US815548A - Process of producing aromatic alcohols and their derivatives. - Google Patents
Process of producing aromatic alcohols and their derivatives. Download PDFInfo
- Publication number
- US815548A US815548A US23114904A US1904231149A US815548A US 815548 A US815548 A US 815548A US 23114904 A US23114904 A US 23114904A US 1904231149 A US1904231149 A US 1904231149A US 815548 A US815548 A US 815548A
- Authority
- US
- United States
- Prior art keywords
- cathode
- derivatives
- alcohol
- aromatic alcohols
- producing aromatic
- 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.)
- Expired - Lifetime
Links
- -1 aromatic alcohols Chemical class 0.000 title description 2
- 238000000034 method Methods 0.000 title description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- WVDDGKGOMKODPV-UHFFFAOYSA-N benzyl alcohol Substances OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 7
- 125000004494 ethyl ester group Chemical group 0.000 description 6
- 239000005711 Benzoic acid Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052571 earthenware Inorganic materials 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- JLWMMYZWEHHTFF-UHFFFAOYSA-N 2-[6-(3-carbamimidoylphenoxy)-4-[di(propan-2-yl)amino]-3,5-difluoropyridin-2-yl]oxy-5-(2-methylpropylcarbamoyl)benzoic acid Chemical compound OC(=O)C1=CC(C(=O)NCC(C)C)=CC=C1OC1=NC(OC=2C=C(C=CC=2)C(N)=N)=C(F)C(N(C(C)C)C(C)C)=C1F JLWMMYZWEHHTFF-UHFFFAOYSA-N 0.000 description 1
- UNDXPKDBFOOQFC-UHFFFAOYSA-N 4-[2-nitro-4-(trifluoromethyl)phenyl]morpholine Chemical compound [O-][N+](=O)C1=CC(C(F)(F)F)=CC=C1N1CCOCC1 UNDXPKDBFOOQFC-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229940044197 ammonium sulfate Drugs 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
Definitions
- Varoi -In'atic ⁇ z-este1s.- ⁇ ⁇ It ⁇ isA particularly of value in that-it also holds'goodfor'substituted aronatic esters. ⁇ Thus whenusin halo enfsub'stituted and I I ethyl athen-.of meta-'- meta-bror'n'lben-y brom-be zoic acid.
- velectrolyti ⁇ c reduction of substances which stitution and temperature play an important part If the methyl ester of benzoic acid is treated, the-production of alcohol .prevails formed, (two parts alcohol, one part ether,) whereas out of ethyl ester of benzoic acid under analogous conditions more etheris formed (one part alcohol, two parts ether.) The formation of ether is still more predominant in the case of the halogen-substituted compounds.
- the ethyl ester of meta-chlor-benzoic acid is exclusively reduced to ethyl ether of meta-chlor-benzyl alcohol.
- the reduction of the esters can also be carried out in an alkaline solution. As main products alcohols are obtained.
- the ethers like the alcohols, can easily be converted into aldehydes, and these form a suitable material for the dyeing industry for triplienyl-'methan dyestuffs and for artificial 1n 1go.
- the cathode-space of an electrolyzing a paratus is charged with a solution having tlIie following composition: three hundred grams of ethyl ester of benzoic acid, three. hundred and iifty grams 'of concentrated sulfuric acid, five hundred grams of alcohol of ninety-six per cent., one hundred grams of water. (In place of water acorrespondinglydilute solution of sulfuric acid can of course beemployed.)
- the anode-space separated by an earthenware cell contains sulfuric acid It is known that the are not readily and easily reduced can be facilitated by employing for the cathode a metal having a high cathodic tension.
- the cathode of my apparatus consists of pure sheet-lead, which is suitably prepared according to Tafels prescription, (Berichte der Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Chem. Deutschen Che
- the-cathode liquid is neutralized with about thirty per cent. soda-lye.
- Two layers are formed, of which the upper one consists of alcohol and the products of reduction of the ethyl ester of benzoic acid. This is separated distilled, and fractionized.
- the benzyl-ethyl ether boils at 184, the benzyl alcohol at 205.
- a cathode liquidy of the following composition namely, one hundred and seventy grams of ethyl ester of meta-brom-benzoic acid, three hundred grams of concentrated sulfuric acid, five hundred grams of alcohol of ninety-six per centis reduced at a lead cathode with the aid of the electric current.
- the reaction product is se ara-ted for the greater art on the bottom of tiie cathodespace as oi It is drawn off and distilled.
- the ethyl etherof metabrom-benzyl alcohol distils.
- a small quantity of meta-brom-benzyl alcohol passes over.
- What I claim is- Process for the roduction of aromatic alcohols and their et ers, which consists in exposing the aromatic esters in a dissolving agent, capable of conducting the electric current in the cathode-space of an electrolytic apparatus in using for the cathode a material of a specially-high cathodic tension, then neutralizing the cathode liquid, then se arating the reaction product and finally distilling, substantially as described.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
. CHARLES METTLER OF MUNICH;y GERMANY i! "ai f i `P'RocfEss oiPRoDUciNG AROMATICALCQHOLSANDTHEIR D iR|vAT|i/5's.f
Beit known that LCHARLES MErTIiEn,
chemist, aciti'z'enof Switzerland, vof No.1?` Marsstra'ss'e, Munich, rinthe Kingdom' of. Ba-f f yVaria and Empire of Germany, hayeinyented lcertain new and useful improvements in Proc-1 es seslfor the Production of'Aromatic Alco-4 f hols` and their Derivativ lowing isaspecication. f
It has nothitherto been known that aire-7" duction ofY aromatic esters to f alcoholspforg ex- Y, `ample, vfromy ethyl-ester of benzoic' acidto `benzylaloohol t i (1,115*oooomflwni:CGHEomOH-Fcuon f has eyerbeen realized.y i
I have new yfound i that i minnie sjeefs lhave'they 'roperty,'` under thefconditions suit-y able fort e saine, of taking upjhydrogen `and changing into compounds comparatively poor in oxygen. y; Th1-'secours when arornaticesters g are reduced atinetal cathodes-'for i example,y
at lea'd `cathodeS- by means of yelectrolyti'c- .ally-separated hydrogen. For thiS purpose it t cornes into consideration, concentrated Sul-y furie acid which can be diluted with watera`l 1 o' i coholo r acetic acid. In lieu'thereof an aque'- f alsobe carried out in'an alkaline or neutral so@ i Intiem, in whichv case anf aqueous solution 7 which contains the electrolyte s-rnixed withv the quantity of alcohol nec'eSSaryforthe soluv tion of the ester'.4 Ifone operates in yana'cid sol lution andreducesfplyway .of example ethyl after'afeufcient time.V l my i is advantageous. to'v employ a dissolving agent for the ester, which iS at' the Sametime capable l Y of conducting theielect'ric current, as Such ous alcoholic .solutiony of hydrochloric acid can be' employed, andfinally such a reduction `can specification of retten;"Patent l' L r i Application illallNmvitilier@@9044k Serial Noi-231,149. 'V
es,of which the fol@ a 1k w This courseof reactionsisgnotjonly vfthe Variousethylestersofbenzoicacid;'1butiity t methyl estei' o1 aniscpaeid. 'i
limited .150,
relates to. anew general class reaction of Varoi -In'atic`z-este1s.-` {It} isA particularly of value in that-it also holds'goodfor'substituted aronatic esters. `Thus whenusin halo enfsub'stituted and I I ethyl athen-.of meta-'- meta-bror'n'lben-y brom-be zoic acid.
1 Withregard tothe riroportionsi of :etherl andofalcoholthe`se epend uponl uite" af lI iurr'lberof'cir'cumstances.v Forexai'n'p e, con-y Patented l f formed out `'of',Inethylester of 'b enzoic acid,
' l oon I' iethyl ether otanisic alco- `h 225 f.
`diluted with water.
velectrolyti`c reduction of substances which stitution and temperature play an important part. If the methyl ester of benzoic acid is treated, the-production of alcohol .prevails formed, (two parts alcohol, one part ether,) whereas out of ethyl ester of benzoic acid under analogous conditions more etheris formed (one part alcohol, two parts ether.) The formation of ether is still more predominant in the case of the halogen-substituted compounds. Thus, for example, the ethyl ester of meta-chlor-benzoic acid is exclusively reduced to ethyl ether of meta-chlor-benzyl alcohol. The reduction of the esters can also be carried out in an alkaline solution. As main products alcohols are obtained.
By means of suitable oxidizing agents the ethers, like the alcohols, can easily be converted into aldehydes, and these form a suitable material for the dyeing industry for triplienyl-'methan dyestuffs and for artificial 1n 1go.
The following examples will now be given:
1. The cathode-space of an electrolyzing a paratus is charged with a solution having tlIie following composition: three hundred grams of ethyl ester of benzoic acid, three. hundred and iifty grams 'of concentrated sulfuric acid, five hundred grams of alcohol of ninety-six per cent., one hundred grams of water. (In place of water acorrespondinglydilute solution of sulfuric acid can of course beemployed.) The anode-space separated by an earthenware cell contains sulfuric acid It is known that the are not readily and easily reduced can be facilitated by employing for the cathode a metal having a high cathodic tension. Therefore the cathode of my apparatus consists of pure sheet-lead, which is suitably prepared according to Tafels prescription, (Berichte der Deutschen Chem. Gesellschaft 332215,) and pure lead is employed for the anode. A current of seven amperes per one hundred square centimeters cathode-surface is sent through the liquid; but the streng-th of the current can be materially varied without disadvantage. By means of cooling the temperat-ure is kept between 20 and 30 centigrade. `When no more hydrogen is absorbed,
`grams of alcohol.
the-cathode liquid is neutralized with about thirty per cent. soda-lye. Two layers are formed, of which the upper one consists of alcohol and the products of reduction of the ethyl ester of benzoic acid. This is separated distilled, and fractionized. The benzyl-ethyl ether boils at 184, the benzyl alcohol at 205.
2. Under similar conditions as in Case 1 a cathode liquidy of the following compositionnamely, one hundred and seventy grams of ethyl ester of meta-brom-benzoic acid, three hundred grams of concentrated sulfuric acid, five hundred grams of alcohol of ninety-six per centis reduced at a lead cathode with the aid of the electric current. During the electrolysis the reaction product is se ara-ted for the greater art on the bottom of tiie cathodespace as oi It is drawn off and distilled. Between 235 to 239 the ethyl etherof metabrom-benzyl alcohol distils. At 250 a small quantity of meta-brom-benzyl alcohol passes over.
3. In the cathode-space of an electrolyzing apparatus a solution as follows is laced: one hundred grams ofethyl ester of enzoic acid, six hundred grams of thirty-per-cent. aqueous sal-ammoniac solution, six hundred The anode-space separated by an earthenware cell contains dilute sulfuric acid or ammonium-sulfate solution. Cathode and anode consist of urelead. Electrolysis proceeds while the iquid is cooled, the current having a strength of six amperes per one hundred square centimeters cathodesurface. When no more. hydrogen is absorbed, the alcohol is distilled off and the liquid is acidulated. Benzyl alcohol separates for the most part. It is removed and disuned. (195%0 205.)
What I claim is- Process for the roduction of aromatic alcohols and their et ers, which consists in exposing the aromatic esters in a dissolving agent, capable of conducting the electric current in the cathode-space of an electrolytic apparatus in using for the cathode a material of a specially-high cathodic tension, then neutralizing the cathode liquid, then se arating the reaction product and finally distilling, substantially as described.
In witness whereof I have hereunto set my hand in the presence of two witnesses.
CHARLES METTLER.
Witnesses:
ULYssEs J. BYWATER, ABRAHAM ScHLEsiNGER.
IOC
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US23114904A US815548A (en) | 1904-11-02 | 1904-11-02 | Process of producing aromatic alcohols and their derivatives. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US23114904A US815548A (en) | 1904-11-02 | 1904-11-02 | Process of producing aromatic alcohols and their derivatives. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US815548A true US815548A (en) | 1906-03-20 |
Family
ID=2884030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US23114904A Expired - Lifetime US815548A (en) | 1904-11-02 | 1904-11-02 | Process of producing aromatic alcohols and their derivatives. |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US815548A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3929613A (en) * | 1972-12-01 | 1975-12-30 | Rhone Poulenc Sa | Preparation of glyoxylic acid |
| US4055573A (en) * | 1976-05-06 | 1977-10-25 | Smithkline Corporation | Electrochemical reduction of imidazolecarboxylic esters |
| CN105064263A (en) * | 2015-07-16 | 2015-11-18 | 上海市园林设计院有限公司 | Water system of waterfront green space landscape |
-
1904
- 1904-11-02 US US23114904A patent/US815548A/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3929613A (en) * | 1972-12-01 | 1975-12-30 | Rhone Poulenc Sa | Preparation of glyoxylic acid |
| US4055573A (en) * | 1976-05-06 | 1977-10-25 | Smithkline Corporation | Electrochemical reduction of imidazolecarboxylic esters |
| CN105064263A (en) * | 2015-07-16 | 2015-11-18 | 上海市园林设计院有限公司 | Water system of waterfront green space landscape |
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