Conclusion: STORY OF PURE SYNTHETICS

This malady was the result of methyl-iodide poisoning. Helen was not affected at all; yet we spent that Sunday working together in our plant. At first the neurologist thought that I had some kind of malfunction (or tumor, perhaps) of the cerebellum. A young resident Jerry Apel (now a nephrologist at Columbia Presbyterian) took an interest in my predicament and, after asking Helen about all the chemicals we used, searched out the effects caused by poisoning by methyl iodide. Helen later told me that she told him that I had told her that methyl iodide was the only chemical about whose toxicity I wasn't sure. Or perhaps it was just a process of elimination. The remainder of the chemicals would not be expected to cause the same kinds of symptoms.

At any rate, he found reports of six prior cases of poisoning by methyl iodide resulting in three deaths and two long-term-disability cases. The sixth, a Spaniard, was reported to be asymptomatic within about four months. These reports did suggest that the best treatment was no treatment: just keep the patient alive and let nature take its course. One of the major symptoms which arises in cases like this is the onset of what psychology books refer to as toxic psychosis which in my case was an induced paranoia. The result of this was that I didn't believe anyone that I was suffering from something as mundane as methyl-iodide poisoning.

After six weeks in the hospital, I was released to go home. I had improved considerably. I could walk without falling, but all the muscles were weak as if my brain could not communicate effectively with them. Even the heart muscle was weakened, because every time I stood up for more than a minute or two, I would feel a kind of "rattling" in my brain and discovered that I couldn't think as clearly as when I was reclining or even sitting (result of oxygen-deprivation to the brain). I had entered weighing 180 LBS and left weighing 160. People around me making the normal amount of noise caused me pain from the level of noise - - - and I feared the whole world was out to get me but couldn't figure out why. I rationalized that the reason I wasn't murdered immediately was that they wanted to scare me to death. I tried to put up a brave front to show them it wouldn't work, but my fear surfaced occasionally. In addition to being weak, I was so uncoordinated that writing my own name resulted in an illegible scrawl. It remains pretty illegible even to me to this day. Trying to write several lines or to type several lines with a mechanical typewriter led to severe chest pains as if someone had been tightening steel bands around my chest.

Don't misunderstand me, the hospital was a clean, friendly place; my mental state from the methyl-iodide aftereffects just made it the wrong environment to continue my recovery: it was too busy and noisy. On the other hand, home was quiet, familiar and altogether more relaxing. Recovery continued very slowly, and I was able to work half-days in my plant at the end of about thirteen years. Through approximately the first six or eight years, I was very weak with my strength fluctuating up and down over the months like the Dow-Jones Industrials. I often told myself during this time that, if I didn't improve in six months, then there would be no point going on. In a jocular vein, I say now that I made the period of time long enough to give my body the best chance at this longed-for improvement. Amazingly, I am still here.

On the positive side, I developed an upbeat attitude toward life which Helen noticed. She said one day after a few years, "You know, Paul. You seem less moody than you used to be!"

I replied something like this, "I used to worry about the future a lot - - -what new bad thing could happen? After suffering this ultimate indignity, I finally, after accepting it, told myself that I shouldn't worry about what might happen. The worst has already occurred, and worrying won't help."

During the time I was hospitalized, our friend John had been coming up to help Helen with the plant work. They actually ran reactions with the methyl iodide I had made that fateful day, but, when it became clear that methyl iodide was the culprit, Helen wisely stopped that and just purified the final product already prepared. John continued to help throughout the years to come and became a part owner of the company.

Shortly after I arrived home from the hospital, Helen decided that she wanted to do the lab work to develop the methylation reaction using dimethyl sulfate. Now as most chemists know, dimethyl sulfate is an extremely dangerous chemical in itself: it's very corrosive. Its saving grace, in my book, is that it is easier to handle safely because it is not very volatile - - - still you have to be very careful with it. I am saying all of this so that I don't get a barrage of E-mail back on the dangers of dimethyl sulfate.

Back to Helen's proposal: I didn't want her doing this work because I didn't think she was skilled enough (foolish thought!), and I said, "Just give me a few more weeks to recover, and I'll do it." If we had waited for me to recover, it would have been a long wait!

But she insisted and ran the first trial very quickly. Of course, I, being a careful chemist, insisted that she do paper chromatography on the product mixture to see if any methylation had occurred. When I didn't see that flesh-colored spot on spraying the paper with ferric chloride solution, I told her that the reaction hadn't worked, and it would be little use running the hydrolysis because she wouldn't get the product. But she was a driven woman and thankfully didn't listen to me. She told me that she had come that far and would do the acid hydrolysis just to see what happened. She did it, and when she opened the flask up, the strong odor of sweet maple permeated the room. The explanation of this seemingly contradictory finding comes from the fact that the methylation reaction gives a complex mixture of products one of which masks the flesh-colored spot. Also the final product comes principally from an intermediate not formed in the methyl-iodide methylation at all and not colorized with ferric chloride solution. If you are a chemist, you can take a side trip here to my explanation of the course of this reaction before continuing. After this quick success, Helen ran fifteen more lab batches and was ready to take it to the plant. Elapsed time from conception to first plant trials of about three weeks.

After the success of this method was evident, we made an effort to patent the method since it appeared to be a novel one. In conjunction with this effort, I had to get a competent translation of an article from a Russian journal [Knunyants (spelling approximate) in Zh. Obsh. Khim. 7, 2832 (1937)] in pre-WWII Stalinist Russia. Helen located a man living in Ridgewood who was fluent in Russian and agreed to help us on a gratis basis - - - I think we brought a bottle of Vodka as a gift. We went to his house one evening with the manuscript and he read all the tough Russian text with me supplying the meanings of the obvious cognates in the chemical nomenclature. The Russian had the right idea, but he didn't have the necessary modern instrumentation in the Russia of the 1930s because it hadn't been invented yet. I believe that Beckman introduced the pH meter in this country in 1937. For more details, see MAKING REAL MAPLE FLAVORING: For chemists! Far-out way to make MCP!.

After the gentleman had finished translating the article, we spent a few minutes giving him some background of why we had an interest in this subject telling him that we were pursuing a patent on this technology. Since he seemed well-schooled in science, we inquired about his profession and place of employment. We learned that he was a biologist (safe-enough), but I was petrified to learn that he worked for Pfizer, Inc. whom I considered my main competition for synthetic MCP. He assured us that he would respect the confidence and had no reason to interfere with our patent attempt. This turned out to be true as far as I know. The pursuit of this patent proved to be maddeningly frustrating and ultimately foundered. This failure in my view does not reflect on the novelty and usefulness of the method. It is the product of the nature of the patenting process.

Even with this great advance, our process at that time was still a beginning one with a number of laborious or awkward parts. One case in point was our purification of the final product. After the third step, the product crystallizes upon cooling the hydrolysis mixture. After filtration and washing, it was still dark-brown to black, whereas a salable product had to be white like sugar. We purified the brown-black material in two crystallizations and ended with a product which was very good - - -still it was at best off-white. In these two crystallizations, we used activated charcoal to absorb the colored impurities, but this meant handling powdered charcoal in the plant. Slowly, but ever so slowly, no matter how careful she was (I wasn't doing much in those days), a puff of charcoal was released into the air each time she carefully ladled it out. She could see the writing on the wall: carbon black all over the plant eventually.

Early in 1975, Helen had used up our raw materials, and we had to wait until someone bought something to order more raw materials to go on. At this time she said, "Well, Paul, I don't like the fact that we are using charcoal because the plant is starting to turn black. I'M NOT GOING TO USE CHARCOAL ANYMORE!"

Remember the muffler commercial: "I'M NOT GOING TO PAY A LOT FOR THAT MUFFLER!"?

She continued, "Therefore, before I do anything more in the plant, you've got to work out a new purification. That idea you had late last year; work it out!"

What she was referring to was an experiment where I tried to distill A-2, the intermediate just prior to hydrolysis to MCP. But the sample from the plant I used had become partially hydrolyzed to MCP. I would heat the still and the MCP would begin to distill only to condense as crystals and clog the condenser and the vacuum tube attached to the receiver. I stopped the distillation many times to clean these ports, and I began to dream of having a refluxing solvent there to do it for me. I never succeeded in distilling the methylation product nor did I succeed in even distilling out all the MCP. I finally gave it up because in those days I was still functioning at a very low level from fatigue.

Upon Helen's insistence, I just had to grit my teeth and get that refluxing solvent going. The idea worked the first time and again we were ready to go to the plant in a few weeks using this new method: ENTRAINMENT-CONDENSATION DISTILLATION!

In those early years, she was not only the main "worker" as she called herself, but also the crack salesperson. She landed International Flavors & Fragrances, Crompton & Knowles, and the PFW Division of Hercules among others.

In those early years, I helped some, but it was all Helen. She successfully worked two jobs and still had time to spend with our son Stanley. Even Stanley helped some by building things, repairing other things and notably doing some of our hairier electrical-wiring jobs. I don't think he was ever thrilled with the organic chemistry our fledgling business practiced. At Rice University, he took the organic course we persuaded him to take, but, although he distinguished himself in the laboratory by always dressing in a white shirt and tie and never spilling a drop of anything on his clothing, he chose to major in physics. After college, he became a real computer person and currently is in charge of the US Geological Survey's VAX computers that monitor all the seismographs from Bakersfield, CA to the Mexican border in conjunction with the Department of Geology at Caltech. For the current earth-shaking report for southern California right now, take a side trip to USGS's Pasadena Field Office where you can also see Stan's own web page to check up on his activities. If you are a baby boomer you will find here a kindred spirit.

Occasionally we found time to invest in lab work, and were able to introduce 3,5-dimethyl cyclopentenolone (caramel aroma) in 1981, 3-ethyl cyclopentenolone (licorice taste) in 1983 and 3,4-dimethyl cyclopentenolone (black-walnut aroma) in 1985. Also in 1985, I bought my first computer, an Apple IIc. Shortly before, I had learned to use the AppleWriter word-processing program on an Apple IIe that someone had donated to the Ridgewood library. Using the Apple IIe was free which was all I could afford in those days. Buying the IIc strained our resources, but it allowed me to present an elegant face for Pure Synthetics. I liked to think that our announcements, specification sheets, and other paperwork now made us look as good as DuPont or Proctor & Gamble. I even made our logo in a photo-offset-printing course at the Ridgewood-Adult School, and, throughout the life of the company, the company colors were Regal Blue and Golden Orange (offset-press inks of A. B. Dick Pure Synthetics' logoCompany, Chicago). Coincidentally, these were also the colors of the Lincoln School (my grade school in Lombard, Illinois), the U. of Illinois (my undergrad college) and U. of California, Berkeley (my grad school).

There's even a story about that 1981 campaign. I found the work of Tonari and coworkers appearing in a Japanese journal in Japanese. Since I don't read Japanese, I had to rely on the English summary, but it seemed to be clear enough. They used acid catalysis to condense morpholine, formaldehyde and MCP in a Mannich reaction to form what they reported as the 5-morpholinomethyl derivative (15% yield). They reduced this with zinc in acetic acid to the desired 3,5-dimethyl cyclopentenolone. I thought we could surely improve on 15%, but, after making two totally-failed attempts to do this Mannich reaction, I rested by reading everything there was to read about Mannich reactions. Finally, Helen, remembering former triumphs, said something like this, "Couldn't do that reaction; could you? Just give me the recipe, and I'll make it go!" Great chefs always think in terms of recipes! My conclusion from all the reading was that, since most Mannich reactions are done using base catalysis, she should try this. She ran the reaction not only getting the reported product on the first try but increasing the yield to over 90% by recycling the mother liquors. She never let me forget that! There is more to this story; therefore, chemists, look for the complete exposé in a future update to this page.

For 1987, we succeeded in getting a yearly contract with CA Aromatics in Long Island. It meant more sales and, of course, required more production, but, thirteen years after the poisoning episode, I felt strong enough to do more. Helen couldn't really do more - - - she had already been working at the maximum rate: she was tireless.

That is about as much as I want to relate right now. We decided to terminate production and sell off the inventory at the end of the 1990-91 process season in preparation to sell the plant building (our third plant) and prepare to move to California after Helen's retirement from her counseling job in June, 1994.

She became ill on May 1, 1994 and died on June 4, 1994 of ovarian cancer. We had realized earlier that she was at risk because her mother and sister had died of cancer, but this just overwhelmed her suddenly with no noticeable symptoms until it was too late.

We had our house in Ridgewood, NJ on the market when she died. I didn't waver and sold the house in order to move to San Diego completing that much of our earlier plan. And so ended that phase of life.

AND SO ENDS THIS STORY

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