Chain Compounds Amine

Method 2. Place a 3 0 g. sample of the mixture of amines in a flask, add 6g. (4-5 ml.) of benzenesulphonyl chloride (or 6 g. of p-toluenesulphonyl chloride) and 100 ml. of a 5 per cent, solution of sodium hydroxide. Stopper the flask and shake vigorously until the odour of the acid chloride has disappeared open the flask occasionally to release the pressure developed by the heat of the reaction. AUow the mixture to cool, and dissolve any insoluble material in 60-75 ml. of ether. If a solid insoluble in both the aqueous and ether layer appears at this point (it is probably the sparingly soluble salt of a primary amine, e.g., a long chain compound of the type CjH5(CH2) NHj), add 25 ml. of water and shake if it does not dissolve, filter it off. Separate the ether and aqueous layers. The ether layer will contain the unchanged tertiary amine and the sulphonamide of the secondary amine. Acidify the alkaline aqueous layer with dilute hydrochloric acid, filter off the sulphonamide of the primary amine, and recrystaUise it from dilute alcohol. Extract the ether layer with sufficient 5 per cent, hydrochloric acid to remove all the tertiary amine present. Evaporate the ether to obtain the sulphonamide of the secondary amine recrystaUise it from alcohol or dilute alcohol. FinaUy, render the hydrochloric acid extract alkaline by the addition of dilute sodium hydroxide solution, and isolate the tertiary amine. 

Flotation. Tallow amines contain small amounts of short-chain compounds, eg, the octyl, lauryl, and myristyl (C ) groups. These amines usually produce enough froth for the flotation. Small quantities of specialized synthetic alcohols, eg, Dowfroth P, are frequentiy added to the flotation system to supplement the natural frothers. The quantities of the reagents used ia potash flotation plants are Hsted ia Table 5. 

Derivatives of pyrrolidine containing the ring in its fully reduced form are discussed in earlier sections of this book. To recapitulate, compounds containing this moiety seldom show activities that differ greatly in kind from the corresponding open-chain tertiary amine. 

Besides piperidine alkaloids, a total of 19 pyrrolidines have been found in the secretions of thief ants and fire ants of the genera Solenopsis and Monomorium. Among these, compounds 80-84 are simple pyrrolidines with two saturated linear all-carbon side chains only in Solenopsis latinode is there a secondary amine (82) and its methylated analog (85). One or two terminal unsaturations are present in compounds 86-91, which all possess a (hex-l-en)-6-yl chain and a 5-, 7-, or 9-carbon saturated chain. Compounds 93, 94, 96, 97, and 98 are the A-l-pyrrolines corresponding to pyrrolidines 80, 82, 90 (93 and 96 corresponding to 80, 94 to 82, and 97 and 98 to 90). 

The determination of cationic surfactants in the environment by GC and GC-MS is very scarce, as described above, but this is not the case for several compounds related to cationic surfactants. Thus, long chain tertiary amines that are amenable to direct analysis by GC have been... 

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]. 

The sensitivity of position 2 in 4-chloroquinazoline for nucleophilic addition was also demonstrated in the reaction with lithium piperidide (73RTC460). Whereas in the amination with potassium amide/liquid ammonia no open-chain intermediate could be isolated, with lithium piperi-dide/piperidine the open-chain compound ort/z6>-(piperidinomethy-leneamino)benzonitrile (78,60%) was obtained, in addition to 4-piperidino-quinazoline (80,19%) (Scheme 11.35). The formation of 80 from 78 involves... 

In a more detailed study of the reaction of 51 with butylamine and ben-zylamine, it was observed that trifluoroacetic acid was beneficial for the ring closure of the open-chain compounds, yielding the 1-t-butylinosine and 1-benzylinosine derivatives. Based on NMR spectroscopic studies, it was established that in the intermediate, obtained from 2, 3, 5 -tri-0-acetyl-l-nitroinosine with [ Njbenzylamine, the N-NO2 group is attached to the C(0) group, i.e., 56, justifying the conclusion that the attack of the ben-zylamine (and presumably that of the other amines) takes place at C-2 in the 1-nitroinosines. Further reaction of (56) gives the dibenzylamino compound 57. 

For example, Figure 2.3 shows plots of the a constants of X vs. log p/T of aliphatic carboxylic acids (XCOaH) and vs. log k for the dehydration of acetaldehyde hydrate by XC02H. Deviations from Equations 2.18 and 2.19 occurwhen the rate of reaction or position of equilibrium becomes dependent on steric factors. For example, Taft studied the enthalpies of dissociation, A Hd, of the addition compounds formed between boron trimethyl and amines (X1X2X3N) and found that when the amine is ammonia or a straight-chain primary amine the dissociation conforms to Equation 2.20, in which 2 ° is the sum of the a values for the... 

The special types of bonding in three-membered ethyleneimine rings (41—43) have been studied using microwave spectroscopy (44—47), electron diffraction (48), and photoelectron spectroscopy (49—51), and have occupied theoretical chemists up to the present day (52). These studies reveal that ethyleneimine has a distincdy shortened C—C bond of 0.148 nm (as compared to 0.154 nm in open-chain compounds) and a noticeably lengthened C—N bond of 0.149 nm (compared to 0.146 nm). Because of the high s character of the free electron pair on the nitrogen, ethyleneimine also shows a lower basicity (p Ka = 7.98) than noncyclic aliphatic amines such as dimethyl amine (p Ka = 10.7) (53). 

Table 1 summarizes the experimental results obtained in our laboratory on the kinetics of the normal dehydrogenation of hydrocarbons (hexahydro-aromatics to aromatics, the open chain compounds butylene to butadiene, and ethylbenzene to styrene), of amines to ketimines, and of alcohols to aldehydes or to ketones, respectively, in the presence of metallic or oxide catalysts. Equation (1) was found to apply in all cases. Ko and h are given by... 

Lane, E.S., Thin-layer chromatography of long-chain tertiary amines and related compounds, J. Chromatogr., 18, 426, 1965 Chem. Abs., 63, 7630f, 1965. 

Straight Chain Compounds Q to about Cio and more in many cases Alcohols, alkyl halides, acids, aldehydes, amines, nitriles, ketones. 

All the four series have high values of —dy/dT or dF/dT for the shorter chain compounds, which fall gradually to a nearly constant value as the chains are lengthened. The limiting value for the hydrocarbons, acids, and probably the amines also, is about 0 07 the triglycerides approach a decidedly lower value,... 

It is not necessary to have an all-carbon ring to preserve the cis geometry of a double bond. Lactones (cyclic esters) and cyclic anhydrides are useful too. A double bond in a five- or six-member ed compound must have a cis configuration and compounds like these are readily made. Dehydration of this hydroxylactone can give only a cis double bond and ring-opening with a nucleophile (alcohol, hydroxide, amine) gives an open-chain compound also with a cis double bond. The next section starts with an anhydride example. 

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