decades for the soft"drin$ industry<1,<
II' Illicit Cocaine Production $' Illicit atural Cocaine
roduction of illicit natural cocaine involves three stepsB &. ;xtraction of crude coca paste from the coca leaf? . urification of coca paste to co$e base? and /. 'onversion of co$e base to cocaine hydrochloride. 'lassically, each of the individual processin# steps are accomplished in separate so"called 7paste,7 7base,7 and 7crystal7 laboratories (separate meanin# any+here from several meters to several thousand $ilometers apart). More recently and increasin#ly, ho+ever, the traditionally separate, seuential paste and base operations are bein# condensed into direct leaf"to"base laboratories, s$ippin# the isolation of coca paste. aste, base, and direct leaf"to"base laboratories represent a deeply entrenched, +idespread cotta#e industry, +ith thousands of individual operations located throu#hout the coca" producin# re#ions of 0outh :merica. n contrast, crystal laboratories are #enerally much lar#er, more sophisticated and centrali!ed operations, varyin# up to semi"industrial pilot"plant type laboratories involvin# extensive chemical and en#ineerin# expertise. They are usually located in remote locales in order to avoid enforcement efforts. t is important to reco#ni!e that there is no one method for obtainin# coca paste, co$e base, or cocaine hydrochloride. An the contrary, there are numerous procedural variations from lab to lab, especially in the substitution of alternate chemicals. n addition, illicit manufacture of cocaine is not a static situation, but rather is constantly evolvin# " an evolution that has, in fact, been forcibly accelerated by recent, successful enforcement initiatives. ;xperimentation +ith ne+ procedures desi#ned to evade controls on essential chemicals or develop more convenient%less expensive methodolo#ies is common and, in contrast to past secretiveness, ne+ procedures are commonly +idely shared. To date, ho+ever, the critical elements of cocaine processin# remain common to all variants. 1' Coca Paste
There are currently t+o #eneral methods for processin# coca leaves into coca paste, hereafter referred to as the solvent extraction techniue and the acid extraction techniue. The solvent
techniue (the traditional methodolo#y) +as directly derived from one of the ori#inal commercial processes developed in the early 6th century /, and remains the most commonly used method in eru, 'olombia, and ;cuador. The acid techniue (a much more recently developed methodolo#y) is a considerably more labor"intensive procedure also directly derived from yet another, even older commercial process<4. t reuires relatively little or#anic solvent (+hich is controlled in certain areas of 0outh :merica), and is currently the most commonly used method in olivia. t should be noted that, to the authors> $no+led#e, all previous literature reports to date summari!in# illicit cocaine processin# have only detailed out versions of the solvent techniue, i.e., this is the first detailed report of the acid techniue. a' &e Solvent ./traction &ecniue !Scee 1#
Scee 1' llicit production of coca paste via the solvent extraction techniue (see text for details).
The coca leaves are macerated, dusted +ith an inor#anic base (usually lime or a carbonate salt), dampened +ith a minimal amount of +ater, and placed in a maceration pit " typically either a <<"#allon drum or lar#e plastic barrel, a lar#e metal trou#h or a sta$ed"out pit lined +ith heavy"duty plastic. :lternately, an aueous solution of the inor#anic base is pre"mixed, then poured over the macerated leaves. f fresh (i.e., not sun"dried) leaf is used, the operators may not add any +ater. The addition of the inor#anic base ensures that the cocaine is in its free base form. : +ater"immiscible or#anic solvent (usually $erosene, less commonly diesel fuel or #asoline) is added to the dampened coca leaf slurry and the mixture is either vi#orously mixed for several hours or left standin# +ith occasional stirrin# for up to / days, thereby extractin# the cocaine free base into the solvent. The efficiency of the extraction is hi#hly dependent on ho+ much time the leaves spend in contact +ith the solvent and ho+ much effort the operators have put into maceratin# the leaves (the finer the leaves have been chopped up, the more efficient the transfer of cocaine base to the solvent). Mechani!ation of the maceration (e.#., +ith leaf mulchers) and extraction processes (e.#., +ith +ashin#
machines or cement mixers, etc.) is common. n addition, in certain operations the leaves are reportedly repeatedly extracted to ensure more uantitative recovery of cocaine. :fter completion of the extraction procedure, the solvent is removed from the mixture either by pressin#, filterin#, drainin# from a plu#, siphonin# or other similar means. The resultin# solution is usually completely or#anic, but may contain a small aueous layer underlyin# the or#anic layer. f necessary, the liuid is re"filtered to remove any remainin# ve#etable matter and, if t+o layers remain, the lo+er (aueous) layer (+hich is extremely basic due to dissolved lime or carbonate) is separated by pour"off and siphonin# and discarded. The lar#e volume of or#anic solvent resultin# from the leaf extraction(s) is then bac$" extracted +ith a much smaller volume of dilute sulfuric acid, +hich is added directly to the or#anic solvent, mixed vi#orously for to &6 minutes, then allo+ed to sit and re"separate. The acid converts the cocaine free base to cocaine sulfate, +hich dissolves in the aueous layer. The or#anic solvent is then separated, leavin# only the dilute sulfuric acid solution of cocaine sulfate. This latter yello+ish"bro+n solution is commonly referred to as "agua rica" or "guarapo" (agua rica). The or#anic solvent is usually re"used indefinitely, +ith additions of fresh solvent to ma$e up natural attrition due to handlin# and irrecoverable absorption into the leaf mulch. n the final phase of coca paste isolation, an excess of base, usually lime, carbonate, or caustic soda, is slo+ly added to the agua rica solution +ith stirrin#. The base neutrali!es the sulfuric acid and converts cocaine sulfate bac$ to the free base, +hich precipitates out of the solution as a #ummy, yello+ish solid. This solid is coca paste, +hich is filtered, dried, pac$a#ed, and shipped to a base lab. The cocaine content of coca paste #enerated by the solvent extraction techniue varies from /6 to 56@. t contains numerous additional components other than cocaine, includin# other coca al$aloids and inor#anics. Ho+ever, most of the free carboxylic acids have been removed because of their limited solubility in dilute acid and solubility in dilute al$ali solutions. The dried material usually has a 7ca$ey7 consistency and usually +ill not free"flo+ easily. :lthou#h $erosene and diesel fuel are the extraction solvents of choice, many other +ater" immiscible or#anic solvents or solvent mixtures may be substituted. 0imilarly, +hile any soluble inor#anic base may be effectively used for the neutrali!ation of the agua rica solution, carbonate salts are traditionally the most popular because they act as their o+n visual endpoint indicators. The addition of any carbonate salt to the acidic solution causes vi#orous foamin# from the release of carbon dioxide #as? thus, the neutrali!ation endpoint is +here the addition of carbonate no lon#er causes foamin# of the reaction mixture. This visual endpoint indicator is very useful to operators +ithout access to sophisticated euipment. %' Bazuco
: variant of the solvent techniue involves the production of bazuco, a crude preliminary run of coca paste +ith a lo+ cocaine content. Bazuco is often #iven to paste laboratory +or$ers as payment or co"payment. t is commonly mixed +ith tobacco and smo$ed by the user, and represents a very rapidly #ro+in# abuse and addiction problem throu#hout the cocaine" producin# re#ions of 0outh :merica ,1. n the most common variant, bazuco is obtained by mixin# an insoluble diluent (e.#., flour or #round mai!e) into the dilute sulfuric acid solution prior to bac$"extraction of the or#anic solvent. Follo+in# extraction, the diluent"slurred aueous layer is separated from the or#anic solvent in the previously described manner, and a
base is added to the solution Cust to the point +here some initial precipitation is observed. The solution is allo+ed to stand a fe+ minutes and is then filtered to co"capture the diluent and this initial crude precipitate of coca paste, +hich is then air dried to #ive bazuco. :dditional base is then added to the filtrate to precipitate the remainder of the coca paste in the usual manner. 'hemically, the preparation of bazuco serves t+o purposesB &. The diluent"slurred aueous solution ma$es an excellent visual indicator of the interface boundary bet+een the t+o layers? and . The first precipitate reportedly contains a relatively hi#h content of the cinnamoylcocaines. Thus, isolation of bazuco reduces the amount of oxidi!in# a#ent reuired in the next step for the production of co$e base (vide infra). 'oca paste obtained follo+in# preliminary isolation of bazuco is purer and usually +hiter in appearance. c' &e $cid ./traction &ecniue !Scee 2#
Scee 2' llicit production of coca paste via the acid extraction techniue (see text for details).
The coca leaves are placed directly in a maceration pit (almost al+ays a sta$ed"out pit lined +ith heavy"duty plastic, commonly referred to as a "pozo" ) containin# Cust enou#h dilute sulfuric acid to cover the leaves. The leaf%dilute sulfuric acid mixture is vi#orously macerated, typically by +or$ers +ho #et in the pit and forcefully stomp the leaves for & to hours. The acid converts the cocaine free base in the leaves to cocaine sulfate, +hich dissolves in the
aueous solution. :s +ith the solvent extraction techniue, the efficiency of the extraction depends on ho+ much time the leaves spend in contact +ith the dilute sulfuric acid solution and ho+ much effort the +or$ers put into stompin# the leaves. :fter the stompin# is complete, the acidic coca Cuice is removed (usually by buc$etin#) and poured throu#h a coarse filter (to remove any remainin# ve#etable matter) into a separate decant pit (commonly referred to as a "chiquero" ). :t this point, an excess of lime or carbonate is added to the isolated dilute sulfuric acid solution +ith vi#orous stirrin#, thus neutrali!in# the cocaine sulfate and any remainin# sulfuric acid and precipitatin# a very crude curdled coca paste. The endpoint of the base addition is monitored via spot"testin# of small aliuots of the solution +ith an ethanolic solution of phenolphthalein (called "punto" ). The curdled coca paste in the solution is not collectable as such, but is rather bac$"extracted +ith a much smaller volume of $erosene, +hich is thorou#hly mixed in for to &6 minutes and allo+ed to re"separate. :fter isolation, the $erosene fraction is then handled exactly as in the solvent techniue? i.e., the $erosene is bac$"extracted +ith a yet smaller volume of fresh dilute sulfuric acid, a#ain #eneratin# an agua rica solution. The acid techniue al+ays involves multiple (/ to <) extractions of the leaves? i.e., the already stomped leaves are treated +ith another fresh solution of dilute sulfuric acid and re"stomped. ;ach pozo extract is handled identically in turn, except that the same agua rica solution is used to bac$"extract all of the $erosene extracts (thus continually enrichin# its cocaine content). Follo+in# processin# of the final pozo extract, the isolated agua rica solution is a#ain handled exactly as in the solvent techniue? i.e., made basic via addition of an inor#anic base, thereby precipitatin# coca paste. 'oca paste #enerated by the acid techniue is essentially euivalent to that produced via the solvent method, and similarly contains from /6 to 56@ cocaine. The advanta#e of the acid versus solvent techniue is the use of a minimal volume of or#anic solvent? ho+ever, it is considerably more labor"intensive. This variant is used extensively throu#hout olivia, +here personal possession of lar#e volumes (more than <6 liters) of or#anic solvents (e.#., $erosene) in the coca"#ro+in# re#ions is ille#al. 'hemically, coca paste from either extraction procedure has a #ummy consistency and a limited shelf"life. f continuously exposed to excessive heat and humidity, it +ill slo+ly self" dissolve, turnin# into an oily liuid +ith a pun#ent, unpleasant odor. This dra+bac$ is +ell $no+n to the clandestine operators? for this reason, coca paste is usually immediately processed to co$e base. f this is not possible, it is usually stored as agua rica until further processin# is possible. 2' Co3e 4ase !Scee "#
Scee "' llicit production of co$e base from coca paste (see text for details).
'onversion of coca paste to co$e base is a purification procedure. :s +as noted above, the cocaine purity level of coca paste varies from /6 to 56@, dependin# on the extraction techniue, variety of coca, and competence of the operators. The remainder consists of inor#anic salts and various al$aloidal impurities, notably cis" and trans"cinnamoylcocaine, +hich are co"extracted from the leaves. Failure to remove these impurities results in a final product (i.e., cocaine hydrochloride) of poorer uality +ith respect to cocaine content and especially color and appearance. This is +ell $no+n amon# laboratory operators, and as a result, this step is rarely s$ipped. 'oca paste is first re"dissolved in a small amount of dilute sulfuric acid (thus reconstitutin# a fresh agua rica solution)? as previously noted, the solution has a yello+ish"bro+n color similar to beer. 0ome operators then sli#htly increase the pH of the solution +ith careful addition of base. The solution is then titrated a#ainst a concentrated aueous solution of potassium perman#anate, a po+erful oxidi!in# a#ent. otassium perman#anate #ives an intensely purple solution +hen dissolved in +ater? as it reacts +ith the oxidi!able al$aloidal impurities in coca paste, it is reduced to man#anese dioxide (an insoluble, bro+n"blac$ solid), +hich precipitates out of solution. Dhile many operators Cust add a set volume of concentrated aueous perman#anate to a #iven +ei#ht of coca paste%volume of agua rica (as determined by experience), the more usual method is to slo+ly add the solution +ith vi#orous stirrin#, +ait a fe+ minutes, and then chec$ to see if the solution has any yello+ish"bro+n color remainin#. This is determined by visual inspection of the solution after +aitin# for the precipitated man#anese dioxide to settle out? if the solution is still colored, the addition of the perman#anate solution is continued until the solution is finally colorless. Thus, potassium perman#anate also acts as its o+n visual endpoint indicator. Aver"addition or too rapid addition of perman#anate is $no+n to result in decomposition and loss of cocaine, so the operators +or$ carefully to #et it Cust ri#ht.
Dhen the perman#anate addition is Cud#ed to be complete, the solution is filtered to remove the precipitated man#anese dioxide. The resultin# colorless, sli#htly acidic solution (still commonly referred to as agua rica, hereafter oxidi!ed agua rica) is a#ain treated +ith a solution of base (usually dilute ammonia at this sta#e) +ith stirrin#. :#ain, the ammonia neutrali!es the cocaine sulfate and any remainin# sulfuric acid, thereby precipitatin# purified co$e base, +hich is filtered, dried, pac$a#ed, and transferred to a crystal laboratory. a' irect +eaf-to-4ase +a%oratories
n a recently developed and currently uite common variant, both solvent and acid extraction laboratories are bein# extended to production of co$e base. n this alternate, coca paste is never isolated? rather, the unoxidi!ed agua rica solution recovered from bac$"extractin# the $erosene solution is filtered, adCusted (if desired) to hi#her pH +ith a carbonate or bicarbonate salt, and then treated directly +ith the potassium perman#anate solution. This is a short"cut techniue directly convertin# coca leaf to co$e base, and offers several advanta#es to the clandestine operatorsB &. There is a net savin#s of +hatever inor#anic base is bein# used to precipitate coca paste and the sulfuric acid reuired to reconstitute the agua rica? . The previously described difficulties associated +ith the poor shelf"life of coca paste are avoided (co$e base is much more stable than coca paste)? and /. The operators save a lot of time. 'o$e base #enerally varies from 56 to 4<@ cocaine. 0ince potassium perman#anate oxidation tends to remove both the cinnamoylcocaines and other colored impurities typically found in coca paste, the appearance of co$e base is usually much li#hter, varyin# from li#ht tan to +hite? in addition, it has a drier, more mobile (free"flo+in#) consistency versus coca paste. f too little potassium perman#anate is used, an individual co$e base exhibit may retain si#nificant levels of cinnamoylcocaines (varyin# as hi#h as &<@ relative to cocaine for co$e base derived from ;'3'). 'onversely, if improper mixin#, poor pH control, or excess perman#anate is used, cocaine itself may be oxidi!ed to -"formylcocaine, +hich in turn can be hydroly!ed to -"norcocaine5,&6,9,//,96. -"norcocaine can also under#o an intramolecular transamination reaction, #ivin# -"ben!oyl norec#onine methyl ester 9,96. Thus, poor potassium perman#anate oxidation techniues contribute directly to the relative amounts and types of impurities found in the co$e base and eventually in the resultin# cocaine hydrochloride (i.e., hi#h cinnamoylcocaines +ith lo+ -"norcocaine and -"formyl cocaine contents or lo+ cinnamoylcocaines +ith hi#her -"norcocaine, -"formylcocaine, and -"ben!oyl norec#onine methyl ester contents). %' $lternate 6/idi7in) $)ents
:lthou#h potassium perman#anate is the most popular oxidi!in# a#ent (primarily because of its ready availability and the color chan#e associated +ith its use), several alternate oxidi!in# a#ents have been increasin#ly reported. The efficacy of these latter rea#ents is under current investi#ation at this laboratory. "' Cocaine *8drocloride !Scee #
Scee ' llicit production of cocaine hydrochloride from co$e base (see text for details).
:s +as previously noted, crystal laboratories mar$ the s+itchover from the cotta#e industry of paste, base, and direct leaf"to"base laboratories to much lar#er, more sophisticated and centrali!ed operations. 'rystal laboratories are usually supplied +ith co$e base either from a specific net+or$ of feeder base laboratories or from open"mar$et middlemen. :s +as previously noted, the uality of the co$e base is directly reflected in the correspondin# uality of the final product? therefore, all co$e base is spot"chec$ed prior to conversion to the hydrochloride. oor uality base is either returned to the suppliers or re"oxidi!ed (i.e., resubmitted to perman#anate oxidation) either on"site or in separate, lar#e"scale re"oxidation laboratories. n some operations, all co$e base is re"oxidi!ed as a normal matter of course. The illicit production of cocaine hydrochloride is not handled in lar#e batches, but rather as a very lar#e number of small batches. -early all operations +or$ on a & $# scale, +ith a fe+ varyin# up to as much as < $#%batch. : very lar#e crystal laboratory may have hundreds of individual batches runnin# simultaneously in a 1 h%day operation. rocedures often vary dramatically from laboratory to laboratory, especially +ith respect to solvent use. n the classic variant, for each batch, the co$e base is dissolved into diethyl ether, filtered or decanted from any remainin# insoluble impurities, and an eual volume of acetone containin# a stoichiometric uantity of concentrated hydrochloric acid added to the filtrate +ith stirrin#. The hydrochloric acid immediately ion"pairs +ith the co$e base to #ive cocaine hydrochloride, +hich be#ins to precipitate out of the solution as shiny +hite, fla$y crystals. The use of excess concentrated hydrochloric acid is avoided due to the development of a distinct yello+ color (especially in acetone), +hich in turn can be partially conferred upon the cocaine hydrochloride? this is unacceptable from a mar$etin# vie+point. f time is not a critical factor, the resultin# solution is allo+ed to sit from / to 9 hours in order to complete the crystalli!ation process. f the laboratory operators are rushed, ho+ever, the individual batches are placed in a hot +ater bath (called a 7baño María7), +hich reduces the total reaction time to approximately /6 min. 8se of the baño María techniue reportedly results in cocaine hydrochloride of sli#htly reduced uality +ith respect to appearance. :fter completion of the crystalli!ation process, the product is filtered, dried under heat"lamps and%or micro+ave ovens, pressed, pac$a#ed, and shipped to distribution net+or$s. 0pent solvents are usually recycled, either on"site or at a separate recyclin# facility. The insoluble
impurities filtered off from the initial diethyl ether solution are not discarded, but rather are re"dissolved in dilute sulfuric acid, precipitated via addition of dilute ammonia and handled as bazuco (vide supra). :s +as noted before, diethyl ether%acetone &B& is the classic solvent combination for the crystalli!ation process. Ho+ever, due to the current difficulties in obtainin# acetone and (especially) diethyl ether in 0outh :merica, use of alternate solvents or solvent mixtures for the above $ E 4 addition procedure is uite common. The critical factors in solvent mixture composition areB &. 0olubility of co$e base in solvent $? . Miscibility of solvent 4 +ith concentrated hydrochloric acid? and /. nsolubility of cocaine hydrochloride in the combined $ E 4 solvent mixture. 8nsubstantiated reports su##est that laboratory operators select solvent mixtures based on density? i.e., by attemptin# to match the 7ideal7 densities of diethyl ether (6.=&< #%mL), acetone (6.=4< #%mL) and diethyl ether%acetone &B& (ca. 6.=<< #%mL). The most common solvents currently identified in illicit cocaine include (in approximate order of importance)B methyl ethyl $etone, toluene, methylene chloride, ethyl acetate, aliphatic hydrocarbons (hexanes, etc.), acetone, ben!ene, methyl acetate, isobutyl alcohol, and diethyl ether 1,5,/. 8se of standard industrial, cleanin#, or processin# solvent mixtures, e.#., ;00A &6%6, is also common. The overall effects of the use of these alternate solvents on the impurity profile of the resultin# cocaine hydrochloride is under current investi#ation at this laboratory. llicit, unadulterated cocaine hydrochloride #enerally varies from 56 to 4=@ purity, and can vary in appearance from an off"+hite po+der to +hite, iridescent crystals virtually indistin#uishable (visually) from pharmaceutical cocaine. -ot unexpectedly, most of the al$aloidal impurities present in the startin# co$e base are carried throu#h the crystalli!ation procedure and appear in the final product. Fi)' 1' llicit synthetic cocaine, step &"/&B
&. roduction of "carbomethoxytropinone? . ts conversion to Methyl ;c#onine? and /. en!oylation to 'ocaine. Anly sin#le enantiomers depicted for simplicity.
4' Illicit S8ntetic Cocaine
The classic total synthesis of cocaine involves three synthetic, one enantiomeric resolution and one diastereomeric purification steps (Fi#ure 1&,), and reuires a si#nificantly hi#h level of synthetic expertise and +ell"euipped laboratory facilities. The synthesis +ill produce a pair of racemic diastereomers (of +hich only one, i.e., (")"cocaine, is physiolo#ically active) if the enantiomeric resolution and diastereomeric purification steps are omitted. To date, there have been only three sei!ures of illicit synthetic cocaine laboratories in the 8nited 0tates. :ll three follo+ed the classic synthesis? ho+ever, none of the three performed the enantiomeric resolution step. T+o of these laboratories +ere run by clandestine operators +ith advanced chemical trainin#, and successfully produced very lo+ yields of racemic cocaine. The first step involves a rin# couplin# Mannich reaction usin# methylamine, succindialdehyde, and acetonedicarboxylic acid monomethyl ester in hi#h dilution in a buffered, aueous solution at <'. :fter days, the reaction mixture is made basic and extracted +ith chloroform to #ive racemic "carbomethoxytropinone? tropinone is the maCor impurity. ;nantiomeric resolution of the racemate can be accomplished at this point +ith (E)" and (")"tartaric acid? ho+ever, as noted above, none of the operators of the three clandestine laboratories sei!ed to date attempted such a resolution. n step t+o, the "carbomethoxytropinone is dissolved in a minimal volume of ice"cold dilute sulfuric acid and reduced to methyl ec#onine +ith a & to &.<@ -a%H# amal#am at pH /.< and <'. Reaction conditions are critical? poor pH and%or temperature control results in both decarboxylation of "carbomethoxytropinone to tropinone (+hich is, in turn, reduced to tropine and pseudotropine) and '" epimeri!ation of methyl ec#onine to pseudoec#onine methyl ester. :fter several hours, the reaction is made basic, extracted +ith chloroform, and evaporated to an oil containin# methyl ec#onine and pseudoec#onine methyl ester in an approximate /B& ratio. :dditional impurities usually include tropinone, tropine, pseudotropine and unreacted "carbomethoxytropinone. The maCority of pseudoec#onine methyl ester is precipitated from the oil by the addition of diethyl ether and removed via filtration. The filtrate is evaporated to dryness, dissolved in diethyl ether and converted to the hydrochloride. -one of the operators of the three clandestine laboratories sei!ed to date attempted to purify their methyl ec#onine any further than the pseudoec#onine methyl ester precipitation step. n step three, the methyl ec#onine hydrochloride is ben!oylated +ith ben!oyl chloride in pyridine near 6'. :fter 1 h, the reaction mixture is allo+ed to +arm to room temperature and is diluted +ith diethyl ether, +hich precipitates a cocaine H'l%pyridine H'l complex. This precipitate is filtered and +ashed +ith additional ether to remove excess pyridine, dissolved in +ater, and extracted +ith additional ether to remove ben!oic acid. The resultin# aueous solution is made basic +ith dilute ammonium hydroxide (causin# dissociation of the cocaine H'l%pyridine H'l complex), and repeatedly extracted +ith methylene chloride. The combined extracts, +hich also contain the remainin# free pyridine, are evaporated to dryness to #ive cocaine base, +hich is re"dissolved in diethyl ether%acetone &B& and converted to the hydrochloride via addition of a stoichiometric amount of concentrated hydrochloric acid. :s noted above, the clandestine manufacture of illicit synthetic cocaine is extremely unusual. This is not surprisin#, because " even +hen attempted by a s$illed chemist " the preparation of (")"cocaine via total synthesis proceeds in less than &6@ overall yield. This is clearly economically infeasible in vie+ of the relatively lo+ cost and ready availability of illicit natural cocaine.
III' +icit !Paraceutical# Cocaine Production harmaceutical cocaine is a by"product from the industrial extraction from coca of flavorin# a#ents used in the soft"drin$ industry. The isolation process is proprietary and cannot be detailed in this study? ho+ever, it is $no+n to proceed throu#h numerous recrystalli!ation and purification steps. The final product, cocaine hydrochloride, is #enerally of better than 44.<@ purity.
I:' Forensic ifferentiation of +icit :ersus Illicit Cocaine llicit natural cocaine accounts for more than 44.44@ of all sei!ed exhibits. ;xhibits of illicit synthetic cocaine are extremely rare. harmaceutical cocaine is rarely seen and is invariably the result of licit dru# diversion or ille#al prescriptions. The individual processes used to obtain each type of cocaine are distinct and #ive products that are chemically uniue +ith respect to the presence and%or relative enhancement or diminution of various impurities. Therefore, detailed forensic analysis can differentiate bet+een all three types. $' Illicit atural Cocaine
:s previously detailed, the purity of illicit natural cocaine typically varies from 56 to 4=@. 3irtually all unadulterated illicit natural cocaine contains numerous impurities at levels readily detected by chromato#raphic and spectrometric techniues /,9,5"&&,&1,&9"6,1"=,4"/&,//"
The purity of uncut illicit synthetic cocaine can vary dramatically dependin# on the s$ill of the clandestine operator performin# the synthesis. llicit synthetic cocaine +ill not contain many of the al$aloidal impurities commonly identified in illicit natural cocaine, e.#., trimethoxycocaine, the cinnamoylcocaines or the truxillines, but can include any of a +ide variety of synthetic by"products (some of +hich match naturally occurrin# al$aloidal impurities). Af these, pseudococaine, ben!oyltropine and tropacocaine, resultin# from ben!oylation of pseudoec#onine methyl ester, tropine and pseudotropine, respectively, are the most li$ely. :dditional impurities +hich are indicative of synthetic cocaine include /" ben!oyloxy""carbomethoxytropidine (,/"didehydrococaine), /"ben!oyloxytropidine (,/" didehydrotropacocaine), and "carbomethoxy"/"methylaminotropidine . ,/" 2idehydrococaine and ,/"didehydrotropacocaine result from the ben!oylation of unreduced "carbomethoxytropinone and tropinone, respectivel y, and "carbomethoxy"/"
methylaminotropidine from the irreversible rearran#ement of the " carbomethoxytropinone%methylamine imine formed durin# the initial Mannich condensation reaction. C' Paraceutical Cocaine
harmaceutical cocaine usually has a purity better than 44.<@ and typically has little (if any) coca"related impurities. For example, none of the cinnamoylcocaines or truxillines (the most common al$aloids co"extracted +ith cocaine from coca leaf) have been detected in pharmaceutical cocaine. The most commonly identified impurities include ben!oylec#onine, cocaethylene (ethyl cocaine), ec#onine, methyl ec#onine, and norcocaine. The hydrolytic impurities, i.e., ben!oyl ec#onine, ec#onine, and methyl ec#onine, are not a result of the production process itself, but rather arise from de#radative hydrolysis of cocaine hydrochloride over time. 'ocaethylene results from transesterification of the '" carbomethoxy moiety durin# the initial industrial extraction of the coca leaf &<, +hile norcocaine results from the overoxidation of cocaine base durin# one of the purification steps.
References $utors; ote< The comprehensive reference list for this revie+ +ould easily surpass <66 citations. ndeed, an 7annotated7 biblio#raphy on cocaine published in &455 (current throu#h &459) lists over <,666 citations 9&, and, as an even cursory #lance at 'hemical :bstracts +ould confirm, at least half a#ain that many articles have been added to the literature over the last = years. The reference list belo+ is therefore su##estive only, and primarily emphasi!es more recent advances. -ote that many of the selected references include extensive citation lists.
&. :bru!!ese RB 'oca leaf production in the countries of the :ndean 0ubre#ion? 4ull arc 1, 95 !19=9# . :#reda, RFB 2ru# abuse problems in countries of the :ndean 0ubre#ion? 4ull arc "=, 2 !19=># /. :llen :', 'ooper 2:, Giser DA, 'ottrell R'B The cocaine diastereomers? J Forensic Sci 2>, 12 !19=1# 1. :vdovich HD, Leelle M, 0avard', Dilson DLB -uclear ma#netic resonance identification and estimation of solvent residues in cocaine? Forensic Sci Int 9, 225 !1991# <. alic$ M, Rivier L, lo+man TB The effects of field preservation on al$aloid content of fresh coca leaves (erythroxylum spp.)? J .tno?aracol >, 2= !19=2# 9. au#h L2, Liu RHB 0ample differentiationB cocaine example? Forensic Sci Rev ", 102 !1991# =. ohm :, *anders FR, lo+man TB iosystematics and evolution of cultivated coca (erythroxylaceae)? S8st 4ot , 121 !19=2# 5. re+er LM, :llen :'B -"Formyl cocaineB a study of cocaine comparison parameters? J Forensic Sci ">, >9 !1991# 4. y :D, Lod#e :, 0y DDB 'haracteri!ation of cis"cinnamoylcocaine? J Can Soc Forensic Sci 21, 1 !19==# &6. 'asale FB -":cetylnorcocaineB a ne+ cocaine impurity from clandestine processin#. .? Journal of te Clandestine +a%orator8 Investi)atin) Ceists $ssociation 1, 2" !1991#
&&. 'asale FB 2etection of pseudoec#onine and differentiation from ec#onine in illicit cocaine? Forensic Sci Int , 2 !1990# &. 'asale FB : practical total synthesis of cocaine>s enantiomers? Forensic Sci Int "", 25 !19=# &/. 'asale F, Meyers R, Glein RFIB :n in"depth study of cocaine base processin# in the 'hapare 3alley, olivia? manuscript in preparation. &1. 'asale F, Moore MB 2etermination of pseudococaine in coca leaves and illicit cocaine exhibits? 'hromato#r? manuscript submitted . &<. 'asale F, Moore MB :n in"depth analysis of pharmaceutical cocaineB cocaethylene and other impurities? harm 0ci? manuscript submitted . &9. 'asale F, Moore MB />,1>,<>"Trimethoxy"substituted analo#s of cocaine, cis"%trans" cinnamoylcocaine and tropacocaineB characteri!ation and uantitation of ne+ al$aloids in coca leaf, coca paste and refined illicit cocaine? Forensic 0ci? in press. &=. 'asale F, Da##oner RDB : chromato#raphic impurity si#nature profile analysis for cocaine usin# capillary #as chromato#raphy? J Forensic Sci ">, 1"12 !1991# &5. 'asale F, Datterson DB : computeri!ed neural net+or$ method for pattern reco#nition of cocaine si#natures? J Forensic Sci "=, 292 !199"# &4. 'asale F, Datterson DB : neural net+or$ method for pattern reco#nition of chromato#raphic si#nature patterns of forensic trace evidence? roceedin#s of the nternational 0ymposium on the Forensic :spects of Trace ;vidence? 8.0. Federal ureau of nvesti#ation :cademyB Juantico, 3:? in press. 6. 'hiarotti M, Fucci -B HL' analysis of cocaine diastereomers by chiral stationary phase? Forensic Sci Int , " !1990# &. 'ooper 2:B 'landestine production processes for cocaine and heroin? in roceedin#s of the nternational 'onference on :ssessment of 2ru# 'ontrol ssues of 'ontrolled 0ubstance :nalo#s? Rabat, Morocco? p 4< (&45=) . 'ooper 2:, :llen :'B 0ynthetic cocaine impurities? J Forensic Sci 29, 105 !19=# /. 2uiliusB 'ocaine? Ce @t) 5, "1 !19"0# K Ceical $%stracts 2, ""22 !19"0# 1. ;l0ohly M:, renneisen R, ones :B 'oca pasteB chemical analysis and smo$in# experiments? J Forensic Sci ">, 9" !1991# <. ;nsin# *, de eeu+ R:B 2etection, isolation and identification of truxillines in illicit cocaine by means of thin"layer chromato#raphy and mass spectrometry? J Forensic Sci ">,1299 !1991# 9. ;nsin# *, Hummelen 'B solation, identification and ori#in of three previously un$no+n con#eners in illicit cocaine? J Forensic Sci ">, 1>>> !1991# =. ;asin# *, Racamy ', de eeu+ R:B : rapid #as chromato#raphic method for the fin#erprintin# of illicit cocaine samples? J Forensic Sci ", > !1992# 5. Fortuna B 0tatistical analysis of cocaine head"space vapors? 0ubstance 2etection 0ystems, 3ol 64, ;uropto 0eries, resentation " nternational 0ymposium and ;xhibition on 0ubstance dentification Technolo#ies? nnsbruc$, :ustria? Act. &44/. 4. *ill R, :bbott RD, Moffat :'B Hi#h"performance liuid chromato#raphy systems for the separation of local anaesthetic dru#s +ith applicability to the analysis of illicit cocaine samples? J Croato)r "01, 155 !19=# /6. ane , 0cott :, 0harpe RDL, Dhite 'B Juantitation of cocaine in a variety of matrices by hi#h"performance liuid chromato#raphy? J Croato)r 21, 2" !19=1# /&. an!en G;, Dalter L, Fernando :RB 'omparison analysis of illicit cocaine samples? J Forensic Sci ", "> !1992# /. Gram T'B Hydro#en"& nuclear ma#netic resonance spectroscopic analysis of or#anic solvents implicated in illicit cocaine processin#? manuscript in preparation.
//. Leelle M, 'allahan 0:, Latham 2, Lauriault *B dentification and determination of norcocaine in illicit cocaine and coca leaves by #as chromato#raphy"mass spectrometry and hi#h"performance liuid chromato#raphy? $nal8st 11", 121" !19==# /1. Leelle M, 'allahan 0:, Latham 2, Lauriault *, 0avard 'B 'omparison of illicit cocaine by determination of minor components? J Forensic Sci ">, 1102 !1991# /<. Leelle M, Lauriault *, 'allahan 0:, Latham 2, 'hiarelli ', ec$stead HB The examination of illicit cocaine? J Forensic Sci "", >>2 !19==# /9. Le+in :H, ar$er 0R, 'arroll FlB ositive identification and uantitation of isomeric cocaines by hi#h"performance liuid chromato#raphy? J Croato)r 19", "1 !19=0# /=. Lu$as!e+s$i T, effery DGB mpurities and artifacts of illicit cocaine? J Forensic Sci 25, 99 !19=0# /5. Lurie 0, Moore M, 'ooper 2:, Gram T'B :nalysis of manufacturin# by"products and impurities in illicit cocaine via hi#h"performance liuid chromato#raphy and photodiode array detection? J Croato)r 05, 2" !19=# /4. Lurie 0, Moore M, Gram T', 'ooper 2:B solation, identification and separation of isomeric truxillines in illicit cocaine? J Croato)r 50, "91 !1990# 16. Medina FB :nhydroec#onine methyl ester in cocaine sei!ures? Aicro)ra 12, 1"9 !199# 1&. Moore MB personal communication? 8.0. 2ru# ;nforcement :dministration 0pecial Testin# and Research LaboratoryB McLean, 3:? &44/. 1. Moore MB The application of chemical derivati!ation in forensic dru# chemistry for #as and hi#h performance liuid chromato#raphic methods of analysis? Forensic Sci Rev 2, 9 !1990# 1/. Moore MB 2etermination of total truxillines in illicit cocaine sei!ures usin# capillary #as chromato#raphy"electron capture detection? in roceedin#s of the nternational 0ymposium of the Forensic :spects of 'ontrolled 0ubstances? 8.0. Federal ureau of nvesti#ation :cademyB Juantico, 3:? p &4&? &455. 11. Moore MB The application of derivati!ation techniues in forensic dru# analysis? in Glein M, Grue#el :3, 0obol 0 (;ds)B nstrumental :pplication of Forensic 2ru# 'hemis"try? 8.0. 2epartment of ustice, 2ru# ;nforcement :dministrationB Dashin#ton, 2'? p &56 (&4=5) 1<. Moore MB *as chromato#raphic detection of ec#onine and ben!oylec#onine in cocaine? J Croato)r 101, 215 !19# 19. Moore MB dentification of cis" and trans"cinnamoylcocaine in illicit cocaine sei!ures? J $ssoc 6ff $nal Ce 5>, 1199 !19"# 1=. Moore M, 'asale FB The in"depth chromato#raphic analyses of illicit cocaine and its precursor, coca leaves " recent advances? 'hromato#r? in press. 15. Moore M, 'ooper 2:B The application of capillary #as chromato#raphy"electron capture detection in the comparative analyses of illicit cocaine samples? J Forensic Sci "=, 12=> !199"# 14. Moore M, 'ooper 2:, Lurie 0, Gram T', 'arr 0, Harper ', Neh B 'apillary #as chromato#raphic"electron capture detection of coca"leaf"related impurities in illicit cocaineB ,1"diphenylcyclobutane"&,/"dicarboxylic acids, &,1"diphenylcyclobutane" ,/"dicarboxylic acids and their al$aloidal precursors, the truxillines? J Croato)r 10, 29 !19=# <6. Moore M, Meyers R, imene! M2B The anatomy of a cocaine comparison caseB a prosecutorial and chemistry perspective? J Forensic Sci "=, 1"05 !199"# <&. -o##le FT r, 'lar$ 'RB Liuid chromato#raphic analysis of samples containin# cocaine, local anesthetics, and other amines? J $ssoc 6ff $nal Ce >>, 151 !19="#
<. -o##le FT r, 'lar$e 'RB Liuid chromato#raphic identification of cis" and trans" cinnamoylcocaine in illicit cocaine? J $ssoc 6ff $nal Ce >5, 5> !19=2# 2 !19=# <<. lo+man TB :ma!onian coca? J .tno?aracol ", 195 !19=1# <9. lo+man T, Rivier LB 'ocaine and cinnamoylcocaine content of erythroxylum species? $nn 4ot 51, >1 !19="# <=. 0chlesin#er HLB Topics in the chemistry of cocaine? 4ull arc ", >" !19=5# <5. 0chultes R;B 'oca (erythroxylon coca ipadu, ethnobotany, cultivation, processin#) in the -orth+est :ma!on? J .tno?aracol ", 1" !19=1# <4. 0perber AB 'ocaine manufacture in eru? &ro?en?flan7er 15, >= !1911# KCeical $%stracts >, 19 !1912# 96. 0tenber# 3, -arain -G, 0in#h 0, armar 00B :n improved synthesis of norcocaine? J *eteroc8cl Ce 1", ">" !19># 9&. Turner ';, 8rbane$ 0, Dall *M, Daller 'DB 'ocaine? 8niversity ress of MississippiB ac$son, M0? &45&. 9. 8.0. 2epartment of ustice, 2ru# ;nforcement :dministration, Affice of ntelli#enceB 'oca cultivation and cocaine pocessin#B :n overvie+? :rlin#ton, 3:? &44/. 9/. 8.0. 2epartment of ustice, 2ru# ;nforcement :dministration, ntelli#ence 2ivisionB The -ational -arcotics ntelli#ence 'onsumers 'ommittee (--'') Report, &44? :rlin#ton, 3:? &44/ (and prior editions dated &45<"&44&). 91. 8.0. 2epartment of ustice, 2ru# ;nforcement :dministration, ntelli#ence 2ivisionB The lle#al 2ru# 0ituation in the 8nited 0tates? :rlin#ton, 3:? &44/. 9<. 8.0. 2epartment of ustice, 2ru# ;nforcement :dministration, ntelli#ence 2ivisionB 'ocaine 0ituation in ;urope? :rlin#ton, 3:? &44. 99. 8.0. 2epartment of 0tate, ureau of nternational -arcotics MattersB nternational -arcotics 'ontrol 0trate#y Report? Dashin#ton, 2'? &44/.
$%out te $utors J'F' Casale B R'F'X' Klein Jon F' Casale earned his .0. in chemistry from :ppalachian 0tate 8niversity, oone, -', in &45&, and immediately entered the -orth 'arolina 0tate ureau of nvesti#ation Forensic 2ru# Laboratory in Ralei#h. He Coined the 0pecial Testin# and Research Laboratory in &44 as a 0enior Forensic 'hemist +ith the Research *roup. His current interests lie in cocaine si#nature analysis and the isolation and identification of tropanoid al$aloids in coca and cocaine. Ro%ert F' X' Klein earned his h.2. in synthetic or#anic chemistry from *eor#eto+n 8niversity, Dashin#ton, 2', in &45<. His thesis detailed novel syntheses of the 0" pseudoa!ulene thialene and various oxa!ole"based nonsteroidal anti"inflammatory a#ents. 2r. Glein Coined the 0pecial Testin# and Research Laboratory in &45= as a 0enior Forensic 'hemist, and is currently the 0upervisory 'hemist of the Research *roup. His current interests lie in illicit cocaine, heroin, and methamphetamine processin# and the synthesis of desi#ner dru#s.
