Tetrahydrophthalimide

Trichloromethanesulfenyl chloride has also been used for the preparation of lubricant additives (see Lubrication and lubricants). Some higher homologues and analogues of trichloromethanesulfenyl chloride have been reported, ie, trichlorovinylsulfenyl chloride [19411-15-5] 1,1,2,2-tetrachloroethanesulfenyl chloride [1185-09-7] 1,2,2,2-tetrachloroethanesulfenyl chloride [920-62-7] and pentachloroethanesulfenyl chloride [5940-94-3] (70—74). A commercial fungicide, Captafol [2425-06-17, is the reaction product of 1,1,2,2-tetrachloroethanesulfenyl chloride with tetrahydrophthalimide (75). 

Turning to tetrahydrophthalimide derivatives, we find the pyrethroid insecticide tetramethrin (4.191). In the rat, a major metabolic pathway involves... 

CASRN 133-06-2 molecular formula C9H8CI3NO2S3 FW 300.57 Biological. In water, captan reacted with the fungicide i-cysteine forming a compound with an absorption maximum of 272 mm which was identified as 2-thiazolidinethione-4-carboxylic acid. In addition, tetrahydrophthalimide also formed (Lukens and Sisler, 1958). 

The fungitoxic N-perhalogenmethylmercapto moiety was introduced for plant protection in 1950 The. two fungicides captan(l) (N-(trichloromethylthio)-tetrahydrophthalimide and folpet(2) (N-(trichlorome-thylthio)phthalimide) contain a perchlorinated methyl-thio group (1 ). About a decade later substitution of fluorine for one of the chlorines in the perchloro-... 

In the course of developing herbicides possessing N-phenyl tetrahydrophthalimide structure (20), Ohta et al. investigated structural requirements for the activity against sawa millet, Echinochloa utilis, of m- and p-substituted derivatives42 . As shown by Eq. 43, the steric dimensions expressed by the STERIMOL length parameter Lp and maximum width B of p-substituents play a decisive role in determining activity. 

Irrmost correlations in this review, the steric parameters are supposed to be best among others. In deriving Eq. 43 for N-phenyl tetrahydrophthalimide herbicides, STERIMOL parameters are the best ones 42). In Eq. 53 for lindane analogs, Vw works much better than MR 70). However, this does not necessarily mean that the correlations mentioned here are always finalized. Further improvement may be possible using other steric parameters. 

In the same study, maleimides were irradiated in the presence of allyl alcohol and allyl ethyl ether, yielding the respective cyclobutanes with significant exo-preference [115]. Diastereofadal stereocontrol was achieved in the [2 + 2]-photo-cycloaddition of tetrahydrophthalimide by a chiral tether. The valinol-derived sub-... 

Giilten, S., Sharpe, A., Baker, J.R., and Booker-Milburn, K.I. (2007) Use of temporary tethers in the intramolecular [2 + 2] photocydoaddition reactions of tetrahydrophthalimide derivatives a new approach to complex tricydic lactones. Tetrahedron, 63, 3659-3671. 

Captan [Ar-(trichloromethylthio)-l,2,3,6-tetrahydrophthalimide] reacts with resorcinol with the formation of a condensed ring, l,6-dioxa-6aA4-dithiapentalene as indicated in equation (12). Similar results are obtained when captan is replaced by thiophosgene (72T2183). 

N-(TRICHLOROMETHYLMERCAPTO)-A -TETRAHYDROPHTHALIMIDE see CBGOOO TRICHLOROMETHYLNITRILE seeTII750 l,l,l-TRICHLORO-2-METHYI 2-PROPANOL see ABDOOO... 

X-TRICHLOROMETHYLTHIO-3A,4,7,7A-TETRAHYDROPHTHALIMIDE see CBGOOO N-TRICHLOROMETHYLTHIO-cis-A -CYCLOHEXENE-l,2-DICARBOXIMIDE see CBGOOO TRICHLOROMETHYLTIN see MQC750 TRICHLOROMONOFLUOROMETHANE seeTIPSOO TRICHLOROMONOSILANE see TJD500... 

Bis-(dimethylbenzyl) carbonate V-(Trichloro methyl thio)tetrahydrophthalimide... 

Carbon disulfide (1) may be chlorinated by the action of chlorine in the presence of iodine catalyst (Scheme 15). The reaction probably involves initial addition of chlorine to the C=S bond followed by loss of sulfur dichloride to yield trichloromethanesulfenyl chloride (34) (Scheme 15). Trichloromethanesulfenyl chloride (34) is a synthetic intermediate in the commercial manufacture of several valuable agricultural fungicides containing the NSCCI3 moiety (see Chapter 11, p. 235). An important example is the foliage fungicide captan (35), which is prepared from butadiene and maleic anhydride (36) via tetrahydrophthalimide (37)... 

Scheme 16).3 Tetrahydrophthalimide (37) contains an acidic imino hydrogen atom and forms a sodium salt the latter undergoes a nucleophilic substitution reaction with trichloromethanesulfenyl chloride (34), yielding captan (35) (Scheme 16). 

Captafol is poorly absorbed from the gastrointestinal tract. The liver and the gastrointestinal tract are the primary sites of metabolism of captafol. Captafol is eliminated via urine, feces, and expired air. The major single metabolite, tetrahydrophthalimide (THPI), was detected in blood, urine, and feces, but most of the activity in the blood and urine was in the form of more water-soluble metabolites. Following oral administration in animals, captafol is hydrolyzed to THPI and dichloroacetic acid. THPI is degraded to tetrahydrophthalimidic acid and further down to phthalic acid and ammonia. 

Captan and its tetrahydrophthalimide (THPI) metabolites (Figure 6.3) are extracted from grapes, must, and wine with an acetone/petroleum ether 50 50 (v/v) mixture. 

Figure 1. Chemical structures of four typical peroxidizing compounds chlorophthalim, N-(4-chlorophenyl)-3,4,5,6-tetrahydrophthalimide oxadiazon, 3-(2,4-dichloro-5-isopropoxyphenyl)-5-tert-butyl-l,3,4-oxadiazol-2(3H)-one oxyfluorfen, 2-chloro-4-(trifluoromethyl)pheny1-3-ethoxy -4-nitroDhenyl ether LS 82-556, (S)3-N-(methylbenzyl)-carbamoyl-5-propionyl-2,6-lutidine. Also 2,4,5-phenylsubstituted pyrimidinediones exhibit peroxidizing activity, e.g. 3-(4-chloro-5-ethoxy-2-fluorophenyl)-l-methyl-6-(trifluoromethyl) -2,4(lll,3H)pyrimidinedione (34).

A close analog of Folpet is Captan, which also belongs to carboximides. Its chemical name is iV-trichloromethylthio-3a,-4,7,7a-tetrahydrophthalimide. It is of... 

Of the alkylmercury compounds, N-alkylmercury-3,4,5,6,7,7-hexachloro-3,6-en o-methano-l,2,3,6-tetrahydrophthalimide derivatives can be used as foliage fungicides as well as seed-dressings (Kleiman, 19S2). They are fungicides with eradicative and protective activity, particularly against powdery mildews and Venturia spp. The methyl (MEMMI, 5) and ethyl derivatives are known. These compounds are readily soluble in water and are not volatile. 

Captan is not toxic to warm-blooded animals. The acute oral lDj for rats is 9000 mg/ kg. No evidence of chronic toxicity has been found (Boyd and Carsky, 1971 Seidler er a/., 1971). It is only slightly irritating to the skin. Captan is rapidly absorbed and metabolised in warm-blooded animals, almost the whole quantity being excreted in the feces within 3 days. Unchanged captan could not be detected in rats tetrahydrophthalimide and tetrahydrophthalic acid were found transitorily in the blood. 

Tetrahydrophthalic anhydrine is converted with gaseous ammonia into tetrahydrophthalimide(ll)(Kittleson, 1952 Melnikov e/a/., 1961 Ambruse/a/., 1962). According to Dietz and Nusch (1964), the reaction proceeds in two steps. In the first step, tetrahydrophthalaminic acid is formed (12), and in a subsequent step tetrahydrophthalimide is formed by the splitting off of water ... 

Pfeifer et al. (1972) established by derivatographic thermal analysis that not tetrahydrophthalamide acid, but a tetrahydrophthalimide-water adduct is formed, and from this addition compound water is split off, even at lower temperatures. This finding made it possible to avoid the technical difficulties caused by sublimation during the manufacture of thetrahydrophthalimide, because the higher temperature is in fact not needed for dehydration. 

The last step in the synthesis is the reaction of the sodium salt of tetrahydrophthalimide with trichloromethanesulfenyl chloride (Kittleson, 1952). The reaction is carried out in organic solvent (benzene, dioxane) or in an aqueous medium. To avoid the hydrolysis of tetrahydrophthalimide, the reaction is carried out at low temperature (10-20°C). In aqueous media the use of emulsifiers considerably increases the yield, which can be as high as 90% (Melnikov et al., 1961). The purity of the technical product is 90-95%. 

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