Aldehydes 9- nonane

Fatty Decanal Ethyl nonanoate Heptyl alcohol Lauryl alcohol, aldehyde Nonanal Octanal l-Octanol Undecanal 10-Undecenal. 

An older paper <1971MI873> reported that ozonolysis of alkenes in the presence of tertiary amines resulted in the formation of aldehydes. A recent reinvestigation <20060L3199> has shown that amine oxides were responsible for this reductive ozonolysis . Indeed, pretreatment of the tertiary amines with ozone, giving rise to amine oxides, accounted for this phenomenon. A preparative method emerged, by treating the alkene (e.g., 1-decene) at 0 °C with a solution of 2% 03/02 in dichloromethane (2 equiv of ozone relative to the alkene) in the presence of an excess (about threefold molar excess) of A-methylmorpholine A-oxide, pyridine A-oxide, or l,4-diazabicyclo[2.2.2]octane A-oxide (DABCO A-oxide). Yields of aldehydes (nonanal in the above example) were 80-96%, and the excess of amine oxide ensured the absence of residual ozonide (Scheme 21). 

The spectrum of an unconjugafed aldehyde, nonanal, is shown in Figure 25.28, and fhe conjugated aldehyde, benzaldehyde, is shown in Figure 25.29. 

The components of cooked cauUflower Brassica oleracea var. botrytis) and broccoH B. 0 var. italica) aroma are similar to the aroma components of cabbage. Another important compound is the aldehyde nonanaL The typical odour of cauliflower comes from 3-(methylthio)propyl isothiocyanate (8-192), which is produced from glucosinolate glucoibervirin. The typical odour of broccoli is also due to the presence of 3-(methylsulfinyl)propyl isothiocyanate (8-193), which develops from glucosinolate glucoiberin. 

Erucamide is a particularly popular lubricant. Emcamide is also used, almost universally, as a slip agent in polyolefin closures. In this role, the emcamide functions to reduce the coefficient of fnction between the closure liner (or closure shell) and the container finish. Without such a slip agent, removal torques for such closures would be unacceptably high. Emcamide is widely used as a slip agent and lubricant because of its low cost and useful properties. Emcamide is a C22 fatty acid amide that possesses a double bond at the C13 position. Ozone, in particular, is extremely effective at selectively cleaving this double bond, creating the C9 aldehyde nonanal. ... 

For all studied reactions, 100% substrate conversion was obtained at contact times lower than 1 s at room temperature, that is, at a temperature much higher than commonly used for ozonolysis reactions. Under optimal conditions, the selectivity to triethyl phosphate (56) was higher than 98%. For nitrooctane (60), a selectivity of 80% was achieved while a selectivity of 100% toward the corresponding aldehyde nonanal (62) was observed in the ozonolysis of 1-decene (61). 

The silicon- and sulfur-substituted 9-allyl-9-borabicyclo[3.3.1]nonane 2 is similarly prepared via the hydroboration of l-phenylthio-l-trimethylsilyl-l,2-propadiene with 9-borabicy-clo[3.3.1]nonane36. The stereochemistry indicated for the allylborane is most likely the result of thermodynamic control, since this reagent should be unstable with respect to reversible 1,3-borotropic shifts. Products of the reactions of 2 and aldehydes are easily converted inlo 2-phenylthio-l,3-butadienes via acid- or base-catalyzed Peterson eliminations. 

In a second set of examples, it was shown that the stereoselectivity of the aldehyde allylborations of 9-[( T)-l-trimethylsilyl- or l-trimethylstannyl-2-butenyl]-9-borabicyclo[3.3.1]nonane is controlled to a significant extent by conversion to an ate complex by treatment with butyllithium, MT-butyllithium or pyridine19. 

In contrast to ordinary chiral aldehydes (having no ability to be chelated), the reaction of 9-allyl-9-borabicyclo[3.3.1]nonane(allyl-9-BBN) with the corresponding chiral imines 4 produces the isomer syn-6 either exclusively or predominantly (Cram selectivity Table 8)5,6. The very high 1,2-asymmetric induction is explained by a six-membered. chair-like transition state, in which the inline R group occupies an axial position due to the stereoelectronic effect of imines (R CH = NR). 

Unter milden Bedingungen reduzieren 9-Alkyl-9-bora-bicyclo[3.3.1]nonane Aldehyde zu Alkoholen3. Dabei muB die mit dem 9-[3-Methyl-butyl-(2)]-Derivat entstehende 9-Alkoxy-Verbindung durch Zugabe von 2-Amino-athanol zersetzt werden. 

Enantioselective reduction is not possible for aldehydes, since the products are primary alcohols in which the reduced carbon is not chiral, but deuterated aldehydes RCDO give a chiral product, and these have been reduced enantioselectively with B-(3-pinanyl)-9-borabicyclo[3.3.1]nonane (Alpine-Borane) with almost complete optical purity. ... 

The possibility of carrying out a multistep synthesis makes it possible to obtain P,B-containing derivatives from unstable intermediate a-hydroxyalkylphosphines. Thus, phenylphosphine, salicylic aldehyde, phenylboric acid anhydride, and triethylamine interact to give a bicyc-lic product—2,8,9-trioxa-1 -borata-4-phospha-6,7 -benzobicyclo [3,3,3] nonane (115) [Eq. (74)] (87IZV2118 89IZV946). In this case an aldehyde takes part in the reaction opening up new synthetic possibilities. 

The 10-57-5-hydridosiliconate ion 62 is known in association with lithium,323 tetrabutylammonium,101 and bis(phosphoranyl)iminium93 cations. It is synthesized by hydride addition to the 8-.S7-4-silane 63, which is derived from hexafluoroacetone.101 Benzaldehyde and related aryl aldehydes are reduced by solutions of 62 in dichloromethane at room temperature101 or in tetrahydrofuran at 0°96 within two hours. The alkyl aldehyde, 1-nonanal, is also reduced by 62 in tetrahydrofuran at O0.96 Good to excellent yields of the respective alcohols are obtained following hydrolytic workup. The reactions are not accelerated by addition of excess lithium chloride,96 but neutral 63 catalyzes the reaction, apparently through complexation of its silicon center with the carbonyl oxygen prior to delivery of hydride from 62.101... 

No attempt is made to provide comprehensive coverage of all the work carried out in these different media, but rather to give a flavour of the kind of systems for which the different approaches may be appropriate. In all the chapters, a more detailed discussion of the rhodium catalysed hydroformylation of 1-octene to nonanal, as a representative example of the synthesis of a long chain aldehyde with relatively low volatility, is provided [13, 14], This reaction has been chosen because ... 

The volatility of nonanal is sufficiently low to require unpractically high levels of recycle gas. It would not be possible to remove the aldehyde dimers and trimers of nonanal by gas recycle. Practically speaking, pentanal is at the border of aldehydes that may be isolated this way. Removal of the dimers and trimers of pentanal would be problematic. 

To produce 100 000 tonnes of nonanal per year (25% down time, 100% conversion of substrate, 80% selectivity to nonanal) requires a production rate from the reactors of 19 tonne h 1, so that each batch must be 6.3 tonnes. Assuming a 1 1 ratio by volume of fluorous solventdiquid substrate and a 75 % loading, each reactor must have a volume of 20 m3. If the distillation column were fully integrated into the system it would be required to handle 19 tonnes aldehyde h 1. An increase in selectivity to the linear product, which could be achieved using careful ligand design would reduce the reactor size by up to 25%. 

Fig. 11.4. Electron ionization mass spectrum of nonanal. Unlike the previous example (toluene, Fig. 11.3), this 9-carbon alkyl aldehyde displays extensive fragmentation and a very low abundance molecular ion at mlz 142. The extensive degree of fragmentation exhibited by many compounds under El conditions makes manual interpretation complex and tedious. Consequently, computerized searches of spectral libraries find extensive use in compound identification.

An interesting approach to carbobicyclic polyhydroxylated compounds was proposed by Jarosz.43 It was based on a Lewis acid transformation of sugar allyltins 82 into dieno-aldehydes 83 with the fi-geometry across the internal double bond exclusively. The Wittig-type reaction of 83 afforded a triene, which underwent cyclization under high pressure, providing derivatives of bicyclo[4.3.0]nonane 84. Alternatively, dienoaldehyde 83 was converted into the phosphonate 85, which afforded the bicyclo[4.4.0]-decene derivatives (86) upon reaction with an aldehyde and simultaneous cyclization of the resulting triene.43 (Fig. 29). 

The method outlined here competes well with the method developed earlier by Danheiser, et al.618 Its superiority is based on the fact that phenyl ester enolates give almost the same results as the S-phenyl thiolester enolates. However, handling the malodorous benzenethiol for the preparation of the active acid derivative and during workup of the p-lactone can be avoided. In addition, phenol is much cheaper than benzenethiol. The method is well suited for the preparation of p-lactones from symmetrical and unsymmetrical ketones. In addition to 3,3-dimethyM-oxaspiro[3.5]nonan-2-one, ( )-3-ethyl-1-oxaspiro[3.5]nonan-2-one and (3R, 4R )- and (3R, 4S )-4-isopropyl-4-methyl-3-octyl-2-oxetanone were prepared by this procedure in high yields (Notes 11 and 12). In the case of unsymmetrical ketones the less sterically crowded diasteroisomer is formed preferentially. With aldehydes as the carbonyl component the yields are unsatisfactory, because of the competitive formation of 1,3-dioxan-4-ones.6... 

Representatives of the subfamilies Omaliinae and Proteininae (omaliine group) possess an abdominal defensive gland reservoir that opens out between sternite 7 and 8 [ 120]. The multi-component mixtures contained in these glands are used for defence. In Omaliinae and Proteininae the secretion is characterized by mixtures of acids (e.g. 2-methylpropanoic acid, hexanoic acid, 2-octenoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, butyric acid, and tiglic acid), aldehydes (( )-2-hexenal, heptanal, octanal, nonanal), ketoaldehydes such as 4-oxo-2-hexenal 41 (Scheme 5), 6-methyl-5-hepten-2-one, alcohols (octanol, ( )-2-hexen-l-ol, 2-methylbutan-l-ol), alkanes (nonadecane), esters (2-methylbutyl tiglate 42, various propanoates, 2-hexenyl 3-methylbutanoate, 2-methylbutyl 2-methylbutanoate, octanoates,butanoates), and aromatic compounds (e.g. 2-phenethyl 3-methylbutanoate 43). Unusual compounds are 2-... 

Ehnholt et al.8 produced a broad paper covering raw materials, and in-process and final-product measurements. While the uses are primarily in the food industry, the rancidity was often caused by microorganisms. One case involved off-flavor materials being produced in drying and curing ovens. Marker compounds (concomitant) released during the breakdown process (of saturated and unsaturated compounds) were nonenal, decenal, and octenone for the unsaturated aldehydes and ketones, and nonanal, decanal, and octanone for the saturated molecules. A 10-m folded path gas cell was used with an FT-IR for measurements down to 1 Lig/m3. 

Recently, we reported that the rhodium/BIPHEPHOS-catalyzed hydroformylation of trans-4-octene (Scheme 6) provides an interesting approach for the synthesis of n-nonanal [23]. In this context trans-4-octene can also be seen as a model substance for hydroformylation of internally unsaturated fatty acid esters. This could open up access to the use of renewable resources for the synthesis of valuable n-aldehydes. 

With increasing concentration of methylated /1-cyclodextrin the selectivity to n-nonanal increases from 64% to 72%, while the conversion of the olefin is constantly as high as 97%. Obviously the addition of the methylated /i-cyclodextrin has only a moderate influence on the isomerizing hydroformylation of trans-4-octene to n-nonanal. The addition of only 0.2 mol.-% of methylated /3-cyclodextrin lowers the isomerization rate which results in the formation of slightly more branched aldehydes. In pharmacy j6-cyclodextrins are established as solvation mediators between polar and less polar solvents. This is one possible explanation for the rise in selectivity to n-nonanal with an increasing j6-cyclodextrin concentration. At higher con-... 

The additional presence of 1-nonanal serves as model for the formation of the linear hydroformylation product of 1-octene and its influence on catalyst solubility. The aldehyde lowers the complex solubility further (Fig. 19) as compared to the mixture with olefln only. 

Both male and female coyotes, C. latrans, are attracted to volatile aldehydes from sheep liver and estrous urine of female coyotes. The most active compoimds were octanal, nonanal, decanal, and imdecanal. The aldehydes released sniffing and rub-rolling, but little lick-chewing and biting. Therefore, these compoimds are better suited to attract coyotes to traps than to toxicant-delivery systems that rely on the latter behaviors (Scrivnereta/., 1984). 

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