(±)-リモネン 化学特性,用途語,生産方法
外観
無色～ほとんど無色透明液体
定義
本品は、次の化学式で表されるテルペンである。
解説
[別用語参照]リモネン
森北出版「化学辞典（第2版）
用途
湿潤剤、分散剤,香料(ネロリ油,マンダリン油などの調合)
構造
リモネンは、分子式C10H16で表される環状モノテルペンの一種です。
この分子はキラルであり、互いに鏡像である2つのエナンチオマーが存在します。いずれのエナンチオマーも天然に存在しますが、独特の強い柑橘臭を有するのはd-リモネンのみです。また、ラセミ体はジペンテンと呼ばれています。
d-リモネンは主に柑橘類の果皮に多く含まれ、l-リモネンはハッカなどに多く含まれています。ラセミ体である字ペン店はに多く含まれます。
リモネンは共役していないC=C二重結合を2つ有しているため、やや不安定で酸化され易いという特徴があります。
化粧品の成分用途
溶剤、香料
説明
D-limonene, which is
a volatile oil, constitutes approximately 98% of orange
peel oil by weight and has moderately good knockdown
activity against ectoparasites of companion animals. The
insecticidal activity of both d-limonene and linalool is
enhanced when synergized by piperonyl butoxide. Apart
from toxicoses reported in cats (65), d-limonene generally
has a high margin of safety.
化学的特性
d-, l- or dl-Limonene has a pleasant, lemon-like odor free from camphoraceous and turpentine-like notes. Limonene
is the most important and widespread terpene; it is known in the d- and l- optically active forms and in the optically inactive dl-form
(known as dipentene).
天然物の起源
It has been reported found in more than 300 essential oils in amounts ranging from 90 to 95% (lemon, orange,
mandarin) to as low as 1% (palmarosa); the most widespread form is the d-limonene, followed by the racemic form and then l-limo nene. Also reported found in ginger, nutmeg, pepper, mace, hop oil, coriander seed, calamus, dill herb, caraway seed and rosemary.
毒性学
D-limonene is a clear colorless mobile liquid with a pleasant lemon-like odor. （(4R)-limonene is an optically active form of limonene having (4R)-configuration. It has a role as a plant metabolite. It is an enantiomer of a (4S)-limonene.）D-limonene is one of the most common terpenes in nature. It is a major constituent in several citrus oils (orange, lemon, mandarin, lime, and grapefruit). D-limonene is listed in the Code of Federal Regulations as generally recognized as safe (GRAS) for a flavoring agent and can be found in common food items such as fruit juices, soft drinks, baked goods, ice cream, and pudding.
使用
d-Limonene is a flavoring agent that is a liquid, colorless with a pleasant odor resembling mild citrus. It is miscible in alcohol, most fixed oils, and mineral oil; soluble in glycerin; and insoluble in water and propylene glycol. It is obtained from citrus oil. It is also termed d-p-mentha-1,8,diene and cinene.
定義
ChEBI: A monoterpene that is cyclohex-1-ene substituted by a methyl group at position 1 and a prop-1-en-2-yl group at position 4 respectively.
製造方法
d-Limonene may be obtained by steam distillation of citrus peels and pulp resulting from the production of juice and cold pressed oils, or from deterpenation of citrus oils; it is sometimes redistilled.
調製方法
Limonene occurs in the oil of many plants and is the
main constituent (≤86%) of the terpenoid fraction of fruit,
flowers, leaves, bark, and pulp from shrubs, annuals, or trees
including anise, mint, caraway, polystachya, pine, lime, and
orange oil. It occurs as a by-product in the
manufacture of terpineol and in various synthetic products
made from α-pinene or turpentine oil. It is found in the gas
phase of tobacco smoke and has been detected in urban
atmospheres.
一般的な説明
A colorless liquid with an odor of lemon. Flash point 113°F. Density about 7.2 lb /gal and insoluble in water. Hence floats on water. Vapors heavier than air. Used as a solvent for rosin, waxes, rubber; as a dispersing agent for oils, resins, paints, lacquers, varnishes, and in floor waxes and furniture polishes.
空気と水の反応
Flammable. Insoluble in water.
反応プロフィール
Cinene may react vigorously with strong oxidizing agents. May react exothermically with reducing agents to release hydrogen gas.
健康ハザード
Liquid irritates eyes; prolonged contact with skin causes irritation. Ingestion causes irritation of gastrointestinal tract.
火災危険
Behavior in Fire: Containers may explode.
物理化学的諸性質
リモネンは柑橘類の精油に含まれる環状テルペンで、特に果皮に多く含まれます。特徴的な柑橘系の香りが特徴です。
リモネンは油脂を溶かす性質があるため、洗浄剤や脱脂剤の溶剤として使用されています。
水に不溶、アルコールに可溶
使用用途
リモネンは独特の爽やかな香りを生かし、食品や香料に多く用いられます。また、そのユニークな特性から、さまざまな産業用途に使用されています。
1. 香料としての利用
リモネンは、飲料や食品、入浴剤等の香料など、身の回りで幅広く用いられています。
2. 化学合成原料としての利用
リモネンは化学原料としても広く用いられる化合物です。
3. スチレンとの構造類似性と発泡スチロール回収剤としての利用
リモネンは、発泡スチロール（＝）の構成単位であると似た構造を有します（図2）。
そのため、『like dissolves like（＝類似した化合物同士はよく溶ける）』という化学の経験則からも予想されるように、リモネンには発泡スチロールを溶解します。この特徴を利用して、d-体のリモネンが発泡スチロールのリサイクル回収剤として利用されています。
化学反応性
Reactivity with Water No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.
接触アレルゲン
Dipentene corresponds to a racemic mixture of d-limonene and l-limonene. Dipentene can be prepared from wood turpentine or by synthesis. It is used as a solvent for waxes, rosin and gums, in printing inks, perfumes, rubber compounds, paints, enamels, and lacquers. An irritant and sensitizer, dipentene caused contact dermatitis mainly in painters, polishers, and varnishers
抗がん研究
Tested as promising antitumor molecules in induced tumor on rat tissues, D-limonenewas tested in preclinical studies in patients with advanced cancer. Limonene inhibitsthe activity of HMG-CoA reductase, subsequently reducing the possibility of cancergrowth. The mechanism of action involves the inhibition of prenyltransferases withthe activation of glutathione-S transferase and uridine diphospho-glucuronosyltransferase.More interest was pointed on the principal metabolite:perillyl alcohol which is more potent than limonene. The interest on perillyl alcoholis based on the necessity of a very high dosage of D-limonene in preclinical studies(about 1000 mg/kg/day in human mammary tumor) that can cause notably importantside effects. The more active perillyl alcohol and the less low active doseshypothesized this molecule as a clinical candidate (Pattanayak et al. 2009; Chenet al. 2013; Fontes et al. 2013; Rani and Sharma 2013).
安全性プロファイル
A skin irritant.
Flammable when exposed to heat or flame;
can react vigorously with oxidzing
materials. When heated to decomposition it
emits acrid smoke and irritating fumes.
発がん性
Induction of kidney neoplasias
has been observed in male rats of strains that have significant
concentrations of the protein a2u-globulin (158a). This
protein is not expressed in females or species other than
the rat; therefore, limonene carcinogenicity appears to be
limited to the male of specific strains of this species.
Subcutaneous injection of the compound or its hydroperoxide
into C57BL/6 mice decreased the incidence of dibenzopyrene-
induced tumors appreciably. Given orally
either 15 min or 1 h prior to nitrosodiethylamine, D-limonene
reduced forestomach tumor formation by about 60% and
pulmonary adenoma formation by about 35%. Reduction of
cancer incidence and metastasis by limonene has also been
reported in other systems (158b).
製造方法
リモネンは、柑橘類の果皮から抽出される天然の物質であり、オレンジ、レモン、ライムなどに含まれています。工業的には、抽出、水蒸気蒸留、あるいは化学合成によって生産されます。
①抽出
柑橘類の果皮を機械的に絞り、得られた液体から脂肪族化合物を除去し、蒸留によって精油を得る方法です。得られた精油中には、リモネンの他にも、カルボン酸、アルデヒド、ケトンなどが含まれます。
②水蒸気蒸留
①の方法にに似ていますが、柑橘類の果皮を水蒸気で蒸留し、得られた蒸気を冷却して油を分離する方法です。
環境運命予測
Limonene is insoluble and is stable in water. Substances like
limonene that are monoterpenes are released in large
amounts mainly to the atmosphere. The chemical and physical
properties of limonene also indicate that limonene is
distributed mainly to air. Based on the physical and chemical
properties of limonene, when this substance is released to
ground, it has low to very low mobility in soil. The soil
adsorption coefficient (Koc), calculated on the basis of the
solubility (13.8 mg l
-1 at 25 ℃) and the log octanol/water
partition coefficient (4.232), ranges from 1030 to 4780.3.
Henry’s Law constant indicates that limonene rapidly
volatilizes from both dry and moist soil; however, its strong
adsorption to soil may slow this process. In the aquatic
environment, limonene is expected to adsorb to sediment and
suspended organic particles to rapidly volatilize to the
atmosphere, based on its physical and chemical properties.
The estimated half-life for volatilization of limonene from
a model river (1 m deep, flow 1 ms
-1, and wind speed
3 ms
-1) is 3.4 h. The bioconcentration factor, calculated on
the basis of water solubility and the log octanol/water
partition coefficient, is 246–262, suggesting that limonene
may accumulate in fish and other aquatic organisms.
(±)-リモネン 上流と下流の製品情報
原材料
準備製品