Industrial production method of benzo [a] anthracene

Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to an industrial production method of benzo [a] anthracene. The invention provides an industrial production method of benzo [a] anthracene, which comprises the following steps: S1, catalyzing o-cyanobenzyl chloride and 2-naphthaleneboronic acid through a metal palladium catalyst, and carrying out Suzuki reaction to prepare 2-(naphthalene-2-ylmethyl) cyanobenzene; s2, 2-(2-naphthyl methyl) benzonitrile and hydrogen are subjected to a reduction reaction through palladium-carbon catalysis, and 2-(2-naphthyl methyl) benzylamine is prepared; s3, salifying the 2-(2-naphthyl methyl) benzylamine and hydrochloric acid, and carrying out Sandmeyer reaction on the salified 2-(2-naphthyl methyl) benzylamine and sodium nitrite to obtain 7, 12-dihydrobenzo [a] anthracene; and S4, carrying out dehydrogenation on the 7, 12-dihydrobenzo [a] anthracene through 2, 3-dichloro-5, 6-dicyanobenzoquinone, so as to prepare the benzo [a] anthracene. The method produces less three wastes in the production process, causes less harm of wastewater to the environment, and is suitable for industrial production.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and specifically relates to an industrial production method of benz[a]anthracene. Background Art

[0002] Benz[a]anthracene is a derivative synthesized as an intermediate and is widely used in the synthesis of materials with conjugated structures. It has wide applications in the fields of field effect transistors, organic light-emitting diodes, etc.

[0003] At present, the common synthesis method of benz[a]anthracene uses 1-bromonaphthalene (method 1) as raw material (J.Med.Chem.2019,62,15,7089–7110; J.Chem.Soc.,1935,1367-1370) or naphthalene (method 2) as raw material (BeilsteinJ.Org.Chem.2019,15,1313–1320), and obtains the product benz[a]anthracene through Friedel-Crafts acylation, strong acid dehydration ring closure, and finally hydrogenation reduction. The main problem of this method is that all three steps of reaction produce a large amount of wastewater. The first step of method 2 produces a large amount of aluminum-containing high-salt wastewater; in the actual implementation of the second step, it was found that the reaction temperature has a great influence on the reaction. If the temperature is too high, a large amount of product will be carbonized, which greatly affects the yield. The reaction process requires 2 times the volume of methanesulfonic acid as a solvent, which cannot be recovered during post-treatment, resulting in a large amount of high-salt wastewater. The third step reaction process requires 10 times the volume of glacial acetic acid as a solvent, and other strong acids (hydriodic acid, hypophosphorous acid, etc.) will produce a large amount of wastewater and are extremely dangerous. As a result, the production cost of benz[a]anthracene is difficult to reduce and is not suitable for mass industrial production.

[0004] The synthetic routes of method 1 and method 2 are as follows:

[0005]

[0006] Therefore, in the field of organic synthesis technology, it is particularly important to provide an industrial production method suitable for benz[a]anthracene, which can achieve high conversion rate in the reaction process, simple post-treatment operation and low amount of three wastes. Summary of the invention

[0007] The object of the present invention is to provide an industrial production method of benz[a]anthracene, which has cheap and readily available raw materials, high conversion rate in the reaction process, simple post-treatment operation, simple and efficient product purification, small amount of three wastes generated in the production process, small relative environmental harm of wastewater, etc., and is suitable for industrial production.

[0008] To achieve the above object, the technical solution of the present invention is as follows:

[0009] In a first aspect, the present invention provides an industrial production method of benz[a]anthracene, comprising the following steps:

[0010] S1. o-cyanobenzyl chloride and 2-naphthaleneboronic acid are catalyzed by a metal palladium catalyst to undergo a Suzuki reaction to obtain 2-(naphthalene-2-ylmethyl)benzonitrile;

[0011] S2. 2-(2-naphthylmethyl)benzonitrile and hydrogen are subjected to a reduction reaction catalyzed by palladium on carbon to obtain 2-(2-naphthylmethyl)benzylamine;

[0012] S3. 2-(2-naphthylmethyl)benzylamine and hydrochloric acid are salified, and the salified salt is subjected to Sandmeyer reaction with sodium nitrite to obtain 7,12-dihydrobenz[a]anthracene;

[0013] S4. Dehydrogenating 7,12-dihydrobenz[a]anthracene through 2,3-dichloro-5,6-dicyanobenzoquinone to obtain the benz[a]anthracene.

[0014] The synthesis route of the benz[a]anthracene is as follows:

[0015]

[0016] Preferably, S1 specifically comprises the following steps:

[0017] Mix o-cyanobenzyl chloride, 2-naphthaleneboronic acid, a metal palladium catalyst, potassium carbonate, toluene, ethanol and water, heat to 75-85°C, and keep warm for reaction for 3-5 hours. After the reaction is completed, adjust the pH of the aqueous phase to 7-8, separate the phases, and concentrate and crystallize the organic phase to obtain 2-(naphthalene-2-ylmethyl)benzonitrile.

[0018] Preferably, the metal palladium catalyst comprises Pd(Amphos) 2 Cl 2 , Pd 2 (dba) 3 、Pd(PPh 3 ) 4 and Pd(PPh 3 ) 2 Cl 2 The molar ratio of the o-cyanobenzyl chloride, the 2-naphthaleneboric acid and the metal palladium catalyst is 1:1-1.2:0.001-0.01.

[0019] Preferably, S2 specifically includes the following steps:

[0020] 2-(Naphthalene-2-ylmethyl)benzonitrile, palladium on carbon and ethanol are mixed, the reaction system is replaced with hydrogen three times, the temperature is raised to 40-50°C under a hydrogen atmosphere, and the reaction is kept warm for 3-5 hours. After the reaction is completed, the palladium on carbon is removed, and the organic phase is concentrated and crystallized to obtain 2-(naphthalene-2-ylmethyl)benzylamine.

[0021] Preferably, the mass ratio of the 2-(naphthalene-2-ylmethyl)benzonitrile to the palladium on carbon is 1:0.05 to 0.1.

[0022] Preferably, S3 specifically includes the following steps:

[0023] Mix 2-(naphthalen-2-ylmethyl)benzylamine and acetonitrile, cool the reaction system to 0-5°C after it dissolves, add hydrochloric acid dropwise at 0-5°C, add an aqueous solution of sodium nitrite dropwise at 0-5°C, heat the reaction system to 70-75°C, reflux, and keep the temperature for 3-5 hours. After the reaction is completed, cool the reaction system, filter, and recrystallize to obtain 7,12-dihydrobenz[a]anthracene.

[0024] Preferably, the volume ratio of the 2-(naphthalene-2-ylmethyl)benzylamine to the hydrochloric acid is 1:1-3, the molar ratio of the 2-(naphthalene-2-ylmethyl)benzylamine to the sodium nitrite is 1:1-1.5, and the recrystallization solvent is ethanol.

[0025] Preferably, S4 specifically comprises the following steps:

[0026] Mix 7,12-dihydrobenz[a]anthracene and toluene, heat the reaction system to 60-70°C, add 2,3-dichloro-5,6-dicyanobenzoquinone, heat the reaction system to 100-110°C, keep the temperature for 2-5 hours, cool the reaction, filter, and recrystallize to obtain benz[a]anthracene.

[0027] Preferably, the molar ratio of the 7,12-dihydrobenz[a]anthracene to the 2,3-dichloro-5,6-dicyanobenzoquinone is 1:2-4, and the recrystallization solvent is a mixed solvent of toluene and ethanol.

[0028] In a second aspect, a benz[a]anthracene is provided, wherein the benz[a]anthracene is prepared by the industrial production method described in the present invention.

[0029] Compared with the prior art, the beneficial effects of the present invention are:

[0030] (1) The method of the present invention successfully converts the raw material into the target product benz[a]anthracene through orderly and efficient chemical reaction steps. Each step of the reaction is carefully designed to ensure high yield and high quality product output.

[0031] (2) A metal palladium catalyst is used in the Suzuki reaction (step S1), and a palladium-carbon catalyst is used in the reduction reaction (step S2); these catalysts can effectively promote the reaction, increase the reaction rate and product selectivity, thereby reducing production costs and improving production efficiency.

[0032] (3) The reaction temperature, time and ratio of raw materials are specified in detail for each step to ensure that the reaction can proceed smoothly and efficiently; this fine control helps to reduce the formation of by-products and improve the purity of the product.

[0033] (4) The entire production process uses relatively environmentally friendly solvents and reagents, and the reaction conditions are relatively mild, which is easy to implement on an industrial scale. In addition, the process also includes effective post-processing steps such as phase separation, concentration, crystallization and recrystallization to further purify the product.

[0034] In summary, by precisely controlling the reaction conditions and selecting a suitable catalyst, the method of the present invention can produce high-quality benz[a]anthracene, which is very important for downstream applications requiring high-purity raw materials, and provides reliable technical support for the large-scale production of benz[a]anthracene, meeting the growing market demand for this compound. Compared with the existing benz[a]anthracene synthesis method, the raw materials are cheap and easy to obtain, the reaction process conversion rate is high, the operation is simple, the product purification is simple and efficient, and the production process generates less three wastes, the wastewater has less environmental harm, and is convenient for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 This is the HPLC spectrum of benz[a]anthracene prepared in Example 1.

[0036] Figure 2 This is the GCMS result of the benz[a]anthracene prepared in Example 1. DETAILED DESCRIPTION

[0037] The present invention will be described in detail below in conjunction with specific implementations and examples, and the advantages and various effects of the present invention will be more clearly presented. It should be understood by those skilled in the art that these specific implementations and examples are used to illustrate the present invention, rather than to limit the present invention.

[0038] The technical scheme of the present invention is described below in conjunction with the examples, but the present invention is not limited to the following examples. The experimental methods and detection methods described in each example are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0039] Example 1

[0040] This embodiment provides an industrial production method of benz[a]anthracene, comprising the following steps:

[0041] S1. To a 1L three-necked round-bottom flask, 172 mL of toluene, 86 mL of ethanol, 86 mL of water, 16.58 g (0.12 mol) of potassium carbonate, 15.16 g (0.1 mol) of o-cyanobenzyl chloride, 17.20 g (0.1 mol) of 2-naphthaleneboronic acid, and Pd(Amphos) were added in sequence. 2 Cl 2 71mg (0.1mmol), the system was heated to 75-85℃, kept warm for 3-5h, and the reaction was completed. The temperature was lowered to 20-30℃, water was added to wash until pH=7, phases were separated, and the organic phase was concentrated at normal pressure until 34mL remained in the system, placed in a refrigerator for crystallization for 3h, filtered, and dried to constant weight to obtain 20.48g of a white solid of formula (1), with a yield of 84.17%, that is, 2-(naphthalene-2-ylmethyl)benzonitrile was obtained. LC-MS: calculation for C 18 H 13 N(M + ),243;found,243.

[0042] Its synthetic route is as follows:

[0043]

[0044] S2. Add 243 mL of ethanol, 24.33 g (0.1 mol) of 2-(naphthalene-2-ylmethyl)benzonitrile and 2.43 g of palladium carbon to a 1L three-necked round-bottom flask in sequence, replace the system with hydrogen three times, raise the temperature to 40°C to 50°C, keep the temperature for 3 to 5 hours, and the reaction is completed. Cool down to 20 to 30°C, filter to remove palladium carbon, concentrate the organic phase at normal pressure until 48 mL remains in the system, put it in a refrigerator for freezing and crystallization for 3 hours, filter, and dry to constant weight to obtain 23.74 g of a white solid of formula (2), with a yield of 96.00%, that is, 2-(naphthalene-2-ylmethyl)benzylamine is obtained. LC-MS: calcd for C 18 H 17 N(M + ),247;found,247.

[0045] Its synthetic route is as follows:

[0046]

[0047] S3. Add 124 mL of acetonitrile and 24.73 g (0.1 mol) of 2-(naphthalene-2-ylmethyl)benzylamine to a 1L three-necked round-bottom flask in sequence. After the system is dissolved, cool it to 0-5°C, keep it at 0-5°C and add 32 mL of hydrochloric acid dropwise. After the addition is complete, keep it at 0-5°C and add an aqueous solution of sodium nitrite dropwise [preparation method: 6.9 g (0.1 mol) of sodium nitrite is dissolved in 69 mL of tap water]. After the addition is complete, heat the system to 70-75°C and reflux. Keep it at this temperature for 3-5 hours. After the reaction is complete, cool it to 20-30°C, filter it, rinse the filter cake with tap water, add 1035 mL of ethanol, reflux it to dissolve completely, cool it to 20-30°C, filter it and dry it to constant weight to obtain 17.27 g of a white solid of formula (3), with a yield of 74.99%. That is, 7,12-dihydrobenz[a]anthracene is obtained. LC-MS: calcd for C 18 H 14 (M + ),230;found,230.

[0048] The synthetic route is as follows:

[0049]

[0050] S4. To a 500mL three-necked round-bottom flask, 230mL of toluene and 23.03g (0.1mol) of 7,12-dihydrobenzo[a]anthracene were added in sequence. The system was heated to 60-70°C and dissolved completely. 49.94g (0.22mol) of 2,3-dichloro-5,6-dicyanobenzoquinone was added in three batches. After the addition was completed, the system was heated to 100-110°C and kept warm for 2-5h. After the reaction was completed, the temperature was lowered to 20-30°C, filtered, and the filtrate was collected. The filtrate was concentrated at normal pressure until 46mL of toluene remained. The temperature was lowered to 70-80°C, 115mL of ethanol was added, the system was heated to reflux, dissolved completely, cooled to 20-30°C, filtered, and dried to constant weight to obtain 19.40g of a white solid of formula (4), with a yield of 84.97%, that is, benz[a]anthracene was obtained. LC-MS: calcd for C 18 H 12 (M + ),228;found,228.

[0051] The synthetic route is as follows:

[0052]

[0053] Among them, the HPLC spectrum of benz[a]anthracene is as follows Figure 1 As shown, the GCMS results of benz[a]anthracene are as follows Figure 2 As shown. Figure 1 , Figure 2It can be seen that the benz[a]anthracene prepared in the embodiment of the present invention has a high purity (>99.5%), and the GCMS ion peak and fragment peak characterize the correct structure.

[0054] Example 2

[0055] This embodiment provides an industrial production method of benz[a]anthracene, comprising the following steps:

[0056] S1. To a 1L three-necked round-bottom flask, 172 mL of toluene, 86 mL of ethanol, 86 mL of water, 16.58 g (0.12 mol) of potassium carbonate, 15.16 g (0.1 mol) of o-cyanobenzyl chloride, 20.64 g (0.12 mol) of 2-naphthaleneboronic acid, and Pd(PPh 3 ) 4 1.156g (1mmol), the system was heated to 75-85℃, kept warm for 3-5h, and the reaction was completed. The temperature was lowered to 20-30℃, water was added to wash until pH=7, phases were separated, and the organic phase was concentrated at normal pressure until 34mL remained in the system, placed in a refrigerator for crystallization for 3h, filtered, and dried to constant weight to obtain 19.95g of a white solid of formula (1), with a yield of 81.99%, that is, 2-(naphthalene-2-ylmethyl)benzonitrile was obtained. LC-MS: calculation for C 18 H 13 N(M + ),243;found,243.

[0057] The synthetic route is as follows:

[0058]

[0059] S2. Add 243 mL of ethanol, 24.33 g (0.1 mol) of 2-(naphthalene-2-ylmethyl)benzonitrile, and 1.22 g of palladium carbon to a 1L three-necked round-bottom flask in sequence, replace the system with hydrogen three times, raise the temperature to 40°C to 50°C, and keep the temperature for 3 to 5 hours to complete the reaction. Cool down to 20 to 30°C, filter to remove palladium carbon, concentrate the organic phase at normal pressure to a residual 48 mL in the system, put it in a refrigerator for freezing and crystallization for 3 hours, filter, and dry to constant weight to obtain 23.74 g of a white solid of formula (2), with a yield of 88.47%, that is, 2-(naphthalene-2-ylmethyl)benzylamine. LC-MS: calcd for C 18 H 17 N(M + ),247;found,247.

[0060] The synthetic route is as follows:

[0061]

[0062] S3. Into a 1L three-necked round-bottom flask, add 124mL of acetonitrile and 24.73g (0.1mol) of 2-(naphthalene-2-ylmethyl)benzylamine in sequence. After the system is dissolved, cool to 0-5°C, keep the temperature at 0-5°C, add 64mL of hydrochloric acid dropwise, and after the addition is complete, keep the temperature at 0-5°C and add an aqueous solution of sodium nitrite dropwise [preparation method: 10.35g (0.15mol) of sodium nitrite is dissolved in 104mL of tap water]. After the addition is complete, heat the system to 70-75°C and reflux, keep the temperature for reaction for 3-5h, and after the reaction is completed, cool to 20-30°C, filter, rinse the filter cake with tap water, add 1035mL of ethanol, reflux and dissolve completely, cool to 20-30°C, filter and dry the material to constant weight to obtain 16.71g of white solid of formula (3) with a yield of 72.56%, i.e., 7,12-dihydrobenz[a]anthracene. LC-MS: calculation for C 18 H 14 (M + ),230;found,230.

[0063] The synthetic route is as follows:

[0064]

[0065] S4. To a 500mL three-necked round-bottom flask, 230mL of toluene and 23.03g (0.1mol) of 7,12-dihydrobenzo[a]anthracene were added in sequence. The system was heated to 60-70°C and dissolved completely. 72.64g (0.32mol) of 2,3-dichloro-5,6-dicyanobenzoquinone was added in three batches. After the addition was completed, the system was heated to 100-110°C and kept warm for 2-5h. After the reaction was completed, the temperature was lowered to 20-30°C, filtered, and the filtrate was collected. The filtrate was concentrated at normal pressure until 46ml of toluene remained. The temperature was lowered to 70-80°C, 115mL of ethanol was added, the system was heated to reflux, dissolved completely, cooled to 20-30°C, filtered, and dried to constant weight to obtain 18.51g of a white solid of formula (4), with a yield of 81.06%, that is, benz[a]anthracene was obtained. LC-MS: calcd for C 18 H 12 (M + ),228;found,228.

[0066] The synthetic route is as follows:

[0067]

[0068] As can be seen from the above embodiments, the present invention successfully synthesizes benz[a]anthracene through 4 steps, and the raw materials used in each step of the reaction can be purchased in large quantities on the market at a low price. The post-reaction treatment is simple, the product purification is simple and efficient, and a large amount of wastewater will not be generated. The overall production cost is low and suitable for industrial production applications. Specifically, on the one hand, the method of the present invention successfully converts the raw materials into the target product benz[a]anthracene through orderly and efficient chemical reaction steps, and each step of the reaction is carefully designed to ensure high yield and high-quality product output. On the other hand, the present invention uses a metal palladium catalyst in the Suzuki reaction (step S1) and a palladium carbon catalyst in the reduction reaction (step S2); these catalysts can effectively promote the reaction, improve the reaction rate and product selectivity, thereby reducing production costs and improving production efficiency. On the other hand, each step of the present invention specifies the reaction temperature, time and the ratio of raw materials in detail to ensure that the reaction can be carried out smoothly and efficiently; this fine control helps to reduce the generation of by-products and improve the purity of the product. On the other hand, the entire production process of the present invention uses relatively environmentally friendly solvents and reagents, and the reaction conditions are relatively mild, which is easy to implement on an industrial scale. In addition, the process also includes effective post-processing steps, such as phase separation, concentration, crystallization and recrystallization, to further purify the product.

[0069] In summary, by precisely controlling the reaction conditions and selecting a suitable catalyst, the method of the present invention can produce high-quality benz[a]anthracene, which is very important for downstream applications requiring high-purity raw materials, and provides reliable technical support for the large-scale production of benz[a]anthracene, meeting the growing market demand for this compound. Compared with the existing benz[a]anthracene synthesis method, the raw materials are cheap and easy to obtain, the reaction process conversion rate is high, the operation is simple, the product purification is simple and efficient, and the production process generates less three wastes, the wastewater has less environmental harm, and is convenient for industrial production.

[0070] It should be understood that the disclosed invention is not limited only to the specific method, scheme and material of description, because these all can change.It should also be understood that the terminology used herein is only for the purpose of describing specific embodiment scheme, rather than being intended to limit the scope of the present invention, and the scope of the present invention is only limited to the appended claims.

[0071] Those skilled in the art will also recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are also intended to be encompassed by the appended claims.

Claims

1. An industrial production method of benz[a]anthracene, characterized in that: The following steps are involved: S1. o-cyanobenzyl chloride and 2-naphthaleneboronic acid are catalyzed by a metal palladium catalyst to undergo a Suzuki reaction to obtain 2-(naphthalene-2-ylmethyl)benzonitrile; S2. 2-(2-naphthylmethyl)benzonitrile and hydrogen are subjected to a reduction reaction catalyzed by palladium on carbon to obtain 2-(2-naphthylmethyl)benzylamine; S3. 2-(2-naphthylmethyl)benzylamine and hydrochloric acid are salified, and the salified salt is subjected to Sandmeyer reaction with sodium nitrite to obtain 7,12-dihydrobenz[a]anthracene; S4. Dehydrogenating 7,12-dihydrobenz[a]anthracene through 2,3-dichloro-5,6-dicyanobenzoquinone to obtain the benz[a]anthracene.

2. The industrial production method according to claim 1, characterized in that: S1 specifically includes the following steps: Mix o-cyanobenzyl chloride, 2-naphthaleneboronic acid, a metal palladium catalyst, potassium carbonate, toluene, ethanol and water, heat to 75-85°C, and keep warm for reaction for 3-5 hours. After the reaction is completed, adjust the pH of the aqueous phase to 7-8, separate the phases, and concentrate and crystallize the organic phase to obtain 2-(naphthalene-2-ylmethyl)benzonitrile.

3. The production method according to claim 2, characterized in that: The metal palladium catalyst includes Pd(Amphos)2Cl2, Pd2(dba)3, Pd(PPh3)4 and Pd(PPh3)2Cl2, and the molar ratio of the o-cyanobenzyl chloride, the 2-naphthaleneboric acid and the metal palladium catalyst is 1:1-1.2:0.001-0.

01.

4. The industrial production method according to claim 1, characterized in that: S2 specifically includes the following steps: 2-(Naphthalene-2-ylmethyl)benzonitrile, palladium on carbon and ethanol are mixed, the reaction system is replaced with hydrogen, the temperature is raised to 40-50° C. under a hydrogen atmosphere, and the reaction is kept warm for 3-5 hours. After the reaction is completed, the palladium on carbon is removed, and the organic phase is concentrated and crystallized to obtain 2-(naphthalene-2-ylmethyl)benzylamine.

5. The industrial production method according to claim 4, characterized in that: The mass ratio of the 2-(naphthalene-2-ylmethyl)benzonitrile to the palladium carbon is 1:0.05-0.

1.

6. The industrial production method according to claim 1, characterized in that: S3 specifically includes the following steps: Mix 2-(naphthalen-2-ylmethyl)benzylamine and acetonitrile, cool the reaction system to 0-5°C after it dissolves, add hydrochloric acid dropwise at 0-5°C, add an aqueous solution of sodium nitrite dropwise at 0-5°C, heat the reaction system to 70-75°C, reflux, and keep the temperature for 3-5 hours. After the reaction is completed, cool the reaction system, filter, and recrystallize to obtain 7,12-dihydrobenz[a]anthracene.

7. The industrial production method according to claim 6, characterized in that: The volume ratio of the 2-(naphthalene-2-ylmethyl)benzylamine to the hydrochloric acid is 1:1-3, the molar ratio of the 2-(naphthalene-2-ylmethyl)benzylamine to the sodium nitrite is 1:1-1.5, and the solvent for recrystallization is ethanol.

8. The industrial production method according to claim 1, characterized in that: S4 specifically includes the following steps: Mix 7,12-dihydrobenz[a]anthracene and toluene, heat the reaction system to 60-70°C, add 2,3-dichloro-5,6-dicyanobenzoquinone, heat the reaction system to 100-110°C, keep the temperature for 2-5 hours, cool the reaction, filter, and recrystallize to obtain benz[a]anthracene.

9. The industrial production method according to claim 8, characterized in that: The molar ratio of the 7,12-dihydrobenz[a]anthracene to the 2,3-dichloro-5,6-dicyanobenzoquinone is 1:2-4, and the recrystallization solvent is a mixed solvent of toluene and ethanol.

10. A benzo[a]anthracene, characterized in that The benz[a]anthracene is prepared by the industrial production method according to any one of claims 1 to 9.

Images