Acetone homologues

By using acetone homologues, homologous or reduced ionones are produced which have intense odom-s of a similar character. 

Methyl Ethyl Ketone. Methyl ethyl ketone (MEK) (2-butanone), CH2COCH2CH2, is the next higher aUphatic ketone homologue to acetone, and third to acetone and cyclohexanone as the most important commercially produced ketone. 

Tetraethylammonium tetraphenylborate [12099-10-4] M 449.4. Recrystd from aqueous acetone. Dried in a vacuum oven at 60° for several days. Similarly for the propyl and butyl homologues. 

The phenylhydrazones of benzaldehyde and its homologues, (or of acetone) are readily autoxidised in solution and rearrange to give the azo-hydroperoxides, isolable as solids which may explode after a short time on standing, though not on friction or impact [1], Contact with flame or with cone, sulfuric or nitric acids also initiates explosion [2]. 

As expected, LC separation of the dichloromethane/acetone SPE eluate in the RP-mode, presented as FIA-APCI-MS(+) in Fig. 2.12.13, was impossible because the alkyl ethoxy amines as cationic surfactants could not be eluted under conventional RP-separation conditions [37, 53]. The use of methane sulfonic acid for ion-pairing resulted in the separation of the compounds in the methanol eluate as shown as TIC (d) and selected ion trace masses (m/z 504 (a), 670 (b), and 802 (c)) in Fig. 2.12.14. Here, the short-chain ethoxy amines were eluted later than the more polar long-chain homologues [39]. 

Optica] resolution of these and related carboxylic acids were achieved using salt formation with alkaloids (strychnine, brucine, cinchonidine) 33,39,44 or with optically active amines [1-phenyl- or l-( 3-naphthyl)ethylamine]4o,44). The following rotations [a]D have been reported [8]paracyclophanecarboxylic acid (13) +18° (chloroform)441 [10]homologue (14) +80° (chloroform)39 and +67° (chloroform)40 its methyl-derivative (75) —28° (methanol)44 . Dioxa[10]paracyclophanecarboxylic acid (16) + 104° (ethanol)36 and bromo-dioxa[12]paracyclophanecarboxylic acid (79) —37° (acetone)33). 

Volney patented in 1874 an expl intended for use in torpedoes contg Mononitronaphthalene 20.8, K nitrate 68.6 and S 10.6%. Another patent (1897) for cannon smokeless powder described the mixing of 86.00 p of dodecanitro-cellulose with 7.82 p of rosaniline or its homologues and 6.18 p of benzene, all dissolved in acetone. According to Ref 3, the production of Nitro-starch started in the USA in about 1888, under the name Volney s Powder ... 

Xanthene reacts differently with alkynes to give mostly the 9-xanthylidene derivative (462) and a small amount of its cyclized analogue (463) (73RTC845). The spiran (464) is formed in 15% yield when xanthone and l,3-diacetylimidazol-2-one or its homologues are irradiated in acetone (67CB3961). 

The case of propionylacetone has been dealt with already, and the higher homologues, n-butyrylacetone, n-valerylacetone and n-hexoyl-acetone behave in a similar manner. The chief product of the reaction has the general formula (I) and yields on reduction compound (II) ... 

The determination of acetone and its homologues in presence of methyl alcohol may be carried out by Messinger s method (Vol. I, p. 40). 

The two possible homologues, with either one or two methyl groups on the methylene carbon of the methylenedioxy group of MDA, are also known. The ethylidene compound (the acetaldehyde addition to the catechol group) has been encoded as EDA, and the acetone (isopropylidine addition to the catechol group) is... 

Industrial poisoning. The production of silicone products uses substances harmful for human health. These are inorganic substances (ammonia, chlorine, sodium and potassium hydroxides, sulfuric and hydrochloric acids, hydrogen chloride) and organic compounds of various types, such as hydrocarbons (methane, benzene and its homologues), chlorine derivatives (methyl- and ethylchloride, chlorobenzene), alcohols (methyl, ethyl, n-butyl, hydrosite), acetone, pyridine, etc. The information about their toxicity, explosion hazard, effect on human body, as well as maximum allowable concentrations of gases and vapours in the air at workplace can be found in special references.(Ryabov 1970). A comprehensive description of silicone substances is given in Table 29. 

Azine approach. Reactions of unsymmetrically substituted pyrimidine-2-thiones with 1,2-difunctional ethanes may yield two isomeric products on ring fusion, e.g. from 2-thiouracil (511) (71JCS(C)1527). For the 6-amino homologue, however, only the 5-oxo isomer (512) was obtained <77ACS(B)167). In the absence of a base, cyclization of the dichloro-2-thiouracil (513) is solvent dependent. Heating (513) in DMF, when the HBr from the reaction is boiled off, gives the 5-oxo product (514), whereas in acetone the HBr salt of the 7-oxo isomer (515) is precipitated (72ACS947). 

At 400 °C, the formation of acetone and formaldehyde (or perhaps formic acid) in the induction period is more important, while in the subsequent stages formaldehyde formation is again increased relative to the higher homologues (cf. /i-butanol). 

---