Ethyl chloro formate

Treatment of 2-acetyl- or 2-formyl-benzimidazole 587 with hydrazines gave the corresponding hydrazones 588, which cyclized with ethyl chloro-formate to give [84JCR(S)384] triazinobenzimidazoles 589. 

Acyclic ADC compounds, which are more correctly named as derivatives of diazene, are generally prepared from hydrazine derivatives. For example, diethyl azodicarboxylate (Chemical Abstracts name diethyl diazene-1,2-dicarboxylate)5 is prepared from hydrazine by treatment with ethyl chloro-formate followed by oxidation with chlorine in benzene-water.6 Other oxidants which have been used include JV-bromosuccinimide,7 nitric acid,8 inorganic nitrates,9 potassium dichromate,10 silver carbonate on celite,11 and phenyl iodosotrifluoroacetate.12 The hydrazine derivative may also be... 

The reaction between 2-fluoroethyl alcohol and ethyl chloro-formate at 100° for 10 hr. gave pure ethyl 2-fluoroethyl carbonate, F [CHa]2 O COgEt. 

Phenyl-3-ureido-1,2,4-thiadiazoles (222) are obtainable by successive treatment of the 3-amino heterocycle (220) with ethyl chloro-formate at 120° and the appropriate amine.188 Direct action of aryl-sulfonylurethanes (on 220) affords 3-arylsulfonylureido-5-phenyl-l,2,4 4-thiadiazole8 (223) in one stage.188... 

When magnesium bromohydroselenide reacts with ethyl chloro-formate or acetyl chloride it gives, respectively, ethoxyseleno-formic acid, C2H5O.COSeH, and selenoacetic acid, CH3.COSeH, products in which one atom of oxygen in the carboxyl group is replaced by selenium. 

The oxazolidin-2-ones 53 (R = H=CCH=CH2 or COEt) are obtained in a one-pot reaction of amino alcohol carbamates 52 with sodium hydroxide, followed by allyl bromide or propi-onyl chloride (94TL9533). A modified procedure for the preparation of chiral oxazolidin-2-ones 56 from a-amino acids 54, which avoids the hazardous reduction of the acids with borane and the intermediacy of water-soluble amino alcohols, is treatment of the methyl ester of the amino acid with ethyl chloro-formate to give 55, followed by reduction with sodium borohydride and thermal ring-closure of the resulting carbamate f95SC561). The 2-prop-ynylcarbamates 57 (R = Ts, Ac, Bz, Ph or allyl) cyclize to the methyleneoxazolidinones 58 under the influence of silver cyanate or copper(I) chloride/triethylamine (94BCJ2838). 

Pyridopyrimidine systems may also be accessed by in situ generation of pyridylisocyanates <2003TL2745>. Treatment of 2,3-pyridinccarboxylic anhydride with methanol leads to the formation of 2-(methoxycarbonyl)nicotinic acid that undergoes Curtius rearrangement on conversion to the 3-acyl azide with sodium azide and ethyl chloro-formate. Condensation of the resulting isocyanate with a series of amino acids leads to the synthesis of pyrido[3,2- T pyrimidines in good to excellent yield (Scheme 19). 

Besides the synthesis of 1-chloroalkyl carbonates, this method is general enough to be used for the preparation of 1-fluoroalkyl, 1-bromoalkyl or 1-iodoalkylcarbonates as shown in table 3-7. However, the method gives poor results or even failed when the haloformate is too unstable in presence of the catalyst (see section 3-2-1). For example, attempts to prepare 1-chloroethyl ethyl carbonate (CEEC) itself in 1,2 dichloroethane at 60°C with 0.05 equ. pyridine, gave almost total decomposition of ethyl chloro-formate. 

Ethyl chloroacetate, 1039, 1094 Ethyl rcchloroacetoacetate, 1128 Ethyl chlorocarbonate, see Ethyl chloro-formate... 

Methoxydioxocanadine (283) on pyrolysis affords a 15% yield of the lactone (284), convertible by 4 -methylation and reduction into racemic a and 6-hydrastine (Elango and Shamma, J.org. Chem., 1983, 48, 4879). Treatment of o-acetylophiocarpine with ethyl chloro-formate yields (285, R=C1), hydrolysable to (265, R=0H) and oxidation of this followed by hydrolysis of the acetoxy group yields the hemi-acetal (286, R=H). Conversion of this into the mixed acetal (286, R=Et) allows the N-COOEt group to be reduced to NMe and subsequent hydrolysis gives the aldehyde (287) which can be oxidised to a-hydrastine. A similar reaction sequence starting from epiophiocarpine yields g-hydrastine (Hanaoka, K. Nagami and Imanishi, Chem. Pharm.Bull., 1979, 1947). The reverse conversion of a... 

Ethyl Chloro- formate 61 82 Data not available Data not available Water, dry chemical, carbon dioxide Not pertinent Not pertinent 932 Slow reaction with water, evolving hydrogen chloride (hydrochloric acid) ... 

A superior synthesis of 3-amino-4-alkyl- and 3-amino-4-aryl-4//-l,2,4-benzothiadiazine 1,1-dioxides (135), involving the amino-dechlorination of chloro compounds (130 R = alkyl or aryl) with aqueous ammonia in chloroform has been reported <86S864> yields are excellent (86-94%). It has been shown that l,5-diphenyl-6-bromo-lA 2,4-thiadiazine 1-oxide (136) (see Section 6.14.6.3.3) undergoes metal exchange with butyllithium and, on quenching the mixture with ethyl chloro-formate, the 6-ethoxycarbonyl derivative (137) is obtained in moderate yield (31%). Displacement... 

Hydroxyphenamate. 2-Phenyl-l,2-butanediol 1-carbamate carbamic acid ft -ethyl -0-hydroxy phenethy] ester d-ethyl-p-hydroxyphenethy] carbamic acid ester 0-ethyl-0-hydroxy phenethyl carbemate 2-hydroxy-2-phenyl-butyl carbamate Al 0361 Listica. C.,H.sNOv mol wt 209.24. C 63.14%, H 7.23%, N 6.69%, O 22 94%. Prepd from d-ethyl -d-hydroxyphenethyl alcohol and ethyl chloro-formate followed by reaction with ammonia Sifferd, Brait-berg. U,S. pat. 3,066,164 (1962 to Armour-Pharm.). Pharmacology and toxicology Bastian, Clements, Di-V. Nerv. Sys. 22, 9 (1961). 

Beilstein Handbook Reference) AI3-19852 BRN 0385653 Carbonochloridic acid, ethyl ester Cathyl chloride Chlorameisensaureathylester Chloro-carbonate d ethyle Chlorocarbonic acid ethyl ester Chloroformic acid ethyl ester Cloroformiato de etilo ECF EINECS 208-778-5 Ethoxycarbonyl chloride Ethyl carbonochloridate Ethyl chlorocarbonate Ethyl chloro-formate Ethyl chloromethanoate Ethylchloorformiaat Ethyle, chloroformiat d Ethylester kyseliny chlor-mravenoi Etil clorooarbonato Etil cloroformiato Formic xid, chloro-, ethyl ester HSDB 409 TL 423 UN1182. Liquid mp = -80.6° bp = 95° very soluble in CeHe, EtzO. CHC13. 

Although cyclic and acyclic carbonates of monosaccharides have been known for some time, little interest had been taken in such derivatives of polysaccharides, probably because the conditions could not be controlled to give any degree of specificity. The formation of cyclic carbonate rings involves treatment of the polysaccharide with ethyl chloro-formate heterogeneous reactions occur, and acyclic carbonate (ethy-oxycarbonyl) groups are also formed. The reaction conditions suitable for maximum cyclic carbonate and minimum acyclic substitution have been investigated in detail for cellulose. Other chloroformates have... 

A type of mixed anhydride derivative (2, see p. 322) has been produced by reaction of O-(carboxymethyl) cellulose with ethyl chloro-formate, and is useful in insolubilization of macromolecules because of its nucleophilic susceptibility. ... 

Ethyl chloro formate/triethylamine Lactams from aminocarboxylic acids s. 24, 513 s. a. F. Gatta and R. Landi Vittory, Farmaco, Ed. Sci., 25, 991 (1970)... 

NitroA-pyridone and 3-amino-4-pyridone are N-acylated by ethyl chloro-formate in aqueous sodium carbonate. ... 

Reaction of the known 6 -hydroxymethyIlaudanosine with ethyl chloro-formate results in opening of ring B with simultaneous formation of a six-membered cyclic ether (see Sec. 20.1.4) ... 

A new method for the epoxidation of alkenes utilizing O-ethylperoxycarbonic acid, prepared in situ by the reaction of hydrogen peroxide and ethyl chloro-formate, has been described. The reaction is carried out in an alkaline biphasic... 

Benzylideneaminoacetoaldehyde acetals prepared from benzaldehydes have been key intermediates of a well-established method for isoquinoline synthesis known as the Pomeranz-Fritsch reaction (Scheme 16, route a) [49,50], Intramolecular cycliza-tion of this type of imines under acidic conditions provided isoquinolines, where the two-carbon substituent on the nitrogen atom was transformed into a part of the isoquinoline ring. For the synthesis of 8-fluoroisoquinohne, the application of the standard procedure gave a low yield of the desired product (3 % in two steps from 2-fluorobenzaldehyde) [51]. However, in the modified procedure using ethyl chloro-formate, trimethyl phosphite, and titanium tetrachloride for the cyclization step [52] provided 6-fluoroisoquinoline from 4-fluorobenzaldehyde in 34 % overall yield (Scheme 17) [25],... 

Several observations indicate that this is reasonable. When a mixture of benzaldehyde and wo-butyryl chloride is treated with the organotin hydride, benzyl iro-butyrate is formed, but iro-butyl benzoate is not. Similarly when a mixture of benzoyl chloride and wo-butyraldehyde is reduced wo-butyl benzoate is formed, but benzyl iso-butyrate is not. Ethyl chloro-formate is reduced very slowly at 80° C by tri-n-butyltin hydride, but the addition of 2 mole-% of azobisisobutyronitrile leads to facile reduction. When triphenylacetyl chloride is reduced at 100° C with the same hydride the products include triphenylacetaldehyde, triphenylmethane, and carbon monoxide, but little, if any, j8,j8,j3-triphenylethyl triphenylacetate. The formation of carbon monoxide and triphenylmethane can be attributed to decarbonylation of the intermediate acyl radical to the more stable trityl radical, Eq. (61), which subsequently abstracts a hydrogen atom from the... 

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