Shulgin was born in Berkeley, California to Theodore Stevens Shulgin (1893-1978) and Henrietta D. Shulgin (1888-1960). The 1930 Federal Census gives Theodore's place of birth as Orenburg, Russia, which is just north of Kazakhstan, but says that Theodore's parents were both born in Kiev. His date of immigration to the United States is given as 1923, which is before his date of birth given above as 1925. Henrietta was born in Illinois. Both Theodore and Henrietta were public school teachers in Alameda County.

Shulgin began studying organic chemistry as a Harvard University scholarship student. In 1943, at the age of 19, he dropped out of school, and joined the U.S. Navy, where he eventually became interested in pharmacology. After serving in the Navy (veteran of World War II), he returned to Berkeley, California, and in 1954 earned his Ph.D. in biochemistry from the University of California, Berkeley. Through the late 1950s, Shulgin completed post-doctoral work in the fields of psychiatry and pharmacology at University of California, San Francisco. After working at Bio-Rad Laboratories as a research director for a brief period, he began work at Dow Chemical Company as a senior research chemist.

It was at this time that he had a series of psychedelic experiences that helped to shape his further goals and research, beginning with an experience with mescaline.

He would later write that everything he saw and thought "had been brought about by a fraction of a gram of a white solid, but that in no way whatsoever could it be argued that these memories had been contained within the white solid... I understood that our entire universe is contained in the mind and the spirit. We may choose not to find access to it, we may even deny its existence, but it is indeed there inside us, and there are chemicals that can catalyze its availability."

Shulgin's professional activities continued to lean in the direction of psychopharmacology, furthered by his personal experiences with psychedelics. But during this period he was unable to do much independent research. His opportunity for further research came with his development of Zectran, the first biodegradable pesticide, a highly profitable product. Dow Chemical Company, in return for Zectran's valuable patent, gave Shulgin great freedom. During this time, he created and patented drugs when Dow asked, and published findings on other drugs in journals such as Nature and Journal of Organic Chemistry. Eventually, Dow Chemical requested that he no longer use their name on his publications.

In 1965, Shulgin left Dow to pursue his own interests, and became a private consultant, also frequently teaching classes in the local universities and at the San Francisco General Hospital. Through his friend Bob Sager, head of the U.S. DEA's Western Laboratories, Shulgin formed a relationship with the DEA and began holding pharmacology seminars for the agents, supplying the DEA with samples of various compounds, and occasionally serving as an expert witness in court. He also authored a definitive law enforcement reference book on controlled substances and received several awards from the DEA.

On April 8, 2008, the 82 year old Dr. Shulgin underwent surgery to replace a defective aortic valve. Currently, Shulgin is working on a series of N-allylated tryptamines including 5-MeO-DALT and 5-MeO-MALT.

In order to carry out consulting work with the DEA, Shulgin obtained a DEA Schedule I license for an analytical laboratory, which allowed him to possess and synthesize any otherwise illicit drug. Shulgin set up a chemical synthesis laboratory in a small building behind his house, which gave him a great deal of career autonomy. Shulgin used this freedom to synthesize and test the effects of psychoactive drugs.

In 1967, Shulgin was introduced to MDMA (ecstasy) by Merrie Kleinman, a graduate student in the medicinal chemistry group he advised at San Francisco State University. MDMA had been synthesized in 1912 by Merck and patented in 1912 as a byproduct of another synthesis, but was considered useless, and was never explored. Shulgin went on to develop a new synthesis method, and in 1976, introduced the chemical to Leo Zeff, a psychologist from Oakland, California. Zeff used the substance in his practice in small doses as an aid to talk therapy. Zeff introduced the substance to hundreds of psychologists around the nation, including Ann Shulgin, whom Alexander Shulgin met in 1979, and married in 1981.

After judicious self-experiments, Shulgin enlisted a small group of friends with whom he regularly tested his creations, starting in 1960. They developed a systematic way of ranking the effects of the various drugs, known as the Shulgin Rating Scale, with a vocabulary to describe the visual, auditory and physical sensations. He personally tested hundreds of drugs, mainly analogues of various phenethylamines (family containing MDMA and mescaline), and tryptamines (family containing DMT and psilocybin). There are a seemingly infinite number of slight chemical variations, all of which produce variations in effect—some pleasant and some unpleasant, depending on the person, substance, and situation—all of which are meticulously recorded in Shulgin's lab notebooks. Shulgin published many of these objective and subjective reports in his books and papers.

In 1994, two years after the publication of PiHKAL, the DEA raided his lab; allegedly finding problems with his record keeping, the agency requested that Shulgin turn over his license for violating the license's terms, and he was fined $25,000 for possession of anonymous samples sent to him for quality testing. In the 15 years preceding the publication of PiHKAL, two announced and scheduled reviews failed to find any irregularities. Richard Meyer, spokesman for DEA's San Francisco Field Division, has stated that, "It is our opinion that those books are pretty much cookbooks on how to make illegal drugs. Agents tell me that in clandestine labs that they have raided, they have found copies of those books," suggesting to many that the publication of PiHKAL and the termination of Shulgin's license were related.

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Other notable publications

• 1960-1979 lab notebooks of Dr. Shulgin
• 1963. "Psychotomimetic agents related to mescaline". Experientia 19: 127. 19
• 1963. "Composition of the myristicin fraction from oil of nutmeg". Nature 197: 379. 20
• 1963. "Concerning the pharmacology of nutmeg". Mind 1: 299-302. 23
• 1964. "3-methoxy-4,5-methylenedioxy amphetamine, a new psychotomimetic agent". Nature 201: 1120-1121. 29
• 1964. "Psychotomimetic amphetamines: methoxy 3,4-dialkoxyamphetamines". Experientia 20: 366. 30
• 1964. with H. O. Kerlinger. "Isolation of methoxyeugenol and trans-isoelemicin from oil of nutmeg". Naturwissenschaften 15: 360-361. 31
• 1965. "Synthesis of the trimethoxyphenylpropenes". Can. J. Chem. 43: 3437-3440. 43
• 1966. "Possible implication of myristicin as a psychotropic substance". Nature 210: 380-384. 45
• 1966. "The six trimethoxyphenylisopropylamines (trimethoxyamphetamines)". J. Med. Chem. 9: 445-446. 46
• 1966. with T. Sargent, and C. Naranjo. "Role of 3,4-dimethoxyphenethylamin in schizophrenia". Nature 212: 1606-1607. 48
• 1967. with T. Sargent, and C. Naranjo. "The chemistry and psychopharmacology of nutmeg and of several related phenylisopropylamines". In D. H. Efron [ed.]: Ethnopharmacologic search for psychoactive drugs. U. S. Dept. of H. E. W., Public Health Service Publication No. 1645. Pp. 202—214. Discussion: ibid. pp. 223—229. 49
• 1967. with T. Sargent. "Psychotropic phenylisopropylamines derived from apiole and dillapiole". Nature 215: 1494-1495. 50
• 1967. with Sargent, T. W., D. M. Israelstam, S. A. Landaw, and N. N. Finley. "A note concerning the fate of the 4-methoxyl group in 3,4-dimethoxyphenethylamine (DMPEA)". Biochem. Biophys. Res. Commun. 29: 126-130. 52
• 1967. with Naranjo, C. and T. Sargent. "Evaluation of 3,4-methylenedioxyamphetamine (MDA) as an adjunct to psychotherapy". Med. Pharmacol. Exp. 17: 359-364. 53
• 1968. "The ethyl homologs of 2,4,5-trimethoxyphenylisopropylamine". J. Med. Chem. 11: 186-187. 54
• 1969. with T. Sargent and C. Naranjo. "Structure activity relationships of one-ring psychotomimetics". Nature 221: 537-541. 57
• 1969. "Recent developments in cannabis chemistry". J. Psyched. Drugs 2: 15-29. 58
• 1969. "Psychotomimetic agents related to the catecholamines". J. Psyched. Drugs 2(2): 12-26. 59
• 1970. "Chemistry and structure-activity relationships of the psychotomimetics". In D. H. Efron [ed.]. "Psychotomimetic Drugs". Raven Press, New York. Pp. 21—41. 60
• 1970. "The mode of action of psychotomimetic drugs; some qualitative properties of the psychotomimetics". Neur. Res. Prog. Bull. 8: 72-78. 61
• 1970. "4-alkyl-dialkoxy-alpha-methyl-phenethylamines and their pharmacologically-acceptable salts". U. S. Patent 3,547,999, issued Dec. 15, 1970. 63
• 1971. with T. Sargent and C. Naranjo. "4-bromo-2,5-dimethoxyphenylisopropylamine, a new centrally active amphetamine analog". Pharmacology 5: 103-107. 64
• 1971. "Chemistry and sources". In S. S. Epstein [ed]. "Drugs of abuse: their genetic and other chronic nonpsychiatric hazards". The MIT Press, Cambridge, Mass. Pp 3—26. 65
• 1971. "Preliminary studies of the synthesis of nitrogen analogs of Delta1-THC". Acta Pharm. Suec. 8: 680-681. 66
• 1972. "Hallucinogens, CNS stimulants, and cannabis. In S. J. Mulé and H. Brill [eds.]: Chemical and biological aspects of drug dependence". CRC Press, Cleveland, Ohio. Pp. 163—175. 67
• 1973. "Stereospecific requirements for hallucinogenesis". J. Pharm. Pharmac. 25: 271-272. 68
• 1973. "Mescaline: the chemistry and pharmacology of its analogs". Lloydia 36: 46-58. 69
• 1973. "The narcotic pepper - the chemistry and pharmacology of Piper methysticum and related species". Bull. Narc. 25: 59-1974. "Le poivre stupéfiant - chemie et pharmacologie du Piper methysticum et des espéces apparentées". Bull. Stupéfiants 25: 61-77. 70
• 1973. with T. Sargent and C. Naranjo. "Animal pharmacology and human psychopharmacology of 3-methoxy-4,5-methylenedioxyphenylisopropylamine (MMDA)". Pharmacology 10: 12-18. 71
• 1974. with Kalbhen, D. A., T. Sargent, G. Braun, H. Stauffer, N. Kusubov, and M. L. Nohr. "Human pharmacodynamics of the psychodysleptic 4-bromo-2,5-dimethoxyphenylisopropylamine labelled with [82]Br". IRCS (Int. Res. Comm. Sys.) 2: 1091. 73
• 1975. with Sargent, T., D. A. Kalbhen, H. Stauffer, and N. Kusubov. "A potential new brain-scanning agent: 4-[77]Br-2,5-dimethoxyphenylisopropylamine (4-Br-DPIA)". J. Nucl. Med. 16: 243-245. 74
• 1975. with M. F. Carter. "Centrally active phenethylamines". Psychopharm. Commun. 1: 93-98. 75
• 1975. with Sargent, T., D. A. Kalbhen, G. Braun, H. Stauffer, and N. Kusubov. "In vivo human pharmacodynamics of the psychodysleptic 4-Br-2,5-dimethoxyphenylisopropylamine labelled with [82]Br or [77]Br". Neuropharmacology 14: 165-174. 76
• 1975. "The chemical catalysis of altered states of consciousness. Altered states of consciousness, current views and research problems". The drug abuse council, Washington, D. C. Pp. 123—134. 77
• 1975. "Drug use and anti-drug legislation". The PharmChem Newsletter 4 (#8). 79
• 1975. with D. C. Dyer. "Psychotomimetic phenylisopropylamines. 5. 4-alkyl-2,5-dimethoxyphenylisopropylamines". J. Med. Chem. 18: 1201-1204. 80
• 1975. with C. Helisten. "Differentiation of PCP, TCP, and a contaminating precursor PCC, by thin layer chromatography". Microgram 8: 171-172. 81
• 1975. with Helisten, C. "The detection of 1-piperidinodydlohexanecarbonitrile contamination in illicit preparations of 1-(1-phenylcyclohexyl)piperidine and 1-(1-(2-thienyl)cyclohexyl)piperidine". J. Chrom. 117: 232-235. 82
• 1976. "Psychotomimetic agents". In M. Gordon [ed.] "Psychopharmacological agents", Vol. 4. Academic Press, New York. Pp. 59—146. 83
• 1976. "Abuse of the term 'amphetamines'". Clin. Tox. 9: 351-352. 84
• 1976. "Profiles of psychedelic drugs. 1. DMT". J. Psychedelic Drugs 8: 167-168. 85
• 1976. "Profiles of psychedelic drugs. 2. TMA-2". J. Psychedelic Drugs 8: 169. 86
• 1976. with D. E. MacLean. "Illicit synthesis of phencyclidine (PCP) and several of its analogs". Clin. Tox. 9: 553-560. 87
• 1976. with Nichols, D. E. "Sulfur analogs of psychotomimetic amines". J. Pharm. Sci. 65: 1554-1556. 89
• 1976. with Sargent, T. and N. Kusubov. "Quantitative measurement of demethylation of [14]C-methoxyl labeled DMPEA and TMA-2 in rats". Psychopharm. Commun. 2: 199-206. 90
• 1976. with Standridge, R. T., H. G. Howell, J. A. Gylys, R. A. Partyka. "Phenylalkylamines with potential psychotherapeutic utility. 1. 2-amino-1-(2,5,-dimethoxy-4-methylphenyl)butane". J. Med. Chem. 19: 1400-1404. 91
• 1976. "Profiles of psychedelic drugs. 3. MMDA". J. Psychedelic Drugs 8: 331. 92
• 1977. "Profiles of psychedelic drugs. 4. Harmaline". J. Psychedelic Drugs 9: 79-80. 93
• 1977. "Profiles of psychedelic drugs. 5. STP". J. Psychedelic Drugs 9: 171-172. 94
• 1977. with Nichols, D. E., and D. C. Dyer. "Directional lipophilic character in a series of psychotomimetic phenethylamine derivatives". Life Sciences 21: 569-576. 95
• 1977. with Jacob, P. III, G. Anderson III, C. K. Meshul, and N. Castagnoli Jr. "Mononethylthio analogues of 1-(2,4,5-trimethoxyphenyl)2-aminopropane". J. Med. Chem. 20: 1235-1239. 96