Pihkal
Page 82
(with 25 mg) This was a marvelous and strange evening. This 2C-T-7
is good and friendly and wonderful as I remember it. I think it is going to take the place of 2C-T-2 in my heart. It is a truly good material. I got involved with a documentary on television. It was about certain people of Bolivia, people living in the high mountains and about a small village which Q perhaps alone among all the places in the country Q maintains the old Inca ways, the old traditions, the old language. Which is, I gather, against the law in Bolivia. It showed a yearly meeting of shamans and it was quite clear that hallucinogens played a major part in this meeting. The shaman faces, male and female, were startling in their intensity and earthy depth.
The Virgin Mary is worshipped as another version of the ancient Pacha Mama, the Earth Mother. Wonderful dark, vivid look at places and people who are not usually to be seen or even known about.
(with 30 mg) The visuals have an adaptable character to them. I can use them to recreate any hallucinogenic substance I have known and loved. With open eyes, I can go easily into LSD flowing visuals, or into the warm earth world of Peyote, or I can stop them altogether.
With closed eyes, there are Escher-like graphics with a lot of chiaroscuro, geometric patterns with oppositional play of sculptured light and dark values. Green light.
EXTENSIONS AND COMMENTARY: If all the phenethylamines were to be ranked as to their acceptability and their intrinsic richness, 2C-T-7
would be right up there near the top, along with 2C-T-2, 2C-B, mescaline and 2C-E. The range is intentionally extended on the lower side to include 10 milligrams, as there have been numerous people who have found 10 or so milligrams to be quite adequate for their tastes.
One Tweetio related to 2C-T-7 has been made and evaluated. This is the 2-EtO-homologue of 2C-T-7,
2-ethoxy-5-methoxy-4-(n)-propylthiophenethyl-amine, or 2CT7-2ETO. The benzaldehyde (2-ethoxy-5-methoxy-4-(n-propyl-thio)benzaldehyde had a melting point of 69-71 !C, the nitrostyrene intermediate a melting point of 106-106.5 !C, and the final hydrochloride a melting point of 187-189 C!. At the 20 milligram level, the effects were felt quickly, and the eyes-closed visuals were modest but real. It was very short-lived, with baseline recovery at about the fifth hour. The next day there was an uncomfortable headache which seemed on an intuitive level to be an after-effect of the compound.
The unusual properties of a number of N-methyl-N-(i)-propyltryptamines suggested the possibility of something like a similar set of N-methyl-N-(i)-propylphenethylamines. Why not try one from 2C-T-7?
The thought was, maybe N-methylate this compound, then put on an isopropyl group with reductive alkylation, using acetone as the carbon source and sodium cyanoborohydride. Towards this end, the free base of 2C-T-7 (from one gram of the hydrochloride) was refluxed for 2 h in 1.3 g butyl formate, and on removing the solvent/reactant the residue spontaneously crystallized. This formamide (0.7 g) was reduced with lithium hydride in cold THF to provide 2,5-dimethoxy-4-(n)-propyl-N-methyl-phenethylamine, METHYL-2C-T-7, which distilled at 150-170 !C at 0.4 mm/Hg. A very small amount of the hydrochloride salt was obtained (65 milligrams) and it had a brown color. Too small an amount of an impure product; the entire project was dropped.
44 2C-T-8; 2,5-DIMETHOXY-4-CYCLOPROPYLMETHYLTHIOPHENETHYLAMINE
SYNTHESIS: To a solution of 2.8 g of KOH pellets in 25 mL hot MeOH, there was added a mixture of 5.9 g 2,5-dimethoxythiophenol (see under 2C-T-2 for its preparation) and 5.0 g of cyclopropylmethyl bromide.
There was an immediate exothermic reaction with spontaneous boiling and the formation of white crystals. This was heated on the steam bath for 4 h, and then added to 400 mL of H2O. After extraction with 3x75 mL CH2Cl2, the pooled extracts were washed first with dilute NaOH, then with saturated brine, then the solvent was removed under vacuum. The residue, 8.45 g of crude 2,5-dimethoxyphenyl cyclopropyl methyl sulfide, was distilled at 120-140 !C at 0.3 mm/Hg to give a white oil weighing 7.5 g.
A mixture of 13.5 g POCl3 and 13.5 g N-methylformanilide was heated for 10 min on the steam bath. To this claret-colored solution was added 7.28 g of 2,5-dimethoxyphenyl cyclopropylmethyl sulfide, and the spontaneously exothermic mixture was heated for an additional 10 min on the steam bath, and then quenched in 400 mL of 55 !C H2O with good stirring. After a few minutes a reddish solid phase separated. This was removed by filtration, and washed with additional H2O. After sucking as dry as possible, this 8.75 g of ochre-colored solid was dissolved in 14 mL of boiling MeOH, and after cooling, filtering, washing sparsely with MeOH, and air drying, gave 7.27 g of white solid crystals of 2,5-dimethoxy-4-(cyclopropylmethylthio)benzaldehyde. The proton NMR spectrum was impeccable; CHO 9.38, ArH 7.27, 6.81 2 s., OCH3 3.93, 3.90 2 s., SCH2 t. 2.96, CH2, m. 1.72, and CH2, t. 1.11.
To a solution of 6.6 g 2,5-dimethoxy-4-(cyclopropylthio)benzaldehyde in 82 g of nitromethane there was added 0.12 g of anhydrous ammonium acetate, and the mixture was heated on the steam bath for 6 h. The reaction mixture was allowed to stand overnight producing a heavy crystallization crop. Filtration, washing lightly with MeOH, and air drying gave 4.72 g of orange crystals of 2,5-dimethoxy-4-cyclopropylmethylthio-'-nitrostyrene as yellow crystals. The evaporation of the mother liquors and grinding of the resulting solids with MeOH provided another 2.0 g of the product.
A solution LAH (40 mL of a 1 M solution in THF) was cooled, under He, to 0 !C with an external ice bath. With good stirring there was added 1.05 mL 100% H2SO4 dropwise over 10 min, to minimize charring. This was followed by the addition of 2.95 g 2,5-dimethoxy-4-cyclopropylmethylthio-'-nitrostyrene as a solid, over the course of 10 min. After a few min further stirring, the temperature was brought up to a gentle reflux on the steam bath, then all was cooled again to 0 !C. The excess hydride was destroyed by the cautious addition of 6 mL IPA followed by 3 mL 15% NaOH which gave the aluminum oxide as a curdy white solid. The reaction mixture was filtered, and the filter cake washed with additional THF. The filtrate and washes were stripped of solvent under vacuum providing about 1.8 g of a colorless oil. The addition of dilute H2SO4 produced a thick mass of white solids. This was washed with CH2Cl2, and the remaining aqueous phase, still containing solids, was made basic with 25% NaOH. The aqueous phase was extracted with 3x75 mL CH2Cl2, and the combined extracts stripped of solvent under vacuum. The result was 1.4 g of colorless oil. This was distilled at 150-165 !C at 0.2
mm/Hg to give 1.2 g of a white oil. This was dissolved in 6 mL IPA, neutralized with 0.6 mL concentrated HCl producing spontaneous white crystals. These were diluted with 8 mL additional IPA, and suspended under 60 mL anhydrous Et2O to provide, after filtering and air drying, 1.13 g of 2,5-dimethoxy-4-cyclo-propylmethylthiophenethylamine hydrochloride (2C-T-8) as white crystals.
DOSAGE: 30 - 50 mg.
DURATION: 10 - 15 h.
QUALITATIVE COMMENTS: (with 30 mg) Bad taste, worse smell. But I like it. I can paint easily, and wouldnUt hesitate to take a little more next time, but this is enough with no one to talk to. Manual dexterity good. Body rather warm. WouldnUt mind fooling around. In retrospect, it has a smooth onset, and is not too stimulating. This is a good one.
(with 40 mg) This is beginning to develop at one and a half hours into it. High energy, good feeling. I have had a heavy, dense feeling between me and my work for several days now, but this is rapidly dissolving, and with this loss, the day continues into one of the most remarkable experiences I have ever had. Excellent feelings, tremendous opening of insight and understanding, a real awakening as if I had never used these materials effectively before. For the next several hours it was an internal journey for me; I wished to interact with myself. I cannot recall all the details, but I did review many aspects of myself and my personal relations. I know that I am the better for all of this.
(with 40 mg) I first noted the effects at three quarters of an hour, and at two hours I have pain in my sinuses. My head is split in two Q
this is not being two or three different people Q this is one person with a head living in two different
universes at the same time. Not a crisis experience, but one of extreme and prolonged discomfort.
Hypersensitivity to light, noise, motion, with the belief that it would not go away when the chemical wore off. My visual and spatial perceptions were divided in two along a vertical axis, with both halves moving in uncoordinated ways. A feeling that the eyes were working independently of each other. Nausea without vomiting, even when I tried to. Vertigo became intolerable if I closed my eyes or lay down, so I felt that I would never lie down or close my eyes again. Problems with 'boundaries.' The outside environment seemed to be getting inside my head. The parts of myself seemed to either separate uncontrollably or run together into someone I didnUt know. A late movie, and Tranxene, and a little sleep all helped me out of this. However, a buzzing in the head, an uncertain balance, and an out-of-it feeling lasted for 3 days, and was still faintly present after a week.
(with 43 mg) For the first two hours I rocked in place and felt quite happy not trying to 'do' anything useful or expected, but watched some excellent programs on TV. Later I sat at the typewriter and felt the energy and the opening of the particular kind of thinking-connection that I associate with 2C-T-2. I felt this very strongly; I was fully into my own energy and capable of being aggressive if I decided to. I was very good humored and completely anchored to the earth. In the late evening I went to bed and felt that I would not allow myself to sleep, since the tendency to go completely out of conscious body was quite strong. However, before I could get up and continue happily writing, as I intended, I fell asleep. I slept thoroughly, well, and woke up the next day with good energy and a willingness to get on with the day.
(with 50 mg) The whole experience was somewhat negative, self-doubting, paranoid. Basically, I am not in a good place. No constructive values ever knit, and although there was a lot of talking, nothing positive developed. I was glad of sleep at about twelve hours into it, and this aspect of it was completely friendly.
Next day, no deficit. Strange. Maybe too much.
EXTENSIONS AND COMMENTARY: With 2C-T-8, there are as many negatives as there are positives, and the particular substitution pattern is not one to set the world on fire. The first step was made towards the synthesis of the 3-carbon counterpart, 2,5-dimethoxy-4-cyclopropylmethylthioamphetamine, ALEPH-8. The above benzaldehyde (2.2 g) was cooked overnight on the steam bath in nitroethane (20 mL) containing ammonium acetate (0.4 g) and when the solvent was removed, the residue was converted to orange crystals by the addition of a little MeOH. This was not pursued further.
Although the cyclopropylmethyl group was quite something on the mescaline oxygen atom, it is less appealing on the 2C-T-X sulfur atom, and there is even less enthusiasm to put it into an ALEPH. That's the way it is, and who could have guessed!
45 2C-T-9; 2,5-DIMETHOXY-4-(t)-BUTYLTHIOPHENETHYLAMINE
SYNTHESIS: To a well-stirred ice-cold suspension of 2.8 g p-dimethoxybenzene and 3.2 mL N,N,NU,NU-tetramethylethylenediamine in 100 mL petroleum ether under an inert atmosphere of He, there was added 13 mL of a 1.6 N solution of butyllithium in hexane. The suspended dimethoxybenzene became opaque and there was a pale yellow color generated. The reaction mixture was warmed to room temperature which converted it to light white solids. After an additional 0.5 h stirring, there was added, slowly, 3.6 g of di-(t)-butyldisulfide.
The yellow color deepened, the solids dissolved and, after 1 h, the color was a clear deep brown. This solution was poured into 100 mL
dilute HCl and the organic phase was separated. The aqueous fraction was extracted with 3x75 mL CH2Cl2. The combined organic phases were washed with dilute aqueous NaOH, with H2O, and then stripped of solvents under vacuum. The residue was distilled at 95-105 !C at 0.5
mm/Hg to provide 3.7 g of 2,5-dimethoxyphenyl (t)-butyl sulfide as a white, mobile liquid. Anal. (C12H18O2S) C,H. A solid derivative was found in the nitration product,
2,5-dimethoxy-4-(t)-butylthio-1-nitrobenzene, which came from the addition of 0.11 mL of concentrated HNO3 to a solution of 0.23 g of the above sulfide in 5 mL ice cold acetic acid. Dilution with H2O
provided yellow solids which, on recrystallization from MeOH, had a mp of 92-93 !C. Anal. (C12H17NO4S) C,H. Attempts to make either the picrate salt or the sulfonamide derivative were not satisfactory.
A mixture of 72 g POCl3 and 67 g N-methylformanilide was heated for 10
min on the steam bath. To this claret-colored solution was added 28 g of 2,5-dimethoxyphenyl (t)-butyl sulfide, and the mixture heated for 10 min on the steam bath. This was then added to 1 L of H2O and stirred overnight. The residual brown oil was separated from the water mechanically, and treated with 150 mL boiling hexane. The hexane solution was decanted from some insoluble tars, and on cooling deposited a dark oil which did not crystallize. The remaining hexane was removed under vacuum and the residue combined with the above hexane-insoluble dark oil, and all distilled at 0.2 mm/Hg. An early fraction (70-110 !C) was largely N-methyl-formanilide and was discarded. Crude 2,5-dimethoxy-4-(t-butylthio)benzaldehyde came over at 120-130 !C and weighed 12.0 g. This was never satisfactorily crystallized despite the successful formation of seed. It was a complex mixture by TLC, containing several components. It was used for the next step as the crude distilled fraction.
To a solution of 10 g impure 2,5-dimethoxy-(t-butylthio)benzaldehyde in 75 mL of nitromethane there was added 1.0 g of anhydrous ammonium acetate, and the mixture was heated on the steam bath 1.5 h. Removal of the excess solvent/reagent under vacuum produced an orange oil that was (not surprisingly) complex by TLC and which would not crystallize.
A hot hexane solution of this oil was allowed to slowly cool and stand at room temperature for several days, yielding a mixture of yellow crystals and a brown viscous syrup. The solids were separated and recrystallized from 40 mL MeOH to give 3.7 g 2,5-dimethoxy-4-(t)-butylthio-'-nitrostyrene as fine lemon-yellow crystals, with a mp of 93-94 !C. A second crop of 1.4 g had a mp of 91-92 !C. Anal. (C14H19NO4S) C,H.
A solution of LAH (70 mL of a 1 M solution in THF) was cooled, under He, to 0 !C with an external ice bath. With good stirring there was added 2.1 mL 100% H2SO4 dropwise, over the course of 20 min. This was followed by the addition of 4.7 g
2,5-dimethoxy-4-(t)-butylthio-'-nitrostyrene in 20 mL anhydrous THF.
There was an immediate loss of color. After a few min further stirring, the mixture was allowed to come to room temperature, and the stirring was continued for 5 h. The excess hydride was destroyed by the cautious addition of 10 mL IPA followed by 6 mL 15% NaOH and finally 6 mL H2O. The loose white solids were removed by filtration, and the filter cake washed with THF. The filtrate and washes were combined and, after stripping off the solvent under vacuum, there was obtained 4.66 g of a pale yellow oil. Without any further purification, this was distilled at 0.2 mm/Hg. A first fraction came over at up to 120 !C and was a light colorless oil that was not identified. The correct product distilled at 130-160 !C as a pale yellow viscous oil that weighed 1.66 g. This was dissolved in 10 mL
IPA, neutralized with 20 drops of concentrated HCl and diluted with 80
mL anhydrous Et2O. After standing a few min there was the spontaneous generation of white crystals of
2,5-dimethoxy-4-(t)-butylthiophenethylamine hydrochloride (2C-T-9) which were removed by filtration, and air dried. The weight was 1.10
g.
DOSAGE: 60 - 100 mg.
DURATION: 12 - 18 h.
QUALITATIVE COMMENTS: (with 90 mg) 2C-T-9 tastes the way that old crank-case motor oil smells. I was up to something above a plus two at the third hour. Although there were no visuals noted, I certainly would not choose to drive. Somehow this does more to the body than to the head. I feel that the effects are waning at maybe the sixth hour, but there is a very strong body memory that makes sleeping difficult.
Finally, at sometime after midnight and with the help of a glass of wine, some sleep.
(with 125 mg) There was a steady climb to a +++ over the first couple of hours. So far, the body has been qu
ite peaceful without any strong energy push or stomach problems, although my tummy insists on being treated with quiet respect, perhaps out of habit, perhaps not. At the fifth hour, the body energy is quite strong, and I have the choice of focusing it into some activity, such as love-making or writing, or having to deal with tapping toes and floor-pacing. For a novice this would be a murderously difficult experience. Too much energy, too long a time. I suppose I could get used to it, but let me judge by when I get to sleep, and just what kind of sleep it is. It turned out that sleep was OK, but for the next couple of days there was a continuing awareness of some residue in the body Q some kind of low-level poisoning. I feel in general that there is not the excitement or creativity to connect with, certainly not enough to justify the cost to the body.
EXTENSIONS AND COMMENTARY: The three-carbon analog of 2C-T-9 (this would be one of the ALEPH series) has never been made and, for that matter, none of the higher numbered 2C-T's have had the amphetamine counterparts synthesized. They are, as of the present time, unknown compounds. This nifty reaction with di-(t)-butyl disulfide worked so well, that three additional disulfides that were at hand were immediately thrown into the chemical program, with the quick assignment of the names 2C-T-10, 2C-T-11, and 2C-T-12.
The lithiated dimethoxybenzene reaction with 2,2-dipyridyl disulfide produced 2,5-dimethoxyphenyl 2-pyridyl sulfide which distilled at 135-150 !C at 0.4 mm/Hg and could be recrystallized from cyclohexane containing 2% EtOH to give a product that melted at 66-67.5 !C. Anal.
(C13H13NO2S) C,H. This would have produced 2,5-dimethoxy-4-(2-pyridylthio)phenethylamine (2C-T-10) but it was never pursued.