Photo‐Nitrosierung und ‐Oximierung gesättigter Kohlenwasserstoffe

Metzger, Hor̊st; Fries, Dorla; Heuschkel, Ulrich; Witte, Kristin; Waidelich, E.; Schmid, Gerd

doi:10.1002/ange.19590710702

Cited by 10 publications

(3 citation statements)

References 41 publications

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“…A major drawback of this design is that stirring is usually inefficient, with the result that different molecules experience different irradiation times within the reactor. Nevertheless, several photochemical reactions have successfully been run at industrial scales over the past 100 years, several of which are still in use today. , An example of which is the irradiation of cyclohexane with NOCl and HCl to produce caprolactam, which is used in the manufacture of nylon . The production of 1α-hydroxy-vitamin D 3 , and several other related compounds involves a photochemical isomerization step.…”

Section: Introductionmentioning

confidence: 99%

“…29,30 An example of which is the irradiation of cyclohexane with NOCl and HCl to produce caprolactam, which is used in the manufacture of nylon. 31 The production of 1α-hydroxy-vitamin D 3 32,33 pounds involves a photochemical isomerization step. Singlet oxygen has also been used at scale, as shown in the manufacture of rose oxide, a compound important in the fragrance industry, 34 and in the semisynthetic production of artemisinin developed by Sanofi and recently described in this journal.…”

Section: ■ Introductionmentioning

confidence: 99%

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A Simple and Versatile Reactor for Photochemistry

Clark¹,

Lee²,

Pickering³

et al. 2016

Org. Process Res. Dev.

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Safety warning: Any experiment involving flammable organic solvents and air or pure oxygen is potentially hazardous, especially when partially contained, as is the case of the flask of our reactor. We took the following precautions and encountered no problems but we stress the need for readers to make safety assessments for their own experiments as peripheral circumstances may be different from ours. All experiments were carried out in a fume hood or ventilated enclosure with adequate ventilation and the front lowered. Any obvious sources of ignition were removed. Oxygen was fed from a cylinder fitted with a compliant regulator and was delivered at a maintained pressure of 1 bar using a mass flow controller compatible with oxygen. The equipment was maintained and cleaned free of grease at all times to prevent any incompatibilities with oxygen. Temperatures were kept at ambient. When working above the solvent flash point and LOC, care must be taken to ensure that all possible risks have been considered. Appropriate safeguards and suitable safety measures must be implemented.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

A Simple and Versatile Reactor for Photochemistry

Clark¹,

Lee²,

Pickering³

et al. 2016

Org. Process Res. Dev.

View full text Add to dashboard Cite

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“…Photochemistry has also made the transition to industrial-scale synthesis. For example the Toray process [8–10] for the synthesis of caprolactam, used to manufacture Nylon 6, proceeds by irradiation of cyclohexane with NOCl and HCl, and is carried out in dedicated plants producing >100,000 tons per annum.…”

Section: Introductionmentioning

confidence: 99%

Flow photochemistry: Old light through new windows

Knowles

Elliott²,

Booker‐Milburn³

2012

Beilstein J. Org. Chem.

374

190

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SummarySynthetic photochemistry carried out in classic batch reactors has, for over half a century, proved to be a powerful but under-utilised technique in general organic synthesis. Recent developments in flow photochemistry have the potential to allow this technique to be applied in a more mainstream setting. This review highlights the use of flow reactors in organic photochemistry, allowing a comparison of the various reactor types to be made.

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Pyrrolidone, Capryllactam and Laurolactam as new Monomers for Polyamide Fibers

Dachs¹,

Schwartz²

1962

Angew. Chem. Int. Ed. Engl.

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carriers promcite disperse dyeability of the nytril fiber at 100 "C is not completely understood but may involve an increase in both affinity and diffusion rate. Typical carriers such as methyl p-toluate and o-phenylphenol combine strongly with many disperse dyes and, when inside the fiber, may act as temporary dye sites. In addition, these compounds are strong solvating agents for sites of dipole interaction and thus may be expected to lower the wet glass transition temperature to some degree, resulting in improved diffusion rate.While a discussion of the properties and performance of fabrics made from Darvan@ nytril fiber is beyond the scope of this paper, it should be stated that the postulates concerning performance which have been derived from fiber properties have been borne out by extensive fabric trials. Soft texture, resilience, shape retention throughout wearing and laundering, and a high degree of resistance to wrinkling have been experienced with such fabrics. Relationship of Properties to Fiber StructureThe outstanding features of softness, elasticity, resilience, and resistance to moisture displayed by the nytril fiber may be traced directly to its chemical constitution and fine structure. The relatively low degree of orientation and lateral order, together with the large number of points of intermolecular attraction provided by the polarized cyano groups, result in a strong, flexible network of molecules. This, in turn, is responsible for the soft, resilient texture of the fiber. The strength of the dipole-pair intermolecular bond, which is of the order of 8-10 kcal./mol. for alkyl cyanides [7] and which is probably much higher for vinylidene cyanide, owing to resonance, together with the large number of such bonds, probably accounts for the high degree of elastic recovery, the good wrinkle resistance, and the relative insensitivity to hot water. These same factors, of course, would tend to increase the wet glass transition temperature and reduce the dye diffusion rate. The industrial production of capryllactam (I-azacyclononan-2-one) and of laurolactam (I-azacyclotridecan-2-one) starts with cyclization of acetylene or butadiene to give cyclooctatetraene or cyclooctadiene, or cyclization of butadiene to give cyclododecatriene. Further steps are: oxidation of the cyclic hydrocarbon to the ketone, formation of the oxime, and rearrangement of the latter with sulfuric acid. Pyrrolidone can be prepared from acetylene and formaldehyde by way of butyrolactone. The behavior of the lactams during polycondensation is described and the properties of the resulting fibers are compared with those of the known polyamide fibers. It is impossible to give individual credit for specific aspects

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Photo‐Nitrosierung und ‐Oximierung gesättigter Kohlenwasserstoffe

Cited by 10 publications

References 41 publications

A Simple and Versatile Reactor for Photochemistry

A Simple and Versatile Reactor for Photochemistry

Flow photochemistry: Old light through new windows

Pyrrolidone, Capryllactam and Laurolactam as new Monomers for Polyamide Fibers

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