Methylene, detection

Measurement of Unsaturation. The presence of double bonds in a fatty acid side chain can be detected chemically or through use of instmmentation. Iodine value (IV) (74) is a measure of extent of the reaction of iodine with double bonds the higher the IV, the more unsaturated the oil. IV may also be calculated from fatty acid composition. The cis—trans configuration of double bonds may be deterrnined by infrared (59) or nmr spectroscopy. Naturally occurring oils have methylene-intermpted double bonds that do not absorb in the uv however, conjugated dienes maybe deterrnined in an appropriate solvent at 233 nm. 

Health and Safety. Remover formulas that are nonflammable may be used in any area that provides adequate ventilation. Most manufacturers recommend a use environment of 50—100 parts per million (ppm) time weighted average (TWA). The environment can be monitored with passive detection badges or by active air sampling and charcoal absorption tube analysis. The vapor of methylene chloride produces hydrogen chloride and phosgene gas when burned. Methylene chloride-type removers should not be used in the presence of an open flame or other heat sources such as kerosene heaters (8). 

Because of the time and expense involved, biological assays are used primarily for research purposes. The first chemical method for assaying L-ascorbic acid was the titration with 2,6-dichlorophenolindophenol solution (76). This method is not appHcable in the presence of a variety of interfering substances, eg, reduced metal ions, sulfites, tannins, or colored dyes. This 2,6-dichlorophenolindophenol method and other chemical and physiochemical methods are based on the reducing character of L-ascorbic acid (77). Colorimetric reactions with metal ions as weU as other redox systems, eg, potassium hexacyanoferrate(III), methylene blue, chloramine, etc, have been used for the assay, but they are unspecific because of interferences from a large number of reducing substances contained in foods and natural products (78). These methods have been used extensively in fish research (79). A specific photometric method for the assay of vitamin C in biological samples is based on the oxidation of ascorbic acid to dehydroascorbic acid with 2,4-dinitrophenylhydrazine (80). In the microfluorometric method, ascorbic acid is oxidized to dehydroascorbic acid in the presence of charcoal. The oxidized form is reacted with o-phenylenediamine to produce a fluorescent compound that is detected with an excitation maximum of ca 350 nm and an emission maximum of ca 430 nm (81). 

The avermectins also possess a number of aUyflc positions that are susceptible to oxidative modification. In particular the 8a-methylene group, which is both aUyflc and alpha to an ether oxygen, is susceptible to radical oxidation. The primary product is the 8a-hydroperoxide, which has been isolated occasionally as an impurity of an avermectin B reaction (such as the catalytic hydrogenation of avermectin B with Wilkinson s rhodium chloride-triphenylphosphine catalyst to obtain ivermectin). An 8a-hydroxy derivative can also be detected occasionally as a metaboUte (42) or as an impurity arising presumably by air oxidation. An 8a-oxo-derivative can be obtained by oxidizing 5-0-protected avermectins with pyridinium dichromate (43). This also can arise by treating the 8a-hydroperoxide with base. 

Figure 2.15. HC HSQC experiment (contour plot) of a-pinene [ CDCI3, 5 % v/v, 25 °C, 125 MHz for C, 500 MHz for h, 4 scans, 256 experiments]. This experiment gives the same information as Fig. 2.14 within 8 minutes instead of two hours required for the CH-COSY in Fig. 2.14 due to higher sensitivity because of proton detection and stronger magnetic field. Deviations of proton shifts from those in Fig. 2.14 arise from the change of the solvent. The methylene protons collapsing in Fig. 2.14 at Sh = 2.19 (200 MHz) display in this experiment an AB system with = 2.17 and Sg = 2.21 (500 MHz)...

Aqueous solutions of dyes ean also be employed instead of water. In the ease of hydrophilic dyes such as methylene blue or patent fast blue the transparent background of the TLC/HPTLC plate is stained blue. Pale spots occur where there are nonwetted zones. Dauble [89] detected anion-active detergents in this way on silica gel layers as pale zones on a blue background with palatine fast blue GGN... 

A reagent which is primarily of interest as a means of converting alcohols into fluorides has been used to dehydrate C-11 alcohols in high yields. 1 la-Alcohols dehydrate rapidly with 2-chloro-l-diethylamino-l,l,2-trifluoro-ethane reagent at low temperature, while 11 j5-alcohols require refluxing methylene chloride. Traces of fluoro compounds have been detected in the products. 

J. Staniewski, H. G. Janssen, J. A. Rijks and C. A. Cramers, Inti oduction of large volumes of methylene cWoi ide in capillaiy GC with electron capture detection , in... 

Figure 12.18 LC-SFC analysis of mono- and di-laurates of poly (ethylene glycol) ( = 10) in a surfactant sample (a) normal phase HPLC trace (b) chromatogram obtained without prior fractionation (c) chromatogram of fraction 1 (FI) (d) chromatogram of fraction 2 (F2). LC conditions column (20 cm X 0.25 cm i.d.) packed with Shimpak diol mobile phase, w-hexane/methylene chloride/ethanol (75/25/1) flow rate, 4 p.L/min UV detection at 220 nm. SFC conditions fused-silica capillary column (15 m X 0.1 mm i.d.) with OV-17 (0.25 p.m film thickness) Pressure-programmed at a rate of 10 atm/min from 80 atm to 150 atm, and then at arate of 5 atm/min FID detection. Reprinted with permission from Ref. (23).

Shimizu and Ohtsu [69] have proposed a chemical method to determine head-to-head structures in PVC. Mitani et al. [70] found 2.5-7.0 head-to-head structures per 1,000 monomer units, increasing with the polymerization temperature. It has not been possible to detect internal head-to-head structure by C-NMR spectroscopy with the detection limit of 2 per 1,000 monomer units [71]. Starnes et al. [71] found evidence for the absence of neighboring methylene groups by C-NMR spectroscopy. However, the proposed reaiTangement of head-to-head units at the radical chain ends resulting in chloromethyl branches [Eq. (6)] would partially explain their consumption during polymerization and their absence in the final product. 

Subsequently, it was shown that ring expansion of these bicyclic systems is followed by a series of proton shifts involving the isomeric 2- and 5-methyleneazepines. The former were detected spectroscopically ( H NMR) whereas, in some cases, the latter were isolated.127 For example, 4,6-dimethyl-2-methylene-3-phenyl-3-azabicyclo[4.1,0]hept-4-ene-l, 5-dicarbonitrile (28), on treatment with hydrochloric acid in chloroform, yields the 4-methyleneazepine 29, which on prolonged heating with acid is converted into the 1//-azepine 30. 

Isolation of Citronellal and Citral. At the close of each experiment (7 to 10 days), the nests were frozen intact. Groups of 200 workers were placed in a micro-Soxhlet apparatus and extracted for 8 hours with methylene chloride. A few milligrams of carrier citronellal and citral were added and the mixture was applied to a thin-layer chromatoplate (silica gel G) which was developed with hexane-ethyl acetate (92 to 8) to separate citronellal and citral (3). The aldehydes were detected by spraying with a solution of 2, 4-dini-trophenylhydrazine in tetrahydrofuran (20) and the citronellal and citral peaks were scraped off and allowed to react with excess dinitro-phenylhydrazine reagent for a further 12 hours. 

It is hence easy to detect by this technique different polymorphic forms having different chain conformations. For instance, the a or p forms of s-PS (tram-planar chain conformations) present only a single methylene resonance at 48.1 ppm (vs.TMS), while the y form (helical conformation) presents two methylene resonances at 37.3 and 47.3 ppm (Fig. 20) [114]. 

Of all the solvents, THF gave the greatest amount of axial conformer for sulfoxides 166, 167 and 168. For 167, the axial conformer was not detected in methylene chloride, but was present to the extent of 20% in THF. For 168, the amount of axial conformer increased from 75 to over 95%. 

Olah and coworkers56 found that treatment of dialkyl, arylalkyl and diaryl sulphides with nitronium hexafluorophosphate (or tetrafluoroborate) 32 at —78° in methylene chloride resulted in the formation of sulphoxides in moderate to high yields (Table 3). In the oxidation of diphenyl sulphide which affords diphenyl sulphoxide in 95% yield, small amounts of the ring nitration products (o- and p-nitrophenyl phenyl sulphides) were formed. However, diphenyl sulphone and nitrophenyl phenyl sulphoxide were not detected among the reaction products. 

Other detection methods are based on optical transmittance [228-231], Alcohol sulfates have been determined by spectrophotometric titration with barium chloride in aqueous acetone at pH 3 and an indicator [232] or by titration with Septonex (carbethoxypentadecyltrimethylammonium bromide) and neutral red as indicator at pH 8.2-8.4 and 540 nm [233]. In a modified two-phase back-titration method, the anionic surfactant solution is treated with hyamine solution, methylene blue, and chloroform and then titrated with standard sodium dodecyl sulfate. The chloroform passing through a porous PTFE membrane is circulated through a spectrometer and the surfactant is analyzed by determining the absorbance at 655 nm [234]. The use of a stirred titration vessel combined with spectrophotometric measurement has also been suggested [235]. Alternative endpoint detections are based on physical methods, such as stalag-mometry [236] and nonfaradaic potentiometry [237]. 

Two-dimensional thin-layer chromatography. This method is used to verify the presence of terminal 5-sultones, terminal unsaturated y-sultone, and terminal 2-chloro-y-sultone, if they are detected in the gas chromatographic determination. After extraction of the neutral oil from the AOS sample, the neutral oil is made up volumetrically to at least a 10% solution in hexane. Of this solution 3 pi is spotted onto a silica gel TLC plate together with standard sultones. It is twice developed with 2-propyl ether and then after turning the plate 90° twice developed with 60/40 n-butyl chloride/methylene chloride. The... 

Another approach to a donor adduct of the methylene phosphenium cation is the addition of a phosphonium cation to the phosphaalkyne. The reaction of the protic cation [HPPhal + lCFaSOa] with CjoHuCP produced a white powder which was identified as the P-phosphonio-substituted phosphaalkene [74]. Alternatively to the elimination reaction the phosphaalkynes were protonated. C-protonation of adamantylphosphaacetylene and ferf-butylphosphaacetylene occurred in superacid media under formation of phosphavinyl cations. From these spirocyclic betaines by reaction of l-Ad-C=P (Ad = adamantyl) withB(OTf)3 a phosphavinyl cation could be detected [75]. 

The comparatively small size of the simplest carbene (methylene) ensures that it has a definite mobility in frozen inert matrices, which leads to the formation of dimerization products under these conditions. It became possible only in 1981 to detect in the spectra of the diazomethane photolysis products bands at 1115 cm (Ar matrix) and 1109 cm (Xe matrix) which were attributed to the deformation vibration of methylene in its ground triplet state (Lee and Pimentel, 1981). 

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