US963254A - Phenol sulfonate of opium alkaloids. - Google Patents
Phenol sulfonate of opium alkaloids. Download PDFInfo
- Publication number
- US963254A US963254A US43223308A US1908432233A US963254A US 963254 A US963254 A US 963254A US 43223308 A US43223308 A US 43223308A US 1908432233 A US1908432233 A US 1908432233A US 963254 A US963254 A US 963254A
- Authority
- US
- United States
- Prior art keywords
- guaiacol
- sulfonic acid
- codein
- salt
- ortho
- 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
- 229930013930 alkaloid Natural products 0.000 title description 15
- 239000008896 Opium Substances 0.000 title description 5
- 229960001027 opium Drugs 0.000 title description 5
- 229940044652 phenolsulfonate Drugs 0.000 title 1
- 150000003839 salts Chemical class 0.000 description 30
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 28
- OROGSEYTTFOCAN-DNJOTXNNSA-N codeine Chemical compound C([C@H]1[C@H](N(CC[C@@]112)C)C3)=C[C@H](O)[C@@H]1OC1=C2C3=CC=C1OC OROGSEYTTFOCAN-DNJOTXNNSA-N 0.000 description 27
- OROGSEYTTFOCAN-UHFFFAOYSA-N hydrocodone Natural products C1C(N(CCC234)C)C2C=CC(O)C3OC2=C4C1=CC=C2OC OROGSEYTTFOCAN-UHFFFAOYSA-N 0.000 description 22
- 229940057818 guaiacolsulfonic acid Drugs 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- QDRCGSIKAHSALR-UHFFFAOYSA-N 4-hydroxy-3-methoxybenzene-1-sulfonic acid Chemical compound COC1=CC(S(O)(=O)=O)=CC=C1O QDRCGSIKAHSALR-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 10
- 235000006173 Larrea tridentata Nutrition 0.000 description 9
- 244000073231 Larrea tridentata Species 0.000 description 9
- 229960002126 creosote Drugs 0.000 description 9
- 150000003797 alkaloid derivatives Chemical class 0.000 description 8
- 229960001867 guaiacol Drugs 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- WHRZCXAVMTUTDD-UHFFFAOYSA-N 1h-furo[2,3-d]pyrimidin-2-one Chemical compound N1C(=O)N=C2OC=CC2=C1 WHRZCXAVMTUTDD-UHFFFAOYSA-N 0.000 description 7
- -1 Phenol Sulfonates Chemical class 0.000 description 6
- 229960003360 guaiacolsulfonate Drugs 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 235000011118 potassium hydroxide Nutrition 0.000 description 4
- MMAFPMQOIUHLNH-UHFFFAOYSA-N 2-hydroxy-3-methoxybenzenesulfonic acid Chemical class COC1=CC=CC(S(O)(=O)=O)=C1O MMAFPMQOIUHLNH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- BQJCRHHNABKAKU-KBQPJGBKSA-N morphine Chemical compound O([C@H]1[C@H](C=C[C@H]23)O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4O BQJCRHHNABKAKU-KBQPJGBKSA-N 0.000 description 3
- 229940072033 potash Drugs 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 235000021513 Cinchona Nutrition 0.000 description 2
- 241000157855 Cinchona Species 0.000 description 2
- ORFFGRQMMWVHIB-UHFFFAOYSA-N Meconine Chemical compound COC1=CC=C2COC(=O)C2=C1OC ORFFGRQMMWVHIB-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 210000004400 mucous membrane Anatomy 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- OGDVEMNWJVYAJL-LEPYJNQMSA-N Ethyl morphine Chemical compound C([C@H]1[C@H](N(CC[C@@]112)C)C3)=C[C@H](O)[C@@H]1OC1=C2C3=CC=C1OCC OGDVEMNWJVYAJL-LEPYJNQMSA-N 0.000 description 1
- AQTYXAPIHMXAAV-UHFFFAOYSA-N O-methoxycatechol-O-sulphate Chemical compound COC1=CC=CC=C1OS(O)(=O)=O AQTYXAPIHMXAAV-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007721 medicinal effect Effects 0.000 description 1
- 229960005181 morphine Drugs 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000000246 remedial effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D489/00—Heterocyclic compounds containing 4aH-8, 9 c- Iminoethano-phenanthro [4, 5-b, c, d] furan ring systems, e.g. derivatives of [4, 5-epoxy]-morphinan of the formula:
- C07D489/02—Heterocyclic compounds containing 4aH-8, 9 c- Iminoethano-phenanthro [4, 5-b, c, d] furan ring systems, e.g. derivatives of [4, 5-epoxy]-morphinan of the formula: with oxygen atoms attached in positions 3 and 6, e.g. morphine, morphinone
Definitions
- This invention relates to new chemical compounds intended more especially for use as medicinal remedies and it relates more particularly to a compound for remedial purposes wherein a sulfonic acid is employed in connection with an alkaloid, presently to be described and defined in the claims.
- salts of the ortho guaiacol sulfonic acid with codein which may serve as typical for this purpose would have the following formula, codein being the preferred type of the said alkaloids and the ortho guaiacol sulfonic acid the preferred type of the various existing guaiacol sulfonic acids in the general composition of the compounds herein referred to:
- Creosote sulfonic acid forms salt of a similar but not quite definite chemical formula, creosote being not a distinct chemical compound.
- a metallic base such as hydrates or carbonates of potassium, barium, calcium, etc.
- a codein compound may be produced by double decomposition of molecular weights between a salt of codein, such as muriate, acetate, prosphate and others, and a compound of the ortho guaiacol sulfonic acid, such as barium, potassium, calcium saltor any other suitable salt, or it may be produced by dissolving the free base of the codein in a corresponding molecular quantity of the diluted ortho guaiacol sulfonic acid.
- a salt of codein such as muriate, acetate, prosphate and others
- a compound of the ortho guaiacol sulfonic acid such as barium, potassium, calcium saltor any other suitable salt
- the codein salt thus obtained can be purified by crystallizing the same from water, alcohol or any other suitable solvent.
- the pure salt forms white orthorhombic crystals or a white crystalline powder. Itis easily soluble in hot water but less so in cold water. It is sparingly soluble in strong alcohol, more freely soluble in methyl alcohol and diluted alcohol.
- the watery solution gives the characteristic reaction for guaiacol with ferric chlorid.
- the compound forming, above stated, a crystalline substance possessing the chemical properties of the ortho sulfonic acid of the guaiacol, as well as of codein, is very useful for medicinal purposes, free from caustic effects and objectionable odors, and can be administered in the same quantities as the officinal codein salts.
- the compound possesses also the powerful medicinal properties of both the guaiacol and the alkaloid. While I have specifically referred to codein, other derivatives of the opium group ma be employed to an advanta e, if desirec also any other guaiacol sulfon1c acid in place of the ortho acid may be used.
- the neutral salt of guaiacol sulfonic acid and codein contains in 100 parts 59.44 alkaloid codein (which is the equivalent of 63.20 alkaloid codein U. S. P.) and 40.56 guaiacol sulfonic acid. Both are the neutral salts and true chemical compounds.
- the melting point of the ortho-guaiacol sulfonate of codein is 16t165 G. This salt can be identified by adding a drop of ferric chlorid solution to the cold saturated solution of the salt, whereby the characteristic blue color indicates guaiacol sulfonic acid.
- This codein compound also differs from the ortho guaiacol sulfonate of codein by its greater solubility.
- quantities of materials to produce these salts I used in the specification molecular weights, that is for instance: 1. 1 molecular weight of acetate of codein or 374.5 parts is dissolved in boiling water 2000 parts and to this a hot solution of 1 molecular weight (or a slight excess) or about 241 parts of ortho guaiacol sulfonate of potash in 1000 parts of water is added to produce the codein salt by double decomposition. 2.
- guaiacol sulfonic acid 1 molecular weight or 315 parts of codein alkaloid are dissolved in 1200 parts of hot alcohol and this solution neutralized with diluted (about 50: 1.) guaiacol sulfonic acid to a slightly acid reaction, requiring about A06 parts of this diluted acid, equal to 1 molecular weight or 203 parts of the pure ortho guaiacol sulfonic acid.
- a chemical compound being a neutral salt, a derivative of an alkaloid base of opium, and a sulfonic acid of a phenol, said salt being of a white crystalline character and being soluble in water, a solution of the salt reacting with an excess of caustic potash to precipitate the corresponding alkaloid.
- a chemical compound being a neutral salt resulting from a morphin derivative and guaiacol sulfonic acid, the solution of the salt reacting withan excess of caustic potash to precipitate the corresponding alkaloid.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
GEORGE LUDWIG SCI-IAEFER, OF BROOKLYN, NEW YORK.
PI-IENOL SULFONATE OF OPIUM ALKALOIDS.
No Drawing.
Specification of Letters Patent.
Patented July 5, 1910.
Application filed May 11, 1908. Serial No. 432,233.
To all whom it may concern:
Be it known that I, GEORGE L. SGHAEFER, a citizen of the United States, residing at Brooklyn, in the county of Kings and State of New York, have invented certain new and useful Improvements in Phenol Sulfonates of Opium Alkaloids, of which the following is a specification.
This invention relates to new chemical compounds intended more especially for use as medicinal remedies and it relates more particularly to a compound for remedial purposes wherein a sulfonic acid is employed in connection with an alkaloid, presently to be described and defined in the claims.
It is well known that phenol and some of the derivatives thereof, such as guaiacol,creosote, as well as other derivatives thereof, have a very strong corrosive and caustic action or effect upon the mucous membranes and have a very unpleasant taste, rendering them, in view of that fact, objectionable for medicinal purposes. To overcome the objectionable properties of such phenols or derivatives thereof, various substances have been produced, as an instance of which is the sulfonic acid thereof which has been combined with organic or other suitable bases. I11 U. S. Letters Patent No. 579,898, dated March 30, 1897 and issued to myself, I have described a chemical compound possessing the characteristics of a compound relieved of the objectionable caustic and corrosive qualities of the phenol and its de-- rivatives. In that patent I have described a compound for medicinal purposes wherein guaiacol sulfonic acid is used in connection with an alkaloid of the cinchona group, preferably quinin. The combination or chemical compounds of guaiacol sulfonic acid and cinchona alkaloids described in said patent are amorphous and not crystallizable, as are also the salts of most of the other known alkaloids. So far as I am advised, no crystallizable salts of the alkaloids and sulfonic acid derivatives, such as guaiacol or creosote sulfonic acids, has ever been known or produced. I have, however, discovered that some alkaloids existing in opium or derivatives thereof, such as morphin, methyl-morphin, ethyl morphin, meconin and others, form crystallizable compounds with guaiacol sulfonic acid and creosote sulfonic acid. These salts are produced as neutral salts so that, for instance, the salts of the ortho guaiacol sulfonic acid with codein which may serve as typical for this purpose, would have the following formula, codein being the preferred type of the said alkaloids and the ortho guaiacol sulfonic acid the preferred type of the various existing guaiacol sulfonic acids in the general composition of the compounds herein referred to:
1. For the neutral salt:
Creosote sulfonic acid forms salt of a similar but not quite definite chemical formula, creosote being not a distinct chemical compound. To produce these salts, I make, for instance, the ortho guaiacol sulfonic acid in the usual way, by treating guaiacol with concentrated sulfuric acid, adding to the suitably diluted product, hydrate of barium, 0Xid of lead, or any other suitable base, to remove the excess of sulfuric acid, then filtering off the insoluble material, leaving a mixture of various guaiacol sulfonic acids in solution which is neutralized by a metallic base, such as hydrates or carbonates of potassium, barium, calcium, etc., whereby a solution of the respective guaiacol sulfonates is formed. This solution is then evaporated, leaving an impure product, from which the pure salt of the ortho guaiacol sulfonic acid can be obtained by recrystallization. From this salt a codein compound may be produced by double decomposition of molecular weights between a salt of codein, such as muriate, acetate, prosphate and others, and a compound of the ortho guaiacol sulfonic acid, such as barium, potassium, calcium saltor any other suitable salt, or it may be produced by dissolving the free base of the codein in a corresponding molecular quantity of the diluted ortho guaiacol sulfonic acid. The codein salt thus obtained can be purified by crystallizing the same from water, alcohol or any other suitable solvent. The pure salt forms white orthorhombic crystals or a white crystalline powder. Itis easily soluble in hot water but less so in cold water. It is sparingly soluble in strong alcohol, more freely soluble in methyl alcohol and diluted alcohol. The watery solution gives the characteristic reaction for guaiacol with ferric chlorid.
The compound forming, above stated, a crystalline substance possessing the chemical properties of the ortho sulfonic acid of the guaiacol, as well as of codein, is very useful for medicinal purposes, free from caustic effects and objectionable odors, and can be administered in the same quantities as the officinal codein salts. The compound possesses also the powerful medicinal properties of both the guaiacol and the alkaloid. While I have specifically referred to codein, other derivatives of the opium group ma be employed to an advanta e, if desirec also any other guaiacol sulfon1c acid in place of the ortho acid may be used. I, however, find that a compound comprising codein and ortho guaiacol sulfonic acid is, as a remedy, very useful for treating the mucous membranes. It is to be understood that creosote sulfonic acid may be employed in lieu of the guaiacol sulfonic acid in some cases, if found desirable.
The neutral salt of guaiacol sulfonic acid and codein contains in 100 parts 59.44 alkaloid codein (which is the equivalent of 63.20 alkaloid codein U. S. P.) and 40.56 guaiacol sulfonic acid. Both are the neutral salts and true chemical compounds. The melting point of the ortho-guaiacol sulfonate of codein is 16t165 G. This salt can be identified by adding a drop of ferric chlorid solution to the cold saturated solution of the salt, whereby the characteristic blue color indicates guaiacol sulfonic acid. If the salt is dissolved in hot water 1 :10 quickly cooled to prevent crystallization and precipitated by a very slight excess of caustic potash, the resulting precipitate will respond to the requirements of the U. S. P. for codein alkaloid. The liquor contains ortho guaiacol sulfonate of potash and if carefully neutralized with diluted sulfuric acid yields the characteristic guaiacol reaction with ferric chlorid. The compound of creosote sulfonic acid and codein has a lower, but not distinct melting point, creosote being a mixture of phenols, not being of a definite chemical composition or formula. This codein compound also differs from the ortho guaiacol sulfonate of codein by its greater solubility. As to quantities of materials to produce these salts I used in the specification molecular weights, that is for instance: 1. 1 molecular weight of acetate of codein or 374.5 parts is dissolved in boiling water 2000 parts and to this a hot solution of 1 molecular weight (or a slight excess) or about 241 parts of ortho guaiacol sulfonate of potash in 1000 parts of water is added to produce the codein salt by double decomposition. 2. If free guaiacol sulfonic acid is used: 1 molecular weight or 315 parts of codein alkaloid are dissolved in 1200 parts of hot alcohol and this solution neutralized with diluted (about 50: 1.) guaiacol sulfonic acid to a slightly acid reaction, requiring about A06 parts of this diluted acid, equal to 1 molecular weight or 203 parts of the pure ortho guaiacol sulfonic acid.
The equations of the reactions involved are as follows:
2. C H (OH)OOH3.SO3H+C18H NO Gualacol sulfonic acid. Codein.
Cr,H (OH)OCH .SO H.O gH2 NO3 Guaiacol sulfonate of codein.
potash.
C5H= OH)OCH .SO;;H.C BHQ NO +KCZH O2 Guaiacol sulfonate of codein. POCZLtSSIUIII ace ate.
About the same percentage of codein is contained in the salts formed with creosote sulfonic acid.
Having thus described the invention, what I claim as new, and desire to secure by Letters Patent, is:
1. A chemical compound being a neutral salt, a derivative of an alkaloid base of opium, and a sulfonic acid of a phenol, said salt being of a white crystalline character and being soluble in water, a solution of the salt reacting with an excess of caustic potash to precipitate the corresponding alkaloid.
2. A chemical compound being a neutral salt resulting from a morphin derivative and guaiacol sulfonic acid, the solution of the salt reacting withan excess of caustic potash to precipitate the corresponding alkaloid.
3. A White neutral salt crystalline in character derived from one molecular weight of codein and one molecular weight of guaiacol sulfonic acid, said salt having a melting point of 164:165 C. and a solution of the salt showing a blue color when ferric chlorid is added thereto.
4. A white neutral salt crystalline in character derived from codein and a sulfonic acid of a phenol, said salt being soluble in water, a solution of the salt reacting with an excess of caustic potash to precipitate codein alkaloid.
In testimony whereof I aiiix my signature in presence of two witnesses.
GEORGE LUDWIG SGI-IAEFER.
lVitnesses:
ALFRED G. MANcoLD, l VILLIAM SCHAD.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US43223308A US963254A (en) | 1908-05-11 | 1908-05-11 | Phenol sulfonate of opium alkaloids. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US43223308A US963254A (en) | 1908-05-11 | 1908-05-11 | Phenol sulfonate of opium alkaloids. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US963254A true US963254A (en) | 1910-07-05 |
Family
ID=3031652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US43223308A Expired - Lifetime US963254A (en) | 1908-05-11 | 1908-05-11 | Phenol sulfonate of opium alkaloids. |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US963254A (en) |
-
1908
- 1908-05-11 US US43223308A patent/US963254A/en not_active Expired - Lifetime
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