Industrial Alchemy, Part 4: Organic Chemical Feedstocks and Product Timeline

Here, I expand upon the introduction to natural feedstocks which appeared in part 3, and then discuss some products which might be made, and when they might be available.

Coal Feedstocks

Coal Pyrolysis and Coal Tar Distillation

In 1856, Perkins reacted aniline from coal tar with potassium dichromate, serendipitously obtaining the new silk dye mauveine. In the half-century that followed, the organic chemical industry primarily derived its products from coal tar.

Coal tar is a byproduct of the production of coke from coal. Coke is the solid residue (mostly carbon) resulting from destructive distillation (heating in absence of air; “pyrolysis,” “carbonization”) of a coal or petroleum.

Coke. Coke is already produced down-time for use as a fuel. Early on, the up-timers will point out that coke can be used, in place of charcoal, as the fuel and reducing agent for a blast furnace. (As EA points out, coke is mechanically stronger than charcoal, and thus can support a larger charge.) This can be expected to lead to an increased demand for coke.

The up-timers know of the relationship among coke production, steelmaking, and the organic chemical industry. Josh and Colette Modi are visited by the metal magnate Louis de Geer (Colette’s uncle) in April 1632, and they suggest to him that “given the chemicals that can be distilled from coal tar gases when making coke, a chemical company might be very profitable.” Mackey, “The Essen Steel Chronicles, Part 2: Louis de Geer,” Grantville Gazette 8.

The down-timers produce coke in crude beehive ovens, which wastefully allow the liquid and gaseous byproducts to escape. EA/Coke has a surprisingly detailed description of both the old-fashioned beehive ovens, and “byproduct ovens” designed to capture all of the byproducts. In the old timeline, the first such oven was built in 1881.

The carbonization temperature has a large influence on the nature of the products. If the temperature is less than 200oC, they are mainly methane, water and carbon dioxide. In the range 200-400oC, the methane is replaced by carbon monoxide. Passing beyond 400oC, hydrogen begins to appear and once you exceed 800oC, it is the main gaseous product. Only the coke produced by high temperature carbonization (over 800oC) is used for metallurgical purposes (EA/”Coke”). EB15 says 900-1200oC, with the low end for making town gas and the high end for metallurgical coke.

Coal Tar. All of the coal products, save for the coke, are initially part of the coke oven gas. As the coke oven gas is cooled, the components which are solid (“crude tar”) or liquid (“ammoniacal liquor”) at room temperature are separated from the light gas. Then the ammoniacal liquor is decanted from the tar, and the latter is distilled.

EB11 warns that the tar must be dehydrated before distillation. It’s then pumped into a tar still. In OTL, 3-6 distillation fractions were taken. The “Grantville literature” refers to four such fractions—light (“benzoil”), middle (“carbolic”), heavy (“creosote”) and anthracene (“green”)—leaving a residue of pitch. The distilleries varied with respect to the precise distillation temperatures and specific gravities by which these fractions were defined, and this naturally also affects their relative proportions and composition. See Fig. 4-1 (EA; Shreve 84) for one example; others in Appendix.

Figure 4-1 Coal Pyrolysis Products

The fractions (which are complex mixtures) may be used as is (e.g., as solvents), or subjected to further work up as described in EB11/Coal Tar:

Light Oil: (1) extract tar acids (phenol, cresols) with caustic soda, (2) extract tar bases (pyridine) with dilute sulfuric acid, (3) remove some aliphatic hydrocarbons with concentrated sulfuric acid, and (4) steam distill to obtain benzene, toluene, xylenes, and cumenes.

Middle and Heavy Oils: (1) crystallize out naphthalene, and (2) recover the tar acids and bases.

Green Oil: (1) crystallize out anthracene, redistilling if need be; (2) extract phenanthrene with naphtha, (3) extract carbazole with pyridine.

There are hundreds of chemicals in coal tar, and the amount of each depends on the coal and how it’s processed. There is quantitative data, sometimes contradictory, in Grantville Literature (McGHEST, EA, EB15, M&B373, EB11/Coal Tar; see Appendix). While not part of that literature, reasonable production estimates would be:

benzene, toluene, xylene: 1-2.5% (in proportions 6.67:2:1 per EB11)

naphthalene 4-10%

anthracene 0.25-2%

phenol 0.4-0.5%

cresols 2-3%

pyridine and quinoline 0.2-0.3%

creosote oil 25-30%

pitch 50-60%

(Chamberlain 500)

A coal gas plant opened in Magdeburg in November 1633 (Flint, 1634: The Baltic War, Chapter 2). Its gas was used for lighting and heating. From chapter 3, we know that the furnace was hot enough to generate hydrogen gas. The Magdeburg plant separated the coal tar into different products, including pitch and “light benzoils” (benzene and related compounds). Production was such that it generated a barrel or two of the light benzoils every day. It also produced ammonium nitrate for use as fertilizer. (Ammonium sulfate can be recovered from the ammoniacal liquor; figure 10 kg/metric ton coal; McGHEST.)

Coal Gasification. Since World War II, there have been efforts to convert coal into a fuel gas (EA/”Coal Gasification”). Depending on the precise process used, the gas can have a high or a low heating value, the latter having the advantage of a low sulfur content. The low BTU gas, curiously, has been made at a plant in Morgantown, West Virginia, and it is possible that some of the Grantville residents have read about its operations or even worked there.

From our perspective, a more interesting form of coal gasification is the older (Twenties) use of coal to make “synthesis gas” (syngas), a mixture of carbon monoxide and hydrogen. I discussed this in part 3.

Coal Liquefaction. The purpose of coal liquefaction is to convert the solid hydrocarbons into ones liquid at room temperature, especially those in the gasoline size range. The usual use of the liquefaction product is as fuel, but in theory the compounds could instead be used as starting materials in organic synthesis.

Coal gasification and liquefaction are advantageous if coal is cheap and petroleum is expensive.

Natural Gas Feedstocks

Natural gas is potentially an important industrial source of the lower molecular weight alkanes, notably methane, ethane, n-propane, isopropane, n-butane and isobutane. These can be separated by fractional distillation.

We know that the residents of Grantville have made an effort to switch from gasoline to natural gas (and alcohol) as fuel for their vehicles.

Many natural gas wells can be found in Grantville. The town is heated with local natural gas, and Willie Hudson runs his farm off gas from his own land (Flint, 1632, Chapter 8). There are also wells on the properties of “Birdie” Newhouse. (Huff and Goodlett, “Birdie’s Farm,” (1634: The Ram Rebellion), George Blanton (Jones, “Anna’s Story,” (Grantville Gazette 1), and John and Millie. (Huston, “Seasons,” Grantville Gazette 7), and unnamed others.

Under West Virginia law, a “gas well” is a well which has an initial production such that the gas-oil ratio (GOR) is at least 6,000 cubic feet of gas for each barrel of oil. (The two then have the same energy value.) Since these gas wells in Grantville were not in commercial production at the time of the Ring of Fire, they probably fall into the category of stripper wells. A stripper well is defined by Interstate Oil and Gas Compact Commission as one producing not more than 60,000 cf gas or 10 barrels oil/day. But the average production for marginal wells in West Virginia was 0.6 barrels oil or 11,000 cf gas/day. (IPAA2004).

Natural gas is often trapped near petroleum. It may be produced (“dry gas”) from a pure gas well (which in turn is tapping a gas cap above the oil horizon), from a gas-condensate well (so-called because some of the gas condenses when brought to the surface), or from an oil well, dissolved (“wet gas”) in petroleum. Generally speaking, in “dry gas”, methane is 70-98%, ethane 1-10%, propane 0-5%, butane 0-2%, and in wet or condensate gas, methane 50-92%, ethane 5-15%, propane 2-14%, butane 1-10%. (Rojey 80). The propane and butane are called “petroleum gas.”

A 1904 analysis of natural gas from Fairmont, West Virginia reported 81.6% methane, 14.09% ethane, 3.21% nitrogen, and 0.2% heavier hydrocarbons, and Morgantown gas was similar. (UGSK 242). Hence, I think we must assume production of propane is under 0.1%.

German natural gas may not be much better as a source of propane. The natural gas produced in Neuengamme, Germany in 1910 was 91.6% methane, 0.8% heavy hydrocarbons. (Molinari, 36).

Petroleum Feedstocks

Petroleum contains a greater variety of organic compounds than does natural gas.

Fractional distillation separates the petrochemicals more or less by carbon number (Table 4-1A). To separate one class of hydrocarbon from another (e.g., aromatics vs. aliphatics), you need to use a selective solvent. The solvents used include liquid sulfur dioxide, liquid propane, furfural, and phenol (EA/Petroleum, Furfural).

Table 4-1A: Petroleum Distillation Fractions

Distillation Temp oC

Name

Carbon Number

Boiling Points oC,

Selected Compounds

<20

Gas

C1-C4

propane -42

butane 0

20-60

Petroleum Ether

(overlaps gasoline)

C5-C6

pentane 36

40-205

Gasoline

C5-C11

hexane 69

benzene 80

cyclohexane 81

toluene 111

octane 126

xylenes 138-144

undecane 196

60-100

Light Naphtha (ligroin)

(Gasoline Subrange)

C6-C7

heptane 98

175-325

Kerosene (Jet Fuel)

C12-C18

naphthalene 218

275-400

Gas Oil (Diesel, Furnace)

C12-C20

anthracene 354

non-volatile liquid

Lubricating Oil

C20+

non-volatile solid

Asphalt, Petroleum Coke

C20+

(M&B 109; Solomons 112 almost identical. EB15 has light naphtha 20-95, heavy naphtha 90-165, kerosene 150-245, light gas oil 215-315, heavy gas oil, 285-370. )

Our initial sources of petroleum are the natural gas wells in Grantville. 1633 chapter 34 says that they were “upgraded” to produce what Mike calls a “fair amount,” and Quentin, a “trickle,” of oil. The implication is that the gas wells are what are sometimes called “condensate wells.” Condensates are hydrocarbons, heavier than butane, which occur naturally in gaseous form in the reservoir, but which condense (liquefy) in the reservoir (after drilling), at the wellhead, or in a field separator, and can thus be separated from the natural gas. A typical composition is 40-90% C7-C8, 10-20% C9, 1-15% C6, 3-10.5% C5, and 0-4% hydrogen sulfide. (Marathon).

As for oil wells, oil composition varies from field to field, from well to well, and from formation to formation. Oils are classified as light, medium or heavy, based on their density. As you might expect, the light oils are rich in the volatile, low carbon number compounds, whereas the opposite is true of the heavy oils. The oils are mostly hydrocarbons, but include small amounts of compounds containing oxygen, nitrogen and sulfur. Oils with a low sulfur content are said to be “sweet”, and those with a high content are labeled “sour.” Heavy oils tend to be sour, too.

Pennsylvania oils are of the simple paraffin type (primarily linear alkanes), whereas Caucasian petroleums are more complex. (EB11 and EA “Petroleum”). At least some of the oils of Oelheim and Wietze are naphthene/asphalt type. (Bacon 888). These have a lower alkane content, but compensate by being richer in cycloalkanes (naphthenes), alkenes (olefins) and aromatic compounds (e.g., benzene, naphthalene, anthracene). They are more chemically reactive, hence more versatile, than alkanes.

By 1633, the up-timers are collecting oil at Wietze. Wietze is actually one of a dozen or so small oil fields near Hanover, and it is only a matter of time before others are discovered.

For the composition of Wietze heavy (shallow) and light (ca. 1000′) oil, see Table 4-1B. In general, it’s good for the organic chemical industry, not so good for automobiles.

Table 4-1B: Wietze and Nienhagen Oil

Wietze

Analysis 1

Wietze

Analysis 2

Nienhagen

Heavy Crude

Light Crude

Upper Triassic (Rhaet)

Lower Cretaceous (Wealden)

Middle Jurassic

(Dogger)

Lower Cretaceous (Neokom)

Distillation Commenced

245oC

118oC

220oC

130oC

Cumulative

%Distilled by

150oC

2-2.5%

2.0

0.5

250

0-2

16.5-17.5

17.5

5.0

9.5

275

2.8-5.5

22.5-23.5

23.5

1.5

10.5

13.8

300

8.5-12

30.0-31.5

31.5

6.0

15.0

19.5

325

14.5-19.5

37.5-28.5

38.5

12.5

25.2

350

31.5-34

49.5-51.0

51.0

26

35.5

30.2

.

(Holde 82)

(Kauenhowen 482)

By comparison, ~20-30% of Pennsylvanian and Galician petroleum distills at under 150oC, and 35-50% at 150-200oC. (Lucas 369).

Petrochemical Conversion. Initially, oil wells were drilled to obtain kerosene for use as in illumination and heating. When the automobile became popular, the emphasis switched to gasoline, especially the lighter “straight run” component (distilling at 20-150 oC). With the advent of high compression ratio engines, the heavier naphthas (150-200 oC) became more popular.

Up-time, the demand for gasoline had been great for many years, and hence processes were developed, and integrated into refinery operations, for converting heavier or lighter fractions into the hydrocarbons most suitable for auto engines. (Wittcoff).

There are three methods of down-converting. Thermal cracking uses high pressures and temperatures (exceeding the boiling points of the target hydrocarbons at the process pressure) to break carbon-carbon and carbon-hydrogen bonds, converting the heavier fractions into C5-C12 aliphatics, and in the process also converting some alkanes into alkenes M&B 138 says the main product is ethylene. There is some discussion of thermal cracking methods in EB11/Petroleum. EA/Cracking recommends 482-538 oC and 206-735 psi.

Steam cracking features mixing the hydrocarbons with steam, flash heating to 700-900 oC, and then quenching. This produces additional alkenes (ethylene, propylene, butadiene, isoprene, cyclopentadiene).

Catalytic cracking requires less vigorous conditions. EA/Cracking says “catalysts originally used were bentonite clays, but now pellets or granules of alumina, silica, zirconia, or magnesia, or artificial mixtures of these materials are more commonly used.” The catalytic cracking is conducted at 427-482 oC and 10.3-29.4 psi (14.7 psi is normal atmospheric pressure). Catalytic cracking yields heavily branched alkanes and alkenes.

The heaviness of Wietze oil, and many other German oils, provides an incentive to develop these cracking processes, especially catalytic cracking, to provide more gasoline.

We can also up-convert the lighter hydrocarbons. The classic approach was to polymerize olefins using acid catalysts, and it was “neither easy nor inexpensive.” Nowadays, it is more common to “alkylate”, which in this context means to react an olefin with a paraffin to obtain a larger, branched hydrocarbon. It, too, uses an acid catalyst, usually concentrated sulfuric acid or hydrofluoric acid (EA/Petroleum).

These methods beg the question of how we obtain the olefins. It is likely to be a two step process, converting the alkanes into alkyl chlorides or alcohols, and then those intermediates into alkenes.

Up-conversion hurts the organic chemical industry by converting hydrocarbons which it might otherwise use as feedstock into gasoline for fuel use.

Catalytic reforming (1940s) cyclizes (makes open chains into rings), isomerizes (straight chains to branched), and dehydrogenates. The dehydrogenation generates alkenes and aromatics. While they are good for cars, they are great for the organic chemical industry. Indeed, catalytic reforming is what made it possible for the petroleum industry to overtake the coal industry as a source of benzene, toluene and xylene (“BTX”). Morrison & Boyd (373) say that catalytic reforming requires high temperature and pressure, and a platinum catalyst, but that’s it. There are basic organic chem texts which provide more information; Bordwell (381) refers to use of 0.75% platinum on alumina, 450 oC, and 500 psi hydrogen.

A lot of experimentation will be needed to make any of these conversion methods commercially viable.

Botanical Feedstocks

Plants are a source of carbohydrates (simple sugars, starch, cellulose, carbohydrate gums), protein, fats, resins, and exotic secondary metabolites. The secondary metabolites are usually present in just small quantities but there are exceptions. Quinine is up to 8% of quinine bark; morphine, 16% opium; theobromine, 1.2% cacao bean; diosgenin, 5%, Mexican yam. (SzmantIURR 142, 166ff). Fifteen tons of dried Madagascar periwinkle leaves are needed to produce one ounce of vinblastine, and it takes the bark of more than one Pacific yew tree to yield one gram of anti-cancer taxol. (National Botanic Garden)

The chemical makeup of plants varies from species to species, and is also affected by growing conditions (climate, soil or water, pest activity) and developmental stage. Both land plants and marine plants can be of interest.

The distribution of the chemicals isn’t uniform within the plant; a chemical of interest may occur preferentially in the seeds, fruit, roots, leaves, flowers, stem, buds or branches of the plant. It can be in solid tissue, or in a liquid (saps, resins, latex, etc). In the stems of woody plants, the chemistry of bark, heartwood, and sapwood can vary.

Agar. Agar is a galactose polymer derived from certain red algae and seaweed; “Grantville literature” calls attention to the Gelidium and, to a lesser extent, Gracilaria, Pterocladia, Acanthopeltis, and Ahnfeltia (EB11/Jams and Jellies; CCD; MI; EA, EB15).

I am not sure how much is known about the geographic distribution of these algae, but specialist literature shows that the closest source of Gelidium to the USE is in the coastal waters of northern Spain and Morocco; of Pterocladia, near the Azores; and Gracilaria, western South Africa. (FAO).

Cellulose and Derivatives. Cellulose is a glucose polymer and constitutes about 30% of all plant matter. The best sources are wood (~50% cellulose) and vegetable fibers. Cotton is about 91% cellulose. (Sadtler 275). Several fibers, of course, are used down-time to make textiles, rope and paper.

EB11/Cellulose says that cellulose can be obtained by treating cotton fiber with “boiling dilute alkalis, followed by chlorine gas or bromine water, or simply by alkaline oxidants. The cellulose thus purified is further treated with dilute acids, and then exhaustively with alcohol and ether.” If you are making chemical filter paper, you also use hydrofluoric acid to remove silica.

Cellulose can be used to make methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, cellulose nitrate, cellulose acetate, cellulose proprionate, cellulose xanthate and other cellulose derivatives. EA “Cellulose” is a good source of information on how to make them.

Cellulose nitrate was an early explosive and also an early photographic film base. It is made by treating cellulose with a mixture of nitric and sulfuric acids, and then adding camphor as a plasticizer. Cellulose acetate is used to make rayon. The cellulose is treated with acetic anhydride. Similarly, cellulose propionate is made by treating the fibers with propionic anhydride. Cellulose xanthate is used to make viscose rayon, cellophane film, and cellulose sponges. Making the xanthate requires sodium hydroxide and carbon disulfide.

Oxidative degradation of cellulose yields, depending on conditions, acetic, butyric, oxalic and levulinic acids. (EB11; SzmantIURR 90).

In wood, the cellulose is accompanied by lignin (25%) and hemicellulose (25%). In papermaking, the lignin is disintegrated by the Kraft process (sodium hydroxide and sodium sulfide), or with sulfites or bisulfites.

Lignins. Lignins, which are complex polymers, produce different products, depending not only on their source but how they are isolated. Lignosulfonates and “alkali lignins” are byproducts of acidic and basic wood pulping, respectively. Either can be used to make dimethyl sulfide, which is oxidized to yield the special solvent dimethyl sulfoxide. Lignins can be converted to phenols (Wittcoff 161), such as vanillin (via nitrobenzene). (SzmantIURR 154ff).

Hemicelluloses. These are polymers composed of several sugars, particularly xylose.

The sugars are released by hydrolysis, and xylose can be hydrogenated into the sweetener xylitol (SzmantIURR 99). Under more stringent hydrolysis conditions, the xylose is converted to furfuraldehyde or furfural (100). Furfural is used to make furfural-phenol plastics.

Pentosans. Pentosans are polymers of arabinose and other five-carbon sugars. They can be isolated from oat hulls, corn cobs, sugar cane stalks, wood, and other sources. Acid treatment produces furfural, which as previously mentioned, is used in the petrochemical industry. (Wittcoff 144; EA/Furfural). And from corn cobs, you get acetic and formic acid as byproducts.

Starch. Starch, a composite of amylose and amylopectin, is obtained from corn, rice, potato, wheat, tapioca, arrowroot, and sago. It can be used as is, derivatized, or acid-hydrolyzed to generate glucose. Glucose, in turn, can be converted to gluconic acid, sorbitol or alpha-methyl glucoside.

Resins. Since antiquity, tree resins (e.g., the Biblical frankincense and myrrh) have been distilled to separate them into turpentine (the distillate) and rosin (the solid residue). A pine tree might yield 10 pounds gum, which in turn yields 81% rosin and 19% turpentine (EA/Turpentine).

Turpentine can be used as a solvent, or as a source of starting materials for the synthesis of various flavors and fragrances. The rosin can be cooked to yield pitch. (Dunwody 127).

Chemically, resins are mostly terpenes, which are related to isoprene (the alkene of natural rubber). However, the Jeffrey Pine and Gray Pine are sources of almost pure n-heptane, an alkane. Resins may also contain resin acids.

Essential oils are volatile, fragrant liquids isolated from various parts of plants, usually by distillation or solvent extraction. Almond oil is from a seed, sassafras from a bark, camphor from a wood, ginger from a rhizome, peppermint from a leaf, frankincense from a resin, clove from a flower, lemon from a fruit peel, and valerian from a root. The crude liquids were used in folk medicine and cosmetics.

These oils are mixtures of organic chemicals, including terpenes, camphors, alcohols, phenols, ethers, aldehydes, ketones, esters, and organic acids, and separation is possible. Sometimes one constituent predominates, menthol is about 30-50% of peppermint oil (Gildemeister 643). But the chemicals which give the essential oil its characteristic fragrance aren’t necessarily present in large proportions; the “rose ketones” are less than 1% of attar of roses, but provide about 90% of its “odor content” (Wikipedia/”Rose Oil”).

Oleochemicals. Vegetable fats (solids) and oils (liquids) are rich in triglycerides (triacylglycerols). A bit of chemical nomenclature is appropriate here. Glycerol is an alcohol. Alcohols are compounds comprising at least a hydroxyl (-OH) group connected to a carbon atom. In glycerol, there is a three carbon chain (like that of propane), and there is a hydroxyl attached to each carbon atom.

In a triglyceride, each of the hydroxyl groups is esterified, which means that the hydroxyl group is replaced with a “fatty acid” group. A fatty acid is a kind of “carboxylic acid”; the latter have the form HO-C(=O)-R. In a fatty acid, the R group is a long unbranched aliphatic hydrocarbon.

In soap making, the fats (triglycerides) are saponified, that is, hydrolyzed (reacted with water) in the presence of a strong base (usually sodium hydroxide, potassium hydroxide or sodium carbonate). The water cleaves the ester (-O-C(=O)-) bonds, producing a mixture of the free fatty acids, together with glycerol. Common salt is added to precipitate the mixture as soap.

The soapmakers don’t separate these mixtures. However, the organic chemical industry can isolate the individual fatty acids by distillation or other means. It’s possible to obtain, in purity exceeding 90%, straight chain fatty acids of carbon numbers 6, 8, 10, 12, 14, 16 and 18 (M&B 584). These fatty acids, in turn, can be converted to fatty alcohols, or reduced to the corresponding simple alcohol by treatment with lithium aluminum hydride (M&B 604). Or they can be esterified and the ester reduced to a simple alcohol (M&B 683).

Fatty acid composition varies from plant to plant. That is because they contain different triglycerides. Moreover the triglycerides aren’t necessarily simple glycerides in which the three fatty acid groups are identical; they may be “mixed” glycerides. The fatty acid compositions of coconut, corn, cottonseed, olive, palm, palm kernel, peanut, soybean, linseed and tung oil are given in M&B 684. EB11/Oils sets forth plant or animal sources for each of 32 different fatty acids.

You can obtain about 5 gallons of castor oil from 100 pounds of castor oil (Ricinus communis) seeds. (EB11/Castor Oil). The fatty acids of castor oil are about 85% ricinoleic acid, a triol which can be reacted with isocyanate to make polyurethane. (SzmantIURR 60).

The glycerol byproduct is also of some interest, as it can be used in the manufacture of nitroglycerine.

Plant Juices are liquids found as such in fruit or vegetable tissue. From 1860 to 1919, lemon juice was used as a source of citric acid. (Wikipedia/”Citric Acid”). Likewise, malic acid can be produced from apple juice.

Other botanochemicals include alkaloids (e.g., atropine), tannins, terpenoids (e.g., artemisinin, an antimalarial), glycosides, and proteins. Typically, the exotic botanochemicals are obtained from a particular part of a particular plant, and separated from other chemicals by a combination of distillation, solvent extraction, and recrystallization.

Conversion by Destructive Distillation (Pyrolysis). Like coal and petroleum, plant matter can be pyrolyzed (heated in absence of air) so as to decompose the botanochemicals into simpler forms. Wood was pyrolyzed by the ancient Egyptians and their embalming fluid included methanol.

In this time line, methanol was so isolated by Boyle (1661), and acetic (pyroligneous) acid by Glauber (1648). The acetic acid is readily converted to acetone.

The destructive distillation of wood at 400oC yields methanol (1.5-2.5%), acetic acid (3-7%), charcoal (31-41%), wood tar (11-19%), and gases (hydrogen, carbon monoxide, carbon dioxide, methane) (15-17%). (Kirk-Othmer 25:651; cp. Mills 27; Abraham 184-190; Bordwell 58; Sadtler 350).

The result depends on the species of wood and the temperature employed. Hardwoods produce more acetic acid and methanol than soft woods, but the softwoods produce more wood tar. (Sjostrom 235). EB11/Tar says that pine (a softwood) was favored.

The wood tar (turpentine) can be used for waterproofing, or in theory it can be further fractionated to recover fatty acids, phenol, cresols, guaiacol, and other aromatic compounds. However, such fractionation was not often done commercially in this time line.

Conversion by Fermentation. Plant material rich in carbohydrates, e.g., molasses, can be used as nutrients in fermentation processes. You need a microorganism which will produce the chemical of interest. The advantage of fermentation processes is that they don’t require massive amounts of energy. However, isolating the product can be laborious.

Down-timers ferment grapes to make wine, and barley to make beer. Both are dilute solutions of ethyl alcohol. However, the alchemists know how to distill it to high purity (~95%), calling it aqua ardens(“burning water”).

Wine is perhaps 12% ethyl alcohol, 85% water, and 3% everything else. In red wines, the “everything else” is primarily glycerol, organic acids (tartaric, malic, citric, succinic), and phenols.

“Fusel oil” refers to the dregs left when the liquor of fermented grain, potatoes, molasses, etc. are distilled. It contains longer alcohols, notably amyl (C5) alcohols, and in some cases also propyl (C3) and butyl (C4) alcohol. (EB11/Fusel Oil). They arise by decomposition of amino acids (SzmantIURR 37).

While the wine yeast convert sugar into ethyl alcohol, other organisms make other chemicals. For example, Clostridium acetobutylicum ferments starch to yield 60% n-butyl alcohol, 30% acetone and just 10% ethyl alcohol. This was the World War I Weizmann process, and the acetone was needed to make smokeless powder. The butyl alcohol, originally a worthless byproduct, later became useful in the manufacture of butyl acetate(EA/Alcohols) and consequently more valuable than the acetone. (M&B 506).

For antibiotic production, the most important OTL organisms were Streptomyces (bacteria found in soil and decaying vegetation), Cephalosporium (fungus), and Penicillium (mold). It’s perhaps worth noting that molds are used in folk medicine, and it would be prudent to identify them and culture them out.

It is difficult to predict in advance which fermentation organisms and processes we will discover when, but if we don’t screen (culture soil and water organisms on culture media and see what they produce), we won’t find new antibiotics.

Zoochemical Feedstocks

Rendering separates the animal carcass into fat, protein and bone. Down-time, animal fats were used for soap and candle making. Like vegetable fats and oils, animal fats and oils can be used as a source of triglycerides and their derivatives. As you would expect, they have their own characteristic complement of fatty acids. The fatty acid compositions of beef tallow, butter, lard, and cod liver are given in M&B 684.

In late-nineteenth century practice, fatty matter was extracted from bones with benzene or carbon disulfide for use as soap stock. The remaining material was distilled, and separated into ammonia, “bone oil,” and “bone black.” For the organic chemist, the bone oil is of greatest interest; it contains pyrrole, pyridine, picoline, lutidine, collidine, and quinoline. These are heterocyclic aromatic compounds. (Thorp, 281).

Mills (174) says that horn, hair and leather, when destructively distilled, yield a liquid distillate similar to that from bones.

Animal protein can be hydrolyzed to obtain the twenty genetically encoded amino acids. (That’s still the industrial source of L-cysteine, leucine, asparagine and tyrosine.) (Bhat 328).

Cow’s milk is composed primarily of water (87%), protein (casein and albumin, 4.75%), fat (3.5%), carbohydrate (lactose, 4%), and lactic acid, and the milk of other mammals has the same basic ingredients in somewhat different proportions. (EB11/Milk).

The wool of sheep is a source of both wool fiber (keratin) and wool grease (lanolin) (5-25% wool). Keratin is a protein and thus can be hydrolyzed to yield the individual amino acids. Lanolin, a wax, is a mixture of fatty acids, alcohols, and their esters. Cholesterol (a steroid alcohol) is obtained commercially from lanolin (SzmantIURR 139).

The exoskeletons of crustacea and insects are a source of chitin, a polysaccharide. Chitin can be deacetylated to yield chitosan or hydrolyzed to yield glucosamine.

Miscellaneous Inorganic Feedstocks.

It is also possible to make use of inorganic carbon sources other than coal, such as the carbonates, and the gases carbon monoxide or carbon dioxide. Phosgene (COCl2), a useful albeit toxic reagent, is made by combining carbon monoxide with chlorine at 200oC (M&B 923). Cyanides can be obtained from certain plants (bitter almonds, cassava, appleseeds) or made from other inorganics.

Dude, Where’s My Carbon Skeleton?

Ideally, we keep our syntheses simple. That generally means using, if available at a reasonable price, a starting material which has the same carbon skeleton as our intended product.

Even better, the starting material should be one of the chemicals readily obtainable by processing a “natural feedstock” available in USE territory.

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In general, I don’t see the lower alkanes (methane, ethane, propane, butane) as preferred C1-C4 building blocks. First, since they’re gases, there’s a handling problem. For storage and transport, gases must be compressed, and then pumped into either a pipeline or a tank. So you need a pump, and you need pipes and tanks which can withstand the pressures involved. For cars, natural gas is usually compressed to about 200 times atmospheric pressure. The alternative to simply compressing a gas is to liquefy it, by putting it under moderate pressure and then cooling it below its melting point. You can liquefy crude natural gas (mostly methane; LNG) or petroleum gas (propane and/or butane; LPG).

In fall 1631, when Vicky Emerson told the gas oven investors how “difficult it was to compress natural gas and store it” (Goodlett and Huff, “Poor Little Rich Girls,” Grantville GazetteIV), she wasn’t lying. What she didn’t tell them was that she expected the compression problem to be solved within two or three years. The tanks could be made of copper or steel. (Ashby 143).

Until the compression problem was solved, the organic chemical industry could fractionate natural gas, but it would have to do so near the wellhead, and, on the spot, process the alkanes into something which would be liquid at room temperature, such as methyl alcohol, or ethyl, propyl or butyl bromide.

The second problem is that because alkanes aren’t very reactive, there isn’t much that can be done with them directly. We have the option of converting methane into “synthesis gas” (carbon dioxide and hydrogen). Otherwise, the derivatives most likely to be produced, for conversion into other products, are alkyl chlorides and bromides. Without ultraviolet radiation, you need 250-400oC. With the assistance of UV, we can chlorinate methane, ethane or propane at room temperature, but in the last case, we obtain a nearly equal mixture of n-propane and isopropane. Bromination of propane requires UV treatment at 127oC, but is highly specific for isopropane. (MB 38-40, 116-122) I would expect similar patterns of isomer production as a result of chlorination or bromination of butane.

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I see the preference as being in general for alkenes (from cracking of petroleum), alcohols and organic acids (from fermentation or destructive distillation of biological feedstocks), and simple aromatics (from pyrolysis of coal). But the exploitation of petrochemicals is dependent on both the development of oil supplies beyond that needed to satisfy fuel demands and on the realization of the necessary processing technology.

So, here’re my best guesses as to what the organic chemical industry will use as its basic building blocks, and when they will be available. In general, these building blocks are primary chemicals; they are isolated from processed natural feedstocks, rather than synthesized by reaction of pure chemicals. But of course it’s possible to make the larger building blocks by combining smaller ones.

C1 aliphatic: Perhaps by late 1631, but certainly by 1632, we will producing methanol by destructive distillation of wood. Methanol can be converted into methyl halides, formaldehyde, formic acid, methylamine. Formic acid can instead be obtained by distillation from the bodies of dead ants. (Gmelin VII-271). There are also the inorganic C1s, carbon monoxide and dioxide, but those are mostly used when you want to keep the C=O bond, as in aldehydes and ketones. And there is coke, the progenitor for the carbides, cyanides and related salts, cyanamide, urea, and thiourea.

C2 aliphatic. In 1631—within days after the grocery store runs out of whiskey—we will be distilling ethyl alcohol. Ethanol can be converted into ethylene, ethyl halides, ethylamine, acetaldehyde, and acetic acid. Acetic acid is an alternative C2; it is distilled from vinegar. And there is the possibility of making acetylene, too. Some years later, these will be supplanted by ethylene from steam cracking of petroleum.

C3 aliphatic. There are actually two C3 skeletons, the linear (n-propyl) and branched (isopropyl). The likeliest linear C3 building blocks are acetone (from destructive distillation of wood or, eventually, a Weizmann process fermentation), n-propyl alcohol (from the fusel oil of, e.g., the marc brandy from southern France; EB11/Fusel Oil) These could be available in 1631-32, but 1632-33 is more likely. Other possible building blocks include lactic acid and glycerol (Dimian 439), and propionic acid (by fermentation of molasses, yielding about 10%, or destructive distillation of wood, yielding 2-4%; Molinari 348). In the longer term, we will probably use propylene.

Isopropyl alcohol is not readily available by fermentation. (Meldola 64). However, it can be made by reduction of acetone (M&B 636), and, eventually, hydration of propylene.

C4 aliphatic. There are two different isomers of C4, linear and branched, and two different ways of connecting a single functional group (R) to the carbon skeleton, so we have four different butyl functionalities: n-, iso-, sec- and tert-butyl. We ignore the latter two.

The most likely C4 building blocks are butyl alcohol and butyric acid. Isobutyl alcohol is found in fusel oil, such as that from fermented potato (EB11/Butyl Alcohols) or beet-root molasses(EB11/Fusel Oil). N-butyl alcohol is perhaps obtainable by a “peculiar” fermentation of glycerin (Id.) Figure 1631-33. Some years later, the Weizmann process of making it will come into play.

N-butyl and isobutyl alcohol (and the corresponding aldehydes) are made in modern practice by hydroformylation of propylene (in effect, adding a carbon to a C3 building block). This will be impractical for generations in the 1632verse, because the reaction requires a fancy cobalt or iron carbonyl catalyst. (Szmant 350, M&B 507).

Butyric acid likewise comes in two isomers, with the n-isomer being available from the triglycerides of butter. EB11/Butyric acid says that the iso-form “is found in the free state in carobs (Ceratonia siliqua) and in the root of Arnica dulcis, and as an ethyl ester in croton oil.”

Also in contention, we have several dicarboxylic acids—succinic acid (“spirit of amber”), fumaric acid, malic acid, and levulinic acid. (Dimian 439). Succinic acid can be distilled from amber and various resins, or synthesized by fermentation or oxidation of fats and fatty acids. (EB11/Succinic Acid). “Fumaric acid is found in fumitory (Fumaria officinalis), in various fungi (Agaricus piperatus, &c.), and in Iceland moss.” (EB11/Fumaric and Maleic Acids). It can also be obtained by Rhizopus fermentation of carbohydrates (Szmant 362). And it occurs in many plants (EA). Malic acid was first isolated from apple juice in OTL 1778. It’s “found abundantly in the juices of many plants, particularly in mountain-ash berries, in unripe apples and in grapes. The acid potassium salt is also found in the leaves and stalks of rhubarb.” (EB11/Malic Acid). Levulinic acid is not found in natural feedstocks, but it is obtainable by hot acidification of sucrose. (EB11/Laevulinic Acid).

C5 aliphatic. A mixture of C5 (amyl) alcohols is obtainable from fusel oil, probably 1631-33. Valeric acid and valeric aldehyde are found in certain plant sources (EB11/Valeric Acid, Valerian).

C6 aliphatic. One possible source is caproic acid, in butter fat and coconut oil (EB11/Oils). Another is adipic acid (from fat), used as a nylon precursor. Still others are sorbitol (from Sorbus trees) and lysine (from animal protein) (Dimian), but they have multiple functional groups and hence might need to undergo several conversions in order to arrive at the desired product.

Higher aliphatics. In general, the alkanes can be obtained from petroleum, if the gas guzzlers let us. Straight chain, even carbon number aliphatics are available from selected fats and oils. The gaps might need to be filled in synthetically.

Cyclic Aliphatics. In modern practice these are mainly obtained from petroleum. Some crude oils are naturally rich in cyclic aliphatics, and others can be processed to produce them. Coal tar benzene could be hydrogenated to produce cyclohexane.

Carbocyclic Aromatics. Benzene, naphthalene (two fused rings) and anthracene (three fused rings) will almost certainly be obtained by coal pyrolysis, just as in the nineteenth century.

We know that “light benzoils” (probably benzene, toluene and xylene, “BTX”) are being produced in Magdeburg at the end of 1633, and aniline (aminobenzene) is being produced at Essen in winter 1633-34. Since DDT was made in mid-1633, that implies that there was some coal tar production earlier, perhaps in or near Grantville. Nothing was said specifically about the polyaromatics (those with multiple rings), but they’re in coal tar, too. In modern practice, “BTX” are obtained mainly by catalytic reforming of petroleum, rather than from coal tar.

Biological feedstocks are not especially good sources of the simple aromatics that are the most versatile building blocks. The simplest are benzyl alcohol, found in Peru balsam and storax; benzaldehyde, obtainable by decomposing amygdalin, itself extracted from almonds or apricot kernels; and benzoic acid (from gum benzoin). (EB11) However, we can isolate biologically active compounds from biofeedstocks and then use them outright, or “tweak” the structures a bit (“semisynthesis”).

Heterocyclics. Heterocyclic chemistry is simply too complex to be more than touched upon in this article. In general, the simple heterocyclic rings are synthesized by simple addition or by condensation (a combination of addition and elimination; there is loss of water, alcohol or hydrogen halide) of linear building blocks.

A few heterocylic aromatics warrant special note. Thiophene (4C, 1S) occurs in coal and oil, and can be synthesized from acetylene and sulfur. Furfural comprises the furan (4C, 1O) ring, and is produced from agricultural waste (EA/Furfural). Pyrrole (4C, 1N), pyridine (5C, 1N), quinoline (2 fused rings, 1N), and acridine (3 fused rings, 1N) can be obtained from coal tar or bone oil.

There are numerous biomolecules that comprises heterocycles—notably nicotine (pyridine and pyrrolidine), the amino acids histidine (imidazole), tryptophan (indole) and proline (pyrrole), the purine nucleic acid bases guanine and adenine, and the pyrimidine nucleobases thymine, cytosine and uracil—but the additional substituents on these molecules limit their use as building blocks.

Organic Chemical Timeline

So, what additional organic chemicals will we want, early on? The “wish list” for the chemists will be compiled from encyclopedias, textbooks, and even product labels.

Wanting a chemical, of course, isn’t the same as knowing how to make it. We know from the review of organic chemicals in canon (Part 3) that the chemists have succeeded in synthesizing DDT, chloramphenicol and sulfanilamide (Figure 4-2). So the chemists are clearly capable of synthesizing compounds with a mono- or disubstituted benzene ring. And I don’t think it’s too big a jump to trisubstituted benzenes, although figuring out the correct order of substitution is more involved.

It’s less clear that they will be able to do much with heterocyclic compounds. From M&B, they will learn a bit about the synthesis and derivatization of pyrrole, thiophene, furan, pyridine, quinoline and isoquinoline. CCD reveals that purine (fused imidazole-pyrimidine) can be prepared from uric acid (in turn derived from guano!), and carbazole from the anthracene cake of coal tar.

EB11 has essays on at least the following heterocyclics: xanthone, pyrazoles, pyrimidines, purin(e), pyrrol(e), acridine, thiazoles, triazoles, quinazolines, tetrazoles, quinoxalines, phthalazines, adenine, phenazine, piperazin(e), piperine, indulines, azoximes, imidazoles, indole, oxazoles, pyrazines, pyridine, quinoline, safranine, thiophen(e), tropine and triazines, and the precursor pyrogallol (catechol). These may give information on how they are synthesized and used. McGHEST similarly covers furan, purine, indole, pyridine, pyramidine, and pyrrole. Some of the heterocyclic compound entries (e.g., imidazole) in Merck Index provide synthesis guidance. The richest source of heterocyclic chemistry tips is the Named Organic Reactions section of Merck Index (MI), which includes the Biginelli pyrimidine synthesis, the Bischler indole and triazine syntheses, and much more.

Synthesizing a heterocyclic ring from the basic building blocks will usually involve a minimum of three steps, one for the ring forming itself and the others to make the reactants. In the Debus synthesis of imidazole, the ring is formed by the reaction of a diketone (R-C(=O)-C(=O)-R) with an aldehyde (R’C(=O)-H) and ammonia. But you would need at least one step to make the aldehyde from our building block alcohols or carboxylic acids, and several to make the diketone (e.g., alcohol to ketone to isonitrosoketone to diketone; EB/Ketones).

If the heterocyclic ring is itself substituted then you need to figure out whether to introduce the substituent before, during or after ring formation. Because of all of the complications, I have only listed a few heterocyclic compounds.

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There are three bases for listing an organic chemical in the timeline (Table 4-4):

—it is explicitly referred to as isolated or synthesized in a story, i.e., a canonized chemical;

—it is an “essential precursor” in the manufacture of a canonized chemical by the inferred synthetic route; or

—it is a chemical which this author predicts would have been made at that stage, because it is both industrially important and reasonably obtainable.

By way of example, DDT is a canonical chemical; chlorobenzene, benzene, trichloroacetaldehyde, acetaldehyde, and ethyl alcohol are essential precursors to DDT; and monochloro- and dichloroacetaldehyde are predicted chemicals because if you can make trichloroacetaldehyde, you can make those, too. Of course, ethyl alcohol and benzene also would have qualified as predicted chemicals, based on their availability in wine and in coal tar, respectively.

In placing a chemical which is neither canonized, nor an essential precursor, on the timeline, I have taken into account whether a natural source or synthesis or natural source is likely to be in the books, when the compound was first isolated or synthesized in the old time line, and whether the method of procuring it is likely to run into any kind of problem, e.g., it is found in some exotic plant, or it needs a complex catalyst, or high temperature or pressure.

Precisely when a proposed chemical appears in the timeline depends not only on when it could be made, but also what demand for it would exist. This is, of course, something about which reasonable minds will differ. Based on canon, there is going to be early demand for pharmaceuticals, pesticides, dyes, explosives, and, a bit later, plastics. In turn, that means early demand for the organic building blocks from which those end-products are created. On the other hand, chemicals specific to the automotive industry are going to lag behind, which is why I left isobutylene and MTBE off the timeline.

Table 4-4: Proposed Organic Chemical Timeline (dates are of earliest plausible availability in lab quantities unless already in canon)

1631-32

1633

1634

1635-39

Aliphatic C1

methanol (W)*;

methane (NG);

formaldehyde (S); formic acid (S)

urea (I)

semicarbazide, thiosemicarbazide

Aliphatic C2

ethanol (F)*;

ethane (NG); acetic acid (F)*;

acetaldehyde (S)

chlorinated acetaldehyde (S1); acetic anhydride (S1); 2-nitroethanol; (sodium) ethoxide; acetyl chloride; dichloroacetyl chloride; ethylene; diethyl ether (S)

acetylene; ethylene oxide; ethylene glycol; ethylene dichloride; vinyl chloride; vinyl acetate; tetrachloroethylene

glyphosate?

Aliphatic C3

propane (NG)

n-propanol (F,S); glycerol (NWP, AF); acetone (W).

propylene; propylene oxide; bisphenol A (S); propionic acid, lactic acid, isopropanol; nitroglycerin;

Aliphatic C4

butane (NG);

Rochelle Salt

butanol (F,S); butyric acid (AF)

butadiene (NWP); butyraldehyde (S); succinic acid, fumaric acid, malic acid, levulinic acid; ethambutol

malathion?

Aliphatic C5

amyl alcohol (F,S)

glutaraldehyde; xylitol (NWP); sorbitol,

Aliphatic C6

caproic acid (AF)

mannitol (NWP); sorbic acid (NWP)

aliphatic cyclic

hexamine (S); RDX (S);

penicillin (F); active ingredient of Artemisia (NWP); cyclohexane (P?, S);

simple penicillin derivatives (semi-S); cuminaldehyde thiosemicarbazone

isolated aromatic rings

“light benzoils” (C); benzene (C);

benzaldehyde (S1); chlorinated benzenes (S1); nitrobenzene (S1); aniline (C, S1); acetanilide (S2);

sulfanilamide (S4); toluene (C); xylenes (C): phenol (C,S1); DDT (S3), chloramphenicol (S7); ethylbenzene (S2), aspirin (S2); hexachlororobenzene (S1), hexachlorocyclohexane (S1); carbasone; first azo and triphenylmethane dyes;

styrene (S2), cumene (S2); (S); aliphatic sulfanilamide derivatives; triphenylmethane dyes; lidocaine, benzocaine, novocaine; phenacetin, ibuprofen; acetominophen; dapsone, 4-aminosalicylic acid; probenecid; chloroxylenol; hexachlorophene?; procainamide; TNT, picric acid, PABA; benzophenone; 2,4-D; amidol, hydroquinone, Metol, phenidone, catechol), pyrogallol, Rodinal; p-aminosalicylic acid; anthraquinone (S1)and related dyes; p-aminosalicylic acid; hexylresorcinol; cuminaldehyde

fused aromatic rings

naphthalene (C); anthracene (C)

terephthalic acid (S2); propanalol

heterocyclic (aliphatic or aromatic)

pyridine (C); furfaral (W)

tetrahydrofuran (S1); piperazine; isoniazid

moroxydine; heterocyclic sulfanilamides and nitrofurans;

phenytoin;

chlorpheniramine?;

Notes: Bold=Canonized Chemical; Italics=likely precursor to Canonized Chemical; Normal=Proposed Chemical

* compound made, probably in dilute form, prior to the RoF. Source code: C=Coal, NG=natural gas, P=Petroleum, W=Wood, NWP=Non-Woody Plant, AF=Animal Fat, F=Fermentation, I=inorganic S=synthetic (# indicates number of steps removed from feedstock).

Dyestuffs

Dyers classify dyes by mode of fixation to the fiber. Acid dyes contain sulfonic or carboxylic acid groups, whereas basic dyes provide amino and imino groups. Either can be used to (reversibly) dye protein fibers (wool, silk, leather), but acid dyes are preferred. For acid or basic dyes to be fixed to cellulose fibers (cotton, paper), you need a mordant. The mordants known to the down-timers include alum, tannic acid, and urine.

Direct dyes are those able to bind cellulose (via hydrogen bonds) without the aid of a mordant. That’s great news, as mordants are expensive and mordanting takes days or weeks, but the binding is reversible and so the direct dyed-cottons bleed when washed. A few down-time dyes are direct (turmeric, saffron, annatto, and safflower), but they are faded by light. Direct dyes are preferred for paper. (Roberts 167).

Ingrain (azoic) dyes are really pigments (water-insoluble colors) that are formed within the interstices of the fibers by the reaction of two intermediates. The first synthetic azoic dye was vacanceine red (summary synthesis, EA/Dye). With vat and sulfur dyes, a pigment is converted into a dye and then, after permeating the fibers, reverts to a pigment. Indigo is a vat dye.

The reactive dyes (commercialized 1956) are potentially the most useful, because they have reactive groups (see McGHEST/”Dye” and EB15/reactive dye for examples) that react with the hydroxy or amino groups in the fiber to form wetfast covalent bonds. Pretty much any chromogen can be connected by a bridging group to a reactive group to form a reactive dye. Unfortunately, EA/Dye warns that the original process (1894) was “very complex and of little value industrially” and it wasn’t until 1953 that these problems were overcome. I am not sanguine that the brief descriptions in Grantville literature are sufficient to sidestep a half-century of false starts.

Dyes have uses outside the textile industry; to color other products, and as inks, pH indicators, or clinical laboratory stains. In the Gram stain protocol, bacteria are stained with Crystal Violet (Gentian violet) and counterstained with safranin or basic fuchsin. And several dyes have activity against microbes or parasites.

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Even a synthetic duplicate of a natural dye can be a success in the marketplace. It takes “on average, 440 grams of fresh dye plant to achieve the same tinctorial effect as one gram of synthetic dye.” That makes it expensive to use natural dyes even when the plants are grown right at home. If they are cultivated someplace faraway, then the shipping costs may also be significant. In the late twentieth century, synthetic dyes were perhaps a hundred times cheaper than their natural counterparts. (Kirk-Othmer 673). If the synthetic dye provides a new hue, a greater intensity, or superior dyeing ability, or wash- or lightfastness, all the better.

The Merck Index has structures for at least 150 dyes. So how will Stoner decide which dyes to make first? Here I will look at color, ease of use, and ease of synthesis.

The palette available pre-Ring of Fire in the major Old World civilizations included the following (note that the same source can produce different colors depending on how it was handled):

Black: no good dyes. Best is logwood (banned in England 1581-1673). You could combine blue, red and yellow (expensive), or use a vegetable dye like walnut (more gray than black).(Finlay 107).

Brown: walnut, some barks

Red: kermes, Spanish Red (cochineal), brazilwood; madder, orchil

Orange: safflower (mostly Asia), madder, red sandalwood (Saunders).

Yellow: weld (Reseda luteola) (best), Dyer’s Greenweed (!), buckthorn berries, saffron, European dogwood, turmeric, safflower, fustic

Green: usually a two-pot color (blue plus yellow).

Blue: woad, indigo

Purple: New World Royal Purple (purpura), orchil (lichen), brazilwood, woad + madder.

So blacks and greens would be particularly attractive to Stoner. By September 1633, he had the only “waterproof green dye” in the world, and it was being used on the USE’s paper money. (Flint and Dennis, 1634: The Galileo Affair, Chapter 8). Even in 1911, green printing inks were mixtures (EB11/Ink). So was his green a single dye? And was it organic or inorganic? The early 20c “chrome green” currency ink was made from chrome yellow and Prussian blue.

The ease of synthesis depends on the chemical structure of the dye, and that also affects the dye’s properties. Chemists classify dyes by their chromogen, the structure that is the principal determinant of their ability to absorb light. The substituents can affect the hue and intensity of the color, as well as how the dye is fixed to the fiber.

The most important chromogen in the modern world was azo (-N=N–) (EA/Azo Dyes), and preparation of azo compounds is discussed in all introductory organic chemistry textbooks, as examples of the use of diazonium salts. See also EB11/Azo Compounds. Most of the azo dyes also include benzene or naphthalene rings. Anthraquinones ranked second in importance and they are derived from anthracene. The triphenylmethanes, with three benzene rings, are also of great interest because of their brightness. There are other chromogens, too.

Coal tar benzene, toluene, xylenes, naphthalene, anthracene, phenanthrene, and pyridine are converted to various intermediates such as aniline (also found in coal tar), anthraquinone, beta-naphthol, and “H acid,” and ultimately to the dyestuff. Useful background on the synthesis of the major chromophores, and intermediates used in dye manufacture, can be gleaned from EB11 (triphenylmethane, benzophenone, anthraquinone, aniline, indulines, nitrobenzene, quinoline, benzene, quinones, xanthone, naphthylamines, etc.); EB15 (dye, azo dyes, pigment); EA (dye); McGHEST, etc.

Mauveine (OTL’s first synthetic dye, 1856) was obtained by heating crude aniline with potassium bichromate and sulfuric acid. It was fortunate that toluidine was present in the crude aniline. (EB11/Safranine; EA/Dye)

The dyes for which there is at least “final step” synthetic information in Grantville literature (Merck Index 1968 unless otherwise stated) are as follows:

Table 4-2 New Dyes

Type

Color

Acid

Basic

Direct

Other/Unknown

Black

Acid Black 1* (EB15)

Eriochrome Black* (mordant); Aniline Black (EB11/Aniline, Textile-Printing);

Brown

Bismarck Brown R and Y* (MI; EB15/azo dye);

Red

Amaranth* (color photography); Eosine (Acid Red 91 and 87; xanthene); Rose Bengal (xanthene; stain); Safranin (azine; EB11/Safranine)

Fuchsine (Magenta, Aniline Red) (TPM; MI/rosaniline, EB11/Fuchsine, EB15/pigment; antifungal); Neutral Red (azine; indicator);

Congo Red* (possibly first direct dye; MI; EB15/azo dye; M&B786); Vital Red* (stain); benzopurpurine 4B* (stain);

Alizarin** (mordant) (EB11/Alizarin); Scarlet Red* (solvent; “Biebrich Scarlet”; stimulates wound healing); Methyl Red* (indicator); Trypan Red* (anti-trypanosome); purpurin**; Fast Scarlet R* (EB15/azo dyes)

Orange

Tropaeolin O and OO* (indicator); orange I*; orange II* (MI; Solomons 931); Methyl Orange*

chrysoidine*

alizarin orange** (mordant)

Yellow

Polar Yellow*; Naphthol Yellow (nitro; MI structure only but simple)

Clayton Yellow*

Metachrome Yellow * (mordant); Butter Yellow * (Solomons 932); Chloramine Yellow (EB11/Primuline; thiazole); Chrysaniline (EB11/Acridine); Celliton Fast Yellow RR (nitro; EB15);

Green

Malachite Green (TPM; derived from Butter Yellow; also antiseptic); Brilliant Green (TPM; also antiseptic);

Pigment Green B (nitroso; EB15)

Blue

Sulphan Blue (TPM);

Methylene Blue (thiazine; stain and antiseptic); tolonium chloride (thiazine; stain); benzo azurine G*;

Trypan Blue*; Evan’s Blue*;

indigo (vat; indigoid; sodamide process; EB15/Dye); Celestine Blue (mordant; oxazine); Alizarine Blue** (pH indicator);gallocyanine (mordant; oxazine); Aniline Blue (TPM; EB15/pigment).

Violet

Mauveine (azine), Crystal (Gentian) Violet (TPM; EB15/dye); Rhodamine B (structure only; xanthene); Rosaniline (TPM; EB11/Triphenylmethane);

Quinalizarin (mordant; quinoline); Orcein (archil; EB11/Orcin)

* azo, ** anthraquinone, TPM triphenylmethane

The list above is just a “first cut”; it leaves out some very important dyes because I haven’t found synthesis information, and it includes dyes with serious disadvantages.

Pharmaceuticals

Many useful pharmaceuticals come from natural sources. There are four ways in which the organic chemists can promote public health:

(1) assay the level of the active ingredient in extracts so we know how potent they are, and can use them accordingly.

(2) isolate the active ingredient so we have it in pure form.

(3) synthesize the active ingredient so we have it in pure form, independent of the natural source.

(4) synthesize analogues of the active ingredient which are safer or more potent than the naturally occurring compound.

This section mostly covers the simpler compounds on WHO’s “essential medicines” list (320 compounds!) and some “obsolete” pharmaceuticals that will be of value in the new timeline because they are easier to synthesize.

In the seventeenth century, infectious diseases killed more than half of the population, so I will focus on antimicrobial and antiparasitic agents.

Antimicrobials. We have chloramphenicol, at least one sulfanilamide, and penicillin in canon.

Aplastic anemia is the bete noir of chloramphenicol, and there has been modern experimentation with analogues to avoid it. Thiamphenicol, florfenicol and azidamphenicol are in MI. However, there is no synthetic guidance, and in OTL they weren’t synthesized from chloramphenicol (see appendix).

As mentioned in EA “Sulfonamides,” sulfanilamide was the first of a series of drugs.

MI provides synthetic guidance for sulfacetamide, sulfadiazine, sulfadicramide, sulfaguanidine, sulfamidochrysoidine, sulfathiourea, sulfadiamine, sulfonylbisacetanilide, sulfoxone (anti-leprotic) and the heterocyclics sulfamerazine, sulfamethazine, sulfamethizole, sulfamethoxazole, sulfamethoxypyridazine, sulfapyrazine, sulfapyridine, sulfaquinoxaline, sulfasomizole, sulfathiazole, sulfisoxazole. See also M&B 757; Solomons 937ff.

I am not sure which penicillin is the one that’s being produced in Cologne in 1635. Most likely, it is Penicillin V (phenoxymethylpenicillin), but Penicillin G (benzylpenicillin) can also be produced by fermentation. (Vardanyan 430ff).

Unfortunately, the Penicillium mold is slow growing and finicky, and the concentration of penicillin in the fermentation broth of even a “high yield” strain is low, making the drug difficult to extract. (Sheehan 85). For these reasons, the total synthesis of penicillin remained a goal. However, it was a rather elusive one; penicillin has what Woodward called a “diabolical concatenation of reactive groups.” Even with an MIT laboratory working on the problem, it was 14 years from the structure being determined to it being first synthesized (Sheehan 1959), and the synthesis was never commercially competitive with fermentation methods.

So the best we can do is to semi-synthesize penicillin derivatives. MI reveals that the key intermediate is 6-aminopenicillanic acid (6APA); it can be used to make benzylpenicillin, methicillin, and ticarcillin by a single step acylation reaction the Grantville chemists should be able to figure out. The catch is finagling the fermentation to produce 6APA.

The aminopenicillins amoxicillin and ampicillin are more difficult to make because you need a protecting group. Cloxacillin is also in doubt because the added moiety (an isoxazole) is itself more complex than anything made by the chemists in canon.

Several other major antibiotic classes (cephalosporins, polypeptides, tetracyclines, macrolides, aminoglycosides) are, like the penicillins, complex chemicals produced in the twentieth century either as fermentation products or by semisynthesis. It is not very likely that lightning will strike twice and we will luck upon a production strain for one of these antibiotics in a high school lab refrigerator, as we did with penicillin. Hence, it is unpredictable when we will first see one of these antibiotics; it depends on the fortuitous discovery of a suitable organism. The cephalosporins, for example, were first identified as antibacterial agents in studies of a culture of Cephalosporium acremonium from a Sardinian sewer.

The nitrofurans weren’t major antibacterial agents in this time line (4 million prescriptions in 1989—Kirk-Othmer 2:870), even though they have the advantage that they attack multiple bacterial metabolic systems and hence the evolution of resistant bacteria will be slow. We have significant synthetic guidance; MI gives the precursors for at least nitrofurantoin, nitrofurazone, and nitrofurtimox, and we should be able to figure out nifuratel, nifurazone and nifuraldezone by analogy. Bear in mind that some of these precursors are themselves complex; the first NTL nitrofuran drug would probably be nitrofurazone.

McGHEST/Nitroaromatic indicates that Furacin is derived by several steps from furfural. Indeed, furfural, which is in natural feedstocks, is undoubtedly the source of the furan ring in all of these compounds. Furan chemistry is briefly discussed in M&B 1078ff and McGHEST/Furans.

Forget Salvarsan, the organoarsenic compound that was the first effective anti-syphilitic, fosfomycin (the simplest known antibiotic, a C3), and the quinolones. (for reasons, see Appendix).

Antivirals (other than vaccines and antibodies). Yeast RNA (about 8-12% dry weight; Halasz 29) can be hydrolyzed to supply raw materials for synthesizing the antiviral nucleic acid analogues. The component RNA nucleobases are heterocyclic compounds falling into two categories, the pyrimidines (cytosine, uracil) and the more complex purines (adenine, guanine). If a ribose sugar is attached we have the corresponding nucleosides.

The antiviral pyrimidines include cytarabine, dideoxycytidine, edoxudine, floxuridine, idoxuridine, trifluridine and zidovudine. To make cytarabine, we must replace the ribose of cytosine with arabinose. Arabinose is found in many plants but of course we need to learn to identify and isolate it. Edoxudine is uracil attached to deoxyribose (obtainable from DNA) rather than ribose.

While it is conceptually simple to replace one sugar with another, Hardewijn (xix) warns that “between the 1950s and 1970s the synthesis of a modified nucleoside was a difficult undertaking.” Part of the problem is assuring that the correct sugar oxygen reacts with the correct nucleobase nitrogen. The Merck Index “Named Organic Reactions” does set forth two nucleoside syntheses, the Hilbert-Johnson reaction (1930) and the Vorbruggen glycosylation (1970). The former requires knowledge of how to synthesize a 2,4-dialkoxypyrimidine and the latter requires knowledge and availability of silylating agents.

The antiviral purines include acyclovir and ganciclovir, which don’t contain sugar, and dideoxyadenosine, dideoxyinosine, and vidarabine, which do. MI says, for acyclovir, that there’s a “convenient synthesis from guanine,” which is true, but the catch is that guanine has five nitrogens and you want to derivatize just one of them. It took decades to develop the synthesis in question. (Cabri).

As to other reported antivirals, we could make cuminaldehyde thiosemicarbazone and moroxydine, as there is useful synthetic info (MI, CCD). We just know the structure of kethoxal, but it’s aliphatic and possible for the late 1630s.

Amantadine is less likely. We do know how to make adamantane (MI), and there are hints that amantadine can be made by a route involving adamantyl chloride (the standard routes actually involve bromide), but I think it far from obvious how one proceeds from there (Vardanyan 551).

Even if we can make a drug reported to have some antiviral activity, it may not be effective against the viruses we need to fight, or at least not enough to justify the investment of resources into developing a commercial-scale synthesis.

****

The likeliest near-term pharmaceuticals are reviewed below. Synthetic info is usually just the final step, but you can look up the precursors and work backward.

Table 4-3 Pharmaceuticals

Compound

Structure

Isolation/Synthesis

S/O=structure only (usually MI)

Comments

Anti-Bacterial

Chloramphenicol

see discussion

Sulfonamides

Nitrofurans

Penicillin

trimethoprim

2 rings, 1 pyrimidine

from guanidine (MI)

synergistic with sulfonamides

probenecid

disubstituted benzene

MI

potentiates penicillin

sulfoxone

sulfonamide analogue

MI

vs. leprosy

Anti-Viral

cuminaldehyde thiosemicarbazone

disubstituted benzene

MI

moroxydine

from morpholine (MI)

Anti-Malarial

Quinine

Isolation: cinchona bark

Artemisinin

Isolation: Artemisia annua

Pamaquine

disubstituted quinoline

multisteps (M&B 1095); MI; EB15

1st synthetic

Primaquine

by analogy (MI)

Chloroquine

M&B 1090 (aniline->quinoline); MI (final)

precursor for nalidixic acid

Dapsone

essentially two anilines linked by SO2

MI (p-chloronitrobenzene is precursor)

also anti-leprosy

Anti-Amebic

Emetine

Isolation: dried root of Ipecac

Carbarsone

final step (MI); intermediates (CCD)

Metronidazole

trisubstituted imidazole

see above for steps needed just to build the imidazole ring. After that, it’s actually fairly straightforward (Vardanyan 576), but the up-timers don’t know that . . . .

also antibacterial;

Anti-tuberculotic

p-aminosalicylic acid

aspirin-related

MI

isoniazid

pyridine

MI

Ethambutol

C2, C4

MI

Anti-helmintic

???

oleoresin of aspidium

vs. tapeworms; known to down-timers

tetrachloroethylene

C2

alternative syntheses (MI, CCD)

hexylresorcinol

trisubstituted benzene

resorcinol syntheses (MI; EB11/resorcin)

piperazine

heterocyclic

syntheses (MI; CCD; EB11/Pyrazine).

Antiseptics

various alcohols (ethyl, n-propyl, isopropyl and phenyl)

Glutaraldehyde

C5

reduce glutaric acid; latter (CCD)

Brilliant Green

dye

hexachlorophene

CCD

chloroxylenol

disubstituted benzene

S/O

Diuretics

Mannitol

isolated: manna, seaweeds

Cardiovascular

Aspirin

see part 3

Digoxin

isolated: foxglove

procainamide

disubstituted benzene

S/O

antiarrhythmic

nitroglycerin

trisubstituted glycerol

CCD

vs. angina

epinephrine

trisubstituted benzene

from pyrocatechol (CCD); cp. EB11/pyrocatechin

phenytoin

imidazoline + 2 benzene rings

alternative syntheses (MI)

antiarrhythmic; antiepileptic

propanalol

monosubstituted naphthalene

S/O

beta-blocker

heparin

isolated: mammals

anticoagulant

methyl dopa

trisubstituted benzene

S/O

antihypertensive

hydralazine

phthalazine

from phenoxyphthalazine (MI); phthalazine synthesis (MI)

vasodilator

Preoperative

atropine

isolated: deadly nightshade

General Anesthetic

diethyl ether

see part 3

cyclopropane

(synthesis M&B 302ff)

halothane

C2

MI

Local Anesthetic

lidocaine

trisubstituted benzene

CCD; about three steps removed from aniline, and the final two steps have been carried out in introductory organic chemistry labs. (Reilly).

not available until after spring 1632 (Viehl, A Matter of Consultation, ROF)

benzocaine

disubstituted benzene

CCD

novocaine (procaine)

Solomons 995.

ephedrine

monosubstituted benzene

isolated: Ephedra (Chinese herbalists); synthesized

Sedative/Hypnotic

barbiturates

M&B 925

chloral hydrate

CCD

meprobamate

multistep (Solomons 996)

Analgesics, Antipyretics

Aspirin

Phenacetin

aniline derivative

Solomons 932

rather toxic

acetaminophen

CCD; MI

ibuprofen

disubstituted benzene

S/O

morphine

isolated: poppy

THC

isolated: marijuana

Antihistamine

chlorpheniramine

pyridine derivative

S/O

marginally possible (Varanyan 225).

diphenhydramine

(Benadryl)

MI

Antidotes

Gelatinous calcium gluconate

C6

CCD, MI

HF burns

Dimercaprol

C3

MI

antidote for the poison gas Lewisite

Penicillamine

related to butanoic acid

lead and mercury poisoning

EDTA

CCD

Anticonvulsants

Valproic acid

C7

S/O (PDR)

Antidiabetic

Insulin

isolated: pigs

Explosives

Yes, there’s a war on, so we need chemicals that go “Bang!” We have RDX. I would expect that trinitrotoluene (TNT), picric acid (also a dye!), nitroglycerin (also pharmaceutical) and nitrocellulose will be available within a few years of the Ring of Fire.

Sunscreens

This may seem a trivial application of up-time knowledge, but imagine spending days on the deck of a ship trapped in the doldrums (the sun was said to have “dried the feces within the body”; Dash 78) or working under the baleful glare illuminating the fields of a tropical colony. Several standard UV blockers, notably benzophenone and PABA (Field 2ff), are well within the demonstrated synthetic capability. They will compete with the inorganic pigments titanium dioxide and zinc oxide.

Flavors and Fragrances

Many of these will be isolated from natural sources, such as the essential oils of select plants. These include various phenol derivatives, such as eugenol (cloves), isoeugenol (nutmeg), anethole (aniseed), vanillin (vanilla bean), thymol (thyme, mint), safrole (sassafras). (M&B 794) M&B 620 discloses how to convert eugenol or isoeugenol into vanillin.

Offord, “White Gold” (Grantville Gazette 9) discusses sugar (sucrose, fructose) from sugarcane, sugar maple, sugar beets, and sweet sorghum. However, we can also isolate the sweeteners mannitol (Fraxinus ornus; seaweed), sorbitol (mountain ash berries), and xylitol (Finnish birch trees). (MI). Xylitol can be made from the xylose of wood lignin.

Preservatives

We have acetic acid, we can easily synthesize benzoic and propionic acids, and sorbic acid can be isolated from rowan berries or synthesized (MI).

Pesticides

In the seventeenth century, a considerable part of the food supply was consumed by pests rather than people. Insects also spread disease. Hence, there’s a market for pesticides. There are several inorganic pesticides, but they’re outside the scope of this essay.

Natural organic insecticides include nicotine (partial synthesis, M&B 1065; Solomons 1000), various garlic oil components, and pyrethrins (pyrethrum flower).

Among the organochlorines, DDT and hexachlorobenzene are in canon. We can also make hexachlorocyclohexane (Lindane); EB11/polymethylenes says that it’s “formed by the action of chlorine on benzene in sunlight” (probably better to have a ultraviolet light source) and Merck Index notes that this results in formation of eight stereoisomers, the gamma being the one that’s pesticidally active. It gives the physical properties of the alpha, beta and gamma isomers, and it seems as though we could separate the alpha by distillation and the beta by extraction. We can also make pentachlorophenol by chlorination of phenol, much as we do hexachlorobenzene. The popular herbicide 2,4-dichlorophenoxyacetic acid should also be feasible. And there’re synthetic plans for the (banned) insecticides chlordan and aldrin (Solomons 1025).

Unlike the organochlorines, the organophosphates are biodegradable. Unfortunately, they are also more toxic to people. One of the safer ones is malathion; CCD has a summary synthesis. There’s also glyphosate (1970), a glycine analog, but I am not sure how much guidance there will be on how to make it.

We know starting materials for the synthesis of the herbicide naproanilide (Solomons 951).

Fertilizers

Urea is used as a fertilizer because of its high nitrogen content. Any chemist would know that urea was the first (1828) organic chemical to be synthesized from inorganic starting materials; particulars are given by EB11. The modern route (EA) is by brute force (high temperature, high pressure) combination of liquid ammonia and liquid carbon dioxide.

Photographic Chemicals

Organic chemicals used in the darkroom include acetanilide (chloramphenicol precursor), acetic acid (vinegar), amidol (from chlorobenzene, M&B813), hydroquinone (from aniline, M&B976), Metol (from hydroquinone and methylamine, EB15), phenidone (from phenylhydrazine, MI), catechol (from salicylaldehyde, MI), pyrogallol (from gallic acid, CCD 735), and Rodinal (p-aminophenol) (two routes, CCD 45).

Polymers

Synthetic rubbers and plastics are among the most important end-products of the modern chemical industry. However, they deserve an article of their own. Suffice it to say that many of the top organic chemicals shown in Table 3-2 are “top” because of their use in manufacturing polymers.

****

Next: Part 5, Polymers and Composites

Author’s note: Bibliography will be in Appendix published in “Gazette Extras” on www.1632.org after Part 5 is published.

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About Iver P. Cooper

Iver P. Cooper, an intellectual property law attorney, lives in Arlington, Virginia with his wife and two children. Two cats and a chinchilla rule the household with iron paws. Iver has received legal writing awards from the American Patent Law Association, the U.S. Trademark Association, and the American Society of Composers, Authors and Publishers, and is the sole author of Biotechnology and the Law, now in its twenty-something edition. He has frequently contributed both fiction and nonfiction to The Grantville Gazette.

 

When not writing (or trying to get an “orange blob” off his chair so he can start writing), he has been known to teach swing dancing and folk dancing, or to compete in local photo club competitions. Iver adds, “I can’t get my wife to read my fiction, but she has no trouble cashing the checks.”

Iver’s story “The Chase” is in Ring of Fire II