Diamines with carbon disulfide

Diacetylmethane, 20, 6 Diamines with carbon disulfide, 26, 35 4,4 -Diaminobiphenyl-3,3 -dicarboxylic acid, 27, 47... 

The reactions of diamines with carbon disulfide in the presence of alkali afford a useful synthetic route to the ethylenebisdithiocarbamates (6) (see p. 148). Several of these compounds, such as the manganese salt maneb (7), are important fungicides, especially for the control of potato and tomato blight.3... 

Recently. Ohishi el al. [26] measured dielectric properties of aliphatic polylhiourcas which were synthesized by thermal condensation of diamine with carbon disulfide as shown below. Polymerization of carbon disulfide and ali 4iatic diamine polymer Is called polythiourea-Af. where AT is the number of Of, groiqis. 

The same diamine, when treated with carbon disulfide in alkaline medium, yielded 2-mercapto- l//-imidazo[4,5-/]quinoline (88PS267,88SC973,86IJC264), which, on treatment with alkyl, aralkyl, and acid halides, gave the corresponding thioethers and thioesters 111, respectively (88PS267, 86IJC264). 

Treatment of the heterocycle, 38 (obtained from ethylene-diamine and carbon disulfide), with nitrous acid affords the N-nitroso compound, 39. Reduction with zinc leads to the corre-... 

Reaction of 2-substituted 1,3-propanediamines 617 with carbon disulfide, followed by ring closure under micro-wave conditions gave 2-pyrimidinethiones 619, while reaction of the same diamines with cyanogen bromide in a one-pot microwave procedure gave cyclic guanidines 620 <2004JOC1571>. 

The reactivity of amino functions on diazotization and condensation with dimethylformamide dimethyl acetal has been discussed in CHEC-II <1996CHEC-II(7)431>. The diamine 220 is readily converted into a variety of tricyclic pyrazolo[3,4-r/ pyrimidines under a variety of conditions <2004T5093>. Thus with chloroacetyl chloride the chlor-oacetyl derivative 221 was formed. This could not be further cyclized into 222. Refluxing 220 with diethyl oxalate afforded 223 while 224 was formed when the reaction was conducted at 40 °C. Treatment of 224 with POCI3 afforded 223. Reacting 220 with carbon disulfide afforded 225 (Scheme 14) <2004T5093>. 

Kempter and co-workers prepared benzodiazocines 134 (R = R1 = H R2 = H, Me) from 135 (R = H, Me) by reduction and subsequent cyclo-condensation with the appropriate carbonyl compound (75MI7 87ZC36). For example, these workers condensed 3-(o-aminophenyl)propylamine with either phosgene or alkyl chloroformate to obtain 134 (R = R1 = R2 = H, X = O). Reaction of the same diamine (77MI5 87ZC36) and substituted derivatives (77MI5) with carbon disulfide afforded thio-... 

Inulin can be modified to compounds that display good heavy metal complexing properties similar to ethylene diamine tetra-acetic acid (EDTA) but with better biodegradation properties (Bogaert et al., 1998). Inulin is first oxidized using sodium periodate to the dialdehyde, and then reduced to a polyol using Pt/C and hydrogen. The polyol can then be modified with carbon disulfide to form xanthate or with S03-pyridine to obtain an inulin sulfate. Alternatively, the dialdehyde can be animated with diaminoethane and sodium cyanoborohydride and the product reacted with monochloroacetic acid sodium salt to form carboxymethylamino inulin. Each of these compounds can be used to precipitate heavy metals. 

Analogous methods lead to benzimidazolethiones when o-phenylene-diamine.s arc treated with carbon disulfide, ihiophosgene, l.l -thiocarbonyldi-imidazolc, thioureas, thiocyanates or potassium ethyl xanthate [123, 126-129]. The reactions with carbon disulfide take place in basic media, e.g. with KOH or pyridine. Again, microwave irradiation offers advantages 1123]. 

It is not always necessary to use the o-diamines as starting material. o-Nitroaniline in the presence of a reducing agent, such as zinc dust, can give a good yield of benzimidazoline-2-thione (XVIII) when reacted with carbon disulfide in sodium hydroxide (2d9). 

Heterocyclic nitrogen compounds with an amino group in periposition to the nitrogen atom of the hetero-ring (o-arylene diamines with o-condensed N-alkylene substitution) also react with carbon disulfide. An example of such a reaction is that of 8-amino-1,2,3,4-tetrahydro-quinoline (XXII) which yields 2,4,5,6-tetrahydro-lH-imidazo[4,5,l-i,j] quinoline-2-thione (XXIII) (m.p. 214.5—215.5° C) 2S9). 

The members of the second subgroup are prepared from ethylene diamine (20) or its derivatives by reaction with carbon disulfide. In a sodium hydroxyde medium the disodium salt nabam, in an ammonium hydroxide medium, the diammonium salt amobam is formed (21). The sodium-ammonium salt, nambam, can also be prepared. These active substances are soluble in water. They cannot be used as foliage fungicides because of their phytotoxicity. On the other hand, they can be applied with good results for seed treatment. These compounds are intermediate products of the water-insoluble metal salts of N,N-ethylene-bisdithiocarbamic acid. c... 

When the diamine 67 (R = NHa) is treated with, for example, triethyl orthoacetate, the products are usually 3,4-dihydropteridines. However, when the diamine is heated with carbon disulfide in pyridine, none of the expected product is formed. Instead the 8-aminoimidazo[l,5-a]pyrazine 65 is formed in 90% yield. 2,3-Dihydro-3-thioxoimidazo[l,5-ajpyrazine may be prepared in excellent yield from the aminomethyl-pyrazine 67 (R = H) using this method. ... 

The use of carbon disulfide dates from 1895, when Busch condensed 2-aminobenzylamine with this reagent in boiling ethanolic sodium ethoxide to give 3,4-dihydroquinazoline-2-thiones.68 This procedure was also suitable for 2-amino-JV-alkyl- and -arylbenzylamines. When ammonia replaced the stronger base, the intermediate dithiocarbamate (74) was isolated in the absence of base, a salt of 74 with the original diamine was obtained. As is usual with carbon disulfide, the aliphatic rather than the aromatic amino group is preferentially attacked.68... 

Diamine 61 was then subjected to condensation reactions. Unsubstituted S-SFs-benzimidazole (67) was obtained in 90% yield after reaction of 61 with an excess amount of trimethyl orthoformate in the presence of hydrochloric acid. Condensation with carbon disulfide under basic conditions... 

Monodithiocarbamates can be prepared from phenylene diamines in the presence of a second, more basic amine. For example, addition of carbon disulfide and NEta to 1,2-diaminobenzene affords the yellow triethylammonium dithiocarbamate salt in high yield (115). The latter can then be reacted with various a-halogenated carbonyl derivatives resulting in cyclization and dehydration to give the new amines. These in turn react with carbon disulfide and... 

Diketones with Diamines—qiiinazolines 11. Diketones with NH OH—isoxazolines 12. Diketones with NH NH,—pyrazoles 13. Diketones with semi-carbazide—pyrazoles 14. Diketones with ammonia—pyrazoles 15. Carbon disulfide with ammoacetamide—thiazolone 16. Nitriles and ethylene diamines—imidazolines D D D D D A D ... 

The condensation of 1,4-diamines with a variety of carboxylic acid derivatives, e.g. imidate esters, orthoformic esters, /V-ethoxycarbonylthioamides (77JOC2530), nitriles and ethoxyacetylene, produces the cyclic amidine linkage —N = C(R)NH— (67AHC(8)2l, p. 40). Cyclic ureas, —NHC(0)NH—, have been similarly produced using carbonyl chloride, A, A -carbonyldi imidazole, carbon monoxide, thiocarbonyl chloride or carbon disulfide (67AHC(8)21, p. 38). 

The reaction of secondary diamines, carbon disulfide, and alkali metal hydroxides gives bisdithiocarbamate salts, which, upon reaction with bischloro-methylated aromatics, afford soluble polydithiocarbamates (392). The coordination chemistry of these polymers should be investigated. They may prove to be interesting, and, perhaps, specific, metal-sequestering agents. 

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