Cyanoacetate

EACNOx = ethyl 2-(hydroxyimino)-2-cyanoacetate TBTU = 0-(Benzotriazol-l-yl)-A, N, N, A -tetramethyluronium tetrafluoroborate... 

The 6//-l,3-thiazin-6-iminium hydroperchlorate salts 78-81 give interesting products when treated with nucleophiles <2003H(60)2273>. Hydrolysis of 6-imino-6//-l,3-thiazine hydroperchlorate 78 affords (2Z,4Z)-2-cyano-5-hydroxy-5-phenyM-azapenta-2,4-dienethioamide 82 in excellent yield, while treatment with morpholine gives 2-(morpholinomethylene)malononitrile 83 and thiobenzamide. The 5-(ethoxycarbonyl) -(methylthio)-2-aryl-6/7-l,3-thiazin-6-iminium salts 79 and 80 react with hydroxide or morpholine to afford ethyl 4-(methylthio)-2-aryl-6-thioxo-l,6-dihydropyrimidine-5-carboxylates 84 and 85. In the case of the 4-chloro analogue 80, the (Z)-ethyl 2-(5-(4-chlorophenyl)-37/-l,2,4-dithiazol-3-ylidene)-2-cyanoacetate 87 is also formed for the reaction with sodium hydroxide. The 1,2,4-dithiazoles 86 and 87 can be obtained as the sole product when 79 and 80 are treated with sodium acetate in DMSO. Benzoxazine 88 is isolated when the iminium salt 81 is treated with morpholine or triethylamine. Nitrile 89 is formed as a ( /Z)-mixture when 6-imino-67/-l,3-thiazine hydroperchlorate 79 is reacted with triethylamine and iodomethane in methanol <2003H(60)2273>. 

Of the many substituted and functionalized alkenes that have been combined with diazo dipoles to give A -pyrazolines or products derived from them (i.e., A -pyrazolines, pyrazoles, cyclopropanes), only a selection will be mentioned. These include ot-alkylidene-cycloalkanones (62), -flavanones, -thioflavanones, -chroma-nones, and thiochromanones (63,64) a-arylidene-indanones and -indolones (65) diarylideneacetones (66) l-benzopyran-2(77)-ones (coumarins) (67,68) 4-nitro-1,2-oxazoles (69) 2-alkylidene-2-cyanoacetates (70) dimethyl 2,3-dicyanofuma-rate (71) tetracyanoethylene (72) tetraethyl ethylenetetracarboxylate (72) 1,4-quinones (35,73-75) 2-X-l,l,l-trifluoro-2-propene [X = Br, (76), SPh, SOPh, S02Ph (77)] nitroalkenes (78) including sugar nitroalkenes (79) 1-diethoxyphos-phoryl-1-alkenyl-sulfoxides (80) methyl 2-(acetylamino)cinnamate and -acrylate... 

Likewise, 1,3-cyclohexanediones react with 3-methyloxazolidines 93 to afford tricyclic 477-pyrans (Equation 48) <1996T14273>. In the presence of malononitrile or ethyl 2-cyanoacetate, 1,3-cyclohexanediones react with oxazinanes 94 to afford bicyclic 2-amino-4/7-pyrans (Equation 49) <1996T14273>. 

Naturally occurring and synthetically accessible siderophores (iron carriers) contain predominantly bidentate pyrocatechinato- or hydroxamato ligands and are of special interest because of their high affinity towards trivalent metal ions, especially towards iron(III) ions [5, 118-127]. The methyl ( )-2-(l-alkyl/aryl-4,5-dihydro-l//-tetrazol-5-ylidene)-2-cyanoacetates 41a-c, first prepared by us [128], also appeared to be suitable as siderophores. 

Methyl 2-(/8-aminostyrylimino)-2-cyanoacetate (48) gave methyl 3-amino-5-phenyl-2-pyrazinecarboxylate (49) (MeONa, MeOH—CH2C12, 20°C, 15 min 70%).941... 

Ethyl 2-amino-2-cyanoacetate (282) and 2-hydroxyimino-4-methylvaleric acid (283) gave ethyl 3-amino-5-isobutyl-6-oxo-l,6-dihydro-2-pyrazinecarboxy-late 4-oxide (284) (N,N -dicyclohexylcarbctdiimide %).1259... 

The promising analgesic activity of 3-hydroxy-17-methylmorphinan stimulated Schnider and Hellerbach(11,12) to seek a commercial synthesis of it via 8. Bromoacetic ester reacted with cyclohexanone to give 10, which was converted rather laboriously to 8 (Scheme 3.2), Cyanoacetic ester afforded a more fluent route by way of cyclohexenylacetonitrile (11). In the presence of... 

Dimerization of ethyl 2-amino-2-cyanoacetate gives diethyl 5-aminoimidazole-2,4-dicar-boxylate (92) as in Scheme 53. At reflux temperatures in propanol, 1,1-dimethyl-1-phenacyl-hydrazinium bromide is converted into 2-benzyl-4-phenylimidazole (93). Again the cycliz-ation is a dimerization process (Scheme 53) (80AHC(27)24l). 

Selenazofurin (72), a promising antitumor agent, has been synthesized from methyl 2,5-anhydroalloni-midate (68), as illustrated in Scheme 20. The key step of the synthesis is the fonnation of the selenazole (71) by the condensation of the selenoester (69) with ethyl 2-amino-2-cyanoacetate (70). ... 

From ethyl 2-cyanoacetate. 5-Aminopyrazol-3-ones can be conveniently prepared from /7-keto esters with hydrazines. Thus, heating ethyl 2-cyanoacetate 142 with (4-ferf-butylphenyl)hydrazine 143 in ethanolic sodium ethoxide afforded 5-amino-2-(4-ferf-butylphenyl)-2,4-dihydropyrazol-3-one 144 (01JMC3730) (Scheme 33). The reaction that takes place under acidic conditions, between ethyl 2-cyanoacetate 142 and 2-hydrazino-6-oxopyrimidine-5-carbonitrile 145 in boiling acetic... 

A completely different approach initially involves the addition of the carbanion of ethyl 2-cyanoacetate 142 in the presence of base to the imine group of 2-naphthylsulfonyl hydrazone 147 followed by cyclization and oxidation to pyrazol-3-one 150 (02NN469) (Scheme 34). The reaction requires heating in ethanol with triethylamine and it is suggested that intermediate 148 is first produced, and then undergoes an intramolecular acyl substitution resulting in the unstable pyrazol-3-one 149. The latter is prone to oxidation by molecular oxygen and is converted to stable pyrazol-3-one 150. 

Dibromo-2-carbamoylacetonitrile Dibromooyanoacetamide 2,2-Dibromo-2-cyanoacetamide 2,2-Dibromo-3-nitrilo-propionamide EINECS 233-639-7 EPA Pesticide Chemical Code 101801 HSDB 6982 NSC 98283 XD-1603 XD-72871 Antimicrobial XD 7287L 2,2-Dibromo-2-carbamoylacetonitrile 2,2-Dibromo-2-cyanoacet-amide ... 

Thiadiazoles. - Synthesis. 5-Amino-1,2,3-thiadiazole is prepared from N CCN and I S in the presence of a tertiary amine327 Similarly, 2-diazo-2-cyanoacetic acid derivatives react with H S/... 

Other derivatives containing two electron-withdrawing groups can be used in the reaction, including malononitrile (200). When condensed with 2,3-benzocycloheptanone (199), the dicyanoalkylidene product (201) was isolated in 46% yield. Cyanoacetic acid derivatives (such as ethyl 2-cyanoacetate) are also common partners in the Knoevenagel condensation. 120... 

As a further modification of EHNA, condensation of ethyl-2-amino-2-cyanoacetate or aminomalononitrile with erythro-3-amino-2-nonanol in... 

Carboxamido-2-/3-D-ribofuranosyloxazole (oxazofurin) (512), the oxygen analog of the two synthetic C-nucleoside antitumor agents tiazofurin (575) and selenazofurin (576) (Section XII,A,1), was synthesized from the 2,5-anhydro-D-allonoyl chloride derivative 507 and ethyl 2-amino-2-cyanoacetate (90JMC2849) (Scheme 131). A similar synthesis by rhodium-catalyzed reaction of the nitrile of 507 with ethyl 2-formydiazoacetate has been reported (93MI11). 

M Itoh, Racemization suppression by the use of ethyl hydroximino-2-cyanoacetate in Chemistry and Biology of Peptides (J. Meienhofer, ed.) Ann Arbor Science Pub. Ann Arbor, Michigan 1972 pp. 365-367... 

---