CN103772158A - Benzyl-2-naphthyl ether preparation method - Google Patents

Benzyl-2-naphthyl ether preparation method Download PDF

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CN103772158A
CN103772158A CN 201210408414 CN201210408414A CN103772158A CN 103772158 A CN103772158 A CN 103772158A CN 201210408414 CN201210408414 CN 201210408414 CN 201210408414 A CN201210408414 A CN 201210408414A CN 103772158 A CN103772158 A CN 103772158A
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benzyl
naphthyl
ether
naphthol
benzyl ether
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CN 201210408414
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Chinese (zh)
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张秀岩
李善柱
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沈阳感光化工研究院
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01Preparation of ethers
    • C07C41/16Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups

Abstract

The invention relates to a preparation method of a thermosensitive sensitizer, and particularly relates to a benzyl-2-naphthyl ether preparation method. The benzyl-2-naphthyl ether preparation method provided by the invention is simple in operation, high in yield, safe, free of pollution and low in cost, benzyl chloride and 2-naphthol are used as raw materials for reaction under solvent-free conditions to obtain benzyl-2-naphthyl ether. The benzyl-2-naphthyl ether preparation method has the advantages of simple operation, less side reaction products, short reaction time, simple post treatment, high yield, no pollution, low cost, and suitability for industrialized production.

Description

苄基-2-萘基醚的制备方法 The method of preparing benzyl-2-naphthyl ethers

[0001] 技术领域: [0001] Technical Field:

本发明涉及一种热敏增感剂的制备方法,更具体地说,是涉及一种苄基-2-萘基醚的制备方法。 The present invention relates to a method for preparing a heat-sensitive sensitizer, more particularly, is directed to a process for the preparation of 2-naphthyl benzyl ether.

[0002] 背景技术: [0002] BACKGROUND:

热敏记录纸作为热敏打印的介质之一,被广泛应用在传真、医疗记录、电子收银系统等领域,其用途日益广泛,市场前景非常广阔。 Thermosensitive paper as one of the medium thermal printing, is widely used in the fields of fax, medical records, electronic cash register system, which is increasingly widespread, the market prospects are very bright.

[0003]目前热敏记录纸由于在新材料的使用和热敏涂料配方方面的差异而导致不同的公司生产的热敏记录纸在发色敏感度和反射光度方面有着很大的差异,为了提高热敏记录纸的发色敏感度和反色光度,而向热敏涂料中添加的一种化学成分以实现热敏记录纸的高感度化。 [0003] The present thermal recording paper due to a difference in the use of new materials and heat sensitive coating formulations result in different aspects of the produced thermal recording paper are quite different in color-sensitivity and reflectance photometry aspect, in order to improve the thermosensitive recording sensitivity and anti color-shade of the paper, and a chemical added to the heat sensitive coating composition to achieve a sensitivity of thermal recording paper. 添加的这种化学成分就叫热敏增感剂。 This is called a thermal chemical components added sensitizer.

[0004] 增感剂有化学增感剂和光学增感剂两类。 [0004] The sensitizer chemical sensitizers, and two optical sensitizer. 光学增感剂因多为一种特殊的染料,又称增感染料,加入这种染料后,可使感色范围扩大至整个可见光区域。 The optical sensitizer mostly because a special dye known as a sensitizing dye, the addition of such dyes, color sensing can be extended to the entire range of the visible region. 这种增感剂用量极少,但对照相性能却产生很大影响。 Such sensitizers little amount, but has a great influence on the photographic properties. 热敏染料始于1950年,当时美国NCR公司开发的结品紫内酯(CVL)是最早的热敏染料。 Thermal dye began in 1950, when the United States developed by NCR end product violet lactone (CVL) is the oldest thermal dye. 随着情报记录体系的发展特别是传真机的普及,1969年该公司又开发了新一代热敏染料即发黑色的荧烷化合物ODBn]。 With the development of information-recording system, in particular the popularity of fax machines, in 1969 the company has developed a new generation of fluoran compound ODBn thermal dye that is made black]. 此后热敏染料发展更快,目前市场前景非常广阔。 After thermal dye faster development, the market prospects are very bright.

[0005] 苄基-2-萘基醚,别名:苄基-2-萘醚,BON ;CAS:613-62-7 ;分子式;C17H140,分子量:234.3,结构式为: [0005] benzyl 2-naphthyl ether, alias: 2-naphthyl benzyl ether, BON; CAS: 613-62-7; molecular formula; C17H140, molecular weight: 234.3, of the formula:

Figure CN103772158AD00031

[0006] 制备苄基-2-萘基醚的传统方法是威廉森法,但是该合成方法生产条件要求苛亥IJ,反应时间长,操作复杂,产品收率低。 [0006] The conventional method of preparing benzyl-2-naphthyl ethers are Williamson method, but this method of synthesis requires harsh Hai IJ production conditions, the reaction time is long, complicated operation, low production yield. 还有就是国内报导的相转移催化合成方法,虽然该方法操作简单,收率较高,为80%左右,但是需要价格较高的相转移催化剂四丁基溴化铵,而且后处理相对较复杂,相对成本较高。 There is reported the synthesis of domestic phase transfer catalysis method, although the method is simple, a high yield of about 80%, but requires more expensive phase transfer catalyst is tetrabutylammonium bromide, and the relatively complicated post-treatment , relatively high cost.

[0007] 发明内容: [0007] SUMMARY OF THE INVENTION:

本发明就是针对上述问题,提供了一种操作简单、收率高、安全无污染、成本低的苄基-2-萘基醚的制备方法。 The present invention addresses the above problems, a method of preparing a simple, high yield, safety and no pollution, and low cost-benzyl-2-naphthyl ether.

[0008] 为了实现本发明的上述目的,本发明采用如下技术方案, [0008] To achieve the above object of the present invention, the present invention employs the following technical solution,

其以氯化苄和2-萘酚为原料,在无溶剂条件下反应得到苄基-2-萘基醚,反应方程式 Which is 2-naphthol and benzyl chloride as starting material, the reaction in the absence of a solvent gave benzyl 2-naphthyl ether, reaction equation

为, for,

Figure CN103772158AD00032

[0009] 制备步骤为,将摩尔为1.1~1.5:1的氯化苄和2-萘酚混合,最好是1.2:1,在110-120°C下反应3~5小时,然后将体系温度降至90°C,滴加有机溶剂进行结晶,过滤、干燥后得到苄基_2_萘基醚。 [0009] The preparation step, a 1.1 to 1.5 mol: 1 benzyl chloride and 2-naphthol mixed, preferably 1.2: 1, the reaction at 110-120 ° C 3 ~ 5 hours, then the temperature of the system down to 90 ° C, dropwise addition of an organic solvent for crystallization, filtration, and dried to give _2_ naphthyl benzyl ether.

[0010] 所述的有机溶剂为甲醇、乙醇或丙醇。 [0010] The organic solvent is methanol, ethanol or propanol.

[0011] 反应中加入缚酸剂,其添加量与2-萘酚的摩尔比为1.0~1.5:1。 [0011] The reaction molar ratio of the acid binding agent is added, the addition amount of 2-naphthol with 1.0 to 1.5: 1.

[0012] 所述的缚酸剂为碳酸钠、碳酸钾、氢氧化钠、氢氧化钾中的一种以上。 The acid-binding agents [0012], wherein sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, one or more.

[0013] 将过滤、干燥后得到的苄基-2-萘基醚继续加到水中,料液比为1:5~10g/ml,加热至40-50°C,搅拌I小时,过滤,干燥,得到终产物苄基-2-萘基醚。 [0013] The filtration and dried to give benzyl 2-naphthyl ether was added to continue the water liquid ratio of 1: 5 ~ 10g / ml, was heated to 40-50 ° C, stirred for I h, filtered and dried to give the final product benzyl-2-naphthyl ethers.

[0014] 缚酸剂与2-萘酚的摩尔比为1.0:1。 [0014] The molar ratio of acid-binding agents with 2-naphthol was 1.0: 1.

[0015] 苄基-2-萘基醚与水的料液比为1:5 g/ml。 [0015] benzyl-2-naphthyl ether and the solid-liquid ratio of water to 1: 5 g / ml.

[0016] 本发明的有益效果: [0016] Advantageous effects of the invention:

本发明操作简单,副反应物极少,反应时间短,后处理简单,高收率,不污染环境,低成本,适合于工业化生产。 The present invention is simple, little side reaction product, short reaction time, simple workup, high yield, no environmental pollution, low cost, suitable for industrial production.

[0017] 附图说明: [0017] BRIEF DESCRIPTION OF DRAWINGS:

图1为本发明实施例1的核磁谱图。 1 NMR spectrum of Example 1 of the present embodiment of the invention.

[0018] 具体实施方式; [0018] DETAILED DESCRIPTION;

实施例1: Example 1:

于250毫升三口反应瓶中,依次加入40克2-萘酚,19.5克氯化苄,升温至110°C,此时反应物均为液态,然后在此温度下反应5小时,将我温度降至90°C,滴加200毫升甲醇,滴加完毕,降温至室温,搅拌I小时,过滤得白色固体结晶,干燥得产品苄基-2-萘基醚58克,HPLC检测含量99%,收率89.2%.苄基-2-萘基醚的红外检测结果是:方醚(=COC)特征吸收峰为1256,1217,1218cm-l,萘环的特征吸收峰为842,818 cm_l,2-取代位特征峰是758 cm_l,方环(c=c)的特征吸收峰1628,1595,1520 cm_l,方环(=c_H)的特征吸收峰为765,735 cm_l,2-萘酚羟基的吸收峰完全消失。 Three 250 ml reaction flask were added 40 g of 2-naphthol, 19.5 g of benzyl chloride was heated to 110 ° C, the reactants are liquid at this time, and then reacted at this temperature for 5 hours, the temperature drop I to 90 ° C, 200 ml of methanol was added dropwise, the addition was complete, cooled to room temperature and stirred for I h, filtered to give a white crystalline solid product dried to give 2-naphthyl benzyl ether 58 g, HPLC detected content 99% yield . infrared detection result of the rate of 89.2% 2-naphthyl benzyl ether is: square ether (= COC) is a characteristic absorption peak 1256,1217,1218cm-l, characteristic absorption peak naphthalene ring 842,818 cm_l, 2- position substituent characteristic peak is 758 cm_l, characterized in square loop (c = c) an absorption peak 1628,1595,1520 cm_l, wherein the ring side (= c_H) absorption peak is 765,735 cm_l, 2-naphthol hydroxyl absorption peak disappeared completely . 与标准谱图一致。 And consistent standard spectra. 证实产物为苄基-2-萘基醚。 Confirmed the product as 2-naphthyl benzyl ether.

核磁检测结果见图1:萘环上的7个氢在7.2-7.7之间的,苯环上的5个氢在7.19的位置上,亚甲基(-CH2-)的2个氢在4.8的位置上。 NMR detection results shown in Figure 1: 7 hydrogens on the naphthalene ring between 7.2-7.7, five hydrogens on the benzene ring in a position of 7.19, the methylene (-CH2-) two hydrogen 4.8 position. 所以结构是正确的。 So the structure is correct.

[0019] 实施例2: [0019] Example 2:

于250毫升三口反应瓶中,依次加入40克2-萘酚,19.5克氯化苄,29.5克碳酸钠,升温至100°C,反应3小时,将温度降至90°C,滴加200毫升甲醇,滴加完毕,降温至室温,搅拌I小时,过滤得白色固体结晶,干燥得粗品苄基-2-萘基醚,再将该粗品溶于500毫升水中,加热至50°C,搅拌I小时,过滤,干燥得白色产品苄基-2-萘基醚56克,HPLC检测含量99%,收率86.1%。 Three 250 ml reaction flask were added 40 g of 2-naphthol, 19.5 g of benzyl chloride, 29.5 g of sodium carbonate, heated to 100 ° C, reacted for 3 hours, the temperature was lowered to 90 ° C, was added dropwise 200 ml methanol, addition was complete, cooled to room temperature and stirred for I h, filtered to give a white crystalline solid, and dried to give crude 2-naphthyl benzyl ether, and the crude product was dissolved in 500 ml of water and heated to 50 ° C, stirred for I h, filtered, and dried to give the white product, 2-naphthyl benzyl ether 56 g, HPLC detected content 99%, yield 86.1%.

[0020] 实施例3: [0020] Example 3:

于250毫升三口反应瓶中,依次加入40克2-萘酚,19.5克氯化苄,29.5克碳酸钠,升温至100°C,反应3小时,将温度降至90°C,滴加200毫升乙醇,滴加完毕,降温至室温,搅拌I小时,过滤得白色固体结晶,干燥得粗品苄基-2-萘基醚,再将该粗品溶于500毫升水中,加热至50°C,搅拌I小时,过滤,干燥得白色产品苄基-2-萘基醚54克,HPLC检测含量99%,收率83.1%。 Three 250 ml reaction flask were added 40 g of 2-naphthol, 19.5 g of benzyl chloride, 29.5 g of sodium carbonate, heated to 100 ° C, reacted for 3 hours, the temperature was lowered to 90 ° C, was added dropwise 200 ml ethanol, addition was complete, cooled to room temperature and stirred for I h, filtered to give a white crystalline solid, and dried to give crude 2-naphthyl benzyl ether, and the crude product was dissolved in 500 ml of water and heated to 50 ° C, stirred for I h, filtered, and dried to give the white product, 2-naphthyl benzyl ether 54 g, HPLC detected content 99%, yield 83.1%.

Claims (8)

  1. 1.苄基-2-萘基醚的制备方法,其特征在于,其以氯化苄和2-萘酚为原料,在无溶剂条件下反应得到苄基-2-萘基醚,反应方程式为, A method for the preparation of 2-naphthyl benzyl ether, characterized in that, which is 2-naphthol and benzyl chloride as starting material, the reaction in the absence of a solvent gave benzyl 2-naphthyl ether, the reaction equation is ,
    Figure CN103772158AC00021
  2. 2.根据权利要求1所述的苄基-2-萘基醚的制备方法,其特征在于,将摩尔为1.1~1.5:1的氯化苄和2-萘酚混合,最好是1.2:1,在110-120°C下反应3~5小时,然后将体系温度降至90°C,滴加有机溶剂进行结晶,过滤、干燥后得到苄基-2-萘基醚。 The preparation of 2-naphthyl benzyl ether according to claim 1, characterized in that 1.1 to 1.5 mol: 1, benzyl chloride and 2-naphthol mixed, preferably 1.2: 1 reaction for 3 to 5 hours at 110-120 ° C, and then the system temperature was lowered to 90 ° C, dropwise addition of an organic solvent and crystallized, filtered and dried to give benzyl 2-naphthyl ether.
  3. 3.根据权利要求2所述的苄基-2-萘基醚的制备方法,其特征在于,所述的有机溶剂为甲醇、乙醇或丙醇。 3. Preparation method of 2-naphthyl benzyl ether according to claim 2, wherein said organic solvent is methanol, ethanol or propanol.
  4. 4.根据权利要求2所述的苄基-2-萘基醚的制备方法,其特征在于,反应中加入缚酸剂,其添加量与2-萘酚的摩尔比为1.0~1.5:1。 4. A method for preparing 2-naphthyl benzyl ether according to claim 2, characterized in that the acid binding agent added to the reaction, the molar ratio of the addition amount of 2-naphthol with 1.0 to 1.5: 1.
  5. 5.根据权利要求4所述的苄基-2-萘基醚的制备方法,其特征在于,所述的缚酸剂为碳酸钠、碳酸钾、氢氧化钠、氢氧化钾中的一种以上。 The preparation of 2-naphthyl benzyl ether as claimed in claim 4, wherein said acid binding agent is potassium carbonate, sodium hydroxide, potassium hydroxide, one or more .
  6. 6.根据权利要求4所述的苄基-2-萘基醚的制备方法,其特征在于,将过滤、干燥后得到的苄基-2-萘基醚继续加到水中,料液比为1:5~10g/ml,加热至40-50°C,搅拌I小时,过滤,干燥,得到终产物苄基-2-萘基醚。 6. The production method according to 4-benzyl-2-naphthyl ethers as claimed in claim, characterized in that the filtration and dried to give 2-naphthyl benzyl ether, water was added to continue, solid-liquid ratio of 1 : 5 ~ 10g / ml, was heated to 40-50 ° C, stirred for I h, filtered and dried, to give the final product benzyl-2-naphthyl ethers.
  7. 7.根据权利要求4所述的苄基-2-萘基醚的制备方法,其特征在于,缚酸剂与2-萘酚的摩尔比为1.0:1。 7. A method for preparing 2-naphthyl benzyl ether as claimed in claim 4, wherein the molar ratio of acid-binding agents with 2-naphthol was 1.0: 1.
  8. 8.根据权利要求6所述的苄基-2-萘基醚的制备方法,其特征在于,苄基-2-萘基醚与水的料液比为1:5 g/ml。 8. A method for preparing 2-naphthyl benzyl ether as claimed in claim 6, wherein the solid to liquid ratio 2-naphthyl benzyl ether and water is 1: 5 g / ml.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5352843A (en) * 1992-06-06 1994-10-04 Basf Aktiengesellschaft Preparation of β-naphthyl benzyl ether
CN102276431A (en) * 2011-05-17 2011-12-14 潍坊大有生物化工有限公司 Benzyl-2-naphthyl ether synthesis thermosensitive sensitizer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5352843A (en) * 1992-06-06 1994-10-04 Basf Aktiengesellschaft Preparation of β-naphthyl benzyl ether
CN102276431A (en) * 2011-05-17 2011-12-14 潍坊大有生物化工有限公司 Benzyl-2-naphthyl ether synthesis thermosensitive sensitizer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XIULI BU,ET AL.: "Organic base catalyzed O-alkylation of phenols under solvent-free condition", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》, vol. 259, 20 July 2006 (2006-07-20), pages 121 - 124 *

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