Miscellaneous compounds

These two compounds are not alkylating agents. Hence, the fact that they possess sterilising potency justifies either the assumption of another mechanism of action, or the revision of theories of the mode of action of aziridine derivatives. Oxidative conversion of the dimethylamino groups to aziridine groups may serve as a further explanation. 

Several authors established the sterilising activity of urea and thiourea derivatives such as 4-imidazolidin-2-one (31) (Flint et al.. 1968 Simkover, 1964), 

Ascher et al. (1967) found that triphenyl tin hydroxide (fentin hydroxide, 34) and triphenyltin acetate (fentin acetate, 35), already known for their fungicidal and insect antifeedant effect, also show insect sterilising activity. They assumed that the sterilisation of male insects is brought about by a slow poisoning of the sperm. 

DeMilo and co-workers (1974) reported on the male sterility of houseflies induced by 2,5-dichloro-N-(2,4-dinitrophenyl)-benzenesulfonamide (36). In subsequent studies aimed at optimalisation of the sterilising effectiveness, they found the 3,4-dichloro-analogue (37) to be the most active, within this group (DeMilo et al., 1977). 

An interesting type of insect chemosterilants has been reported by Jurd et al. (1979). They found that benzyl derivatives of 2,4-di-/-butylphenol and of 1,3-benzodioxoles sterilise houseflies when fed at concentrations as low as 0.025% in the diet. The most active members of this group are 2,4-bis(l,l-dimethylethyl)- 

A number of volatile aliphatic compounds that contain nitrogen or sulfur atoms are important aroma constituents. Alkyl thiols, dialkyl sulfides and disulfides, and alkyl thiocyanates belong to this group. They occur widely in foods and spices and determine the odor of, for example, onions, garlic, and mustard. Because of their potent smell, they are used in high dilution and are often produced only in small quantities. The same is true for the following  

4-mercapto-4-methyl-2-pentanone [19872-52-7], the so-called catty compound found in blackcurrant flavor and the wine variety scheurebe . 

Allyl isothiocyanate, however, is an exception in that it is produced in large quantities. A heptanone oxime and the 2-tridecenenitrile have become important as fragrance materials. 

CH2 =CHCH2N = C = S, C4H5NS, M, 99.14, 6pioi.3kPa 152°C, df 1.0126, is the main component of mustard oil ( 95%). It is a colorless oil with a typical mustard odor and can be prepared by reacting allyl chloride with alkaline-earth or alkali rhodanides [28]. 

It is used in compositions with agrumen notes for perfuming, e.g., cosmetics, soaps, and detergents. 

C8H17NO, Mr 143.23, bpo.i i-pa 70 °C, wf 1.4519, is not reported as being found in nature. It is a colorless to pale yellow liquid with a powerful, green, leafy odor. 5-Methyl-3-heptanone oxime is prepared by oximation of the corresponding ketone. It imparts natural and fresh nuances to fragrance notes and is used in fine perfumery as well as in cosmetics, soaps, and detergents. 

There are many other organometallic compounds which have not been covered in the preceding sections. For these, the reader should consult general references such as the following  

Greenwood, ed.. Spectroscopic Properties of fnorganic and Organometailic Compounds, Vol. 1 (196B) to present, The Chemical Society, London. 

OrganometaUic Compounds Methods of Synthesis. PhysictdCorrstants and Chemical Reactions, Vols. 1-3, Springer-Verlag, New York, 1966. 

Maslowsky, Jr, Vifcratiofic/ Spectra of Organometailic Corttpounds, Wiley, New York, 1977. 

Nakamoto, Characterization of OrganometaUic Compounds by Infrared Spectroscopy , in M. Tsutsui cd., C/jaracterirati o of Organometailic Compounds, Part I, Wiley-Interscience, New York, 1969. 

This section presents a brief overview of a few other compounds that have not been described in previous sections. Because it can function as a nonmetal, silicon forms sihcides with several metals. These materials are often considered as alloys in which the metal and silicon atoms surround each other in a pattern that may lead to unusual stoichiometry. Examples of this type are Mo3Si and TiSi2. In some sihcides, the Si-Si distance is about 235 pm, a distance that is quite close to the value of 234 pm found in the diamond-type structure of elemental silicon. This indicates that the structure contains Si22-, and CaSi2 is a compound of this type. This compound is analogous to calcium carbide, CaC2 (actually an acetylide that contains C22- ions (see Chapter 10)). 

Silicon combines with carbon to form silicon carbide or carborundum, SiC, and forms are known that have the wurtzite and zinc blende structures. It is a very hard, tough material that is used as an abrasive and a refractory. The powdered material is crushed after mixing with clay and heated in molds to make grinding wheels. It is prepared by the reaction 

There is also a silicon nitride, Si3N4, which is prepared in an electric furnace by the reaction 

Germanium also forms a +2 compound with nitrogen, Ge3N2, as well as an imine, GeNH. These compounds are obtained by the reactions 

Sulfide compounds are formed by all of the Group IVA elements, and lead is found as the sulfide in its principle ore galena that has Pb2+ and S2 ions in a sodium chloride lattice (see Chapter 3). A chain structure is shown by SiS2 in which each Si is surrounded by four S atoms in an approximately tetrahedral environment  

Chan and Reineccius [35] also have published some kinetic work on other aroma compounds (isovaleraldehyde, phenylacetaldehyde, 2-acetyl-l-pyrroline, 2-acetyl-furan, and di(H)di(OH)-6-methyl pyranone). All of these volatiles followed pseudo zero order reaction kinetics in their early stages of reaction (Table 5.2). The fact that the concentrations of isovaleraldehyde, phenylacetaldehyde, and the methylpyr-anone reached plateaus late in heating suggests that a first order fit, as proposed by Jusino et al. [32], might be more appropriate. 

The very low activation energy for 2-acetyl-l-pyrroline may help explain why this volatile is found by sniffing methods in nearly every food stndied. It appears that this compound is very readily formed even nnder mild heating conditions. This fact, coupled with its extremely low sensory threshold, make its detection in foods likely. The Strecker aldehydes, isovaleraldehyde and phenylacetaldehyde, followed similar kinetics during heating. This is due to the similar mechanism of formation and the fact that they are both consumed through reaction to form 5-methyl-2-phenyl-2-hexenal [39]. 

Marshall [117] prepared several enantiomericaUy pure aUenylstannanes 485 either by cuprate Sn2 displacement of propargylic mesylate 486 or via a Claisen-Johnson rearrangement from alcohol 483. After functional group transformations, correlation was achieved between the two series of compounds 

In this case allylic alcohol 487 afforded the rearranged ester 488 in moderate yield. 

Fluorinated analogues of biologically active molecules have received, in the past twenty years, an increasing interest. The Claisen-Johnson rearrangement applied to fluoro-substituted allylic alcohols appeared rapidly as a method of choice for the synthesis of various fluoro-polyfunctionalized compounds. Claisen rearrangement and Claisen-Johnson rearrangement of trifluoromethyl allylic alcohols 533 developed by Ishikawa [131] afforded selectively the anticipated esters 534 and 535. Z,syn-config- 

1 For recent comprehensive reviews concerning the Claisen rearrangement and related reactions, see (a) F. E. Ziegler, Chem Rev. 1988, 88, 1423-1452, 

4 (a) G. Saucy, R. Marbet, Helv. Chim. Acta, 1967, 50, 1158-1167 (b) G. Saucy, R. Marbet, Helv. Chim. Acta, 1967, 50, 2091-2100. 

A structurally very simple carboxylic acid, modafinil (62-4), increases alertness and inhibits narcolepsy as a result of its activity as a cerebral ai-adrenergic agonist. The short synthesis begins with the reaction of benzhydrol proper (62-1) with chloroacetic 

A modihcation on verapamil uses a spiro-dithiane moiety to supply the quaternary center. Reaction of veratraldehyde (64-1) with propane 1,3-dithiol leads to dithiane (64-2). Reaction with hydrogen peroxide oxidizes the ring sulfur atoms to 

Yamazaki, M. Hamana, M. Chem. Pharm. Bull. 1971, 19, 2050. 

For a review of research leading to these drugs see Nicholson, J. S., in Chronicles of Drug Discovery, Vol. 1, Bindra, J. S. Lednicer, D., eds. Wiley, New York, 1982, 149. 

Zwierak, A. Gajda, T. Koziara, A. Zawadski, S. Osawa-Pacewicka, K. Olejniczak, B. Wasilewska, W. Kotlicki, S. Cichon, J. Pohsh Patent, 1992, 156975. 

Rodenticides are used to control rats and mice in fields, in storage areas, and in household environments. Rodents not only destroy harvested products, but are also vectors for contagious diseases. Most rodenticides belong to the coumarin group and act as anticoagulants. Bromadiolone is an example of a relative selective rodenticide that is highly toxic to rodents, but less toxic to domestic animals such as dogs and cats. 

Common name or chemical name Chemical class Mode of action Typical uses Structure 

Copper salts Inorganic Prevents spore germination nonsystemic Control of powdery mildew, blights, and rust — 

Sulfur Inorganic Inhibits respiration nonsystemic Control of mildew, shot-hole, mites  

Mancoceb or manganese ethylenebis(dithiocarba-mate) polymeric, complex with Zn salt Dithio- carbamate Inhibits respiration, nonspecific with protective action Control of many fungal diseases in field crops, fruit, flowers 11-26 

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MISCELLANEOUS COMPOUNDS DERIVED FROM PRIMARY AMINES... 

Other auxin-like herbicides (2,48) include the chlorobenzoic acids, eg, dicamba and chloramben, and miscellaneous compounds such as picloram, a substituted picolinic acid, and naptalam (see Table 1). Naptalam is not halogenated and is reported to function as an antiauxin, competitively blocking lAA action (199). TIBA is an antiauxin used in receptor site and other plant growth studies at the molecular level (201). Diclofop-methyl and diclofop are also potent, rapid inhibitors of auxin-stimulated response in monocots (93,94). Diclofop is reported to act as a proton ionophore, dissipating cell membrane potential and perturbing membrane functions. 

Other miscellaneous compounds that have been used as inhibitors are sulfur and certain sulfur compounds (qv), picryUiydrazyl derivatives, carbon black, and a number of soluble transition-metal salts (151). Both inhibition and acceleration have been reported for styrene polymerized in the presence of oxygen. The complexity of this system has been clearly demonstrated (152). The key reaction is the alternating copolymerization of styrene with oxygen to produce a polyperoxide, which at above 100°C decomposes to initiating alkoxy radicals. Therefore, depending on the temperature, oxygen can inhibit or accelerate the rate of polymerization. 

Miscellaneous Compounds. Among simple ionic salts cerium(III) acetate [17829-82-2] as commercially prepared, has lV2 H2O, has a moderate (- 100 g/L) aqueous solubiUty that decreases with increased temperature, and is an attractive precursor to the oxide. Cerous sulfate [13454-94-9] can be made in a wide range of hydrated forms and has solubiUty behavior comparable to that of the acetate. Many double sulfates having alkaU metal and/or ammonium cations, and varying degrees of aqueous solubiUty are known. Cerium(III) phosphate [13454-71 -2] being equivalent to mona2ite, is very stable. 

Miscellaneous compounds such as biopesticides (for example. Bacillus thuringiensis and pherhormones), heterocycles (for example, atrazine), pyrethroids (for example, cypermethrin), and urea derivatives (for example, diuron). 

Some examples of metal ion indicators. Numerous compounds have been proposed for use as pM indicators a selected few of these will be described. Where applicable, Colour Index (C.I.) references are given.12 It has been pointed out by West,11 that apart from a few miscellaneous compounds, the important visual metallochromic indicators fall into three main groups (a) hydroxyazo compounds (b) phenolic compounds and hydroxy-substituted triphenylmethane compounds (c) compounds containing an aminomethyldicarboxymethyl group many of these are also triphenylmethane compounds. 

Abscisin II may be viewed as a monocyclic analog of these two anomalous sesquiterpenes. Alternatively, it may be one of a larger group of miscellaneous compounds which do not necessarily possess exactly 10 or 15 carbon atoms but may be looked upon formally (and perhaps actually) as degradation products of the carotenoids. This view is favored by the fact that the carotenoids are the only class of plant products in which cyclization of the type found in abscisin II is very common. Other examples of these compounds in-... 

Table 27 Miscellaneous compounds T8[(CH2)3NRiR2]8 obtained from T8[(CH2)3NH2]8 or T8[(CH2)3NH3Cl]8... 

SECTION 45 ALCOHOLS AND THIOLS FROM MISCELLANEOUS COMPOUNDS... 

Esters from carboxylic acids and halides, sulfoxides and miscellaneous compounds... 

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