Penta methylene

Trimethylene dibromide (Section 111,35) is easily prepared from commercial trimethj lene glycol, whilst hexamethylene dibromide (1 O dibromohexane) is obtained by the red P - Br reaction upon the glycol 1 6-hexanediol is prepared by the reduction of diethyl adipate (sodium and alcohol lithium aluminium hydride or copper-chromium oxide and hydrogen under pressure). Penta-methylene dibromide (1 5-dibromopentane) is readily produced by the red P-Brj method from the commercially available 1 5 pentanediol or tetra-hydropyran (Section 111,37). Pentamethylene dibromide is also formed by the action of phosphorus pentabromide upon benzoyl piperidine (I) (from benzoyl chloride and piperidine) ... 

Woker attempts to apply this strain theory to ring compounds, and considers that the five carbon atom ring produces less strongly odoured substances than any other and points out that, according to Baeyer s strain theory, the five carbon ring has the least internal tension. It is very doubtful if this contention is correct, since the penta-methylenes do not seem to be less strongly odoured than other polymethylene ring compounds. ... 

Loss straightforward are results secured with aryl-substituted glycidic esters. Difficult to reconcile with the Parker-Isaacs model, for instance, are the reactions (Kqs. 029 and 630) of ethyl 3>penta-methylene glyojdate111 -l115-uz0 and ethyl 3-p-anisylgIyeid te.1128... 

N,N -Bi s(phenylazo) cyclo>2,3,5,7-penta> methylene-1,4-diamine or N,N -Bis(phenylazo) -ethylenetrimethylenediamine called N.N -Bis -benzoldiafco-[athylen-trimethylen-diamin] in... 

Preparation of the simplest diamine, ethylene diamine, by ammonolysis of the dihalide is accompanied by the formation of diethylenediamine and triethylenetetramine other methods for its preparation are more suitable. Only the higher homologs of /3-dialkylaminoethyl bromide respond favorably to this treatment. Thus, di-n-butylaminoethyl bromide is converted to the diamine in 55% yield whereas the dimethylaminoethyl bromide undergoes extensive dimerization. Triniethylene bromide reacts with liquid ammonia to form trimethylenediamine (50%) however, experimental details are lacking. When the two halogens in the dihalide approach one another in space as in tetra- and penta-methylene dibromides, then nitrogen spiranes are the main products. ... 

Imines.—The compounds so formed and containing the group (—NH—), are known as imines. The four carbon imine given above is named pjrrrolidine, and the di-amine from which it is formed, as tetra-methylene di-amine, also as putrescine. It is found as a putrefaction product of animal flesh. The analogous five carbon compounds are, penta-methylene di-amine, or, cadaverine, and the imine is piperidine. The last compound is found in pepper in combination as the alkaloid, piperine. 

CsHe Tri-methylene C4H8 Tetra-methylene C5H10 Penta-methylene C6H12 Hexa-methylene... 

While, however, penta-methylene is the most stable ali-cyclic compound of the poly-methylene group it is hexa-methylene which is of special interest and importance. This importance is due to the fact that it is the connecting link between the ali-cyclic compounds (carbo-cyclic compounds not derived from benzene, i.e. the poly methylenes) and benzene itself. Thus it becomes the connecting link between the aliphatic open-chain compounds and the very large and important division including benzene and its derivatives. 

The most important di-cyclic terpenes belong to the camphane group in which a penta-methylene ring is present. This five carbon... 

The constitution of pyrridine is established by numerous syntheses. The only one we shall mention is the one from cadaverine or penta-methylene di-amine. The corresponding tetra-methylene di-amine, as already stated (p. 855), loses ammonia and yields pyrrolidine, the saturated hydrogenated pyrrole. By an exactly similar reaction penta-methylene di-amine loses ammonia and yields the saturated hydrogenated pyridine which is known as piperidine. 

This compound, the hexa-hydro pyridine has just been referred to, and also previously, in connection with penta-methylene di-amine (p. 194). In both these connections its constitution has been established. As its name indicates, it is obtained from pepper in which it is present in amide combination with an acid known as piperic acid. The compound thus formed is the alkaloid of black pepper and is called pipeline. 

These two compounds have been mentioned previously (p. 193). They are respectively tetra-methylene di-amine and penta-methylene di-amine. 

Dinitroso(bicyelo)-2,4,6,8,9-penta-methylene-l,3,5,7-tetramine or 3,7-Dinitroso-... 

Methylsulfanyl)-5,6-tetra-(and penta)-methylene-l,4,2-dithiazines are thermolyzed in refluxing dioxane to yield methyl rhodanide and 1,4-dithiins, e.g. 2 (see Houben-Weyl, Vol. E9a, p 250, 268). It is assumed that the corresponding thietes or the a-dithiones are intermediates, because thermolysis of 3-(methylsulfanyl)-5,6-tetramethylene-l,4,2-dithiazine in the presence of dimethyl fumarate affords a 19% yield of dimethyl 5,6-tetramethylene-2,3-dihydro-1,4-ditkiin-2,3-di-carboxylate (4).1,2,20... 

As discussed previously, only chelates with a slow exchange rate remain stable in vivo. Indium-113m chelates with EDTA and DTPA have been utilized for the detection of brain tumors and for the study of renal funcions (26.27). Indium-113m chelates with ethylenediamine tetra(methylene phosphonic acid) (EDTMP) and diethylenetriamine penta(methylene phosphonic acid) (DTPMP) have been utilized to study bone tumors (28. 2Q). These agents also have promise for the detection of myocardial infarcts (3il). 

Briquest 462C-30S. See Sodium cyclohexane-1,2-diaminetetrakis (methylenephosphonate) Briquest 462D-AO. See Bis (hexamethylene) triaminepentakis (methylenephosphonic acid) Briquest 543-25S] Briquest 543-33S. See Sodium diethylenetriamine penta (methylene phosphonate)... 

Dequest 2066A. See Sodium diethylenetriamine penta (methylene... 

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