Camphor industrial

The production of camphor was started much earlier, probably at the end of 13th century. In the middle of the 15th century, numerous camphor industries were established in China, Japan and Formosa. Any how the major production of camphor was obtained from Japan and Formosa. The production of camphor from the natural source is well summarised belbw ... 

The first plastic was celluloid, made of nitrocellulose softened by vegetable oils and camphor. It was used for car windshields and for movie film. The first completely synthetic plastic was bakelite (1910) produced from phenol and formaldehyde for use in the electrical industry. 

Boeluinger Ingelheim (Germany) Camphor Allied Products (India) Daicel Chemical Industries (Japan) Degussa-Huls (Geiinany)... 

Used industrially as a chemical intermediate in the production of rayon, carbon tetrachloride, xanthogenates, flotation agents, and pesticides used in the cold vulcanization of vulcanized rubber, in adhesive compositions for food packaging as a solvent for phosphorus, sulfur, selenium, bromine, iodine, fats, resins, rubbers, waxes, lacquers, camphor, resins and in the production of optical glass, paints, enamels, varnishes, paint removers, tallow, putty preservatives, rubber cement, soil disinfectants, explosives, rocket fuel, and electronic vacuum tubes. 

Phthalates were first introduced in the 1920s and quickly replaced the volatile and odorous camphor. In the earliest 1930s, the commercial availability of PVC and the development of DEHP caused the boom of the plasticizer PVC industry. 

Pure a-pinene is obtained by distillation of turpentine oils. As a fragrance substance it is used to improve the odor of industrial products. However, it is far more important as a starting material in industrial syntheses, for example, terpineols, borneol, and camphor. 

Bomeol is oxidized to camphor with chromic or nitric acid dehydration with dilute acids yields camphene. Bomeol is readily esterified with acids, but on an industrial scale bornyl esters are prepared by other routes. For example, levorotatory bomeol is synthesized industrially from levorotatory pinenes by Wagner Meerwein rearrangement with dilute acid, followed by hydrolysis of the resulting esters [86]. 

Due to its characteristic penetrating, slightly minty odor, camphor is only used in perfuming industrial products. It is far more important as a plasticizer. 

Most synthetic camphor (43) is produced from camphene (13) made from a-pinene. The conversion to isobomyl acetate followed by saponification produces isobomeol (42) in good yield. Although chemical oxidations of isobomeol with sulfuric/nitric acid mixtures, chromic acid, and others have been developed, catalytic dehydrogenation methods are more suitable on an industrial scale. A copper chromite catalyst is usually used to dehydrogenate isobomeol to camphor (171). Dehydrogenation has also been performed over catalysts such as zinc, indium, gallium, and thallium (172). 

In 1855, the moldable features of collodion were exploited by the British inventor and chemist Alexander Parkes, who marketed the material as Parkesine. Combs, earrings, buttons, bracelets, billiard balls, and even false teeth were manufactured in his factories. Parkes chose to focus more on quantity than on quality, however. Because he used low-grade cotton and cheap but unsuitable solvents, many of his products lacked durability, which led to commercial failure. In 1870, John Hyatt, a young inventor from Albany, New York, discovered that collodions moldable properties were vastly improved by using camphor as a solvent. Hyatts brother Isaiah named this camphor-based nitrocellulose material celluloid. Because of its greater workability, celluloid became the plastic of choice for the manufacture of many household items. In addition, thin transparent films of celluloid made excellent supports for photosensitive emulsions, a boon to the photography industry and a first step in the development of motion pictures. 

HYATT, JOHN WESLEY (1837-1920). Hyatt is generally credited as being the father of the plastics industry. In 1869. he and his brother patented a mixture of cellulose nitrate and camphor which could be molded and hardened. Its lirsl commercial use was lor billiard balls. The TM Celluloid" was the first ever applied to a synthetic plastic ptoduci, it hammahtlity hazard limits its use. 

WALLACH, OTTO (1847-1931). German chemist who received the Nobel prize for chemistry in 1910 for recognition of his services to organic chemistry and the chemical industry by his pioneer work tn the field of alic.yclic compounds. His mentors were Hofmann and Wahler, and he worked at the University of Bonn under Kekule. He studied pharmacy and did work on terpenes. camphors, and essential oils. This was followed by research in aromatic oils, perfumes, and spices. His research of terpenes revealed their significance in sex hormones and vitamins. Ethereal oils and industrial uses were made possible by his work. 

Exercise 30-7 Camphor can be made on an industrial scale from a-pinene (turpentine) by the following reactions, some of which involve carbocation rearrangements of a type particularly prevalent in the bicyclic terpenes and the scourge of the earlier workers in the field trying to determine terpene structures. 

Camphor is of considerable importance technically, being used in the manufacture of celluloid and medicinal products. It is manufactured industrially from a-pinene, obtained from turpentine, by several processes (66-107) which differ mainly in detail. Synthetic camphor is usually obtained as the racemic modification. The formation of camphor involves the Wagner-Meerwein rearrangements, e.g. ... 

Company, makers of billiard balls. Previously, billiard balls had been made of ivory obtained from elephant tusks. Because of the devastation of the elephant population in Africa, however, ivory was becoming more difficult to obtain, and Phelan and Collender were looking for an inexpensive substitute. Hyatt discovered that substitute when he found a way (nearly identical to that of Parkes s) to dissolve nitrated cellulose in a mixture of alcohol, ether, and camphor. Hyatt called his product celluloid. Although he was not awarded the 10,000-prize, he was honored later in life for this and other discoveries with the Perkin Medal of Honor from the Society of Chemical Industry. 

Naphthalene, also known as tar camphor, and its alkyl derivatives, such as l-(2-propyl)naph-thalene (Figure 13.10), are important industrial chemicals. Used to make mothballs, naphthalene is a volatile white crystalline solid with a characteristic odor. Coal tar and petroleum are the major sources of naphthalene. Numerous industrial chemical derivatives are manufactured from it. The most important of these is phthalic anhydride (Figure 13.10), used to make phthalic acid plasticizers, which are discussed in Chapter 14. 

In addition, monoterpenes can provide some useful chiral reagents, such as the pinene-based organoborane reagents for chiral reductions, which have been reviewed extensively.42 Camphor-derived organic acids such as camphenesulfonic acid can be used for the resolution of racemic bases and is a common practice in industry (Chapter 6). 

Such an example is formed by the resolution of 4-hydroxyphenylglycine (Hpg) (Figure 7.8). Hpg cannot be resolved by (+)-camphor-10-sulfonic acid [(+)-Csa] and is, therefore, resolved on industrial scale with the more expensive and difficult to recycle (lR)-(+)-(endo,anti)-3-bromo-camphor-8-sulfonic acid. However, if racemic or (R)-phenylglycine (Phg) is added to the resolution of Hpg with (+)-Csa, co-resolution of both phenylglycines is possible. (R)-(-)-Hpg is incorporated in the crystal lattice of the (R)-(-)-Phg—(+)-Csa salt by partial replacement of (R)-(-)-Phg.27... 

The industrial change and expansion of the nineteenth century had many strands and among them attention was given to man-made replacements for resinous compositions and horn. Alexander Parkes, a prolific inventor and manufacturer, was involved closely with the search for commercial materials he showed articles of Parkesine (a cellulosic) at the Universal Exhibition in London in 1862. Further investigations and development led eventually in Britain, Germany, the USA, and elsewhere to the industry based on a cellulose nitrate plasticized with camphor and (somewhat later) to cellulose acetate and to other cellulose plastics (cellulose acetate butyrate, ethyl cellulose, etc.). 

P. C. Ashlee, The bogus butterfly collector camphor and the early plastics industry , Plastiquarian, Spring 1991, 7, 14—15. 

The hybrid (Lavandula intermedia) lavender shows an intermediate composition between the true and spike for all major components. Ester content is lower and camphor content higher than in the true lavender. It is generally considered to be an inferior essential oil as it was initially bred for the perfumery industry. However, it has been attributed with many therapeutic applications with rare contraindications when used correctly. 

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