Carbon disulfide, reaction with hydrazines

Hydrazine as Nucleophile. Reaction of hydrazine and carbon dioxide or carbon disulfide gives, respectively, hydrazinecarboxyhc acid [471-31-8], NH2NHCOOH, and hydrazinecarbodithioic acid [471-32-9], NH2NHCSSH, in the form of the hydrazinium salts. These compounds are useful starting materials for further synthesis. For example, if carbon disulfide reacts with hydrazine in basic medium with an alkyl haUde, an alkyl dithiocarbazate ester is obtained in a one-step reaction ... 

Hydrazinotriazine 749 was prepared by the condensation of the respective quinone with thiosemicarbazide followed by sequential cyclization, chlorination with phosphorus oxychloride, and reaction with hydrazine (88JHC1139). Cyclocondensation of 749 with formic acid or carbon disulfide gave triazolotriazines 750 (88JHC1139) (Scheme 156). 

Treatment of (181) with carbon disulfide in the presence of sodium hydride gave the mesoionic compound (182) which upon reaction with hydrazine gave (183) <75YZ980>. 

Mercapto pyrimidines 82 were synthesized from acetoacetanilide, dihydroxybenzaldehyde, and thiourea, which were readily alkylated with benzyl chloride to afford 2-benzylthio derivatives 83 (Scheme 32). 83 when reacted with different amines in acetic acid furnished 2-amino derivatives 84 (R = Ar), whereas upon reaction with hydrazine hydrate 83 afforded 2-hydrazinyl derivative 84 (R = NH2), which with different aldehydes gave hydrazones 85 (R = 2-furyl, 2-thienyl). Arylidene thiazolidinone 86 was obtained from 84 with carbon disulfide, monochloroacetic acid, and aryl aldehydes, while 84 with ethyl acetoacetate and different aromatic aldehydes provided pyrazoles 87 (Scheme 32) (10MI9). Such tetrasubstituted pyrimidines act as cyclin-dependent kinase (CDK2) inhibitors. 

Condensation of syn- or anti-27 with hydrazine afforded new pyrazole derivatives 28 with a stereodefined and protected amino diol side chain [64]. The preparation of push-pull substituted unsaturated monosaccharide derivatives and their use in the synthesis of nucleoside analogs have been reviewed [65]. Thus, the 2-formyl pentose glycals were transformed to the corresponding acyclo-C-nucleosides 29 [66]. Similarly, the benzy-lated 2-formylglycals reacted with hydrazine derivatives to afford the substituted l,2,4-tri-0-benzyl-lC-(lH-pyrazol-4-yl)-D-tetritols the deprotection of which was achieved with Pd/H2 to yield the lC-( 1-methyl-lH-pyrazol-4-yl)-D-tetritols [67]. 3-0-Benzyl-6-deoxy-l,2-0-isopropylidene-o -D-xylo-hept-5-ulofuranurono-nitrile was reacted with f, N-dimethylformamide dimethyl-acetal in THF to furnish the (E)-3-0-benzyl-6-deoxy-6-dimethyl-aminometh-ylene-l,2-0-isopropylidene-Q -D-xylo-hept-5-ulofuranurono-nitrile as a major product, and on treatment with carbon disulfide and methyl iodide under basic conditions afforded 3-0-benzyl-6-deoxy-l,2-0-isopropylidene-6-[bis(methylsulfanyl)methylene]-a-D-xylo-hept-5-ulofuranurono-nitrile. Further reaction with hydrazines yielded the reversed pyrazole-C-nucleoside analogs [68]. 

Hydrazine 835 underwent ring closure with one carbon cyclizing reagents to afford 837 and/or /V-acyl derivatives 836. The N-acyl derivatives underwent cyclization on treatment with phosphorus oxychloride. They were also prepared by the reaction of hydrazones 838 with thionyl chloride (84JHC1565). Compound 835 underwent ring closure with carbon disulfide and ethyl chloroformate to give 839 (Scheme 169). 

N204 also forms expl mixts with incompletely halogenated hydrocarbons, NGu, carbon disulfide, etc (Ref 33). The effect of spontaneous decompn by oxidation-reduction reactions when N204 is mixed with a number of fuels (hydrazine, gasoline, liq paraffin, etc) has resulted in its extensive use in liq propint rocket engines (Refs 12, 22, 27 35)... 

Thiadiazinotriazolopyrimidines can be prepared in several ways from the hydrazine-substituted thiadiazino-pyrimidine 186. Reaction with carbon disulfide gives the thione 187 reaction with either anhydrides or orthoformates with sulfuric acid gives the substituted triazoles 188, and reaction with cyanogen iodide gives the aminotriazole 189 (Scheme 47) <2004HC0335>. 

Thiation of [l,2,4]triazino[3,2-h]quinazoline-3,10-dione 782 with phosphorus pentasulfide in pyridine proceeded selectively to give the 3-thioxo analogue 783. The latter was converted to the corresponding 3-methylthio derivative 784 by reaction with methyl iodide. Treatment of 784 with hydrazine gave 785, which was converted to 786 and 787 by cyclization with formic acid or carbon disulfide (90JHC591). Cyclization of 785 with sodium nitrite in hydrochloric acid gave 788 (90JHC591). 

The reaction of compound 376 with hydrazine gives product 377 that has been transformed into similar triazoles 378, after reaction with carbon disulfide in the presence of alcoholic potassium hydroxide, benzoic acid in the presence of phosphoms oxychloride, or 3-[bis-(methylthiomethylene)]pentan-2,4-dione and l,l-dicyano-2,2-dimethylthioethylene, in refluxing -butanol (Scheme 40) (Table 55) <2000FES641>. 

Hydrazines of type 89 react with various carbonic acid derivatives to furnish cyclized product. Under basic conditions (KOH), in the presence of carbon disulfide or arylisothiocyanates, the cyclized thione 90 is obtained (Scheme 7) <1966JOG3528, 1984JCCS315>. Analogous reactions performed in the absence of base gave 91 as a 3-thiol when performed with carbon disulfide, as a 3-hydroxyl with methyl chloroformate, or as a 3-arylamino with arylisothiocyanates in the presence of dicyclohexylcarbodiimide (Scheme 7) <1986JHC1339, 1992IJB467>. 

Nucleophilic substitution of the 4-chloro group of the 4-pyranotriazines 103 with hydrazine gives the 4-hydrazino-triazines 104, which can be further elaborated to the corresponding azides 105 or cyclized upon reaction with formic acid or carbon disulfide to give the triazolotriazines 106 or thioxotriazolotriazines 107, respectively (Scheme 11) <2005HC0495>. 

The 4-aminopyrimidines 367 and 368 were prepared by the reaction of the benzylidene malononitriles with thiourea or S-methylisothiourea, respectively. Nucleophilic substitution at the 2-position of 368 with hydrazine gave the 2-hydrazino derivative 369, whose treatment with carbon disulfide yielded the triazolopyrimidine 373 rather than its isomeric compound [83ZN(B)1686]. Heating 369 with benzoyl chloride in anhydrous dioxane,... 

Ignition or explosive reaction with metals (e.g., aluminum, antimony powder, bismuth powder, brass, calcium powder, copper, germanium, iron, manganese, potassium, tin, vanadium powder). Reaction with some metals requires moist CI2 or heat. Ignites with diethyl zinc (on contact), polyisobutylene (at 130°), metal acetylides, metal carbides, metal hydrides (e.g., potassium hydride, sodium hydride, copper hydride), metal phosphides (e.g., copper(II) phosphide), methane + oxygen, hydrazine, hydroxylamine, calcium nitride, nonmetals (e.g., boron, active carbon, silicon, phosphoms), nonmetal hydrides (e.g., arsine, phosphine, silane), steel (above 200° or as low as 50° when impurities are present), sulfides (e.g., arsenic disulfide, boron trisulfide, mercuric sulfide), trialkyl boranes. 

Dithiocarbazates (CCXV), which are themselves the reaction products of hydrazines with carbon disulfide, can react further with another carbon disulfide molecule. In this manner l,3,4-thiadiazolidine-2,5-dithiones (CCXXXI) are formed 57, 58, 66, 69, 71). 1,3,4-thiadiazolidine-... 

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