UNITED STATES PATENT OFFICE.

SILAS LAMSON, OF CUMMINGTON, MASSACHUSETTS.

SCYTHE.

Specification of Letters Patent No. 72, dated October 29, 1836.

To all whom it may concern:

Be it known that I, SILAS LAMSON, of Cummington, in the county of Hampshire and Commonwealth of Massachusetts, have invented a new and Improved Mode of Constructing Scythes; and I do hereby declare that the following is a full and exact description.

My improved scythe resembles in general appearance a common scythe with the web thickened or stiffened back of the cutting part of the improved scythe behind the edge, the blade increases gradually in thickness to the back part of tile web, and gradually diminishes again in thickness outward to the back edge. The greatest thickness is along the web through its whole length. The thickness must be sufficient to give the proper degree of stiffness, and strength although it may be varied to suit the purposes to which the instrument is to be applied, some uses requiring greater firmness of structure than others.

From the thickest part of the web, the back part of the scythe blade is curved upward or downward one side of the web, when the scythe lays horizontally, presents a surface rounded outward, the other a surface rounded inward, either may be turned so downward next to the earth in cutting as convenience may require. Instead of the heavy and solid back of the common scythe, the back of the improved scythe is thin, the weight of the instrument is thereby diminished and the ease with which it operates in mowing much increased. The scythe may be made of any suitable length or width according to the kind of mowing for which it is intended. It has the common curved form of edge, and blade, and is fastened to a snathe or handle in the mode usually practiced. The blade may be made entirely of steel or partly of iron, and partly of steel, and is wrought and tempered in the manner usually adopted in the manufacture of such implements.

Description of the drawing.

Figure I represents the scythe with the rounded side upward. Fig. II, exhibits the side of the scythe rounded inward. Fig. III, is a section of the scythe with the side of the same rounded inward as represented in Fig. II. Fig. IV, is a section of the scythe represented in Fig. I, with the side rounded inward; the thickness of the web is here shown, as thrown farther backward than in the former figures.

A, is the thick part of the web, also indicated by c, c.

a, is the front or cutting edge of the scythe. b, the back or part which in the common scythe would be called back, in the improved scythe made thin.

c, c, is the thick part of the web.

d, is the heel of the scythe fastened with a screw, or otherwise to the snathe, or handle.

That which I claim as my invention, and desire to secure by Letters Patent is-

Thickening and strengthening the web of the common scythe in the manner before described in this specification.

SILAS LAMSON.

Witnesses:

REJOICE NEWTON,
WILLIAM LINCOLN.

UNITED STATES PATENT OFFICE.

JOHN CRABTREE, OF NEW YORK, N. Y.

MODE OF FORMING BLOCKS FOR PRINTING COLORS ON SILK, LINEN, COTTON, AND OTHER CLOTH.

Specification of Letters Patent No. 507, dated December 7, 1837.

To all whom it may concern:

Be it known that I, JOHN CRABTREE, silk, linen, and cotton printers, in the employ of the New York dyeing and printing establishment, in the city of New York, have invented a new and useful improvement in the mode of forming blocks for printing colors on silk, linen, cotton, and woolen goods and other fabrics to which such mode of printing is applicable, which mode of forming said blocks has not been known or so used prior to my invention of the same, and for which I am seeking a patent of the United States, and that the mode of forming said blocks, as distinguished from the mode hitherto generally practiced of doing the same, is freely set forth and shown in the following description, and in the drawings annexed to and making a part of this specification, as follows:

Figure 1, is a linear representation of the mode hitherto practiced, of laying a set of printing blocks for use, in which the parts marked 1, form the sides of the border, and are mitered at the angles; the parts marked 2, form the middle, so that twelve layings are required for the border, and nine for the filling, for each color used; by this mode, the shrinkage and warping of the mitered pieces, causes the mitered joint to open, and when in use, this leaves the miter of the printed pattern imperfect, on the goods, and this imperfection is frequently made worse, by the block, for the second color, shrinking, printed pattern imperfect, on the goods, and or warping, in a different direction. This injury may be prevented by having a third block, expressly for the angle, but such a mode will add materially to the expense of printing.

The mode I propose to remedy or prevent this injury, is shown in Fig. 2, which is a linear representation of the mode, for which I seek a patent, for laying a set of printing blocks for use, in which the angle pieces marked 1, are solid, and contain the angle or corner patter, with its own parts mitered in the solid block, so that when the goods are printed, the pattern comes off perfect, which cannot be attained when this part of the block is in two pieces. The same blocks contain each a portion of the middle of the pattern, and the pieces marked 2, and 3, complete the square. By this arrangement, only eight layings, for each color, are required, to complete the printing of the goods, and much less labor is required, and the work is more neatly executed, than by the ordinary mode first described herein. The drawing represents a square but the mode is equally applicable to any other form.

What I claim as my invention, and for which I seek a patent, is-

The forming the angle blocks in one piece, so that they shall contain the angle or corner patterns, each having its own parts mitered in the solid block, in combination with the arrangement herein substantially described and set forth by which a less number of layings for each color are required and the work is more neatly executed than heretofore by the mode in general use.

In witness whereof I have hereunto set my hand in New York this eighteenth day of November one thousand eight hundred and thirty-seven.

JOHN CRABTREE.

Witnesses:
S. M. W. BROOKS,
W. SERRELL.

UNITED STATES PATENT OFFICE.

THOMAS THORPE, OF WEST CAMBRIDGE, MASSACHUSETTS.

DOOR-SPRING.

Specification of Letters Patent No. 506, dated December 7, 1837.

To all whom it may concern:

Be it known that I, THOMAS THORPE, of West Cambridge, county of Middlesex, and State of Massachusetts, have invented a new and useful Improvement in Door-Springs. The said improvement, the principle thereof, and modes in which I have contemplated the application of the same, together with such parts, combinations, or characteristics by which it may be distinguished from other inventions, and which I claim I have fully set forth in the following specification and drawings referred to herein.

A. A represents the outer casing of brass, or other suitable metal, shaped as seen in the drawings, or otherwise properly formed.

B is the door on which the spring is to be fastened; C, the door frame.

E is a metallic rod, turning on a hinge at a, in the side of the piece of metal F, screwed to the door frame. The rod E passes through holes in the ends b, c of the casing A, moving freely back and forth in said holes.

G is a cross bar, attached to the rod E in a proper manner, and has connected to each extremity the end of a wound spring, H H, whose opposite end is confined to the end b of the casing, or to a pin d, passing through the sides thereof.

When the door is opened, the spring H H are extended by the movement of the rod E through the slots in the ends b, c of the casing, and on withdrawing the force applied to open the door, the springs contract, and immediately close the same.

Instead of two springs, I may use only one, or I may employ three or more, should it be deemed advisable.

The main advantage of this spring consists in the exertion of a strong force to close the door, when nearly shut. Other kinds of door spring generally fail in this part of their operation.

I claim as my improvement-

The above arrangement of springs acting on a rod E, and operating in manner above described.

In testimony that the above is a true description of my said invention, I have hereto set my hand this ninth day of November, in the year eighteen hundred and thirty seven.

THOMAS THORPE.

Witnesses:
R. H. EDDY,
A. E. WILSON.

UNITED STATES PATENT OFFICE.

STEPHEN C. SMITH, OF NEW YORK, N. Y.

IMPROVEMENT IN THE MANUFACTURE OF INDIA-RUBBER BOOTS AND SHOES.

Specification forming part of Letters Patent No. 503, dated December 7, 1837.

To all whom it may concern:

Be it known that I, STEPHEN C. SMITH, of New York, in the county of New York and State of New York, have invented a new and Improved Mode of Manufacturing Boots and Shoes of Sheet India-Rubber; and I do hereby declare that the following is a full and exact description of the process of manufacture.

A cloth or leather lining is fitted to the last and sewed or cemented to an insole of leather. Over this are then spread with a brush two or three coats of dissolved india-rubber to render it sticky. The sheet-rubber is then cut into the proper shape and two or three coats of dissolved india-rubber spread on one side of it. The sheet-rubber is then put onto the cloth lining and rubbed down. The cement on it causes it to adhere to the cloth. A sole of leather or india-rubber is then cemented to the bottom. The boot or shoe is then taken from the last, bound round the top, blacked, and is ready for use.

What I claim as my invention, and desire to secure by Letters Patent, is —

The making of boots, bootees, shoes, overshoes, and slippers of sheet India rubber, in the manner herein described.

STEPHEN C. SMITH.

Witnesses:

W. V. WHITE.
S. WM. SMITH.

UNITED STATES PATENT OFFICE.

JOHN HUMPHRIES, OF NEW YORK, N. Y.

MANUFACTURE OF CARPETING AND RUGS.

Specification of Letters Patent No. 1,028, dated December 10, 1838.

To all whom it may concern:

Be it known that I, JOHN HUMPHRIES, of the city, county, and State of New York, have invented a new and useful Improvement in the Manufacture of Carpeting and Rugs; and I do hereby declare that the following is a full and exact description thereof, reference being had to the drawings accompanying and making part of this specification.

My invention is of the following nature- viz., that of attaching a ply, rib or knit substance to the back or bottom of carpeting and rugs.

Figure 1 of the drawings shows the back or bottom of a carpet or rug with the additional ply attached to it. a represents this additional ply, rib, knit substance, or body of material of weft attached, connected and added by any suitable process to the back or bottom b of carpeting and rugs, generally known, invoiced, and designated, at the present time, by the names of Brussels, Brussels back, Wilton, Royal Wilton, Saxony, Embossed imperial, and Imperial.

The method of attaching the additional ply to carpets is very simple. As represented at a Fig. 1, the additional ply is laid transversely upon the bottom and secured to it by means of threads h passing longitudinally and alternately over and under the ply and through the carpet or rug. As represented at g, the thread passes transversely over the ply, and is secured to the bottom of the carpet by an additional thread i passing over and under the transverse thread and into the bottom of the carpet or rug, thus confining both the transverse thread and ply to it.

What I claim as my invention and desire to secure by Letters Patent is-

The attaching to the back or bottom of carpeting and rugs known and designated by the names of Brussels, Brussels back, Wilton, Royal Wilton, Saxony, Embossed Imperial and Imperial, made with any material whatsoever, an additional ply, rib, knit surface or body of material of warp and weft, as hereinbefore described.

JOHN HUMPHRIES.

Witnesses:
JOHN W. HUBBARD,
C. H. WILTBERGER.

THOMAS CHASE, OF NEW, YORK, N. Y., ASSIGNOR TO GEORGE H. RICHARDS.

IMPROVEMENT IN THE PROCESS OF TANNING.

Specification forming part of Letters Patent No. 1,018, dated November 25, 1838.

To all whom it may concern:

Be it known that I, THOMAS CHASE, of the city of New York, have invented an Improvement in the Process of Tanning Hides and Skins, for which process Letters Patent of the United States were granted to George H. Richards, of the said city, dated the 16th day of December, in the year 1833, by which improvement the process is much simplified, room is economized, and the effect is more certain and rapid; and I do hereby declare that the following is a full and exact description thereof.

Instead of employing two vats, as in the process described by the said George H. Richards, I perform the whole operation in one single air-tight vat, which I use in the following manner:

I make an air-tight vat, cistern, or case of sufficient strength to sustain the pressure of the atmosphere when the air is exhausted therefrom. Within this vat or cistern I suspend or lay the hides or skins in any convenient manner and completely cover the same with the tanning liquor. The top of the cistern is fixed and secured to the body of the vat or box by means of screws, or otherwise, with the intervention of leather or other suitable substance to render the same air-tight. By means of an air-pump or other apparatus affixed on or near the top of the cistern I exhaust the air therefrom as completely as possible, and after this I work the air pump from time to time, as air will continua to be exhausted from the liquid and from the pores of the skins in consequence of the remova1 of the pressure of the atmosphere from the surface of the liquid. The expansion or extraction of the air in the pores of the skin opens them and gives a ready admission to the liquor or ooze, which in consequence penetrates to the interior of the skin, pervading its whole mass and tanning it perfectly throughout. I sometimes, after having continued this state of exhaustion for some hours, admit the atmosphere into the vat, so as to exert its pressure upon the surface of the liquid, allowing it to do so for a short period of time, that it may aid in forcing the liquid into the exhausted pores, after which I again work the air-pump and remove the pressure. As occasion may require, I renew the liquor in the vat by withdrawing it by a pump or other means and returning it to a reservoir of bark or other tanning substance, from which reservoir it is again freshly supplied by a tube or other means to the tanning vat. I also have a barometer or gage connected with the vat, by which to ascertain the degree of atmospheric pressure. After the tanning-liquor has completely penetrated the hides or skins and become incorporated with them extra atmospheric or hydraulic pressure (the latter of which I think the more convenient) may be applied in order to give the hides or skins an additional solidity or firmness.

I do not prescribe any particular mode of constructing the vats or cisterns, there not being anything peculiar in these or in any other part of their apparatus, the whole being such as any competent workman can construct without special directions from me, such apparatus having been before known and used for various purposes, and not being of my invention.

What I claim as constituting my improvement is-

The application of the principle of exhaustion to tan-vats after the skins or hides have been suspended or laid therein and they have been covered with the tanning liquor, in the manner and for the purpose herein fully set forth.

THOMAS CHASE. [L. S.]

Witnesses:
GILBERT GOLDING,
J. R. LOWZANA.

2,794,028 Patented May 28, 1957
EPOXY DERIVATIVES

Benjamin Phillips and Paul S. Starcher, Charleston, W. Va., assignors to Union Carbide and Carbon Corporation, a corporation of New York

No Drawing. Application August 13, 1953, Serial No. 374,141

3 Claims. (Cl. 260— 348)

This invention relates to new organic compounds and has for an object the provision of new types of organic compounds suitable for use in the plastics and resins industry, as well as other important industrial uses. More particularly, this invention relates to epoxy compounds prepared from tetrahydrophthalic anhydride and tetrahydrophthalic acid.

The new compounds of this invention are useful as modifiers for various condensation resins and as plasticizers and stabilizers for various synthetic resins.

The epoxides obtained by the epoxidation of the tetrahydrophthalic acid and its derivatives are particularly attractive, in view of the fact that they are potentially low cost chemicals since the tetrahydrophthalic anhydride is readily obtained by the reaction of butadiene and maleic anhydride, both of which are commercially available in large quantities.

More specifically, the compounds which comprise this invention are useful as chemical intermediates in preparing a large number of chemical compounds by virtue of their reactive epoxide group which can be reacted with a large number of compounds having a labile hydrogen atom.

The compounds of this invention may be conveniently illustrated by the following structural formula:

[see figure]

The compounds of this invention are produced by the oxidation of the olefinic linkage contained in the starting material, as in the oxidation of the tetrahydrophthalic anhydride to yield the 4,5-epoxycyclohexane-l,2-dicarboxylic anhydride otherwise known as 7-oxabicyclo-[4.1.0]heptane-3,4-dicarboxylic anhydride.

The oxidizing agents employed in the production of these new compounds are the peracids, such as, for example, peracetic acid, perpropionic acid, perbenzoic acid and the like. More particularly, peracetic acid is employed as the oxidizing agent to produce these epoxy compounds.

The use of the peracids to obtain certain beneficial oxidation results is not new in the art of oxidizing organic compounds. In fact, the history of the peracids dates back to the work of Baeyer and Villiger, who, in 1900, were able to prepare perbenzoic acid by the saponification of dibenzoyl peroxide. The tremendous interest displayed over the peracids is due to the fact that the peracids occupy somewhat a unique position as oxidizing agents. The peracids have the ability to effect several specific chemical transformations with very high efficiencies, whereas, other well known oxidizing agents, such as, for example potassium permanganate, have no such ability.

Among the most interesting types of chemical transformations peculiar to the peracids is that type of reaction which makes available the compounds of this invention, that is, the oxidation of unsaturated organic compounds to yield the corresponding epoxides. It is this particular oxidation ability of the peracids that makes available a host of chemical compounds that may have previously been produced only through laborious and tedious means and in minute quantities or were never heretofore obtainable. For purposes of illustration, the reaction whereby the epoxide derivative of tetrahydrophthalic anhydride is produced in accordance with our invention, may be written as follows:

[see figure]

The following examples will serve to illustrate the practice of the invention:

EXAMPLE I

Preparation of 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylic acid

Fifty grams of tetrahydrophthalic acid was dissolved in 150 grams of acetone and the mixture was heated to 40° C. To this mixture was added 132 grams of a 25.4% solution of peracetic acid in acetone over a period of 40 minutes. The reaction mixture was heated at 40° C. for an additional six hours. To 100 grams of this reaction mixture was added enough petroleum ether to cause layer separation. The lower layer was recovered and titrated with petroleum ether until crystallization occurred. The crystals, after being washed with petroleum ether and dried weighed 11.1 grams. An analysis for epoxide content by the hydrogen bromide method indicated a purity of 64.2% calculated as 7-oxabicyclo-[4.1.0]heptane-3,4-dicarboxylic acid. The rest of the original reaction mixture was placed in a brine bath at —50° C. for eight days. The crystalline phase which separated, was filtered off, washed several times with petroleum ether, and dried. It weighed 7 grams. An analysis for epoxide groups by the hydrogen bromide method indicated a purity of 75.5% calculated as the epoxy acid. Titration of the acid groups followed by saponification, indicated that 82% of the theoretical carboxyl groups were still available. The product melted with foaming at 145°-150° C.

EXAMPLE II

Preparation of 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylic anhydride

One mol of tetrahydrophthalic anhydride was dissolved in 900 grams of ethylbenzene. One and one-half mols of a 23.4% peracetic acid solution in ethyl acetate was added to the anhydride solution over a period of two hours at a temperature of approximately 30° C. The reaction mixture was allowed to stand over night. White crystals of the reaction product was separated from the solution. This crude product had a melting point in the range 141°-143° C. and upon further purification, by two recrystallizations from dioxane, gave 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylic anhydride having the following properties:

[see figure]

What is claimed is:

1. An epoxide selected from the group consisting of 4,5-epoxycyc1ohexane-1,2-dicarboxylic acid and 4,5-epoxycyc1ohexane-l,2-dicarboxylic anhydride.

2. As a new epoxide, 4,5-epoxycyc1ohexane-l,2-dicarboxylic acid.

3. As a new epoxide, 4,5-epoxycyc1ohexane-l,2-dicarboxylic anhydride.

References Cited in the file of this patent

UNITED STATES PATENTS
2,550,494 Olin Apr. 24, 1951
2,570,029 Fluchaire Oct. 2, 1951

OTHER REFERENCES

Ziegler et al.: Annalen, vol. 551, pp. 17-18 (1942).
Gill: J. Chem. Soc., 1952: 4630-4632.

US patent 2794028 full text in PDF format

United States Patent Office.

3,120,529

Patented Feb. 4, 1964

10-ACYL DERIVATIVES OF APOYOHIMBINE AND PROCESS THEREFOR

John Shavel, Jr., Mendham, N.J., assignor to Warner-Lambert Pharmaceutical Company, Morris Plains, N.J., a corporation of Delaware

No Drawing. Filed Feb. 10, 1961, Ser. No. 88,307
4 Claims. (Cl. 260—287)

The present invention relates to new and novel 10-acyl derivatives of apoyohimbine of the formula:

[see figure]

wherein R is the acyl radical of an aliphatic carboxylic acid containing 1 to 6 carbon atoms and to the non-toxic acid addition and quaternary ammonium salts thereof. This invention also relates to a method of producing these compounds.

The compounds of this invention are derivatives of the alkaloid apoyohimbine of the yohimbane series. They have interesting pharmacological activity and are useful as analgesics, tranquilizers and hypotensive agents. In addition, they are valuable intermediates in the production of other compounds of the yohimbane series. Included within the scope of this invention are such 10-acyl derivatives of apoyohimbine as 10-acetylapoyohmibine, 10-propionylapoyobimbine, 10-butyrylapoyohimbine, 10-valerylapoyohimbine and the like.

It has now been found that the compounds of my invention of the above formula may be prepared by treating the known apoyohimbine at between +25° C. and — 40° C. with an acid anhydride or acyl halide having R acyl groups in the presence of a Friedel-Crafts catalyst. The reaction is one of acylation with an R acyl group being substituted at the 10-position of the apoyohimbine starting material. The reaction is carried out in the liquid phase under anhydrous conditions in the presence of a Friedel-Crafts catalyst such as boron trifluoride, aluminum chloride, aluminum bromide, stannic chloride, ferric chloride, ferric bromide, hydrofluoric acid, polyphosphoric acid, titanium tetrachloride, sulfuric acid and the like, with boron trifluoride being particularly effective. The reaction mixture may also contain a carboxylic acid or a carboxylic acid ester corresponding to the acid halide or acid anhydride, that is, a carboxylic acid of the formula ROH, or an ester of the formula ROR₁, wherein R₁ is a lower alkyl group.

In carrying out the reaction the acylating agent (acid anhydride or acyl halide), either with, or without the corresponding acid or ester, is initially saturated with catalyst at a temperature between about —20° C. and + 10° C. The temperature of the mixture is then adjusted to the desired reaction temperature and the apoyohimbine starting material is added, either as a solid or as a solution in the acylating agent or in an inert organic solvent, such as rnethylene chloride, dioxan, tetrahydrofuran and the like. The reaction mixture is then stirred at the reaction temperature to completion and the product is recovered therefrom by conventional techniques of extraction, crystallization and chromatography.

It is to be understood that the new and novel compounds of this invention may be used as the free base or may be converted into the corresponding pharmaceutically acceptable non-toxic acid addition and quaternary ammonium salts. Exemplary of non-toxic acid addition salts are those formed with maleic, fumaric, benzoic, ascorbic, succinic, bismethylensalicylic, methylsulfonic, ethanedisulfonic, acetic, propionic, tartaric, salicyclic, citric, gluconic, lactic, malic, mandelic, cinnamic, citraconic, stearic, palmitic, itaconic, glyolic, benzenesulfonic, hydrochloric, hydrobromic, sulfuric, sulfamic, phosphoric and nitric acids. The acid addition salts may be prepared in the conventional manner, for example, by treating a solution or suspension of the free base in an organic solvent with the desired acid, and then recovering the salt which forms by crystallization techniques. The quaternary salts are prepared by heating a suspension of the base in a suitable solvent with a reactive alkyl halide such as methyl iodide, ethyl bromide, n-hexyl bromide, benzyl chloride or a reactive ester such as methyl sulfate, ethyl sulfate or methyl p-toluene sulfonate.

For therapeutic use, the new and novel compounds of this invention, as the free base, or as their acid addition or quaternary ammonium salts, may be formulated with conventional pharmaceutical carriers into dosage unit forms, such as tablets, capsules, elixirs, suppositories, solution, suspensions and the like. The following example is included in order further to illustrate the present invention:

Example

45 A mixture of 25 ml. glacial acetic acid and 150 ml. acetic anhydride is saturated with boron trifluoride at —10° C. by passing boron trifluoride into the solution for 15 minutes. The resulting mixture is cooled to —20° C. and 25 g. apoyohimbine are added. The reaction mixture is agitated for two hours and then is poured onto crushed ice. The suspension formed is made basic with ammonium hydroxide and extracted with chloroform. The extract is dried over sodium sulfate, filtered and evaporated to dryness. The residue, an oil, is crystallized from methanol to yield 19.9 g. of crystals, which on two further recrystallizations from methanol yield pure 10-acetylapoyohimbine (as the hydrate), M.P. 204-206° C. (dec.), [α]_D²⁵ +38° (pyridine, c.= l.l).

Analysis.—Calc.: C, 69.67; H, 7.12; N, 7.07. Found: 60 C, 69.73; H, 7.43; N, 7.35. It is understood that the foregoing detailed description is given merely by way of illustration and that many variations may be made therein without departing from the spirit of my invention.

Having described my invention, what I desire to secure by Letters Patent is:

1. A member selected from the group consisting of compounds of the formula:

[see figure]

wherein R is the acyl radical of an unsubstituted saturated aliphatic carboxylic acid of 1 to 6 carbon atoms and the pharmaceutically acceptable non-toxic acid addition and quaternary ammonium salts thereof with a compound selected from the group consisting of methyl iodide, ethyl bromide, n-hexyl bromide, benzyl chloride, methyl sulfate, ethyl sulfate and methyl p-toluene sulfonate.

2. 10-acetylapoyohimbine.

3. A method of preparing a compound of the formula:

[see figure]

wherein R is the acyl radical of an unsubstituted saturated aliphatic carboxylic acid of 1 to 6 carbon atoms which comprises treating apoyohimbine with a member selected from the group consisting of a carboxylic acid anhydride (R)2O and a carboxylic acid halide R—X wherein X is halogen and R has the meaning above at a temperature between +25° C. and —40° C. in the presence of a Friedel-Crafts catalyst.

4. A method according to claim 3 wherein said Friedel- Crafts catalyst is boron trifluoride.

No references cited.

PDF of United States Patent Number 3120529

UNITED STATES PATENT OFFICE.

CHRISTIAN RUDOLPH, OF HOCHST-ON-THE-MAIN, GERMANY, ASSIGNOR TO FARBWERKE, VORMALS MEISTER, LUCIUS & BRUNING, OF SAME PLACE.

MANUFACTURE OF ARTIFICIAL INDIGO.

SPECIFICATION forming part of Letters Patent No. 262,695, dated August 15, 1882.
Application filed April 18, 1882. (Specimens.)

To all whom it may concern:

Be it known that I, CHRISTIAN RUDOLPH, a citizen of Germany, residing at Hochst-on-the-Main, Germany, have invented certain new and useful Improvements in the Production of Artificial Indigo; and I do hereby declare that the following is a full, clear, and exact description of the invention, which will enable others skilled in the art to which it appertains to make and use the same.

My invention relates to an improvement in the production of artificial indigo. It consists in producing artificial indigo from benzaldehyde in the manner hereinafter to be described.

In producing monobenzylidenacetone I use the simplest known method, which is that described by Schmidt Claisen in “Berichte der Deutschen Chemischen Gesellschaft,”(1881, pp. 2,472,) — viz., from benzaldehyde and acetone in a weak solution of caustic soda. The next step is the conversion of the monobenzylidenacetone into its orthonitromono substitution product, which is done as follows: one part monobenzylidenacetone is mixed with the quintuple quantity of sulphuric acid. Into this mixture I pour slowly the calculated quantity of nitric acid at a temperature of 32.59° Fahrenheit, (0.15° centigrade,) and having a specific gravity of 1.46, dissolved in the double quantity of sulphuric acid. After this operation is completed the nitro compounds which remain in solution in the sulphuric acid are separated by pouring this solution into a large quantity of water. Said nitro compounds are afterward collected on a filter, and after being carefully washed in water they are dissolved in one and a half time the quantity of alcohol. After this solution has been standing for several hours the paranitromonobenzylidenacetone will have separated almost completely. The residual liquor or nitrate contains the orthonitrobenzylidenacetone, which can be obtained by distilling off the alcohol or by adding to the residual liquor the triple to quadruple quantity of water. If, now, the orthonitrobenzylidenacetone be digested for some time in an alcoholic soda-lye, (one part of the nitrate, five parts alcohol, and three parts of soda-lye of ten per cent.,) it becomes converted into a new substance, which, after the acidulation of the solution, can be separated by washing it out with ether.

From this substance I obtain, by heating its aqueous solution, or, better still, by adding alkalies — such as soda or caustic soda — to the solution, a considerable quantity of artificial indigo, which may be obtained in a pure state by further washing the same with water and alcohol.

Having thus described my invention, what I claim as new, and desire to secure by Letters Patent, is—

1. The process of manufacturing an artificial indigo from benzaldehyde, which consists in first converting the same into monobenzylidenacetone by the ordinary well-known method, then converting said monobenzylidenacetone into its orthonitro substitution derivative, separating this orthonitro product from isomers by crystallization, filtration, and distillation, and finally converting it into the indigo-blue coloring- matter by digestion in a weak alkaline lye.

2. A blue coloring-matter or dye-stuff (an artificial indigo) prepared by the process herein set forth. In testimony that I claim the foregoing as my own I affix my signature in presence of two witnesses.

CHRISTIAN RUDOLPH.

Witnesses:
JOSEPH EUGEN REVERDY,
ALBERT FROSCHMANN.

UNITED STATES PATENT OFFICE.
FREDERICK D. CRANE, OF MONTCLAIRE, NEW JERSEY.
ARTIFICIAL RESINOUS BODY.
No drawing. Application filed September 30, 1920. Serial No. 413,890.

To all whom it may concern;

Be it known that I, FREDERICK. D. CRANE, a citizen of the United States, and having a post-office address at No. 74 North Willow Street, Montclair, county of Essex, and State of New Jersey, have invented certain new and useful Improvements in Artificial Resinous Bodies, of which the following is a specification.

My invention relates to artificial resinous bodies.

In accordance with the present invention artificial resinous bodies are produced by reacting upon an aromatic compound having a benzene ring and one or more attached aliphatic groups, in at least one of which a halogen atom has been substituted, with a compound of the resinous acid or, acids in which a metal has been substituted for the acid hydrogen.

Aromatic compounds suitable for use in making the product of the present invention may be, for example, such compounds as benzyl chloride, chlor-xylene, and the like, and suitable rosin acids for use in this connection are, for example, those of pine rosins, ordinarily called abietic acids.

The following examples illustrate manners in which the new product may be made.

A suitable compound is derived from the abietic acid of rosin with an alkali such as caustic potash in the following manner: 98 parts of rosin are heated with 12 parts of caustic potash and 400 parts of water, and the so called “resene” or insoluble portion, may be filtered out, if desired. To the mixture obtained are added 37 parts of commercial benzyl chloride, and the resulting mixture is boiled, under a reflux condenser for about four hours. The excess benzyl chloride is then removed, preferably by steam distillation. A resinous mass, somewhat softer than the original rosin, is produced, having a brownish color, the depth of which varies with the quality of rosin used.

Instead of benzyl chloride, chlor xylene may be substituted in the above example, the molecular equivalent thereof being used. The chlor xylene may, if desired, be prepared by the introduction of chlorine into xylene by the usual chlorination method, the equivalent quality of resulting chlorinated compound being then determined by estimation of the chlorine content. The presence of unchlorinated xylene does not inhibit reaction. A resinous product of the same general character as that derived by the use of the benzyl chloride, being somewhat harder, is produced. The corresponding brom-derivative, such as benzyl bromide, brom toluene, etc., may likewise be employed.

The resinous bodies obtained from the abietic acid of rosin in the manner above described may be hydrogenated, if desired, or oxygen may be added thereto by treatment with ozone. In either case the stability of the molecule of the resinous compound is improved. The resinous compound may likewise be vulcanized by the addition of sulphur and moderate heating, with the formation of a hardened product having the characteristics of varnish gum.

Before treatment with the alkali and the aromatic compounds of the character described, the rosin may be subjected to the action of an alcoholic solution of hydrochloric acid, which is generally regarded as resulting in the splitting of the abietic acid into two acids having generally similar properties to the abietic acid. The proportion of the halogenated aromatic compound used in this case must be doubled, the method of procedure otherwise remaining the same. The resulting resinous compound is of the same general character as that derived from the abietic acids being, however, somewhat softer.

The acidic varnish gums, such as animi or elemi, may be substituted for the rosins in the examples above given. The product resulting from the present invention may be utilized in the production of chewing gums, varnishes, plastics, sizing, waterproofing material for papers, and generally as substitutes for resinous and varnish gums.

It is believed that the resinous bodies obtained as above described are of the character of esters, the composition of which may be generally expressed by the formula RCOOR’, in which —R— represents the radical of the acid constituent of the rosin, and — R’ — represents an aromatic body having a benzene ring to which one or more aliphatic groups are attached.

The examples and theory above recited are given for the purpose of affording an understanding of the invention and ways in which it may be carried out; but it is not intended that the details of the examples nor the theories hereinbefore expressed are to be regarded as limitations on the scope of the invention.

I claim:

1. As a new article of manufacture, a benzyl ester of a resinous acid material.

2. As a new article of manufacture, an ester benzyl resinate or abietate.

In witness whereof, I have signed my name hereto. FREDERICK D. CRANE.