Diamines reactions, carbon disulfide

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... 

The aprotic solvents, which do not possess hydrogen bond, are highly polar. Therefore, the aprotic solvents possess high alkalinity and nucleophilicity required to obtain a high conversion of o-phenylene diamine in the synthesis of mercaptobenzimidazole (MBI). A larger conversion is obtained when using a protic solvent or aprotic solvent of high polarity. However, the structure of DMF, which is an amide, is similar to that the tertiary amine. It possesses similar catalytic property to dimethylaminopyridine (DMAP). The effect of DMF on the conversion of o-phenylene diamine is more pronounced than that of DMSO. The Arrhenius rate equations in various solvents for the reaction of o-phenylene diamine and carbon disulfide catalyzed by tributylamine are as follows ... 

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>. 

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. 

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-... 

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]. 

The reaction of carbon disulfide with 1,2-alkylene diamines (I) yields N-(2-aminoethyl) dithiocarbamic acids (II) which split off hydrogen sulfide thermally to give imidazolidine-2-thiones (III) (Hofmann-process). The simplest example, the reaction of carbon disulfide with ethylenediamine, is described in Organic Synthesis (5). The reaction is general for N,N -dialkyl-, N,N -diaryI, as well as for N,N -bis-(arylakyl) ethylene diamines. The rate of reaction is determined by the basicity of the diamine. Electron-donor substituents in the para-position of N-aromatically substituted ethylene diamines accelerate dithiocarbamate formation electron-acceptor groups retard it. 

The reaction of carbon disulfide with o-amino benzyl amines (X) is analogous to that with I.J-diamines. In the former 1,2,3,4-tetrahydro-quinazoline-2-thiones (XI) are formed 56, 59, 60, 269). Cyclization of the intermediate dithiocarbamic acids here is generally done by refluxing with alkali. These compounds are reviewed in Table 3. 

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). 

Since the reactions with phosphorus compounds give relatively high yields of carboxylic amides and esters and ureas, they have been extended to the direct polycondensations of dicarboxylic acids with diamines and bisphenols, of free a-amino acids or dipeptides, and of carbon dioxide and carbon disulfide with diamines under mild conditions to give polyamides, polyesters, polyureas, and polythioureas. 

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... 

The reaction of the aminothienopyrimidine nitrile 46 with ethylene diamine and subsequent condensation with triethyl orthoformate, carbon disulfide, or aldehydes, yields partially reduced imidazo[l,2-c]pyrimido[5, 4 4,5]thieno[2,3-e]pyrimidines 47. Triazolo compounds 49 can be obtained from the hydrazino compounds 48 <97PHA500 97CA(127)205545>. 

Quaternary ammonium salts, PEGs and crown ethers are the eommon compounds, employed as PTC. The inexpensive tertiary amines have also been used as the phase transfer catalysts (PTC) in recent years. The synthetic process for producing 2-mercaptobcnzimidazolc (MBI) is a reaction of o-phenylene diamine (C6H4(NH2)2) and carbon disulfide (CSj) in a two-phase medium affected by appropriate choice of solvent. 

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... 

The reaction of ethylene diamine, carbon disulfide and dilute sodium hydroxide in a aqueous medium afforded disodium ethylenebis-dithiocarbamate, known by the tradename Nabam (8-11), and the treatment of the salt with zinc chloride furnished zinc ethyleneblsdithio-carbamate, known by the tradename Zlneb (10, 12, 13). 

Dithiocarbamates can also be prepared from diamines. For example, as early as 1872, Hofmann (97) reported the reaction of carbon disulfide with 1,2-diaminoethane. Later in the 1960s, addition of 2 equiv of sodium hydroxide and carbon disulfide to 1,2-diaminoethane was shown to afford the bis(dithiocarba-mate) compound in an exothermic reaction (98-102) 1,6-diaminohexane behaving in a similar manner (98). A wide range of polymeric transition metal complexes have been prepared using these salts (98). All are insoluble in water and common organic solvents, and some examples have been developed as fungicides (14, 31). 

Dicarbonyl(cyclopentadienyl)(iodo)iron (152 mg, 0.50 mmol), palladium(II) acetate (5.6 mg, 0.025 mmol), (l.l ,2/ )-iV,iV,iV ,JV -tetramethylcyclohexane-l,2-diamine (6.0 mg, 0.030 mmol), and tetrahydrofuran (1.0 mL) are sequentially added in a 20-mL reaction flask under argon. The mixture is cooled to 0 °C and then phenylmagnesium bromide (1.1-M tetrahy ofiiran solution, 0.68 mL, 0.75 mmol) is added. After the resulting mixture is stirred for 15 min at 0 °C, a saturated ammonium chloride solution (0.2 mL) is added to the reaction mixture. The mixture is filtered through a pad of Florisil, and the filtrate is concentrated. Silica gel column purification (eluent carbon disulfide) of the crude product provided dicarbonyl(cyclopentadienyl)(phenyl)iron 110 mg (87%). ... 

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