Amines, naphthyl, from

The isocyanates (9) were transformed into amino derivatives by standard reactions. Acid-sensitive aminocyclopropanes were obtained preferentially from benzyr ) -naphthyl or trifluorethyl-urethanes which were cleaved by hydrogen, EtSNa/DMF or alkaline hydrolysis. The hydrazinolysis of phthalimido compounds obtained from the urethane and phthalic anhydride also was useful Trimethylsilylethanol proved to be advantageous for the isocyanate-amine conversion the resulting urethanes gave amines upon addition of Bu4N p- 161 (e.g. synthesis of amine (21) from truns-crysanthemic acid via isocyanate (20) S equation 3). Contrarily to... 

In the laboratory, other metals, like iron, zinc, etc., in connection with an add, are only rarely used in the place of tin or stannous chloride, for the. reduction of nitro-compounds. On the large scale, iron, owing to its cheapness, is used in the preparation of bases like aniline, toluidine, a-naphthyl amine, etc., from the corresponding nitrocompounds. By the use of iron and hydrochloric acid, the reduction should theoretically take place in accordance with the following equation ... 

Amination of aromatic nitro compounds often occurs smoothly and directly also on condensation with hydroxylamine in alkaline solution, the amino group normally entering ortho or para to the nitro group. One nitro group activates naphthalene derivatives sufficiently, but in the benzene series two are necessary to induce this reaction. 2-Nitro-l-naphthylamine was thus obtained (80%) from 2-nitronaphthalene,400 and 4-nitro-l-naphthyl-amine (60%) from 1-nitronaphthylamine.401 The amino group also enters the nitrated ring of quinoline derivatives. 

Physical properties. Majority are liquids except p toluidine and 1- and 2-naphthylamine. All are colourless when pure, but rapidly darken on exposure to air and light. All are very sparingly soluble in water, but dissolve readily in dilute mineral acids (except the naphthyl-amines, which are only moderately soluble in adds). They form colourless crystalline salts e.g., CjHjNH2,HCl) which are soluble in water these aqueous solutions usually have an add reaction owing to hydrolysis, and give the reactions of both the amine and the acid from which they are derived. Addition of alkali to the acid solution liberates the amine. 

R NHa + C.HjNCO = RNH CO NHC,Hj Traces of water will contaminate the product with diphenylurea (p. 336) if the solution is boiled hence the need for anhydrous conditions. i-Naphthylisocyanate reacts more slowly with water, and the i-naphthyl-urea derivative can often be obtained using a cold aqueous solution of an aliphatic amine it is particularly necessary in such cases to purify the product by recrystallisation from, or extraction with, boiling petroleum, leaving behind any insoluble di i-naphthylurea. Note that the amine must also be free from alcohols (p. 335) and phenols (p. 337). 

Oxidation of LLDPE starts at temperatures above 150°C. This reaction produces hydroxyl and carboxyl groups in polymer molecules as well as low molecular weight compounds such as water, aldehydes, ketones, and alcohols. Oxidation reactions can occur during LLDPE pelletization and processing to protect molten resins from oxygen attack during these operations, antioxidants (radical inhibitors) must be used. These antioxidants (qv) are added to LLDPE resins in concentrations of 0.1—0.5 wt %, and maybe naphthyl amines or phenylenediamines, substituted phenols, quinones, and alkyl phosphites (4), although inhibitors based on hindered phenols are preferred. 

Condensation of an o-nitrosophenol with an amine hydrochloride in acetic acid (10) Nile Blue [2381-85-3] is formed from the hydrochloride of 1-naphthyl amine. 

Determination of ethyleneamines in air can be accomplished by absorbing the amines on NITC (1-naphthyl isothiocyanate) treated XAD-2 resin, then desorbing the derivative from the treated tubes and quantifying the amount using high performance Hquid chromatography (hplc). Sensitivity is reported as 0.37 and 0.016 mg/m for EDA and DETA, respectively, pet sample (153,154). 

The method described is rather general. With appropriate modifications for the purification of the aim ne the method yields a- -tolylethylamine (72 per cent), a-p-chlorophenylethyl-amine (65 per cent), a -/)-bromophenylethylamine (63 per cent), a- -xenylethylamine (66 per cent), and a-(/9-naphthyl)-ethylamine (84 per cent) from the corresponding ketones. 

Chiral imines derived from 1-phenylethanone and (I. Sj-exo-l, 7,7-trimethyIbicyclo-[2.2.1]heptan-2-amine [(S)-isobornylamine], (.S>1-phenylethanamine or (R)-l-(1-naphthyl) ethanamine are transformed into the corresponding (vinylamino)dichloroboranes (e.g., 3) by treatment with trichloroborane and triethylamine in dichloromethane. Reaction of the chiral boron azaenolates with aromatic aldehydes at 25 "C, and subsequent acidic hydrolysis, furnishes aldol adducts with enantiomeric excesses in the range of 2.5 to 47.7%. Significantly lower asymmetric inductions are obtained from additions of the corresponding lithium and magnesium azaenolates. Best results arc achieved using (.S )-isobornylamine as the chiral auxiliary 3. 

Sl-a-Phenylethylaminc (2a 94% ee) and (.S)-2-heptylamine (2b 82% ec) were synthesized from enantiomerically pure nitrones 1 a and 1 b (33-39% overall yield). The enantiomeric purity of the amines was determined by HPLC analysis of their 3,5-dinitrobenzamidines on a D-naphthyl alanine column,... 

Dinitronaphthalene (Delta-dinitronaphtha-lenet 1,6-DNN). Crysts from acet ac, mp 166-67°, bp at 10mm 235°, 360° with decompn (Refs 2 31) CA Registry No 60746-5. It is prepd by the nitration of 2-nitronaphtha- ene with nitric ac/sulfuric ac in hot acet ac (Ref 21) by diazotization of 5-nitro-2-naphthyl-amine followed by treatment of the diazonium salt with Na cobaltinitrite, yield 40% (Ref 36) or by removal of the amino group from 1,6-dinitro-2-naphthylamine by diazotization followed by redn (Ref 17). The temp of expin is 492°(Refl7)... 

Benzodiazepin-2-ones are converted efficiently into the 3-amino derivatives by reaction with triisopropylbenzenesulfonyl (trisyl) azide followed by reduction <96TL6685>. Imines from these amines undergo thermal or lithium catalysed cycloaddition to dipolarophiles to yield 3-spiro-pyrrolidine derivatives <96T13455>. Thus, treatment of the imine 50 (R = naphthyl) with LiBr/DBU in the presence of methyl acrylate affords 51 in high yield. 

If it is heated alone at 160°, ammonia comes off rapidly, the aniline and phenylisocyanate may be detected by their odor but they combine in large part to form 5ym.-diphenyliu ea which crystallizes out from the hot liquid, and cyanic acid may be detected by means of silver nitrate in the water with which the apparatus is washed out after the experiment. When an aqueous solution of phenylurea is distilled, aniline may be detected in the distillate and 5ym.-diphenylurea crystallizes from the boiling liquid. By heating urea with the amine or with its hydrochloride at 160°, or by refluxing urea in aqueous solution with the amine or its hydrochloride, we have prepared sym.-6i-o- and />-tolyl, di-a- andjS-naphthyl, dimethyl, di-w-butyl, di-w- and i5 -amyl and dibenzylureas in satisfactory yield. 

In an acetone extract from a neoprene/SBR hose compound, Lattimer et al. [92] distinguished dioctylph-thalate (m/z 390), di(r-octyl)diphenylamine (m/z 393), 1,3,5-tris(3,5-di-f-butyl-4-hydroxybenzyl)-isocyanurate m/z 783), hydrocarbon oil and a paraffin wax (numerous molecular ions in the m/z range of 200-500) by means of FD-MS. Since cross-linked rubbers are insoluble, more complex extraction procedures must be carried out (Chapter 2). The method of Dinsmore and Smith [257], or a modification thereof, is normally used. Mass spectrometry (and other analytical techniques) is then used to characterise the various rubber fractions. The mass-spectral identification of numerous antioxidants (hindered phenols and aromatic amines, e.g. phenyl-/ -naphthyl-amine, 6-dodecyl-2,2,4-trimethyl-l,2-dihydroquinoline, butylated bisphenol-A, HPPD, poly-TMDQ, di-(t-octyl)diphenylamine) in rubber extracts by means of direct probe EI-MS with programmed heating, has been reported [252]. The main problem reported consisted of the numerous ions arising from hydrocarbon oil in the recipe. In older work, mass spectrometry has been used to qualitatively identify volatile AOs in sheet samples of SBR and rubber-type vulcanisates after extraction of the polymer with acetone [51,246]. 

Aryl alcohol oxidase from the ligninolytic fungus Pleurotus eryngii had a strong preference for benzylic and allylic alcohols, showing activity on phenyl-substituted benzyl, cinnamyl, naphthyl and 2,4-hexadien-l-ol [103,104]. Another aryl alcohol oxidase, vanillyl alcohol oxidase (VAO) from the ascomycete Penicillium simplicissimum catalyzed the oxidation of vanillyl alcohol and the demethylation of 4-(methoxymethyl)phenol to vanillin and 4-hydro-xybenzaldehyde. In addition, VAO also catalyzed deamination of vanillyl amine to vanillin, and hydroxylation and dehydrogenation of 4-alkylphenols. For the oxidation of 4-alkylphenol, the ratio between the alcohol and alkene product depended on the length and bulkiness of the alkyl side-chain [105,106]. 4-Ethylphenol and 4-propylphenol, were mainly converted to (R)-l-(4 -hydroxyphenyl) alcohols, whereas medium-chain 4-alkylphenols such as 4-butylphenol were converted to l-(4 -hydroxyphenyl)alkenes. 

Hexacoordinate spirocyclic phosphorus compounds have been prepared in which the spirocyclic system involves dative bonds from the dimethylamino-l-naphthyl ligand <1996JOM173, 1997PS181, 1999IC1336> for example 113 (Equation 29). Spirophosphoranide 122 was synthesized by deprotonation of the acid precursor 121 with triethyl-amine (Equation 30) <2001IC6229, 2002IC1645>. 

Van den Berg [131] used this technique to determine nanomolar levels of nitrate in seawater. Samples of seawater from the Menai Straits were filtered and nitrite present reacted with sulfanilamide and naphthyl-amine at pH 2.5. The pH was then adjusted to 8.4 with borate buffer, the solution de-aerated, and then subjected to absorptive cathodic stripping voltammetry. The concentration of dye was linearly related to the height of the reduction peak in the range 0.3-200 nM nitrate. The optimal concentrations of sulfanilamide and naphthyl-amine were 2 mM and 0.1 mM, respectively, at pH 2.5. The standard deviation of a determination of 4 nM nitrite was 2%. The detection was 0.3 nM for an adsorption time of 60 sec. The sensitivity of the method in seawater was the same as in fresh water. 

The rare example of synergistic action of a binary mixture of 1-naphthyl-A-phcnylaminc and phenol (1-naphthol, 2-(l,l-dimethylethyl)hydroquinone) on the initiated oxidation of cholesterol esters was evidenced by Vardanyan [34]. The mixture of two antioxidants was proved to terminate more chains than both inhibitors can do separately ( > /[xj). For example, 1-naphtol in a concentration of 5 x 10 5 mol L-1 creates the induction period t=170s, 1 -naphthyl-A-phenylamine in a concentration of 1.0 x 10-4 mol L 1 creates the induction period t = 400s, and together both antioxidants create the induction period r = 770 s (oxidation of ester of pelargonic acid cholesterol at 7= 348 K with AIBN as initiator). Hence, the ratio fs/ZfjXi was found equal to 2.78. The formation of an efficient intermediate inhibitor as a result of interaction of intermediate free radicals formed from phenol and amine was postulated. This inhibitor was proved to be produced by the interaction of oxidation products of phenol and amine. 

The high catalyst loading typical of sol gel entrapped catalysts ensures a desirably high substrate/catalyst (S/C) ratio as the major part of the heterogeneous catalyst weight originates from the silicate matrix. For example, in a preparative-scale reaction of the alcohol raol-(2-naphthyl)-ethanol only 250 mg of sol-gel CaLB immobilizate could be used per 10 g of substrate. For comparison, all this makes the process based on sol-gel immobilized lipase very competitive with the commercial BASF process using lipase immobilized on Amberlite to produce the amine at a scale of 1000 tons per year. 

An easily accessible DA CSP derived from L-A-(2-naphthyl)valine (80) was used to separate appropriately derivatized amines, amino alcohols and thiols, derivatization consisting of N-, O- and 5-acylation with 3,5-dinitrobenzoyl chloride or 3,5-dinitrophenyl... 

For example22, separation of enantiomers of chiral molecules (amines, alcohols, amino acids) is possible by using a chiral stationary phase obtained from 10-undecenyl esters of Af-(2-naphthyl)-a-amino acids (4). Amino groups are of fundamental importance in this practical application of the chiral recognition. 

A variety of benzylamines 124 (R1 = Ph, Ar, 2-naphthyl, or 3- or 4-pyridyl etc NR22 = piperidin-l-yl or morpholin-4-yl) was obtained from benzotriazole, an aldehyde R CIIO and an amine HNR22 and subsequent reduction of the products with sodium borohydride (equation 44)125. 

R)-(+)-1-(1-Naphthyl)ethylamine is purchased from Aldrich Chemical Company, Inc. The reagent is purified by recrystallization of its tartaric acid salt three times from 94% aqueous methanol followed by treatment with base and distillation of the free amine. 

From photoreduction (> 280 nm) in diethylamine, low yields of 1-naphthyl-amine and the corresponding azo- and azoxy compounds have been obtained Photolysis (366 nm) in acidified 50% aqueous 2-propanol at varied HCl-concentrations results in remarkable enhancement of photoreduction compared to neutral 2-propanol. The highest disappearance quantum yield measured was 1.28 X 10 2 for 6 M HCl 4-chloro-l-naphthylamine is formed as main product 74.75). 

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