Page:EB1911 - Volume 22.djvu/47

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Tropilene, Cyl-li0O, is obtained in small quantities by the distillation of a-methyltropine methyl hydroxide, and by the hydrolysis of /Smethyltropidine with dilute hydrochloric acid. It is an oily liquid, with ati odour resembling that of benzaldehyde. It forms a benzal compound, and gives an oyxrnethylene derivative and cannot be oxidized to an acid, reactions which point to it being a ketone containing the grouping -CH2~CO-. It is thus to be regarded as a cyclo-heptene-1-one-7.

Cyclo-heptane carboxylic acid (suberanic acid), C7H|3CO2H, is obtained by the reduction of cyclo-heptene-I-carboxylic acid; from brom-cyclo-heptane by the Grignard reaction; and by the reduction of hydrotropilidine carboxylic acid by sodium in alcoholic solution (R. Willstiitter, Ber., 1898, 31. p. 2504). The corresponding oxyacid is obtained by the hydrolysis of the nitrile, which is formed by the addition of hydrocyanic acid to suberone (A. Spiegel, Ann., 1882, 211, p. 117).

Four cyclo-heptene carboxylic acids are known. Cyclo-heptene-1carboxylic acid-1 is prepared from oxysuberanic acid. This acld when heated with concentrated hydrochloric acid to I2O-130° C. yields a chlor-acid, which on warming with alcoholic potash is transformed into the cyclo-heptene compound. Cyclo-heptene-2-carboxylic acid-1 is formed by the reduction of cycla-heptatriene 2~4°6-carboxylic acid-1. On boiling with caustic soda it isomerizes to the corresponding 1-acid.

Cyclo-heplatriene carboxylic acids, C, H-, COZH. All four are known. According to F. Buchner (Ber., 1898, 31, p. 2242) they may be represented as follows:-

n co, n com, Zn


A.I,5.s»~L AL5.¢°vP~ A|.4 s°rr, ;z¢ c, .s

The at-acid (a-isophenylacetic acid) is obtained by the hydrolysis of pseudophenylacetamide, formed by condensing diazoacetic ester with benzene, the resulting pseudophenyl' acetic ester being then left in Contact with strong ammonia for a long time. B-Isoplienylacelic acid is formed by strongly heating pseudophenylacetic ester in an air-free sealed tube and hydrolysing the resulting B-isophenylacetic ester. 7-Isophenylacelic acid is obtained by heating the B and 5 acids for a long time with alcoholic potash (A. Einhorn, Ber., 1894, 27, p. 2828; E. Buchner, Ber., 1898, 31, p. 2249). 6-Isophenylacetic acid is obtained by heating the iodmethylate of anhydroecgonine ester with dilute caustic soda (A. Einhorn, Bef., 1893, 26, P- 329)-

Numerous amino-derivatives of the cyclo-heptane series have been prepared by R. Willstatter in the course of his investigations on the constitution of tropine (q.z'.). Amino-cyclo-hepiane (suberylamine) is obtained by the reduction of suberone oxime or by the action of sodium hypo bro mite on the amide of cycloheptane carboxylic acid. Cyclo-octane Group.

Few members of this group are known. By the distillation of the calcium salt of azelaic acid H. Mayer (Ann., 1893, 275, p. 363) obtained azelain ketone, CBHMO, a liquid of peppermint odour. It boils at 90-91° C. (23 mm.) and is readily oxidized by potassium permanganate to oxysuberic acid. It is apparently cyclo-octanone (see8a;so W. Miller and A. Tschitschkin, Cenlralblalt, 1899, 2., p. 1 1

Pseudapelletierine (methyl granatonine), C91-INNO, an alkaloid of the pomegranate, is a derivative of cyclo-octane, and resembles tropine in that it contains a nitrogen bridge between two carbon atoms. It is an inactive base, and also has ketonic properties. On oxidation it yields methyl granatic ester, which, by the exhaustive methylation process, is converted into homopiperylene dicarboxylic ester, HO2C~Cl-l:CH~C'H2-CH2'CH:CH~CO2H, from which suberic acid may be obtained on reduction. When reduced in alcoholic solution by means of sodium amalgam it yields methyl ranatoline, C, ,H', ;OH-NCI-lg; this substance, on oxidation with colri potassium permanganate, is converted into granatoline, CSHHNO, which on distillation over zinc dust yields pyridine. Methyl granatoline on treatment with hydriodic acid and red phosphorus, followed by caustic potash, yields methyl granatinine, CQHWN, which when heated with hydriodic acid and phosphorus to 240° C. is converted into methyl granatanine, CSHWNCH3, and granatanine, CBHHNH. The hydrochloride of the latter base when distilled over zinc dust yields a-propyl pyridine. By the electrolytic reduction of pseudopelletierine, N-methyl granatanine is obtained, and this by exhaustive methylation is converted into A'des-dimethyl granatanine. This latter compound readily forms an iodmethylate, which on treatment with silver oxide yields the corresponding ammonium hydroxide. The ammonium hydroxide on distillation decomposes into trim ethyl amine, water and cyclo-octadiene-1~3.


CH2NMe C0 -» CH, NM¢ CH2 -»CH2HO-NMe2CH2-CH.-CH-CH. CH2-CH-CH,

Pseudopelletierine N-methyl,


C H2-C H-C Hg

C Hr-C H-C H,



CH1 NMQ CH2+-CH2HO- N1v1e, CH.<-CH, CH

CH. CH = CH CH2 — CH =cH CH2~CH2~CH

A -*des-methyl cyclo-octadiene


Cyclo-ocladiene, CSHU, as above prepared, is a strong-smelling oil which decolonizes potassium permanganate solution instantaneously . It readily polymerizes to a di-cyclo-octadiene and polymer (C8H, ¢§ , . (R. Willstatter, Bef., 1905, 38, pp. 1975, 1984; G. Ciamician and P. Silber, Bef., 1893, 26, p. 2750; A. Piccinini, Gazz., 1902, 32, 1 p. 260). B-cyclo-octadiene has been prepared from methyl granatinine iodmethylate.

Cyclo-octane, CSHH, is obtained by the reduction of the above unsaturated hydrocarbon by the Sabatier and Senderens's method. It is a liquid which boils at 146 '3-148° C. and possesses a strong camphor odour. On oxidation it yields suberic' acid (R. Willstatter, Bei., 1907, 40, pp. 957). O. Doebner (Ben, 1902, 35, pp. 2129, 2538; 1903, 36, p.- 4318) obtained compounds, which in all probability -are cyclo-octadienes, by the distillation of /3-vinyl acrylic acid, sorbic acid, and cinnamenyl acrylic acid with anhydrous baryta. Cyclo-nonane Group.

According to N. Zelinsky (Ber., 1907, 40, p. 780) cyclononanone, CQHNO, a liquid boiling at 95~97° C., is formed on distilling sebacic acid with lime, and from this, by reduction to the corresponding secondary alcohol, conversion of the latter into the iodide, and subsequent reduction of this with zinc, cyclo-nonane, CgH,8, .a liquid boiling at 170~172° C. is obtained.

POLYNESIA, (Gr. 1ro}~z9s, many, and v'?';aos, island), a term sometimes used to cover the whole of the oceanic islands in the central and western Pacific, but properly for the eastern of the three great divisions ofithese islands. The chief groups thus included are Hawaii, the Ellice, Phoenix, Union, Manihiki and Marquesas groups, Samoa and Tonga, the Cook, Society, Tubuai and Tuamotu groups, and many other lesser islands. (See PACIFIC OCEAN, section on Island, and separate articles on the principal groups, &c.)

The Polynesian Race.-For the ethnological problems oiiered by Polynesia no thoroughly satisfactory solutions have yet been found. By some the term Polynesian has been treated as a synonym for MalayolPolynesian, and has been made to include all the brown races of Malaysia, Melanesia, Micronesia and Polynesia. Linguistically, physically and mentally this view is untenable. Whatever be the origin of the Polynesians, they are not Malays, though, themselves of mixed blood, they have probably certain racial elements in common with the latter, who are undoubtedly hybrids. There is every reason to believe that the Polynesians are ethnologically a far older race than the Malays, who, as they now exist, are a comparatively modern people; and thus Friedrich Mi.iller's and D. G. Brinton's theory, that they form a. branch of the Malays, fails. Joseph Deniker declares the Polynesians a separate ethnic group of the Indo-Pacific area, and in this view he is followed by A. H. Keane, who suggests that they are a branch of the Caucasic division of mankind who possibly migrated in the Neolithic period from the Asiatic mainland. Of the migration itself no doubt is now felt, but the first entrance of the Polynesians into the Pacific must have been an event so remote that neither by tradition nor otherwise can it be even approximately fixed. The journey of these Caucasians would naturally be in stages. Their earliest halting place was probably the Malay Archipelago, where a few of their kin linger in the Mentawi Islands on the west coast of Sumatra. Thence at a date within historic

times a migration eastward took place. The absence of Sanskrit roots in the Polynesian languages appears to indicate that this migration was in pre-Sanskritic times. Whether anything like a definite date can be lixed for it may well be questioned. Abraham Fornander[1] has, however, with great probability, traced back the history of the Hawaiians to the 5th century. He has studied the folk-lore of those islands exhaustively, and from this source comes to the conclusion that the Polynesian migration from the Indian Archipelago may be approximately assigned to the close of the 1st or to the 2nd century. The traditions of many of the Polynesian peoples tend to make Savaii, the largest of the Samoan Islands, their ancestral home in the East Pacific, and linguistic and other evidence goes to

  1. An Account of the Polynesian Race (1878), i. 168.