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Experts suspect Valium gas used in Russian troops' theater raid


By JOSEPH B. VERRENGIA
The Associated Press
10/26/02 6:09 PM


Military experts and toxicologists say Russian commandos probably pumped a gas containing Valium into a Moscow theater to subtly disable and disorient heavily armed Chechen rebels prior to Saturday's dramatic assault.

Russian authorities didn't identify the gas used in the operation, which freed hundreds of hostages but also resulted in the deaths of more than 100 captives and rebels. Officials claimed none of the hostages were killed by the gas.

Several nations, including the United States, have developed a variety of non-lethal incapacitating agents, which can also induce choking, nausea or blurry vision, depending on their recipes.

According to some hostages inside the theater, they realized they were becoming sleepy and confused, but no one reported seeing a vapor cloud, smelling a chemical or experiencing the sort of irritating symptoms associated with tear gas and pepper spray.

Experts said the Russians may have released a gas concentration of a powerful sedative like Valium or may have used a form of BZ gas, a hallucinogenic drug widely researched in the 1960s that works more slowly.

"The thing that pops into my mind is aerosolized Valium," said Dr. Christopher Holstege, medical toxicology director at the University of Virginia. "But there isn't much literature out there on it. There is talk of using it as a riot control agent."

Others said the agent used by the Russians didn't seem to be like anything that has been part of the U.S. arsenal.

"It's no surprise that the Russians have that kind of stuff," said Ron Madrid, a former Marine and an expert on non-lethal weaponry at Pennsylvania State University. "They spent 30 years putting it together. We're prevented from doing that by treaty and executive order."

Russian television reported the gas was dispersed through the theater's ventilation system. Workers were seen digging around sewers and steam pipes near the theater in the first day of the crisis.

One Interfax News Agency employee among the captives in the theater said the rebels appeared ready to kill all the hostages, "then something happened."

"I lost consciousness and woke up in the emergency room," said Olga Chernyak. "It must have been some special gas."

Outside City Hospital No. 13, Galina Dolotova said her 32-year-old daughter, Olga, appeared to have been one of the hostages least affected by the gas, but even at that "she was in terrible shape" when she was brought in.

Holstege said people exposed to aerosolized Valium would feel sleepy and confused. At sufficiently high levels, it could compromise breathing and oxygen supply to vital organs.

"It sedates you, so you would feel hung over," Holstege said "People don't remember events well afterward. If it was administered in a theater full of people with guns and explosives, it might confuse them as to what was going on so they could not shoot."

Experts also mentioned BZ, or 3-quinuclidinyl benzilate, as a possibility for the gas used by the Russians.

BZ was a research focus of the U.S. Army during the Cold War at the former Edgewood Area labs near Washington. It belongs to a class of drugs known as anticholinergics that interrupt the brain's chemical messaging system between cells, leading to confusion and hallucinations. It needs an hour to take effect, so authorities would've had to release it into the theater long before the actual assault.

BZ also produces a tendency to fall asleep, and government reports show that soldiers in its U.S. development program nicknamed it the "sleeping agent." The delirium it induces can last two or three days.

"The Russians could've used BZ in the theater, but perhaps in higher concentrations," Holstege said.

A recent U.S. Air Force paper on nonlethal weapons said "calmative" agents reportedly were used by Soviet troops against Afghan guerrillas during their 1980-89 war.

The American and British militaries have discussed developing calmative weapons that would incapacitate or repel people. The effort intensified in the 1990s after hostile mobs confronted U.S. troops during peacekeeping and humanitarian missions in places like Somalia, Bosnia and Haiti.

In 2000, researchers at a Pentagon-funded institute at Penn State prepared a 50-page report that said developing calmative weapons "is achievable and desirable" and suggested drugs like Valium for further research.

However, it is unclear whether such weapons would violate the convention banning the use of chemical weapons, officials said.

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#21 3C-BZ; 4-BENZYLOXY-3,5-DIMETHOXYAMPHETAM INE

SYNTHESIS: A solution of 268 g 2,6-dimethoxyphenol and 212 g allyl bromide in 700 mL dry acetone was treated with 315 g anhydrous K2CO3 and held at reflux for 16 h. The solvent was removed under vacuum, and the residue dissolved in H2O and extracted with 3x100 mL CH2Cl2. The pooled extracts were washed with 5% NaOH, then with H2O, and the solvent removed under vacuum. The residue, which weighed 245 g, was stirred and heated in an oil bath to 230 ?C at which point an exothermic reaction set in. The heating was maintained at 230 ?C for 0.5 h, and then the reaction mixture distilled. There was obtained a total of 127 g of 5-allyl-1,3-dimethoxy-2-hydroxybenzene as a colorless distillate, that was identical in all respects to natural 5-methoxyeugenol obtained from Oil of Nutmeg.

A solution containing 40.4 g 5-methoxyeugenol and 26.6 g benzyl chloride in 65 mL EtOH was added, all at once, to a hot and well stirred solution of 11.7 g KOH in 500 mL EtOH. The potassium salt of the phenol crystallized out immediately. By maintaining reflux conditions, this slowly redissolved, and was replaced by the steady deposition of KCl. After 6 h, the reaction mixture was cooled, and the solids removed by filtration. The filtrate was stripped of solvent under vacuum to give 57 g of crude 5-allyl-2-benzyloxy-1,3-dimethoxybenzene. This was dissolved in a solution of 60 g KOH in 80 mL EtOH and heated on the steam bath for 16 h. The reaction mixture was quenched in 500 mL H2O, and extracted with 2x200 mL CH2Cl2. Removal of the solvent under vacuum gave 35.6 g of crude 2-benzyloxy-1,3-dimethoxy-5-propenylbenzene.

To a stirred, ice-cold solution of 33.6 g of the above impure 2-benzyloxy-1,3-dimethoxy-5-propenylbenzene and 13.6 g pyridine in 142 mL acetone, there was added 24.6 g tetranitromethane. After stirring for 3 min, there was added a solution of 7.9 g KOH in 132 mL H2O, followed by additional H2O. The oily phase that remained was H2O washed, and then diluted with an equal volume of MeOH. This slowly set up to yellow crystals, which were removed by filtration and washed sparingly with MeOH. There was obtained 9.2 g 1-(4-benzyloxy-3,5-dimethoxyphenyl)-2-nitropropene with a mp of 84-85 ?C. An analytical sample, from EtOH, had a mp of 86-87 ?C.

To a refluxing suspension of 5.5 g LAH in 360 mL anhydrous Et2O under an inert atmosphere, there was added 8.6 g 1-(4-benzyloxy-3,5-dimethoxyphenyl)-2-nitropropene by letting the condensing Et2O leach out a saturated solution from a modified Soxhlet condenser. The addition took 1.5 h and the refluxing was maintained for an additional 4 h. After cooling, the excess hydride was destroyed by the cautious addition of 330 mL of 1.5 N H2SO4. The aqueous phase was heated up to 80 ?C, filtered through paper to remove a small amount of insoluble material, and treated with a solution of 8 g picric acid in 150 mL boiling EtOH. Cooling in the ice chest overnight gave globs of the amine picrate, but no clear signs of crystallization. These were washed with cold H2O, then dissolved in 5% NaOH to give a bright yellow solution. This was extracted with 3x150 mL CH2Cl2, the solvent removed under vacuum, the residue dissolved in 300 mL anhydrous Et2O, freed from a little particulate material by filtration through paper, and then saturated with hydrogen chloride gas. There was thus obtained, after filtering, Et2O washing and air drying, 2.5 g 4-benzyloxy-3,5-dimethoxyamphetamine hydrochloride (3C-BZ) as a white solid with a mp of 161-164 ?C.

DOSAGE: 25 - 200 mg.

DURATION: 18 - 24 h.

QUANTITATIVE COMMENTS: (with 25 mg) I went into an emotionally brittle place, and for a while I was uncomfortable with childhood reminiscences. The seeing of my family's Christmas tree in my mind was almost too much. I cried.

(with 50 mg) The action is distinct--wakeful--alerting and wound up. Hypnogogic imagery, and I could not sleep at night with my mind doing many uncontrolled, tangential, busy things. I had fleeting nausea early in the process.

(with 100 mg) I took this in two portions. Following 50 milligrams I was aware of a slight light-headedness at a half-hour, but there was little else. At 1 1/2 hours, I took the second 50 milligrams and the augmentation of effects was noted in another half hour. The experience quietly built up to about the fifth hour, with some erotic fantasy and suggestions of changes in the visual field. I could not sleep until the twelfth hour, and my dreams were wild and not too friendly. There was no body threat from this, but I was not completely baseline until the next day. I am not too keen to do this again--it lasts too long.

(with 100 mg) No effects.

(with 150 mg) This is in every way identical to 100 micrograms of LSD.

(with 180 mg) I can compare this directly to TMA which was the material I took last week. Many similarities, but this is unquestionably more intense than the TMA was at 200 milligrams. It is hard to separate the degree of impact that this drug has, from the simple fact that it lasts forever, and I was getting physically tired but I couldn't sleep. There is some amphetamine-like component, more than with TMA.

EXTENSIONS AND COMMENTARY: Two points are worthy of commentary; the potency and the promise of 3C-BZ.

As to potency, there is such uncertainty as to the effective dose, that it is for all intents and purposes impossible to predict just what dose should be considered for a person's first time with this. The choice of quotations was made with the intention of giving a picture of this scatter. A total of ten subjects have explored this compound, and the very broad range given above, 25 to 200 milligrams, reflects the degree of variation that has been encountered.

Which is a shame, because the concept of a new ring such as is found here on the 4-position would have allowed an extremely wide array of substituents. Electron-rich things, electron-poor things, heavy things, light things, and on and on. This could have been a location of much variation, but it is a possibility that the uncertainties of dosage might extrapolate to these novel ring substitutions as well. Only a single variation was made, the 4-fluorobenzyl analogue. This was prepared following exactly the procedure given here for 3C-BZ, except for the replacement of benzyl chloride with 4-fluorobenzyl chloride. The allyl intermediate was an oil, but the propenyl isomer gave solids with a melting point of 59-60 ?C from hexane. The nitrostyrene was a yellow crystalline solid from methanol with a melting point of 98-99 ?C. The end product, 3,5-dimethoxy-4-(4-fluorobenzyloxy)amphetamine hydrochloride (3C-FBZ) was a white solid with a melting point of 149-150 ?C. It has been assayed only up to 4 milligrams and there was absolutely no activity of any kind observed at that level.

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