Diacyl dichlorides

The highest flexibility for a variation of the functional group and the chains X and Y (i.e. the size of the rim of the lamp shade) will be realiad when the synthesis of 3 is convergent and modular (Scheme 1). Amide bonds can easily be formed in macrocyclizations [13], therefore macrocyclic diamines 7 and diacyl dichlorides 8 had to be prepared. For the synthesis of macrocyclic diamines 7, also a large number of reactions are known. However, in this case a reduction of a macrocyclic diamide could not be achieved [11]. Therefore, another route was used the formation of macrocyclic diimines 6 (bis-Schiff bases) followed by NaBH4 reduction to the macrocyclic diamines 7. This approach has the advantage that for the construction of macrocyclic diimines 6, the metal ion template effect [14] may be exploited. 

A large number of concave pyridines 3 have been synthesized starting from pyridine-2,6-dicarbaldehydes 4, heteroatom containing a,o>-diamines 5 and diacyl dichlorides 8 (Scheme 1). In the first macrocyclization, the dialdehyde 4 and the diamine 5 were condensed in the presence of an alkaline earth metal ion to give a complex of a macrocyclic diimine 6 which was then reduced to the macrocyclic diamine 7. The yields of this reaction are excellent ( > 90%) when the size of the metal ion is adjusted to the size of the macrocycle formed. Mg was used for the formation of 15-membered, Ca for 18-membered and Sr for 21-membered rings. The macrocyclic diamines 7 were oils which could be purified in some cases. However, for the synthesis of the concave pyridines 3 the purity of the crude diamines 7 was sufficient. 

In the second macrocyclization, the reaction of the diamine 7 with a diacyl dichloride 8, the high dilution technique was used. Depending on the dia-mine/diacyl dichloride combination, the bimacrocycles 3 were obtained in yields... 

The synthetic strategy used for the construction of concave pyridine bislactams 3 (Scheme 1) can also be applied to other concave bases. When instead of a pyridine-2,6-dialdehyde 4, l,10-phenanthroline-2,9-dicarbaldehyde (9) was used in a metal ion template directed synthesis of macrocyclic diimines, after reduction, also macrocyclic 1,10-phenanthroline diamines 10 could be obtained in good yields. Here too, the crude diamines 10 were used in the next reaction step. Bridging of 10 with diacyl dichlorides 8 gave concave 1,10-phenanthroline bislactams 11. Scheme 2 summarizes the synthesis and lists the synthesized bimacrocycles 11 [18]. 

Surprisingly, the reaction of diacyl dichloride electrophiles with 3,4-dimethylphospholide affords the 3,3 -bis(phos-pholyl)lactones 225a and, 225b, which result from attack of the second molecule of phospholide at the phospholyl-C(0) group rather than the acyl chloride moiety (Scheme 72) <2005JOM450>. Note that the second attack was not observed using chloroformates as electrophiles (Scheme 72) <2004CC1144>. 

The bis(trimethylsilyl)phosphines (37 R = Ph, Bu ) react with the diacyl dichloride (38) to give the dibenzophosphepin derivatives (39) <87CC1753>. 

Dichloride and Another Diacyl Dichloride in the Ratio 1 1 1 in Pyridine (Sixfold Quantity of Diol) or Triethyl Amine (Twofold Quantity of Diol) at 40P C, The r Values for the Monochlorobisphenol A Were Set Equal to Unity for Reference Purposes... 

Ein weiteres effektives Mittel zur Cyclodehydratisierung von 1,2-Diacyl-hydrazinen ist Phos-phorsaure-dichlorid-phenylester in Dimethylformamid359. Diese Methode zeichnet sich durch hohe Ausbeuten bei relativ milden Reaktionsbedingungen aus. 

Cyclooctylester-0,0-diethylester XII/2, 629 -decylamid-hexylamid-myristylamid XII/2, 787 -S-decylester-dimethylamid-O-methylester E2, 627 0,0-Diacetyl- -dimethylamid XII/2, 819 S-(diacyl-methylester)-0,0-diester E2, 593 -di alkylamid-dichlorid... 

Though many open-chain diacyl peroxides have been described, very few cyclic compounds of this type are known. Monomeric cyclic phthaloyl peroxide (84) is prepared by treatment of phthaloyl chloride in chloroform with aqueous sodium peroxide solution in the presence of phosphate buffer, or by reaction of phthaloyl chloride with ethereal hydrogen peroxide in the presence of sodium carbonate.70-72 Russell71 has also obtained cyclic diacyl peroxides from the dichlorides of the C10, C12, and C14 dicarboxylic acids. Only polymeric diacyl peroxides were obtained from lower dicarboxylic acids. 

These studies allow the efficient synthesis of anfhraquinones under mild conditions, including anthracyclinones, by direcf ortho-bisacylafion of aromatic compounds with orf/io-phthaloyl dichlorides a few examples are reported in Table 2.6. Similarly, aromatic cycloalkanediones can be easily prepared by bis-acylation of aromafic compounds wifh different aliphatic diacyl chlorides. ... 

Diacylation products should be obtained by acylation reactions with dicarboxylic acid dichlorides. We carried out the reaction of methyl 10-undecenoate [2b] with adipic acid dichloride and EtA.lCl2 in a ratio of 2 1 4 (Scheme 3). After a reaction time of 2 h at room temperatoe, the product was crystallized from petroleum ether/ether (9 1) and identified as the methyl diketocarboxylate [9]. The aeylation took place at only one acyl chloride functionality of the dicarboxylic acid. The second acyl chloride functionality reacted with one equivalent of EtAlCl2in a Grignard analogous reaction to give the ethyl ketone. 

Carbonyl dichloride (CICOCI), a highly toxic compound that is also called phosgene, can be thought of as the diacyl chloride of carbonic add. Carbonyl dichloride reacts by nucleophilic addition-elimination with two molar equivalents of an alcohol to yield a dialkyl carbonate ... 

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