JP2000273059A - Method for producing alkyl adamantane monol - Google Patents
Method for producing alkyl adamantane monolInfo
- Publication number
- JP2000273059A JP2000273059A JP11079394A JP7939499A JP2000273059A JP 2000273059 A JP2000273059 A JP 2000273059A JP 11079394 A JP11079394 A JP 11079394A JP 7939499 A JP7939499 A JP 7939499A JP 2000273059 A JP2000273059 A JP 2000273059A
- Authority
- JP
- Japan
- Prior art keywords
- adamantane
- monol
- alkyl
- alkyl adamantane
- sulfate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 title claims abstract description 56
- PLFFHJWXOGYWPR-HEDMGYOXSA-N (4r)-4-[(3r,3as,5ar,5br,7as,11as,11br,13ar,13bs)-5a,5b,8,8,11a,13b-hexamethyl-1,2,3,3a,4,5,6,7,7a,9,10,11,11b,12,13,13a-hexadecahydrocyclopenta[a]chrysen-3-yl]pentan-1-ol Chemical compound C([C@]1(C)[C@H]2CC[C@H]34)CCC(C)(C)[C@@H]1CC[C@@]2(C)[C@]4(C)CC[C@@H]1[C@]3(C)CC[C@@H]1[C@@H](CCCO)C PLFFHJWXOGYWPR-HEDMGYOXSA-N 0.000 title claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- -1 alkyl adamantane Chemical compound 0.000 claims abstract description 19
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 229920001002 functional polymer Polymers 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LBWCITVBZLTEKW-UHFFFAOYSA-N 3,5-dimethyladamantan-1-ol Chemical compound C1C(C2)CC3(C)CC1(C)CC2(O)C3 LBWCITVBZLTEKW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- CWNOIUTVJRWADX-UHFFFAOYSA-N 1,3-dimethyladamantane Chemical compound C1C(C2)CC3CC1(C)CC2(C)C3 CWNOIUTVJRWADX-UHFFFAOYSA-N 0.000 description 2
- LXTHCCWEYOKFSR-UHFFFAOYSA-N 1-ethyladamantane Chemical compound C1C(C2)CC3CC2CC1(CC)C3 LXTHCCWEYOKFSR-UHFFFAOYSA-N 0.000 description 2
- UZUCFTVAWGRMTQ-UHFFFAOYSA-N 1-methyladamantane Chemical compound C1C(C2)CC3CC2CC1(C)C3 UZUCFTVAWGRMTQ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229940117975 chromium trioxide Drugs 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- WCACLGXPFTYVEL-UHFFFAOYSA-N 1,3,5-trimethyladamantane Chemical compound C1C(C2)CC3(C)CC1(C)CC2(C)C3 WCACLGXPFTYVEL-UHFFFAOYSA-N 0.000 description 1
- GEJJWNXPMJYYKJ-UHFFFAOYSA-N 1,3-di(propan-2-yl)adamantane Chemical compound C1C(C2)CC3CC1(C(C)C)CC2(C(C)C)C3 GEJJWNXPMJYYKJ-UHFFFAOYSA-N 0.000 description 1
- PIPGXRXMMAMUAB-UHFFFAOYSA-N 1,3-dibutyladamantane Chemical compound C1C(C2)CC3CC1(CCCC)CC2(CCCC)C3 PIPGXRXMMAMUAB-UHFFFAOYSA-N 0.000 description 1
- XHQDEOWLMBIVBU-UHFFFAOYSA-N 1,3-diethyladamantane Chemical compound C1C(C2)CC3CC1(CC)CC2(CC)C3 XHQDEOWLMBIVBU-UHFFFAOYSA-N 0.000 description 1
- AZCUIXHZJHFUFI-UHFFFAOYSA-N 1-butyladamantane Chemical compound C1C(C2)CC3CC2CC1(CCCC)C3 AZCUIXHZJHFUFI-UHFFFAOYSA-N 0.000 description 1
- HUCLCMAVGXHPPK-UHFFFAOYSA-N 1-ethyl-3-methyladamantane Chemical compound C1C(C2)CC3CC2(C)CC1(CC)C3 HUCLCMAVGXHPPK-UHFFFAOYSA-N 0.000 description 1
- ISDSLPMQFWIUPU-UHFFFAOYSA-N 1-propan-2-yladamantane Chemical compound C1C(C2)CC3CC2CC1(C(C)C)C3 ISDSLPMQFWIUPU-UHFFFAOYSA-N 0.000 description 1
- LJFGNNHKXSJWFF-UHFFFAOYSA-N 3-ethyladamantan-1-ol Chemical compound C1C(C2)CC3CC2(O)CC1(CC)C3 LJFGNNHKXSJWFF-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
(57)【要約】
【課題】 機能性高分子材料、フォトレジスト材料等の
合成中間体として有用なアルキルアダマンタンモノオー
ルを、容易かつ安価に入手しうる原料を用い、高い選択
率で安価に製造する。
【解決手段】 アルキルアダマンタン類を発煙硫酸と反
応させてアルキルアダマンタン硫酸塩とする。このアル
キルアダマンタン硫酸塩は、加水分解すれば高い選択率
で安価にアルキルアダマンタンモノオールを製造でき
る。PROBLEM TO BE SOLVED: To produce an alkyladamantane monool useful as a synthetic intermediate for a functional polymer material, a photoresist material, etc., at a high selectivity and at a low cost using raw materials which can be easily and inexpensively obtained. I do. SOLUTION: An alkyl adamantane is reacted with fuming sulfuric acid to obtain an alkyl adamantane sulfate. When this alkyl adamantane sulfate is hydrolyzed, an alkyl adamantane monol can be produced at a high selectivity and at low cost.
Description
【0001】[0001]
【発明の属する技術分野】この発明は、機能性高分子材
料、フォトレジスト材料等の合成中間体として有用なア
ルキルアダマンタンモノオール(分子中に1つのヒドロキ
シル基を有するアルキルアダマンタン)の製造方法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an alkyl adamantane monool (an alkyl adamantane having one hydroxyl group in a molecule) useful as a synthetic intermediate for a functional polymer material, a photoresist material and the like.
【0002】[0002]
【従来の技術】アダマンタンまたはその同族体のヒドロ
キシル誘導体の製造方法としては、アダマンタンまたは
その同族体を金属塩酸化触媒の存在下、空気酸化する方
法(日本特許第518869号)、アダマンタンまたはその同族
体を、酢酸中において三酸化クロムを用いて酸化する方
法(日本特許第510654号)がある。2. Description of the Related Art As a method for producing adamantane or a homologous hydroxyl derivative thereof, adamantane or a homologue thereof is air-oxidized in the presence of a metal oxidation catalyst (Japanese Patent No. 518869), and adamantane or a homologue thereof is produced. Is oxidized using chromium trioxide in acetic acid (Japanese Patent No. 510654).
【0003】また、他のアダマンタンのヒドロキシル誘導体
の製造方法としては、アダマンタンまたはその同族体を
臭素化し、生成する臭素誘導体を加水分解する方法があ
る。アダマンタンまたはその同族体を臭素化し(Chem.Be
r.,92.1629(1959))、生成する臭素誘導体を化学量論量
を超える過剰で高価な銀塩(硫酸銀)を用いて加水分解す
る方法(Chem.Ber.,93.1366(1960).:J.Org.Chem.,26.220
7(1961).)が知られている。[0003] As another method for producing a hydroxyl derivative of adamantane, there is a method in which adamantane or a homolog thereof is brominated, and the resulting bromine derivative is hydrolyzed. Adamantane or its homologs are brominated (Chem.
r., 92 .1629 (1959) ), excessive and expensive silver salt (Method hydrolyzed using silver sulfate) the resulting bromine derivative exceeding stoichiometric amount (Chem.Ber., 93 .1366 (1960 ) .: J.Org.Chem., 26 .220
7 (1961).) Is known.
【0004】[0004]
【発明が解決しようとする課題】上記日本特許第518869
号に開示の方法は、酸化中幾つかのケトンが同時に生成
して、アダマンタンまたはその同族体のモノオール合成
の選択性が低いという欠点がある。また、日本特許第51
0654号に開示の方法は、アダマンタンまたはその同族体
のモノオールのみを得ることが困難であり、しかも、比
較的高価な三酸化クロムが過剰必要であるため、工業的
な製造方法として有利な方法ではない。The above Japanese Patent No. 518869
The process disclosed in US Pat. No. 6,077,086 has the disadvantage that during the oxidation several ketones are formed simultaneously, resulting in low selectivity of the monol synthesis of adamantane or its homologues. Also, Japanese Patent No. 51
In the method disclosed in No. 0654, it is difficult to obtain only the monol of adamantane or a homolog thereof, and furthermore, a relatively expensive chromium trioxide is required in excess, which is an advantageous method as an industrial production method. is not.
【0005】また、Chem.Ber.,92.1629(1959)に開示の方法
は、臭素化にアダマンタンまたはその同族体1モルに対
し、高価な臭素を少なくとも10倍モル以上の過剰に使用
することが必要であり、製造コストが高くなる原因とな
っている。さらに、Chem.Ber.,93.1366(1960):J.Org.Ch
em.,26.2207(1961).に開示の方法は、2段の反応工程を
経るため、生産性、作業性、設備費、収率等のいずれに
おいても大きな欠点となる。Further, Chem.Ber., In the disclosed method to adamantane or its homolog 1 mole bromination, the use of expensive bromine at least 10-fold mol excess 92.1629 (1959) Is necessary, which causes an increase in manufacturing cost. In addition, Chem.Ber, 93 .1366 (1960) :. J.Org.Ch
The method disclosed in Em., 26. 2207 (1961) involves two reaction steps, and therefore has major drawbacks in terms of productivity, workability, equipment cost, yield, and the like.
【0006】このように、アダマンタンまたはその同族体の
モノオールを容易かつ安価に入手しうる原料を用いて経
済的に製造する方法は、これまでに見い出されていない
のが実情である。[0006] As described above, a method for economically producing adamantane or a homologous monol thereof using a raw material which can be obtained easily and inexpensively has not been found so far.
【0007】この発明の目的は、上記従来技術の欠点を解消
し、容易かつ安価に入手しうる原料を用い、高い選択率
でアルキルアダマンタンモノオール類を製造できる方法
を提供することにある。[0007] An object of the present invention is to solve the above-mentioned drawbacks of the prior art, and to provide a method for producing alkyladamantane monols with high selectivity using raw materials that can be obtained easily and inexpensively.
【0008】[0008]
【課題を解決するための手段】本発明者らは、前記目的
を達成するために鋭意研究を重ねた。その結果、アルキ
ルアダマンタン類を安価で容易に入手できる発煙硫酸と
撹拌混合して反応させると、短時間で硫酸塩が生成し、
その硫酸塩を加水分解することによって、高い選択率で
アルキルアダマンタンモノオール類を収率よく製造でき
ることを見い出し、この発明を完成させた。Means for Solving the Problems The present inventors have intensively studied to achieve the above object. As a result, when alkyladamantanes are mixed and reacted with fuming sulfuric acid, which is inexpensive and easily available, sulfate is generated in a short time,
By hydrolyzing the sulfate, it has been found that alkyladamantanemonols can be produced with high selectivity with high yield, and the present invention has been completed.
【0009】すなわち、この発明のアルキルアダマンタンモ
ノオールの製造方法は、アルキルアダマンタン類を発煙
硫酸と反応させてアルキルアダマンタン硫酸塩としたの
ち、加水分解するのである。このアルキルアダマンタン
硫酸塩の加水分解においては、希釈した硫酸で撹拌混合
して加水分解する。That is, according to the method for producing an alkyl adamantane monol of the present invention, an alkyl adamantane is reacted with fuming sulfuric acid to form an alkyl adamantane sulfate and then hydrolyzed. In the hydrolysis of this alkyl adamantane sulfate, hydrolysis is carried out by stirring and mixing with diluted sulfuric acid.
【0010】[0010]
【発明の実施の形態】この発明においてヒドロキシル化
反応に供する原料は、橋頭位にヒドロキシル基が置換で
きる3個以下のアルキル置換基を有するアルキルアダマ
ンタン類であり、例えば、1-メチルアダマンタン、1-エ
チルアダマンタン、1-イソプロピルアダマンタン、1-n-
ブチルアダマンタン、1,3-ジメチルアダマンタン、1,3-
ジエチルアダマンタン、1-エチル-3-メチルアダマンタ
ン、1,3-ジイソプロピルアダマンタン、1,3-ジ-n-ブチ
ルアダマンタン、1,3,5-トリメチルアダマンタン、1,3-
ジエチル-5-メチルアダマンタン等を挙げることができ
る。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the raw materials to be subjected to the hydroxylation reaction are alkyl adamantanes having three or less alkyl substituents capable of substituting a hydroxyl group at the bridgehead, such as 1-methyladamantane, 1-methyladamantane, Ethyl adamantane, 1-isopropyl adamantane, 1-n-
Butyl adamantane, 1,3-dimethyl adamantane, 1,3-
Diethyl adamantane, 1-ethyl-3-methyl adamantane, 1,3-diisopropyl adamantane, 1,3-di-n-butyl adamantane, 1,3,5-trimethyl adamantane, 1,3-
Diethyl-5-methyladamantane and the like can be mentioned.
【0011】使用する発煙硫酸としては、SO3濃度が5%〜50%
の範囲であればよく、好ましくは10%〜25%である。発煙
硫酸の使用量は、原料であるアルキルアダマンタン類1
モルに対してH2SO4のモル数が10倍モル以上であればよ
く、好ましくは20〜50倍モルの範囲が適当である。発煙
硫酸の使用量がアルキルアダマンタン類1モルに対してH
2SO4のモル数で10倍モル以下では、硫酸塩の生成反応が
進行し難いので、硫酸塩の加水分解によりアルキルアダ
マンタンモノオールを収率よく合成することはできな
い。また、50倍モルを超えて使用しても、アルキルアダ
マンタンモノオールの収率向上の効果が見られず、使用
量の増大による製造コストの上昇を招き、経済的に得策
ではない。The fuming sulfuric acid used has an SO 3 concentration of 5% to 50%.
And it is preferably 10% to 25%. The amount of fuming sulfuric acid used depends on the amount of alkyl adamantane 1
The number of moles of H 2 SO 4 may be 10 moles or more with respect to the mole, and is preferably in the range of 20 to 50 moles. The amount of fuming sulfuric acid is H per mole of alkyl adamantane.
If the number of moles of 2 SO 4 is less than 10 moles, the formation reaction of sulfate is difficult to proceed, so that alkyladamantane monol cannot be synthesized with high yield by hydrolysis of sulfate. Further, even if it is used in a molar amount exceeding 50 times, the effect of improving the yield of alkyl adamantane monol is not seen, and the production cost is increased due to an increase in the amount used, which is not economically advantageous.
【0012】反応温度は、10℃以下、好ましくは0〜10℃が
適当であり、発煙硫酸とアルキルアダマンタン類を撹拌
混合しながら、前記反応温度に保持することによって硫
酸塩の生成反応と部分的なアルキルアダマンタンモノオ
ール生成反応が円滑に進行する。The reaction temperature is suitably 10 ° C. or lower, preferably 0 ° C. to 10 ° C., while maintaining the above-mentioned reaction temperature while stirring and mixing fuming sulfuric acid and alkyl adamantanes, the reaction for forming a sulfate salt partially occurs. The alkyl adamantane monol production reaction proceeds smoothly.
【0013】反応時間は、発煙硫酸濃度により若干異なる
が、1時間から2時間の極めて短時間で反応が完了する。
反応終了後の反応生成物は、アルキルアダマンタン硫酸
塩が生成しており(一部分がアルキルアダマンタンモノ
オールとなっている)、次に氷水中に投入して希釈した
硫酸濃度下で撹拌混合して加水分解させる。希釈した硫
酸濃度は、5〜95重量%の範囲であればよく、好ましくは
20〜50重量%である。The reaction time varies slightly depending on the concentration of fuming sulfuric acid, but the reaction is completed in a very short time of 1 to 2 hours.
After the completion of the reaction, the reaction product contains alkyl adamantane sulfate (partly alkyl adamantane monol). Let it break down. The diluted sulfuric acid concentration may be in the range of 5 to 95% by weight, preferably
20 to 50% by weight.
【0014】この加水分解反応は、10分間程度の極めて短時
間で完了する。反応終了後、アルキルアダマンタンモノ
オールは結晶として析出する。この結晶には、硫酸根が
包含されているので、洗浄して除去する必要がある。結
晶を分離してそのまま水洗浄してもよいが、効率的に洗
浄するには、結晶を有機溶媒に溶解させたのち、水から
分液した溶媒層を水および/または亜硫酸水素アルカリ
水で洗浄すればよい。The hydrolysis reaction is completed in a very short time of about 10 minutes. After completion of the reaction, the alkyl adamantane monol precipitates as crystals. Since these crystals contain sulfate groups, they need to be removed by washing. The crystals may be separated and washed with water as is, but for efficient washing, the crystals are dissolved in an organic solvent, and the solvent layer separated from water is washed with water and / or alkaline hydrogen sulfite. do it.
【0015】アルキルアダマンタンモノオール結晶を溶解さ
せる有機溶媒としては、水に対して分液可能であるエー
テル類、沸点50〜150℃の脂肪族炭化水素あるいは脂環
式炭化水素を使用する。例えば、ジエチルエーテル、ア
ニソール、ペンタン、ヘキサン、ヘプタン、オクタン、
石油エーテル、シクロヘキサン、メチルシクロヘキサン
等を挙げることができる。As the organic solvent for dissolving the alkyl adamantane monol crystal, ethers that can be separated from water, aliphatic hydrocarbons having a boiling point of 50 to 150 ° C., or alicyclic hydrocarbons are used. For example, diethyl ether, anisole, pentane, hexane, heptane, octane,
Examples thereof include petroleum ether, cyclohexane, and methylcyclohexane.
【0016】有機溶媒の使用量は、目的とするアルキルアダ
マンタンモノオール結晶を完全に溶解できる量であれば
よく、析出した結晶量に対して10重量倍以上が好適であ
る。[0016] The amount of the organic solvent used may be an amount capable of completely dissolving the target alkyl adamantane monol crystal, and is preferably at least 10 times the weight of the precipitated crystal.
【0017】アルキルアダマンタンモノオールは、溶媒層を
水層から分液し、溶媒層中に残存する硫酸根を洗浄して
除去したのち、溶媒層を乾燥、あるいは脱水した後、溶
媒を留去して結晶として回収する。また、必要ならば、
再結晶法、水蒸気蒸留法などの適当な手段により精製す
ることによって、高品質のアルキルアダマンタンモノオ
ールを得ることができる。Alkyl adamantane monol is obtained by separating the solvent layer from the aqueous layer, washing and removing the sulfate groups remaining in the solvent layer, and then drying or dehydrating the solvent layer. To recover as crystals. If necessary,
By refining by an appropriate means such as a recrystallization method and a steam distillation method, a high-quality alkyl adamantane monol can be obtained.
【0018】[0018]
【実施例】以下、実施例によってこの発明を具体的に説
明するが、この発明は、これらの実施例に限定されるも
のではない。実施例における生成物の純度は、無極性キ
ャピラリーカラムを用いたガスクロマトグラフィー分析
において、フレームイオン化検出器(Flame ionization
detector)で求めた純度(ガスクロ面積百分率純度)であ
る。EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. The purity of the product in the examples was determined by gas chromatography analysis using a non-polar capillary column using a flame ionization detector.
detector (purity (gas chromatography area percentage purity)).
【0019】実施例1 撹拌機、滴下ロート付の容量300mlの三口フラスコに25%
発煙硫酸200ml(3.87モル)を仕込み、10℃以下に冷却し
たままで撹拌下に、1,3-ジメチルアダマンタン20g(0.12
2モル)を容量50mlの滴下ロートにより30分間で添加し、
反応させた。さらに、反応液は、8〜10℃に保持して30
分間撹拌混合した。反応混合物は、1kgの氷水中に投入
して30分間撹拌して加水分解し、析出した結晶を濾過し
て粗結晶23.34gを得た。Example 1 A 300% three-necked flask equipped with a stirrer and a dropping funnel was charged with 25%
200 ml (3.87 mol) of fuming sulfuric acid was charged, and 20 g of 1,3-dimethyladamantane (0.12
2 mol) was added in a dropping funnel having a capacity of 50 ml in 30 minutes,
Reacted. Further, the reaction solution is kept at 8 to 10 ° C. for 30 minutes.
Stir and mix for minutes. The reaction mixture was poured into 1 kg of ice water, stirred for 30 minutes, hydrolyzed, and the precipitated crystals were filtered to obtain 23.34 g of crude crystals.
【0020】この粗結晶にヘキサン250gと水50gを添加し、
室温で30分間撹拌した後、ヘキサン層と水層とを分液し
た。ヘキサン層は、亜硫酸水素ナトリウム水溶液および
水で洗浄水がpH5程度になるまで洗浄した。洗浄済のヘ
キサン層は、蒸留してヘキサンを留去させ、結晶16.08g
を得た。この結晶は、ガスクロマトグラフィーの分析に
よって、1,3-ジメチルアダマンタン-5-オール純度が98.
3%、その収率は72モル%であった。[0020] 250 g of hexane and 50 g of water are added to the crude crystals,
After stirring at room temperature for 30 minutes, the hexane layer and the aqueous layer were separated. The hexane layer was washed with an aqueous solution of sodium hydrogen sulfite and water until the washing water reached about pH 5. The washed hexane layer is distilled to remove hexane, resulting in 16.08 g of crystals.
I got The crystals were found to have 1,3-dimethyladamantan-5-ol purity of 98.
3%, and the yield was 72 mol%.
【0021】実施例2 原料を1-エチルアダマンタンに代えた以外は、実施例1
と同様の操作を行い、結晶14.45gを得た。この結晶は、
1-エチルアダマンタン-3-オール純度が97.6%、その収率
は68モル%であった。Example 2 Example 1 was repeated except that the raw material was changed to 1-ethyladamantane.
The same operation as described above was performed to obtain 14.45 g of crystals. This crystal is
The purity of 1-ethyladamantan-3-ol was 97.6%, and the yield was 68 mol%.
【0022】実施例3 原料を1.3.5-トリメチルアダマンタン29g(0.163モル)に
代えた以外は、実施例1と同様の操作を行い、結晶29.07
gを得た。この結晶は、1-3-5-トリメチルアダマンタン-
7-オール純度が99.5%、その収率は91.5モル%であった。Example 3 The same operation as in Example 1 was carried out except that the raw material was changed to 1.3.5-trimethyladamantane 29 g (0.163 mol), to obtain a crystal 29.07.
g was obtained. This crystal is composed of 1-3-5-trimethyladamantane-
The purity of 7-ol was 99.5%, and the yield was 91.5 mol%.
【0023】実施例4 実施例1の25%発煙硫酸量を150ml(2.90モル)とした以外
は、実施例1と同様の操作を行い、結晶13.15gを得た。
この結晶は、1,3-ジメチルアダマンタン-5-オール純度
が95.4%、その収率は60.5モル%であった。Example 4 The procedure of Example 1 was repeated, except that the 25% fuming sulfuric acid content was changed to 150 ml (2.90 mol), to obtain 13.15 g of crystals.
The crystals had a 1,3-dimethyladamantan-5-ol purity of 95.4% and a yield of 60.5 mol%.
【0024】実施例5 実施例1の25%発煙硫酸量を100ml(1.94モル)とした以外
は、実施例1と同様の操作を行い、結晶9.2gを得た。こ
の結晶は、1,3-ジメチルアダマンタン-5-オール純度が8
8.6%、その収率は39.3モル%であった。Example 5 The same operation as in Example 1 was carried out except that the amount of 25% fuming sulfuric acid in Example 1 was changed to 100 ml (1.94 mol), to obtain 9.2 g of crystals. This crystal has a 1,3-dimethyladamantan-5-ol purity of 8
8.6% and the yield was 39.3 mol%.
【0025】[0025]
【発明の効果】この発明のアルキルアダマンタンモノオ
ールの製造方法は、アルキルアダマンタン類を安価で容
易に入手できる発煙硫酸と撹拌混合させる。これによっ
て、短い反応時間で、かつ高い選択性でアルキルアダマ
ンタンモノオールを収率よく製造することができる。し
たがって、この発明の方法は、機能性高分子材料、フォ
トレジスト材料等の合成中間体として有用なアルキルア
ダマンタンモノオールを工業的に安価に製造できる。According to the process for producing an alkyl adamantane monol of the present invention, an alkyl adamantane is mixed with fuming sulfuric acid which is inexpensive and easily available. As a result, alkyladamantane monol can be produced with high yield in a short reaction time and with high selectivity. Therefore, the method of the present invention can industrially and inexpensively produce an alkyl adamantane monol useful as a synthetic intermediate for a functional polymer material, a photoresist material and the like.
Claims (2)
応させてアルキルアダマンタン硫酸塩としたのち、加水
分解することを特徴とするアルキルアダマンタンモノオ
ールの製造方法。1. A method for producing an alkyl adamantane monol, which comprises reacting an alkyl adamantane with fuming sulfuric acid to form an alkyl adamantane sulfate and then hydrolyzing it.
酸によって加水分解することを特徴とする請求項1記載
のアルキルアダマンタンモノオールの製造方法。2. The method for producing an alkyl adamantane monol according to claim 1, wherein the alkyl adamantane sulfate is hydrolyzed with dilute sulfuric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11079394A JP2000273059A (en) | 1999-03-24 | 1999-03-24 | Method for producing alkyl adamantane monol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11079394A JP2000273059A (en) | 1999-03-24 | 1999-03-24 | Method for producing alkyl adamantane monol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000273059A true JP2000273059A (en) | 2000-10-03 |
Family
ID=13688653
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11079394A Pending JP2000273059A (en) | 1999-03-24 | 1999-03-24 | Method for producing alkyl adamantane monol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000273059A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010270028A (en) * | 2009-05-20 | 2010-12-02 | Idemitsu Kosan Co Ltd | Method for producing adamantanols |
| RU2510962C2 (en) * | 2012-06-19 | 2014-04-10 | Федеральное государственное бюджетное учреждение науки Институт нефтехимии и катализа Российской академии наук | Method of obtaining 1,3-dimethyladamantan-5-ol |
| JP2014101280A (en) * | 2012-11-16 | 2014-06-05 | Mitsubishi Gas Chemical Co Inc | Method for producing hydroxy adamantane polycarboxylic acid compound |
-
1999
- 1999-03-24 JP JP11079394A patent/JP2000273059A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010270028A (en) * | 2009-05-20 | 2010-12-02 | Idemitsu Kosan Co Ltd | Method for producing adamantanols |
| RU2510962C2 (en) * | 2012-06-19 | 2014-04-10 | Федеральное государственное бюджетное учреждение науки Институт нефтехимии и катализа Российской академии наук | Method of obtaining 1,3-dimethyladamantan-5-ol |
| JP2014101280A (en) * | 2012-11-16 | 2014-06-05 | Mitsubishi Gas Chemical Co Inc | Method for producing hydroxy adamantane polycarboxylic acid compound |
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