JPS59176229A - Preparation of alpha-disubstituted monocarboxylic acid - Google Patents
Preparation of alpha-disubstituted monocarboxylic acidInfo
- Publication number
- JPS59176229A JPS59176229A JP59055200A JP5520084A JPS59176229A JP S59176229 A JPS59176229 A JP S59176229A JP 59055200 A JP59055200 A JP 59055200A JP 5520084 A JP5520084 A JP 5520084A JP S59176229 A JPS59176229 A JP S59176229A
- Authority
- JP
- Japan
- Prior art keywords
- ether
- acid
- reaction
- formula
- reaction temperature
- 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
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 title claims 2
- 238000002360 preparation method Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical group COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 8
- 125000001033 ether group Chemical group 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 claims 1
- 229910052785 arsenic Inorganic materials 0.000 claims 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 6
- 235000019253 formic acid Nutrition 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- -1 Alkyl formates Chemical class 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- VUAXHMVRKOTJKP-UHFFFAOYSA-M 2,2-dimethylbutanoate Chemical compound CCC(C)(C)C([O-])=O VUAXHMVRKOTJKP-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000002170 ethers Chemical group 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000272201 Columbiformes Species 0.000 description 1
- 241000257303 Hymenoptera Species 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
本発明はα−二置換モノカルホン酸及びそのエステルの
調製１去に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the preparation of α-disubstituted monocarphonic acids and their esters.
こイｔらの酸はシェル・ケミカル・カンパニーにより商
品名［ＶＥＲ８Ａ、Ｔ Ｉ ＣＪとして、またエクソン
により「Ｎｅｏ −Ａｃ１ｄｓ Ｊとして販売さイｔて
いる。Their acid is sold by the Shell Chemical Company under the trade name VER8A, TICJ and by Exxon under the tradename "Neo-Ac1ds J."
ご’ｒ％らの遊離酸、その塩及びそのエステルは医薬品
及び化粧品の分野で多くの用途を有している。The free acids, their salts and their esters have many uses in the pharmaceutical and cosmetic fields.
こイｔらの化合物はまた農業の分野で、また潤滑油用添
卯剤として使用されている。Their compounds are also used in the agricultural field and as additives for lubricating oils.
現在、α−二置換モノカルボン酸は、ＣＯ及び水の作用
により、対応するオレフィンをカルホキシル化すること
により工業的に製造さｉｔている（ＫＯＣＩ−１反応）
。この反応はオキソ（Ｏｘｏ ）合成と関連し、加圧を
心安とする。Currently, α-disubstituted monocarboxylic acids are produced industrially by carboxylation of the corresponding olefins by the action of CO and water (KOCI-1 reaction).
. This reaction is related to oxo synthesis and is pressurized.
本発明の要旨
本発明（こよれば、大気圧下てα−二置換モノカルホン
酸が調製できる。この方法は、式：％式％（
（たたし、）ｔ、、Ｒ２及び１（３は同−又は異なる、
飽和又は不飽和の脂肪族又は環式Ｃ１乃至ＣＩ２の一価
炭化水素基であり、そして、Ｒ４は水素、又はＣ１乃至
Ｃ３の飽和−価炭化水素基であり、飽和又は不飽和炭化
水素基は反応に影響を与えない置換基を有してもよい）
を有するα−二置埃モノカルホン酸及びそのエステルを
調製する方法であって、式：（
］
％式％（）
】
（たたし、ａｌ、ｉｔ２及び几、は前述の通りであり、
几、はＣ１乃至Ｃ３の箆和−価炭化水素基てある）を、
弐白１− Ｃｏ２−Ｒ＜ （Ｉｔ （たたし、１モ
、は前述の通りである）で示さ、ｆする蟻酸又はそのア
ルキルホルメートにより、濃縮プロトン酸の存在下でカ
ルボキシル化する方法である。SUMMARY OF THE INVENTION According to the present invention, α-disubstituted monocarphonic acids can be prepared under atmospheric pressure. Same or different
a saturated or unsaturated aliphatic or cyclic C1 to CI2 monovalent hydrocarbon group, and R4 is hydrogen or a C1 to C3 saturated-valent hydrocarbon group, and the saturated or unsaturated hydrocarbon group is (May have substituents that do not affect the reaction)
A method for preparing α-dioxymonocarphonic acid and its ester having the formula:
几 is a C1 to C3 valent hydrocarbon group),
1-Co2-R be.
アルキルホルメートは蟻酸と対応するアルコールから現
場で形成できる。Alkyl formates can be formed in situ from formic acid and the corresponding alcohol.
蟻酸の使用により、遊雅酸が合成できまた、アルキルポ
ルメートは対応上ヌチルを形成する。The use of formic acid allows the synthesis of free acid and alkylpormates correspondingly form nutyl.
直接遊ｊ冊酸又はエステルが得らイするかの能力は、イ
１用でかつ本発明の方法の重要な特徴である。The ability to directly obtain free acids or esters is an important feature of the process of the present invention.
全ての反応体は室温及び反応ｍ＆で液状であり、そのγ
こめ取扱い及び使用が容易である。All reactants are liquid at room temperature and reaction m&, and their γ
Easy to handle and use.
本発明の方法で調製できる多くの酸及びエステルには、
ジメチル−２，２−プロピオン酸（ピハル酸）及びその
メチルエステル、並ひにジメチル−２，２−ブクン酸及
びそのメチルエステル７Ｊ）ある。Many of the acids and esters that can be prepared by the method of the invention include:
Dimethyl-2,2-propionic acid (pihalic acid) and its methyl ester, as well as dimethyl-2,2-buconic acid and its methyl ester (7J).
第三級エーテルの内、メチルｔｅｒｔ−アミルエーテル
（ＴＡＭＥ ）か特に有用である。エーテルは、無鉛ガ
ソリンの主成分であり、工業的に多量に製造されている
。、−
カルホキシル化剤の内、蟻酸及びそのメチルホルメート
が反応性、利用性及び価格の点て最も有用である。Among the tertiary ethers, methyl tert-amyl ether (TAME) is particularly useful. Ether is the main component of unleaded gasoline and is produced industrially in large quantities. , - Among the carboxylating agents, formic acid and its methyl formate are the most useful in terms of reactivity, availability and cost.
反応温度は広い範囲に亘る。反応は、約Ｏ乃至８０°Ｃ
１特に約５乃至４０°Ｃが好適である。はとんどの鳩舎
、約１５乃至２０°Ｃで反応を実施する必要はない。Reaction temperatures span a wide range. The reaction is carried out at approximately 0 to 80°C.
1 Particularly preferred is a temperature of about 5 to 40°C. In most pigeon houses, it is not necessary to carry out the reaction at about 15-20°C.
反応媒体は、濃縮プロトン酸であり、約８５東量係以上
の濃度の硫酸が適当である。The reaction medium is a concentrated protonic acid, suitably sulfuric acid at a concentration of about 85 parts or more.
使用する蟻酸は、約８０東量係、好ましくは、約９８東
量係の濃度でなけわばならない。蟻ば又はアルキルホル
メ−１〜及び第三級エーテルの容量は広範囲に亘るが、
過剰のカルホキシル化剤（蟻酸又はアルキルホルメート
）を使用するのが好ましい。また、第三級エーテル１モ
ル当り、約ｌ乃至１０モル、好ましくは約３乃至７モル
の化合物ｊ１１１）を使用するのが好ましい。The formic acid used should be at a concentration of about 80 parts, preferably about 98 parts. The capacity of ants or alkyl form-1 and tertiary ethers ranges over a wide range, but
Preference is given to using an excess of carboxylating agent (formic acid or alkyl formate). It is also preferred to use about 1 to 10 mol, preferably about 3 to 7 mol, of compound j111) per mole of tertiary ether.
不発・９］の方法は、異なる方法で試薬を徽触して実施
することかできる。例えば、第三級エーテル及び化合物
（■）の混合物を濃縮プロトン酸に導入し、望ましい温
度範囲に維持する。The method described in ``Misfire 9'' can be carried out by adding reagents in different ways. For example, a mixture of a tertiary ether and compound (■) is introduced into a concentrated protic acid and maintained in the desired temperature range.
また、反応媒体に蟻酸と第三級エーテルを導入すると同
時に、又はその後にアルコールを添加することにより、
その場でアルキルホルメートを形成することもできる。Alternatively, by adding alcohol at the same time or after introducing formic acid and tertiary ether into the reaction medium,
Alkyl formates can also be formed in situ.
本発明の方法で得らイ％たカルホン酸又はそのエステル
は、公知の方法で反応混合物から分離できる。この反応
混合物は、水で拠埋でき、得らイｔた酸又はエステルは
有機溶媒で抽出できる。倚ら、Ｔした改は、そのナトＩ
Ｊウム塩を形成することによりＩＭＦＭできる。エステ
ルは、そのエステルを含む有機層を、痕跡量の酸を塩の
型で中和するための布塩基で洗浄することにより回収、
精製し、エステルは有機相から蒸留により回収する。The carbonic acid or ester thereof obtained by the method of the present invention can be separated from the reaction mixture by known methods. The reaction mixture can be filled with water and the resulting acid or ester extracted with an organic solvent. The change that I made was that Nato I
IMFM can be achieved by forming a Jium salt. The ester is recovered by washing the organic layer containing the ester with a cloth base to neutralize traces of acid in the form of a salt.
After purification, the ester is recovered from the organic phase by distillation.
以下、実施例により本発明を説明するが、これらの実施
例は本発明を何ら限定するものではない。EXAMPLES Hereinafter, the present invention will be explained with reference to Examples, but these Examples are not intended to limit the present invention in any way.
実施例１
９５重量％Ｈ２ＳＯ４１１０−を、滴下ロー１・、還流
冷却器、温度計及び攪拌器を具備する２５０ｍ１反応器
に導入した。ｏ：ｔｚ５モルのメチルｔｅｒｔ−ブチル
エーテルと０．５モルの１−］、ＣＯＯ１（とを含む、
９８重量係混合物を約３０分に亘って激しく攪拌する反
応器に−ｉ％ごとに添加した。反応混合物を約１５０°
ＣＫ維持し１こ。反応混合物を同一条件下で更に２時間
攪拌した。Example 1 95% by weight H2SO4110- was introduced into a 250 ml reactor equipped with a dropping row 1, a reflux condenser, a thermometer and a stirrer. o:tz5 moles of methyl tert-butyl ether and 0.5 moles of 1-], COO1 (,
The 98% by weight mixture was added in -i% increments to the reactor with vigorous stirring over about 30 minutes. The reaction mixture was heated at approximately 150°
CK maintained and 1. The reaction mixture was stirred for an additional 2 hours under the same conditions.
反応混合物を粉砕木で加水分解した。反応混合物を５０
ゴのヘキサノで３回抽出し、濃縮１−１ｃｌで再酸性化
した２規定力リウム化合物（ｐｏｔａｓｈ ）でカリウ
ム塩に変換し、そしてベンセンで抽出した。ピバル酸収
率はヘンセンの蒸発後５４％である（ｂｌ）１６２〜１
６３°Ｃ）。The reaction mixture was hydrolyzed with ground wood. 50% of the reaction mixture
Extracted three times with hexanoate, converted to potassium salt with 2N potash, re-acidified with 1-1 ml of concentrate, and extracted with benzene. Pivalic acid yield is 54% after evaporation of Hensen (bl) 162~1
63°C).
実施例２
９９重ｉ係のＨ２ＳＯ４１１０ｍｌを、滴下ロート、還
流冷却器、温度計及び攪拌器を備える２５０ｍ１の反応
器に導入した。０．１２５モルのメチルｔｅｒｔ−ブチ
ルエーテル（ＭＴＢＢ）及び０．５モルメチルホルメー
トの混合物を１５時間ζこ亘って、激しく攪拌した反応
器中に一滴ごとに添加した。反応混合物を約１５°Ｃに
維持した。攪拌は更に２時間同一条件下に維持し、攪拌
速度は低下させ、１モルのメタノールをゆっくりと、温
度が４５゛０を超えないように反応器に添加した。次に
、攪拌を１時間続けた。反応混合物を２５１’の粉砕氷
上に流し入れた。水相を５０−のヘキサンで３回洗浄し
た。有機相は回収し、水相がアルカリ性となるまで２Ｎ
ＫＯＨで処理した。有機相６と含まわるエステルは
ヘキサンの蒸発により単離し１こ。ピバル酸メチルを蒸
留した。このピバル酸メチルの収率は５０％（ｂｐｌｏ
ｏ、５〜１ ｏ ｉ、 ５°Ｃ）である。Example 2 110 ml of 99% H2SO4 were introduced into a 250 ml reactor equipped with a dropping funnel, a reflux condenser, a thermometer and a stirrer. A mixture of 0.125 mole methyl tert-butyl ether (MTBB) and 0.5 mole methyl formate was added dropwise into the vigorously stirred reactor over a period of 15 hours. The reaction mixture was maintained at approximately 15°C. Stirring was maintained under the same conditions for a further 2 hours, the stirring speed was reduced and 1 mol of methanol was slowly added to the reactor such that the temperature did not exceed 45°C. Stirring was then continued for 1 hour. The reaction mixture was poured onto 251' crushed ice. The aqueous phase was washed three times with 50-hexane. Collect the organic phase and add 2N until the aqueous phase becomes alkaline.
Treated with KOH. The ester contained in the organic phase 6 was isolated by evaporation of hexane. Methyl pivalate was distilled. The yield of methyl pivalate was 50% (bplo
o, 5 to 1 o i, 5°C).
実施例３
上述の実施例の通り、９５重量％）Ｉ２Ｓｏ４１１０−
を反応器に導入した。０．１２５モルのメチルｔｅｒｔ
−アミルエーテルと、０．５モルの９８重量係＠酸との
混合物を、反応温度が約Ｉ５°Ｃに維持さ７１、るよう
に反応器に一滴ごとに添加した。Example 3 As in the above example, 95% by weight) I2So4110-
was introduced into the reactor. 0.125 mole methyl tert
A mixture of -amyl ether and 0.5 mol of 98% acid was added dropwise to the reactor such that the reaction temperature was maintained at about 15°C.
反応混合物を実施例１のように処理した。ジメチル−２
，２−ブタン酸の収率は５２係（ｂｐ２０ａｍ Ｈ９で
９５°Ｃ）であった。The reaction mixture was worked up as in Example 1. dimethyl-2
, the yield of 2-butanoic acid was 52% (bp 20 am H9 at 95°C).
Claims (1)
１乃至Ｃ１□の飽和又は不飽和の脂肪族又は環式−１ｔ
ｆｉ炭化水素基であり、Ｒ，は水素又はＣ１乃至Ｃ３の
飽オロー価炭化水素基であり、また前記炭（ヒ水素基が
反応（・こ影響を与えない置換基を含んてもよ（りを有
するα−二置換モノカルポン酸又はそのエステルのＡ製
法であって、 式： ％式％（［１ （たたし、Ｒ，Ｒ２及びＲ３は上記に定義した通りであ
り、Ｒ５はＣ１乃至Ｃ３の飽和−価炭化水素基である）
を有する第三級エーテルを、式： ％式％（） （たたし、Ｒ４は上記に定義した通りである）とを、濃
厚ブロー・ン酸の存在下で反応させることを特徴とする
方法。 （２、特許請求の範囲第１項記載の方法において、Ｒ５
かメチル基である方法。 （３）特許請求の範囲第１項記載の方法において、第二
級エーテルがメチルｔｅｒ ｔ−ブチルエーテル又はメ
チルｔｅｒｔ−アミルエーテルである方法。 （４）特許請求の範囲第２項に記載の方法において、前
記第三級エーテルがメチルｔｅｒｔ−ブチルエーチル又
はメチルｔｅｒｔ−アミルエーテルである方法。 （５）特許請求の範囲第１項（こ記載の方法において、
反応温度が約Ｏ乃至８０’（：！である方法。 （６）特許請求の範囲第２項（こ記載の方法ζこおいて
、反応温度か約０乃至８０′Ｃ！である方法。 （７） ′＋＋許請求の範囲第３項に記載の方法番こ
おいて、反ｊ芯温度か約Ｏ乃至８０゛ｃである方法。 （８）＋＋許ｄ肖求の範囲第１項に記載の方法（こおい
て、前記濃縮プロトン酸か約８５卓鐘係以上のｍ１度の
イ流酸である方法。 （９）特許請求の範囲第２項に記ｉ戊の方法において、
前記ｆ濃縮プロトン酸か約８５重量％け一ヒの一度の硫
酸である方法。 １１０） 特許請求の範囲第３項に記載の方法におい
て、前記嬢縮プロトン酸が約８５重量％以上の濃度の１
流酸である方法。 （１υ 特許請求の範囲第４項に記載の方法において、
前記濃縮プロトン酸が約８５卓鐘係以上の濃度の硫酸で
ある方法。 （１つ 特許請求の範囲第１項に記載の方法において、
反応混合物に導入する第三級エーテルの１モル当り化合
物（Ｉｆｆ）の約１乃至１０モルを前記反応混合物に導
入する方法。 ０３）特許請求の範囲第２項に記載の方法において、反
応混合物に導入する第三級エーテル１モル当り化合物（
ｍｌの約１乃至１０モルを前記反応混合物に導入する方
法。 Ｉ 特許請求の範囲第１項に記載の方法において、反応
温度が約５乃至４０°Ｃである方法。 ０５）特許請求の範囲第２項に記載の方法において、反
１芯温度か約５乃至４０℃である方法。 １６１ 特許請求の範囲第８項に記載の方法において
、反応温度が約５乃至４０℃である方法。 α′７）特許請求の範囲第１２項に記載の方法において
、反応温度が約５乃至４０°Ｃである方法。 １１８）特許請求の範囲第１６項に記載の方法において
、第三級エーテル１モル当り約３乃至７モルの化合物＋
１ｔｌｌを使用する方法。[Claims] (1) The following formula: ( ] % formula % ( (where L(,, R2 and R3 are the same or different, C
1 to C1□ saturated or unsaturated aliphatic or cyclic -1t
fi is a hydrocarbon group, and R is hydrogen or a C1 to C3 saturated orohyl hydrocarbon group, and the carbon (arsenic group) may contain a substituent that does not affect the reaction. A method for producing an α-disubstituted monocarboxylic acid or an ester thereof having the formula: %formula%([1 (where R, R2 and R3 are as defined above, and R5 is C1 to C3 is a saturated-valent hydrocarbon group)
A process characterized in that a tertiary ether having the formula: . (2. In the method described in claim 1, R5
or methyl group method. (3) The method according to claim 1, wherein the secondary ether is methyl tert-butyl ether or methyl tert-amyl ether. (4) The method according to claim 2, wherein the tertiary ether is methyl tert-butyl ether or methyl tert-amyl ether. (5) Claim 1 (In the method described in this claim,
A method in which the reaction temperature is about 0 to 80'C! (6) Claim 2 (method ζ of this description) in which the reaction temperature is about 0 to 80'C! ( 7) '++ The method described in claim 3, wherein the core temperature is about 0 to 80°C. (8)++ The method described in claim 1. (9) In the method of claim 2,
A method in which the f concentrated protic acid is about 85% by weight of sulfuric acid. 110) The method of claim 3, wherein the condensed protonic acid has a concentration of about 85% or more by weight.
How to be acidic. (1υ In the method described in claim 4,
The method wherein the concentrated protonic acid is sulfuric acid at a concentration of about 85 degrees centigrade or more. (1) In the method described in claim 1,
A method in which about 1 to 10 moles of the compound (Iff) are introduced into the reaction mixture per mole of tertiary ether introduced into the reaction mixture. 03) In the method according to claim 2, the compound (
A method in which about 1 to 10 moles per ml are introduced into the reaction mixture. I. A method according to claim 1, wherein the reaction temperature is about 5 to 40°C. 05) The method according to claim 2, wherein the temperature is about 5 to 40°C. 161. The method of claim 8, wherein the reaction temperature is about 5 to 40°C. α'7) The method according to claim 12, wherein the reaction temperature is about 5 to 40°C. 118) In the method according to claim 16, about 3 to 7 moles of the compound+ per mole of tertiary ether.
How to use 1tll.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8304571 | 1983-03-21 | ||
| FR838304571A FR2543135B1 (en) | 1983-03-21 | 1983-03-21 | PROCESS FOR THE PREPARATION OF MONOCARBOXYLIC ACIDS DISUBSTITUTED IN A AND THEIR ESTERS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59176229A true JPS59176229A (en) | 1984-10-05 |
Family
ID=9287056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59055200A Pending JPS59176229A (en) | 1983-03-21 | 1984-03-21 | Preparation of alpha-disubstituted monocarboxylic acid |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS59176229A (en) |
| BE (1) | BE899188A (en) |
| CA (1) | CA1204123A (en) |
| DE (1) | DE3410202A1 (en) |
| FR (1) | FR2543135B1 (en) |
| GB (1) | GB2136808B (en) |
| IT (1) | IT1173440B (en) |
| NL (1) | NL8400866A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438217B (en) * | 2018-12-05 | 2021-07-16 | 大连奇凯医药科技有限公司 | Preparation method of 2, 2-dimethylbutyric acid |
-
1983
- 1983-03-21 FR FR838304571A patent/FR2543135B1/en not_active Expired
-
1984
- 1984-03-13 IT IT20042/84A patent/IT1173440B/en active
- 1984-03-16 NL NL8400866A patent/NL8400866A/en not_active Application Discontinuation
- 1984-03-19 BE BE0/212586A patent/BE899188A/en not_active IP Right Cessation
- 1984-03-20 CA CA000449994A patent/CA1204123A/en not_active Expired
- 1984-03-20 DE DE19843410202 patent/DE3410202A1/en not_active Withdrawn
- 1984-03-20 GB GB08407204A patent/GB2136808B/en not_active Expired
- 1984-03-21 JP JP59055200A patent/JPS59176229A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| BE899188A (en) | 1984-07-16 |
| IT8420042A0 (en) | 1984-03-13 |
| NL8400866A (en) | 1984-10-16 |
| GB2136808B (en) | 1986-01-22 |
| FR2543135A1 (en) | 1984-09-28 |
| IT1173440B (en) | 1987-06-24 |
| CA1204123A (en) | 1986-05-06 |
| GB8407204D0 (en) | 1984-04-26 |
| FR2543135B1 (en) | 1985-07-26 |
| GB2136808A (en) | 1984-09-26 |
| DE3410202A1 (en) | 1984-09-27 |
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