Soviet hydrazine route - C&EN Global Enterprise (ACS Publications)

Chem. Eng. News , 1971, 49 (49), p 10. DOI: 10.1021/cen-v049n049.p010a. Publication Date: November 29, 1971. Copyright © 1971 AMERICAN CHEMICAL ...
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Chemical world This week chlorine or organophosphate insecticides. The Monsanto scientist asserts that MON-0585 is practically inactive against nontarget species, practically nontoxic to fish (even the wriggler-eating Gambusia appears to be unharmed by field concentrations), and extremely safe for mammals. For example, the acute oral LD50 for rats is 1890 mg./kg., the minimum dermal lethal dose for rabbits is greater than 3160 mg./kg. MON-0585's mode of action is not understood. Dr. Sacher notes that pupae die "in a characteristic compact, stalky, unmelanized [undarkened] form/' which suggests that the chemical might inhibit the enzyme tyrosinase, known to play a key role in the hardening and darkening of the develping pupa. Tests show, however, that tyrosinase-inhibiting activity is not very high. MON-0585 might act by upsetting the insect's oxygen metabolism, but tyrosinase may also be involved, Dr. Sacher says. NARCOTICS:

animals showed a revulsion to morphine three and a half weeks after the compound was supposedly "washed out" of their systems. PMA says this suggests a wholly new approach to the narcotic addiction problem. Another promising approach uses McNeil Laboratories' nonaddicting tranquilizer, haloperidol, which has been evaluated in several hundred patients. Useful in the acute detoxification stage from both heroin and methadone, haloperidol might also be combined with a narcotic antagonist to provide protection against heroin challenge while removing craving for drugs. Four other drug firms currently have five agents under study. Some results: •Winthrop Laboratories' 1-cyclazocine, unlike racemic cyclazocine, produces no psychotomimetic effects in limited human studies. • Endo Laboratories' EN 1639, a relative of naloxone, is twice as potent and longer acting than naloxone. Studies on addict volunteers suggest that oral doses one tenth to

one thirtieth those of naloxone may be adequate for 24-hour protection against heroin challenge. • Bristol Laboratories' 1-BC 2605, a synthetic compound not requiring opium derivatives for its manufacture, is longer acting and more potent than both naloxone and cyclazocine. • Ciba-Geigy's new antagonist, GPA 2163, appears to be a "pure" antagonist in laboratory animals. PROCESSES:

Soviet hydrazine route A research group at the Institute of Chemical Physics of the U.S.S.R. Academy of Sciences has revealed the first results from a project to produce hydrazine under mild conditions. The group, headed by Prof. Aleksandr Shilov, believes that the new process is the closest thing yet to the biological fixation of nitrogen. The process reduces molecular nitrogen in aqueous and alcoholic media with titanium, vanadium, or chromium salts as reducing agents

Antidotes for addiction While the drug industry is still short of a major breakthrough in its search for safe and suitable agents to block and treat narcotic addiction, five agents under study offer advantages over the narcotic antagonists naloxone and cyclazocine and two new approaches appear promising, according to an industry task force. What's more, important research leads may be provided by declassification of the Department of Defense's long-secret work on antidotes to some of its chemical warfare agents. Compounds similar to opium alkaloids and their antagonists have been prepared by DOD, says Dr. John Adams, who represented the Pharmaceutical Manufacturers Association's task force at a news conference called by Rep. Paul G. Rogers (D.-Fla.), chairman of the Subcommittee on Public Health and En\dronment. Some of the DOD work has been declassified and received by the White House's special action office for drug abuse, and more is expected. Serendipity was involved in one of the two new and promising approaches. An unidentified drug firm experimenting with a new and also unidentified compound found that when testing the compound's analgesic properties on monkeys, the 10 C&EN NOV. 29, 1971

Mariner 9 photographs Martian south polar cap The dust storm that has obscured Mars from Mariner 9 cameras cleared sufficiently last week to permit this series of overlapping wide-angle pictures revealing the entire Martian south polar cap. The cap (at lower right in the photo) is about 200 miles in diameter and laced with fine, dark, frost-free markings reflecting a topographic pattern apparently unique to this area of

Mars. The dust storm appears to be subsiding first in the south polar cap region, NASA scientists say. Photos transmitted to earth as C&EN goes to press reveal surface features in the south polar region showing dimly through the haze for the first time since Mariner swung into its 90-day orbit. Equipment will measure water, oxygen, temperature, and pressure variations.

and molybdenum compounds as catalysts. Nitrogen fixation occurs at room temperature and atmospheric pressure, although higher temperatures and pressures enhance the yield. Initial results indicate that fixation of nitrogen occurs only in alkaline media. The alkaline media are believed to serve two functions —raising the reduction potential of the titanium, vanadium, and chromium ions, and permitting the formation of a solid hydroxide as a reaction product. At room conditions the reaction is complete in a few minutes to a half hour, depending on the catalyst used. The process is favorably influenced by the addition of barium and magnesium compounds, but carbon monoxide acts as an inhibitor. In the same aqueous and alcoholic media, acetylene has been reduced to ethylene without catalysts. No data have yet been made available on the reaction mechanism involved. However, the research team believes that the molybdenum catalyst activates the nitrogen in a bimolecular complex during the first stage of reaction. The further development of the process is aimed at making it profitable for the production of hydrazine. Although the principal volume use of hydrazine is as a rocket fuel, it is also used as an oxygen scavenger, a polymerization terminator, an extender in several types of plastics, and an intermediate in the synthesis of nylon 6. The two leading processes for making hydrazine in the U.S. are the Olin process, which uses ammonia and sodium hypochlorite as starting materials, and the urea process, in which urea is degraded by sodium hypochlorite. PROFITS:

Better days ahead for CPI Profits and their prospects were subjects very much on the minds of executives attending the 21st Semiannual Manufacturing Chemists Association Meeting in New York City last week. Speakers at a panel on chemical profits and their prospects agreed that the industry did, indeed, have a profit problem. They also agreed that better days were ahead. Panel moderator F. Perry Wilson, chairman of the board of Union Carbide, says that higher profits will prevail in the 1970's simply because

will lack attention, he says. Problems of pricing and the cost of government regulations are more likely to be ignored by the chemical industry, he believes. Pricing is basically an internal problem that each company can attack. Government regulation, at a stage of world economic development where the U.S. can no longer afford tô operate under an outmoded ad hoc policy of antitrust administration, needs reform, Mr. Newton says. "Such reform, however, can only come about if we seriously organize to address ourselves to the problem and push for the requisite action from Congress," he adds. TIRES:

Glamour growth product Garvin:

past mistakes

they must if the chemical industry is to remain viable. Panelist Clifton C. Garvin, Jr., executive vice president of Standard Oil Co. (N.J.), seeks the answer to higher profits in the future from the industry's past mistakes. Mr. Garvin explains that the chemical industry has lost much of its premium profitability over other manufacturing industries by expanding at too high a rate and by permitting prices to decline past the point where unit costs could be reduced by technology, less costly processes, or the economies of larger plants. Profitability in the seventies will increase substantially by remembering these lessons learned from the past five years, he adds. Mr. Garvin also accuses chemical managers of having some mistaken concepts on diversification. Probably the decision by many managers to diversify into some additional chemical lines in the 1960's added substantially to the overcapacity problem. "Investment decisions are likely to be far better if we stick to fields we know," he explains. Mr. Garvin suggests a return to higher profits by having more pricing decisions scrutinized harder by top industry management. Wilbert F. Newton, vice president of marketing and sales for PPG Industries, foresees four major threats to profits in the years ahead. The problems of foreign competition and inflation are highly visible, and there is little danger that they

Dollar sales of the replacement passenger tire business have grown about 12% per year since 1965, says William H. Campbell; other figures offered by the B. F. Goodrich Tire Co. senior vice president suggest that this growth will be even better through 1975. This performance, he says, matches that of such "glamour industries" as airlines, electronics, and space-age hardware in their most productive years since 1965. Furthermore, says Ross M. Ormsby, president of the Rubber Manufacturers Association (RMA), passenger tire shipments for the replacement market will increase 5°/o in 1971 from last year to an all-time high of 136 million—41 million more than in 1965—and should reach 160 million by 1975. Addressing a New Orleans convention of Louisiana and Mississippi tire dealers last week, Mr. Campbell attributed the strong industry growth to a definite trend toward better tires and "a much improved product mix for dealers to sell." That trend will become even more pronounced in the future, he says, as radial and beltedbias tires grab a much larger share of the market. In 1968, he notes, about 87% of replacement passenger tire sales went to bias-ply tires. By 1975, bias-ply tires will have only 37% of that market; radiais will have 18%, and belted-bias tires will have 42%. The net effect of this change in market shares is that the average retail price of passenger tires will increase from about $31 this year to about $45 in 1975—producing a $7.2 billion market. NOV. 29, 1971 C&EN 11