Esters chloride

Dicarboxylic acids have been prepared by the stepwise acylation and Wolff-Kishner reduction of thiophene or di-2-thienylmethane with ester chlorides of dicarboxylic acids. Another method consists of the AICI3 catalyzed acylation of w-phenylalkylthiophenes which occurs both in the free thiophenic position and in the para position of the ring (226). Hypochlorite oxidation and desulfurization then give diacides such as (227)... 

Chemical Name Oi-Hydroxybenzeneacetic acid 8-methyl-8-[(2-oxo-2-phenyl)-ethyl]-8-azoniabicyclo[3.2.1 ]oct-3-yl ester chloride... 

It would be reasonable to expect that the decomposition of the N,N-dimethylimino ester chlorides proceeds via a bimolecular mechanism already demonstrated for the thermal decomposition of simple imino ester salts (79). In the carbohydrate series, where an isolated secondary hydroxyl group is involved, such a process would result in chlorodeoxy sugar derivatives with overall inversion of configuration, provided that the approach of the chloride ion is not sterically hindered. Further experiments are in progress in this laboratory utilizing additional model substance to establish the scope and stereochemical course of the chlorination reaction. 

Chlorodeoxy sugars by thermal decomposition of O-imino ester chlorides, synthesis of. .. 192 N-( 2-Chloro-l,l,2-trifluoroethyl) -... 

C-i )f<, O-, 406-76-S) see Carnitine carnitine ethyl ester chloride (C,H2 CIN0, 5S52-97-1) see Carnitine carnitinenitrile chloride (C7H1SCIN2O IS933-33-0) see Carnitine L-carnosine... 

C,Hj04 2613-89-0) see Carfecillin Carindacillin phenylmalonic acid benzyl ester chloride (Ci Hi ClO 35353-13-0) see Carbenicillin phenylmalonic acid diethyl ester see under diethyl phenylmalonate phenylmcrcuric acetate... 

Ylagen, L., Benjamin, A., Gupta, A., and Engel, R., Organophosphorus chemistry. Ester-chloride conversion under mild conditions at phosphorus, Synthetic Commun., 18, 285, 1988. 

Remarkably, the hydrozirconation can be applied to functionalized alkenylzinc reagents bearing an ester, chloride, or cyano functionality (Scheme 7.37) [230], The functionalized bimetallic species 129c—e gave significantly lower yields (55—64%) but excellent stereoselectivities (>94% ( ) Scheme 7.39). Although the (E)/(Z) ratio was always reproducible,... 

Thus, 4-substituted 5-amino-3-benzylsulfanyl-l/7-pyrazole 65 derivatives (R = CN or COOEt) were treated with phosphoric acid ethyl ester chloride isocyanate in the presence of triethylamine under mild conditions (0-20 °C) for 3 h to give the ring-closed product 66 in medium to good yields (70% and 61%, respectively). 

The reactions with the esters, chlorides, and anhydrides are somewhat more complicated. 

Cagniant and Cagniant have reported that succinoylation of benzo[6]thiophene under Friedel-Crafts conditions yields a separable mixture of the y-ketobutyric acids 42a and 43a in a ratio of 9 1 (combined yield 85%). Huang-Minlon reduction of 42a to the butyric acid (90%) followed by cyclization of the derived acid chloride (90%) was reported to yield 4-keto-l,2,3,4-tetrahydrodibenzothiophene (44a) (69% overall). Likewise, acylation of benzo[6]thiophene with the ester chloride of succinic acid in carbon disulfide-aluminum chloride gave a separable mixture (80%) of the 2- and 3-y-ketobutyric esters. Two alternative... 

Octahydrodibenzothiophene (73) has been prepared by the following sequence. Friedel-Crafts acylation of 4,5,6,7-tetra-hydrobenzo[6]thiophene with succinic anhydride (87%) or with the ester chloride of succinic acid followed by hydrolysis (80%), yields the keto acid (74). Huang-Minlon reduction of 74 followed by cyclization of the derived acid chloride with stannic chloride yields l-keto-1,2,3,4,6,7,-8,9-octahydrodibenzothiophene (53) (Section V,A). Reduction of 53 gives 73 as a solid (overall yield 32%). 

Carbenicillin Carbenicillin, [25 -(2a,5a,6j3)]-3,3-dimethyl-7-oxo-6-(2-carboxy-2-phenylacetamido)-4-thia-l-azabicyclo[3.2.0]-heptan-2-carboxylic acid (32.1.1.32), is synthesized by direct acylation of 6-APA in the presence of sodium bicarbonate by phenylmalonic acid monobenzyl ester chloride, which forms the benzyl ester of carbenicillin (32.1.1.31), the hydrogenolysis of which using palladium on carbon or calcium carbonate as catalyst gives the desired product (32.1.1.32) [51-58]. 

Tetradecanoic acid, methyl-pyridinium ester, chloride Lapyrium chloride 6272-74-8... 

Other polymers like polypropylene or polystyrene modified by maleic anhydride or maleamide, with the add groups converted to amide, ester or ester chloride and then reacted on Nylon fibers, have been claimed in a Japanese patent (101). Two patents report grafting of olefinic polymers on polycaprolactam (102,103). Grafting of polysiloxanes on polyamides can be induced by X-rays (104). 

Formylation of alcohols formate esters.2 The Vilsmeier adduct 1 of DMF and benzoyl chloride reacts with alcohols to give stable imidate ester chlorides (2). These are hydrolyzed by dilute acid to formate esters (3). 

Ger), C6Hs.CO.NH.OH or CgH8.C(OH) N.OHj mw 137.13, N 10.21% rhom ifts(exists in two isometric types), mp 124-6° 131-2° (values reported by various investigators) exp or rapid heating v sol in ale si sol in w or eth insol in benz. Can t>c prepd by the action of hydroxyl s id in c on the esters, chloride or amide of benzoic acid and by otu methous(Ref 1). It forms numerous addn compds and salts, such as the Copper salt, Cu-(C7H6N02)2, It blue cryst which expi mildly on heating(Ref 2)... 

Esters, chlorides, and anhydrides are reduced by lithium aluminum hydride in the same general way as the parent acids (Section 18-3C), the difference being that no hydrogen is evolved. The products after hydrolysis are primary alcohols ... 

Friedel-Crafts acylation of benzo[6]thiophene and its derivatives with succinic anhydride132,439,662,663 or the ester chloride of succinic acid614, 618, 650,662 gives a y-keto acid (or ester), which is reduced to the corresponding y-(benzo[6]thienyl)butyric acid by the Huang Minion or Clemmensen method. y-(Benzo[6]thienyl)butyric acids may alternatively be prepared by the diethyl malonate synthesis on the appropriate halide,439,499 by the Arndt-Eistert reaction on the corresponding propionyl chloride,409,618 or by cyclization.347,618 The ketones (317 R = Hor OMe)347 have been prepared by cyclization... 

Friedel-Crafts reaction of benzo[6]thiophene with ester chlorides of the type Et02C(CH2) C0Cl (w = 4-8) gives a mixture of the corresponding 2- and 3-keto ester.135 The 3-isomers may also be obtained by reaction of di(3-benzo[6]thienyl)cadmium with the above ester chlorides.135... 

Ar-(2-Pyridyl)malonamates 115, obtained in the reaction of 2-aminopyri-dines and malonic acid half-ester chloride, were cyclized in a mixture of phosphoryl chloride-polyphosphoric acid at 130°C for 2-5.5 hours to give 2-chloro-4//-pyrido[ 1,2-a]pyrimidin-4-ones 116 (84S152). 

The moderate yield may be due to the purification by reverse-phase chromatography, because 1 contains a tertiary amine. Preparation of other derivatives of 2 has shown that the radical annulation normally proceeds with 50-60 % yield and that many functional groups are tolerated (free alcohols, amines, esters, chlorides and terminal alkenes). Also (Me3Si)4Si may be a useful substitute for hexamethylditin, because tin residues are toxic and difficult to separate from the products. 

Phenylethylmalonic acid ethyl ester chloride Sodium carbonate N,N-Diethylethylenediamine... 

To a solution of 25.5 g of phenylethylmalonic acid ethyl ester chloride in 100 ml of anhydrous benzene 5.3 g of anhydrous sodium carbonate are added followed by 11.6 g of N,N-diethylethylenediamine in small portion. After the spontaneous heat evolution has subsided the mixture is refluxed for 2 hours until the evolution of carbon dioxide ceases. After cooling the mixture is... 

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