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山形県上倉山のクロベ(Thuja standishii Carr.)葉のヘキサン抽出成分について

高橋 孝悦 渡部 大寛 斉藤 正一 楠本 倫久 芦谷 竜矢 山形大学

2021.02.26

概要

The leaf n-hexane extracts (neutral and acidic fractions) in Kurobe (Thuja standishii) collected from Mt. Kamikura in Yamagata prefecture were analyzed by GC and GC-MS comparing with four other conifer leaves.
The results showed that the main constituents in the neutral fraction were α-pinene, sabinene and bornyl acetate for monoterpenes, and hibaene, dolabradiene and nezukol for diterpenes. There was a variation in the contents of nezukol among individuals. The results also showed that the main constituents in acidic fraction were palmitic acid for fatty acid and trans-communic acid for diterpene carboxylic acid, and variation was also found in the content of trans-communic acid among individuals. These results suggested that Kurobe have chemotypes.
As the results of the other conifers, the main constituents in the neutral fraction of Sugi (Cryptomeria japonica) were α-pinene, sabinene and limonene for monoterpenes, elemol and hydroxygermacrene for sesquiterpenes, and kaurene for diterpene. Unknown diterpene carboxylic acids were also found as main constituents in the acidic fraction. The main constituents in the neutral fraction of Hiba (Thujopsis dolabrata) were sabinene for monoterpene, elemol for sesquiterpene, and hibaene and dolabradiene for diterpenes. The main constituent in the acidic fraction was trans-communic acid for diterpene carboxylic acid. The main constituents in the neutral fraction of Hinoki (Chamaecyparis obtusa) were sabinene, β-myrcene, limonene, bornyl acetate and α-terpinyl acetate for monoterpenes, elemol for sesquiterpene, and hibaene for diterpene. Unknown lignans were also found as main constituents in the neutral fraction. Hinoki acid, sesquiterpene carboxylic acid, was also found as a main constituent in the acidic fraction. The main constituents in the neutral fraction of Kouyamaki (Sciadopitys verticillata) were α-pinene for monoterpene, and sclarene, kaurene and six unknown furano-type compounds for diterpenes. trans-Communic acid and unknown diterpene carboxylic acids were also found as main constituents in the acidic fraction.
The cluster analysis was carried out by using Ward’s method on the 53 major constituents found in neutral and acidic fraction. The results suggested that Kurobe (Thuja) had a near relationship with Hiba (Thujopsis), and far relationships with Kouyamaki (Sciadopitys) and Hinoki (Chamaecyparis).

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361

170

山形大学紀要(農学)第 18 巻 第 4 号

A0 peak : M+136 Tricyclene

Kouyamaki #:1: 5.880

A1 peak : M+136 α-Pinene

SugiT#:2: 6.165, Thuja #:2: 6.165, Hinoki #:2: 6.165, Kouyamaki #:2: 6.170

A2 peak : M+136 Sabinene

SugiT #:4: 7.190, Thuja #:5: 7.180, Hiba#:3: 7.185, HibaK #:4: 7.200

A3 peak : M+136 β-Myrcene

SugiT #:6: 7.630, Kouyamaki #:4: 7.630, HibaK #:6: 7.630

A4 peak : M+136 Limonene

SugiT #:8: 8.690

A5 peak : M+136 γ- Terpinene

Hinoki #:9: 9.555

A6 peak : M+152 Fenchone

Thuja3 #:11: 10.425

B1 peak : M+196

Thuja #:15: 14.305

B1-1 peak : M+154

Hinoki #:14: 14.265

(continued on next page)

Fig.8 MS spectrum of maim constituents in the leaf neutral fractions of Kurobe and four conifers.

362

山形県上倉山のクロベ(Thuja standishii Carr.)葉のヘキサン抽出成分について ─ 高橋・渡部・斉藤・楠本・芦谷

B2 peak : M+154

Hinoki #:15: 15.285

B3 peak : M+196 Bornyl acetate

Thuja #:16: 16.205, HibaK #:16: 16.225, Hinoki #:16: 16.225

B4 peak : M+ (181) α-Terpinyl acetate

C1 peak : M+204 Germacrene-D

C1-1 peak : M+204

C1-2 peak : M+222 Cubebol

C2 peak : M+(204) Elemol

Thuja #:17: 17.955, HibaK #:17: 18.000, Hinoki #:17: 18.000

SugiT #:9: 21.555, HibaK #:19: 21.555, Hinoki #:19: 21.555

Hinok #:20: 22.550

Hinoki #:21: 22.805

SugiT #:11: 23.275, Hiba #:9: 23.250, HibaK #:22: 23.305, Hinoki #:22: 23.305

C3 peak : M+222 Hydroxygermacrene

C3-1 peak : M+222

SugiT #:12: 23.945, HibaK #:24: 23.950, Hinoki #:24: 23.950

Kouyamaki #:10: 24.66012

Fig.8 (continued)

363

171

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山形大学紀要(農学)第 18 巻 第 4 号

C4 peak : M+222 β-Eudesmol

SugiT #:14: 25.765, Hinoki #:28: 25.765

α-Eudesmol

C5 peak :

SugiT #:15: 25.825 ,Hinoki #:29: 25.830

Hedycaryol Not detect

D0 peak : M+272 Rimuene

Thuja3 #:21: 31.225

D1 peak : M+272 Sclarene

Kouyamaki #:11: 31.925

D2 peak : M+272

Thuja #:19: 31.925, Hiba #:10: 31.935, HibaK #:17: 31.935, Hinoki #:35: 31.940

Hibaene

D3 peak : M+272 Dolabradiene

D4 peak : M+272

Iso-kaurene

D5 peak : M+272 Kaurene

Thuja #:21: 32.720, Hiba #:12: 32.755, HibaK #:18: 32.735

Thuja #:22: 33.245

SugiT: #:18: 34.220, Kouyamaki #:14: 34.200

Fig.8 (continued)

364

山形県上倉山のクロベ(Thuja standishii Carr.)葉のヘキサン抽出成分について ─ 高橋・渡部・斉藤・楠本・芦谷

D6 peak : M+290 Nezukol

D7 peak : M+286

SugiT #:20: 35.840

Sempervirol

Hiba #:19: 39.090, HibaK #:26: 39.100

D7-1 peak : M+374

Thuja #:31: 39.295

D8 peak : M+(271)

SugiT #:28: 41.530

E1 peak : M+374

Kouyamaki #:20:41.550

E2 peak : M+344

Kouyamaki #:21: 42.855

E3 peak : M+388

Kouyamaki #:23: 44.660

E4 peak : M+358

Kouyamaki #:24: 44.855

E5 peak : M+342

Kouyamaki #:25: 46.230

Fig.8 (continued)

365

173

174

E6 peak : M+328 Sciadin

山形大学紀要(農学)第 18 巻 第 4 号

Kouyamaki #:26: 46.360

F1 peak : M+354

Hinoki #:40: 51.810

F1-1 peak : M+400

Hinoki #:41: 52.340

F2 peak : M+352

Hinoki #:42: 52.705

F3 peak : M+398

HibaK #:32: 53.110

Fig.8 (continued)

366

山形県上倉山のクロベ(Thuja standishii Carr.)葉のヘキサン抽出成分について ─ 高橋・渡部・斉藤・楠本・芦谷

M1 peak : M+248

Hinoki acid methyl ester

M2 peak : M+270

Palmitic acid methyl ester

175

Hinoki #:29.925

SugiT #:6:31.910, Thuja1 #:20:31.915, Thuja2 #:18:31.910,

Thuja3 #:8:31.910, HibaK #:18:31.910, HinokiK #:31.920, KouyamakiK #:8:31.910

M3-0 peak : M+294

SugiT #:7:35.275, Thuja3#:35.270

M3 peak : M+292

SugiT #:8:35.410, Thuja2 #:19:35.415, Thuja3#:35.415, HibaK #:20:35.410,

HinokiK #:14:35.415,KouyamakiK #:9:35.405

M4 peak : M+316

Thuja3 #:11:37.025

M5-0 peak : M+316

SugiT #:11:37.985

M5 peak : M+316 trans-Communic acid methyl ester

Thuja1 #:2:38.465, Thuja2 #:20:38.465,

Thuja3 #:12:38.455, HibaK #:23:38.465, HinokiK #:16:38.455, KouyamakiK #:10:38.450

M6 peak : M+316

SugiT #:14: 39.310, HinokiK #:18:39.310

(continued on next page)

Fig.9 MS spectrum of maim constituent methyl esters in the leaf acidic fraction of Kurobe and four conifers

367

176

山形大学紀要(農学)第 18 巻 第 4 号

M7 peak : M+330

KouyamakiK #:11:39.755

M8 peak : M+348

SugiT #:16:41.665

M9 peak : M+334

SugiT #:19:42.455

M10 peak : M+328

KouyamakiK #:12:46.740

M11 peak : M+398

HibaK #:28:54.195

Fig.9 (continued)

368

...

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