1,5-Naphthalene ester

Synonyms/Trade Names 1,5-Diisocyanatonaphthalene 1,5-Naphthalene diisocyanate 1,5-Naphthalene ester of isocyanic acid NDI ... 

Suggest at least two mechanisms for the formation of the naphthalene ester. 

FIGURE 15 The Rebek group s self-replicating system a naphthalene ester and a heterocyclic amine self-assemble via hydrogen bonding and 7t-7t stacking (53,54). (For a color version of this figure, the reader is referred to the Web version of this chapter.)... 

Naphthalene is formed from the N-nitrosoimine 69 at 45°C via a cheletropic reaction.62 In some instances benzyne induces deamination of naphthalen-l,4-imines, since naphthalene was a by-product of the reaction of benzyne with N-methylpyrrole,63 and the naphthalene ester 79 is produced by reaction of 78 with benzyne.68 An indication of the fate of the extruded nitrogen-containing fragment is provided by the identification of N-methylcarbazole as a product of the reaction of 82 with benzyne. 

If, however, 6 -acetyl-3,4-dihydropapaverine methiodide is treated with an excess of ethyl chloroformate and base, the product is the naphthalene ester... 

Two equivalents of allenes and two equivalents of acetylene dicarboxylate, in the presence of diazadiene-stabilized palladacyclopentadiene as the catalyst, afford high yields of the hydronaphthalene intermediates 105, which are readily oxidized with DDQ to give tetrasubstituted-naphthalene esters 106 useful for the preparation of polyimides. ... 

Asymmetric hydrogenolysis of allylic esters with formic acid with satisfactory ee was observed[387], Geranyl methyl carbonate (594) was reduced to 570 with formic acid using l,8-bis(dimethylamino)naphthalene as a base and MOP-Phen as the best chiral ligand, achieving 85% ee. 

NaOH solution is added dropwise to an aqueous suspension of this ester at 40—70°C over 1 h and the reaction mixture kept for 2 h to give 86.6% DHNA of 98.7% purity (74), which is then esterified with (CgH O) to obtain PDNA. The esterification process is dramatically improved by adding a small amount of inorganic or organic acid, preferably methanesulfonic acid, benzene sulfonic acid, or naphthalene sulfonic acid subsequent isolation and crystallisation gives a pure product (75). 

AIkyl-Ai,A/-diaLkyl-l-naphthalenecarboxamides are useful herbicides (86) and the 2,2-dimeth5lhydra2ide of 1-naphthalenecarboxyhc acid has been patented as a plant growth regulator (87). 2-Propynyl-2-naphthalenecarboxylate [53548-27-9] and similar esters are insecticides (88). 1-Naphthaleneacetic acid, the plant growth regulator, has been prepared from naphthalene, concentrated HCl, and paraformaldehyde without isolation of intermediate 1-chloromethylnaphthalene or l-naphthaleneacetonitnle (89). 

Two important widely used sulfonic acids are known as TwitcheU s reagents, or as in Russia, the Petrov catalysts. These reagents are based on benzene or naphthalene ( ) and (12), [3055-92-3] and [82415-39-2] respectively. The materials are typically made by the coupling of an unsaturated fatty acid with benzene or naphthalene in the presence of concentrated sulfuric acid (128). These sulfonic acids have been used extensively in the hydrolysis of fats and oils, such as beef tallow (129), coconut oil (130,131), fatty methyl esters (132), and various other fats and oils (133—135). TwitcheU reagents have also found use as acidic esterification catalysts (136) and dispersing agents (137). 

Solids. —It may Idc a hydrocM bon (c .g., paraffin wa, naphthalene) highei alcohol eg., cetyl alcohol) aldehyde e.g., z5-hydroxybenzaldehyde) ketone and qiiinonc e.g., benzo-phenone, camphor) acid (higher fatty, e.g., palmitic acid or aromatic acid) ester (of glycerol, phenols or aromatic alcohols) phenol e.g., thymol),... 

The complex thioamide lolrestat (8) is an inhibitor of aldose reductase. This enzyme catalyzes the reduction of glucose to sorbitol. The enzyme is not very active, but in diabetic individuals where blood glucose levels can. spike to quite high levels in tissues where insulin is not required for glucose uptake (nerve, kidney, retina and lens) sorbitol is formed by the action of aldose reductase and contributes to diabetic complications very prominent among which are eye problems (diabetic retinopathy). Tolrestat is intended for oral administration to prevent this. One of its syntheses proceeds by conversion of 6-methoxy-5-(trifluoroniethyl)naphthalene-l-carboxyl-ic acid (6) to its acid chloride followed by carboxamide formation (7) with methyl N-methyl sarcosinate. Reaction of amide 7 with phosphorous pentasulfide produces the methyl ester thioamide which, on treatment with KOH, hydrolyzes to tolrestat (8) 2[. 

Rather similar was the paper [PolG36a] which also derives asymptotic formulae for the number of several kinds of chemical compounds, for example the alcohols and benzene and naphthalene derivatives. Unlike the paper previously mentioned, this one gives proofs of the recursion formulae from which the asymptotic results are derived. A third paper on this topic [PolG36] covers the same sort of ground but ranges more broadly over the chemical compounds. Derivatives of anthracene, pyrene, phenanthrene, and thiophene are considered as well as primary, secondary, and tertiary alcohols, esters, and ketones. In this paper Polya addresses the question of enumerating stereoisomers -- a topic to which we shall return later. 

Irradiation of complex 6 in the presence of ethyl acrylate provides the [6 + 2] 7t-adduct 9 as the single enrfo-diastereomer,276 which may also be obtained by heating a mixture of methyl l//-azepine-l-carboxylate with the ester in the presence of a catalytic amount of tricarbonyl(>]6-naphthalene)chromium(O).277... 

Trinitro-5-hydroxy-l-acetoxy-naphthalene, acetic acid-[2,6,8-trinitro-5-hydroxy-1 -naphthyl-ester], [2,6,8-trinitro-5-hyd roxy-1 -naphthyl] -acetate). (O2N)3C10H3(OCOCH3).OH, mw 337.22, N 12.46%, OB to C02 -87.78%, yellow needles... 

It must finally be kept in mind that it is extremely easy to adjust the properties of polyesters to desired values by adding small quantities (usually less than 10%) of comonomers in starting monomer feed. Isophthalic, adipic, dodecanedioic, p-hydroxybenzoic acids or esters and diethylene glycol, cyclohexanedimethanol, or bisphenol-A are often used for this purpose. Examples of property adjustment are the modification of solvent diffusivity of PET membranes by the addition of low levels of isophthalate or naphthalene dicarboxylate units in polymer chains139... 

An excellent discussion on derivatization techniques has been given by Lawrence (17) including a detailed discussion on pre-column derivatization (18) and post-column derivatization (19). Probably, the more popular procedures are those that produce fluorescing derivatives to improve detector sensitivity. One of the more commonly used reagents is dansyl chloride (20), 5-dimethylamino-naphthalene-1-sulphonyl chloride (sometimes called DNS-chloride or DNS-C1). The reagent reacts with phenols and primary and secondary amines under slightly basic conditions forming sulphonate esters or sulphonamides. 

The formation of the naphthalene (73) from the bis-ylide (72) and diethyl ketomalonate involves an unusual olefin synthesis on the carbonyl of an ester group. The methylene-pyrans (75) were formed when the diethyl malonates (74) were refluxed with j3-keto-ylides in xylene or decalin. Possible intermediates are the ketens (76) and the allenes (77). Addition of ylide to the allenes gives the betaines (78) which form methylene-pyrans either directly or via acetylenes as shown. 

The Popik group has recently begun to explore the potential of phenols to photorelease ethers and alcohols attached to an ortho-hem,y c group. For example, they have shown that esters and ethers of (3-hydroxymethyl)naphthalene-2-ol (i.e., 70) efficiently release the corresponding alcohols and acids upon exposure to UV irradiation ( 0.3),50 with formation of naphthoquinone methide 71 occurring in the process (Eq. 1.17). 

The reaction of potassium 3-amino-4-oxo-3,4-dihydroquinazoline-2-thiolate 62 with a-bromophenylacetic acid 63 resulted in the formation of (3-amino-4-oxo-3,4-dihydroquinazolin-2-ylsulfanyl)-phenyl-acetic acid methyl ester 64 which on alkali treatment and subsequent acidification resulted in the synthesis of 2-phenyl- 1-thia-4,4a,9-triaza-anthracene-3,10-dione 65 <1999JCR(S)86>. Similarly, the reaction of potassium 3-amino-5,6-dimethyl-4-oxo-3,4,4a,7a-tetrahydrothieno[2,3- pyrimidine-2-thiolate 66 with a-bromo-ester 67 resulted in the formation of 2-(3-amino-5,6-dimethyl-4-oxo-3,4,4a,7a-tetrahydrothieno[2,3- / pyrimidin-2-ylsulfanyl)-propionic acid ethyl ester 68. Subsequent treatment with alkali followed by acidification resulted in the formation of 2,3,7-trimethyl-3a,9a-dihydro-l,8-dithia-4a,5,9-triazacyclopenta[ ]naphthalene-4,6-dione 69 <2000JHC1161>... 

---