121-33-5 香兰素

中文别名 英文别名 CAS

密度：1.06 熔点：81-84℃ 沸点：170℃ (15 mmHg)

危险标志：GHS07 危险品标志：Xn 信号词：Warning 含量分析：方法一 用紫外吸收分光光度法分析(参见GT-29)。标准溶液的制备 准确称取药用参比标准香兰素约100mg，放入一250ml容量瓶中，用甲醇定容，混合。取该溶液2.0ml，放入一100ml容量瓶中，用甲醇定容后混匀。试样液的制备 准确称取试样约100mg，制备方法与上述标准溶液的制备相同。操作 取上述各溶液分别放入一1cm石英池中，在最大吸收波长约308nm处测定吸光度。按下式计算试样中香兰素(C8H8O3)的含量(X)(mg)：X=12.5c(Au/As)式中 c——标准溶液中香兰素的浓度，μg/ml；Au——试样液的吸光度；As——标准溶液的吸光度。方法二按气相色谱法(GT-10-4)中用非极性柱方法测定。 危险类别码：R22 安全说明编码 ：S22;S24/25 危险类别：43898 危险品运输编号：NONH for all modes of transport 危险性防范说明：P305 + P351 + P338 WGK Germany：1 RTECS号：YW5775000 敏感性：空气&光敏性 食品添加剂最大允许使用量最大允许残留量标准：FEMA(mg/kg)：软饮料63；冷饮95；糖果200；焙烤食品220；布丁类120；胶姆糖270；巧克力970；裱花层150；人造奶油0.20；糖浆330～20000。
按FAO/WHO规定：用于方便食品的罐头婴儿食品和谷类食品的最高允许用量为70mg/kg(1992)。 使用极限最大值：

添加剂中文名称	允许使用该种添加剂的食品中文名称	添加剂功能	最大允许使用量（g/kg）	最大允许残留量（g/kg）
香兰素	婴幼儿谷类食品（婴幼儿配方谷粉除外）	食品用香料	7mg /100g（100g以即食食品计，生产企业应按照冲调比例折算成谷类食品中的使用量）
香兰素	较大婴儿和幼儿配方食品	食品用香料	5mg／100ml（100ml以即食食品计，生产企业应按照冲调比例折算成配方食品中的使用量）
香兰素	食品	食品用香料	用于配制香精的各香料成分不得超过在GB 2760中的最大允许使用量和最大允许残留量

制造方法 1.将N，N-二甲基苯胺用盐酸酸化成盐，用亚硝酸钠硝化掉得对亚硝基-N，N-二甲苯胺盐酸盐。将其与愈创木酚、甲醛在41-43℃缩合。然后用苯萃取。第一次蒸馏，用苯重结晶，再进行第二次蒸馏，用水重结晶。50℃干燥得成品。亚硫酸纸浆废液中，含有桦柏醇结构单位的木质素磺酸盐，在碱性条件下氧化，然后水解可得到香草醛。原料消耗（kg/t）愈创木酚（98%） 1460亚硝酸钠 640N，N-二甲基苯胺（98%） 974盐酸（30%） 6000甲醛（99%） 320

2.将N,N-二甲基苯胺在30%的盐酸、亚硝酸钠存在下进行亚硝化反应，所得亚硝基化合物与邻甲氧基苯酚、甲醛进行缩合反应，再水解制得香草醛粗品：

含有对氨基N,N- 二甲基苯胺盐酸盐的粗品香草醛经萃取，二次蒸馏，用石油醚重结晶，干燥得到提纯。
3.将2- 甲氧基苯酚、乙醛酸钠、氢氧化钠在搅拌下加到水中，维持25℃反应24h ［2-甲氧基苯酚∶乙醛酸钠∶氢氧化钠∶水＝40∶24∶13 ∶ 950（ 质量比） ］ 。反应结束后，用硫酸调节混合物ph值为5，用苯萃取出未反应的2-甲氧基苯酚。然后于高压釜中与水、氢氧化钠、氧化铜混合，加175℃，控制压力303.9kPa ，边搅拌边以2L/min速度通入空气90min进行氧化反应。反应结束后，过滤除去氧化铜。所得反应产物用硫酸ph值为1.5，用甲基异丁基酮萃取5次，分去水层后，再用硫酸调ph值为7.0，于20℃下用甲基异丁基酮再萃取5次，分去水层。加热甲基异丁基酮层以蒸出甲基异丁基酮，之后，在666Pa下蒸馏，收集149～151℃馏分为目的产物香草醛成品。

4.以丁香油为基本原料，用酚钠盐法单离出丁香酚以后，按下列反应制取香兰素。
丁香酚异构化生成异丁香酚：

异丁香酚乙酰化生成乙酰基异丁香酚:

乙酰基异丁香酚氧化反应生成乙酰基香兰素：

乙酰基香兰素水解生成香兰素钾盐:

香兰素钾盐酸化生成香兰素：

② 以黄樟油素为原料制取。黄樟油素异构化生成异黄樟油素酚醚：

异黄樟油素酚醚甲基化、水解和氧化反应生成香兰素

③ 以木质素为原料制取。近年来许多国家采用造纸工业亚硫酸纸浆废液中的木质素来生产香兰素，由于原料来源丰富，是很有发展前途的合成方法。其反应过程如下：

④ 以愈创木酚为原料制取。

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Physicochemical properties Vanillin has strong and unique vanilla beans, naturally found in vanilla and clove oil, oil, oakmoss, balsam of Peru, and the rest of tolu balsam. Sulfite solution or red pulp softwood lignin sulfonate, under the alkaline conditions, reacted by high-pressure oxidation hydrolysis precipitation to get white to light yellow crystalline powder or acicular crystal. From petroleum ether precipitation can also generate tetragonal crystal. It has Aroma, Bitter sweet. In the air, it is gradually oxidized. In case of light, it generated decomposition. In case of alkali, it generated discoloration. The relative molecular mass is 152.15. The relative density is 1.056. melting point is different form tetragonal crystalline to another, tetragonal crystal is 81 to 83℃. Acicular crystal ranged from 77 to 79℃, the boiling point is 285℃ (in CO2 gas), 170℃ (2 x 103Pa), 162℃ (1.33 x 103Pa), 146 C (0.533 x 103Pa). It can generate sublimation without decomposition. The flash point is162 ℃. Slightly soluble in cold water, soluble in hot water, soluble in ethanol, ethyl ether, propylene Ketone, benzene, chloroform, carbon disulfide, glacial acetic acid, pyridine and volatile oil. Water and FeCl3 generate blue purple solution. For rats, by oral LD 50 1580mg/kg, mice is by percutaneous LD 50 1500mg/kg.
Industrial production method is that eugenol in the presence of potassium hydroxide, produce to ISO eugenol, then reacted with acetic anhydride formation of isoeugenol acetate, followed by oxidation and hydrolysis reaction to produce. It is an important raw material for mixing chocolate, ice cream, chewing gum the pastry and tobacco flavor. It can also be used as cosmetics fragrance coordination agent and a flavor enhancer. It is also the pharmaceutical raw materials of industry.
In recent years, it appeared a new fashion in the commodity of vanillin. Use oil of clove or basil oil provided out of eugenol as raw material, vanillin obtained by isomerization and oxidation, as it can be regarded as a natural equivalent quality, therefore it is called natural vanillin and into the spice market, its price is about 5 times that of the synthetic product. Side Effects General Side Effects
Using of vanillin in large quantity(over 30g a time) could lead to headache, nausea, vomiting, difficulty breathing, and even kidney damage.Don’t get too frightened, vanillin isn’t one of the most toxic food additives you’ll find and in fact usually won’t trigger much more than a headache or allergic reaction in sensitive folks. Usually, switching from artificial vanilla extract to pure vanilla extract is all that is needed to avoid issues. Many connoisseurs of the vanilla bean claim vanillin to be an inferior product to pure vanilla extract anyway. If you’re making an attempt to eat quality food, you probably won’t encounter much vanillin anyway.
Special Groups Precaution
Special groups refer to newborns, children, pregnant and any other applicable vulnerable groups.
There is no evidence that Vanillin could have any negative effects on these vulnerable groups. It should be safe to use Vanillin in food for newborns and pregnant. However, we still recommend consumers to consult professionals before using large quantity of Vanillin for long period in food for newborns or pregnant.
GRAS Affirmation: Yes
Generally recognized as safe(GRAS) is a FDA designation that a specific substance or ingredient is generally considered safe by experts, and so is exempted from the usual Federal Food, Drug, and Cosmetic Act (FFDCA) food additive tolerance requirements. Vanillin is considered safe by FDA according to existing data and granted GRAS status.