Malonyl chlorides

Polystyrene can be cross-linked by its acylation with bifunctional acylating agents such as adipoyl, sebacoyl, or malonyl chlorides ia the presence of AlCl iu CS2 solution at 0°C (106). 

Sanna reported that l,3-di(3-indolyl)-l,3-dioxo-%-propanc (266) and l,4-di(3-indolyl)-l,4-dioxo-M-butane (267) were formed by the action of malonyl chloride and succinyl chloride, respectively, on the indole Grignard reagent in ether, and analogous products could be obtained from 2-methylindole. 

Methyl- and 3-phenyl-4-hydroxy-2-oxo-2//-pyrido[2,1 -Z)]oxazinium inner salts were prepared in the reaction of 2-pyridone and 2-substituted malonyl chloride, prepared in situ from 2-substituted malonic acid with PCI5 in CH2CI2 (00JCS(P2)2096). 

Dimethylamino-(1.2-Dihydro-1,2,4-ben20trla2ine) Diethyl Propyl Malonate 3-Dimethylamlno-1,2,4-ben2otria2ine Oxide Propyl Malonyl Chloride... 

It is interesting to note that some 1,5-benzodiazepines such as 29 also possess CNS depressant activity. Treatment of substituted diphenylamine 26 with methyl malonyl chloride and reduction with Raney nickel led to orthophenylenediamine analogue 27. Sodium alkoxide treatment led to lactam formation (28), and alkylation in the usual way with NaH and methyl iodide produced clobazam (29). °... 

The cyclizations to obtain cyclic thioureas have been performed using thiocarbonyldiimidazole.232 Reaction of methyl acetoacetate, thiourea and an aliphatic aldehyde in the presence of the zinc iodide (Znl2) was studied. Under the normal pressure, reaction has not been occurred whereas at high pressure (300 MPa) conditions 3,4-dihydropyrimidine-2-thione was obtained only in 10% yield.233 The same one-pot three-component cyclocondensation reaction in the presence of iodide (I2) provides a variety of 3,4-dihydropyrimi-dine-2-thione in high yields.234 Condensation reaction of thioureas with a,p-unsaturated ketones in the presence of the sodium methoxide in methanol affords 3,4-dihydropyrimidine-2-thione derivatives.235,236 Acylation of N,N -disubstituted thioureas with methyl malonyl chloride followed by base-catalysed cyclization leads in the formation of l,3-disubstituted-2-thiobarbituric acids (Scheme 78).237... 

Ethyl tert-butyl malonate has been prepared by adding tert-butyl acetate and ethyl carbonate to sodium triphenylmethyl,3 and from ethyl malonyl chloride and fer/-butyl alcohol.4 The present procedure is an adaptation of that for the preparation of di-fer(-butyl malonate.2... 

Unusual transallenation reactions were discovered by Saalfrank et al. [29] during the reaction of the substituted malonyl chlorides 13 with the nucleophilic allene 14 (Scheme 7.3). In this case, 14 contributes only one and 13 the remaining two carbon atoms to the allene framework of the product 15. 

Several pyrazolo[l,2-a]pyrazoles are prepared by alkylation of pyrazoles with 1,3-dihalo compounds or with malonyl chloride (66FRP1441519 82LA420 86AP70). For example, treatments of 183 with disubstituted malonyl chlorides afford 184. Very similar to this is the formation of pyrazolo[l,2-a]-pyrazolium bromide from 1/f-pyrazoles and bromomethyloxirane (71JHC489 79JOC4473). 

Among dichloro bis-electrophiles, malonyl chloride with enamine 183b affords pyridone 189, probably resulting from C-alkylation and cyclocondensation followed by aromatization (02T2821). Finally, o-chloro-benzoylchloride leads to C-benzoylation and subsequent intramolecular substitution of the isolable intermediate to yield quinoline 190 (03ARK (is.2)146). 

Malonyl chloride reacted with boiling acetone to give the bicyclic 2 1 adduct 210 comprising a pyranone and a l,3-dioxan-4-one moiety (Scheme 99). The modest yield was compensated for by the ease of its preparation. Compound 210 bears a chloride which is almost as reactive as an acyl chloride and which can be substituted by various nucleophiles in a Stille coupling in modest yields <1997SL895>. Treatment of malonyl chloride with ketene and acetone at low temperature afforded symmetric bis(l,3-dioxin-4-ones) in 60% yield although a different reaction pathway may be assumed (Scheme 99) <2000TL4959>. 

This procedure is a modification 2 of the method of Altschul3 for preparing tert-butyl esters. Di-ferf-butyl malonate has been prepared by the reaction of malonyl chloride with tert-butyl alcohol in the presence of a tertiary amine.4... 

Barbituric acid may also be prepared by condensing urea with malonyl chloride [75] or with malonic acid in the presence of acetic anhydride [76]. 

Schulte and coworkers (62AP801) have prepared a number of 3-propargyl-4-hydroxy-2-pyrone derivatives (210) by condensation of /3-dicarbonyl compounds (208) with propargyl-malonyl chloride (209). On heating (210) with zinc carbonate, ring closure took place to give the corresponding furo[3,2-c]pyrone derivatives (211 Scheme 40). 

Although the structures of a series of 6-substituted 4-methoxypyran-2-ones have been established by chemical means, their alternative formulation as derivatives of 2-methoxy-pyran-4-ones was mainly excluded on the basis of an absorption at 1733 cm-1 attributable to the pyran-2-one system (59JA2427). This report concludes that pyran-2-ones exhibit their first carbonyl band at ca. 1725 cm-1, whereas pyran-4-ones absorb at ca. 1667 cm-1. Similarly, absorption at 1724 cm-1 indicated a pyran-2-one structure for yangonin (98), the major constituent of kava resin, and this has been confirmed by an unambiguous synthesis. Pseudoyangonin (99) absorbs at 1667 cm-1, characteristic of a pyran-4-one (60JCS502). Comparison of the spectra of some constituents of the rosewoods with that of yangonin established them as pyran-2-ones. The products from the reaction of malonyl chloride with some 1,3-diketones were identified in part by IR spectroscopy. 

Oxazine and -thiazine betaines (59) are prepared by reacting malonyl chlorides with secondary amides or thioamides respectively (Scheme 18). Carbon suboxide can be used instead of the acid chlorides, giving salts unsubstituted at C-5 (72S312). 

CARBON SUBOXIDE. Cy02, formula weight 68.03, colorless, toxic, gas at room temperature, very unpleasant odor, sp gr 2.10 (air = 1.00). 1.24 (liquid at -87°C). mp — I07 C. bp 7°C (760 lorr). bums with a blue smoky Haute, producing CO . When condensed to liquid, the oxide slowly changes at ordinary temperature to a dark red solid, soluble in water to a red solution. Reacts with water to form malonic acid, with hydrogen chloride to form malonyl chloride, with ammonia to form malonamide. Made by heating malonic acid or its ester at 300°C under diminished pressure, and separation from simultaneously formed carbon dioxide and ethylene by condensation and fractional distillation. 

A diamide and malonyl chloride gave a compound with two dioxo-tetrahydro-l,3-oxazine rings.116 Diacylamines were also used to produce tetrahydro-1,3-oxazine-4,6-dione.117... 

Monosubstituted malonyl chlorides can also be used to obtain 3,4-dihydro-l,3-oxazine-2,4-diones. Ziegler et al.1B reported the formation of 53 by heating benzylmalonyl chloride with phenyl isocyanate [Eq. (41)]. By carrying out the reaction in the presence of stannic chloride, the temperature can be considerably lowered.185 Mono-... 

Interaction of 1,2-dimethylindole with malonyl chloride or diketene gives 1,2,5-tri-substituted benzo[c /]indole-3-ones 199 (78S685 80LA971). 

Established methods for making 1,2,6-thiadiazines that have no 1,1-dioxide group include reactions of (i) sulfur diimides with malonyl chlorides and 1,3-diaminopropanes, (ii) sulfur dichloride with 1,3-diaminopropanes, and (iii) thionyl chloride with N.N-l,5-dinucleophiles such as 1,3-diaminopropanes or /3-amino a,/3-unsaturated aldimines and ketimines to give 5-oxides (79MI1 84MI1). 

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