Commentary: Autobiography:

Bonded to People, Part III

 

Professor Dr Dr Randolph Riemschneider, LBFel

Institute of Biochemistry, Free University of Berlin (FUB), Germany

Central Institute of Chemistry, Universidade Federal de Santa Maria (UFSM), Santa Maria, Rio Grande do Sul, Brazil

 

 BWW Life Fellow Member Professor Randolph Riemschneider has summarized his lifetime work in a soon to be published book [1] in which readers will find some enlightening reports about the numerous people who influenced his life. With this paper the author also continues his essay “Bonded to Compounds – Providence” from the July-August 2005 issue of this Journal [2]

Chemistry has always been and remains the author’s life. For the sake of his devotion to chemistry, the author has resisted and confronted all problems which politics can involve, and has fought against resistances and intrigues. Here it is shown from whom and in what manner he received support and sorely-needed assistance.

This essay also represents a piece of contemporary history, especially from the 1940s to the 1960s, regarding Nobel Prize winners such as Profs Alder/Diels, Butenandt, R.Kuhn, Pauling, Natta/Ziegler and in Germany well-known personages such as Profs. Dinghas (mathematician), Lohmann (ATP), Sauerbruch, General Nobile, Dir. Dr. Scherer (Freon HOECHST), and Dr. Ronge (attorney) as well as personages from Japan and Brazil who have influenced the life of the author.      - The Editor

 

In Norway, a hexachlorocyclohexane having a melting point of 146°C (I) was isolated from cyclohexane chlorination products and was deemed to be another stereoisomer of the C₆H₆Cl₆-isomer of the 1,2,3,4,5,6 series resulting from the chlorination of benzene. O. Hassel determined its dipole moment, i.e. of I, and placed I by mistake as a zeta-isomer in the series of the five stereoisomers alpha, beta, gamma, delta, epsilon already known without checking by a simple reaction which positional isomer it actually was.

 

[For reference:

E)      eta-1,2,3,4,5,6-Hexachloro-cyclohexane (eta-I), chair-configuration 1e2e3e4a5e6a (and zeta-I: 1e2e3a4e5a6a)

Constitution of eta-I:     

That the new isomer eta-I belongs to the 1,2,3,4,5,6-serie is shown by the treatment with Zn-dust (→ benzene), and with alkali (→trichlorobenzenes), carried out with micro amounts

Configuration of eta-I:

Determined by dipolmoment measurements: e.e.e.a.e.a, found: 3,2 D, calc. 3,5 D [14b]. RAMAN-spectra - 611b in [1].     

With exception of  the isomer e.a.e.a.e.a all theorectical possible chair-configurations of the 1,2,3,4,5,6-series were isolated and determined; so performed from the author on 15 Aug 1964 in the colloquium held in Sala de Atos, Edificio sede da UFSM, Santa Maria, RS, Brasil  

List of the isolated C₆H₆Cl₆-isomers

                                alpha     - C₆H₆Cl₆       mp. 159°C           (e.e.e.e.a.a)

                      beta       - C₆H₆Cl₆       mp. 309°C           (e.e.e.e.e.e)

                      gamma   - C₆H₆Cl₆       mp. 113°C           (e.e.e.a.a.a)

                      delta      - C₆H₆Cl₆       mp. 139°C           (e.e.e.e.e.a)

                      epsilon   - C₆H₆Cl₆       mp. 218°C           (e.e.a.e.e.a)

                      zeta       - C₆H₆Cl₆       mp. 88/89°C        (e.e.a.e.a.a) *

                      eta         - C₆H₆Cl₆       mp. from 70°C    (e.e.e.a.e.a)

In Table 2a there will be shown the spatial structure of the seven isomers.

* zeta-I: The real** zeta-1,2,3,4,5,6-Hexachloro-cyclohexan, mp 88-89°C (zeta-I)        is described in ref (608) in PROJ IX (1), here ref (20)

Our proof of constitution:  zeta-I belongs to the 1,2,3,4,5,6 series because it is converted to benzene through the zinc dust treatment, cleaving 6 Cl atoms. When exposed to alkali it reacts, forming trichlorobenzenes (cleaving 3 HCl).

Our proof of configuration:  Short-term chlorination of zeta-I  in an open vessel to CCl₄ resulted in an oil from which were obtained by means of chromatographic adsorption: delta-1,1,2,3,4,5,6-hepta­chloro-cyclohexane with a melting point of 138 to 140° C (delta-IV of the configuration ea.e.e.a.a.e) and alpha-1,1,2,3,4,4,5,6-octachloro-cyclohexane with a melting point of 93°C (alpha-III of the configuration ea.e.e.ea.e.a).

stepwise chlorination of zeta-I:    zeta-C₆H₆Cl₆ mp 88 - 89°C (e.e.a.e.a.a)  to      delta-C₆H₅Cl₇ mp 138 - 140°C (ea.e.e.a.a.e)  [delta-IV]  to   alpha-C₆H₄Cl₈ mp   93°C (ea.e.e.ea.e.a)  [alpha-III]

**    About the  so-called zeta-isomer, an C₆H₆Cl₆ isomer[i] with Cl-atoms in the position 1,1,2,4,4,5 [and not in 1,2,3,4,5,6 as believed Hassel and co-worker and called it by mistake zeta-isomer] see 5 publications in  [21] and also next page.

"zeta-Gezeter" (Gezeter: Much ado about nothing) over the zeta-isomer or the "zeta-isomers" of C₆H₆Cl₆   (zeta-C₆H₆Cl₆)]

 

A determination of the constitution always ranks before determination of the configuration (constellation)!

 

The author was able to put right this mistake when he early started systematic studies of the chlorination of cyclohexane and developed the so-called "cyclohexane family tree" of the chlorination products of cyclohexane: Table 2b. The so-called zeta-isomer of Hassel turned out to be 1,1,2,4,4,5-hexachloro-cyclohexane. The author proposed to eliminate the designation zeta for it and to use the letter zeta for the sixth stereoisomer of the 1,2,3,4,5,6 series by then actually isolated from the so-called delta-oils from the chlorination of benzene: zeta-1,2,3,4,5,6-hexachloro-cyclohexane having a melting point of 88 - 89°C and the chair configuration 1e2e3a4e5a6a [20].

 

Unfortunately, American experimentators caused some confusion by calling the sixth stereoisomer they isolated eta-isomer, even though they were aware of our experimental results. The author has given a comprehensive report of this case in PROJ IX in "Re-reading - 66 years of chemistry" and also described the real eta-isomer he isolated; cf. [20] and [21].

 

 

 

 

 

 

 

 

 

 

 

Table 2a:  The isolated 1,2,3,4,5,6-hexachloro-cyclohexanes [16,15]

 

 

 

 

 

 

It is still lacking the eighth theoretically possible C₆H₆Cl₆-isomer of the chair-configuration 1e2a3e4a5e6a. In case of realisation, it would be the theta-isomer.

 

Of the 1,2-dibromo-3,4,5,6-hexachloro-cyclohexanes we isolated 4 isomers: PROJ IX in [1].

 

 

 

Table 2b:

Cyclohexane chlorination products: "Cyclohexane family tree”*

 

The products obtained in crystallised form from the chlorination of cyclohexane are preferably Cl-substituted in the positions 1,2,4,5, i.e. some CH₂ groups remain intact in favour of the formation of CCl₂ groups: Substitution products bearing Cl atoms on all C atoms were not obtained until the Cl number 8 was reached: Plate 4:

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 *  Based on the results described in Mitt. XI, XII, XVI, XXXI, XXXII, XXXIII,  XLVII, XLVIII, LI in [1]; also see summary in Mh.Chem.86, 101-116 (1955).

 

F)        “Reactions in compressed CO₂” [lecture 1]  -   “Inorganic-organic solvents having a low melting point (polar ionic, non-aqueous solvents)” [lecture 2]

 

When looking 1947 for suitable solvents for aminoacids +

hexachlorocyclohexane isomers, “low melting salts like alkylated imidazoles and AlCl₃” turned to be useful: Inorganic-organic solvents: PROJ IX.

 

1949 we used compressed CO₂ as a solvent and as a reaction medium, for instance : “C₆H₆Cl₆-isomers + amino acids in CO₂  with and without solvent addition” [10a] and other reactions in or with CO₂; continued for many years (unpublished).

 

1998/99 we studied the reaction of compressed CO₂ with several gas-clathrate compounds according to the following equation:

 

    CO₂   +     Y(H₂0)_x    →   Y  +  CO₂(H₂0)_{x ,}

 

in the case of   Y = CH₄   with the aim to gain CH₄ from CH₄(H₂0)_x and simultaneously to eliminate CO₂ - which would concile two things.

In our methan-ice-experiments we tried to find out the best pressure and temperature for the methane-reaction in presence and absence of NaCl [10b].

 

The method to use CO₂ injections (CO₂ as an "expensive" waste product) to improve mineral oil recovery^[ii] has been in use since the nineteen nineties; for example, STATOIL-HYDRO has been depositing CO₂ below ground in the Sleipnir West Field since 1996. Oil companies take the unpopular "anti-climate" gas and pump it into their reservoirs to improve oil recovery.

 

Those industries using methane ice will become a large CO₂ consumer and thus CO₂ customer.

 

Already at the beginning  of our solvent experiments we made a big difference between “low melting ionic liquids (I , low viscous) and salt melts with high melting point (II, high viscous), when it was a question of the substitution of conventional organic solvents.  Compressed CO₂ (III) belongs to nonpolar solvents, I-systems melting below 10°C are to take into consideration as substitute for polar organic solvents.

 

The two lectures mentioned in the title were held at HOECHST on Dec 15, 1952 [10a]: Introduction and summary as memorandum

 

Content:

Starting in PROJ. IX with experiments about the reaction of the 1,2,3,4,5,6-hexachloro-cyclohexane isomers with elementary sulfur in melted form, the focus being on the search for a use and/or as a solvent   of the alpha-isomer produced in large quantities as a "by-product". Attempts at reacting more than 240 compounds with the alpha- and gamma-isomers, including anthranilic acid and alpha-D and alpha-L-amino acids, but also beta-alanine and many peptides. Test protocols from the years 1948 to 1951, 41 pages (secreted). The reaction of alpha-isomer with sulfur produced very interesting results (secreted).

 

When gammexane is ground with anthranilic acid in ether a clear solution is produced which, after evaporation of the ether, yields a light-green product having a melting point of 126° to 127°C and containing 2 moles of anthranilic acid per 1 mole of gammexane. The bis-(anthranilic acid)-gammexane (I) obtained (molecule aggregate) dissolves in methanol/H₂O, namely in 1 g I + 2 ml H₂O + 5 ml of methanol. Dissolution stops when the water content exceeds 50 %. When looking for suitable solvents for alpha-amino acids + hexachlorocyclohexane isomers, "low melting salts" of alkylated imidazoles and aluminium chloride turned to be useful: "Inorganic-organic solvents"

 

In the lab report from the year 1949 prepared together with cand. chem. Hein, first tests regarding the use of compressed CO₂ as a solvent: a) C₆H₆Cl₆-isomers + amino acids in CO₂ with and without the addition of benzene, other hydrocarbons and alcohols. b) 12 other reactions in or with compressed CO₂ (secreted)

 

Manuscript (memorandum) 1950, 15 pages, based on the lectures held at Hoechst on December 15, 1952.

This memorandum resulting from experimental protocols on the "solubility of HCH isomer in imidazoles + AlCl₃"  and “reactions in CO₂” had been submitted to the management of Farbwerke HOECHST in December 1950 with the request to pursue this field systematically in any way possible.

The replacement of organic solvents by low-melting, non-aqueous inorganic-organic solvents that are suitable for regeneration opens a wide experimental field which the author was unfortunately unable to pursue because of time constraints.

The correspondence in this matter exchanged in 1949 with Prof. Dr. G. Rienäcker, Director of the Institute of Inorganic Chemistry of the Rostock University, had been attached to the manuscript (which has the function of a memorandum) to emphasise the significance of this new direction of work; cf. re 3)

Unfortunately, this proposal backed by two lectures on December 15, 1952, was not taken up by Farbwerke HOECHST [lecture held on the occasion of a visit to the plant].

It is suggested to read the summary of the results on "ionic liquids" from the 90s in Chemical Reviews by Th. Welton [Chem. Rev. 1999, 2071 - 2083].

 

 

G)        Regarding the visits to Brazil

 

As mentioned under "re 14)", the author started travelling to Brazil for one or two months at least once a year from 1964 onwards at the request of UFSM to build up and organize a Chemical Central Institute with all chemical branches in Santa Maria, Rio Grande do Sul and to run this as a Coordinating Director after it opened in 1973, all at the expense of the Brazilian government. This was to continue for more than 20 years. This also applied for all travel within Brazil from Santa Maria to Rio de Janeiro, Sao Paulo, Brasilia and Roraima.

During all the time the author worked in Santa Maria, he had a chauffeur-driven car at his disposal, as well as a secretary and a personal assistant by the name of W. Pollack (photograph) who also acted as his interpreter during the first few years. The author also received remarkable support from the personal secretary of the vice-chancellor (by the name of Machado, Chefe do Gabinete da Reitoria: photograph). The author was also assigned a full-service apartment on the UFSM campus which included drinks and a janitor (Zelador).

 

Another fringe benefit was à la carte dining at the best restaurant of the town run by a Portuguese, again at no expense whatsoever to the author. An "Underberg" was served for disinfection purposes at the beginning of each meal.

 

These descriptions of the one- to two-months sojourns in Brazil would not be complete without a few comments on the mentality of the people of this country.

 

They exude a cheerfulness which becomes catching after a while. This is well characterised by two proverbs "God is a Brazilian; he will put things right" or "Da un jetinho" (There is always a knack"). This good mood always stayed with me for a good while after I returned to Berlin.

 

One must exercise great care when criticising anything, because Brazilians are very sensitive, but one quickly adjusts to this. The same applies for the topics of punctuality and scheduling appointments. "Yes" in the Portuguese language is "si", but often "pois não" is often used in the same sense.

 

Illustration 15: 

Photograph of the author's collaborator of many years, W. Pollack (right-hand side: personal assistant, secretary, translator) and R. Machado (left-hand side: chief aide at the vice-chancellor's office).

Photograph       

 

Mr. Pollack was also the go-between with the university printers. He arranged for the translation of all lecture notes [34] and the production of the slides required for the author's lectures. He was also in charge of the 30 diagrams [Plates of large scale 1x2 to 2x3 meters] produced in Germany (samples in Plates 7, 8, 9, 10c,  also illustration 6; origin of the plates in [8]).

 

 

H)        “Correspondenze dall’estero (dalla Germania)” per la

           Rivista „La Chimica e l’Industria“, Milano

 

The editor of the above-mentioned Italian technical publication, Professor Dr. A. Coppadoro, made the author an offer to become a correspondent based in Berlin after he had given a lecture in Italian at the VIII Congresso Nazionale di Chimica in Genoa in June 1954.

 

Here are a few quotations of the many articles sent to the editor of "La Chimica e l’Industria" sent over 14 years: one example in Plate 12 (next page but one)

 

La Chimica e l’Industria:

          …38, 654 – 655 (1956)                    41, 104 – 106 (1959)

            39, 145 – 147 (1957)                     41, 170 – 172 (1959)

            39, 424 – 425 (1957)                     41, 257 – 259 (1959)                                                                                                                                                                               

            39, 536 (1957)                                          41, 364 – 365 (1959)                                                                                                   

            39, 762 – 763 (1957)                     41, 714 – 715 (1959)                                                                                                                 

            39, 798 (1957)                                          41, 845 – 846 (1959)

            40, 78 – 79 (1958)                         41, 935 – 936 (1959)

            40, 243 – 244 (1958)                     41, 1043 (1959)

            40, 325 – 326 (1958)                     42, 1187 – 1188 (1960)

            40, 605 (1958)                                          43, 100 – 102 (1961)

            40, 799 – 800 (1958)                     43, 1348 – 1349 (1961)

            40, 965 – 966 (1958)                     44, 138 – 139 (1962) … ecc.

 

This cooperation with the important Italian technical publication LA CHIMICA E L’INDUSTRIA «Giornale di Chimica Industriale ed Applicata» and «L’Industria Chimica», Milano, had the following history: In September 1940, the author had sent an original manuscript to the editor of GAZZETTA CHIMICA ITALIANA, Rome, and asked to keep it until after the War [23, 4]. In 1947 and 1951, several of his own papers were published in this journal; cf [1]. The chief editor at the time was Prof. Dr. D. Marotta, who was also acting President of the SOCIETÀ CHIMICA ITALIANA. His recommendation played an important role when the author was asked to become a correspondent of the technical journal LA CHIMICA E L’INDUSTRIA, as did the echo to the two monographs on contact insecticides published in 1947/49 [6]: Table 3.

 

Table 3:  Start of the cooperation of many years with the following scientists and institutions  -             w/o Lohmann [re 5)], Matter [re 4b)], Mariano [re 14)]

 

First contakt       country     scientists                                  institutions                                                   time

1948                  Japan       Professor Dr. S. Takei              Institute of Agricultural

                                           Professor Dr. M. Nakajima       Chemistry, University Kyoto                  1953 – 1990

1948                  Japan       Professor Dr. Y. Morino            Chemical Institute, University Tokyo     1949 -- 1995       

                                           Dr. J. Shimozawa                     Tokyo and Saitama-University              1950 –  2005

1948                  Brasil       Professor Dr. R. Wasicky,         Pharmaceutical Institute, Universi-

                                          Senior                                        dade S. Paulo, SP                                 1955 – 1972

1960                  Brasil       Professor Dr. R. Wasicky, Jr     Pharmacognosia, Univ S. Paulo            1960 – 1990

1962                  Brasil       Professor Dr. R. Wasicky,         Biochemical Institute, Universidade

                                          Senior                                        S.Maria, Santa Maria, RS                      1960 – 1980

1949                  Italy         Professor Dr. D. Marotta           Instituto Superiore di Sanitá, Roma        1949 – 1980

                                          Professor Dr. M.E. Alessandrini

1950                  Italy         Professor Dr. G. Natta               Università Técnica, Milano                     1951 – 1970

                                          Professor D. A. Coppadoro        Milano, Redazione „LA CHIMICA e

                                                                                             L’INDUSTRIA“                                       1954 – 1968

1950                 Sweden     Chemische Industrie                 Skoghallverken, Skoghall                      1951 – 1958

1948                 Germany   Direktor Dr. F. Scherer,             Farbwerke HOECHST AG                     1949 – 1985

                                           Professor Dr. Winnacker

1949                 Germany   Direktor Dr. A. Peters,              Bergwerke AG, Essen                            1949 – 1958

                                           Dr. H. Brodkorb                                                            1949 – 1958

1950                  USA          Direktor Dr. W.B. Ligett            Ethyl-Corporation, Detroit, USA             1950 – 1965

                                           Dr. H. Klopfer                                                               1948 – 1975

1950                  Italy          Direktor Dr. Paesano                 Montecatini, Milano                                1951 – 1956

 

 

 

Plate 12: Esempio per „CORRISPONDENZE DALL‘ ESTERO

                dalla Germania“ nella Rivista: LA CHIMICA E L’INDUSTRIA  40, 605 (1958)

 

          

 

Die in zweiten Artikel formulierten Verbindungen sind „LOST-Analoge“. Experimentelles über die Grundverbindung ß,ß-dichlor-diethylsulfid,  in PROJEKT XVIII: „Permeation problems“ [1].

           

           

 

 

J)         Start and development of hexachlorocyclopentadiene         chemistry in Germany (C₅Cl₆-chemistry):

 

Overview in chronological order 1930-45:

 

1930:        F. Strauss, L. Kollek, W. Heyn,

                 Preparation of C₅Cl₆ from cyclopentadien & hypochlorite   

                 Ber dtsch chem Ges  1930, 63,1868 (orientational experiments only) - Prof. Strauss died in 1930.

 

1941:        R. Riemschneider, 

                 Preparation of C₅Cl₆ from C₅H₆ and hypochlorite

When studying chemistry in Hamburg, Riemschneider received the task to prepare hexachlorocyclopentadien (a so-called „Literaturpräparat“) in a course of organic chemistry.

Just during the preparation from cyclopentadiene and hypochlorite a reaction between C₅Cl₆ and the starting material C₅H₆ seemed to take place, forming waxy residues in more or less large amounts. Further investigations of the waxy products were projected as soon as possible: Table 4

Table 4 : The possible reactions taken into consideration concerning the preparation mentioned above

  Main reactions:

  1)          C₅H₆  +  6 OCl’  +  x OH’  =   C₅Cl₆  +  (6 + x) OH’

  2)          C₅H₆  +  5 OCl’  +  x OH’  =   C₅HCl₅ + (5 + x) OH’

  Follow reactions:

  3)          C₅Cl₆    +  C₅H₆       =      C₁₀H₆Cl₆    :    C₅Cl₆     as diene

  4)          C₅H₆     +  C₅Cl₆      =      C₁₀H₆Cl₆    :    C₅H₆      as diene

  5)          C₅HCl₅  +  C₅H₆      =      C₁₀H₇Cl₅    :    C₅HCl₅   as diene

  6)          C₅H₆     +  C₅HCl₅    =      C₁₀H₇Cl₅   :     C₅H₆     as diene

  7)          C₅H₆     +  C₅H₆        =      C₁₀H₁₂       :          dimere

  8)          C₅Cl₆    +  C₅Cl₆      =       C₁₀Cl₁₂       :          dimere[iii]

  9)         Polymerisations of monomers

 

  Reactions 1-8 are realized and described in PROJ.XI and XVII.

   Also there report about the following reactions:

                 C₅Cl₆    +  C₁₀H₆Cl₆  from reaction 4):   C₁₅H₆Cl₁₂

                 C₅HCl₅  + C₁₀H₆Cl₆   from reaction 4):   C₁₅H₇Cl₁₁

                 C₅Cl₆    +  C₁₀H₇Cl₅   from reaction 6):   C₁₅H₇Cl₁₁

                 C₅HCl₅  +  C₁₀H₇Cl₇  from reaction 6):   C₁₅H₈Cl₁₂

          

1942          R Riemschneider,  F. Maaz

Reaction of C₅H₆ and hypochlorite and investigations of the waxy by-product (follow-product),

lab report June 1942, experiments carried out in leisure time in the laboratory of “Schule Base” in Brindisi, still in military service: Heeresbetreungskompanie, serving the Africa corps.

Results : The “wax” contained the C₅ components [ C₅Cl₆, C₅H₆] in the ratio 1:1 of the summary formula (C₁₀H₆Cl₆)_n   [ n = 1, if polymerism excluded]

 

1942                 R Riemschneider

Investigations about the constitution and properties of the waxy product “C₁₀H₆Cl₆” (I), resulting during the preparation of C₅Cl₆ + OCl’  [according to prescriptions of 1941 (Hamburg), of 1942 (Brindisi) ]

Preliminary report June 1942 (secreted)

Results: In series experiments of C₅Cl₆-preparations, experimentating with a surplus of C₅H₆, the yield of the waxy part I  was increased.

First hints as to insecticidal effect (flies) of I: Sometimes we found a lot of dead flies on or near the lab table.

Treatment of I (melting within a certain range) in CCl₄ with Cl₂-gas resulted in an oil (II), containing 2 Cl more than I.  II was more effective than I (flies).

Experiments concerning C₅Cl₆-preparation and C₅Cl₆chemistry continued in Prag and Bottrop

 

1943         R. Riemschneider

“Comparison of “explosive” properties of C₂Cl₂ and C₅Cl₆”

Lecture given 8 Febr 1943 in Prag in the German Army Explosives and Warfare Agents Research Establishment, “Heeresforschungsinstitut für Explosivstoffe”.

Lab report of these experiments issued in 1943 in the mentioned Institute in charge of military service.

Results:  C₅Cl₆ did not come up to the expectations of the direction board of the institute: C₅Cl₆ was – contrary to C₂Cl₂  - not qualified as explosive,

but it showed unexpectately – corresponding to our own earlier observations (see above) – high chemical reactivity in general with unsaturated compounds of all kind. 

 

1943         R Riemschneider (lecturer), A Kühnl, O Schmidt

Hexachlorocylopentadiene, C₅Cl₆: 2 lectures

1: “The action of sodium hypochlorite on cylopentadiene: hexachlorocyclopentadiene and higher-melting reaction products” (Table 4)

Lecture given on 15 Feb 43,  20 p

2: “Properties and reactions of C₅Cl₆”

Lecture given on 15 Mar 43 in German Army Explosives and Warfare Agents Research Establishment in Prague

The “example” of dichloroacetylene, C₂Cl₂, made it seem appropriate to test if C₅Cl₆ was also suited for an explosive or warfare agent. Result: negative (see experiments described earlier, also carried out in Prague)

In this lecture, the author did not mention his observations from 1942 about the insecticidal activity of the waxy residues and its chlorination products.

 

1943         R Riemschneider

New waxy “DIELS-ALDER-adducts”

a)        isolated from C₅Cl₆-preparations as “by-product” (Table 4)

b)        prepared from pure C₅Cl₆ + C₅H₆ (in an exotherm reaction)

Continuation of the experiments carried out in 1942 in Brindisi and later in Prague concerning pest control

Lab reports, April 1943, 16 p, RUHRÖL, Bottrop (secreted)

 

1943         R Riemschneider

Constitution and properties of wax-like side products, and their properties, obtained when preparing hexachlorocyclopentadiene from cyclopentadiene and hypochlorite. In fact new DIELS-ADLER adducts

Lab reports, May 43, 30 p, RUHRÖL, Bottrop (secreted)

 

1943/        R Riemschneider

1944         On using hexachlorocyclopentadiene, C₅Cl₆, as starting material for “synthesis of chlorine compounds with new spatial distribution of chlorine”: OET group (later: DIENE group)

                 Lab reports, Dec 43, 9 p (secreted)

Experiments conducted at RUHRÖL GmbH, Bottrop, 1943-44 and repeated in Chem Lab, Inst of Hygiene, Univ of Jena, from Oct 44.

 

1943/        R Riemschneider

1945         On the remarkable properties of post-chlorinated adducts from C₅Cl₆and cyclopentadiene, C₁₀H₆Cl₆ – M 410  identified as octachloroendomethylenetetrahydrohydrindene (OET),

 C₁₀H₆Cl₈ (mol wt 410):    C₁₀H₆Cl₆  + Cl₂            C₁₀H₆Cl₈

Lab reports 1944 and to Mar 45. Experiments conducted at RUHRÖL GmbH and in Inst of Hyg, Univ of Jena

Further public ations in PROJ XI and XVII in [1].

 

At the end of the 40ies Riemschneider visited[iv] the discoverers of the DIEN-synthesis profs Dres Dr.K.Alder, Cologne, and O.P.H. Diels, Kiel, - both Nobel prize winners -  to inform them personally about his discovery concerning the unexpected C₅Cl₆-chemistry and especially to reach consent to “leave this research field to him”.

 

CN-analogues C₅(CN)₆,  (CN)₂C=C(CN)₂

It had been the obvious thing to try - after our discovery of the unexpected high reactivity of C₅Cl₆ – to check the reaction of high substituted CN-analogues in DIEN synthesis,  i.e. hexacyanocyclopentadien, C₅(CN)₆ (I) and tetracyanoethylene,     (CN)₂C=C(CN)₂ (II).

In the case of II we were already in 1949 lucky enough to find out that II reacted as philodien: PROJ I: there ref (34,102). The synthesis of I remaines still open, today.

 

In the case of II the author thought it advisable to contact once more the DIEN “pope” professor Alder, informing and asking him to leave this field for a certain time to the author. -

Together with Dipl.Ing.O.Matter, Vitznau, the author made a Swiss patent application.

 

1944         R Riemschneider (lecturer)

Lecture 1: "The spatial distribution of the Cl-atoms of Gesarol's active ingredient (later DDT) and of halogenated adducts from hexachlorocyclopentadiene and cyclopentadiene: DIENE group insecticides, eg M 410 (C₁₀H₆Cl₈) as well as M 393, M 377, M 344"

20 min lecture in Inst of Hyg at Univ of Jena on 15 Dec 44, invited by Prof Dr H Schloßberger (chair). Present: Profs Dr H Bredereck (org chem), Dr H Brintzinger (tech chem) [at instigation of Dr G R Schultze, Braunschweig Tech Coll, author's doctoral supervisor], Dr F Hein (anorg chem), Dr H Keller (phar-ma) and Dr Scheffler, dean of Fac of Math and Nat Sc

Lecture 2: "The naturally occurring insect toxin cantharidin  as a model substance for developing synthetic insecticides with a five-membered ring structure, eg M 410 "

given in colloquium of Inst of Hyg, Univ of Jena on 10 Dec 44, chair Prof Dr H Schloßberger

 

Cantharidin  as model substance for insecticides with five-membered ring structure, eg M 410

 

                 

       Cantharidin                                        M 410

                                              

 

 

 

 

 

 

1945         R Riemschneider

“A new type of insecticidal halogen compounds, starting from C₅Cl₆ – after first tests, very promising: M 410” Lecture given on 31 Jan 45 in Inst of Pharmaceutics, Univ of Jena

Insecticidal activity of M 410 on Musca domestica, Drosophila melanogaster, Calandra granaria, Blatta orientalis and five other insects greater than DDT

The author wants to take this opportunity to thank Prof. Dr. Pflugfelder, Zoological institute of Jena University for his help in this experiments.

 

This report about the hexachlorocyclopentadien chemistry was handed over in Dec 1947 to Farbwerke HOECHST for the Patent Department and for the Department of Plant Protection – together with some material collected as „Mitteilungen des Physiologisch-chemischen Instituts der Universität Berlin“.

More details about hexachlorocyclopentadien chemistry in PROJ XI [1] and XVII [39].

 

According to the opinion and justification of

-   Director Dr Scherer (HOECHST),

-   Nobelprice winners profs Dres A. Alder and H. Diels,

A. Butenandt and Richard Kuhn

the discovery of the unexpected high reactivity  of hexachlorocyclopentadiene and the insecticidal properties of pertinent adducts are entirely due to Riemschneider M 410, C₁₀H₆Cl₈;  cf  SPECIAL PART J).

 

In his lawsuit between the HYMAN Company of Denver and VELSICOL Company of Chicago HYMAN asked Riemschneider for proof that he had had discovered M 410 (C₅Cl₆ based) before him[v] and VELSICOL. However, this only succeded in part.

Privately speaking HYMAN was convinced; cf. ADDENDUM next page.

 

The two directions of work „C₅Cl₆ chemistry” (Riemschneider, Hyman) and “metalorganic Sandwich compounds, based on cyclopentadien” (Wilkinson, Fischer) were taken into consideration by the committee at the Nobel prize deliberations in 1972/73. In 1973 collegues from America informed Riemschneider of the situation and that Hyman had already passed away [36].

 

Since 1968 there was a contact between the Nobel committee and Riemschneider as one can see from a copy of the letter by the committee inviting Riemschneider to propose a candidate.

yman already passed

away.

According to the opinion and justification of Dr.F.Scherer (HOECHST),

Nobelprize winners profs Dr.A.Butenandt and Dr.Richard Kuhn,  the discovery of the high reactivity of hexachlorocyclopentadien and the insecticidal properties of pertinent adducts are entirely due to Riemschneider: M 410, C₁₀H₆Cl_8.    

 

 

Since 1968 there was a contact between The Nobel committee and

Riemschneider as you can see from a copy of the letter  written from the committee inviting Riemschneider to propose a candidate.

 

 

 

 

 

 

 

 

In USA: The lawsuit between VELSICOL-Corporation and HYMAN -

Company concerning CHLORDANE, ALDRIN and DIELDRIN (Hyman’s two own later developments[vi]) went through tree instances. Results: VELSICOL was permitted to produce CHLORDANE and SHELL took over the production of Hyman’s ALDRIN and DIELDRIN; cf. endnote 26.

In Germany: Independent of all this trouble, Farbwerke HOECHST  produced - in cooperation with Riemschneider - THIODANE [11b].

Regarding M 410 and analogues there were the following patents (cited in http://www.bwwsociety.org/journal/html/pestcontrol.htm  2005):

 

R Riemschneider (inventor), O Matter (applicant)

Two patent applications entitled "Pest control agents"

           

1) Insecticides based on hexachlorocyclopentadiene (C₅Cl₆) adducts from cyclo-pentadiene and hypochlorite and post-chlorination of chlorine number 6 [or 5] to 7 or 9 [or 6 to 7]" If pentachlorocyclopentadiene forms as a by-product while preparing C₅Cl₆ by hypochlorite-chlorination

2) "Insecticides based on adducts from tetrachlorodifluorocyclo-pentadiene (C₅Cl₄F₂) and cyclopentadiene and post-chlorination on chlorine number 6: C₁₀H₆Cl₆F₂".

 

Due to the circumstances of the time, it was only possible to apply for these patents in 26 May and June 47 with the help of Swiss friends, namely Dipl Ing O Matter [naming Dr R Riemschneider as inventor], after the author had left the Soviet occupation zone for Berlin. The applications were prepared from autumn 46 by coded correspondence* between Jena and Vitznau, Switzerland [mail censored by occupying powers] Only the general formulas A and B were used in application 1 for the insecticidal and / or fungicidal active agents of the pest control agents to be patented to avoid a collision with the structural formulas,

                      A                                                                                 B

 

           

 

 

already worked out and published, of the chlorine compounds C₁₀H₆Cl₈ (M 410) [or C₁₀H₇Cl₇] and the adduct precursors C₁₀H₆Cl₆ [or C₁₀H₇Cl₅], known to be active.

 

Patent claim to application 1 (26 May 1947):

Pest control agents, containing chorinated hydrocarbons of the general formulation A and B, that are obtained as follows: Chlorination of cyclopentadiene with alkaline hypochlorite solution [1 : 6 to 1 : 7], initially in the cold, then at temperatures up to 60°C and subsequent direct chlorination of the organic phase of the reaction mixture in the presence of UV light or other catalyzers, preferably post-chlorinated on a chlorine number of a reaction mixture from 8 or 7, related to C₁₀.

A patent application by Farbwerke HOECHST became known on 06 Sept 56 [F 8439 Iva/45 I, entitled Pest Control Agents, applied for on 26 Feb 52, ie 5 years after receipt of the text of the patent applications of 26 May and in June 47] in which the active agents formulated by the author in the patent claim to application 1 were claimed by reason of tests by Hoechst's Plant Protection. The chemical page of the specification corresponds exactly to the application text the author had made available to the management 5 years before the application. However, so as not to endanger HOECHST's application, the author agreed in 1955 that literature as well as his papers on hypochlorination not be quoted after the fact. The author forwent being named as the inventor as the experimental part of the application by and large only contained biological data and as it was already clear at the time that - in view of developments in America: aldrin, dieldrin - the object of the patent would hardly become significant [39].

K) Explosives

 

On the occasion of the presentation at the OKH in Berlin in December 1942 and after his two lectures (819a, b) in [1], also in Berlin at Jebenstrasse, the author had suggested to Major Kassuba who chaired the presentation and gave the introductory address to the lectures to use a class of compounds rich in N such as tetrazoles, pentazoles, their amino derivatives such as diaminotetrazole (V) and their salts (e.g. V-perchlorates,              V-azides), azotetrazolates, etc. in combination with compounds containing NO₂ groups as high-energy compounds.

 

In this respect, see

Formula Summary I: "Projected high-energy compounds of the class of representatives in N: N₃ to N₁₀ (1942)"; cf. also [1]: (819b) there para. g).   

 

The starting point for these proposals were the publications of J. Thiele (1892 - 98) and R. Stolle (1933) [cited under 4b)Oskar Matter]. As already mentioned, first experiments were conducted in Prague in 1943:

Formula Summaries II: "Nitration of 5-amino-tetrazole (IV) and IV-derivatives such as VII to VIII" and

Formula Summary III: "1,5-Diamino-tetrazole (V) starting from thiosemicarbazide" [second synthesis of V appears to be more advantageous]

Formula Summary IV: Azotetrazolate-salts.

 

These experiments were then continued together with engineer O. Matter in Switzerland from 1953 and in Brazil from 1970 onwards; cf. in [1]: PROJ. I 5,2.

 

The combination of V or V-derivatives with trinitro compounds and the use of azo­tetrazolate salts (IX in Formula Summary I) had yielded excellent results regarding the characteristics required of explosives in 1954: Experiments carried out by Matter at his own explosion site on Vierwaldstätter lake (unpublished, secreted - even after Matter's death). He developed data regarding the heat of explosion and detonation (P, D), stability (impact, heat, friction, electrostatics). During his visit in 1954, Mr. Matter entrusted the author both with all the data and the information regarding the compounds used.

 

Formula Summary I¹⁾

Projected high-energy compounds of the class of representatives in N : N₃ to N₁₀   (presented to the OKH in 1942: I-V; IX-XI)²⁾

                         

           

Amino-I derivates:  IV, V

                    

 

IV- derivates:  VI to VIII

 

                

 

azotetrazolate-salts: IX

 

biuret-nitration product, i.e.: X

 

                        O₂N-NH-CO-NH-CO-NH-NO₂       X

 

 

Diamino-dinitro-ethylene: XI

 

(H₂N)₂-C=C-(NO₂)₂             XI

 

 

¹⁾    with letter from Dec 12th, 1956 sent to the “Bundesministerium für Verteidigung” in Bonn, confirmed with letter from Dec 21st, 1956.

²⁾     starting from J. Thiele, Liebigs Ann.Chem. 270,1 (1892) and R. Stolle, H. Netz, O. Kramer, S. Rotschild, O.    Schick, J. prakt.Chem. 138, 1 (1933).

 

 

 

 

Formula Summary II:     Nitration of 5-amino-tetrazol (IV)

and IV-derivates i. e. VII to VIII

                                               (experiments carried out in Prag 1943)

 

HNO3

                                

 

 

                                   (CH₃)₂SO₄

                                      CH₃J

 

 

HNO3

                                    

 

IV synthesized according to J. Thiele

 

 

 

 

 

Formula Summary III: 1,5-Diamino-tetrazol (V) starting from Thiosemicarbazid                                       (experiments started in spring 1943 in Prague, continued in Switzerland 1953 and later in Brasil,  from 1970 on)

 

 

 

N3H

PbO

                           

 

 

Thiosemicarbazide was converted into 1,5-diamino-tetrazole (V) with PbO and NaN₃ in a CO₂ atmosphere via an intermediate with HN₃.

The Pb azide resulting as a side product causes problems and is therefore unsuitable for industrial use.

Another method of production for I is desirable: I forms salts with perchloric acid and hydrogen azide.

 

1972:

New synthesis of V :

Diazo treatment of diaminoguanodinium-halogenids in a narrow pH range 7,6-8,2 at room temperture (30-35° C).

Reaction also dangerous: azid formation if pH not taken into consideration. To find out the best pH range we carried out 14 series experiments behind a protecting iron plate because of the expected azid formation.

The author owes thank to drs M M Faria and F R Pesserl for co-operation and their courage -  8  explosions!

 

Experimental Part to 1,5-diamino-tetrazol (V) experiments

R.Riemschneider,1943 and R.Riemschneider,O.Matter, 1953

1,5-Diamino-tetrazol  (V) and V-nitrat, V-perchlorat, V-azid

Patentapplication O.Matter, inventor: Riemschneider und Matter.

V was prepared in accordance with R. Stolle et al., J. Prakt. Chem. 1933, 138, 1. Because of the risk of explosion, very small batches were used to obtain sufficient V.

 

Preparation of 1,5-diamino tetrazole ( V):

55 ml of an aqueous solution containing 4.5 g of diamino guadininium chloride and 1.5 ml of concentrated HCl are prepared under an exhaust hood behind an iron plate. Diazotisation with sodium nitrite is carried out under an N₂ flow at 2 to 4°C: 20 ml of nitrite solution containing 2.5 g of NaNO₃ are added dropwise with strict observation of the required temperature. After 45 minutes, the pH value of the reaction mixture is adjusted to 8.0 to 8.2 with Na₂CO₃ and stirred slowly at 45°C for 25 minutes, still under nitrogen. After that, the N₂ flow is concentrated in vacuo until dry (keep a safe distance!). After cooling, repeated extraction with a little ethyl alcohol at 60°C and recrystallisation from water as before is carried out, V mp 185°C (low yield).

A total of 19 serial experiments were required to determine the optimal conditions for preparing V. In the present case, we benefited from the experience with V gained as early as 1943 and in the 1950s. After a heavy explosion occurred during the second serial experiments, we worked with grip arms wherever possible, just as in our experiments with dichloroacetylene and monochloroacetylene [R. Riemschneider, A. Brendel, Liebigs Ann. Chem. 640, 1 - 15 (1961)] und in the nitration of meta-dinitrobenzene to form trinitrobenzene:

R. Riemschneider, A. Kühnl (1943).

 

V-nitrate 

The formula to prepare is the same as indicated in the patent application of 1953. Observing the precautions specified above:

4 g of fresh prepared V are added to 3,0 ml of 66% HNO₃ at 20° C in N₂-stream and very slowly heated, then under cooling given to the clear solution ethylether in amount of 25-35 ml. The precipitated cristals are filtered off and washed with ether, dried over P₂O₅ after cristallisation from ethanol:             2,5g V-nitrate, mp 135-138°C.

 

V-perchlorate:

Observing the above precautions and working with grip arms, 2 g of V are dissolved in 25 ml of high-purity methyl alcohol. 1.5 g of concentrated perchloric acid are added gradually with slow stirring, still under nitrogen. After reacting at 20°C for 1.5 hours, the mixture is extracted with ethyl ether, mp 97-98°C.

 

V-azide: high explosive, difficult to handle

 

V-preparation	CH4N6	100,07	calc.	C 12,0%,  H 4,0%, N 84,0%
			found	C 12,2%   H 4,0%  N 83,8%
V-nitrate	CH5N703	163,1	calc.	C   7,4%   H 3,1%  N 60,1%
			found	C   7,3%   H 3,0%  N 60,0%
V-perchlorate	CH5N6Cl04	200,5	Calc.	C   5,9%   H 2,5%  N 41,9%
			found	C   5,8%   H 2,9%  N 41,6%

 

The explosive characteristics of these compounds prepared in Vitznau and Berlin. V, V-nitrate and V-chlorate, were expertly tested by engineer O. Matter at his testing site for explosives on Vierwaldstättersee (near the Rütli field) and compared with TNT and the pentaerythrite nitric acid esters we developed later. Data regarding the heat of explosion and detonation (P,D), stability (impact, heat, friction, electrostatics) were collected.

 

Result: V-nitrate, V-perchlorate, and V-azide are comparable with TNT.

Detailed experimental data are set forth in specification of the Swiss Patent applied for by O. Matter, inventors: R. Riemschneider and O. Matter. The letter from Mr. Matter to the author in December 1954 expresses delight that the three V-salts have explosive characteristics comparable with TNT.

 

More details in the essay “High Energy Compounds – Explosives“ later to be published in this JOURNAL with the ten Formula Summaries  A - J  plus Experimental part, 40pages.

 

Summary

The author considers his activities in chemistry in Brazil, in Japan, in Italy and in his own country and shows who helped in his career.

This paper gives an impression how politics influenced the author’s life and activities - more or less negatively – and his “fights” against politics - looking for ways-out. All resistances and intrigues have been got over, and in the end chemistry won.

 

 

Acknowledgements:

The presented results, >1400 references in [1], have been be possible only with the help of many, many co-workers like students, candidates of examination papers, collegues, and employees in Germany, Japan and Brazil, named in [1]. The author wants to thank all of them herewith once more.- The long list of Diplomanden, Doktoranden and Lehramtskandidaten incl. titles of the papers, presented in different universities (HU, FU, UFSM, and together with collegues in others) will be published separately elswhere, corresponding to the XXVI projects and other data, not regarded in [1].

It is planned to publish the above mentioned extensive co-worker list together with the author’s patents and expert witnesses, every title containing a summary of the main results, the patent claims and reasons for expert opinion.

 

 

ADDENDUM - re [32, 33]:

Prof. L. Pauling and the ortho-molecular medicine[vii] (definition in last paragraphs)

 

Citation [32] goes into discussions of the author with Professor Linus Pauling [double Nobel Prize winner: Chemistry and Peace], namely discussions from the years 1969 - 72 primarily dealing with the vitamin C-complex [L-ascorbic acid plus dehydro-ascorbic acid].

 

It is well known that Prof. Pauling reported "Successes in the field of cancer prevention" on the occasion of a convention of Nobel Prize winners in Lindau; these successes are due to the oral intake of vitamin C in doses significantly exceeding those needed every day. In private talks, the author had voiced his concerns regarding high vitamin C quantities on the basis of his own toxicological experiments with rats: The oxalate concentrations in the rats' blood plasma increased after the oral application of 20 mg of vitamin C per kg (determined DL₅₀ per rat: 12 g/kg). The author had set forth his considerations regarding the following points:

-  "Stability of hydride ions in aqueous solutions"

-  "Organic compounds like vitamin C-complex, vitamin E-complex (NADH, flavonoids) acting as “transport vessel” for hydride ions[viii] (H atoms, respectively)"

 -  "radical-scavenger effect of hydride-ions" [33]

He thus asked Prof. Pauling whether tests had been carried out "how tumours react to vitamin C applied intravenously, because the advantages vis-à-vis high oral daily administration are obvious"; when orally taken only small amounts of vitamin C will get into the blood. The author had not only cancer prevention in mind but also cancer treatment. Paulings answer to the above mentioned question was: "Not as far as I know. Also Dr. Iwan Cameron applied Vitamin C only orally (pure powder teaspoonwise) in his cancer prevention experiments. - Keep me informed about your activities!"

 

In the 1970ies, together with his candidate for a senior university post, Dr.Lipp[ix], of the Robert-Koch-Institute, Berlin-Dahlem, the author was able to show in experiments with mice and rats that vitamin C applied intravenously inhibits the growth of ascites cells. Injected Vitamin C inhibited the growth of stomach- and pancreas tumor cells which were generated before in rats. In some experiments we had success with dehydracet acid [x], too

In parallel running cell culture experiments, vitamin C - also given in comparatively high doses - had a negative influence on the growth of several cancer cell types, up to 30-40% growth inhibition, but it did not injure healty cells  [unpublished at the request of Prof. Henneberg, director of the Robert-Koch-Institute, to gain time for clinical experiments. Professor Pauling agreed with this].

 

The first clinical experiments with intravenous vitamin C - intending cancer “chemotherapy” - were not carried out until 1977 [xi]:

-  at Klinikum-Westend, Berlin, under Prof Dr. H. Gerhartz, Head of Ward Vb,  Oncology,

-  later at the university teaching hospital of UFSM, Santa Maria, RS, Brazil, under Prof. José Mariano da Rocha Filho (former rector of UFSM).

Only when comparatively high doses of vitamin C were injected, some success was shown in cases of cancer of the pancreas and the prostate.

At the time, it was not possible to continue the clinical experiments:

 -  Prof. Gerhartz was retired; once again, the "democratised“ Free University failed.

-   Professor Mariano was not a specialist in oncology and primarily had to devote his time to other duties.

-  The author was deprived of any possibility to continue this important research at the Free University ^xi.

 

In Brazil, during the years 1987 to 1992, the author had organised studies on the inhibition of the growth of ascites cells (of the mouse), once again in cell culture experiments, under the influence of

-  1)  the vitamin C complex under varied conditions,

-  2)  compounds constitutionally related to the C- and E-complex

-  3)  fruit and vegetable juices in suction flasks for drinking water for a "therapy with hydride ions" for at least three months [33],

-  4) combination of 3) with 1) respectively 2) with 1) [33]

These results were communicated to Prof. Pauling in the hope that he would arrange clinical tests. Unfortunately, this did not come about, because Pauling died in 1994.

 

Conclusion:

Without the much criticised extensive "vitamin C experiments for cancer prevention" of Prof. Pauling (people said the oral dose was too high) and without Pauling's activities, ortho-molecular medicine^vii would certainly not have been developed in such a prominent way.

Without such suggestions, the author would not have developed "synthetic organ and plant extracts" (EP 0 552 616 B1) up to the production-line stage and organised their application in Asia.

Nor would the author have arranged intravenous vit C-complex applications in hospitals based on his own cell culture experiments without the encouragement of Prof. Pauling.

Without such encouragement and without the first positive clinical experimental results the author would not have carried out additional cell culture tests starting from the vit C-complex as described in the previous paragraph.

 

Definition of “ortho-molecular medicine” according to R.Rowghani, cited in the endnotes:

“L. Pauling geht bei der menschlichen Gesundheit davon aus, dass man in den gesamten Körperzellen  „gut angeordnete Moleküle“  vorfindet, ein zu erreichender Zustand, welchen Pauling in den 60er Jahren ORTHOMOLEKULAR nennt (orthos = richtig;  molekular = Moleküle betreffend). So enstand die mittlerweile bekannt gewordene und bei Ärzten angewandte ORTHOMOLEKULARE  HEILKUNDE, die besagt, dass der Mensch erkrankt, wenn er nicht mehr in den Körperzellen die lebensnotwendigen Moleküle aufweist, was zuerst zu Fehl-funktionen und schliesslich zu bisweilen schweren Krankheiten führt.“

 

According to the author’s opinion [33] Norman W. Walker had achieved pioneerwork in this field; and as result of living in this way:

              - Walker himself reached an age of 116 years.

           -  Pauling reached an age of 93 years.

 

Walker founded the “Norwalk Laboratory for Nutrition and Research” in New York in 1910.

 

 

ADDENDUM

to „RONGO“ refering to Plate 6 (Part II)

 

The German translation of the Confucius quotation mentioned in Plate 6 was superimposed in German language during the TV broadcast of the opening ceremony of the Olympic Games in Peking on 8.8.2008   by the first German channel, ARD.

 

During the 5-hour ceremony, significant phases of the 5000 year history of China were presented, for example the outstanding invention of gun powder, the production of paper, of typefaces, print, compass, Chinese legendary creatures (dragons), Chinese opera. The choreography with bamboo scrolls presented by 3000 Confucius students (with the words from the work "RONGO" superimposed  -  same words calligraphed by Professor Morino for the author in Plate 6) was most impressive. To make such a presentation successful, all of the participants had to have an excellent memory and ability of cooperation. There were also choreo­graphies involving 2008 Kung-Fu students and others, always presenting 2008 participants. On the whole, 15,000 different costumes were used, including the traditional costumes of the 57 different nations of China. This was possible only after many years of preparation and rehearsal of thousands of protagonists.

 

The gigantic opening ceremony was complemented by breath-taking fireworks any many colourful light effects with huge projections. 

 

Colourful fireworks went up not only in the air and not only around the stadium - no, these extended over half of Peking, for example, the introductory footsteps that moved towards the stadium to the beat of seconds.

 

The ARD-TV commentary did not do justice to this fantastic event; rather, it showed that the commentator did not know the theme and, like the closing interview, contained anti-Chinese slogans.

 

Most of the major states had sent their presidents or high-ranking representatives to the Middle Kingdom; unfortunately, no important German politician was present.

 

The performance given by the Chinese did not surprise the author in the least. In contacts with Chinese candidates for diplomas and doctorates and with representatives of the Chinese industry over many years, the author was able to see with his own eyes what these people can achieve. - Two outstanding associates of the author in a university career of more than 50 years came from China.

 

 

BIBLIOGRAPHY

 

[1]       R.Riemschneider,

            “Re-reading – 66 years chemistry” (in preparation)

 

[2]       R.Riemschneider,

            Bonded to Compounds – Providence, 12p

            http://www.bwwsociety.org/journal/html/bcompounds.htm 2005

In this essay the author treated the subject „Yeast“ only briefly.

More details, especially about the author’s yeast patents, in the publication “Way out of the BSE-crisis” [38].

 

[3]       VITA  Riemschneider,

            written from Prof.Dr.Heimo Reinitzer, president of the Hamburg Akademie der Wissenschaften, published in [1]

 

[4]       R.Riemschneider,

            Oxidation of ethylbenzene, o-,m-,p-diethylbenzene and   o-ethylaceto-phenone with potassium permanganate in buffer solution:

            o-diacetylbenzene  -  Permanganate oxidation in organic solvents.

Voluntary Year’s Paper in chemistry for graduation at Matthias Claudius High School in Hamburg-Wandsbek, done from June 1937 till December 1938, submitted in Jan 1939: ms 96 p.

Summary of some results published 1947 as bulletin I in series “Acylderivate cyclischer Verbindungen”, deposited on 12 Sept. 1940 with editors of GAZZ. CHIM. ITAL., Rome [23]

 

[5]       R.Riemschneider

Oxidation of Decalin^TM (decahydronaphthalene) in acetic anhydride with potassium permanganate to cis-β-decalolacetate  degree thesis, University of Leipzig, Sept.1941, 40 p; excerpt published in 2. Beih., 1. Erg.-Bd. Z. Pharmazie 1947, p 142

 

[6]       R.Riemschneider

            Zur Kenntnis der Kontakt-Insektizide I und II“,

2. und 9. Beiheft zur Zeitschrift „Die Pharmazie“ 1947 und 1949 Verlag Dr.Werner Saenger, Berlin(OST) 

The largest part of the monograph "Knowledge of Contact Insecticides II" comprising 150 printed pages was written during the time of the Soviet blockade of Berlin(WEST): Berlin(WEST) was the official designation in the West for the three West Sectors. In contrast, Westberlin was written in one word starting with a "W" in the East . Instead of Berlin(EAST), the name used there was “Berlin, Capital of the GDR”.

Since electricity was available in the West Sectors of the city for only two to four hours a day during that time and was usually cut when needed, the author rented a room in Berlin(EAST) near the Institute [The Humboldt University, at the time the only university of Berlin, and therefore also the Physiological-Chemical Institute were located in the East Sector of the city] unofficially, so to speak. This also had the advantage that the author saved the time for the twice-daily Underground trip of one hour each and was able to use the laboratories longer (During the time of the blockage, the underground ran only until 6 p.m.). Moving completely to the East Sector was no option for obvious reasons.

 

[7]       R.Riemschneider

            Lecture „Molekulare Asymmetrie“, given on  28. 2.1948,  cf also PROJEKT II in [1] and in [19]: stereochem.

 

[8]       R.Riemschneider

            „Material für biochemische Einführungsvorlesungen“ (1969 1.Ed) 1986, 74 p, 4. Edition, W Hilke KG, Berlin 30: Plate 10a-c, 7-9  - translation into Portugese by W. Pollack; cf. [34]

 

[9]       Ministério da Educação e Cultura, UFSM, Centro de Estudos Basicos. “Inauguração do Istituto Central de Química, S.Maria , 24 de Agosto de 1973” , 16 p

             “Autorga do Titulo Prof.honoris causa ao Prof.Randolph Riemschneider” 24 de Agosto de 1973”

 

[10a]    R.Riemschneider  (lecturer)

“Reactions in compressed CO₂”  - “Inorganic-organic solvents having a low melting point (polar ionic, non-aqueous solvents) Experimental data reports 1948 – 1952

Ms (leaf sheet) 1950,  15 pages + 14 pages experiments

2 lectures held at HOECHST on December 15, 1952 (secreted), Experiments in compressed CO₂ continued 1965-2007

 

[10b]   R.Riemschneider, F.R.Pesserl, D. Kirstein

Clathrates in compressed CO₂  - Preparation of methane-ice (I) –           

Investigation of the reaction  between I and CO₂-compressed

ms 1999, 18p (secreted)

Experiments carried out in 1998/99 in the labs of BRASTONE, Curitiba, PR, Brasil; cf. SPECIAL PART F).

 

[11a]    R. Riemschneider (lecturer), J C Hilscher, E B Grabitz

            “Chemistry of Polychloro-bicycloheptene-bis-hydroxymethyl and cyclic sulphite esters (THIODANE group)”

            Lecture given Aug 61 in Inst of Agric Chem, Univ of Kyoto;

            Ms 1960, 17 p, Diagrammatic representation of formulas in Pl 13 and 14: PROJ XI in [1]

 

[11b]   R. Riemschneider, J. C. Hilscher, F.Franco, R.Schlepergrell, B.Götze, R.Remke, W.Ernst

Thiodan and related compounds

Bull I:     The quantitative determinateion of thiodan,

               Z.analyt Chemie 165, 278-280 (1959)

   Bull II:    The stereochemistry of norbornene series cyclic sulphite esters and       sulphoxides,  Botyu Kagaku, Kyoto 26, 1-4  (1961)

Bull III:   Butane-2-diol-1,4-cyclosulphite and other sulphite ester,

              Z.Naturforschg 15b, 552-554 (1960)

Bull IV:    The state of research into of thiodan isomerism,

                Z.Naturforschg 15b, 809-810 (1960)

further data in:                                                                                                                     

Chemistry of Polyhalocylopentadienes: The Chemistry on DIEN-group, World Review of Pest Control, Vol 2, 29-61 (1963)

http://www.bwwsociety.org/journal/html/pestcontrol.htm  2005, 16 p

 

[12]     R. Riemschneider

            INSTITUTO DE QUíMICA – Projeto Prof. Dr. Randolph Riemschneider

            Ministério da Educação e Cultura, UFSM, 1965, 136 p: Plate 3a and b

 

[13]     R. Riemschneider

            Thalidomide  -  a remedy with two faces

http://www.bwwsociety.org/journal/html/thalidomide.htm  2004; 16p; cf [19]: thalidomide

 

[14a]    R. Riemschneider (Vortragender), F.R. Pesserl, O. Matter,

            T.J. Shimozawa

„η-1,2,3,4,5,6-Hexachlor-cyclohexane isolated from δ-oils“; (545) in [1]

Lecture from 15.9.1961, held at the Chemical Institute

Tokyo-University, chair: Prof. Dr. Y. Morino; PROJ. IX in [1]

 

[14b]   Y. Morino, R. Riemschneider

Dipolmoment measurement of h-1,2,3,4,5,6-hexachloro-cyclohexane

            ms 1961, 3 p; cf. [14a, 15]

      

[15]      R. Riemschneider,

„7 stereoisomeric 1,2,3,4,5,6-Hexachloro-cyclohexanes“

Lecture, held on 15 Aug 1964, colloquium Uni Santa Maria, in Sala de Atos, Edificio sede da USM [Universidade de Santa Maria], Santa Maria, RS, Brasil.

ms, Aug 1964, 19 p (with Portuguese Summary), chair: Prof. Dr. José Mariano da Rocha Filho, Reitor USM;  cf.  Table 2 in SPECIAL PART E); zur Bezeichnungsweise: [16] 

 

[16]     R.Riemschneider:

Über „vereinfacht eben“ und „Sessel-Konfigurationen“ von Cyclohexansubstitutionsprodukten,

Z.Naturforschg. 10b, 605-613 (1955); vgl. auch Z.Naturforschg. 10b, 177-178 (1955)

 

[17]     List of some Riemschneiders publications issued in the Japanese periodical Botyu-Kagaku, Kyoto (Scientific Insect Control, Kyoto) between 1955 and 1963:

 

Chair configuration catalogue for  C₆H₁₁X to C₆X₁₂

Botyu Kagaku, Kyoto 20, 27-46 (1955)

 

Method  for positional isomers of cyclohexane

Botyu Kagaku, Kyoto 20, 60-70 (1955)

 

The spacial structure of hexachlorocyclopentadiene adducts

Botyu-Kagaku, Kyoto 25, 123-131 (1960), Silver Jubilee Issue

 

Pentachloro- and hexachloro-cyclopentadiene as philodienes

Botyu-Kagaku, Kyoto 28, 83-91 (1963)

 

The stereochemistry of 7 cyclic sulfitic esters and 8 sulphoxides

Botyu-Kagaku, Kyoto 26, 1-4 (1961)

 

[18a]      R.Riemschneider

Cell line based organ material beats risk in animal organ extracts

http://www.vevy.com/relata   issues, Articles 2001, 2p:

International Electronic Journal on Dermopharmacological Research, Dermopharmaceutical Technology and related cosmetic subjects

 

[18b]     R.Riemschneider, M. Heisler

Porcine based organ extracts guarantee full substitution of bovine extracts

http://www.vevy.com/relata ,issues, Articles 2001, 2p; as [18a]

 

[18c]     R.Riemschneider

             Additivi cosmetici a base vegetale

             www.riemschneider.org  6p

 

[18d]     R.Riemschneider

             Two Notes on Progress in  BSE-Crisis

              http://www.bwwsociety.org/journal/html/bsicrisis.htm

The BWW Society/The Institute for the Advancement of positive Global Solutions  2003 ,  4p

 

[18e]      R.Riemschneider

              Cytocatalyzer, Cellryel, and Collaplant PO

http://www.bwwsociety.org/journal)html/cytocatalyzer.htm  2003 

6 p; journal as [18d]  

 

[18f]      R. Riemschneider

              Vegetal Placenta Extracts Substitute Animal Placenta Extracts

http://www.vevy.com/relata   ,issues, Articles 2008, 7p:

International Electronic Journal on Dermopharmacological Research, Dermopharmaceutical Technology and related cosmetic subjects

 

[19]       R.Riemschneider

              some publications between 2004 and 2008   in:  

              http://www.bwwsociety.org/Journal/html/X.htm 

X	( subject )	year	pages
pestcontrol	(chlorine insecticides)	2005	16
thalidomide	(Contergan, two faces)	2004	15
bcompounds	(heptachlorodioxanes)	2005	7
heptachloro	(heptachlorodioxanes)	2006	11
isomerie	(conversion-isomerie)	2007	24
stereochem	(cis-trans, axis-ring)	2006	38
planttech	(plant technology)	2008	28
silanes	(silanes)	2007	22
viscosity	(vT-behaviour, Cmax)	2006	22
heptites	(stereochemistry)	2007	15

 

[20]        R. Riemschneider, M. Spät, W. Rausch, E. Böttger

1,2,3,4,5,6-hexachloro-cyclohexane mp 88–89 °C (I) alias the real zeta-I-isomer e.e.a.e.a.a,

Mh.Chem. 84, 1068 – 1070 (1953): Tab 2

 

[21]       R.Riemschneider

Bull I – VI, The so-called “zeta-hexachlorocyclohexane” resp

hexachlorocyclohexane, mp 146°C,

Z.Naturforschg. 5b, 246, 307; 6b, 48, 338, 41o (1950/51)

In these papers the author cleared up constitution

and configuration of the so-called zeta-isomer and identified it as 1,1,2,4,4,5.hexachloro-cyclohexane with chair configuration

1ea2e4ea5e(Cl).

For this compound the letter „ zeta” has to be cancelled. For this letter now belongs to the sixth isomer of the 1,2,3,4,5,6-hexachloro-cyclohexane series; see [20] and “zeta-Gezeter” in SPECIAL PART E).

 

              [22a] R. Riemschneider, Y. Morino

"Calculation and determination of dipole moments of theoretically possible HCH isomers and generally of polyhalo-cyclohexanes"

Manuscript June 1953, 14 pages, written after a 5-hour meeting with Prof. Morino in Hamburg; cf. PROJ XIX in [1].

 

[22b]      S. Miyagawa, Y. Morino, R. Riemschneider

Dipolmoments of Polyhalocyclohexanes I,

Bull Chem. Soc. Japan 27, 177 – 180 (1954)

 

[22c]      J.T. Shimozawa, Y. Morino, R. Riemschneider

Dipolmoments of Polyhalocyclohexanes III,

Bull Chem. Soc. Japan 28, 393 – 396 (1955)

 

[23]        R Riemschneider

Mitt I: Derivati acetilici di combinazioni isocicliche: o-, m-, and

 p-diacetil benzolo

Gazz Chim Italiana 77, 607 - 611 (1947), date of receipt 12 September 1940, deposited in agreement with Prof C Weygand, University of Leipzig. Reason for the late release for publication at “re 1) WONDE” and PROJ. I 2 in [1]; cf. also [4].

 

[24]        R Riemschneider

              „Tiocarbammati“

Lecture given to VII National Congress of Pure and Applied Chemistry in Milan, Italy on 19 Sept 1950. Abstract: La Chimica e l’Industria 64, (3) 99 (1950).

 

[25]        R.Riemschneider

Lubricating oil-like hydrocarbons from products of pitch high-pressure hydrogen plant

Angew.Chemie B 19, 92-93 (1947)

 

[26]        R.Riemschneider

Formulas and indices for rating viscosity-temperature

dependency in liquids

Bi-Monthly Journal Of BWW Society, Jan 2006, 22 p

www.bwwsociety.org/journal/html/viscosity.htm

 

[27]        R.Riemschneider, Gg R.Schultze

„Aromatizing unsaturated aliphatic compounds“

Synopsis of the investigations in this field, covering from 1943 on; ref (232, 233, 235, 237,240-242) in PROJ III in [1]

 

[28]        K.Schmidt, P.Kollek-Bös

Some Alkyl Thiocarbamates prepared from Thiocyanates by RIEMSCHNEDER’s reaction

J.Amer.Chem.Soc.1953, 6063; 1951, 5905;

cf also: H.Krauch,  W.Kunz, F.Richter, Namensreaktionen der Organischen Chemie, Dr.A.Hüthig Verlag GmbH, Heidelberg 2001.

 

[29]        R. Riemschneider

              Heptachloro-1,4-dioxane mp 57°C -  a compound of merely academic interest

Bi-Monthly Journal Of BWW Society, 2008 www.bwwsociety.org/journal/html/heptachloro2.htm [xii] 

 

[30]        R. Riemschneider

              PEST CONTROL RESEARCH: Consequences of the complete ban of some synthetic insecticides - Less chemical pest control

Bi-Monthly Journal Of BWW Society, 2008, 32 p

www.bwwsociety.org/journal/html/ pestcontrol2.htm  [36]

 

[31]        R.Riemschneider

Plant Technology – based on Chemistry, Botany, and Architecture,

published in Internet 2008, 28 p     http://www.bwwsociety.org/journal/html/planttechnology,htm

 

[32]        R.Riemschneider

Useful and questionable applications of several vitamins and anti-vitamins,

published in Internet 2008, 30 p

http://www.bwwsociety.org/journal/html/vitamins.htm

 

[33]        R. Riemschneider

Nutritional Supplement by Hydrid Ions acting as Antioxidants and Hydrid Ions and H Atoms as "Energy Currency" for Living Systems

published in Internet 2004

http://www.bwwsociety.org/journal/html/hydrid.htm   ;also published in [32]

 

[34]        R. Riemschneider

Lecture notes in the Portuguese language (translated by W. Pollack), printed at the printing shop of UFSM:

 

"Biochemical Laboratory Courses I, II, III", all in all 180p

"Synthesis of biochemically relevant compounds" 80 p            

"Organo-chemical preparations", 120 p

"Analytical organic chemistry", 80 p

"Collagene chemistry", 25 p

 

Manuals for all laboratory courses (each course with 20 to 50 participants) were supplied to prepare for practical experiments and to set up the apparatuses.

 

In order to get these laboratory courses going, all of the necessary chemicals and apparatuses were supplied from Germany by GTZ (Society for Technical Cooperation) as specified by the author, in quantities sufficient for 500 to 600 participants (DM 2 millions for the UFSM project).

 

[35]        R.Riemschneider, M.M.Faria, F.R.Pesserl

A new synthesis of 1,5-diamino-tetrazol (V):  Diazo treatment of diaminoguanodinium-halogenids (VI) in the pH range 7,6-8,2 at room  temperature 30-35° C,

Lab report Nov 1973, 12 p, BRASTONE Company, Curitiba, and UFSM, S.Maria – patent appl. pending       

Remark:  pH range important to avoid formation of dangerous azides.

 

[36]        R. Riemschneider

              Chlorine chemistry for pest control research - starting in the 1940s - with regard to the inventors and their "fights"

http://www.bwwsociety.org/journal/html/pestcontrol.htm     2005

complete article in APPENDIX  to  PROJ III  5,3;

 

[37]        R. Riemschneider

ortho-Diacetylbenzene (o-Di) and some analogues in amino acid analytics and as marker in criminalistics - o-Di competitor of ninhydrin?

http://www.bwwsociety.org/journal/html/ortho.htm    2006

 

[38]        R.Riemschneider

              Way out of BSE-crisis

http://www.bwwwsociety.org/journal/html/bsiwayout.htm. 2008

The Bi-Monthly Journal of the BWW Society;  cf. also the essay

http://www.bwwsociety.org/journal/html/bsicrisis.htm  2002  

 

[39]        R. Riemschneider

Chemistry of Polyhalocyclopentadienes, Bull XXXV: The Chemistry of the insectizides of the DIEN-group,

World Review of Pest Control, Vol 2 29-61 (1963).

 

[40]        R.Riemschneider, H.Schlossberger

Discussion about the question: „Are there microorganisms which

can function as pollutant killer exterminating Cl-compounds?

Where to detect?“

15 Dec 1944 after the lecture of the author, held in colloquium Hyg. Inst., Jena Univ (SPECIAL PART J).